CHEMICAL ENGINEERING METHODS AND TECHNOLOGY

SONOCHEMISTRY: THEORY,
REACTIONS, SYNTHESES,
AND APPLICATIONS



No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or
by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no
expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No
liability is assumed for incidental or consequential damages in connection with or arising out of information
contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in
rendering legal, medical or any other professional services.
CHEMICAL ENGINEERING METHODS
AND TECHNOLOGY


Additional books in this series can be found on Nova‘s website
under the Series tab.


Additional E-books in this series can be found on Nova‘s website
under the E-books tab.

CHEMICAL ENGINEERING METHODS AND TECHNOLOGY









SONOCHEMISTRY: THEORY,
REACTIONS, SYNTHESES,
AND APPLICATIONS







FILIP M. NOWAK
EDITOR










Nova Science Publishers, Inc.
New York
Copyright © 2010 by Nova Science Publishers, Inc.

All rights reserved. No part of this book may be reproduced, stored in a retrieval system or
transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical
photocopying, recording or otherwise without the written permission of the Publisher.

For permission to use material from this book please contact us:
Telephone 631-231-7269; Fax 631-231-8175
Web Site: http://www.novapublishers.com

NOTICE TO THE READER
The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or
implied warranty of any kind and assumes no responsibility for any errors or omissions. No
liability is assumed for incidental or consequential damages in connection with or arising out of
information contained in this book. The Publisher shall not be liable for any special,
consequential, or exemplary damages resulting, in whole or in part, from the readers‘ use of, or
reliance upon, this material. Any parts of this book based on government reports are so indicated
and copyright is claimed for those parts to the extent applicable to compilations of such works.

Independent verification should be sought for any data, advice or recommendations contained in
this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage
to persons or property arising from any methods, products, instructions, ideas or otherwise
contained in this publication.

This publication is designed to provide accurate and authoritative information with regard to the
subject matter covered herein. It is sold with the clear understanding that the Publisher is not
engaged in rendering legal or any other professional services. If legal or any other expert
assistance is required, the services of a competent person should be sought. FROM A
DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE
AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS.

LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA
Sonochemistry : theory, reactions, syntheses, and applications / [edited by]
Filip M. Nowak.
p. cm.
Includes index.
ISBN 978-1-62100-147-8 (eBook)
1. Sonochemistry. I. Nowak, Filip M.
QD801.S665 2009
660'.2842--dc22
2010025362




Published by Nova Science Publishers, Inc.  New York










CONTENTS

Preface vii
Chapter 1 Sonochemistry: A Suitable Method for Synthesis of Nano-
Structured Materials 1
M. F. Mousavi and S. Ghasemi
Chapter 2 Industrial-Scale Processing of Liquids by High-Intensity Acoustic
Cavitation: The Underlying Theory and Ultrasonic Equipment
Design Principles 63
Alexey S. Peshkovsky and Sergei L. Peshkovsky
Chapter 3 Some Applications of Ultrasound Irradiation in Pinacol Coupling of
Carbonyl Compounds 105
Zhi-Ping Lin

and Ji-Tai Li
Chapter 4 Ultrasound and Hydrophobic Interactions in Solutions 129
Ants Tuulmets, Siim Salmar and Jaak Järv
Chapter 5 Synthetic Methodologies Using Sonincation Techniques 157
Ziyauddin S. Qureshi, Krishna M. Deshmukh
and Bhalchandra M. Bhanage
Chapter 6 Sonochemotherapy Against Cancers 189
Tinghe Yu

and Yi Zhang
Chapter 7 Application of Ultrasound for Water Disinfection Processes 201
Vincenzo Naddeo, Milena Landi and Vincenzo Belgiorno
Chapter 8 Use Of Ultrasonication in the Production and Reaction of C
60
and
C
70
Fullerenes 213
Anne C. Gaquere-Parker and Cass D. Parker
Chapter 9 Application of Ultrasounds to Carbon Nanotubes 231
Anne C. Gaquere-Parker and Cass D. Parker
Index 265










PREFACE

The study of sonochemistry is concerned with understanding the effect of sonic waves
and wave properties on chemical systems. This book reviews research data in the study of
sonochemistry including the application of sonochemistry for the synthesis of various nano-
structured materials, ultrasound irradiation in pinacol coupling of carbonyl compounds,
ultrasound and hydrophobic interactions in solutions, as well as the use of ultrasound to
enhance anticancer agents in sonochemotherapy and the ultrasound-enhanced synthesis and
chemical modification of fullerenes.
Chapter 1 - Recently, sonochemistry has been employed extensively in the synthesis
of nano-structured materials. Rapid reaction rate, controllable reaction conditions, simplicity
and safety of the technique as well as the uniform shape, narrow size distribution, and high
purity of prepared nano-sized materials are some of the main advantage of sonochemistry.
Sonochemistry uses the ultrasonic irradiation to induce the formation of particles with smaller
size and high surface area.
Because of its importance, sonochemistry has experienced a large promotion in various fields
concerned with production of new nano-structured materials and improvement of their
properties during the recent years. However, it has encountered limitations in the case of
production of some nano-materials with specific morphology, size and properties, but the
growth of the number of researches and published articles in the field of sonochemistry
during the recent years shows a large interest and attempt to apply sonochemistry in
nanotechnology. The improvement of shape, size, purity and some other chemical and
physical properties of such produced materials has been the scope of the researchers recently.
Sonochemistry uses the powerful ultrasound irradiation (20 kHz to 10 MHz) to induce
chemical reaction of molecules. During the ultrasonic irradiation, the acoustic cavitations will
occur which consist of the formation, growth and implosive collapse of bubbles in a liquid.
The implosive collapse of the bubbles generates a localized hotspot or shock wave formation
within the gas phase of the collapsing bubbles (The hot-spot theory).
This chapter is planned to deal with the application of sonochemistry for the synthesis of
various nano-structured materials such as metals, metal carbides, metal oxides, chalcogenides
and nanocomposites with unique properties. The effect of different ultrasonic parameters on
the prepared structures including their size, morphology and properties are investigated. Also,
some applications of prepared nano-materials are introduced, e.g. electrochemical energy
storage, catalysis, biosensor and electrooxidation.
Chapter 2 - A multitude of useful physical and chemical processes promoted by
ultrasonic cavitation have been described in laboratory studies. Industrial-scale
Filip M. Nowak viii
implementation of high-intensity ultrasound has, however, been hindered by several
technological limitations, making it difficult to directly scale up ultrasonic systems in order to
transfer the results of the laboratory studies to the plant floor. High-capacity flow-through
ultrasonic reactor systems required for commercial-scale processing of liquids can only be
properly designed if all energy parameters of the cavitation region are correctly evaluated.
Conditions which must be fulfilled to ensure effective and continuous operation of an
ultrasonic reactor system are provided in this chapter, followed by a detailed description of
"shockwave model of acoustic cavitation", which shows how ultrasonic energy is absorbed in
the cavitation region, owing to the formation of a spherical micro-shock wave inside each
vapor-gas bubble, and makes it possible to explain some newly discovered properties of
acoustic cavitation that occur at extremely high intensities of ultrasound. After the theoretical
background is laid out, fundamental practical aspects of industrial-scale ultrasonic equipment
design are provided, specifically focusing on:
- electromechanical transducer selection principles;
- operation principles and calculation methodology of high-amplitude acoustic horns used
for the generation of high-intensity acoustic cavitation in liquids;
- detailed theory of matching acoustic impedances of transducers and cavitating liquids in
order to maximize the ultrasonic power transfer efficiency;
- calculation methodology of ―barbell horns‖, which provide the impedance matching and
can help achieving the transference of all available acoustic energy from transducers into the
liquids. These horns are key to industrial implementation of high-power ultrasound because
they permit producing extremely high ultrasonic amplitudes, while the output horn diameters
and the resulting liquid processing capacity remain very large;
- optimization of the reactor chamber geometry.
Chapter 3 - Carbon-carbon bond formation is one of the most important topics in
organic synthesis. One of the most powerful methods for constructing a carbon-carbon bond
is the reductive coupling of carbonyl compounds giving 1,2-diols. Of these methods, the
pinacol coupling, which was described in 1859, is still a useful tool for the synthesis of
vicinal diols. 1, 2-Diols obtained in the reaction were very useful synthons for a variety of
organic synthesis, and were also used as intermediates for the construction of biologically
important natural product skeletons and asymmetric ligands for catalytic asymmetric reaction.
In particular, pinacol coupling has been employed as a key step in the construction of HIV-
protease inhibitors.
Generally, the reaction is effected by treatment of carbonyl compounds with an appropriate
metal reagent and/or metal complex to give rise to the corresponding alcohols and coupled
products, The coupling products can have two newly chiral centers formed. Threo, erythro
mixtures of diols are usually obtained from reactions. As a consequence, efficient reaction
conditions have been required to control the stereochemistry of the 1,2-diols. Recent efforts
have focused on the development of new reagents and reaction systems to improve the
reactivity of the reagents and diastereoselectivity of the products.
In some of the described methods, anhydrous conditions and long reaction time are required
to get satisfactory yields of the reaction products, some of the used reductants are expensive
or toxic; excess amounts of metal are needed. Sonication can cause metal in the form of a
powder particle rupture, with a consequent decrease in particle size, expose new surface and
increase the effective area available for reaction. It was effective in enhancing the reactivity
Preface ix
of metal and favorable for single electron transfer reaction of the aldehydes or ketones with
metal to form diols. Some recent applications of ultrasound in pinacol coupling reactions are
reviewed. The results are mostly from the author research group.
Chapter 4 - Sonochemistry and solution chemistry have been explicitly brought
together by analyzing the effect of ultrasound on kinetics of ester hydrolysis and benzoin
condensation, measured by the authors, and similar kinetic data for the solvolysis of tert-butyl
chloride, compiled from literature. For the first time the power ultrasound, reaction kinetics
and linear free-energy relationships were simultaneously exploited to study ionic reactions in
water and aqueous-organic binary solvents and the importance of hydrophobic ground-state
stabilization of reagents in aqueous solutions was discussed. This approach has opened novel
perspectives for wider understanding of the effect of sonication on chemical reactions in
solution, as well as on solvation phenomena in general.
Chapter 5 - Ultrasound generates cavitation, which is "the formation, growth, and
implosive collapse of bubbles in a liquid. Cavitation collapse produces intense local heating
(~5000 K), high pressures (~1000 atm), and enormous heating and cooling rates (>109
K/sec)" and liquid jet streams (~400 km/h), which can be used as a source of energy for a
wide range of chemical processes. This review will concentrate on theory, reactions and
synthetic applications of ultrasound in both homogeneous liquids and in liquid-solid systems.
Some recent applications of ultrasound in organic synthesis, such as, Suzuki reaction,
Sonogashira reaction, Biginelli reaction, Ullmann coupling reaction, Knoevenagel
condensation, Claisen-Schmidt condensation, Reformatsky reaction, Bouveault reaction,
Baylis-Hillman reaction, Michael addition, Curtius rearrangement, Diels-Alder reaction,
Friedal-Craft acylation, Heck reaction, Mannich type reaction, Pechmann condensation and
effect of ultrasound on phase transfer catalysis, oxidation-reduction reactions, ionic liquids
and photochemistry are reviewed. Ultrasound found to provide an alternative to traditional
techniques by means of enhancing the rate, yield and selectivity to the reactions.
Chapter 6 - Sonochemotherpy is the use of ultrasound to enhance anticancer agents.
Preclinical trials have manifested this modality is effective against cancers including
chemoresistant lesions. Sonochemotherapy is a target therapy, in which cavitation plays the
leading role. Making the occurrence and level of cavitation under control improves the safety
and therapeutic efficacy. Sonosensitizers and microbubbles enhance cavitation, being a
measure to adjust the level of cavitation. Free radicals due to cavitation have the potentials of
restructuring a molecule and changing the conformation; thus the molecular structure and
anticancer potency of a cytotoxic agent must be investigated, especially when sonosensitizer
and microbubble are employed. A potential clinical model for investigating
sonochemotherapy is the residual cancer tissues when performing palliative high intensity
focused ultrasound treatment.
Chapter 7 - Ultrasound (US) is a sound wave of a frequency greater than the superior
audibility threshold of the human hearing. Sonochemistry is the application of ultrasound in
chemistry. It became an exciting new field of research over the past decade. Some
applications date back to the 1920s. The 1950s and 1960s subsequently represented the first
extensive sonochemical research years and significant progresses were made throughout
them. Then it was realized that ultrasound power has a great potential for uses in a wide
variety of processes in the chemical and allied industries. In these early years, experiments
were often performed without any real knowledge of the fundamental physical background
about the US action. The situation changed in the 1980s when a new surge of activity started
Filip M. Nowak x
and the use of US as a real tool in chemistry began. It was in 1986 that the first ever
international symposium on Sonochemistry was held at Warwick University U.K.
Chapter 8 - In this chapter, the use of ultrasounds on fullerenes (C
60
and C
70
) and
fullerene derivatives is described. The focus is on the articles reporting the ultrasound-
promoted treatment of these nanoparticles written in English. The ultrasound-enhanced
synthesis and chemical modification of fullerenes are detailed. The improvement obtained by
sonicating the reaction mixtures while carrying out traditional organic reactions is discussed.
This includes many types of reactions, such as oxidation, cycloaddition, reduction and
amination. Also the ultrasound-enhanced crystallization of fullerenes, producing fullerites,
and the formation of colloids when the fullerenes are sonicated in various solvent mixtures
are detailed, providing the role of ultrasound in these processes.
Chapter 9 - In this chapter, the use of ultrasounds on carbon based nanotubes is
reviewed with a focus on the English written articles. The synthesis of carbon nanotubes and
their surface modification such as oxidation and covalent functionalization under ultrasounds
are reported. The synthesis of hybrid nanocomposite materials where carbon nanotubes are
added as a reinforcement agent via ultrasound-induced assembly is not described in this
chapter. A detailed survey of the literature concerning the purification and separation of
carbon nanotubes under ultrasounds is provided. The effect of sonication on carbon nanotubes
suspensions which covers aqueous and organic solutions in the presence of surfactants is
discussed with an emphasis being placed on the effect that ultrasounds have on non-covalent
interactions between the carbon nanotubes and the components of the suspensions. The effect
of ultrasounds on the physical properties of the carbon nanotubes, especially the introduction
of wall defects is analyzed. Finally the advantages and shortcomings of sonochemistry
described in this chapter are summarized, showing a possible trend in the direction of future
research in this field.
In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 1



SONOCHEMISTRY: A SUITABLE METHOD FOR
SYNTHESIS OF NANO-STRUCTURED MATERIALS


M. F. Mousavi
1
and S. Ghasemi
1
Department of Chemistry, Tarbiat Modares
University, Tehran, Iran

2
Department of Chemistry, The University of Qom,
Qom, Iran
ABSTRACT
Recently, sonochemistry has been employed extensively in the synthesis of nano-
structured materials. Rapid reaction rate, controllable reaction conditions, simplicity and
safety of the technique as well as the uniform shape, narrow size distribution, and high
purity of prepared nano-sized materials are some of the main advantage of
sonochemistry. Sonochemistry uses the ultrasonic irradiation to induce the formation of
particles with smaller size and high surface area [1].
Because of its importance, sonochemistry has experienced a large promotion in
various fields concerned with production of new nano-structured materials and
improvement of their properties during the recent years. However, it has encountered
limitations in the case of production of some nano-materials with specific morphology,
size and properties, but the growth of the number of researches and published articles in
the field of sonochemistry during the recent years shows a large interest and attempt to
apply sonochemistry in nanotechnology. The improvement of shape, size, purity and
some other chemical and physical properties of such produced materials has been the
scope of the researchers recently [2].
Sonochemistry uses the powerful ultrasound irradiation (20 kHz to 10 MHz) to
induce chemical reaction of molecules. During the ultrasonic irradiation, the acoustic
cavitations will occur which consist of the formation, growth and implosive collapse of
bubbles in a liquid. The implosive collapse of the bubbles generates a localized hotspot or

1
Corresponding author. M.F. Mousavi, Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-
175, Tehran, Iran Tel.: +98 21 82883474/9; fax: +98 21 82883455. E-mail addresses:
mousavim@modares.ac.ir, mfmousavi@yahoo.com (M.F. Mousavi).
M. F. Mousavi and S. Ghasemi 2
shock wave formation within the gas phase of the collapsing bubbles (The hot-spot
theory) [3].
This chapter is planned to deal with the application of sonochemistry for the
synthesis of various nano-structured materials such as metals, metal carbides, metal
oxides, chalcogenides and nanocomposites with unique properties. The effect of different
ultrasonic parameters on the prepared structures including their size, morphology and
properties are investigated. Also, some applications of prepared nano-materials are
introduced, e.g. electrochemical energy storage, catalysis, biosensor and electrooxidation.
1. INTRODUCTION
When ultrasound radiations interact with molecules, chemical reactions can be initiated.
Sonochemistry is an interesting research area deal with the processes occurs during the
application of powerful ultrasound (20 KHz–10 MHz). Sonochemistry arises from acoustic
cavitations. Bubbles undergo the formation, growth, and implosive collapse in a liquid under
ultrasonic irradiation. Bubble growth occurs through the diffusion of solute vapor into the
bubble. A bubble can be included evaporated water molecules and dissolved gas molecules.
When the bubble size reaches to a radius down to several µm, the bubbles collapse provides
extreme conditions of transient high temperature(as high as 5000K) and high pressure (up to
~1800 atm) within the collapsing bubbles, shock wave generation, and radical formation. The
collapsing bubbles provide reaction sites, named hot spots. At this sites, sonolysis of water
molecules to hydrogen radicals (H•) and hydroxyl radicals (OH•) is occurred which is
responsible to sonochemical reaction. Also, organic molecules in solution can form organic
radicals with a reducing ability. The size of a bubble depends on ultrasonic frequency and
intensity. Bubbles collapse occurs in very short time (nanosecond) and cooling rate of 1011
K/s is obtained. The fast kinetics of such process can hinders the growth of nuclei produced
during the collapse of bubbles. This may be the reason of formation of nanostructured
materials.
Sonochemical synthesis of different types of nanostructured materials consisted of metals
and their oxides, alloy, semiconductors, carbon carbonic and polymeric materials and their
nanocomposite have received much attention in recent years.
A number of factors can influence on cavitation efficiency and the properties of the
products. The dissolved gas, ultrasonic power and frequency, temperature of the bulk
solution, and type of solvent are all important factors that control the yield and properties of
the synthesized materials.
In the field of sonochemistry, a number of book chapter and reviews have been published
4. Y. Mastai and A. Gedanken reviewed articles in the field of sonochemistry published
before 2004 in a chapter of book entitled ―Sonochemistry and Other Novel Methods
Developed for the Synthesis of Nanoparticles‖ [2]. Also a review articles was published by
Gedanken in 2004 entitled ―Using sonochemistry for the fabrication of nanomaterials‖
focused on the typical shape of products obtained in sonochemistry [1]. Another review
articles also published dealt with insertion of nanoparticles into mesoporous materials [5] and
the sonochemical doping of various nanoparticles into ceramics and polymers [6].
In this chapter, we will present a literature survey on the various inorganic,
organic/inorganic and inorganic/inorganic systems more recently have been synthesized by
using ultrasonic method from January 2004 to January 2010s.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 3
2. SYNTHESIS OF NANOMETALS
Intensive works on metal nanostructures such as noble metals (Au, Pt, Pd) with various
size and morphology have been achieved due to their potential applications in the fabrication
of electronic, optical, optoelectronic, and magnetic devices. They can be obtained form
sonication of solution containing related metal ion in the absence and presence of capping
agents. With controlling size, shape, and crystallinity of nanometals, it can be possible to tune
the intrinsic properties of a metal nanostructure.
2.1. Gold

Gold and other noble metal nanoparticles have been extensively considered in recent
years because of their potential applications in optics, electronics, and catalysis, etc. Okitsu et
al reported the synthesis of Au nanoparticles and investigate the dependence of sonochemical
reduction rate of Au(III) to Au nanoparticles in aqueous solutions containing 1-propanol as
accelerator and their particle size to the ultrasound frequency so that the highest reduction rate
was at 213 kHz in the range of 20 to 1062 kHz [7]. The average size of Au particles was 15.5
nm in 20 mM 1-propanol.
This group also synthesized Gold nanorods by using sonochemical reduction (frequency,
200 kHz; power, 200 W) of gold ions in aqueous solution (60 mL) containing of HAuCl4 and
CTAB including 1.2 mL of AgNO3 (4.0 mM) and 240 μL of ascorbic acid (0.050 M) with pH
3.5 [8]. During the reaction, Au (III) is immediately reduced to Au (I) by reaction with the
ascorbic acid. CTAB and AgNO3 act as effective capping agents for the shape controlled
growth of gold seeds. The solution was purged with argon for 15 min and then sonicated in a
water bath (at 27 ºC) by a water circulation system. In the presence of ultrasonic, the
following reactions are proposed:

- -
+ ÷÷ ÷ OH H O H
)))
2
(1)

) ( ) (
2 2
H O H H OH CTAB ÷ +
- -
+ reducing species (2)

÷ + O H CTAB
2
pyrolysis radicals and unstable products (3)

M H Au M Au ' + + ÷ +
+ + 0
(4)

n
Au nAu ) (
0 0
÷ (5)

1
0 0 0
) ( ) (
+
÷ +
n n
Au Au Au (6)

Where M corresponds to various reducing species, pyrolysis radicals and unstable
products. In reaction 3, pyrolysis radicals and unstable products are formed via pyrolysis of
M. F. Mousavi and S. Ghasemi 4
CTAB and water. The size of the sonochemically formed gold nanorods was less than 50 nm,
and their average aspect ratio decreased with increasing pH of the solution.
At pH 7.7, irregular shaped gold nanoparticles were formed. At pH 9.8, most of the
particles formed had a spherical shape with a smaller particle size than those formed in the
lower pH solutions. Based on the obtained results, it was clear that the size and shape of the
sonochemically formed gold nanoparticles are dramatically dependent on the pH value of the
solution (Figure 1).
From the obtained results, it was demonstrated that longer gold nanorods would be
obtained if the synthesis was performed in solution with acidic pH.
Li et al. reported the synthesis of single-crystal Au nanoprisms with triangular or
hexagonal shape, 30-40 nm planar dimensions, and 6-10 nm thickness from solution of
HAuCl4 and PVP in ethylene glycol solution [9]. Ethylene glycol, the surfactant
poly(vinylpyrrolidone), and ultrasonic irradiation play important roles in the formation of Au
nanoprisms.
Single-crystalline gold nanobelts have been prepared sonochemically from aqueous
solution of HAuCl4 in the presence of α-D-glucose, a biological directing agent, under
ambient conditions (Figure 2).


Figure 1. TEM images of gold nanorods and nanoparticles formed in different pH solutions of (a) pH
3.5, (b) pH 5.0, (c) pH 6.5, (d) pH 7.7, and (e) pH 9.8 after 180 min irradiation under argon. (f) TEM
image of gold nanoparticles formed in pH 9.8 without ultrasonic irradiation.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 5

Figure 2. a,b) SEM images and c,d) high-magnification SEM images of as-synthesized gold nanobelts;
[HAuCl
4
]=50 mgmL
-1
, [α-D-glucose]= 0.2 m, ultrasound time=1 h.
The formation of gold nanobelts depends on the concentration of α-D-glucose. When its
concentration was as low as 0.05 M, only gold particles with a size of approximately 40 nm
were obtained [10]. In the dilute solution, the glucose can not provide effective coverage or
passivation of gold facets. The gold nanobelts have a width of 30–50 nm and a length of
several micrometers with highly flexibility. Nanobelts have thickness of approximately 10
nm. Authors also showed that only spherical particles with a diameter of approximately 30
nm were obtained in the presence of β-cyclodextrin. It was mentioned that ultrasound
irradiation can enhance the entanglement and rearrangement of the α-D-glucose molecules on
gold crystals.
Park et al. showed the effects of concentration of stabilizer (sodium dodecylsulfate: SDS)
and ultrasonic irradiation power on the formation of gold nanoparticles (Au-NPs) [11]. The
multiple shapes and size distribution of Au-NPs are observed by different ratio of Au (III)
ion/SDS and ultrasonic irradiation power.
A sonochemical method in preparation of gold nanoparticles capped by thiol-
functionalized ionic liquid (TFIL) in the presence of hydrogen peroxide as a reducing agent
reported by Jin et al. [12]. It was demonstrated that the molar ratio of gold atom in
chloroauric acid to thiol group in TFIL (Au/S) has great effects on the particles size and
distribution of gold nanoparticles. Small gold nanoparticles size of 2.7±0.3 nm can be
synthesized when ultrasound irradiation applied to a solution with the molar ratio of Au/S =
1:2 for 12 h.


M. F. Mousavi and S. Ghasemi 6
2.2. Palladium

Nemamcha et al reported the sonochemical synthesis of stable palladium nanoparticles by
ultrasonic irradiation of palladium (II) nitrate solution in ethylene glycol and in the presence
of poly(vinylpyrrolidone) (PVP) for 180 min [13]. During the ultrasonic irradiation of the
palladium (II) nitrate mixture, the color of the solutions turned from the initial pale yellow to
a dark brown. The following mechanism was proposed:

- -
+ ÷÷ ÷ H OH O H
))))
2
(7)

) ( ) (
2 2 2 2 2
H O H HOH C HOCH OH OH OH CH HOCH + ÷ +
- - -
(8)

+ -
+ + ÷ + nH CHO nHOCH nPd HOH C nHOCH II nPd
2 2
2 ) 0 ( 2 ) ( (9)

The coordination of the PVP carbonyl group to the palladium atoms causes to the
stabilization of the Pd nanoparticles in ethylene glycol. It has been shown by TEM that the
increase of the Pd (II)/PVP molar ratio from 0.13 ×10-3 to 0.53 ×10-3 decreases the number
of palladium nanoparticles with a slight increase in particle size. For the highest Pd (II)/PVP
value, 0.53 × 10-3, the reduction reaction leads to the unexpected smallest aggregated
nanoparticles.
2. 3. Tellurium

Crystalline tellurium nanorods and nanorod branched structures are successfully prepared
at room temperature via an ultrasonic-induced process in alkaline aqueous solution containing
tellurium nitrate, D-glucose and polyethylene glycol (PEG-400,CP) for 2 h treatment in an
ultrasonic bath [14]. A yellow sol was produced and was kept in darkness for 24 h to allow
the growth of Te nanocrystals. The as-obtained nanorods are single crystalline with [0 0 1]
growth orientation, and have 30–60 nm in diameter with 200–300 nm in length. Some
branched architectures, consisting of several nanorods, are also found in the products. The
formation of the branched structures is suggested to be the result of multi-nuclei growth in
monomer colloid.
2.4. Tin

Metallic tin nanorods were synthesized by a sonochemical method employing the polyol
process [15]. In the reaction a solution of SnCl2 in ethylene glycol was exposed to high-
intense ultrasound irradiation. The crystallized metallic tin nanorods have diameters of 50–
100 nm and lengths of up to 3 µm were synthesized. In the absence of the high-intensity
ultrasonic irradiation, no reduction of tin ions occurs even at temperatures as high as 500 ºC
in a closed cell.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 7
2.5. Ruthenium

Ruthenium nanoparticles have been prepared by sonochemical reduction of a ruthenium
chloride solution in 0.1 M perchloric acid containing propanol and SDS for almost 13 h [16].
The effects of different ultrasound frequencies in the range 20–1056 kHz were investigated.
The Ru particles have diameters between 10 and 20 nm. The rate of Ru (III) reduction by the
sonochemical method is very slow. The sonochemical reduction rate has been found to
influence by ultrasound frequency. An optimum reduction rate was determined in the
frequency range 213–355 kHz.
2.6. Germanium

Wu et al. reported a method based on ultrasonic solution reduction of GeCl4 by metal
hydride (LiAlH4 and NaBH4) or alkaline (N2H4· H2O) in tetrahydrofuran (THF) and in
ambient condition [17]. The germanium nanocrystals have narrow size distribution with
average grain sizes ranging from 3 to 10 nm. Octanol was used as capping agent. To prevent
the formation of GeO2 formed in the presence of water, the anhydrous salt is added to form a
transparent ionic solution in THF.
2.7. Selenium

Single crystalline trigonal selenium (t-Se) nanotubes with diameters of less than 200 nm
and nanowires with diameters of 20-50 nm have been synthesized by the reduction of
H2SeO3 in different solvents with a sonochemical method [18]. The morphology of the
products depends on the reaction conditions including ultrasonic parameters (e.g., frequency,
power, and time), aging time, and solvent. Hydrazine hydrate was dissolved in ethylene
glycol, water, etc. to form solutions. The solution was added dropwise to the corresponding
selenious acid solution. At the same time, ultrasound was preceded to the solution, and the
ultrasonic time is 30-60 min. Selenium nanotube and nanowire formation involved several
stage:

) (
) ( ) (
)))
))) )))
4 2 3 2
Se t Nanowires
Se t like Spherical Se Spherical H N SeO H
÷ ÷÷ ÷
÷ ÷ ÷÷ ÷ ÷ ÷÷ ÷ + o
(10)
2.8. Silver

Dendritic silver nanostructures were formed by means of ultrasonic irradiation[19] of an
aqueous solution of silver nitrate with isopropanol as reducing agent and PEG400 as disperser
for 2 h.

M. F. Mousavi and S. Ghasemi 8

Figure3. TEM image of a silver dendritic nanostructures obtained with ultrasonic irradiation of the
aqueous solutions of 0.04 M AgNO
3
, 4.0 M isopropanol and 0.01 M PEG400 for 2 h .
The side branches of the dendritic silver are constructed of well crystallized small
nanorods (Figure 3). The selected area electron diffraction (SAED) image of dendritic silver
nanostructures has single crystal nature with cubic phase and the side branch direction
assembles along <011> direction.
The irradiation time, the concentration of Ag+ and the molar ratio of PEG to AgNO3 are
parameters can influence the morphology of silver nanostructured. The low molar ratio of
PEG400 to AgNO3 (1:4 ~ 1:1) result in the formation of silver dendritic nanostructures but
the molar ratio of 10:1 will cause to formation of silver nanoparticles (in the range of 40–100
nm ) instead of dendritic nanostructures. Only silver spheroidal nanoparticles were obtained at
the beginning of the reaction but silver dendrites were observed with 1 h sonication. These
dendritic nanostructures transform to hexagonal compact crystals after 6 h later.
In another work, highly monodispersed Ag nanoparticles (NPs) were prepared by a
sonochemical reduction in which Ag+ in an ethanol solution of AgNO3 was reduced by
ultrasound irradiation in the presence of benzyl mercaptan without the additional step of
introducing other reducing reagents or protective reagents [20].
3. SYNTHESIS OF METALLIC NANOALLOYS
The nanoalloys are formed when two or more kinds of metals are melted together.
Nanoalloy materials can exhibit many novel properties, including electronic, catalytic,
magnetic and corrosion-resistant properties. The sonochemical method has been used as a
new technique for preparing alloy nanoparticles. Bimetallic nanoalloys show different
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 9
properties such as high catalytic activity and catalytic selectivity in comparison with the
corresponding monometallic counterparts so that they can be used as catalysts and gas
sensors.
3.1. Sn–Bi

Sn–Bi alloy nanoparticles were prepared by sonicating bulk Sn–Bi alloy directly in
paraffin oil under ambient pressure and room temperature [21]. Twenty grams Sn and 30 g Bi
were melted together in a vessel to obtain the bulk Sn–Bi alloy. Then 0.5 g bulk Sn–Bi alloy
was added to 30 ml paraffin oil in a horniness test tube and the system was irradiated for two
hours at 1000Wcm−2 with a high intensity ultrasonic probe. The product was centrifuged
after cooled to room temperature and washed with chloroform and dried to get some gray-
black powder. They show that when the ultrasonic power was increased from 700 to 1000
Wcm-2, the size distribution reduced from 60-80 nm to 10-25 nm. They also show that the
sonication time had little impact on the size of the nanoparticles.
3.2. Pd–Sn

Kim et al. prepared Pd–Sn nanoparticles from aqueous ethanol solution of Pd(NH4)2Cl4
and SnCl2 in the presence of citric acid by applying ultrasonic irradiation and investigate the
Pd–Sn nanoparticles for the oxygen reduction reaction (ORR) in alkaline media [22]. The
average size of Pd–Sn nanoparticles thus prepared was about 3–5 nm. The initial
concentrations of Pd and Sn and their molar ratio, the concentration of ethanol and the
concentration of citric acid affect the size distribution of the Pd–Sn nanoparticles. The Pd in
Pd–Sn nanoparticles is mostly in the metallic form.
3.3. Pt-Ru

Bimetallic catalysts comprised of Pt and Ru (Pt-Ru) are important in the development of
low temperature (<~120 ºC) H2-air and direct methanol fuel cells. Korzeniewski et al.
prepared Pt-Ru nanoparticles with diameters in the range of 2–6 nm as catalyst materials to
investigate the electrochemical oxidation of CH3OH and CO [23]. In Pt-Ru catalyst, Pt
provides sites for C-H bond cleavage and CO adsorption, and Ru activates water to produce
reactive oxides that enable conversion of carbon containing fragments to CO2.
Pt-Ru Nanoparticle bimetallic electrocatalysts with XRu ≈0.1 and XRu ≈ 0.5 were
synthesized and its response toward the electrochemical oxidation of CO and CH3OH in 0.1
M H2SO4 was investigate [24]. Syntheses were carried out in tetrahydrofuran (THF)
containing Ru3+ and Pt4+ in a fixed mole ratio of either 1:10 or 1:1 using high-intensity
sonochemistry.


M. F. Mousavi and S. Ghasemi 10
3.4. Co-B

Uniform spherical Co-B amorphous alloy nanoparticles were prepared by ultrasound-
assisted reduction of Co(NH3)2+6 with BH−4 in aqueous solution which the particle size
distribution was controlled by changing the ultrasound power and the ultrasonication time
[25]. During liquid-phase cinnamaldehyde (CMA) hydrogenation, the as-prepared Co-B
catalyst exhibited much higher activity and better selectivity to cinnamyl alcohol (CMO) than
the regularCo-B in the absence of ultrasonic waves.
3.5. Au-Ag

Au-Ag nanoalloys were prepared sonochemically form solution containing gold
nanoparticles and silver nitrate in the presence of different surfactant (sodium borohydride in
water; poly(vinyl pyrrolidone) in ethylene glycol; poly(ethylene glycol); sodium dodecyl
sulfate in water or propanol) [26]. It was suggested that the degradation of the surfactants
occurred during the ultrasonic treatment and allowed modification of the shape of gold
nanoparticles in their interaction with silver ions. Monodisperse gold-silver nanocomposite of
triangular or polygonal structure was obtained with reduction of the silver by NaBH
4
on the
gold surface in the presence of ultrasonic irridation. Uniformly distributed gold-silver with
round shapes was resulted after sonication in poly (ethylene glycol). Multiangular Au-Ag
nanocomposites of larger size appeared after ultrasonic irradiation of the gold-silver mixture
in the presence of poly (vinyl pyrrolidone) in ethylene glycol due to the capping effect and the
relatively low rate of degradation of PVP. With SDS, worms or netlike gold-silver
nanostructures obtained after 1 h of ultrasonic irradiation of AgNO
3
in propanol and water,
respectively.
3.6. Bimetallic Nanoparticles with Core-Shell Morphology

Sonochemically assisted synthesis of bimetallic nanoparticles with core-shell morphology
have been reported for materials such as Co/Cu [27], Au/Pd 28 and Pt-Ru [29].
A sequential sonolysis method was used to synthesis of Pt-Ru core shell (Pt@Ru)
structure [29]. Pt-Ru has been used as a methanol oxidation catalyst in direct methanol fuel
cells (DMFC). A potassium tetrachloroplatinate (K2PtCl4) solution containing 8 mM SDS,
200 mM propanol, and 0.1 M HClO4 were sonicated to reduce the Pt (II) to colloidal Pt (0)
during 3h at 20 °C. When all of the Pt (II) has been reduced, the RuCl3 solution was added to
the Pt colloidal solution and sonication continued. TEM image of the nanoparticles showed
that the ruthenium formed a layer around the platinum particles and Pt-Ru core-shell particles
in the range of 5-10 nm were formed (Figure 4). The platinum particle sizes are ~7 nm, while
the thickness of the ruthenium shell was estimated to be between 2 and 3 nm.
When 1mg/mL of polyvinyl-2-pyrrolidone, PVP (MW =55000) is used as the stabilizer,
the formation of colloidal platinum is very rapid and become complete within 1 h of
sonication. At the end of 1 h, when all of the Pt (II) was reduced, the RuCl
3
solution was
added to the Pt colloidal solution and sonication continued.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 11

Figure 4: (a) TEM of Pt-Ru nanoparticles synthesized by sonocation of a solution containing 1 mM
PtCl
4

2-
in 200 mM propanol, 0.1 M HClO
4
, and 8 mM SDS followed by the reduction of 1 mM RuCl
3

under argon atmosphere. The RuCl
3
solution was added after the PtCl
4
2-
solution was sonicated for 4 h.
The total time of sonication was 7h at 213 kHz. (b) Absorption spectra Pt-Ru nanoparticles.
The TEM images showed ultrasmall 2 nm sized particles without core-shell morphology and
only the presence of bimetallic ruthenium and platinum was confirmed by energy-dispersive
X-ray analysis of the TEM.
Figure 4b shows the change in absorption spectra of the colloidal solutions with time.
Curve a shows the absorption spectrum of PtCl4 2- solution at time t = 0 and continuing
through the addition of the RuCl3 and its reduction. Curve e shows the absorption spectrum
immediately upon addition of the ruthenium chloride. Only one prominent peak at 400 nm
appears in the curve indicating an instantaneous partial reduction of Ru (III) upon addition to
the solution.
As mentioned above, Vinodgopal et al used a sequential reduction method to prepare Pt-
Ru core-shell nanoparticles but Anandan and his coworker prepared Au-Ag bimetallic
nanoparticles by the sonochemical co-reduction of Au(III) and Ag(I) ions in aqueous
solutions containing polyethylene glycol (0.1 wt %) and ethylene glycol (0.1 M) [30]. The
average diameter of the bimetallic clusters prepared by the simultaneous reduction is about 20
nm. The stabilizing polymers can coordinate to metal ions before the reduction. This
interaction between the polymer and the metal ions lead to the formation of smaller size core-
M. F. Mousavi and S. Ghasemi 12
shell nanoparticles with a narrow size distribution. They also suggested that the formation of
core-shell morphology is most likely due to the difference in the reduction rates of the
individual metal ions and the involvement of a polymer-Ag ion complex. Gold ions are firstly
reduced under the sonochemical conditions followed by the reduction of Ag+ ions on the
surface of the gold particles.
4. METAL OXIDE

During the last years, the ultrasonically assisted synthesis of metallic oxides and
hydroxides has been considered by some of researchers. Due to their importance in various
area of science, some of them are investigated in the following paragraph.
4.1. ZnO

ZnO is one of the most important multifunctional semiconductors with wide direct energy
band gap of 3.37 eV and large exciton binding energy (about 60 meV). Sonochemical
synthesis of ZnO nanostructures with different shapes such as nanowires, nanotubes,
nanoparticles have been considers by some of authors. The effects of various parameters on
the morphology of ZnO nanostructures were investigated. ZnO nanostructure with
morphologies such as flower-like clusters [31], cauliflower-like [32], nanorods [33], needle-
shape [34], trigonal-shaped [35], nanosheet [36] and Hollow ZnO microspheres [37].
Jung et al fabricated ZnO nanorods, nanocups, nanodisks, nanoflowers, and nanospheres
in a horn-type reaction vessel using an ultrasonic technique at a power of 50 W (intensity of
39.5 W/cm2) and frequency of 20 kHz (Figure 5) [38]. The kind of hydroxide anion-
generating agents, concentration of reactants, sonication time and additives are dominant
factor affect on preparation of different morphology of ZnO. For the production of ZnO
nanorods and ZnO nanocups, different concentration of Zn(NO3)2 and
hexamethylenetetramine (HMT, (CH2)6N4 as well as different sonication time (30 min for
nanorods in comparison with 2h for nanocups) were used. An increase in ultrasonication time
provides such energy indicates to the reaction System that hinders the ZnO nanorod growth.
Triethyl citrate was used as an additional chemical additive to synthesize ZnO nanodisks.
ZnO nanocrystals grow preferentially along the [0001] direction to form nanorods. The
growth rate of the ZnO crystal along the [0001] direction decreases dramatically due to the
addition of triethyl citrate.
For the synthesis of ZnO nanoflowers and nanospheres, ammonia–water (28–30 wt %)
solution were used as hydroxide anion precursors. In the case of ZnO nanospheres, triethyl
citrate was added to the mixture of zinc acetate dihydrate solution (90 mL) and ammonia–
water (10 mL). The sonochemical growth mechanism of ZnO nanostructures was suggested
by authors as follows:

HCHO NH O H N CH 6 4 6 ) (
3 2 4 6 2
+ ÷ + (11)

÷ +
+ ÷ + OH NH O H NH
4 2 3
(12)
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 13
÷ ÷ +
÷ +
2
4
2
) ( 4 OH Zn OH Zn (13)

÷ ÷
+ + ÷÷ ÷ OH O H ZnO OH Zn 2 ) (
2
))) 2
4
(14)

2
)))
2
2
2
3
2 O ZnO O Zn + ÷÷ ÷ +
÷ - +
(15)

The sonolysis of water produces
÷ -
2
O radicals in solution.


Figure 5. SEM (left) and TEM (right) images of ZnO nanostructures. (a,b) Nanorods. (c,d) Nanocups.
(e,f) Nanodisks. (g, h) Nanoflowers. (i, j) Nanospheres. (Insets: HRTEM image) .
The same authors presented in another paper a sonochemical method for fabricating
vertically aligned ZnO nanorods arrays on various substrates such as a large-area Zn sheet, Si
M. F. Mousavi and S. Ghasemi 14
wafer, transparent glass, and flexible polymeric materials, in an aqueous solution under
ambient conditions [39].
A template-free, sonochemical route to prepare porous hexagonal ZnO nano-disks has
been developed by Bhattacharyya and Gedanken. The nano-disks are 260–400 nm across the
edges and 290–430 nm across the vertices[40]. Some of authors used ultrasonic irradiation to
fabricate well-defined dentritic ZnO nanostructures in a room-temperature ionic liquid [41].
The ZnO nanostructures have been used to sensing etanol [42], high performance NO2
gas sensor [43], gas sensitivity to NO [44].
4.2. CuO

The synthesis of one-dimensional (1D) Cu(OH)2 nanowires [45] in a aqueous solution of
CuCl2 and NaOH was done under ultrasound irradiation with 40 kHz ultrasonic waves at the
output power of 100% at 70 ºC for 5-60 min. The morphology of products is highly depends
on time of ultraonication. Under continuous ultrasonic irradiation, Cu(OH)2 nanowires
integrated into nanoribbons, then parts of nanoribbons crosswise grew to form 3D Cu(OH)2
nanostructures; finally, 3D nanostructures disrupted and transformed into 3D CuO
microstructures. The effect of ultrasonic irradiation time on conversion process of Cu(OH)2
to CuO was investigated. A color change of the product from the pale-blue to the black was
observed in the range of 15 to 45 min of irradiation implied the gradual conversion of
Cu(OH)2 to CuO. The XRD analyses of the products confirmed the conversion process. It
was demonstrated that the ultrasound plays two roles besides dispersion: shortening the
conversion time from Cu(OH)2 to CuO and inducing the formation of 3D CuO
microstructures. The CuO microstructures showed better electrochemical property than
Cu(OH)2.
4.3. V
2
O
5


A sonochemical method has been developed to preparation self-assemble V
2
O
5

nanowires with spindle-like morphology (Figure 6). Vanadium oxide (V
2
O
5
, 0.46 g, 2.5
mmol) and sodium fluoride (NaF, 0.21 g, 5 mmol) were dissolved in 50 mL of distilled water
in a 100-mL round-bottom flask and exposed to high-intensity ultrasound irradiation (20 kHz,
100 W/cm
2
) under ambient air for 2 h. The organization of 1D V
2
O
5
nanostructured subunits
into spindle -like V
2
O
5
bundles was occurred
Each bundles composed of several tens of homogeneous nanowires with diameters of 30-
50 nm and lengths of 3-7 µm. Also, a sensitive resonance light scattering (RLS) method was
developed to detect bovine serum albumin (BSA) based on the ultrasonically V2O5 bundles
[46]. An increase in the scattered light signals of V2O5 bundles were observed by the
addition of BSA. The enhanced RLS intensity at 468 nm of V2O5 bundles-BSA varies
linearly with the concentration of BSA in the range from 0.5 to 20 µg mL-1.
Synthesis of self-assembled nanorod vanadium oxide bundles by sonochemical technique
were reported by a Malaysian group [47].

Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 15

Figure6. FE-SEM images of the V
2
O
5
bundles with spindle-like morphology (a) low-magnification
SEM image of V
2
O
5
bundles; (b) low-magnification TEM image.
The morphologies of the nanorod vanadium oxides are depended on the time of sonication so
that a uniform, well defined shapes and smaller size nanorod vanadium oxide bundles were
obtained with higher ultrasound irradiation times. Vanadium oxide bundles showed higher
activity to anaerobic oxidation of n-butane than the bulk material.
4.4. Iron oxide

Suslick and Bang used carbon nanoparticles as a spontaneously removable template for
synthesis of crystalline hollow hematite (α-Fe2O3) [48]. A mixture of Spherical carbon
nanoparticles (0.1 g) (4- 12 nm diameter) and Fe(CO)5 (0.5 mL) in 40 mL of hexadecane was
irradiated by a high-intensity ultrasound horn (operated at 20 kHz and 50 W/cm2 at 20 °C for
3 h under argon flow). The decomposition of Fe(CO)5 form high-surface-area iron shells
around the core carbon nanoparticles. The high-surface-area iron shells rapidly oxidize in
contact with air and release such heat that ignites the carbon particles. The combustion of the
nanosized carbon particles generates enough heat to crystallize the iron oxide shells to hollow
cores α-Fe2O3 (Figure 7). Mössbauer spectra confirm the presence of hematite as the only
iron species. Under the same condition, the sonication of precursor solution in the absence of
carbon nanoparticles produce agglomerated nanoparticles of ~ 6 nm.
M. F. Mousavi and S. Ghasemi 16

Figure 7. (a) Bright-field and (b) dark-field TEM image of nanosized hollow hematit.
Any organic residues were completely removed by annealing the as-produced hollow
hematite at 450 °C for 2 h under air. TEM image and EDS (energy dispersve X-ray
spectroscopy) reveal that the morphology and composition of the hollow hematite remained
unchanged after the heat-treatment. The hollow hematite nanoparticles shows hysteresis loops
for at 5 and 298 K. Also, the hollow hematite nanoparticles are weakly ferromagnetic down to
5 K.
Another work has been reported to sonochemically synthesis of monodispersed magnetit
nanoparticles [49]. Dang et al. used an FeCl2 ethanol–water mixed solvent and a 2 N NaOH
aqueous solution to from a Fe(OH)2 precipitate. The Fe(OH)2 precipitate was irradiated by an
ultrasonic horn in air at 50 ºC to synthesize magnetite nanoparticles. It was demonstrated that
the formation of magnetite was accelerated in ethanol–water solution in the presence of
ultrasonic irradiation.
Monodisperse iron oxide nanoparticles with 5–20 nm can be synthesized by an
inexpensive and simple ultrasonic-assisted method at low temperature [50]. This is based on
the decomposition of iron pentacarbonyl in cis–trans decalin. They found that ultrasonic
irradiation could greatly enhance the crystallization of iron oxide nucleus at 190 °C, after the
react solution was refluxed at this temperature; monodisperse γ-Fe2O3 nanocrystals were
obtained.
4.5. Manganese Oxide

An ultrasonic technique was used to prepare MnO2 nanoparticles inside the pore
channels of ordered mesoporous CMK-3 [51]. MnO2 nanoparticles were anchored in pores of
carbon CMK-3. The size of MnO2 incorporated in CMK-3 is between 0.5 nm and 3.0 nm. In
the pores, KMNO4 reduce to MnO2. Ultrasonic technique controls the amount of loading
MnO2 inside CMK-3. CMK-3 with 20 wt. % loading of MnO2 inside CMK-3 produced an
improved discharge capacity of 223 mAhg-1 at 1 Ag-1.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 17
Colloidal Mn3O4 nanoparticles with diameters of about 5-10 nm has been pepared by an
ultrasonic-assisted method in the absence of any additional nucleation and surfactant at
normal temperature and pressure [52]. It was shown that reveal the size and the crystallinity
of Mn3O4 nanoparticles depends on the growth temperature so that the smaller the average
diameter and the poorer the crystallinity of Mn3O4 nanoparticles was observed at lower
reaction temperature. The magnetic properties of the samples showed that Mn3O4
nanoparticles exhibited ferromagnetic behavior at low temperature (40 K).
Kumar et al. prepared sonochemically a highly dispersed and non-agglomerated α-MnO2
nano-needles of dimensions 20–30 nm from aqueous solution consisting of manganese
Mn(acetate)3 and LiOH with a pH value of 7.2 [53].
The sonochemical preparation of MnO2 was reported through the reduction of MnO4- in
water under Ar atmosphere. The effect of H2O2 formed in the sonolysis of water on the rates
of reduction of MnO4- was investigated [54]. It was shown that the rate of the sonochemical
reduction of MnO4- depend on the amount of sonochemically formed H2O2 molecules.
Mn3O4 nanoparticles were prepared by reacting MnCl2 and NaOH in water at room
temperature through a sonochemical method, operated at 20 kHz and 220 W for 20 min [55].
Also, the LiMn2O4 nanoparticles were also prepared. A thin film of the LiOH with the
thickness of about 4.5–5.5 nm was coated onto the surface of Mn3O4 under the same
sonochemical conditions and the LiOH-coated Mn3O4 particles sample was heated at the
relatively low temperature of 300–500 °C. The thickness of coated LiOH on Mn3O4 obtained
from the reaction ratio of 3:1 between LiOH and Mn3O4 was about 4.5–5.5 nm range. Then,
by heating LiOH-coated Mn3O4 particles at the relatively low temperature of 300–500 °C for
1 h, they were transformed into phase-pure LiMn2O4 nanoparticles of about 50 to 70 nm size
in diameter.
4.6. In
2
O
3


The synthesis of monodispersed In2O3 nanoparticles and doped with rare earth ions
((Eu3+ and Dy3+)) is another work considered to investigate their photoluminescence
properties [56]. To a solution of indium ethoxide, In(OEt)3, in 20 ml ethanol containing 0.36
g cetyltrimethyl ammonium bromide (CTAB), 60 ml water was added and pH of solution was
adjusted to 10 by adding NH4OH. The irradiation of solution with a high-intensity (100
W/cm2) ultrasonic radiation operating at 20 kHz, under air at room temperature resulted in
In(OH)3 nanoparticles. After 1 h sonication, In(OH)3 nanocubes are obtained in the range of
30-35 nm. The In2O3 nanoparticles were formed by heating the In(OH)3 nanoparticles in
furnace under air at 350 °C for 1 h. On exciting at 235 nm, emission peaks around 460 nm
(blue) and two relatively less intense peaks centered around 548 nm (yellow) and 618 nm
(orange) were observed possibly due to the presence of shallow defect levels in the annealed
samples. With Eu3+/Dy3+ incorporation, the In2O3 diffraction peaks broads with respect to
diffraction peaks of undoped In2O3. With Eu3+/Dy3+ incorporation, Eu3+/Dy3+ has gone
into the In2O3 lattice and lattice undergoes distortion. In2O3 doped Dy3+ nanoparticles did
not show any luminescence due to the highly strained and distorted environment around the
dysprosium ions in the In2O3 lattice. A similar strain causes to the low emission intensity in
the In2O3 doped Eu3+ particles.
M. F. Mousavi and S. Ghasemi 18
4.7. TiO
2


TiO2 is an important semiconductor for a broad range of applications, such as hydrogen
production, solar cells, biological coatings and photocatalysis [57]
Mesoporous titanium dioxide nanocrystalline powders were synthesized by ultrasonic-
induced hydrolysis reaction of tetrabutyl titanate (Ti(OC4H9)4 , TBOT). TBOT was added
dropwise to 40 ml pure water in a 100 ml beaker. Pulse irradiation was done with a high
intensity ultrasonic horn (6.3 mm diameter Ti-horn, 20 kHz, and 1200 W/cm2 at 50%
efficiency) for 45 min. In pulse technique, ultrasonic wave is on for 2 s followed by 2 s off
during the whole reaction. The sonication promoted the hydrolysis of TBOT, crystallization
of TiO2 and formation of mesopore TiO2. The as-prepared products by the ultrasonic method
were composed of anatase and brooktie phases Photocatalytic decomposition was investigated
for formaldehyde and acetone. Mesopore TiO2 prepared by ultrasonic method showed better
photocatalytic activities than the samples prepared by conventional hydrolysis method.
Wang et al. prepared mixed-crystal TiO2 powder with high sonocatalytic activity under
ultrasonic irradiation in hydrogen peroxide solution [58]. The nano-sized rutile phase TiO2
powder (10.0 g) and 30% hydrogen peroxide solution (30 mL) were mixed into a glass reactor
and suspension was treated under ultrasonic irradiation for 4.0 h. A white powder was
obtained after washing and drying. This powder was heat-treated at 400 °C for 40 min. The
XRD and the FT-IR spectra of treated mixed-crystal showed both nano-sized rutile phase and
anatase phase TiO2 powders. The sonocatalytic degradation of methylene blue in aqueous
solution was investigated under ultrasonic irradiation in the presence of treated mixed-crystal
TiO2 powder. Effect of different parameters such as heat-treated temperature and heat-treated
time on degredation of methylen blue was studied. It was shown by the UV–vis spectra that
the methylene blue in aqueous solution can be obviously degraded under ultrasonic irradiation
in the presence of treated mixed-crystal TiO2 powder.
Guo et al. prepared the mesoporous TiO2 nanorods using industrial bulk Ti powder [59].
The as prepared materials contained numerous irregular olive-like nanorods aggregates. The
nanorods were 8–12 nm in width and 15–100 nm in length. The products showed higher
photocatalytic activity to toluene than Degussa P25 TiO2.
Crystalline anatase TiO2 nanoparticles was synthesized from titanium tetraisopropoxide
in the ionic liquid 1-(3-hydroxypropyl)-3-methylimidazolium-bis(trifluoromethan esul-
fonyl)amide by ultrasound assisted synthesis [60]. The spherical shaped TiO2 particles have a
small size (~5 nm) with narrow size distribution. TiO2 nanoparticles have high surface area
of 177m2 g−1 with bandgap of 3.3 eV. The spherical TiO2 nanocrystals have good
photocatalytic activity in the degradation of methylorange.
Zhou reported the preparation of nanocrystalline mesoporous Fe-doped TiO2 powders
red by the ultrasonic-induced hydrolysis reaction of tetrabutyl titanate (Ti(OC4H9)4) in a
ferric nitrate aqueous solution [61]. The photocatalytic activities of Fe-doped TiO2 powders
were investigated by the photocatalytic oxidation of acetone in air. The high activities of the
Fe-doped TiO2 powders was observed due to synergetic effects of Fe-doping and large
specific surface area of catalyst.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 19
4.8. PbO
2


Our research group synthesized β-PbO2 nano-powder by the ultrasonic irradiation of an
aqueous suspension of dispersed β-PbO (Pure yellow orthogonal phase), as precursor, in the
presence of ammonium peroxydisulfate as an oxidant [62]. The effect of pararmeters such as
oxidant concentration, temperature and ultrasonic wave amplitude on the morphology,
reaction rate and composition of products were investigated. The reaction rate increased with
an increase in temperature and ammonium peroxydisulfate concentration. It was found that
the applied ultrasonic wave determines the particle size. PbO2 samples prepared under
optimized experimental conditions have lead dioxide particles in the range of 50–100 nm.
It was observed that the use of Pb(NO
3
)
2
, instead of the lead precursor β-PbO, resulted in
the formation of PbSO
4
, which precipitated out at the end of the reaction. Thus, the oxidation
process should be initiated with β-PbO. When ultrasonic waves were applied to β-PbO
particles, only mechanical milling occurred and the particles were cracked. β-PbO was not
oxidized under these conditions, even with an increase in the duration of ultrasonication. In
fact, a proper oxidant is necessary to convert β-PbO to PbO
2
. In the presence of ammonium
peroxydisulfate, the increased concentration of hydroxyl radical facilitated the oxidation of β-
PbO to PbO
2
under ultrasonic irradiation. The XRD results reveal that only β-PbO
2
is formed
under optimum conditions. When the reaction mixture was stirred instead of ultrasonically
irradiated, only a fraction of the lead oxide was converted to lead dioxide, and lead sulfate
was the main reaction product.
4.9. Other Metallic Oxide

Other metallic oxides such as bismuth oxide [63], lead oxide [64 65], magnesium
oxide66, molybdenum oxide [67], mercury oxide [68], Tungsten oxide [69] and tin oxide[70]
have been synthesized by sonochemistry methods in the past several years.


Figure 8. SEM of lead dioxide (β-PbO
2
) samples prepared from a solution containing 0.2 g β-PbO and 5
g (NH
4
)
2
S
2
O
8
at 60 ºC and ultrasonic amplitude of 84µm (Diffrent magnification).

M. F. Mousavi and S. Ghasemi 20
4.10. Rare-Earth Oxide

Wang et al. in 2002 used a sonochemical method to prepare CeO2 nanoparticles [71].
After that, Miao et al. succeed to synthesis of CeO2 nanotubes by a sonochemical method
under ambient air in alkali aqueous solution without any template [72]. The CeO2 nanotubes
had diameters of 10–15nm and length of 150–200 nm. They also showed that when 3 M KOH
aqueous solutions is used, only rod-like assemblies composed of CeO2 nanoparticles with the
size of 5 nm were appeared. The CeO2 nanotubes were obtained only at concentration higher
than 5 M KOH.
In 2007, Zhang et al proposed a sonochemical method to synthesis of Polycrystalline
CeO2 nanorods with 5-10 nm in diameter and 50-150 nm in length at room temperature [73].
Polyethylene glycol (PEG) was used as a structure-directing agent. In the absence of PEG, the
agglomerated nanoparticles was formed instead nanorods. To a solution of Ce(NO3)3
containing 1 g of PEG600, NaOH solution (0.005 g/mL) was added gradually (5 mL/min)
under ultrasonication for ~1 h at room temperature until the pH value was 10. TEM images of
the CeO2 showed nanorods with the clear (111) and (220) lattice fringes with the interplanar
spacing of 0.31 and 0.19 nm, respectively. The UV-vis absorption spectrum of the CeO2
nanorods exhibits a strong absorption band at the UV region due to the charge transfer
transitions from O 2p to Ce 4f bonds. The BET specific surface area of CeO2 nanorods was
calculated 154.5 m2 g-1 in comparison with 5.7 m2 g-1 of commercial CeO2.
Nanoparticles of the single (Eu3+, Dy3+, Tb3+), double(Eu3+/Dy3+, Eu3+/Tb3+,
Dy3+/Tb3+), and triple (Eu3+/Dy3+/Tb3+) doped Gd2O3 (gadolinium oxide) nanoparticles
were prepared via a sonochemical technique [74]. The particles sizes were in the range of 15
to 30 nm. The triple doped samples showed multicolor emission on single wavelength
excitation.
5. THE SONOCHEMICAL SYNTHESIS OF MIXED OXIDES

Mixed Oxides such as aluminates, molybdates, manganates and etc. have been found
many applications in sensors, electrooptic and electromagnetic devices because of their
prominent properties. The sonochemical method is one of the simple route have been used
during the last years to prepare nanostructure mixed oxides.
5.1. MVO
4


Much of work on metal vanadate is focused on bismuth vanadate (BiVO4) because
BiVO4 has been recently recognized as a strong photocatalyst for water water decomposition
and organic pollutant decomposing under visible light irradiation due to its narrow band gap
75.
A facile sonochemical approach has been developed for the synthesis of BiVO4
photocatalyst by Zhou and his coworkers. In a typical preparation, aqueous solutions of
Bi(NO3)3 and NH4VO3 were mixed together in 1:1 molar ratio and exposed to high-intensity
ultrasound irradiation for 60 min. The average crystal size of as-prepared BiVO4 particles is
ca. 50 nm and samples exhibited surface areas of ca. 4.16 m2/g. The as-prepared BiVO4
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 21
nanocrystals had strong absorption in visible light region with an obvious blue-shift compared
with that of the bulk sample. The band gap was estimated to be ca. 2.45 eV. BiVO4
nanocrystals showed high photocatalytic activities to decolorization of methyl orange under
visible light (λ > 400 nm).
Shang et al. used polyethylene glycol (PEG 20000) as surfactant[76]. An aqueous
solutions of Bi(NO3)3 and NH4VO3 in 1:1 molar ratio as well as polyethylene glycol (1 g)
was exposed to high-intensity ultrasonic irradiation (6 mm diameter Ti-horn, 600W, 20 kHz)
for 30 min in ambient condition. The pH value was adjusted to about 7 by NH3. Nanosized
BiVO4 consisted of small nanoparticles with the size of ca. 60 nm. The nanosized BiVO4
exhibited excellent visible-light-driven photocatalytic efficiency for degrading Rhodamine B
(RhB) with good stability. When the RhB solution was irradiated with visible-light (λ > 420
nm) in the presence of calcinated well-crystallized BiVO4 sample, about 95% of RhB was
degraded after being irradiated for 30min and the spectral maximum shifted from 552 to 500
nm.
The lanthanide orthovanadate LnVO4 (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb, Lu) nanoparticles had been prepared from an aqueous solution of Ln(NO3)3 and
NH4VO3 without any surfactant under ultrasonic irradiation[77]. It was observed that the
morphology of the LnVO4 nanoparticles was affected strongly by ultrasonic irradiation. The
as-formed LnVO4 particles have a spindle-like shape with an equatorial diameter of 30-70
nm and a length of 100-200 nm. Each particles (as aggregates) are composed of smaller
nanoparticles of 10-20 nm.
The sonochemical synthesis of Lanthanide orthovanadates RVO4 ( R = La, Ce, Nd, Sm,
Eu and Gd) was reported in the presence of Polyethylene glycol (PEG-900) and amphiphilic
triblock copolymer Pluronic P123 as structure-directing agents at room temperature [78].
When the P123 surfactant was used, the Lanthanide orthovanadates with nanorod shape was
observed. With the surfactant PEG, nanorods of NdVO4, nanospindles of GdVO4 and
nanoparticles of other orthovanadates were obtained.
5.2. MTiO
3


The metal tiatanates, BaTiO3, PbTiO3, and PbTiO3 have been reported to be synthesized
by sonochemical methods [79]. Wang and his coworker prepared PbTiO3 fine powders with
narrow size distribution (40–60 nm) by a sol-gel method with lead acetate Pb(OCOCH3)2,
tetrabutyl titanate Ti(OBu)4 as precursors via ultrasound irradiation.
The formation of BaTiO3 particles was reported by a Japanese group [80]. They used
ultrasonic irradiation to form narrow size distribution of aggregated particles. This method
caused to formation of the aggregation of the original 5–10 nm BaTiO3 particles. It is thought
that under ultrasonic irradiation, Ti-based sol forms by the hydrolysis of TiCl4 in Ba2+
aqueous solution. Ti ions dissolve form the Ti-based sol to form Ti(OH)62- octahedron and
the nucleation of BaTiO3 occurs around the Ti-based sol. Ultrasound influences the synthesis
of BaTiO3 particles mainly through acceleration the dissolution of Ti ion from Ti-based sol
and the nucleation of BaTiO3 particles.
Xu et al. developed a sonochemical method for the synthesis of spherical BaTiO3
nanoparticles by sonicating a strong alkaline solution including BaCl2 and TiCl4 [81]. They
M. F. Mousavi and S. Ghasemi 22
showed that the reactant concentration influence the particle size. This group also synthesizes
the SrTiO3 nanoparticles with the same sonochemical method.
5.3. MAl
2
O
4


Metal aluminate, MAl2O4 (M = Cu, Zn and Mg), has been also prepared by
sonochemical methods [82]. Spinel copper aluminate (CuAl2O4) nanoparticles were prepared
by sonicating an aqueous solution of copper nitrate, aluminium nitrate, and urea. Upon
heating at 900 ◦C for 6 h, the precursor formed nanosized CuAl2O4 particles with an average
size of 17nm. The BET surface area of CuAl2O4 anoparticles was about 110 m2 g−1. The
photochemical catalysis degeneration of methyl orange on CuAl2O4 noparticles as
photocatalyst was investigated under the irradiation of 125W Hg lamp (λ > 400 nm). The rate
of the methyl orange degradation was measured to be as high as 98% in 2 h.
They reported another work that investigate the effect of processing conditions on
preparation of nanosized copper aluminate (CuAl2O4) spinel using Cu(NO3)2 and Al(NO3)3
as starting materials and urea as a precipitation agent at a concentration of 9 M [83]. The
reaction was carried out under ultrasound irradiation at 80 ºC for 4 h and a calcination
temperature of 900 ºC for 6 h.
High surface area MgAl2O4 has been synthesised by a sonochemical method. Two kinds
of precursors were used, alkoxides and aluminium nitrates/magnesium acetates in the
presence and absence of cetyl trimethyl ammonium bromide (CTAB). In the case of alkoxides
precursors the as-made product is a mixture of hydroxides of aluminium and magnesium, and
after heating at 500 ºC pure MgAl2O4 phase was not obtained [84]. While with
nitrates/acetates a gel is obtained after sonication, containing the metal hydroxides and
ammonium nitrate. Heating at 500 ºC transforms the as-made products into MgAl2O4 spinel
phase with the surface area of 267 m2/g. In the case of nitrates/acetates precursors, the CTAB
reduces the formation of large stable aggregates.
Zinc Aluminate ZnAl2O4 and Zinc Gallate ZnGa2O4 doped with Mn2+ and some of
lanthanide ions such as Dy3+, Tb3+, Eu3+ were synthesized through a sonochemical process
85. Photoluminescence studies were done on prepared samples. The doped samples showed
multicolor emission on single wavelength excitation.
5.4. MWO
4


PbWO4 nanostructures with different morphologies, such as polyhedral, spindle-like, and
dot-shaped, have been synthesized via a mild sonochemical route from an aqueous solution of
lead acetate and sodium tungstate (Na2WO4) in the presence of complexing reagent
nitrilotriacetate acid (NTA) [86]. H3NTA is a precursor of a multidentate organic ligand
(NTA3-), incorporating carboxylic acid groups and one N-donor atom, capable of
coordinating to several metal centers. The mechanism of the formation of PbWO4
nanocrystals is probably related to the coordination of Pb2+ and NTA3- to form Pb-NTA
complex. To explain what has been occurred in the reaction vessel, it was suggested that Pb-
NTA complex is formed due to coordination of Pb2+ and NTA3-. In the presence of
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 23
ultrasound irradiation (20 kHz, 60 W/cm2), the dissociation of the complex was occurred and
PbWO4 was formed. The mechanism is summerised as follow:

÷ + ÷
+ ÷
3 2
NTA Pb PbNTA (16)

4
2
4
2
PbWO WO Pb ÷ +
÷ +
(17)

Different shapes of PbWO4 nanocrystals, i.e. polyhedral, spindle-like, and dot-shaped
morphologies were obtained with controlling the pH value and the amount of complexing
reagent. A pH range of 5-9 is optimal. Figure 9a shows that the products prepared at pH 9.0
are polyhedrons with dimension of (400-500) nm × (600-700) nm. At the pH value was
decreased of 7.0, the homogeneous spindle-like nanorods with diameters of 50-60 nm at the
center and lengths of about 200-250 nm (Figure 9b) was obtained. Figure 9c shows the dot-
shaped product prepared with a pH value of 5.0. The average size of these polycrystalline
particles is about 10 nm.
Under pH 7-9, nitrilotriacetic acid exists as NTA3- and the predominant species in
solution remains a 1:1 complex of PbNTA-. With pH decreasing, NTA3- would partly
combine H+ in the solution. When pH was lower than 5, NTA3- would exist as HxNTAx-3
and its complexing ability with metal ions would therefore decrease. At the pH > 11, another
complex, Pb(OH)x2-x, was formed instead of PbWO4 due to the strong complexing ability
between Pb2+ and OH-. Room-temperature photoluminescence of PbWO4 nanocrystals
showed green emissions at 480-500 nm with different luminescence intensity. The optical
properties of these PbWO4 nanocrystals differ from those of the bulk crystals.
In another work, Geng et al. prepared nanosized lead tungstate (PbWO4) hollow spindles
via a sonochemical process by using triblock copolymer Pluronic P123- (EO20PO70EO20) as
a structure directing agent [87]. The concentration of polymer had vital role in preparation of
PbWO4. Hollow PbWO4 nanospindles were obtained in the polymer concentration of 4 gL-1.
PbWO4 hollow spindles can be formed by templating the P123 micellar aggregates induced
by the ultrasonic irradiation. Pb2+ ions in the solution are easily attracted on the micellar
surfaces by forming Pb-(PEO-PPO-PEO) units and provide nucleation domains for the
subsequent reaction between Pb2+ and WO42- to form PbWO4 nanoparticles.


Figure 9. TEM images of samples prepared at pH values of (a) 9.0, (b) 7.0, and (c) 5.0. The initial
concentrations of Pb
2+
, WO
4
2-
, and H
3
NTA were 20, 20, and 40 mM, respectively.
M. F. Mousavi and S. Ghasemi 24
The same procedure was used to preparation of ZnWO4 nanorods [88]. ZnWO4 nanorods
were successfully synthesized via powerful ultrasonic irradiation. An aqueous solution of
sodium tungstate (Na2WO4) was slowly added to a solution of zinc acetate, 3 g P123, 20mL
ethanol and 200mL deionized and Ultrasound irradiation was applied to solution by a high-
intensity ultrasonic probe, 20 kHz, 250 W/cm2. The photocatalytic activity of ZnWO4 in
degradation of rhodamine-B (RhB) under 365nm UV light illumination was investigated.
Also, Metal tungstates (MWO4, M = Ba, Sr and Ca) were synthesized using the
corresponding M(NO3)2 and Na2WO4 in ethylene glycol by ultrasonic irradiation [89]. Their
average sizes of round shaped nanoparticles of metal tungstates were 42.0 ± 10.4, 18.5 ± 5.1
and 13.1 ± 3.3 nm for M = Ba, Sr and Ca, respectively.
5.5. MoO
4


Lead molybdate (PbMoO4) and lead tungstate nanoparticles were synthesized from
solution of Pb(NO3)2 and Na2MO4 dissolved in 50 ml ethylene glycol by applying
ultrasound waves for 1 h [90]. The particle sizes were 29.09 ± 5.22 nm and 21.05 ± 2.68 nm
for PbMoO4 and PbWO4, respectively.
Bismuth molybdate (α-Bi2Mo3O12 phase) nanorods were synthesized by pyridine
intercalative sonochemical method [91]. Spherically α-Bi2Mo3O12 powder was dissolved in
pyridine and sonicated at 30–40°C under nitrogen atmosphere, for varying time periods (2, 4,
6, 8, and 10 h). The diameter of the α-Bi2Mo3O12 nanorods were about 10 nm and length in
few hundreds of nanometer to μm after sonicating in pyridine for 6 h. The controlled heating
of pyridine-intercalated nanorods to 450 °C was resulted in a-Bi2Mo3O12 phase nanorods
free of pyridine.
5.6. Ferrites

Ferrites are widely used in ferrofluid technology, magnetic resonance imaging, drug
delivery and data storage. The synthesis of spinel ferrites MFe2O4 ((M = Mn, Co, Ni, Cu and
Zn)) such as copper ferrite (CuFe2O4) [92] and zinc ferrite (ZnFe2O4) [93a] were reported.
Sivakumar et al. [93b] used a ultrasound assisted emulsion (consisting of rapeseed oil and
aqueous solution of Zn2+ and Fe2+ acetates) and evaporation protocol to synthesize zinc
ferrite (ZnFe2O4) nanoparticles (Figure 10). The as-synthesized sample consisted of
crystalline zinc ferrite particles with an average diameter of ~4 nm and the heat-treated ferrite
particles (350 °C for 3 h) with ~12 nm.
The small amount of oil present on the surface of the as-synthesized ferrite sample was
removed by heat treatment at 350 °C for 3 h.
Ferrites with formula MFeO3 also were reported. Das et al. reported the preparation of
nanosized BiFeO3 powders by sonochemical technique [94].
Nanocrystalline rare earth orthoferrites MFeO3 (M=Gd, Er, Tb and Eu) were prepared by
Sivakumar et al. using Fe(CO)5 and rare earth carbonates precursor through sonochemical
method [95]. A distinct advantage of the sonochemical method is the preparation of
nanocrystalline orthoferrites at a remarkably reduced calcination temperature. The magnetic
properties of different orthoferrites were reported.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 25

Figure 10. TEM of as-prepared and heat-treated ZnFe
2
O
4
nanocrystals (scale bar is 20 nm).
Same authors reported a sonochemical method for preparation of strontium hexaferrite by
a sonochemical method employing Fe(CO)5 and SrCO3 [96]. A SrCO3 hexagonal rod was
synthesized using strontium nitrate and urea in the presence of ultrasonic irradiation.
Stoichiometric amounts of SrCO3 and Fe(CO)5 was dissolved in decalin and irradiated with
ultrasound (using the titanium horn tip with power of 29.7W/cm2) in an air atmosphere at
0°C for 4 h to get the strontium hexaferrite powder. The resultant precursor was then calcined
at 900°C for 14 h in air atmosphere, which is lower than the conventional solid-state reaction
(1300°C). It was suggested that the application of ultrasound on the Fe(CO)5 generates
amorphous Fe2O3. The amorphous Fe2O3 was then dispersed or coated on SrCO3 during the
ultrasound irradiation. SrFe12O19 exhibited an intrinsic coercivity field (Hc) of ~4600 Oe
and a saturation magnetization (Ms) of ~60 emu/g at 20 K and ~32 emu/g at 300 K. The Hc
value remains more or less temperature independent over the 20–300K range. The
magnetization vs. temperature pattern exhibits strong temperature dependence over a range of
300–800 K probably due to the presence of single-domain nanoparticles and consequent
superparamagnetism.
6. NANOCOMPOSITES

Sonochemistery is one of the techniques have been used to synthesis different categories
of nanocomposites such as inorganic/inorganic and inorganic/organic materials [97].
6.1. Metal Oxide-Metal (Oxide) Nanocomposite

Perkas and et al. used sonochemical irradiation of iron (II) acetate aqueous solution in
presence of silver nanopowder to deposite magnetite nanoparticles on silver nanocrystals
[97]. The crystalline size of silver nanoparticles was calculated as 50 nm and magnetite
nanoparticles ~ as 10 nm. Ag-Fe3O4 composite was well arranged in the series of chains
(Figure 11 a and b).
M. F. Mousavi and S. Ghasemi 26

Figure 11. (a) initial nanosilver powder (b) TEM images of Ag–Fe
3
O
4
composite obtained by
sonochemical method and (C) HRTEM image of Ag–Fe
3
O
4
composite.
The characterization of the product reveals the presence of two phases of the silver and
the magnetite without any chemical interaction between them. It was suggested that local
melting of silver occur when the magnetite nucleus is thrown at the silver surface by high
speed sonochemical microjets and this is probably the phenomenon causes the anchoring of
magnetite to the nanosilver surface. The total saturation magnetization of the composite is
rather low – 1.8 Emu/g. However, it most considered that only 5.2 wt% of the nanocomposite
is corresponded to Fe3O4 and its magnetization would be about 35 Emu/g Fe3O4. The Ag-
Fe3O4 nanocomposite showed superparamagnetic behavior in a magnetic field.
Pradhan et al. also synthesized gold-magnetite nanocomposite materials via sonochemical
methods (Figure 12) [98]. Magnetite nanoparticles (1 mg suspended in 100 μL of methanol)
with diameter of ca. 30 nm were added to a 50 mL solution of 0.1 mM HAuCl4 (aq)
containing methanol (100 μL), diethylene glycol (100 μL), or oleic acid (100 μL) as solvent
modifiers sparged with argon during the experiment [99]. The solution was then sonicated in
a jacketed, water cooled (20 C) reaction vessel under an argon atmosphere for 10 min at 50%
amplitude using an ultrasonic processor. The resulting solution was then transferred into a test
tube and kept in front of a magnet. The gold–magnetite nanocomposite material was pulled
against the wall of the test tube by the magnet.
The coercivity of the treated magnetite was 75 Oe, while the gold–magnetite
nanocomposite material exhibited a coercivity of 200 Oe. The changes in magnetic properties
are likely due to changes in the surface characteristics of the magnetite. Gold could contribute
to changes in the surface states and magnetic properties.

Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 27

Figure 12. TEM images of gold–magnetite nanocomposite material formed by sonication of magnetite
in aqueous HAuCl
4
with added (a) methanol (b) oleic acid additives. Dark particles are gold, grey
particles are magnetite.
Also, during sonication, the capping ligands can be removed and cause a change in the
surface charge or magnetic domains. The additives were also found to change the gold
particle loading and the Fe/Au ratio in the composite materials. With oleic acid added,
substantially smaller gold particles were observed, and the Fe/Au ratio was intermediate
between that of the materials prepared with methanol and diethylene glycol.
Mizukoshi et al. reported immobilization of noble metal nanoparticles (Au, Ptand Pd) on
the surface of maghemite with irradiation of aqueous solutions containing noble metal ions
(HAuCl4, Na2PdCl4, H2PtCl6), polyethyleneglycol monostearate (PEG-MS), and magnetic
maghemite nanoparticles [100]. The noble metal ions were reduced by the effects of
ultrasound, and uniformly immobilized on the surface of the maghemite. XRD patterns of
prepared nanocomposites showed peaks originated from 111 planes of noble metals with
peaks of maghemite. TEM images showed that the diameters noble metal particles depended
upon the concentration of PEG-MS, pH of the solution and the concentration of noble metal
ions, but not upon the maghemite concentration. The average diameter of immobilized Au
was 7–13 nm, and the diameters of Pd and Pt were several nm. It was suggested that the
nucleation of noble metal occurred in the homogeneous bulk solution and then the nuclei
were immobilized on the surface of the Maghemite. Then, the growth of noble metal nuclei
were continuing on the surface of the maghemite.
Another work was reported by Mizukoshi et al. which prepared the magnetically
retrievable palladium/Maghemite nanocomposite catalysts by sonochemical reduction method
[101]. Such a catatalyst show high catalytic activities for the reduction of nitrobenzene and
could be readily retrieved by magnets and verified the durability of the catalytic performance.
Mizukoshi et al. also introduced Au/γ-Fe2O3 composite nanoparticles which could
selectively adsorb sulfur-containing amino acids [102]. Adsorbed amino acids were
successfully manipulated by applying all external magnetic fields.
Nanocomposites of Ag nanoparticles/mesoporous γ-Al2O3 were synthesized by
sonochemical method [103]. The as prepared product consisted of Ag nanoparticles dispersed
in the bayerite [Al(OH)3]/boehmite [AlO(OH)] matrix. The Ag nanoparticles were
incorporated in a mesoporous structure of γ-Al2O3 upon calcination of product under Ar
atmosphere at 700 °C for 4 h. For a nanocomposite containing 3.7 wt % Ag nanoparticles, the
BET surface area is more than that of γ-Al2O3 because the Ag nanoparticles remained on the
M. F. Mousavi and S. Ghasemi 28
surface of mesoporous alumina whereas for 10.5 wt % Ag nanoparticles, the BET surface
area decreased. In this case, the Ag nanoparticles blocked the pores, and also increased the
diameter of the pores of mesoporous alumina.
Insertion of Pt nanoparticles into Mesoporous (MSP) CeO2 reported by an ultrasound-
assisted reduction procedure [104]. With incorporation of highly dispersed Pt into the CeO2
(MSP) by the sonochemical method, the specific surface area, pore volume and size of the
CeO2 support decreased. The observed changes could be attributed to incorporation of the
metallic Pt particles in the CeO2 interparticle volume. Pt/CeO2 nanoparticles have excellent
properties in EA combustion at low temperature. The catalytic activity of these catalysts was
higher than that of the Pt catalysts on the CeO2 support prepared by the classic incipient
wetness- impregnation method. It was demonstrated that the higher the dispersion of the
CeO2 support and the Pt phase, the better the catalyst properties. Ultrasonic technique causes
to the homogeneity and better dispersion of the Pt in CeO2 support.
The best results with 100% selectivity to CO2 at the lowest temperature were achieved
with the Pt catalysts sonochemically incorporated into the mesoporous CeO2 support
previously synthesized by the ultrasound method.
ZnO nanorod/Ag nanoparticle composites was synthesized by ultrasonic irradiation of a
mixture of ZnO nanorods, Ag(NH3)2+, and formaldehyde in a aqueous solution 105. TEM
images of ZnO/Ag composites reveal that the ZnO nanorods are coated with spherical Ag
nanoparticles with a mean size of several tens nanometer and fcc structure.
The sonochemically synthesized Pt (Pd) nano-particles (~2 nm) were impregnated into
zirconia (3 mol% yttria-stabilized zirconia, 3Y-TZP) nano-aggregates (20–45 nm) (Figure 13)
106.

Figure 13. TEM of 3Y-TZP porous nano-aggregates impregnated with 1.5 wt.% of platinum.
As shown in Figure 13, the primary crystallites with an average size of ~5nm are
aggregated and nanoaggregates with a mean aggregate size of 20–40 nm are formed. With
low temperature sintering (1150 °C for 30 h), it can be possible to produce the Pt–3Y-TZP
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 29
and Pd–3Y-TZP (0.5–2 wt. % of platinum) nano-composites with uniform distribution of the
Pt (Pd) grains (in the range of 20–60 nm) and with a zirconia average grain size of 120 nm.
Bhattacharyya and Gedanken reported [107] the preparation of γ-Al2O3-doped porous
ZnO nanocomposite by sonochemistry. The nanoparticles of γ-Al2O3 partially or fully block
the pores of porous ZnO.
6.2. Organic-Inorganic Nanocomposite

The sonochemical assisted syntheses of organic-inorganic nanocomposites have been
prepared by some researchers[108].

6.2.1. Natural Fibers

Perelshtein et al prepared CuO-cotton nanocomposite and investigate its antibacterial
activity [108]. Copper oxide nanoparticles (~ 10–15 nm) were synthesized and subsequently
deposited on the surface of cotton fabrics using ultrasound irradiation. The antibacterial
activities of the CuO-fabric composite were tested against Escherichia coli (Gram negative)
and Staphylococcus aureus; (Gram positive) cultures. The antibacterial effect is due to the
copper oxide nanoparticles. CuO nanoparticles can generate some active species that are
responsible for damaging the bacteria's cells.


Figure 14. (a) HR-SEM images of pristine cotton fabric coated with CuO nanoparticles (magnification
×20,000). (Inset: magnified image (×100,000) of the nanoparticles coated the fiber).
In a similar work, silver nanoparticles were deposited on the surface of natural wool
fibers under ultrasonic irradiation [109]. The sonochemical irradiation of slurry containing
wool fibers, silver nitrate, and ammonia in an aqueous medium for 120 min under an argon
M. F. Mousavi and S. Ghasemi 30
atmosphere yielded a silver-wool nanocomposite. The average silver particle size was 5-10
nm, but larger aggregates of 50-100 nm were also observed. Silver adhere strong to the wool
through the interaction of silver with sulfur moieties related to the cysteine group.

6.2.2. Polymeric Based Nanocomposites

6.2.2.1 Poly(Methylacrylate) and Poly(Methylmethacrylate)
Preparation of ceria nanoparticles embedded in polymethylmethacrylate (PMMA) has
been reported by means of sonochemistry [110]. An average size of the ceria is found to be
similar to 5 nm by XRD and TEM measurements. In Ceria–PMMA composite, the band gap
found is 3.55 eV.
Parra et al. studied the preparation of composite materials based on PMMA with
nanometric hydroxyapatite (Ca10(PO4) 6(OH)2) under ultrasonic radiation for different times
[111]. In the synthesis of Hydroxyapatite (HA), ammonium phosphate [(NH4)2HPO4] and
calcium hydroxide [Ca(OH)2] were used as precursors. The precursors of the HA and
commercial PMMA in 2-butanone were placed simultaneously in a reactor under ultrasonic
radiation at 20 kHz, for periods of 15, 25 and 35 min. Composite materials were obtained
from the in situ synthesis of hydroxyapatite (HA) in dissolved PMMA.


Figure 15. TEM bright field image of PMMA/ HA composites.
The FTIR spectra showed the interactions between the ester group of PMMA and the
phosphates groups of HA. Hydroxyapatite particles encapsulated in a thin film of PMMA,
forming ‗‗pockets‘‘ of the composite material (Figure 15). XRD results show the formation of
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 31
HA in the amorphous PMMA matrix. The appearance of broad peak in XRD implies
nanometric crystal size of HA.
In another reported work, wang et al. sonochemically prepared polyacrylamide and
gamma-zirconium phosphate (Zr-P) nanocomposites by intercalative polymerization
112
.

6.2.2.2. Polystyrene
Polystyrene (PS)/Fe3O4 nanocomposite were prepared with miniemulsion
polymerization of styrene in the presence of Fe3O4 nanoparticles under ultrasonic irradiation
[113]. Each (PS)/Fe3O4 nanoparticles and PS latex with no encapsulated Fe3O4
nanoparticles were found in PS/Fe3O4 magnetic emulsion. The nanoparticles are spherical
and their size was in the range of 20 to 80 nm. PS/Fe3O4 emulsion and nanocomposite
exhibit magnetic properties and can be separated from the magnetic emulsion by an external
magnetic field.
In another paper, Kai et al. proposed a method based on sonochemistry to prepare
silver/PS nanocomposite [114]. The preparation of Ag/PS nanocomposite was achieved by
dispersion polymerization of styrene in a water–ethanol (1/6 wt/wt) solution, with poly(N-
vinyl pyrrolidone) (PVP) as stabilizer and 2,2'-azobisizobutyronitrile (AIBN) as initiator in
the presence of nano-silver particles under ultrasonic irradiation with a power output of 300
W at 20 kHz for 3.0 h. The monomer conversion and polymerization increased when nano-
silver particles was added to reaction vessel. The conversion of monomer can reach about
70% in 3.0 h. When bare nano-silver particles without pretreatment are introduced into the
polymerization medium, polystyrene particles are covered with some small silver beads
(because of their high hydrophilicity) and complete encapsulation does not occur. It was
observed that in the presence of the surfactant, SDS, no silver bead is detected on the whole
surface of the samples and the nano-silver particles are encapsulated in the polystyrene
particles.

6.2.2.3. Polypropylene
Deposition of silver nanoparticles on porous Polypropylene (PP) polymer was
investigated by an ultrasound-assisted reduction of AgNO3 in the presence of poly(vinyl
pyrrolidone) (PVP) as stabilizing agent [115]. PVP prevent the agglomeration of the reduced
silver nanoparticles. With PVP, a homogeneous distribution of silver nanocrystals with 50 nm
in size and a relatively high silver content (0.5–0.6 wt % Ag) was formed on the PP beads
surface. It was suggested that microjets formed during the bubble collapsing can throw the
silver nucleus to the polymer‘s surface and cause to local melting of the PP at the collision
sites. At collision sites, the thermal degradation of polymer chains cause to the formation of a
small amount of pure carbon.
The appearance of the high-intensity bands characteristic of pristine carbon at ~1344 and
1580 cm-1 in the Raman spectra of silver coated PP for after coating PP with nanosilver was
caused by the localized melting of the polymer at their points of contact with silver
nanoparticles.
XPS studies also showed the presence of Ag (0) in silver-coated polymer PP. The peaks
observed in the energy region of the Ag 3d transition are symmetric and centered at 367.9 and
373.9 eV. Antimicrobial test show that the beads of the silver PP composite have high
antibacterial activity against microorganisms.

M. F. Mousavi and S. Ghasemi 32
6.2.2.4. Conducting Polymer
Among conductive polymer, polypyrrole and polyaniline have been used to prepare
nanocomposite with different materials such as nobel metal and metal oxide [116]. Colloidal
dispersions of hybrid nanocomposite composed of gold and platinum nanoparticles (Au- and
Pt-NPs) and polypyrrole (PPy) were prepared by a sonochemical method, in which metal ion
and pyrrole monomer in an aqueous solution were reduced and oxidized, respectively, by
ultrasonic irradiation in the presence of sodium dodecyl sulfate (SDS). TEM of Au-NPs show
small Au-NPs dispersed in PPy matrix and the average diameter of Au-NPs/PPy are 15 nm
(Figure 16).


Figure 16. TEM image of (a) Au-NPs/PPy (b) Pt-NPs/PPy nanocomposite prepared by ultrasonic
irradiation for 4 h.
The authors also investigated the effect of poly(N-vinyl-2-pyrrolidone) as a stabilizer in
preparation of Au-NPs/PPy (Figure 16 b)
117
.
Same authors also preapared polypyrrole-encapsulated platinum nanoparticles (PPy/Pt-
NPs) by a sonochemical synthesis and used it as catalysts for the liquid phase hydrogenation
of substituted alkenes in methanol or methanol/water mixtures
118
.
The nanocomposites of polyaniline/silver
119
, polyaniline/Au
120
, polyaniline/Y
2
O
3

121
and
polyaniline/Fe
3
O
4

122
have been synthesis with the aid of ultrasonic irradiation.
The ultrasonically synthesis of PANI/Fe
3
O
4
nanocomposite was reported with in situ
polymerization of aniline in the initially neutral medium and in the presence of Fe
3
O
4

nanoparticles and oxidant. Fe
3
O
4
nanoparticles were dispersed on the nanoscale by ultrasonic
irradiation and the polymerization of aniline was begun by the addition of an oxidant,
ammonium persulfate (APS). PANI deposited on the surfaces of the Fe
3
O
4
particles and all
Fe
3
O
4
nanoparticles was encapsulated with PANI. The maximaum conductivity of PANI was
obtained with 2:1 molar ratios of oxidant to aniline. The conductivity and magnetic properties
of the PANI/Fe
3
O
4
composite can be controlled by the Fe
3
O
4
content so that with increasing
the Fe
3
O
4
content, a decrease in the conductivity and an increase in the magnetic properties of
the PANI/Fe
3
O
4
composite were observed. The decrease of the conductivity is raised from the
addition of nonconducting Fe
3
O
4
nanoparticles.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 33
Polyaniline (PANI) nanotubes containing Fe
3
O
4
nanoparticles were also synthesized
under ultrasonic irradiation of the aqueous solutions of aniline, ammonium peroxydisulfate
(APS), phosphoric acid (H
3
PO
4
), and the quantitative amount of Fe
3
O
4
123
.
6.3. Carbonaceous Nanocomposite

Kawaoka et al. used sonochemical method to synthesized amorphous manganese oxide
and acetylene black (HSMO/AB) [124]. A solution containing 1.20 g of NaMnO4 was
dissolved in 750 ml of deionized water and 0.65 g of acetylene black (AB) was irradiated
with ultrasound (600W of total power and 100 kHz in frequency) was for 6 h in air
atmosphere. The acetylene black particles were homogeneously coated with amorphous
manganese oxide with ca. 35 nm in diameter (Figure 17). The thickness of the amorphous
substance varied from 1 to 10 nm. Energy dispersive spectrometer (EDS) analysis showed
that the amorphous substance was composed of Carbon, oxygen, sodium, and manganese. It
was suggested that AB particles were coated with the amorphous phase of hydrated sodium
manganese Oxide (HSMO).


Figure 17. Low-resolution TEM of HSMO/AB nanocomposite.

The capacity of the HSMO/AB nanocomposite tested under large current density, 10 A g-
1, is 185 mAh g-1. At operating voltage of 2.5 V, the power and energy density are 20 kW
kg-1 and 90 Wh kg-1, respectively.
M. F. Mousavi and S. Ghasemi 34
This Japanese group also published another article in which the preparation of manganese
oxide/carbon nanocomposite was described [125]. They optimized the synthesis conditions,
such as the reaction temperature and pH and specific surface area of the carbon. The
manganese oxide/carbon nanocomposite was used as the cathode material of a high-power
lithium-ion battery. They showed that the use of a carbon with a higher specific surface area
caused to the higher specific capacity and lower capacity drop.
In other work, Cao et al used the sonochemical method to prepare mesoporous carbon-
tin oxide (SnO2) nanocomposite [126]. The resulting nanocomposite is consist of SnO2 with
3 nm in size dispersed on ordered mesoporous carbon.
Jang et al prepared nanocomposites between β-WC (also known as WC1−x ) and Pd
nanoparticles supported on carbon [127]. When a Pd-loaded GKB (Graphitic Ketjen Black),
Pd/C, obtained by reducing PdCl2 with NaBH4 in the presence of GKB, was used as the
support, a nanocomposite composed of Pd and β-WC nanoparticles was obtained by a
sonochemical decomposition of W(CO)6 followed by heat-treatment. By varying the amount
of W(CO)6 in the sonochemical reaction, two samples with different W-contents denoted as
β-WC(12)/Pd/C and β-WC(39)/Pd/C were synthesized. β-WC is a high temperature phase,
stable above 2785 ◦C. The conventional synthesis method such as carburization of tungsten
oxide precursors cannot generate such high temperatures and most of studies on tungsten
carbides have been restricted to W2C or α-WC whereas nanoparticles of β-WC can be
synthesized by a sonochemical reaction method due to extreme conditions generated by this
method. This is an evidence of preference of sonochemistry to other conventional methods.
The prepared tungsten carbide–palladium nanocomposites with different amount of W were
examined as hydrogen oxidation reaction (HOR) catalysts. It was discussed that when too
excessive W was deposited, a part of the deposit reacts with the Pd nanoparticles forming a
Pd–W alloy which showed much lower HOR activity than non-alloy Pd nanoparticles.
Nanocomposite based on carbon nanotube has been considered by some researchers
during last years[128]. After preparation β-WC/Pd/C nanoparticles, Jang et al also used the
similar ultrasonic method to prepare composite of Pt and WC1−x nanoparticles supported on
multiwalled carbon nanotube (MWNT). They investigated the electrochemical properties of
WC1−x/Pt/MWNT nanocomposite especially for the hydrogen oxidation reaction (HOR).
The synthesis of carbon nanotube (CNT)-supported Rh nanoparticles was reported by a
sonochemical method [129]. For this purpose, 20 mg of carboxylate-functionalized MWNTs
were dissolved in 20 mL ethanol, and the solution was sonicated for 1 h. The well-dispersed
CNT solution was added to a solution with 400 µL of 0.1 M RhCl3 aqueous solution and 40
mg of borane morpholine complex (C4H12BNO) and sonication was continued for another
20 min. Borane morpholine complex has a milder reducing ability compared with NaBH4 and
produce Rh nanoparticles with a narrow size distribution. TEM image of sonochemical
synthesized CNT/Rh nanocomposite is shown in Figure 18.
As shown in Figure 18, rhodium (Rh) nanoparticles with an average diameter of 2.5 (0.7
nm is deposited uniformly on multiwalled carbon nanotubes (MWNTs). Also, it was shown
that without sonication and functionalized MWNTs, well-dispersed small metallic
nanoparticles cannot be formed and deposited on CNTs. The carboxylate groups of
functionalized MWNTs (acid washed) provide sites for anchoring the metallic nanoparticles.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 35

Figure 18. TEM images of CNT-supported Rh nanoparticles prepared with sonochemical method.
The XPS spectrum of the Rh/MWNTs shows binding energies (BEs) at 307.2 and 312.1
eV related to BEs of Rh(3d5/2) and Rh(3d3/2), respectively, of Rh(0). The EDX analysis also
showed that the mass of Rh in the composite was 11.2 ±0.1 wt %. The catalytic activities of
the Rh/MWNT catalyst were investigated for hydrogenation of neat benzene and benzene
derivatives in comparison with commercially available Rh nanocatalysts at low-temperature.
Results show that complete ring saturation of polycyclic aromatic hydrocarbons (PAHs) can
be achieved under mild hydrogenation conditions using the Rh/MWNT. The catalytic activity
of the Rh/MWNT catalyst is much higher compared with a commercially available Rh
nanocatalyst.
Sonochemistry can be used to synthesize the metal oxide and carbon nanotube
nanocomposite. Zhang et al. used a simple sonochemical route to prepare CNT/CeO2. Firstly,
CNT was dispersed in a 0.05 g/mL Ce(NO)3 alcohol aqueous solution (Valcohol:Vwater =
1:1) with high-intensity ultrasonic radiation at room temperature [130]. Then, CeO2 was
deposited on CNT with slowly addition of NaOH aqueous solution to above solution. The
final pH value was 10. TEM of CNT/CeO2 composite shows many tiny interconnected grains
with average grain size of 4 nm. The selected area electron diffraction (SAED) pattern shows
a ring pattern corresponding to the face-centered cubic polycrystalline structure of CeO2.
Furthermore, some of articles were focused on preparation of Polymer/CNT
nanocomposites with sonochemistry [131]. Polyaniline/CNT and poly (methyl methacrylate-
co-n-butyl acrylate) (P(MMA-BA))/ carbon nanotubes (CNTs) are example of such
nanocomposites. It was shown that the MWNT/PANI nanocomposites causes enhanced
electric conductivity and thermal stability in comparison with pure PANI. Also, the smooth,
uniform, and flexible P(MMA-BA)/CNTs composite films were prepared from the composite
M. F. Mousavi and S. Ghasemi 36
emulsion [132]. Tensile tests of film suggest that with the modulus and the yield strength of
composite film increased with increasing in the CNTs content.
6.4. Other Nanocomposite

Ghule et al. reported the synthesis of Ag/Bi2Mo3O12 nanocomposite by ultrasonic
method [133]. Silver nanoparticles with an average size of ca. 10 nm were uniformly
deposited on the surface of α-Bi2Mo3O12 nanorods. α-Bi2Mo3O12 nanorods (ca. 100 nm
diameter) was prepared by ultrasonication of preformed α- Bi2Mo3O12 spherical
nanoparticles (ca. 200 nm) in pyridine. To prepare Ag/Bi2Mo3O12 nanocomposite, a mixture
of alpha-Bi2Mo3O12 nanorods and Ag2O in pyridine was irradiated by ultrasonic wave.
Calcination of sample at 450 °C produces pyridine-free α-Bi2Mo3O12 nanorods with
deposited Ag nanoparticles.
7. NANOMATERIALS WITH CORE-SHELL MORPHOLOGY

Nanostructured materials with core-shell morphology can find many applications in areas
such as photonic crystals, catalysts, and biotechnology [134.] In the following paragraph
some of nanoparticls with core shell morphology are reviewed.
7.1. Nanoparticle with Metal Core

Nikitenko et al prepared the air-stable Fe/Fe3C nanocrystalline particles have by
sonicating of Fe(CO)5 in diphenylmethane solutions under argon and subsequently annealing
the as prepared amorphous products in an inert atmosphere for 2 h. Nanocrystalline particles
have a core-shell structure where a coating of Fe3C and carbon protects the body-centered
cubic Fe in the core from oxidation. The iron nanoparticles are coated by a crystalline shell
with a thickness of about 5 nm. The size of the particles, their composition and magnetic
properties could be controlled by changing the sonication conditions and annealing
temperature. Particles heated at 300 and 400 °C have narrow range distribution ca. 20-40 nm
and 20-100 nm and with round shape morphology. Particles annealed at 700 °C are composed
mainly of tetragonal and round particles. An increase in the annealing temperature to 800 °C
causes the formation of hexagonal and tetragonal particles. Material obtained under
appropriate conditions possesses a high saturation magnetization close to that of bulk iron
(Ms/M0 = 0.97-1.06) and good, soft magnetic properties (coercive field HC = 0.50-0.05 A m-
1).
Aluminum-oleic acid core-shell nanoparticles have been synthesized using the titanium-
catalyzed thermal decomposition of Alane N,N-dimethylethylamine in a 0.4 M toluene
solution in which the thermal energy was supplied via acoustic cavitation [135]. Titanium
(IV) isopropoxide was the catalyst of reaction. The aluminum-oleic acid core-shell
nanoparticles prepared with 3.8 mM oleic acid have spherical nanoparticles with an average
size of ~30 nm and a size distribution estimated at 20-70 nm. TEM of the second sample
prepared with the concentration of 11.4 mM oleic acid showed spherical nanoparticles of a
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 37
much smaller diameter with an average size of ~5 nm with a size distribution of 2-15 nm.
Oleic acid may act to cap the surface of the growing nanoparticles, thus limiting particle size.
7.2. Nanoparticles with Metal Oxide Core

Hu et al. reported the sonochemically synthesis of Fe3O4–FeP core–shell nanoparticles
with Fe3O4 core of 5–10 nm and FeP shell of 2–3 nm [136]. They also reported the
preparation of FeP hollow nanoparticles with outer-diameter of 5–10 nm and inner-diameter
of 3–8 nm (Figure 19). Trioctylphosphine (TOP) (as P source) is used to react with iron
pentacarbonyl for the formation of iron phosphide and trioctylphosphine oxide (TOPO) is
used to control the size and growth morphology of resulting materials. The TOPO/TOP
mixture was sonicated under aerobic condition in a sealed bottle at 65–70 ºC in water bath.


Figure 19. Characterization of core–shell Fe
3
O
4
–FeP particles, which have been sonochemically
synthesized for 4 h: (a) SEM image, (b) TEM image.
M. F. Mousavi and S. Ghasemi 38
The core–shell Fe
3
O
4
– FeP particles and FeP hollow nanoparticles showed the M–H loop
at room temperature and low temperature under magnetic field up to 7 T. The M–H curve
shows a soft ferromagnetic behavior. For the core–shell sample, the low temperature
measurement shows that the coercivity reaches 500 Oe, which is smaller than 760 Oe of
sample FeP. Fe
3
O
4
is magnetically a much soft material, at 10 K with coercivity ranging from
200 Oe for 4 nm to 450 Oe for 16 nm nanoparticles, the increasing of Fe
3
O
4
results in a
decreasing of coercivity.
7.3. Nanoparticle with Sio
2
Core

Morel et al. report a rapid sonochemical synthesis of monodisperse nonaggregated Core -
shell Fe
3
O
4
@SiO
2
magnetic nanoparticles (NPs)
137
. The Fe
3
O
4
NPs were prepared by
coprecipitation of Fe(III) and Fe(II) in alkaline solutions in the presence of ultrasonic
irridation. A freshly prepared mixture of 1.5 mmol FeCl
3
and 0.75 mmol FeCl
2
in 5 mL of
0.05 M HCl was rapidly injected via a fine plastic tube to 40 mL of 2 M ammonia solution
containing 0.01 M of hydrazine under power ultrasound at 30-32 °C in an argon flow.

O H O Fe OH II Fe III Fe
2 4 3
8 8 ) ( ) ( 2 + ÷ + +
÷
(18)

Fe
3
O
4
NPs have smaller size and a narrow size distribution (4-8 nm) than the silent
reaction. Sonication of Fe
3
O
4
NPs suspension in alkaline ethanol-water solutions of tetraethyl
orthosilicate (TEOS) cause to hydrolysis of TEOS and Fe
3
O
4
NPs coated with silica are
prepared. The reaction is accelerated many-fold in the presence of a 20 kHz ultrasonic field.
Silica shell thickness of Fe
3
O
4
@SiO
2
magnetic nanoparticles increase with sonication time.
TEM images shows an increase in the silica shell thickness is from 1.0 -1.5 nm after 1 h of
sonication to 3.0-3.5 nm after 3 h of ultrasonic treatment. Fe
3
O
4
@SiO
2
NPs prepared with
sonochemistry exhibit a higher magnetization value than that for NPs obtained under silent
conditions. High speed of sonochemical coating prevents the magnetite from oxidizing.
The sonochemical preparation of FePt/SiO
2
and FePt/ZnS/SiO
2
core-shell was
demonstrated by Wang et al (Figure 20)
138
. Silica microspheres were modified with a two
layer polyelectrolyte of aqueous poly (ethyleneimine) and poly (acrylic acid). In the case of
FePt/SiO
2
,

0.010 g of modified SiO
2
in 12 mL of ethylene glycol was sonicated for about 10
min and platinum (II) acetylacetonate (Pt(acac)
2
) (0.060 g) and iron acetylacetonate (0.078 g
of Fe(acac)
2
or 0.108 g of Fe(acac)
3
were then added into the mixture and sonication was
continued for 2-4 h under an Ar gas flow. It was seen that, magnetic FePt nanoparticles with
size of 3-5 nm, forms a densely packed shell with uniform coating. It was demonstrated that
the amine and carboxylic functional groups in the polyelectrolyte layer provided nucleation
sites for FePt nanoparticles. To prepare FePt/ZnS/SiO
2
core-shell, the unmodified silica was
precoated with ZnS, and then FePt nanoparticles nucleate on the ZnS shell. The thickness of
ZnS shell and FePt shell on FePt/ZnS/SiO
2
is ~30 nm and ~15 nm, respectively.
FePt/SiO
2
core-shell particles exhibit coercivity of 3.5 and 12.5 kOe at room temperature
when annealed under a high vacuum at 400 °C for 20 min and 600 °C for 10 min. the
coercivity of the FePt/ZnS/SiO
2
core-shell sample annealed at 530 °C is 12.0 kOe.

Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 39

Figure 20. TEM images of fcc phase FePt core-shell spheres: (a) average size ~240 nm FePt/SiO
2
using
Fe(III)(acac)
3
as iron precursor, (b) HRTEM image of dense 3-5 nm FePt clusters on the FePt/SiO
2

shell (inset: ~120 nm FePt/SiO
2
using Fe(II)(acac)
2
as iron precursor, and SAED pattern of FePt shows
fcc phase), (c) FePt/ZnS/SiO
2
(inset, the thickness of ZnS shell and FePt shell is ~30 nm and ~15 nm,
respectively), (d) HRTEM of FePt and ZnS nanoparticles on the shell .

Figure 21. (a) TEM of sonochemically prepared hollow MoO3 nanospheres after HF etching of
MoO3/SiO2 (before thermal annealing) (b) After thermal annealing at 350 °C.
M. F. Mousavi and S. Ghasemi 40
Dhas and Suslick reported the synthesis of MoS
2
/SiO
2
and MoO
3
/SiO
2
core shell
materials uniform coating using sonochemical method
139
. Hollow shells of the MoS
2
and
MoO
3
were obtained with washing the MoS
2
- or MoO
3
-coated silica with 10% HF in aqueous
ethanol. Thermal annealing of MoO
3
/SiO
2
at 450 °C before HF etching was caused to
conversion of hollow MoO
3
spheres to truncated cubic hollow crystals (Figure 21).
7.4. Chalcogenide Core-Shell

Ultrasonic irradiation was employed to aqueous synthesis of CdTe/CdS core-shell
nanocrystals by using preformed TG-capped CdTe nanocrystals as template cores and
thiourea as the sulfur source [140]. It was found that ultrasound facilitated the decomposition
of thiourea, leading to the formation of gradient CdS shell on CdTe cores. The resultant core-
shell nanocrystals presented dramatically improved photoluminescence (PL) quantum yields
(QYs), 10 times higher than the original nanocrystals. In comparison with the original CdTe
nanocrystals, CdTe/CdS nanocrystals show bright emission with an obvious red shift of
spectra.
8. OTHER NANOMATERIAL
8.1. Metal Phosphate

Monetite (anhydrous calcium hydrogen phosphate, CaHPO4) with orderly layered
structure assembled by nanosheets was synthesized from solution containing Ca(NO3)2 and
NaH2PO4 in the presence of cetyltrimethylammonium bromide (CTAB) by a sonochemical
method [141]. The thicknesses of the nanosheets are 100-200 nm with the lateral sizes of
about 2 μm.
Hydroxyapatite (Ca10(PO4)6(OH)2, HAP), the prime constituent of tooth and bone
mineral was synthesized sonochemically from aqueous solution of Ca(H2PO4)2 and
glycosaminoglycans (GAGs) with adding saturated Ca(OH)2 aqueous solution [142]. The
mixture was irradiated for different time (0.5 h, 3 h and 5 h) by an ultrasonic cleaner at 40
kHz and 250 W. TEM images showed that nanoparticles with short rod-like shape with 20–50
nm length and 12–25 nm width or spherical shape with 10–25 nm were obtained.
Nanosized, platelike hydroxyapatite (HAp) was synthesized using a homogeneous
precipitation method under ultrasound irradiation[143]. The internal structure of these
platelike formations consists of specifically oriented and laterally connected HAp nanorods
with a length of about 500 nm and a diameter of about 100 nm (Fig . 22)
The SAED pattern indicates that the nanorods are single crystals. The FTIR spectrum
show the characteristic bands for PO43- appear at 472, 583, 601, 961, 1032, and 1108 cm-1.
XRD results also proved the appearance of HAp phases.
Yu et al. reported the preparation of lanthanide orthophosphate LnPO4 (Ln = La, Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho) nanoparticles via ultrasonic irradiation of inorganic salt aqueous
solution under ambient conditions [144].
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 41

Figure 22. (a) TEM and (b) SAED pattern of a single nanorod of Hap.
TEM images show that the hexagonal structured lanthanide orthophosphate LnPO4 (Ln =
La, Ce, Pr, Nd, Sm, Eu, Gd) products have nanorod bundles morphology, while the tetragonal
LnPO4 (Ln = Tb, Dy, Ho) samples prepared under the same experimental conditions are
composed of nanoparticles. HRTEM micrographs and SAED results show that LnPO4
nanostructures are polycrystalline in nature. They also prepared Eu3+-doped LaPO4 samples
and investigated their photoluminescent properties. Eu3+-doped LaPO4 exhibit an orange–
red emission.
BiPO4 nanorods were successfully synthesized via a sonochemical method without any
surfactant under ambient air [145]. Nanorods have diameters of 40-60 nm and lengths of 2-
5µm, which shows a large aspect ratio of 50-80 (Figure 23). The BiPO4 nanorod have single-
crystalline nature with a preferential growth oriented along the (001) crystalline plane.

Figure 23. (a) SEM images of BiPO
4
nanorods, (b) TEM image and SAED pattern recorded on a single
BiPO4 nanorod.
It was demonstrated that the synthetic parameters such as pH of solution and sonication
time effect on morphology of BiPO
4
. Uniform BiPO
4
nanorods with a large aspect ratio could
M. F. Mousavi and S. Ghasemi 42
only be obtained when the pH of reaction system was adjusted at range of 0.5-1. The
morphologies of the products is the result of the sensitive influence of the pH on the solute
concentrations ([Bi
3+
] and [H
n
PO
4
(3-n)-
]).
8.2. Metal Carbonate

Sonochemistry has been used to prepared various type of nanostructure metal carbonate
such as BaCO3[146], CdCO3 147 and CeCO3OH [148]. Yang et al.[149] reported the
sonochemical preparation of MnCO3 submicrocubes and highly oriented MnCO3 nanocrystal
assemblies with an ellipsoidal morphology.
The aqueous solution containing MnCl2 and urea was sonicated with an ultrasonic probe
immersed directly in solution (operate at 20 kHz, ~ 80 W/cm2) at 80 °C for 90 min [150]. The
reaction was repeated in the presence of aerosol OT (AOT) and SDS (sodium dodecyl
sulfate).
In the presence of AOT as a surfactant, MnCO3 submicrocubes with sizes of about 500
nm were observed which is significantly smaller than those prepared without using AOT. In
the presence of SDS, highly oriented ellipsoidal assemblies were observed. The assemblies
were porous and constructed of ca. 5 nm nanocrystals. A thermal treatment of MnCO3 at 600
°C in air produces nanoporous Mn2O3. Thermal treatment of MnCO3 samples prepared
without surfactant and in the presence of AOT produced a nanoporous cubic Morphology.
The ellipsoidal morphology of sample prepared in the presence of SDS was retained after
decomposition of MnCO3 to Mn2O3.
8.3. Metal Fluoride

BaF2 nanocrystals doped with 5.0 mol% Eu3+ (BaF2:Eu3+) nanospheres [151] EuF3
nanoflower [152] and Dumbbell-like YF3 nanostructures [153] are metal fluorides family
were prepared by ultrasonic-assisted method. Rare-earth fluorides with controllable shapes
and sizes have attracted intense research interest due to their particular photoluminescence
properties and potential applications in optics, optoelectronics, biological labeling and
catalysis. EuF3 nanoflower prepared through the reaction of Eu(NO3)3 and KBF4 under mild
ultrasonic irradiation.
To prepare Dumbbell-like YF3 nanostructures, Y2O3 was dissolved in 10% dilute
HNO3. Then, 15.0 mL N,N-dimethylformamide (DMF) was added to the above solution
(water/DMF ratio of 5/15). NH4F (3 mmol) was added under stirring. Subsequently, the
mixed system was transferred into a 50 mL plastic flask and irradiated by ultrasonic wave
with 40 kHz and ultrasonic power of 100% (200 W) at 65 °C for 2 h. TEM images of sample
show a series of dumbbells each comprised of abundant nanorods. The morphology of the
product could be affected by the volume ratios of water/DMF in initial solutions. Table 1
summarizes the observed morphology depended on water/DMF ratio.




Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 43
Table 1. morphology of YF
3
as function of Water/DMF ratio

Water/DMF ratio Morphology of YF3 nanostructures
20/0 (pure water) spindle-like (particles with about 350 nm in length)
15/5 spindle-like
10/10 rod-like
5/15 dumbbell-like
0/20 (pure DMF) near-spherical

When the volume ratio of water/DMF was decreased to 15/5, the morphology does not
change markedly. After the volume ratio was decreased to 10/10, the spindle-like particles
with the thin in two ends and the thick in middle had converted into morphology. Further
decreasing the volume ratio of water/DMF to 5/15 produces particles. When reaction was
completed in pure DMF (0/20), the as-prepared product was composed of a great number of
nanoparticles with a mean diameter of ~30 nm.
8.4. Single-Walled Carbon Nanotube (SWCNT)

Jeong et al. reported a sonochemically method to prepare SWCNT. A solution of
ferrocene and p-xylene was mixture with silica powder (diameters of 2-5 mm) and irradiated
with ultrasonic waves by a 1/2-in. titanium tip 200-W probe pulsed 65% under ambient
conditions for 20 min [154]. Ferrocene is decomposed during sonication and provide Fe
nanoparticles as catalyst for nanotube growth. Also, p-xylene and ferrocene provide carbon
source for SWCNT growth and silica powder acted as a nucleation site for SWCNT growth.
Silica powder was broken into small pieces during the sonication. HF solution was used to
remove silica particles at end of reaction. It was found that high-purity SWCNTs were
obtained at relatively low concentration of ferrocene (0.01 mol %).
Li et al. reported the synthesis of new hydrocarbons (hydrocarbon nanotubes and nano-
onions) and carbon nanostructures (carbon nanotubes and nano-onions) via the sonochemical
reactions of organic solvents such as CHCl3, CH2Cl2, and CH3I on hydrogen-passivated
silicon nanowires (SiNWs) as templates under ambient conditions [155].
8.5. Polyaniline

PANI is one of the most important conducting polymers. PANI nanotubes and nanofibers
doped with different mineral (HNO3, H3PO4, HClO4) and organic acid (camphorsulfonic
acid) were synthesized under ultrasonic irradiation [156]. Ammonium peroxydisulfate was
used to oxidize aniline monomer. It was demonstrated that different dopant acids produced
PANI nanotubes (Figure 24) and nanofibers with similar morphology.
At low concentration of dopant acid, nanotubes could be observed but with high
concentration of dopant acid, nanofibers are formed. Also, the concentration ratio of [dopant
acid]/[aniline] effect the morphology of polyaniline nanostructures.

M. F. Mousavi and S. Ghasemi 44

Figure 24. TEM of PANI nanotubes synthesized under ultrasonic irradiation doped by perchloric acid.
Li et al. reported the chemically synthesized polyaniline nanofiber via ultrasonic
irradiation [157]. The effect of various parameters such as ultrasonic power, frequency, and
reaction temperature was investigated on morphology of polymer. It was found that increase
of ultrasonic power (up to 250 W) or the reaction temperature (up to 75°C) produce PANI
nanofibers with more uniform diameters. The length or aspect ratio of PANI nanofibers
decreased with increasing ultrasonic power, whereas longer nanofibers with larger aspect
ratios were obtained at a higher polymerization temperature. Also, the polymers prepared at
higher frequencies showed higher purity; for example the polymer prepared at 50 kHz
showed the highest uniformity and smoothest surfaces.
8.6. Metal Chalcogenides

Sonochemistry provide a facile synthetic method to prepare nanostructures of metal
chalcogenides. Chalcogenides (S
-2
, Se
-2
, and Te
-2
) of metal have semiconductive properties
and found extensive applications in various fields such as non-linear optic detectors,
photovoltaic solar cells and optical storage media. In next section, various types of
nanochalcogenides i.e. metal sulfides, selenides and tellurides are considered.

8.6.1. Metal Sulfides
Various types of metal sulfides have been synthesized based on ultrasonic techniques
such as ZnS [158], HgS 159, MoS2 [160],Ag2S [161], In2S3 [162]and CuS [163].
Among various types of metal sulfide CdS and PbS have been explored extensively
because of its unique properties 164. Lead sulfide (PbS) is an important π–π semiconductor
with small bulk band gap (0.41 eV at 300 K) and a larger excitation Bohr radius of 18 nm.
Also, CdS is one of the most important II–IV group semiconductors with narrow band gap of
2.4 eV and has received considerable attention in solar cells, catalysis, quantum size effect
semiconductor, optoelectronic devices, photo-electrochemistry and biological labeling.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 45
Wang et al. reported the preparation of PbS hollow nanospheres with diameters of 80-250
nm through a surfactant-assisted sonochemical route (Figure 25). The shells of the hollow
spheres estimated to be around 20 nm and are composed of small PbS nanoparticles with
diameters of about 12 nm. An aqueous solution containing Pb(CH3COO)2, thioacetamide
(TAA), and sodium dodecylbenzenesulfonate (DBS) were transferred to a ultrasonic cleaning
bath (49 Hz, 50W) and sonicated for 4 h. It was suggested that DBS has the tendency to self-
aggregation and to form vesicles with different sizes under the ultrasound wave, which
directly determine the diameters of the spheres. As DBS is an anionic surfactant, the surface
of spheres has negative charge and Pb2+ ions are easily attracted on the vesicle surfaces. The
adsorbed ions provide nucleation domains for the subsequent reaction between Pb2+ and H2S
to form PbS nanoparticles. The formation process of PbS nanoparticles is suggested as
follows:

- -
+ ÷÷ ÷ OH H O H
)))
2
(19)

) ( 2
2 3 2
CSNH CH RS R S H RS H = + ÷ +
- -
(20)

PbS Pb S ÷ +
+
÷
2 2
(21)

n
PbS nPbS ) ( ÷ (22)

The sonochemical process produces H
2
S gradually, which avoids the rapid reaction and
causes that PbS nanoparticles grow on the surface of spheres.
In the absence of surfactant only irregular PbS rods were observed. Moreover, when
cetyltrimethyl ammonium bromide (CTAB) was used as surfactant, well-crystalline PbS rods
with of 0.3-0.4 µm in width and 3.5-7 µm in length were observed. Table 2 and 3 summarize
some of synthetic parameters and morphological structure of PbS and CdS, respectively.


Figure 25. (a) TEM and (b) HRTEM images of the PbS hollow spheres.
M. F. Mousavi and S. Ghasemi 46
Table 2. The conditions of preparation of PbS nanostructures


Table 3. The conditions of preparation of CdS nanostructures

Metal
sources
solvent Sulfur
sources
template
or
structure
directing
agent
Ultrasonic parameters Morphology
(Size)
Ref. no.
CdSO
4
H
2
O
and
(CH3)2
CHOH
Na
2
S
2
O
3
Hydroxyethyl
cellulose
(Mw,
123,000)
40-kHz ultrasonic wave at 100-
W output power at room
temperature
Nanoparticles
, nanowires
and
dendritic-like
shape
[170]
CdCl
2
H
2
O Na
2
S Polyvinylpyrr
olidone K30
(PVP)
Pulse sonication
(t
on
=6s, t
off
=14s),
100 W, 20 kHz, for 30 min to 2 h
Nanoparticles
(3-5 nm)
[171]
CdCl
2
H
2
O Na
2
S Polyacrylica
mide
CdCl
2
solution was added
into the Na
2
S solution within 5
min under ultrasonic condition
Hollow
nanoparticle
chains
[172]
Cadmium
acetate
H
2
O Na
2
S Amino-acid
histidine
(as chelating
agent)
Sonochemical bath (33 kHz, 350
W) at room temperature at
different
ultrasonic irradiation time
Nanoparticles [173]


Metal sources solvent Sulfur sources template
or
structure
directing agent
Ultrasonic
parameters
Morphology
(Size)
Ref.
no.
Pb(CH
3
COO)
2

ethanol,
distilled water,
ethylene glycol
and
polyethylene
glycol-200
Thiourea -
high-intensity
ultrasound
irradiation
under ambient
air for 30 min
Different
morphologic
al shapes
depend on
solvent type
[165]
PbCl
2
Water, pH=7 Na
2
S
2
O
3

EDTA as
complexing
agent
titanium horn,
20 KHz,
40Wcm
-
1 for
4 h at room
temperature
Nanobelts [166]
Pb(CH
3
COO)
2
Water Thioacetamide CTAB
ultrasonic
cleaning bath
(49 Hz, 50 W)
for 2 and 4 h
nanocubes,
nanorods
and
nanotubes
[167]
Pb(CH
3
COO)
2
Water Thioacetamide
Nitrilotriacetic
acid as capping
agent
ultrasonic
cleaning bath (
40kHz 250 W)
for 40 min at
40 and 70 °C
Dentritic
and star like
Nanostructur
es
[168]
Pb(NO
3
)
2
Water Thioacetamide
Polyethylene
glycol-6000 as a
kind of capping
polymer
High-intensity
ultrasound
irradiation (50
kHz, 100 W)
under ambient
air
Nanorods [169]
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 47
8.6.2. Metal Telluride
Metal tellurides are another category of metal chalcogenides that sonochemistry have
been used extensively to prepare them [174].
Mercury telluride (HgTe) nanorods (with diameters of ~15 nm and lengths of up to 200
nm) and nanoparticles were synthesized via sonochemical method from mercury perchlorate
hydrate and tellurium powder in an ethylenediamine solvent system in the presence of 1-
thioglycerol as a complexing agent.
Zheng et al. prepared Nanocrystalline Bi2Te3 by sonochemical methods at 70 °C using
Te and BiCl3 as the reactants and NaBH4 as the reductant [175]. The prepared powders
consist of granular and flake nanoparticles. The size of the particles are about 10~20 nm. It
was observed that the addition of EDTA suppressed the formation of pure Bi2Te3 phase.
EDTA form complex compounds with Bi3+ ions, decreasing the activity of Bi3+ ions in the
solution and hindering the formation of Bi2Te3.
Bi2Te3 hexagonal nanoflakes with controllable edge length ranging from ~150 nm to as
small as ~10 nm were synthesized via an ultrasonic-assisted disproportionation route, using
Te powder and Bi(NO3)3 in the mixed solvent of glycerol and water or ethylene glycol (EG),
or EG containing certain amount of polyvinyl pyrrolidone (PVP, K-30) [176]. The reaction
mechanism may be as followed:

O H TeO Te OH Te
2
2
3
2
3 2 6 3 + + ÷ +
÷ ÷ ÷
(23)

3 2
2 3
3 2 Te Bi Te Bi ÷ +
÷ +
(24)

Te
2-
is produced in the disproportionation of Te in alkaline solution react with Bi(III) to
give out Bi
2
Te
3
. The ultrasonic irradiation accelerates the reaction rate due to the
mechanochemical effects of ultrasound waves and cause to formation of relatively small and
uniform nanocrystals. The size of the Bi
2
Te
3
nanoflakes changed when using different
solvents. Also, When PVP was added into EG, the size of the nanoflakes decreased. PVP
could adsorb onto the faces of the nanoflakes and hinder their growth, resulting in the
formation of nanoflakes with smaller size.

8.6.3. Metal Selenide
Some of metal selenide have been recently synthesized are Ag
2
Se, HgSe, CdSe, Bi
2
Se
3
.
Table 4 present some of works focused on metal selenides and summarized their synthetic
parameters under ultrasonic irradiation.
8.7. Coordination Polymers

The ultrasonic method is also expected to be useful, but few instances have been reported
for nano structures coordination polymers. Some papers have been reported by Morsali and
co-workers. Hedge balls nano-structure of a new Pb(II) two-dimensional coordination
polymer, [Pb(3-pyc)(N3)(H2O)]n (1), {3-Hpyc =3-pyridinecarboxylic acid}, have been
synthesized using a thermal gradient approach and by sonochemical irradiation [182].

M. F. Mousavi and S. Ghasemi 48
Table 4. The conditions of preparation of MeS nanostructures

Metal
sources
solvent
Selenium
sources
template
or
structure
directing agent
Ultrasonic
parameters
Morphology
(Size)
Ref.
no.
AgNO3 Water Se powder
NH3, citric
acid or KSCN
as complexing
agents
Pulse sonication with
Ti-horn at 500 W.
(time of irradiation in
every reaction was 50
working cycles ton=
60 s and toff=10 s)
Ag2Se
Nanoparticles
[177]
Hg(Ac)2
polyol
solvent such
as ethylene
glycol,
diethylene
glycol and
polyethylene
glycol 200
Se
powder
-
Pulse sonication with
a
high-intensity
ultrasonic probe Ti-
horn, 20 kHz, 80
W/cm2)( ton= 27 s
and toff=3 s)
Taper shaped
HgSe nanorods
[178]
CdCl2
Water,
pH=10
Na2SeSO3 β-cyclodextrin
High-intensity
ultrasonic titanium
horn (20 KHz, 75
W/cm2) under
ambient conditions
for 20 min.
Hollow
spherical CdSe
quantum
dot assemblies
[179]
BiCl3 Water H2SeO3 -
High-intensity
ultrasound
(59 kHz, 45 W) for
15 h at 25 °C
Bi2Se3
nanobelts (8–
10nm in
thickness, 20–80
nm in width, and
several
micrometers in
length)
[180]
Bismuth
nitrate
Water,
pH=11
Na2SeSO3
EDTA as
complexing
agent
High-intensity
ultrasonic probe 20
kHz, 60 W/cm2) for
1 h
Bi2Se3
nanoparticles
[181]

Single-crystal X-ray diffraction of compound 1 shows a two-dimensional polymer with
the coordination number seven for Pb(II) ions. Calcination under air produces nano-sized
particles of PbO. Reduction of the particle size of the supramolecular compound to a few
dozen nanometers results in a lower thermal stability when compared to single crystalline
samples.
A new nanostructured Bi(III) supramolecular compound, {Bi2(4,4΄-Hbipy)1.678(4,4΄-
Hbipy)0.322(μ-I)2I5.678]•(4,4΄-bipy)} (1), 4,4΄-bipy = 4,4΄-bipyridine } was synthesized by a
sonochemical method [183]. Calcinations of compound 1 under two different atmospheres,
air and nitrogen, results in nano-structures Bi2O3 and BiI3.
Some others coordination polymers from La (II) [184], Mn(II) [185], Bi(III) [186], Pb(II)
187 with different ligands and morphologies have been prepared.


Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 49
CONCLUSION

The sonochemistry is a new area of research has been considered during last years
because of its simplicity and possibility of operating under ambient conditions.
Sonochemistry have been proven to be a useful route for the preparation of novel materials
with unusual structures and properties which found their application in various technological
applications such as sensors, optoelectronic device, photocatalyst, fuel cells and energy
storage device and etc. The advantages of this method include a rapid reaction rate,
controllable reaction conditions, and the ability to form materials with uniform shapes,
narrow size distributions, and high purities. Also, sonochemistry provide easy conditions for
synthesize of some materials that other methods can not able to operate at these conditions.
The chemical effect of ultrasonic irradiation arises from the acoustic cavitation which is the
formation, growth, and implosive collapse of bubbles in the liquid medium. The implosive
collapse of the bubbles generates local hot spots or shock wave formation within the gas
phase of the collapsing bubble. These local hot spots produce high temperature (~ 5000 K)
and pressure (~1800 K) which provide a unique environment for the growth of materials with
novel structures.
ACKNOWLEDGMENTS

The authors gratefully acknowledge M. Yousef Elahi for her assistance in preparation of
this chapter. Also, the cooperation of M. A. Kiani, A. Abbasi and Z. Bagheryan is
acknolewdeged.
REFERENCES

[1] Gedanken, A., Using sonochemistry for the fabrication of nanomaterials. Ultrason.
Sonochem. 2004, 11 (2), 47-55.
[2] Gedanken, A.; Mastai, Y., Sonochemistry and Other Novel Methods Developed for the
Synthesis of Nanoparticles. In The Chemistry of Nanomaterials, C. N. R. Rao, A. M.,
A. K. Cheetham, Ed. 2005.
[3] Flannigan, D. J.; Suslick, K. S., Plasma formation and temperature measurement during
single-bubble cavitation. Nature 2005, 434 (7029), 52-55.
[4] (a) Rao, C. N. R., The Chemistry of Nanomaterials: Synthesis, Properties and
Applications, 2 Volumes WILEY-VCH Weinheim, 2004; Vol. 1; (b) Manoharan, S. S.;
Rao, M. L., Sonochemical Synthesis of Nanomaterials. American Scientific: 2004; Vol.
10, p 67-82.
[5] Gedanken, A.; Koltypin, Y.; Perkas, N.; Besson, M.; Vradman, L.; Herskowitz, M.;
Landau, M. V., The Sonochemical Insertion of Nanomaterials into Mesostructures.
Trans. Indian Ceram. Soc. 2006, 63 (1), 137.
[6] Gedanken, A., Doping nanoparticles into polymers and ceramics using ultrasound
radiation. Ultrason. Sonochem. 2007, 14 (4), 418-430.
M. F. Mousavi and S. Ghasemi 50
[7] Okitsu, K.; Ashokkumar, M.; Grieser, F., Sonochemical synthesis of gold nanoparticles:
Effects of ultrasound frequency. J. Phys. Chem. B 2005, 109 (44), 20673-20675.
[8] Okitsu, K.; Sharyo, K.; Nishimura, R., One-Pot Synthesis of Gold Nanorods by
Ultrasonic Irradiation: The Effect of pH on the Shape of the Gold Nanorods and
Nanoparticles. Langmuir 2009, 25 (14), 7786-7790.
[9] Li, C. C.; Cai, W. P.; Li, Y.; Hu, J. L.; Liu, P. S., Ultrasonically induced Au nanoprisms
and their size manipulation based on aging. J. Phys. Chem. B 2006, 110 (4), 1546-1552.
[10] Zhang, J. L.; Du, J. M.; Han, B. X.; Liu, Z. M.; Jiang, T.; Zhang, Z. F., Sonochemical
formation of single-crystalline gold nanobelts. Angew. Chem. Int. Edit. 2006, 45 (7),
1116-1119.
[11] Park, J.-E.; Atobe, M.; Fuchigami, T., Synthesis of multiple shapes of gold
nanoparticles with controlled sizes in aqueous solution using ultrasound. Ultrason.
Sonochem. 2006, 13 (3), 237-241.
[12] Jin, Y.; Wang, P. J.; Yin, D. H.; Liu, J. F.; Qin, L. S.; Yu, N. Y.; Xie, G. Y.; Li, B. M.,
Gold nanoparticles prepared by sonochemical method in thiol-functionalized ionic
liquid. Colloid Surf. A:Physicochem. Eng. Aspects 2007, 302 (1-3), 366-370.
[13] Nemamcha, A.; Rehspringer, J. L.; Khatmi, D., Synthesis of palladium nanoparticles by
sonochemical reduction of palladium(II) nitrate in aqueous solution. J. Phys. Chem. B
2006, 110 (1), 383-387.
[14] Zhu, W.; Wang, W.; Xu, H.; Zhou, L.; Zhang, L.; Shi, J., Ultrasonic-induced growth of
crystalline tellurium nanorods and related branched structures. J. Cryst. Growth 2006,
295 (1), 69-74.
[15] Qiu, L. H.; Pol, V. G.; Calderon-Moreno, J.; Gedanken, A., Synthesis of tin nanorods
via a sonochemical method combined with a polyol process. Ultrason. Sonochem. 2005,
12 (4), 243-247.
[16] He, Y. H.; Vinodgopal, K.; Ashokkumar, M.; Grieser, F., Sonochemical synthesis of
ruthenium nanoparticles. Res. Chem. Intermed. 2006, 32 (8), 709-715.
[17] Wu, Y. Z.; Hao, X. P.; Yang, J. X.; Tian, F.; Jiang, M. H., Ultrasound-assisted synthesis
of nanocrystalline ZnS in the ionic liquid BMIM center dot BF4. Mater. Lett. 2006, 60
(21-22), 2764-2766.
[18] Li, X. M.; Li, Y.; Li, S. Q.; Zhou, W. W.; Chu, H. B.; Chen, W.; Li, I. L.; Tang, Z. K.,
Single crystalline trigonal selenium nanotubes and nanowires synthesized by
sonochemical process. Cryst. Growth Des. 2005, 5 (3), 911-916.
[19] Wang, X. K.; Shao, L.; Guo, W. L.; Wang, J. G.; Zhu, Y. P.; Wang, C., Synthesis of
dendritic silver nanostructures by means of ultrasonic irradiation. Ultrason. Sonochem.
2009, 16 (6), 747-751.
[20] Yang, G. W.; Li, H. L., Sonochemical synthesis of highly monodispersed and size
controllable Ag nanoparticles in ethanol solution. Mater. Lett. 2008, 62 (14), 2193-
2195.
[21] Chen, H.; Li, Z.; Wu, Z.; Zhang, Z., A novel route to prepare and characterize Sn-Bi
nanoparticles. J. Alloys Compd. 2005, 394 (1-2), 282-285.
[22] Kim, J.; Park, J. E.; Momma, T.; Osaka, T., Synthesis of Pd-Sn nanoparticles by
ultrasonic irradiation and their electrocatalytic activity for oxygen reduction.
Electrochim. Acta 2009, 54 (12), 3412-3418.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 51
[23] Korzeniewski, C.; Basnayake, R.; Vijayaraghavan, G.; Li, Z. R.; Xu, S. H.; Casadonte,
D. J., Methanol electrochemical oxidation at nanometer-scale PtRu materials. Surf. Sci.
2004, 573 (1), 100-108.
[24] Basnayake, R.; Li, Z. R.; Katar, S.; Zhou, W.; Rivera, H.; Smotkin, E. S.; Casadonte, D.
J.; Korzeniewski, C., PtRu nanoparticle electrocatalyst with bulk alloy properties
prepared through a sonochemical method. Langmuir 2006, 22 (25), 10446-10450.
[25] Li, H. X.; Li, H.; Zhang, J.; Dai, W. L.; Qiao, M. H., Ultrasound-assisted preparation of
a highly active and selective Co-B amorphous alloy catalyst in uniform spherical
nanoparticles. J. Catal. 2007, 246 (2), 301-307.
[26] Radziuk, D.; Shchukin, D.; Mohwald, H., Sonochemical design of engineered gold-
silver nanoparticles. J. Phys. Chem. C 2008, 112 (7), 2462-2468.
[27] Jia, Y.; Niu, H.; Wu, M.; Ning, M.; Zhu, H.; Chen, Q., Sonochemical preparation of
bimetallic Co/Cu nanoparticles in aqueous solution. Mater. Res. Bull. 2005, 40 (9),
1623-1629.
[28] (a) Nakagawa, T.; Nitani, H.; Tanabe, S.; Okitsu, K.; Seino, S.; Mizukoshi, Y.;
Yamamoto, T. A., Structural analysis of sonochemically prepared Au/Pd nanoparticles
dispersed in porous silica matrix. Ultrason. Sonochem. 2005, 12 (4), 249-254.
[29] Vinodgopal, K.; He, Y. H.; Ashokkumar, M.; Grieser, F., Sonochemically prepared
platinum-ruthenium bimetallic nanoparticles. J. Phys. Chem. B 2006, 110 (9), 3849-
3852.
[30] Anandan, S.; Grieser, F.; Ashokkumar, M., Sonochemical synthesis of Au-Ag core-
shell bimetallic nanoparticles. J. Phys. Chem. C 2008, 112 (39), 15102-15105.
[31] Thongtem, T.; Phuruangrat, A.; Thongtem, S., Effect of basicity on the morphologies of
ZnO produced using a sonochemical method. Current Appl. Phys. 2009, 9 (3,
Supplement 1), S197-S200.
[32] Mazloumi, M.; Zanganeh, S.; Kajbafvala, A.; Ghariniyat, P.; Taghavi, S.; Lak, A.;
Mohaierani, M.; Sadrnezhaad, S. K., Ultrasonic induced photoluminescence decay in
sonochemically obtained cauliflower-like ZnO nanostructures with surface 1D
nanoarrays. Ultrason. Sonochem. 2009, 16 (1), 11-14.
[33] (a) Zhang, M. L.; Kim, Y. H.; Kang, Y. S., Low-temperature synthesis and shape
control of ZnO nanorods. Current Applied Physics 2006, 6 (4), 796-800; (b) Jung, S.
H.; Jeong, S. H., Selective-area growth of ZnO nanorod arrays via a sonochemical
route. Mater. Lett. 2008, 62 (21-22), 3673-3675.
[34] Wahab, R.; Ansari, S. G.; Kim, Y. S.; Seo, H. K.; Shin, H. S., Room temperature
synthesis of needle-shaped ZnO nanorods via sonochemical method. Appl. Surf. Sci.
2007, 253 (18), 7622-7626.
[35] Zhang, X.; Zhao, H.; Tao, X.; Zhao, Y.; Zhang, Z., Sonochemical method for the
preparation of ZnO nanorods and trigonal-shaped ultrafine particles. Mater. Lett. 2005,
59 (14-15), 1745-1747.
[36] Xiao, Q.; Huang, S. P.; Zhang, J.; Xiao, C.; Tan, X. O., Sonochemical synthesis of ZnO
nanosheet. J. Alloys Compd. 2008, 459 (1-2), L18-L22.
[37] Jia, X.; Fan, H.; Zhang, F.; Qin, L., Using sonochemistry for the fabrication of hollow
ZnO microspheres. Ultrason. Sonochem. 2010, 17 (2), 284-287.
[38] Jung, S. H.; Oh, E.; Lee, K. H.; Yang, Y.; Park, C. G.; Park, W. J.; Jeong, S. H.,
Sonochemical preparation of shape-selective ZnO nanostructures. Cryst. Growth Des.
2008, 8 (1), 265-269.
M. F. Mousavi and S. Ghasemi 52
[39] Jung, S. H.; Oh, E.; Lee, K. H.; Park, W.; Jeong, S. H., A sonochemical method for
fabricating aligned ZnO nanorods. Adv. Mater. 2007, 19 (5), 749-753.
[40] Bhattacharyya, S.; Gedanken, A., A template-free, sonochemical route to porous ZnO
nano-disks. Micropor. Mesopor. Mat. 2008, 110 (2-3), 553-559.
[41] (a) Hou, X. M.; Zhou, F.; Sun, Y. B.; Liu, W. M., Ultrasound-assisted synthesis of
dentritic ZnO nanostructure in ionic liquid. Mater. Lett. 2007, 61 (8-9), 1789-1792;
[42] (b) Goharshadi, E. K.; Ding, Y.; Jorabchi, M. N.; Nancarrow, P., Ultrasound-assisted
green synthesis of nanocrystalline ZnO in the ionic liquid hmim NTf2. Ultrason.
Sonochem. 2009, 16 (1), 120-123.
[43] Chen, Y. J.; Zhu, C. L.; Xiao, G., Ethanol sensing characteristics of ambient
temperature sonochemically synthesized ZnO nanotubes. Sensors Actuat. B: Chem.
2008, 129 (2), 639-642.
[44] Oh, E.; Choi, H. Y.; Jung, S. H.; Cho, S.; Kim, J. C.; Lee, K. H.; Kang, S. W.; Kim, J.;
Yun, J. Y.; Jeong, S. H., High-performance NO2 gas sensor based on ZnO nanorod
grown by ultrasonic irradiation. Sensors Actuat. B: Chem. 2009, 141 (1), 239-243.
[45] Zhang, S. L.; Park, S. M.; Lim, J. O.; Huh, J. S., Sonochemical Synthesis and Gas
Sensing Properties of Well-Aligned ZnO Nanorods. Met. Mater. Int. 2008, 14 (5), 621-
624.
[46] Ni, Y. H.; Li, H.; Jin, L. A.; Hong, J. M., Synthesis of 1D Cu(OH)(2) Nanowires and
Transition to 3D CuO Microstructures under Ultrasonic Irradiation, and Their
Electrochemical Property. Cryst. Growth Des. 2009, 9 (9), 3868-3873.
[47] Mao, C. J.; Pan, H. C.; Wu, X. C.; Zhu, J. J.; Chen, H. Y., Sonochemical route for self-
assembled V2O5 bundles with spindle-like morphology and their novel application in
serum albumin sensing. J. Phys. Chem. B 2006, 110 (30), 14709-14713.
[48] Taufiq-Yap, Y. H.; Wong, Y. C.; Zainal, Z.; Hussein, M. Z., Synthesis of self-
assembled nanorod vanadium oxide bundles by sonochemical treatment. J. Natural Gas
Chem. 2009, 18 (3), 312-318.
[49] Bang, J. H.; Suslick, K. S., Sonochemical synthesis of nanosized hollow hematite. J.
Am. Chem. Soc. 2007, 129 (8), 2242-2243.
[50] Dang, F.; Enomoto, N.; Hojo, J.; Enpuku, K., Sonochemical synthesis of
monodispersed magnetite nanoparticles by using an ethanol-water mixed solvent.
Ultrason. Sonochem. 2009, 16 (5), 649-654.
[51] Zhang, G. Q.; Wu, H. P.; Ge, M. Y.; Jiang, Q. K.; Chen, L. Y.; Yao, J. M., Ultrasonic-
assisted preparation of monodisperse iron oxide nanoparticles. Mater. Lett. 2007, 61
(11-12), 2204-2207.
[52] Zhu, S. M.; Zhou, H. A.; Hibino, M.; Honma, I.; Ichihara, M., Synthesis of MnO2
nanoparticles confined in ordered mesoporous carbon using a sonochemical method.
Adv Funct. Mater. 2005, 15 (3), 381-386.
[53] Lei, S.; Tang, K.; Fang, Z.; Zheng, H., Ultrasonic-Assisted Synthesis of Colloidal
Mn3O4 Nanoparticles at Normal Temperature and Pressure. Crys. Growth Des. 2006, 6
(8), 1757-1760.
[54] Kumar, V. G.; Kim, K. B., Organized and highly dispersed growth of MnO2 nano-rods
by sonochemical hydrolysis of Mn(3)acetate. Ultrason. Sonochem. 2006, 13 (6), 549-
556.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 53
[55] Okitsu, K.; Iwatani, M.; Nanzai, B.; Nishimura, R.; Maeda, Y., Sonochemical reduction
of permanganate to manganese dioxide: The effects of H2O2 formed in the sonolysis of
water on the rates of reduction. Ultrason. Sonochem. 2009, 16 (3), 387-391.
[56] Park, J. P.; Kim, S. K.; Park, J. Y.; Hwang, C. H.; Choi, M. H.; Kim, J. E.; Ok, K. M.;
Kwak, H. Y.; Shim, I. W., Syntheses of Mn3O4 and LiMn2O4 nanoparticles by a
simple sonochemical method. Mater. Lett. 2009, 63 (26), 2201-2204.
[57] Dutta, D. P.; Sudarsan, V.; Srinivasu, P.; Vinu, A.; Tyagi, A. K., Indium oxide and
europium/dysprosium doped indium oxide nanoparticles: Sonochemical synthesis,
characterization, and photoluminescence studies. J. Phys. Chem. C 2008, 112 (17),
6781-6785.
[58] Yu, J.; Zhou, M.; Cheng, B.; Yu, H.; Zhao, X., Ultrasonic preparation of mesoporous
titanium dioxide nanocrystalline photocatalysts and evaluation of photocatalytic
activity. J. Mol. Catal. A: Chem. 2005, 227 (1-2), 75-80.
[59] Wang, J.; Sun, W.; Zhang, Z. H.; Xing, Z. Q.; Xu, R.; Li, R. H.; Li, Y.; Zhang, X. D.,
Treatment of nano-sized rutile phase TiO2 powder under ultrasonic irradiation in
hydrogen peroxide solution and investigation of its sonocatalytic activity. Ultrason.
Sonochem. 2008, 15 (4), 301-307.
[60] Guo, S.; Wu, Z. B.; Wang, H. Q.; Dong, F., Synthesis of mesoporous TiO2 nanorods
via a mild template-free sonochemical route and their photocatalytic performances.
Catal. Commun. 2009, 10 (13), 1766-1770.
[61] Alammar, T.; Birkner, A.; Shekhah, O.; Mudring, A.-V., Sonochemical preparation of
TiO2 nanoparticles in the ionic liquid 1-(3-hydroxypropyl)-3-methylimidazolium-
bis(trifluoromethylsulfonyl)amide. Mater. Chem. Phys. 2010, 120 (1), 109-113.
[62] Zhou, M. H.; Yu, J. G.; Cheng, B., Effects of Fe-doping on the photocatalytic activity
of mesoporous TiO2 powders prepared by an ultrasonic method. J. Hazard. Mater.
2006, 137 (3), 1838-1847.
[63] Ghasemi, S.; Mousavi, M. F.; Shamsipur, M.; Karami, H., Sonochemical-assisted
synthesis of nano-structured lead dioxide. Ultrason. Sonochem. 2008, 15 (4), 448-455.
[64] Zhang, L. S.; Wang, W. Z.; Yang, J. O.; Chen, Z. G.; Zhang, W. Q.; Zhou, L.; Liu, S.
W., Sonochemical synthesis of nanocrystallite Bi2O3 as a visible-light-driven
photocatalyst. Appl. Catal. A: Gen. 2006, 308, 105-110.
[65] Karami, H.; Karimi, M. A.; Haghdar, S.; Sadeghi, A.; Mir-Ghaserm, R.; Mahdi-Khani,
S., Synthesis of lead oxide nanoparticles by Sonochemical method and its application as
cathode and anode of lead-acid batteries. Mater. Chem. Phys. 2008, 108 (2-3), 337-344.
[66] Sadeghzadeh, H.; Morsali, A.; Retailleau, P., Ultrasonic-assisted synthesis of two new
nano-structured 3D lead(II) coordination polymers: Precursors for preparation of PbO
nano-structures. Polyhedron 2010, 29 (2), 925-933.
[67] Alavi, M. A.; Morsali, A., Syntheses and characterization of Mg(OH)(2) and MgO
nanostructures by ultrasonic method. Ultrason. Sonochem. 2010, 17 (2), 441-446.
[68] Du, K.; Fu, W.; Wei, R.; Yang, H.; Xu, J.; Chang, L.; Yu, Q.; Zou, G., Ultrasonic-
assisted synthesis of highly dispersed MoO3 nanospheres using 3-
mercaptopropyltrimethoxysilane. Ultrason. Sonochem. 2008, 15 (3), 233-238.
[69] Askarinejad, A.; Morsali, A., Synthesis and characterization of mercury oxide unusual
nanostructures by ultrasonic method. Chem. Eng. J. 2009, 153 (1-3), 183-186.
M. F. Mousavi and S. Ghasemi 54
[70] Rangari, V. K.; Hassan, T. A.; Mayo, Q.; Jeelani, S., Size reduction of WO3
nanoparticles by ultrasound irradiation and its applications in structural
nanocomposites. Compos. Sci. Technol. 2009, 69 (14), 2293-2300.
[71] Majumdar, S.; Chakraborty, S.; Devi, P. S.; Sen, A., Room temperature synthesis of
nanocrystalline SnO through sonochemical route. Mater. Lett. 2008, 62 (8-9), 1249-
1251.
[72] Wang, H.; Zhu, J. J.; Zhu, J. M.; Liao, X. H.; Xu, S.; Ding, T.; Chen, H. Y., Preparation
of nanocrystalline ceria particles by sonochemical and microwave assisted heating
methods. PCCP 2002, 4 (15), 3794-3799.
[73] Miao, J. J.; Wang, H.; Li, Y. R.; Zhu, J. M.; Zhu, J. J., Ultrasonic-induced synthesis of
CeO2 nanotubes. J. Crys. Growth 2005, 281 (2-4), 525-529.
[74] Zhang, D.; Fu, H.; Shi, L.; Pan, C.; Li, Q.; Chu, Y.; Yu, W., Synthesis of CeO2
Nanorods via Ultrasonication Assisted by Polyethylene Glycol. Inorg. Chem. 2007, 46
(7), 2446-2451.
[75] Bedekar, V.; Dutta, D. P.; Mohapatra, M.; Godbole, S. V.; Ghildiyal, R.; Tyagi, A. K.,
Rare-earth doped gadolinia based phosphors for potential multicolor and white light
emitting deep UV LEDs. Nanotechnol. 2009, 20 (12).
[76] Zhou, L.; Wang, W. Z.; Liu, S. W.; Zhang, L. S.; Xu, H. L.; Zhu, W., A sonochemical
route to visible-light-driven high-activity BiVO4 photocatalyst. J. Mol. Catal. A: Chem.
2006, 252 (1-2), 120-124.
[77] Shang, M.; Wang, W. Z.; Zhou, L.; Sun, S. M.; Yin, W. Z., Nanosized BiVO4 with
high visible-light-induced photocatalytic activity: Ultrasonic-assisted synthesis and
protective effect of surfactant. J. Hazard. Mater. 2009, 172 (1), 338-344.
[78] Yu, C. C.; Yu, M.; Li, C. X.; Zhang, C. M.; Yang, P. P.; Lin, J., Spindle-like
Lanthanide Orthovanadate Nanoparticles: Facile Synthesis by Ultrasonic Irradiation,
Characterization, and Luminescent Properties. Cryst. Growth Des. 2009, 9 (2), 783-791.
[79] Selvan, R. K.; Gedanken, A.; Anilkumar, P.; Manikandan, G.; Karunakaran, C.,
Synthesis and Characterization of Rare Earth Orthovanadate (RVO4; R = La, Ce, Nd,
Sm, Eu and Gd) Nanorods/Nanocrystals/Nanospindles by a Facile Sonochemical
Method and Their Catalytic Properties. J. Cluster. Sci. 2009, 20 (2), 291-305.
[80] Wang, J. Z.; Hu, Y.; Liu, J.; Chen, Z. Y., Sonochemical preparation of PbTiO3 fine
powders. J. Am. Ceram. Soc. 2005, 88 (1), 34-37.
[81] Dang, F.; Kato, K.; Imai, H.; Wada, S.; Haneda, H.; Kuwabara, M., A new effect of
ultrasonication on the formation of BaTiO3 nanoparticles. Ultrason. Sonochem. 2010,
17 (2), 310-314.
[82] Xu, M.; Lu, Y. N.; Liu, Y. F.; Shi, S. Z.; Qian, T. S.; Lu, D. Y., Sonochemical synthesis
of monosized spherical BaTiO3 particles. Powder Technol. 2006, 161 (3), 185-189.
[83] Lv, W. Z.; Liu, B.; Qiu, Q.; Wang, F.; Luo, Z. K.; Zhang, P. X.; Wei, S. H., Synthesis,
characterization and photocatalytic properties of spinel CuAl2O4 nanoparticles by a
sonochemical method. J. Alloys Compd. 2009, 479 (1-2), 480-483.
[84] Lv, W.; Luo, Z.; Yang, H.; Liu, B.; Weng, W.; Liu, J., Effect of processing conditions
on sonochemical synthesis of nanosized copper aluminate powders. Ultrason.
Sonochem. 2010, 17 (2), 344-351.
[85] Troia, A.; Pavese, M.; Geobaldo, F., Sonochemical preparation of high surface area
MgAl2O4 spinel. Ultrason. Sonochem. 2009, 16 (1), 136-140.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 55
[86] Dutta, D. P.; Ghildiyal, R.; Tyagi, A. K., Luminescent Properties of Doped Zinc
Aluminate and Zinc Gallate White Light Emitting Nanophosphors Prepared via
Sonochemical Method. J. Phys. Chem. C 2009, 113 (39), 16954-16961.
[87] Geng, J.; Zhu, J. J.; Chen, H. Y., Sonochemical preparation of luminescent PbWO4
nanocrystals with morphology evolution. Crys. Growth Des. 2006, 6 (1), 321-326.
[88] Geng, J.; Zhu, J. J.; Lu, D. J.; Chen, H. Y., Hollow PbWO4 nanospindles via a facile
sonochemical route. Inorg. Chem. 2006, 45 (20), 8403-8407.
[89] Yu, C. L.; Yu, J. C., Sonochemical fabrication, characterization and photocatalytic
properties of Ag/ZnWO
4
nanorod catalyst. Mater. Sci. Eng. B 2009, 164 (1), 16-22.
[90] Thongtem, T.; Phuruangrat, A.; Thongtem, S., Characterization of MeWO4 (Me = Ba,
Sr and Ca) nanocrystallines prepared by sonochemical method. Appl. Surf. Sci. 2008,
254 (23), 7581-7585.
[91] Phuruangrat, A.; Thongtem, T.; Thongtem, S., Analysis of lead molybdate and lead
tungstate synthesized by a sonochemical method. Current Appl. Phys. 2010, 10 (1),
342-345.
[92] Ghule, A. V.; Ghule, K. A.; Tzing, S. H.; Chang, J. Y.; Chang, H.; Ling, Y. C., Pyridine
intercalative sonochemical synthesis and characterization of alpha-Bi2Mo3O12 phase
nanorods. Chem. Phys. Lett. 2004, 383 (1-2), 208-213.
[93] Lv, W. Z.; Liu, B.; Luo, Z. K.; Ren, X. Z.; Zhang, P. X., XRD studies on the nanosized
copper ferrite powders synthesized by sonochemical method. J. Alloys Compd. 2008,
465 (1-2), 261-264.
[94] (a) Sivakumar, M.; Takami, T.; Ikuta, H.; Towata, A.; Yasui, K.; Tuziuti, T.; Kozuka,
T.; Bhattacharya, D.; Iida, Y., Fabrication of zinc ferrite nanocrystals by sonochemical
emulsification and evaporation: Observation of magnetization and its relaxation at low
temperature. J. Phys. Chem. B 2006, 110 (31), 15234-15243; (b) Sivakumar, M.;
Towata, A.; Yasui, K.; Tuziuti, T.; Iida, Y., A new ultrasonic cavitation approach for
the synthesis of zinc ferrite nanocrystals. Current Appl. Phys. 2006, 6 (3), 591-593.
[95] Das, N.; Majumdar, R.; Sen, A.; Maiti, H. S., Nanosized bismuth ferrite powder
prepared through sonochemical and microemulsion techniques. Mater. Lett. 2007, 61
(10), 2100-2104.
[96] Sivakumar, M.; Gedanken, A.; Bhattacharya, D.; Brukental, I.; Yeshurun, Y.; Zhong,
W.; Du, Y. W.; Felner, I.; Nowik, I., Sonochemical synthesis of nanocrystalline rare
earth orthoferrites using Fe(CO)(5) precursor. Chem. Mater. 2004, 16 (19), 3623-3632.
[97] Sivakumar, M.; Gedanken, A.; Zhong, W.; Du, Y. W.; Bhattacharya, D.; Yeshurun, Y.;
Felner, I., Nanophase formation of strontium hexaferrite fine powder by the
sonochemical method using Fe(CO)5. J. Magn. Magn. Mater. 2004, 268 (1-2), 95-104.
[98] Perkas, N.; Amirian, G.; Rottman, C.; de la Vega, F.; Gedanken, A., Sonochemical
deposition of magnetite on silver nanocrystals. Ultrason. Sonochem. 2009, 16 (1), 132-
135.
[99] Pradhan, A.; Jones, R. C.; Caruntu, D.; O'Connor, C. J.; Tarr, M. A., Gold-magnetite
nanocomposite materials formed via sonochemical methods. Ultrason. Sonochem.
2008, 15 (5), 891-897.
[100] Caruntu, D.; Remond, Y.; Chou, N. H.; Jun, M.-J.; Caruntu, G.; He, J.; Goloverda, G.;
O'Connor, C.; Kolesnichenko, V., Reactivity of 3d Transition Metal Cations in
Diethylene Glycol Solutions. Synthesis of Transition Metal Ferrites with the Structure
M. F. Mousavi and S. Ghasemi 56
of Discrete Nanoparticles Complexed with Long-Chain Carboxylate Anions. Inorg.
Chem. 2002, 41 (23), 6137-6146.
[101] Mizukoshi, Y.; Tsuru, Y.; Tominaga, A.; Seino, S.; Masahashi, N.; Tanabe, S.;
Yamamoto, T. A., Sonochemical immobilization of noble metal nanoparticles on the
surface of maghemite: Mechanism and morphological control of the products. Ultrason.
Sonochem. 2008, 15 (5), 875-880.
[102] Mizukoshi, Y.; Sato, K.; Konno, T. J.; Masahashi, N.; Tanabe, S., Magnetically
Retrievable Palladium/Maghemite Nanocomposite Catalysts Prepared by Sonochemical
Reduction Method. Chem. Lett. 2008, 37 (9), 922-923.
[103] Mizukoshi, Y.; Seino, S.; Kinoshita, T.; Nakagawa, T.; Yamamoto, T. A.; Tanabe, S.,
Selective magnetic separation of sulfur-containing amino acids by sonochemically
prepared Au/gamma-Fe2O3 composite nanoparticles. Scripta Mater. 2006, 54 (4), 609-
613.
[104] Bhattacharyya, S.; Gabashvili, A.; Perkas, N.; Gedanken, A., Sonochemical insertion of
silver nanoparticles into two-dimensional mesoporous alumina. J. Phys. Chem. C 2007,
111 (30), 11161-11167.
[105] Perkas, N.; Rotter, H.; Vradman, L.; Landau, M. V.; Gedanken, A., Sonochemically
prepared Pt/CeO2 and its application as a catalyst in ethyl acetate combustion.
Langmuir 2006, 22 (16), 7072-7077.
[106] Li, F.; Liu, X. Q.; Qin, Q. H.; Wu, J. F.; Li, Z.; Huang, X. T., Sonochemical synthesis
and characterization of ZnO nanorod/Ag nanoparticle composites. Cryst. Res. Technol.
2009, 44 (11), 1249-1254.
[107] Vasylkiv, O.; Sakka, Y.; Maeda, Y.; Skorokhod, V. V., Nano-engineering of zirconia-
noble metals composites. J. Eur. Ceram. Soc. 2004, 24 (2), 469-473.
[108] Bhattacharyya, S.; Gedanken, A., Interplay of porosity in gamma-Al2O3-doped ZnO
nanocomposites: A comparative study of sonochemical and microwave reaction routes.
J. Phys. Chem. C 2008, 112 (34), 13156-13162.
[109] Perelshtein, I.; Applerot, G.; Perkas, N.; Wehrschuetz-Sigl, E.; Hasmann, A.; Guebitz,
G.; Gedanken, A., CuO-cotton nanocomposite: Formation, morphology, and
antibacterial activity. Surf. Coat. Tech. 2009, 204 (1-2), 54-57.
[110] Hadad, L.; Perkas, N.; Gofer, Y.; Calderon-Moreno, J.; Ghule, A.; Gedanken, A.,
Sonochemical deposition of silver nanoparticles on wool fibers. J. Appl. Polym. Sci.
2007, 104 (3), 1732-1737.
[111] Rangari, V. K.; Srivastava, D. N.; Gedanken, A., Preparation of ceria nanoparticles
embedded in PMMA using sonochemical technique. Mater. Lett. 2006, 60 (29-30),
3766-3768.
[112] Parra, C.; Gonzalez, G.; Albano, C., Synthesis and Characterization of Composite
Materials HDPE/HA and PMMA/HA Prepared by Sonochemistry. Macromol. Symp.
2009, 286, 60-69.
[113] Wang, J. H.; Hu, Y.; Li, B. G.; Gui, Z.; Chen, Z. Y., Preparation of polyacrylamide and
gamma-zirconium phosphate nanocomposites by intercalative polymerization.
Ultrason. Sonochem. 2004, 11 (5), 301-306.
[114] Qiu, G. H.; Wang, Q.; Wang, C.; Lau, W.; Guo, Y. L., Polystyrene/Fe(3)O(4)magnetic
emulsion and nanocomposite prepared by ultrasonically initiated miniemulsion
polymerization. Ultrason. Sonochem. 2007, 14 (1), 55-61.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 57
[115] Zhang, K.; Fu, Q.; Fan, J.; Zhou, D., Preparation of Ag/PS composite particles by
dispersion polymerization under ultrasonic irradiation. Mater. Lett. 2005, 59 (28), 3682-
3686.
[116] Perkas, N.; Shuster, M.; Amirian, G.; Koltypin, Y.; Gedanken, A., Sonochemical
immobilization of silver nanopartides on porous polypropylene. J. Polym. Sci. Part A:
Polym. Chem. 2008, 46 (5), 1719-1729.
[117] Park, J.-E.; Atobe, M.; Fuchigami, T., Sonochemical synthesis of conducting polymer-
metal nanoparticles nanocomposite. Electrochim. Acta 2005, 51 (5), 849-854.
[118] Park, J. E.; Atobe, M.; Fuchigami, T., Sonochemical synthesis of inorganic-organic
hybrid nanocomposite based on gold nanoparticles and polypyrrole. Chem. Lett. 2005,
34 (1), 96-97.
[119] Atobe, M.; Okamoto, M.; Fuchigami, T.; Park, J.-E., Selective hydrogenation by
polymer-encapsulated platinum nanoparticles prepared by an easy single-step
sonochemical synthesis. Ultrason. Sonochem. 2010, 17 (1), 26-29.
[120] de Barros, R. A.; de Azevedo, W. M., Polyaniline/silver nanocomposite preparation
under extreme or non-classical conditions. Synth. Met. 2008, 158 (21-24), 922-926.
[121] Sivakumar, M.; Gedanken, A., A sonochemical method for the synthesis of polyaniline
and Au-polyaniline composites using H2O2 for enhancing rate and yield. Synth. Met.
2005, 148 (3), 301-306.
[122] Kowsari, E.; Faraghi, G., Ultrasound and ionic-liquid-assisted synthesis and
characterization of polyaniline/Y2O3 nanocomposite with controlled conductivity.
Ultrason. Sonochem. In Press, Corrected Proof.
[123] Qiu, G. H.; Wang, Q.; Nie, M., Polyaniline/Fe3O4 magnetic nanocomposite prepared
by ultrasonic irradiation. J. Appl. Polym. Sci. 2006, 102 (3), 2107-2111.
[124] Lu, X.; Mao, H.; Chao, D.; Zhang, W.; Wei, Y., Ultrasonic synthesis of polyaniline
nanotubes containing Fe3O4 nanoparticles. J. Solid State Chem. 2006, 179 (8), 2609-
2615.
[125] Kawaoka, H.; Hibino, M.; Zhou, H. S.; Honma, I., Sonochemical synthesis of
amorphous manganese oxide coated on carbon and application to high power battery. J.
Power Sources 2004, 125 (1), 85-89.
[126] (a) Kawaoka, H.; Hibino, M.; Zhou, H. S.; Honma, I., Optimization of sonochemical
synthesis condition of manganese oxide/acetylene black nanocomposite for high power
lithium-ion batteries. J. Electrochem. Soc 2005, 152 (6), A1217-A1220; (b) Kawaoka,
H.; Hibino, M.; Zhou, H.; Honma, I., Nanostructure and high-rate discharge-charge
property of manganese oxide/acetylene black nanocomposite synthesized by
sonochemical method. Solid State Ionics 2005, 176 (5-6), 621-627.
[127] Cao, Y. L.; Cao, J. M.; Liu, J. S.; Zheng, M. B.; Shen, K., Sonochemical fabrication and
photoluminescence properties of ordered mesoporous carbon-tin oxide nanocomposites.
Chem Lett 2007, 36 (2), 254-255.
[128] Jang, J.-H.; Kim, J.; Lee, Y.-H.; Pak, C.; Kwon, Y.-U., Sonochemical synthesis of
tungsten carbide-palladium nanocomposites and their electrocatalytic activity for
hydrogen oxidation reaction. Electrochim. Acta 2009, 55 (2), 485-490.
[129] Kim, J.; Jang, J. H.; Lee, Y. H.; Kwon, Y. U., Enhancement of electrocatalytic activity
of platinum for hydrogen oxidation reaction by sonochemically synthesized WC1-x
nanoparticles. J. Power Sources 2009, 193 (2), 441-446.
M. F. Mousavi and S. Ghasemi 58
[130] Pan, H. B.; Wai, C. M., Sonochemical One-Pot Synthesis of Carbon Nanotube-
Supported Rhodium Nanoparticles for Room-Temperature Hydrogenation of Arenes. J.
Phys. Chem. C 2009, 113 (46), 19782-19788.
[131] Zhang, D.; Shi, L.; Fu, H.; Fang, J., Ultrasonic-assisted preparation of carbon
nanotube/cerium oxide composites. Carbon 2006, 44 (13), 2853-2855.
[132] Ginic-Markovic, M.; Matisons, J. G.; Cervini, R.; Simon, G. P.; Fredericks, P. M.,
Synthesis of New Polyaniline/Nanotube Composites Using Ultrasonically Initiated
Emulsion Polymerization. Chem. Mater. 2006, 18 (26), 6258-6265.
[133] Xia, H. S.; Qiu, G. H.; Wang, Q., Polymer/carbon nanotube composite emulsion
prepared through ultrasonically assisted in situ emulsion polymerization. J. Appl.
Polym. Sci. 2006, 100 (4), 3123-3130.
[134] Ghule, A. V.; Ghule, K.; Tzing, S. H.; Ling, Y. C., Synthesis and characterization of
silver-nanoparticle-deposited alpha-Bi2Mo3O12 nanorods. Eur. J. Inorg. Chem. 2007,
(21), 3342-3349.
[135] Nikitenko, S. I.; Koltypin, Y.; Felner, L.; Yeshurun, I.; Shames, A. I.; Jiang, J. Z.;
Markovich, V.; Gorodetsky, G.; Gedanken, A., Tailoring the properties of Fe-Fe3C
nanocrystalline particles prepared by sonochemistry. J. Phys. Chem. B 2004, 108 (23),
7620-7626.
[136] Fernando, K. A. S.; Smith, M. J.; Harruff, B. A.; Lewis, W. K.; Guliants, E. A.; Bunker,
C. E., Sonochemically Assisted Thermal Decomposition of Alane N,N-
Dimethylethylamine with Titanium (IV) Isopropoxide in the Presence of Oleic Acid to
Yield Air-Stable and Size-Selective Aluminum Core-Shelll Nanoparticles. J. Phys.
Chem. C 2009, 113 (2), 500-503.
[137] Hu, C. G.; Li, Y.; Liu, J. P.; Zhang, Y. Y.; Bao, G.; Buchine, B.; Wang, Z. L.,
Sonochemical synthesis of ferromagnetic core-shell Fe3O4-FeP nanoparticles and FeP
nanoshells. Chem. Phys. Lett. 2006, 428 (4-6), 343-347.
[138] Morel, A. L.; Nikitenko, S. I.; Gionnet, K.; Wattiaux, A.; Lai-Kee-Him, J.; Labrugere,
C.; Chevalier, B.; Deleris, G.; Petibois, C.; Brisson, A.; Simonoff, M., Sonochemical
approach to the synthesis of Fe3O4@SiO2 core-shell nanoparticles with tunable
properties. Acs. Nano 2008, 2 (5), 847-856.
[139] Wang, J.; Loh, K. P.; Zhong, Y. L.; Lin, M.; Ding, J.; Foo, Y. L., Bifunctional FePt
core-shell and hollow spheres: Sonochemical preparation and self-assembly. Chem.
Mater. 2007, 19 (10), 2566-2572.
[140] Dhas, N. A.; Suslick, K. S., Sonochemical preparation of hollow nanospheres and
hollow nanocrystals. J. Am. Chem. Soc. 2005, 127 (8), 2368-2369.
[141] Wang, C. L.; Zhang, H.; Zhang, J. H.; Li, M. J.; Sun, H. Z.; Yang, B., Application of
ultrasonic irradiation in aqueous synthesis of highly fluorescent CdTe/CdS core-shell
nanocrystals. J. Phys. Chem. C 2007, 111 (6), 2465-2469.
[142] Ruan, Q. C.; Zhu, Y. C.; Zeng, Y.; Qian, H. F.; Xiao, J. W.; Xu, F. F.; Zhang, L. L.;
Zhao, D. H., Ultrasonic-Irradiation-Assisted Oriented Assembly of Ordered Monetite
Nanosheets Stacking. J. Phys. Chem. B 2009, 113 (4), 1100-1106.
[143] Han, Y.; Li, S.; Wang, X.; Bauer, I.; Yin, M., Sonochemical preparation of
hydroxyapatite nanoparticles stabilized by glycosaminoglycans. Ultrason. Sonochem.
2007, 14 (3), 286-290.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 59
[144] Jevtic, M.; Mitric, M.; Skapin, S.; Jancar, B.; Ignjatovic, N.; Uskokovic, D., Crystal
structure of hydroxyapatite nanorods synthesized by sonochemical homogeneous
precipitation. Cryst. Growth Des. 2008, 8 (7), 2217-2222.
[145] Yu, C. C.; Yu, M.; Li, C. X.; Liu, X. M.; Yang, J.; Yang, P. P.; Lin, J., Facile
sonochemical synthesis and photoluminescent properties of lanthanide orthophosphate
nanoparticles. J. Solid State Chem. 2009, 182 (2), 339-347.
[146] Geng, J.; Hou, W. H.; Lv, Y. N.; Zhu, J. J.; Chen, H. Y., One-dimensional BiPO4
nanorods and two-dimensional BiOCl lamellae: Fast low-temperature sonochemical
synthesis, characterization, and growth mechanism. Inorg. Chem. 2005, 44 (23), 8503-
8509.
[147] Alavi, M. A.; Morsali, A., Syntheses of BaCO3 nanostructures by ultrasonic method.
Ultrason. Sonochem. 2008, 15 (5), 833-838.
[148] Askanneiad, A.; Morsali, A., Syntheses and characterization of CdCO3 and CdO
nanoparticles by using a sonochemical method. Mater. Lett. 2008, 62 (3), 478-482.
[149] Li, K.; Zhao, P., Synthesis and characterization of CeCO3OH one-dimensional
quadrangular prisms by a simple method. Mater. Lett. 2009, 63 (23), 2013-2015.
[150] Yang, L. X.; Zhu, Y. J.; Tong, H.; Wang, W. W., Submicrocubes and highly oriented
assemblies of MnCO3 synthesized by ultrasound agitation method and their thermal
transformation to nanoporous Mn2O3. Ultrason. Sonochem. 2007, 14, 259-265.
[151] Yang, L. X.; Zhu, Y. J.; Tong, H.; Wang, W. W., Submicrocubes and highly oriented
assemblies of MnCO3 synthesized by ultrasound agitation method and their thermal
transformation to nanoporous Mn2O3. Ultrason. Sonochem. 2007, 14 (2), 259-265.
[152] Zhu, L.; Meng, J.; Cao, X., Sonochemical synthesis and luminescence properties of
single-crystalline BaF2:Eu3+ nanospheres. J. Solid State Chem. 2007, 180 (11), 3101-
3105.
[153] Zhu, L.; Liu, X. M.; Meng, J.; Cao, X. Q., Facile sonochemical synthesis of single-
crystalline europium fluorine with novel nanostructure. Cryst. Growth Des. 2007, 7
(12), 2505-2511.
[154] Ni, Y.; Li, G.; Hong, J., Ultrasonic assisted synthesis, characterization and influence
factors of monodispersed dumbbell-like YF3 nanostructures. Ultrason. Sonochem.
2010, 17 (3), 509-514.
[155] Jeong, S. H.; Ko, J. H.; Park, J. B.; Park, W. J., A sonochemical route to single-walled
carbon nanotubes under ambient conditions. J. Am. Chem. Soc. 2004, 126 (49), 15982-
15983.
[156] Li, C. P.; Teo, B. K.; Sun, X. H.; Wong, N. B.; Lee, S. T., Hydrocarbon and Carbon
Nanostructures Produced by Sonochemical Reactions of Organic Solvents on
Hydrogen-Passivated Silicon Nanowires under Ambient Conditions. Chem. Mater.
2005, 17 (23), 5780-5788.
[157] Lu, X. F.; Mao, H.; Chao, D. M.; Zhang, W. J.; Wei, Y., Fabrication of polyaniline
nanostructures under ultrasonic irradiation: From nanotubes to nanofibers. Macromol.
Chem. Phys. 2006, 207 (22), 2142-2152.
[158] Li, Y.; Wang, Y. Y.; Wu, D.; Jing, X. L., Effects of Ultrasonic Irradiation on the
Morphology of Chemically Prepared Polyaniline Nanofibers. J. Appl. Polym. Sci. 2009,
113 (2), 868-875.
M. F. Mousavi and S. Ghasemi 60
[159] Gao, X. D.; Li, X. M.; Yu, W. D., Morphology and optical properties of amorphous
ZnS films deposited by ultrasonic-assisted successive ionic layer adsorption and
reaction method. Thin Solid Films 2004, 468 (1-2), 43-47.
[160] Wang, H.; Zhu, J. J., A sonochemical method for the selective synthesis of alpha-HgS
and beta-HgS nanoparticles. Ultrason. Sonochem. 2004, 11 (5), 293-300.
[161] Singh, D.; Pradeep, T.; Bhattacharjee, J.; Waghmare, U. V., Closed-cage clusters in the
gaseous and condensed phases derived from sonochemically synthesized MoS2
nanoflakes. J. Am. Soc. Mass Spect. 2007, 18 (12), 2191-2197.
[162] Du, N.; Zhang, H.; Sun, H.; Yang, D., Sonochemical synthesis of amorphous long
silver sulfide nanowires. Mater. Lett. 2007, 61 (1), 235-238.
[163] Gorai, S.; Chaudhuri, S., Sonochemical synthesis and characterization of cage-like
[beta]-indium sulphide powder. Mater. Chem. Phys. 2005, 89 (2-3), 332-335.
[164] (a) Xu, H.; Wang, W.; Zhu, W., Sonochemical synthesis of crystalline CuS nanoplates
via an in situ template route. Mater. Lett. 2006, 60 (17-18), 2203-2206; (b) Xu, J. Z.;
Xu, S.; Geng, J.; Li, G. X.; Zhu, J. J., The fabrication of hollow spherical copper sulfide
nanoparticle assemblies with 2-hydroxypropyl-beta-cyclodextrin as a template under
sonication. Ultrason. Sonochem. 2006, 13 (5), 451-454.
[165] Wang, S. F.; Gu, F.; Lu, M. K., Sonochemical synthesis of hollow PbS nanospheres.
Langmuir 2006, 22 (1), 398-401.
[166] Zhao, Y.; Liao, X. H.; Hong, J. M.; Zhu, J. J., Synthesis of lead sulfide nanocrystals via
microwave and sonochemical methods. Mater. Chem. Phys. 2004, 87 (1), 149-153.
[167] Zhou, S. M.; Zhang, X. H.; Meng, X. M.; Fan, X.; Lee, S. T.; Wu, S. K., Sonochemical
synthesis of mass single-crystal PbS nanobelts. J. Solid State Chem. 2005, 178 (1), 399-
403.
[168] Wang, S. F.; Gu, F.; Lu, M. K.; Zhou, G. J.; Zhang, A. Y., Sonochemical synthesis of
PbS nanocubes, nanorods and nanotubes. J. Cryst. Growth 2006, 289 (2), 621-625.
[169] Zhao, P. T.; Chen, G.; Hu, Y.; He, X. L.; Wu, K.; Cheng, Y.; Huang, K. X., Preparation
of dentritic PbS nanostructures by ultrasonic method. J. Cryst. Growth 2007, 303 (2),
632-637.
[170] Xiu, Z. L.; Liu, S. W.; Yu, J. X.; Xu, F. X.; Yu, W. N.; Feng, G. J., Sonochemical
synthesis of PbS nanorods. J. Alloys Compd. 2008, 457 (1-2), L9-L11.
[171] Wu, G. S.; Yuan, X. Y.; Xie, T.; Xu, G. C.; Zhang, L. D.; Zhuang, Y. L., A simple
synthesis route to US nanomaterials with different morphologies by sonochemical
reduction. Mater. Lett. 2004, 58 (5), 794-797.
[172] Wu, Y. D.; Wang, L. S.; Xiao, M. W.; Huang, X. J., A novel sonochemical synthesis
and nanostructured assembly of polyvinylpyrrolidone-capped CdS colloidal
nanoparticles. J. Non-Cryst Solids 2008, 354 (26), 2993-3000.
[173] Liu, J.-K.; Luo, C.-X.; Yang, X.-H.; Zhang, X.-Y., Ultrasonic-template method
synthesis of CdS hollow nanoparticle chains. Mater. Lett. 2009, 63 (1), 124-126.
[174] Yadav, R. S.; Mishra, P.; Mishra, R.; Kumar, M.; Pandey, A. C., Growth mechanism
and optical property of CdS nanoparticles synthesized using amino-acid histidine as
chelating agent under sonochemical process. Ultrason. Sonochem. 2010, 17 (1), 116-
122.
[175] Song, H.; Cho, K.; Kim, H.; Lee, J. S.; Min, B.; Kim, H. S.; Kim, S. W.; Noh, T.; Kim,
S., Synthesis and characterization of nanocrystalline mercury telluride by sonochemical
method. J. Cryst. Growth 2004, 269 (2-4), 317-323.
Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 61
[176] Zheng, Y. Y.; Zhu, T. J.; Zhao, X. B.; Tu, J. P.; Cao, G. S., Sonochemical synthesis of
nanocrystalline Bi2Te3 thermoelectric compounds. Mater. Lett. 2005, 59 (23), 2886-
2888.
[177] Zhou, B.; Liu, B.; Jiang, L. P.; Zhu, J. J., Ultrasonic-assisted size-controllable synthesis
of Bi2Te3 nanoflakes with electro generated chemiluminescence. Ultrason. Sonochem.
2007, 14 (2), 229-234.
[178] Li, K. W.; Liu, X.; Wang, H.; Yan, H., Rapid synthesis of Ag2Se nanocrystals by
sonochemical reaction. Mater. Lett. 2006, 60 (25-26), 3038-3040.
[179] Ding, T.; Zhang, J.-R.; Hong, J.-M.; Zhu, J.-J.; Chen, H.-Y., Sonochemical synthesis of
taper shaped HgSe nanorods in polyol solvent. J. Cryst. Growth 2004, 260 (3-4), 527-
531.
[180] Liu, B.; Ren, T.; Zhang, J. R.; Chen, H. Y.; Zhu, J. J.; Burda, C.,
Spectroelectrochemistry of hollow spherical CdSe quantum dot assemblies in water.
Electrochem. Commun. 2007, 9 (4), 551-557.
[181] (a) Cui, H. M.; Liu, H.; Wang, J. Y.; Li, X.; Han, F.; Boughton, R. I., Sonochemical
synthesis of bismuth selenide nanobelts at room temperature. J. Cryst. Growth 2004,
271 (3-4), 456-461.
[182] Qiu, X. F.; Zhu, J. J.; Pu, L.; Shi, Y.; Zheng, Y. D.; Chen, H. Y., Size-controllable
sonochemical synthesis of thermoelectric material of Bi2Se3 nanocrystals. Inorg.
Chem. Commun. 2004, 7 (3), 319-321.
[183] Sadeghzadeh, H.; Morsali, A., Hedge balls nano-structure of a mixed-ligand lead(II)
coordination polymer; thermal, structural and X-ray powder diffraction studies. Cryst.
Eng. Comm. 2010, 12 (2), 370-372.
[184] Soltanzadeh, N.; Morsali, A., Sonochemical synthesis of a new nano-structures
bismuth(III) supramolecular compound: New precursor for the preparation of
bismuth(III) oxide nano-rods and bismuth(III) iodide nano-wires. Ultrason. Sonochem.
2010, 17 (1), 139-144.
[185] Khanjani, S.; Morsali, A., New nano-particle La(III) supramolecular compound as a
precursor for preparation of lanthanum oxybromide-, hydroxide-, and oxide-
nanostructures. J. Coord. Chem. 2009, 62 (20), 3343-3350.
[186] Morsali, A.; Hossieni Monfared, H.; Morsali, A., Syntheses and characterization of
nano-scale of the MnII complex with 4'-(4-pyridyl)-2,2':6',2''-terpyridine (pyterpy): The
influence of the nano-structure upon catalytic properties. Inorg. Chim. Acta 2009, 362
(10), 3427-3432.
[187] Soltanzadeh, N.; Morsali, A., Syntheses and characterization of a new nano-structured
bismuth(III) bromide coordination polymer; new precursor for preparation of
bismuth(III) bromide and bismuth(III) oxide nanostructures. J. Coord. Chem. 2009, 62
(17), 2869-2874.
[188] (a) Aslani, A.; Morsali, A., Sonochemical synthesis of nano-sized metal-organic
lead(II) polymer: A precursor for the preparation of nano-structured lead(II) iodide and
lead(II) oxide. Inorg. Chim. Acta 2009, 362 (14), 5012-5016.
In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 2



INDUSTRIAL-SCALE PROCESSING OF LIQUIDS BY
HIGH-INTENSITY ACOUSTIC CAVITATION: THE
UNDERLYING THEORY AND ULTRASONIC
EQUIPMENT DESIGN PRINCIPLES


Alexey S. Peshkovsky
1
and Sergei L. Peshkovsky
Industrial Sonomechanics, LLC, New York, NY 10040, USA
ABSTRACT
A multitude of useful physical and chemical processes promoted by ultrasonic
cavitation have been described in laboratory studies. Industrial-scale implementation of
high-intensity ultrasound has, however, been hindered by several technological
limitations, making it difficult to directly scale up ultrasonic systems in order to transfer
the results of the laboratory studies to the plant floor. High-capacity flow-through
ultrasonic reactor systems required for commercial-scale processing of liquids can only
be properly designed if all energy parameters of the cavitation region are correctly
evaluated. Conditions which must be fulfilled to ensure effective and continuous
operation of an ultrasonic reactor system are provided in this chapter, followed by a
detailed description of "shockwave model of acoustic cavitation", which shows how
ultrasonic energy is absorbed in the cavitation region, owing to the formation of a
spherical micro-shock wave inside each vapor-gas bubble, and makes it possible to
explain some newly discovered properties of acoustic cavitation that occur at extremely
high intensities of ultrasound. After the theoretical background is laid out, fundamental
practical aspects of industrial-scale ultrasonic equipment design are provided, specifically
focusing on:

- electromechanical transducer selection principles;
- operation principles and calculation methodology of high-amplitude acoustic horns
used for the generation of high-intensity acoustic cavitation in liquids;

1
Correspondence to: Alexey S. Peshkovsky, Ph.D., Industrial Sonomechanics, LLC, 150 Bennett Avenue, Suite
5K, New York, NY 10040, e-mail: alexey@sonomechanics.com.
Alexey S. Peshkovsky and Sergei L. Peshkovsky 64
- detailed theory of matching acoustic impedances of transducers and cavitating
liquids in order to maximize the ultrasonic power transfer efficiency;
- calculation methodology of ―barbell horns‖, which provide the impedance matching
and can help achieving the transference of all available acoustic energy from
transducers into the liquids. These horns are key to industrial implementation of
high-power ultrasound because they permit producing extremely high ultrasonic
amplitudes, while the output horn diameters and the resulting liquid processing
capacity remain very large;
- optimization of the reactor chamber geometry.
1. INTRODUCTION

A multitude of important physical and chemical processes promoted by ultrasonic
cavitation can be implemented on industrial scale by utilizing high-capacity flow-through
ultrasonic reactor systems. These systems permit processing large volumes of liquids and
commonly comprise an ultrasonic-frequency electrical signal generator, an electromechanical
transducer, which converts the electrical signal into an ultrasonic vibration, an ultrasonic
horn, which amplifies and transmits the vibration into the liquid, and a flow-through reactor
chamber (flow cell), which contains the flowing liquid. A general schematic of such system is
presented in Figure 1 [1, 2]. Several conditions must be fulfilled in order to ensure effective
and continuous operation of an ultrasonic reactor system:

a) technologically necessary intensity of ultrasonic cavitation must be achieved in the
liquid;
b) size and homogeneity of the cavitation region formed in the liquid must be
maximized (well developed cavitation region);
c) reactor chamber design should be such that all of the liquid is directed through the
cavitation region (no liquid bypass);
d) utilized electromechanical transducer must be electrically save, capable of
continuous operation for extended periods of time, and able to provide high radiation
power levels;
e) ultrasonic horn must be capable of amplifying the vibration amplitudes (high gain),
while maintaining maximum possible size of the resulting cavitation region (large
output diameter);
f) mechanical stresses present in the electromechanical transducer and the ultrasonic
horn must not approach the limiting values for the fatigue strength of the
corresponding materials;
g) entire system as well as each of its components must not be in danger of becoming
overheated during continuous operation at full power.

High-quality engineering calculations of the ultrasonic reactor system components can
only be properly performed if all energy parameters of the cavitation region itself are
correctly evaluated, since this region represents the active acoustic load of the
electromechanical transducer (through the ultrasonic horn) and is the target "consumer" of all
produced ultrasonic energy.
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 65

Figure 1. Schematic of the Ultrasonic Reactor System is presented. 1 – ultrasonic electrical generator, 2
– electromechanical transducer, 3 – ultrasonic horn (in this case, a barbell horn), 4 – mounting flange, 5
– reactor chamber, 6 – working liquid inlet, 7 - working liquid outlet.
We will, therefore, start by providing a detailed model of acoustic cavitation, explaining
the mechanism by which the ultrasonic energy is absorbed in the cavitation region. A
discussion of the design principles of the main ultrasonic reactor system components will
follow.
2. SHOCK-WAVE MODEL OF ACOUSTIC CAVITATION

In the design and calculation of powerful ultrasonic sources for ultrasonic reactors, it is
necessary to know the exact value of the intensity of acoustic energy radiated into the
working liquid. This information is usually obtained experimentally because no adequate
physical model of acoustic cavitation that would allow one to obtain such data through
calculation exists. The development of an adequate model of acoustic cavitation, although of
great importance, has in the past been severely restricted by considerable mathematical
difficulties connected with the necessity of finding numerical solutions of nonlinear equations
describing the cavitation region (the visible region of large cavitation bubble population) [3].
The utilized direct analytical solutions of these equations in different approximations do not
give practical results suitable for the design of ultrasonic equipment [4, 5].
Alexey S. Peshkovsky and Sergei L. Peshkovsky 66
The literature on acoustic cavitation mainly tends to involve numerical models of spatio-
temporal characteristics of the cavitation region [6-8]. Large number of theoretical acoustic
cavitation models has been developed along with the corresponding methods of numerical
analysis of such models. Computer simulation-based investigations of acoustic cavitation
have also been proposed, involving complex non-linear physicomathematical models and
including many aspects of spatial movement of cavitation bubbles in an acoustic field, spatial
distribution of the characteristics of these fields in a liquid, interaction between the bubbles
themselves, properties of acoustical flow, etc [9-12]. Water is most frequently used for the
experimental verification of such theoretical models.
No adequate explanation of the mechanism by which dissipation of the primary acoustic
energy of a radiator occurs in a liquid at cavitation is, however, available from the literature.
Additionally, no theoretical method permitting to calculate this energy in a manner adequate
to the available experimental data currently exists. Meanwhile, the exact knowledge of the
mechanisms by which the heating of a liquid in the presence of a cavitation-inducing acoustic
wave occurs is quite important not only for the understanding of the related sonochemical
processes, but also for the practical design parameter calculations that would permit
constructing improved high-capacity ultrasonic radiators and reactors.
2.1. Visual Observations of Acoustic Cavitation

Several authors provided common [13], high-speed [14] and stereoscopic high-speed [15]
photographs of the cavitation region, obtained in the presence of relatively low-intensity
acoustic fields. At these conditions, the cavitation region is located some distance away from
the radiating surface and has a typical pattern similar to that of an electrical discharge.
Photographs of the cavitation region formed by powerful ultrasonic radiators have also
been provided [16, 17]. The diameters of the radiating surfaces of the radiators were greater
than the sound wavelengths in the given liquid at the working frequencies. In these cases,
plane acoustic waves are radiated into the liquid. The photographs show that at relatively low
acoustic radiation intensity, the cavitation region is also located some distance away from the
radiating surface, has an irregular pattern and is composed of thread-like collection of
cavitation bubbles. As the radiation intensity goes up, however, the cavitation region
approaches the radiating surface and grows in size. When the intensity reaches the value of,
approximately, 1.5 W/cm
2
, the cavitation region ―sits‖ on the radiating surface and its shape
starts to resemble an upside-down circular cone. The so-called ―cone bubble structure‖ begins
to form. Further radiation intensity increases have little effect on the shape and position of the
cone bubble structure. The photographs in the abovementioned studies show that at high
radiation intensity the cone bubble structure is in contact with the radiating surface. Reference
[18] provides photographs of the radiating surface of a metal radiator which was utilized for a
period of time to create high-intensity cavitation in a liquid. The surface of the radiator
contains clear traces of metal degradation due to cavitation.
Therefore, it can be concluded with certainty that at high radiation intensities, acoustic
cavitation starts at the surface of the acoustic radiator. This location in the liquid is known,
according to theory, to have the lowest value of tensile strength due to the constant presence
of adsorbed gas inclusions at the metal surface [4].
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 67
However, at low radiation intensities just above the cavitation threshold, the cavitation
region is always formed at a significant distance away from the radiating surface, which
contradicts the abovementioned theory. Clearly, the tensile strength of the liquid at any
location away from the metal surface should be higher than near it, since the concentration of
the preexisting bubbles (inceptions) that ―weaken‖ the liquid at that location should diminish
with time.
2.2. Justification for the Shock-Wave Approach

At low radiation intensity, harmonic acoustic wave is not capable of inducing cavitation
even at the weakest location in the liquid near the radiating surface. Formation of cavitation
away from the radiating surface in this case can be explained by the effect of the increase of
the planar acoustic wave-front steepness during its propagation through a liquid. As a result
of such an increase, at some location in the liquid a discontinuity in the wave profile is
formed. Since such discontinuity is physically not possible in a continuous media, a shock-
wave with a steep front is formed as a result. This effect has to do with the acoustic radiation-
induced nonlinearity of the compressible media properties and is very well known and
documented [19].
This explanation, however, seems contradictory to the common shock-wave theory, since
the attainable amplitude of vibration velocity of the radiating surface is always much lower
than the speed of sound in the pure liquid and, therefore, the necessary conditions for the
creation of such a discontinuity in the wave profile are not fulfilled. The explanation may,
nevertheless, still be valid due to the following two considerations. It is well known that
during propagation of an acoustic wave of slightly lower intensity than the cavitation
threshold, an ensemble of tiny bubbles is formed in the liquid. This occurs due to the so-
called ―rectified diffusion‖ [4]. It is also well known that the speed of sound in a liquid
containing gas bubbles is significantly lower than that in a pure liquid [20, 21], and, under
certain conditions, it may become similar to the amplitude of vibration velocity of the
radiating surface.
It may, therefore, be considered that the bubbles formed in an acoustic wave due to
rectified diffusion help forming a discontinuity in the profile of the acoustic wave at a
location away from the radiating surface by significantly lowering the sound speed in the
liquid. Further, at the location of the discontinuity in the acoustic wave, these tiny bubbles
begin to undergo such rapid nonlinear movements that they loose dynamic stability and,
consequentially, rapidly multiply forming the cavitation region.
The abovementioned observations and analysis formed the basis of the shock-wave
model of acoustic cavitation described in this section. The model shows how the primary
energy of an acoustic radiator causing the cavitation of liquid is absorbed in the cavitation
region owing to the formation of spherical shock waves inside each cavitation bubble.
Calculation of the total energy absorbed in the cavitation region using the concept of a
hypothetical spatial wave moving through the cavitation region is possible with this model
using the classical system of the Rankine-Hugoniot equations. Additionally, the proposed
model makes it possible to explain some newly discovered properties of acoustic cavitation of
water that occur at extremely high oscillatory velocities of the radiating surfaces.
Alexey S. Peshkovsky and Sergei L. Peshkovsky 68
2.3. Theory

Let us assume that an acoustic radiator emitting a plane-wave is used to generate
cavitation in a liquid. The diameter of the radiator‘s output surface is comparable with the
length of the acoustic wave in the liquid at the given frequency of vibrations. The frequency
of the acoustic radiator vibrations should be considered to be much lower than the resonance
frequency of the cavitation bubbles. We assume that the liquid always contains an equilibrium
concentration of dissolved gas as well as some cavitation nuclei (tiny spherical bubbles filled
with the gas) and, consequentially, the liquid possesses no tensile strength during rarefaction
caused by the acoustic waves. As, for example, indicated in the reference [4], water that has
not been purified of gas inclusions ruptures at the negative acoustic pressure of,
approximately, 1 bar. The density of the liquid with the tiny cavitation nuclei is taken to be
equal to the density of the pure liquid, ρ
f
. Surface tension of the liquid and the presence of
stable (non-cavitational) gas bubbles are neglected. Thus, within the framework of the model,
only the so-called low-frequency transient gas cavitation is considered. We, additionally,
assume the liquid to be non-viscous, non-compressible and non-volatile.
Let us represent acoustic cavitation in the liquid as a sequence of the following events.
When an acoustic rarefaction wave passes through a volume of the liquid, an explosive
growth of cavitation nuclei occurs, leading to the formation of gas-filled cavitation bubbles.
Possible parameters of such a rarefaction wave are described, for example, in [22]. A mixture
of the spherical bubbles and the liquid is, therefore, formed. The gas dissolved in the volume
of the liquid passes inside the free space formed by the bubbles. The density of the liquid
medium, therefore, drops. At this point, the bubbles are so small, compared to the acoustic
wavelength, that the liquid/bubble mixture can be considered a continuous medium. The
rarefaction wave phase is followed by a compression wave phase, whose passage results in a
collapse of all gas bubbles, restoring the density of the liquid to ρ
f
. The reverse diffusion of
the gas back into the liquid during compression is insignificant and should be ignored. This
particular stage of acoustic cavitation completes the total cavitation cycle and is further
considered here in great detail, since it is this stage that is mainly responsible for the
sonochemical effects of acoustic cavitation.

2.3.1. Oscillations of a Single Gas Bubble
The problem of the liquid motion during compression of an empty spherical bubble in
liquid was solved by Rayleigh (see reviews [4, 5]). On the basis of this solution and Ref. [19],
the instantaneous pressure distribution in the liquid can be written as:

4
2 2
2
2
ç
µ
ç
µ
U U r U
p p
f f
÷
+
+ =
·

(1)

Here, p

is the pressure in the liquid at infinity, U is the velocity of the bubble boundary
(wall), ξ = R/r, r is the current bubble radius, and R is the current radial coordinate. For the
boundary of a gas-filled bubble at ξ = 1, the following equality must be met:

Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 69
)
2
3
(
2
U r U p p
f g
+ + =
·

µ
(2)

Here, p
g
is the gas pressure in the bubble. This expression is the well-known Noltingk-
Neppiras equation (see reviews [4, 5]).
For an empty bubble, taking p
g
= 0 and p

= p
0
, integration of equation (2) gives
Rayleigh‘s equations for the velocity of the bubble wall movement and the time of the bubble
collapse:

) 1
r
r
(
3
p 2
U
3
3
in 0
2
f
÷ =
µ

(3)
5 . 0
0
f
in
p
r 915 . 0
|
|
.
|

\
|
=
µ
t


Here, p
0
is the static pressure, and r
in
is the initial bubble radius.
From equations (1) and (2), an expression for the instantaneous pressure distribution in
the liquid during the compression of a gas-filled bubble can be obtained:

)
1 1
(
2
U p
)
1
1 ( p p
4
2
f g
ç ç
µ
ç ç
÷ + + ÷ =
·
(4)

Let us single out a spherical liquid volume that includes a gas bubble. The gas
bubble/surrounding liquid system has a certain acoustic compressibility, which determines the
velocity of the propagation of small perturbations or the velocity of sound in this volume.
Using the linearized form of the Noltingk-Neppiras equation, one can obtain an expression for
the velocity of sound in such a system, as it was done, for example, in the work [21]. The
velocity of sound, with the abovementioned assumptions taken into account, is determined
using the following expression:

5 . 0
f
g
)
) 1 (
p
( c
o o µ ÷
=
(5)

Here, α is the volumetric gas concentration in the singled-out liquid volume that includes
the gas bubble. From equation (5) it can be seen that the velocity of sound at a given gas
pressure in the bubble has a minimum at α = 0.5. For example, at p
g
= 1 bar the minimum
velocity of sound c
min
= 20 m/s. It should also be noted that the velocity of sound in the range
0.4 < α < 0.6 changes little.
A gas bubble is formed during the half-period of the liquid rarefaction in the acoustic
wave. Under the abovementioned assumptions, this occurs at the moment when the pressure
Alexey S. Peshkovsky and Sergei L. Peshkovsky 70
in the liquid near the wall of a cavitation nucleus decreases to zero, i.e. the negative acoustic
pressure is equal to p
0
. At that point, the gas pressure in the formed bubble is also very small.
Further, during the subsequent period of increase in the acoustic pressure, the bubble is
compressed, and the gas pressure in it also increases. During the subsequent compression
half-period, in the singled-out liquid volume near the gas bubble wall a spherical flow in the
direction of the bubble center is formed, which is described by equation (4). From equation
(5) it is seen that the velocity of sound for the singled-out system gas bubble/surrounding
liquid depends on the gas pressure in the bubble p
g
and the value of coordinate ξ, along which
the boundary of the singled-out volume passes. If we start reducing the singled-out volume,
while the radius of the bubble and the gas pressure in it are constant, the velocity of sound in
this system will fall to a certain limit and then will grow again. This means that in the
considered spherical volume near the moving wall of the bubble, there is a critical spherical
region, where the sound velocity, c
min
, is at the minimum at a given gas pressure in the
bubble, p
g
. The position of this region is determined from the condition 0.4 < α < 0.6. It is
located close to the bubble wall in the coordinate range 1.18 < ξ < 1.35. For the simplicity of
further analysis of equation (4), it is taken that the velocity of the flow of the liquid particles
in the critical region is equal to the velocity of the bubble wall movement, U.
In the model being considered, it is assumed that when the gas bubble/surrounding liquid
system is compressed by the external pressure, p

, the velocity of the flow of the liquid
particles in the critical region near the bubble wall increases to such a degree that at a certain
gas pressure in the bubble, p
g
, it reaches the minimum velocity of sound in the system under
consideration, i.e. U = c
min
.
At a ratio of the initial radius of an empty bubble to its current radius, r
in
/r = 2, and static
pressure, p
0
= 1 bar, the value of U ≈ 21 m/s reached according to equation (3) is indeed close
to c
min
= 20 m/s.
Let us represent the pressure at infinity as a sum of the static and the acoustic (excessive)
pressures, p

= p
0
+p′

and transform equation (4) taking into account that U = c
min
:

)
1 1
( p 2
p
)
1
1 )( p p ( p
4
g
g
0
ç ç ç ç
÷ + + ÷ ' + =
·
(6)

This expression describes the extreme condition of equilibrium of the system. Equation
(6) shows that during compression of the flowing liquid, in the vicinity of the gas bubble a
pressure impulse is formed, which is stationary with respect to the bubble wall. The amplitude
of the excess pressure in this impulse is p - p
0
= 1.4p
g
+ 0.5 δp′

, where δp′

= (p′

- p
0
). This
value is reached at the coordinate ξ ≈ 2 located upstream from the critical region. As we show
below, the quantity, δp′

, does not need to be considered for small oscillation velocities of
acoustic radiators.
When the velocity of the bubble wall motion exceeds the minimum velocity of sound, U
> c
min
, the equilibrium state described by equation (6) becomes destroyed, and the pressure in
the liquid at the bubble wall downstream from the critical region decreases to p
0
. The velocity
of the bubble wall movement also reduces because the driving pressure difference decreases.


Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 71

Figure 2. Instantaneous distribution of the excessive pressure in liquid near the cavitation bubble wall at
U > c
min
is shown. The quantity δp′

is not taken into account.
At the same moment, the excessive pressure amplitude in the impulse increases stepwise
up to the value p - p
0
= 1.4p
0
+ 0.5δp′

, since the boundary condition in equation (2) is
changed and the pressure near the bubble wall becomes p
g
= p
0
. This occurs because the
bubble pressure signal does not penetrate upstream from the bubble wall when U > c
min
.
Due to destruction of the dynamic equilibrium (retardation of a part of the flow), the
pressure impulse located in the liquid upstream from the critical section disintegrates and
begins to move relative to the bubble boundary in the form of a converging spherical wave.
The supposed instantaneous distribution of excessive pressure in the impulse near the gas
bubble wall at U = c
min
is shown in Figure 2.
Phenomena similar in essence are observed during the breakup of arbitrary pressure
discontinuity in a gas, during hydraulic impact, and during the flow of gases and gas-liquid
mixtures through nozzles. See, for example, the works [6, 8], as well as the studies on Laval
nozzles and water hammers.
In accordance with the assumed form of pressure distribution in a converging spherical
wave shown in Figure 2, the excessive pressure at the bubble wall first increases smoothly up
to the value of p - p
0
= 1.4p
g
+ 0.5δp′

, and, accordingly, the gas pressure inside the bubble
increases smoothly (isothermally) as well. Then, when an abrupt excess pressure jump (up to
the value of p - p
0
= 1.4p
0
+ 0.5δp′

) approaches the bubble wall, a spherical shock wave is
formed in the gas inside the bubble. The pressure jump itself, evidently, is equal to 1.4(p
0
-
p
g
). After focusing in the center of the gas bubble, the spherical shock wave is reflected, and
the bubble ―explodes‖ from the inside, breaking up into small fragments. The collapse of the
gas bubble or, more precisely, its shock destruction occurs. Gas pressure and temperature
inside the bubble during the focusing and the subsequent reflection of the shock wave reach
very large, albeit theoretically restricted, values [19]. When the collapse of the gas bubble is
Alexey S. Peshkovsky and Sergei L. Peshkovsky 72
completed, its small fragments are left in the singled-out liquid volume, which are equal in
size to the original cavitation nuclei, and the density of the singled-out liquid volume
becomes close to the initial liquid density, ρ
f
. As we show below, when the oscillation
velocities of the ultrasonic radiators reach very high values, cavitation may follow a different
mechanism, which does not involve breaking the gas bubbles up into small fragments, but
rather exhibits bubble behavior approaching that of an empty Rayleigh cavity.
This approach permits easily eliminating a seemingly clear contradiction that follows
from the Noltingk-Neppiras equation: how can a gas-filled bubble implode with a very high
rate if the gas pressure inside the bubble during compression rapidly increases, while the rate
of the gas diffusion from the bubble, according to [4, 5], is negligible. In the proposed model,
the gas bubble does not implode in the literal sense of the word, but is destroyed by a
spherical shock wave reflected after focusing in its center. The presence of a well-known
phenomena accompanying acoustic cavitation, such as sonoluminescence, erosion and
dispersion of solids, emulsification of liquids, etcetera, can be well explained from this point
of view. Additionally, the mechanism of the dissipation of the primary acoustic energy during
the liquid cavitation becomes clear. This is the mechanism of the heating of a compressible
medium in a shock wave, which is well described in the literature (see, for example, [19]).

2.3.2. Cavitation Region
During the rarefaction of a liquid in an acoustic wave, a mixture of a great number of
spherical gas bubbles with the liquid (cavitation region) is formed. Let us call this gas-liquid
mixture present in the cavitation region, the ―continuum‖. In the previous section, the course
of events during the collapse of a single bubble in some small volume of liquid was
described. To extend these events over the entire continuum, a transition to spatial description
is necessary. At that, the results of this transition must depend neither on the dimensions and
the form of the continuum itself nor on the sizes and the spatial distribution of the bubbles in
it.
During the compression stage, an acoustic radiator creates a pressure impulse in the
liquid beyond the continuum in the form of a plane acoustic wave. Since the velocity of sound
in the continuum is finite, the collapse of a multitude of gas bubbles located arbitrarily in the
continuum must also occur simultaneously only in some narrow layer, as the impulse of the
acoustic pressure approaches it, i.e. it must have a wave character. In the current model
representation, the result of the superposition of many spherical shock waves, which are
formed near each gas bubble during its collapse in a narrow layer of the continuum, is a
spatial wave (SW) moving through the continuum. Such a representation is the most exact
and visual way of extending the events occurring during a single gas bubble collapse, over the
entire continuum.
In the real situation, the cavitation region in a liquid may take very complex, branched
shapes. The spatial distribution of bubbles in the region also may be quite non-uniform and
the sizes of the bubbles may vary. When the transition to the presented spatial description of
cavitation is made, for the results to be independent of the shape of the cavitation region as
well as of the spatial distribution and the sizes of the bubbles, in our initial equations we will
further utilize hypothetical physical parameters related to the cavitation region as a whole. In
other words, instead of operating with local values of density, changes in the internal energy
and so on, we will use the values averaged over the whole cavitation region. As demonstrated
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 73
below, these values disappear when further modifications of the fundamental equations are
made.
The experimental investigations of acoustic cavitation described below conducted for the
verification of the presented model were carried out using calorimetry of the entire
environment and, therefore, provide only the spatially averaged values due to a relatively high
thermal conductivity of the liquid. Therefore, the final purpose of the calculations following
this model is the determination of a cumulative value of the changes in the internal energy of
the environment, as a result of acoustic cavitation.
The spatial wave (SW) described above has a bore wave-like character, however, the
continuum density and pressure inside the SW front change stepwise. This occurs because the
cavitation bubbles collapse inside its front, following the process outlined in section 2.3.1.
The presence of such a wave is the final stage of acoustic cavitation, within one cycle of the
continuum rarefaction - compression. In other words, according to the model, it is assumed
that the collapse of the gas bubbles occurs inside a relatively narrow front of a hypothetical
SW, being formed and moving through the continuum in each compression half-period of an
acoustic radiator.
The width of the SW front, inside which the collapse of the bubbles and the change of the
continuum density occur, can be estimated as the product of the empty bubble collapse time,
according to equation (3) and the wave front movement velocity with respect to the
continuum, h = cτ. A rough estimate for the wave front movement velocity can be made using
expression (5). Then, at α = 0.1 (taken from the literature data [22] and characteristic for the
initial stage of acoustic cavitation) we obtain h ≈ 3r
in
. According to the estimation performed
in the work [4], the maximum radius of a gas bubble in water does not exceed 2∙10
-4
m, since
larger bubbles rapidly rise to the surface. Hence, the value is: h ≤ 6∙10
-4
m, which is smaller
than the dimensions of the continuum itself by many orders of magnitude. Thus, the specified
wave has a front that is very narrow relative to the dimensions of the entire continuum.
Getting over this barrier, therefore, the physical parameters of the continuum change
stepwise.
It is necessary, further, to establish a relation between the continuum parameters ahead of
and behind the SW front, as well as the relationship between these parameters and the
oscillatory velocity of an acoustic radiator. It is important to note that the velocity of the
specified wave can be lower than the velocity of sound in the continuum.
The SW moving through the continuum is not only a physical abstraction used for the
construction of the model, but can, apparently, exists in reality. In this case, however, we are
not faced with an ordinary shock wave, which arises in a compressible continuum when the
piston movement velocity is higher than the sound velocity in the continuum. Such shock
waves in a gas-liquid suspension obtained by bubbling a gas through a liquid are described in
detail in literature [21]. Here, it is assumed that in a gas-liquid suspension formed as a result
of the liquid rarefaction in an acoustic wave, another type of bore wave-like shock waves may
exist, which is associated with the radial movement of the liquid in the vicinity of each
bubble.
It is well known that when a jump (discontinuity) of a physical quantity arises in a
compressible continuum, a solution should be sought using the general conservation laws in
the form of the Rankine-Hugoniot equations [19]. These equations reflect the ratios of the
steady-state physical parameters of the compressible continuum before and after the passage
of the shock wave front.
Alexey S. Peshkovsky and Sergei L. Peshkovsky 74

Figure 3. Schematic of the continuum‘s flow during compression is shown (1 – acoustic radiator, 2 –
flow region after the SW passage, 3 – flow region before the SW passage).

Figure 4. Processes occurring during acoustic cavitation are illustrated. Line 1 represents the rarefaction
of the continuum with cavitation nuclei in an acoustic wave, line 2 represents a nonlinear process of the
growth of cavitation bubbles in the rarefaction wave, line 3 represents a preliminary compression of the
continuum in an acoustic precursor wave, line 4 represents the continuum transition from one state to
the other when the SW passes.
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 75
Additionally, there appears a possibility to analytically calculate the values of important
parameters, without considering in detail the transient processes inside the SW front, which
are connected with the complex kinetics of a collapsing gas bubble.
Let us introduce the following designations: p
h
is the pressure in the liquid phase of the
continuum near the bubble wall after the SW passage; p
l
, ρ
l
= ρ
f
(1- α
l
), α
l
are, respectively,
the pressure in the liquid phase of the continuum near the bubble wall, the density and the
volumetric gas content of the continuum before the SW passage. A scheme of the continuum
flow is presented in Figure 3. It is assumed that a SW moves through the continuum, and that
the gas bubbles collapse inside the narrow front of this wave. Also shown in this figure is the
supposed pressure profile in the continuum.
Figure 4 shows the supposed processes occurring during one cycle of acoustic cavitation
in a liquid. The pressure in the liquid phase of the continuum near the gas bubble wall in an
arbitrary state is plotted on the ordinate, and the continuum specific volume is plotted on the
abscissa. Line 1 represents the rarefaction of the continuum with cavitation nuclei in an
acoustic wave. Line 2 represents a nonlinear process of the growth of cavitation bubbles in
the rarefaction wave. Line 3 represents a preliminary compression of the continuum in an
acoustic wave (for a single gas bubble, this corresponds to a rise in the gas pressure in the
bubble on the smooth section of a converging spherical wave, as described in section 2.3.1).
Line 4 represents the continuum‘s transition from one state to the other when the SW passes
(for a single gas bubble, this corresponds to a rise in the gas pressure in the bubble on the
steep section of a converging spherical wave, as described in section 2.3.1). In this scheme, it
is assumed in advance that the velocity of the SW movement through the continuum can be
lower than the sound velocity in the continuum itself ahead of SW. Additionally, the SW
front itself serves as a source of the acoustic wave, propagating forward in the direction of the
shock wave movement. In this connection, there is a preliminary compression of the
continuum, and line 4 begins above the abscissa axis.
This kind of an acoustic wave is called precursor. Precursor does not cause the collapse
and disintegration of the bubbles because of a small value of its amplitude. Similar
representations are used for initially loose or porous environment. In such environment,
during the compression phase, the shock-wave front is formed only due to the parameters of
the compression process itself since this environment tends to change the specific volume of
pores (cavities) abruptly (stepwise) under pressure [23-25].
Let us introduce the following additional designations: p
l
= p
0
+ p'
l
, p
h
= p
0
+ p'h; p'
l
and
p'
h
are the excessive pressures in the liquid phase of the continuum near the bubble wall
before and after the SW passage, respectively; u
l
and u
h
are the continuum flow velocities
relative to SW before and after its passage, respectively; e
l
and e
h
are the specific internal
energy of the continuum before and after the SW passage, respectively; v is the current
oscillatory velocity of an acoustic radiator; v
t
is the critical oscillatory velocity of an acoustic
radiator, which corresponds to the cavitation onset (cavitation threshold). Note that a stepwise
increase in the continuum density from ρ
l
to ρ
f
at the SW front corresponds to a change in
pressure from p
l
to p
h
. The relative movement of the liquid and the gas bubbles is neglected.
Let us now write the system of conservation equations (Rankine-Hugoniot equations) for
the continuum parameters on both sides of the SW front:

h f l l
u u µ µ =
,
Alexey S. Peshkovsky and Sergei L. Peshkovsky 76
2 2
h f h l l l
u p u p µ µ + ' = + '
,
h
2
h
f
h 0
l
2
l
l
l 0
e
2
u p p
e
2
u p p
+ +
' +
= + +
' +
µ µ
, (7)
h l t
u u v v ÷ = ÷


The fourth equation of system (7) shows that a change in the continuum‘s movement
velocity getting over the SW front is equal to the excessive oscillatory velocity of an acoustic
radiator, which exceeds the critical value, v
t
.
This system of equations can be transformed to the following form:

) v v (
2
) p p p 2 (
I
t
h l 0
÷
' + ' +
=
, (8)

l h
2
t
l
p p
) v v (
' ÷ '
÷
= q


Here, I = (e
h
– e
l

f
u
h
is the flux density of the energy dissipated inside the SW as a
consequence of the dissipation processes related to the bubble collapse and η
l
= α
l

l
is the
volume of all cavitation bubbles per unit mass of the liquid phase of the continuum before the
SW passage.
The average flux density of the acoustic energy (acoustic energy intensity) absorbed in
one acoustic wave period can be presented in the following way:

}
= =
e t
t e
t
e
/
0
a
/ I dt ) t sin( I
2
I
(9)
2.4. Set-up of the Equations for the Experimental Verification

For the resulting equations (8) to be verified experimentally, it is necessary to determine
the particular values of p'
h
, p'
l
, η
l
and v
t
.

2.4.1. Low Oscillatory Velocities of Acoustic Radiator
From equation (6) and the analysis given in section 2.3.1, it follows that the maximum
excessive pressure at the SW front is equal to p'
h
= 1.4p
0
+ δp′

. As mentioned above, the
liquid utilized for the construction of the theoretical model, does not possesses tensile strength
during rarefaction. Consequentially, the explosive growth of the cavitation nuclei and their
conversion into gas bubbles in the rarefaction wave takes place at the negative pressure equal
to the static pressure, p′

= p
0
. It is possible to assume that for small oscillation velocities of
the acoustic radiator near the cavitation threshold a symmetry of acoustic pressure amplitudes
during the half periods of compression and rarefaction is conserved. Consequentially, in this
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 77
case, δp′

= 0 and p'
h
= 1.4p
0
. It will be shown below that for large radiator oscillatory
velocities it is no longer possible to ignore the quantity δp′

. Note that the value of p'
h
≈ 1.4p
0

actually corresponds to the threshold of water cavitation, at least, in its initial stage. This fact
was experimentally established in [26].
Above, it was assumed that during the rarefaction of a liquid in an acoustic wave, all gas
dissolved in a unit volume of the liquid passes into the bubbles formed in this volume. The
oscillations of the gas bubbles before the onset of their collapse are isothermal, and the mass
of the gas in them does not change. From the analysis of equation (6) given in section 2.3.1, it
follows that p'
l
= 1.4p
g
, hence, the condition p
0
η
0
= 0.71p'
l
η
l
must be met. Here, η
0
is the
equilibrium volume of gas dissolved in a unit mass of the liquid at the pressure, p
0
.
The quantity v
t
is the critical oscillatory velocity of an acoustic radiator, which
corresponds to the cavitation threshold. In view of the conditions described above, one can
assume that for a plane acoustic wave, (v
t
)
rms
= 0.71p′

/ ρ
f
c
f
= 0.71p
0
/ ρ
f
c
f
.
It should be borne in mind that the value of v
t
in each particular experimental case can be
different from the specified theoretical value. This is connected with the fact that the practical
value of v
t
depends on a large number of different parameters of liquid (physical nature, purity
degree, gas content, volatility, sample preparation history, etc.). Besides, v
t
also depends on
the conditions of the conducted measurements (frequency of ultrasound, degree of isolation
from external radiation, temperature, etc.)
From the second equation of system (8) we obtain:

2
rms t 0 0
0
2
0
l
) v v ( 42 . 1 p
p 4 . 1
p
÷ +
= '
q
q
(10)

Now from the first equation of system (8) in view of equations (9, 10) we obtain the final
equation for the average flux density of the acoustic energy (intensity of acoustic energy)
absorbed in the cavitation region:

rms t
2
rms t 0 0
0 0
0 a
) v v (
) v v ( 42 . 1 p
p 41 . 0
1 p 76 . 0 I ÷
(
¸
(

¸

÷ +
+ =
q
q
(11)

For the initial stage of acoustic cavitation, at a small value of (v-v
t
)
rms
, the final equation
is as follows:

rms t
0
a
) v v ( 07 . 1
p
I
÷ =
(12)

It is important to point out that in equations (11, 12) the quantities related to the spatial
distribution of gas bubbles in the continuum and their size, as well as the form and shape of
the continuum itself are not present.


Alexey S. Peshkovsky and Sergei L. Peshkovsky 78
2.4.2. High Oscillatory Velocities of Acoustic Radiator

From the main system of equations (7), one can obtain the expression for the SW velocity
relative to the unperturbed continuum, | |
5 . 0
f l h l
) 1 ( / ) p p ( u o o µ ÷ ' ÷ ' = . The ratio of u
l
to
the sound velocity, c, in the continuum according to equation (5), using equation (10) and
taking into account that p
g
= 0.71p′
l
, can be written as:

5 . 0
0 0
2
rms t
5 . 0
g
l h l
p
) v v ( 2
p
p p
c
u
|
|
.
|

\
|
÷
=
|
|
.
|

\
|
' ÷ '
=
q
(13)

From this expression, it is seen that at (v-v
t
)
rms
≥ 1 m/s, the SW movement must become
supersonic, making it a real shock wave in the classical sense. When the SW movement is
supersonic, a precursor is absent because it is absorbed by the faster shock wave. The density
and the pressure of the gas inside the bubbles in this case are initially small since they are not
compressed beforehand by the precursor. From the analysis of equation (10), it is seen that at
(v-v
t
)
rms
> 3 m/s the gas pressure in such bubbles becomes approximately an order of
magnitude lower than the static pressure, p
0
, and continues to decrease. A spherical shock
wave in rarefied gas inside such a bubble is not formed and, accordingly, the bubble does not
break up into small fragments as a result of the collapse. The behavior of the bubble becomes
close to the behavior of an empty Rayleigh cavity.
It is also important to keep in mind that the minimum width of the shock wave front in a
gas is on the order of the molecule free path [19]. At a normal density of the gas, this distance
is about 10
-7
m. With a decreasing gas density, this distance increases proportionally and
becomes close to the characteristic size of the bubble itself 10
–5
m. Under these conditions, a
spherical shock wave inside the bubble cannot be formed, and the bubble is compressed like a
Rayleigh cavity.
At the final stage of the collapse of the bubble, the gas pressure in it increases to such a
degree that it can hold back the liquid‘s pressure. At that, the pressure and temperature of the
compressed gas can reach very high values (theoretically unrestricted under the assumptions
of this model [19]). In this case, at the excess pressure, p'
h
= 1.4p
0
, the continuum behind the
SW is a gas-liquid suspension with some density ρ
h
= ρ
f
(1- α
h
). If the conditions identified in
the beginning of section 2.3, assumed for the construction of the model, are to be met, the
continuum behind the front of SW is additionally compressed by the acoustic radiator until
density ρ
f
is reached. This corresponds to a pressure increase at the SW front up to the value
of p'
h
= 1.4p
0
+ δp′

= 1.4p
0
+ 0.5c
h
2
δρ = 1.4p
0
+ 0.5c
h
2
ρ
f
α
h
, where δρ = ρ
f
– ρ
h
= ρ
f
α
h
is the
additional increase in the continuum‘s density behind the SW front, necessary to reach the
quantity ρ
f
, and c
h
is the speed of sound in the gas-liquid suspension with density ρ
h
. For high
oscillatory velocities of acoustic radiator similar to the sound speed in the continuum, p'
h
=
1.4p
0
+ ρ
f
α
h
v
2
rms
, since in this case it can be taken that c
2
= 2v
2
rms.
The value v
t
is neglected. Since δp'

should be taken into account only at high v

and the
second term of equation (11), which corresponds to the excessive pressure p'
l
, is negligible,
we leave it unchanged. Let us now write equation (11) in the final form in view of equation
(9):
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 79
rms t
0
2
rms h f
2
rms t 0 0
0 0
0 a
) v v (
p
v 29 . 0
) v v ( 42 . 1 p
p 41 . 0
1 p 76 . 0 I ÷
(
(
¸
(

¸

+
÷ +
+ =
o µ
q
q

(14)

2.4.3. Interpretation of the Experimental Results of the Work [26]
A large series of experiments aimed at studying acoustic cavitation of water at low
oscillatory velocities of acoustic radiator are presented in the work [26]. Experiments were
conducted in degassed water with the concentration of the dissolved air equal to 30% of the
nominal concentration in the equilibrium state at the room temperature and the normal static
pressure.
For the interpretation of these data, let us introduce the following designations: ΣI
a
=
0.5(p'
h
)
2
γ = p
0
2
γ is the total intensity of the acoustic energy radiated into water; I
a0
= 0.5(p'
h
)
2
γ
f
= p
0
2
γ
f
is the intensity of the acoustic energy propagating beyond the bounds of the cavitation
region. Here, γ is the specific acoustic radiation admittance of the continuum, γ
f
= 1/ρ
f
c
f
. The
difference of these intensities is the intensity of the acoustic energy absorbed in the cavitation
region. Thus, when compared with the theoretical results of the given model, the experimental
values of γ for each oscillatory velocity obtained in [26] were recalculated by the following
expression:

0 f
0
a
p ) (
p
I
¸ ¸ ÷ =
(15)

In representing the data of the work [26], the values of (v
t
)
rms
were determined directly
from the experimental plots of this work at the point of characteristic inflection.
2.5. Experimental Setup

To measure the acoustic energy absorbed in a cavitating liquid at increased static pressure
p
0
, an acoustic calorimeter described in section 3.2.3 of this chapter was used. Static pressure
in the calorimeter was produced with compressed nitrogen. Settled tap water at 20
0
C was
used. The static pressure, p
0
, varied in the range 1.0 – 5.0 bar; the water density, ρ
f
= 998
kg/m
3
; sound velocity in the water, c
f
= 1500 m/s; the volume of air dissolved in unit mass of
water, η
0
= 2.2∙10
-5
m
3
/kg. Each experimental point shown on the plots was obtained as a
mean value of 10 measurements.
2.6. Experimental Results

Experimental data for small oscillatory velocities of an acoustic radiator, v, and different
static pressures, p
0
, are shown in Figure 5. The values of v
t
used in the treatment of these
experimental data were calculated from the expression (v
t
)
rms
= 0.707p
0

f
c
f
for different
static pressures. Also shown in this figure are the experimental data from [26] for ultrasound
frequencies of 19 and 28 kHz, closest to the frequency 17.8 kHz used in the present work,
which are interpreted by equation (15).
Alexey S. Peshkovsky and Sergei L. Peshkovsky 80

Figure 5. Intensity of acoustic energy absorbed in water at cavitation is shown as a function of the
excessive oscillatory velocity of an acoustic radiator for pressures of × - 1 bar, + - 2 bar, ■ - 3 bar, □ - 4
bar, ○ - 5 bar, at frequencies of ▌- 28 kHz

and

- 19 kHz from the work [26]. Line 1 is plotted from
equation (12); line 2 is plotted from equation (11).
The values of the cavitation threshold obtained from the corresponding plots of [26] for
both frequencies (v
t
)
rms
= 0.08 m/s. Figure 5 also shows the theoretical lines calculated from
equations (11) and (12), which are represented by the solid and the dotted lines, respectively.
A good agreement between the theoretical lines themselves and the experimental data
with these lines at small values of v can be clearly seen. With increasing (v-v
t
)
rms
> 0.2 m/s,
the experimental points diverge from the straight line plotted from equation (12) and
approach the line plotted from equation (11).
Figure 6 shows the experimental results for all oscillatory velocities of the acoustic
radiator, v, which were used in the experiments at normal static pressure, p
0
= 1 bar. Also
shown in this figure are the theoretical lines plotted from equations (11) and (14). From
Figure 6 it is seen that at intermediate values of v the experimental points are located near
practically coincident lines plotted from equations (11) and (14), which are represented by the
dotted and solid lines, respectively.
At high oscillatory velocities, (v-v
t
)
rms
> 3 m/s, the specified theoretical relationships
diverge, and the experimental points are located according to a more general relationship (14)
at α
h
= 0.4. It can be seen that the theoretical and the experimental data are in good agreement
up to the highest values of the oscillatory velocity, v.

Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 81

Figure 6. Intensity of acoustic energy absorbed in water at cavitation is shown as a function of the
excessive oscillatory velocity of an acoustic radiator. Line 1 is plotted from equation (14); line 2 is
plotted from equation (11).
A spread of the experimental points on the curve in Figure 6 in the region 2 m/s < (v-
v
t
)
rms
< 3 m/s is also observed. Here, the beginning of the divergence of the theoretical curves
1 and 2 is observed as well. These phenomena are, apparently, associated with the
establishment of the supersonic regime of the SW movement and a considerable decrease in
the gas pressure in the bubbles. The indication of the possibility of the supersonic regime of
radiation at acoustic cavitation was first made in the work [27]. The phenomenon itself was
called the second threshold of acoustic cavitation. The region located over the second
threshold at (v-v
t
)
rms
> 3 m/s was called the region of acoustic supercavitation. The closest
related known phenomenon is called hydrodynamic supercavitation and is described, for
example, in [28].
Since, as the stated theory assumes, at supercavitation the spherical shock wave is not
formed in the gas inside the bubbles, at oscillatory velocities (v-v
t
)
rms
> 3 m/s the
characteristic changes of the secondary effects of cavitation, which are used in the
sonochemical technology, must be observed.
An experimental verification of this effect was conducted by observing the cavitation-
induced ultrasonic dispersion of solid particles. During the experimental setup, it was
assumed that the transition to the supercavitation regime should in some way be reflected in
the manner in which the dispersion occurs. The experimental study was conducted during the
ultrasonic dispersion of graphite particles with the initial size 200-250 µ in settled tap water
under normal conditions.

Alexey S. Peshkovsky and Sergei L. Peshkovsky 82

Figure 7. Dispersing effect of acoustic cavitation (dispersion of graphite powder in water) determined
by the degree of the 420 nm wavelength light absorption is illustrated as a function of the excessive
oscillatory velocity of an acoustic radiator.
To avoid any possible influence of the reactor geometry on the results of the
measurements, the acoustic calorimeter described in section 3.2.3 was used as an apparatus
for dispersing. For the analysis of the relative transparency of the obtained dispersions, the
degree of the light absorption (at the wavelength of 420 nm) in them was measured using a
photo-colorimeter. From the measurement results presented in Figure 7 in relative units, it can
be seen that the obtained curve reaches a maximum and then discontinues at 2.5 m/s < (v-
v
t
)
rms
< 3 m/s. A subsequent smooth rise of this curve in the supercavitation region is also
observed, which is most likely associated with the intense acoustic streaming, rather than with
the effect of cavitation itself.
It appears that it is in the acoustic supercavitation region where highest possible
temperatures during the compression of the rarefied gas inside the bubble oscillating as a
Rayleigh cavity can be expected. Pressure at the bubble wall at the moment of focusing
theoretically approaches infinitely high values because the gas compression is exerted by the
moving dense bubble wall acting as a spherical plunger, rather than by a spherical acoustic
wave [19]. In the same region, the highest intensities of the cavitation-induced sonochemical
processes occurring at high temperatures may be observed. At the same time, processes
connected with erosion, dispersion of solids and the like can be inhibited in the
supercavitation region.

Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 83
2.7. Section Conclusion

The proposed shock-wave model of acoustic cavitation describes real events occurring in
water at cavitation since calculations based on the equations that follow from the model are in
good agreement with the results of the experiments. The presented experimental data extend
into the region of super-high oscillatory velocities of an acoustic radiator and agree well with
the theoretical model. The model makes it possible to obtain the resulting equation for the
calculation of the energy absorbed by liquids during cavitation without having to consider in
detail all the complex processes of the absorption of the acoustic energy, which are connected
with the nonlinear oscillations of the gas bubbles during their collapse.
Within the framework of this model, the existence of a transition from the subsonic
regime of acoustic cavitation to the supersonic regime is predicted. The possibility of a
change in the character of the oscillations of a cavitation bubble at high values of v is
theoretically shown. The conducted experimental studies confirm such possibility.
As will be shown below, simple algebraic expressions that follow from the proposed
model can be used in practical engineering calculations for designing powerful ultrasonic
horns for sonochemical reactors.
3. SELECTION AND DESIGN OF THE MAIN COMPONENTS OF HIGH-
CAPACITY ULTRASONIC SYSTEMS
The greatest mechanical stress areas in a sonochemical reactor system are concentrated in
the electromechanical transducer and the ultrasonic horn components. The same components
are also exposed to the highest thermal loads, related to the formation and maintenance of
acoustic waves. Selection of the appropriate electromechanical transducer type, therefore, is
of great importance, as is the ultrasonic horn design and the choice of material from which it
is constructed.
3.1. Electromechanical transducer selection considerations

Ultrasonic transducers are devices used to convert electric energy coming from a power
generator into mechanical energy in the form of ultrasonic vibrations. There are two main
types of ultrasonic transducers used in the high-power ultrasonics field: magnetostrictive and
piezoelectric (high-power piezoceramic).
For continuous flow-through liquid processing applications, magnetostrictive transducers
have multiple advantages over the piezoelectric devices. These transducers are constructed
from high-strength metallic alloys (5,000 – 7,000 MPa) and permit reaching high levels of
acoustic power intensity (up to 100 – 150 W/cm
2
). The main disadvantage of magnetostrictive
transducers is their relatively low efficiency (below 50%). On the other hand,
magnetostrictive transducers are electrically safe and do not overheat because they are
relatively low voltage driven and are liquid cooled. In addition, these transducers provide
high total radiation powers and relatively high output amplitudes, are very stable, reliable and
do not age. These devices are, therefore, well suited for continuous long-term industrial
Alexey S. Peshkovsky and Sergei L. Peshkovsky 84
operation under factory conditions and are ideal for industrial liquid processing with flow-
through ultrasonic systems.
For comparison, the advantage of piezoelectric transducers is their high efficiency (up to
95%). These devices, however, are characterized by much lower levels of acoustic power
intensity and relatively short life-spans due to low mechanical strengths of the involved
materials (only about 15 – 30 MPa). Additionally, piezoelectric transducers are high-voltage
driven and are air cooled, which for some applications may make them an explosion hazard.
They can also easily become overheated and damaged, which is why they cannot be used for
extended periods of time or in high-temperature environments. These devices, however, are
widely used in such important high-power ultrasonics fields as plastics welding, cleaning,
machining, etc., where pulsed-mode operation or lower amplitudes are appropriate. This
explains these transducers‘ high popularity and availability. When used in liquid processing
applications, however, piezoelectric transducers are frequently run at a much lower power
than available, in a pulsed mode or with short periods of ―on‖ time [29-31].
In view of the above discussion, we will only consider magnetostrictive transducers in
this chapter.
3.2. High Power Acoustic Horn Design Principles

Despite being capable of producing much higher vibration amplitudes than piezoelectric
devices, magnetostrictive transducers still cannot provide sufficient amplitudes for a correct
operation of an ultrasonic reactor system. Acoustic (ultrasonic) rod horns are, therefore, used
in conjunction with these transducers to amplify the vibration amplitude and deliver the
ultrasonic energy to the working liquid. Commonly used acoustic horns (Figure 8), in general,
consist of two cylindrical sections, input (larger diameter, in contact with transducer) and
output (smaller diameter, in contact with the liquid), which are connected to each other by
one transitional section, which may have a conical, exponential, catenoidal, or a more
complex shape, or may be omitted all together (stepped horn) [32-34]. Although widely used,
these horns suffer from an important limitation: they are incapable of providing matching
between the transducers and the liquid loads, leading to inefficient acoustic power
transmission.
For optimal operation, the maximum cross-sectional dimension of any portion of a
resonant horn or transducer may not exceed, approximately, one quarter-wavelength of the
corresponding longitudinal acoustic wave at the horn‘s resonance frequency [35].
Consequently, a common converging horn (for which the output diameter is smaller than the
input diameter) with a maximum allowed input diameter always ends up having a working
(output) tip diameter that is smaller than this limitation. The final size of the tip depends on
the gain factor of the horn, and becomes reduced as the gain factor increases. This is
problematic when the processes are carried out on industrial scale, since deposition of
substantial acoustic power is needed to create acoustic cavitation in large volumes of water.
While using converging horns permits increasing the acoustic energy intensity (or vibration
amplitude) radiated into the load, it is impossible to achieve the technologically necessary
levels of total radiated acoustic power, since the cross-sectional area of the horn tip in contact
with the load is small.

Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 85

Figure 8. A typical high-gain converging horn is shown. High vibration amplitude of the output tip is
achieved at the expense of the tip area.
Therefore, it is intuitive that the use of the converging horns does not permit transferring
all available power from a transducer into a load.
To increase the total radiation area, the horns are sometimes connected to planar resonant
systems, such as large discs or planes [36]. These additional elements, however, significantly
complicate the construction of the horns, introduce additional mechanical connections and,
therefore, reduce life span and reliability.
In this section we will describe design principles that have been successfully
implemented in the development of a family of acoustic horns, whose shapes permit
achieving high gain factors and large output surfaces simultaneously. These horns can be
designed to accurately match an ultrasonic source (transducer) to a liquid load (water, in this
case) at cavitation, maximizing the transference of the available acoustic energy into the load
and creating a large cavitation zone. These devices are easy to machine and have well-
isolated axial resonances and uniform output amplitudes.

3.2.1. Criteria For Matching Magnetostrictive Transducer to Water at Cavitation
In an ideal case, without accounting for the internal losses, the highest acoustic energy
intensity that a resonant magnetostrictive transducer can transmit into a load is limited by two
main factors - the magnetostrictive stress saturation,
m
t (the maximum mechanical stress
amplitude achievable due to the magnetostrictive effect for a given transducer material), and
the maximum allowed amplitude of oscillatory velocity, limited by the fatigue strength of the
transducer material,
m
V , such that [37]:

c V
E e
m m
m m
µ | o
| t
2
1
=
=

(16)
where
m
e is the deformation amplitude associated with
m
t , E is Young's modulus,
1
|

and
2
|

are the coefficients that take into account the features of the transducer construction [33, 37],
Alexey S. Peshkovsky and Sergei L. Peshkovsky 86
m
o is the stress amplitude of the material fatigue strength, µ is the transducer material‘s
density, and c is the thin-wire speed of sound in the material. The highest potential acoustic
energy intensity radiated under conditions of perfect matching between the transducer and the
load is represented by the quantity:

m m m
V I t 5 . 0 = (17)

It should be noted that the acoustic load under consideration, water at cavitation, has a
purely active character, and, therefore, is appropriately described by the term ―acoustic
resistivity”,
a
r [26], such that v p r
a a
= , where v is the amplitude of the output oscillatory
velocity of acoustic horn and
a
p is the acoustic pressure averaged over the entire radiating
surface of the horn. Practically, this means that virtually all of the acoustic energy deposited
into water at cavitation is converted into heat [38]. Under the term ―matching‖ we will further
mean supplying a magnetostrictive transducer with a multi-element acoustic horn having a
gain factor, 1 >> G (G is defined as a ratio of the output to input oscillatory velocities,
m
V v , which allows the transference of a maximum of the available acoustic power of the
transducer,
m
I , into the load.
Acoustic energy intensity,
a
I , generated in a purely active load by the longitudinal
vibrations of an acoustic rod horn with an output oscillatory velocity amplitude, v , is
represented by:

v p v r I
a a a
5 . 0 5 . 0
2
= = (18)

Taking
out a in m
S I S I = as a matching condition, we obtain:

2
GN
p
a
m
=
t
(19)

where
in out
S S N = ,
in
S and
out
S are, respectively, the input and the output cross-sections
of the acoustic horn, while
in
S is taken to be equal to the output cross-section of the
magnetostrictive transducer,
t
S (please see Figure 9). The left-hand side of equation (19)
reflects the degree of under-loading of an acoustic transducer, and the right-hand side
describes matching capabilities of an acoustic horn.
As shown theoretically in section 2.4 and experimentally confirmed, the connection
between the acoustic pressure,
a
p , and the static pressure,
0
p , during the well developed
cavitation can be expressed by equations (11) and (14).
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 87

Figure 9. General schematic is shown, describing matching between an electromechanical transducer
and a load achieved by using an acoustic rod horn of an arbitrary shape. S
in
and S
out
are, respectively,
the input and the output cross-sections of the acoustic horn; S
t
is the output cross-section of the
electromechanical transducer.
To demonstrate this, let us consider the case of moderate (although much greater than the
threshold value) amplitudes of ultrasonic vibration of the horn and apply equation (12).
Assuming
t
v v >> , and taking into account that v p I
a a
5 . 0 = , we obtain for the amplitude
value of
a
p the expression:
0
2p p
a
~ .
Therefore, the following can be written:

0
1
2p
E e
p
m
a
m
| t
= (20)

It is clear that for high vibration amplitudes, a more complex expression based on
equations (11) and (14) can be derived in a similar manner.
It is seen from equation (20) that the degree of under-loading of an acoustic transducer
depends only on the characteristics of the transducer itself and the static pressure of water.
Theoretically, for most common magnetostrictive materials, the calculated values of
a m
p / t
are between 15 and 44. In this calculation, the values of
0
p = 10
5
N/m
2
and
1
|

= 0.45 were
assumed. However, for a real magnetostrictive transducer, which is an electro-acoustic
instrument, the maximum acoustic energy intensity generally does not exceed 70 -100 W/cm
2
.
This is due to such limitations as an insufficient ultrasonic generator power, voltage and
current rating of the electrical wire forming the transducer's coil, cooling system capacity, etc.
Consequentially, the practical values of the degree of under-loading are much lower than the
corresponding theoretical limits for the magnetostrictive materials themselves, and for most
models are between 5 and 10.
It is less evident how to use the right-hand side of equation (19), which reflects the
matching capabilities of a horn. In this case, before the resonance calculation of a matching
horn it is necessary to determine the maximum acoustic energy intensity for the utilized
magnetostrictive transducer,
e m
W I q = . Then, from (17) and (19) we obtain:

m
e
V p
W
GN
0
2
2q
= , (21)
Alexey S. Peshkovsky and Sergei L. Peshkovsky 88
where
e
W - specific (with respect to S
in
) electrical power of the magnetostrictive transducer,
q
- its efficiency (commonly
5 . 0 = q
).


Figure 10. Schematic defining the parameters of a five-element matching horn is shown. The horn
having d
1
/ d
3
> 1 is shown by a solid line, and the horn with d
1
/ d
3
< 1 is shown by a dotted line.
Parameters L
1
– L
5
correspond to the lengths of each element.
The next step should be selecting an optimal, from the technological standpoint, range of the
values for the gain of the horn, G, which is commonly determined during the preceding
laboratory studies of a given process. It is then easy to derive the value for N necessary for
the resonance calculations of the matching horn and construction of the ultrasonic reactor.
In spite of a variety of types and shapes of the acoustic horns known from the literature
and used in practice, until recently none existed for which the relationship 1
2
> GN , when
1 > G , would hold true. It is, however, clear that in order to be able to match magnetostrictive
transducers to water at cavitation, it is necessary to utilize acoustic horns that would meet the
matching criterion, 1 GN
2
> .

3.2.2. Five-Elements Matching Horns

3.2.2.1. Design Principles
The theory of acoustic horns is based on the mathematical problem of longitudinal
vibrations in multi-element rods that have cylindrical elements as well as elements of variable
cross-sections [39]. We will consider only the horns with axially symmetric shapes. Other
types of horns (for example, wedge-shaped) can be considered in an analogous way. In the
current work, we will restrict the discussion to five-element horns, although no theoretical
restriction for the number of elements exists.
We assume that during the passage of stress waves through a horn, the wave front
remains planar, while the stresses are uniformly distributed over the horn‘s cross-section. This
assumption limits us to "thin" horns, whose resonance lengths significantly exceed their
diameters. For all practical purposes, it is sufficient to require that the maximum cross-
sectional dimension of any portion of a resonant horn not exceed, approximately, one quarter-
wavelength of the corresponding thin wire acoustic wave at the horn‘s resonance frequency
[35].
Schematic and designation of parameters for a general case of a five-element rod horn are
given in Figure 10, where two possible situations are presented: a horn with 1
3 1
> d d is
shown by a solid line; a horn with 1
3 1
< d d is shown by a dotted line. Under the assumed
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 89
approximation, the problem is reduced to one-dimension, and only includes cone-shaped
elements with variable cross-section. For the steady-state mode, the equation of vibrations for
displacements, u , takes the following form:

. 0
1
2
= + ' ' + ' ' u k u S
S
u
(22)

where c k e = is the wave number,
f t e 2 =
is the angular frequency of vibrations,
and
f
is the frequency of vibration.
The solutions of equation (22) for each of the horn‘s elements can be written as:

kz B kz A u sin cos
1 1 1
+ = 0
1
< < ÷ z L


( ) kz B kz A F u sin cos
2 2 2
+ =
2
0 L z < <


kz B kz A u sin cos
3 3 3
+ =
3 2 2
L L z L + < <

(23)

( ) kz B kz A F u sin cos
4 4 4
+ =
4 3 2 3 2
L L L z L L + + < < +


kz B kz A u sin cos
5 5 5
+ =
5 4 3 2 4 3 2
L L L L z L L L + + + < < + +

Then, using the boundary conditions for the horn‘s element, we obtain the system of
equations for displacements, u , and strains, u' .

At
1
L z ÷ = ,
in
u u =
1
,
in
F u ES ÷ = '
1 1
, 0 =
in
F

in
u kL B kL A = ÷
1 1 1 1
sin cos ;
( )
in
F kL B kL A EkS ÷ = +
1 1 1 1 1
cos sin

At 0 = z ,
1 2
u u = ,
1 2
u u ' = '


1 2
A FA = ;

1 2 2
kB k FB A F = + ' ;

( )
1 2 3 1
d L d d ÷ = | ;
1
2 d F = ; | F F = '

At
2
L z = ,
2 3
u u = ,
2 3
u u ' = '

Alexey S. Peshkovsky and Sergei L. Peshkovsky 90
( )
2 2 2 2 2 3 2 3
sin cos sin cos kL B kL A F kL B kL A + = + ;

( ) ( )
2 2 2 2 2 2 2 3 2 3
cos sin cos sin kL FkB A F kL FkA B F kL kB kL kA + ' + ÷ ' = + ÷ ;

( )
1 2 3 1
d L d d ÷ = | ;

3
2 d F = ; ( ) | 1
2
÷ ÷ = ' L F F ; (24)

At
3 2
L L z + = ,
3 4
u u = ,
3 4
u u ' = '

( ) ( ) | | ( ) ( )
3 2 3 3 2 3 3 2 4 3 2 4
sin cos sin cos L L k B L L k A L L k B L L k A F + + + = + + +


( ) ( ) ( ) ( )
( ) ( )
3 2 3 3 2 3
3 2 4 4 3 2 4 4
L L k cos kB L L k sin kA
L L k cos FkB A F L L k sin FkA B F
+ + + ÷ =
= + + ' + + ÷ '
;

( )
3 4 5 3
d L d d ÷ = | ;

3
2 d F = ; | F F = '

At
4 3 2
L L L z + + = ,
4 5
u u = ,
4 5
u u ' = '

( ) ( )
( ) ( ) | |
4 3 2 4 4 3 2 4
4 3 2 5 4 3 2 5
sin cos
sin cos
L L L k B L L L k A F
L L L k B L L L k A
+ + + + + =
= + + + + +
;

( ) ( )
( ) ( ) ( ) ( )
4 3 2 4 4 4 3 2 4 4
4 3 2 5 4 3 2 5
cos sin
cos sin
L L L k FkB A F L L L k FkA B F
L L L k kB L L L k kA
+ + + ' + + + ÷ ' =
= + + + + + ÷
;
( )
3 4 5 3
d L d d ÷ = | ;

5
2 d F = ; ( ) | 1
4
÷ ÷ = ' L F F

At
5 4 3 2
L L L L z + + + = ,
out
u u =
5
, 0
5
= ' u

( ) ( )
out
u L L L L k B L L L L k A = + + + + + + +
5 4 3 2 5 5 4 3 2 5
sin cos
( ) ( ) 0 cos sin
5 4 3 2 5 5 4 3 2 5
= + + + + + + + ÷ L L L L k B L L L L k A

The gain factor of the horn can be expressed as:

Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 91
1 1 1 1
5 4 3 2 5 5 4 3 2 5
sin cos
) ( sin ) ( cos
kL B kL A
L L L L k B L L L L k A
u
u
G
in
out
÷
+ + + + + + +
= = (25)

where
n
d F 2 = ,
n
d is the diameter of the corresponding cylindrical element of the horn,
n
A
and
n
B are the constant coefficients for the corresponding elements of the horn,
n
L is the
length of the corresponding element of the horn, n is the order number of the horn element,
| is the cone index of the horn element with variable cross-section,
in
u and
out
u are the
amplitudes of displacements at the horn input and output, respectively. The boundary
conditions for the force acting on the horn‘s input, 0 =
in
F , and for the strain at the horn
output, 0
5
= ' u , in this system of equations indicate that the horn has a total resonance length
and does not have an acoustic load.
From the system of equations (24), one can obtain all necessary characteristics of a five-
element horn: lengths and diameters of the elements, gain factor, distribution of vibration
amplitudes, and distribution strains along the horn. From this system of equations, it is also
easy to obtain solutions for any horns with conical elements (for example, with fewer than
five elements). Horns with other shapes of the variable cross-section elements (for example,
exponential or catenoidal) can be considered in an analogous way, taking into account the
variation of sound velocity in such elements.

3.2.2.2. Analysis of Five-Element Horns
To solve the system of equations (24) and to present results in a convenient form, a
computer program has been written allowing all the indicated above characteristics of five-
element horns to be obtained in real time for subsequent analysis. The input parameters are:
operating frequency of the horn, acoustic properties and fatigue strength of the horn's
material, and the diameter-to-length ratios of the horn elements. For the convenience of
comparison of horn parameters, we further assume 1
5 1
= d d .
From all possible solutions of the system of equations (24), only the series of five-
element acoustic horns will be considered, which will be referred to as "barbell horns". This
series of horns, in the authors' opinion, is the most useful for industrial applications, in
particular, for building industrial ultrasonic reactor systems.
Figure 11 shows a half-wave barbell horn and its design parameters. A photograph of this
horn is also presented in Figure 14 (b). The maximum value of the matching capability of this
horn is 4
2
~ GN . The resonance length of this horn corresponds to one half of the ultrasonic
wavelength in the metal from which the horn is constructed, with dispersion taken into
account. Its small resonance dimensions are convenient in terms of manufacturing and
minimizing the side surface radiation, and should be particularly noted. Some useful
parameters of this type of horn are presented in Table 1.
Figure 12 shows a spool-shaped barbell horn and its design parameters. This horn is
atypical because its main radiating surface is lateral, and it mainly radiates a cylindrical wave
into the load, as opposed to a plane wave radiated by other matching horns.
Alexey S. Peshkovsky and Sergei L. Peshkovsky 92

Figure 11. Half-wave barbell horn is shown with d
1
= d
5
; d
1
/d
3
= 3.0; kL
2
= 0.5; kL
3
= 0.2; kL
4
= 0.3,
along with (a) the distribution of the oscillatory velocity, V, and strain, e, along the horn; (b) drawing of
the horn; (c) plot of the distribution of the horn‘s parameters.
Table 1.

kL
1
G KL
5

0.5 1.79 0.215
1.0 3.17 0.128
1.5 3.78 0.093
2.0 3.46 0.058

Due to the symmetric form of the spool-shaped barbell horn, its gain factor is always
equal to 1, the node of displacements is located in the middle, and lateral surfaces move in
anti-phase. When using lateral radiation, the horn‘s matching capabilities are quite high since
there are no limitations on its overall length.
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 93

Figure 12. Symmetrical spool-shaped barbell horn is shown with d
1
= d
5
; kL
1
= kL
5
= 0.1; kL
3
= kL
4
=
0.5, along with (a) the distribution of the oscillatory velocity, V, and strain, e, along the horn; (b)
drawing of the horn; (c) plot of the distribution of the horn‘s parameters.
Alexey S. Peshkovsky and Sergei L. Peshkovsky 94
Table 2

d
1
/d
3
KL
3

2.0 0.877
3.0 0.384
4.0 0.179
5.0 0.085

When such horns are connected into a sequential string (radiating part of the long spool-
shaped barbell horn, shown in Figure 17 (a)), they can radiate a cylindrical wave of high total
power and produce a well-developed cavitation region of a large volume. Some useful
parameters of this type of horn are presented in Table 2.
Above, we have considered horns whose lengths are less than or close to half of the
length of the acoustic wave in the horn material, the so-called half-wave barbell horns. The
system of equations (24) also allows one to obtain solutions for full-wave barbell horns. One
of such horns intended for the radiation of a plane acoustic wave of a very high power into
water is full-wave barbell horn shown in Figures 13 and 14 (a). Its design parameters, as a
function of
3 1
d d , are presented in Figure 13 (c). The matching capabilities of full-wave
barbell horn can reach the values of 20
2
= GN or more. These horns are very promising for
matching of high-power magnetostrictive transducers that have large cross-sections.
For example, the highest design power radiated into water at cavitation by this horn,
made of high-quality titanium alloy, taking into account the fatigue strength limitations and
limitations on output diameter under normal static pressure, is about 5 kW at a frequency of
20 kHz.
Due to the significant potential of full-wave barbell horn for industrial applications of
ultrasound, we also provide its exact parameters in Table 3. These parameters are convenient
for practical calculations.

3.2.3. Experimental Results
For the experimental verification of the described horn design principles we have chosen
full-wave barbell horn of the type shown in Figures 13 and 14 (a). Direct calorimetric
measurement of acoustic energy transmitted by this horn into water at cavitation was selected
as a method of this horn‘s performance evaluation, as well as for obtaining experimental
results presented in section 2.6. The measurements of the acoustic energy absorbed in the
cavitation region were conducted with the apparatus shown in Figure 15. Settled tap water at
the temperature of 20
0
С was used. The apparatus was based on an acoustic radiator
consisting of a titanium horn connected to a magnetostrictive transducer, which operated at
the resonance frequency of 17.8 kHz. The working power of the ultrasonic generator coupled
to the magnetostrictive transducer was 5 kW. The oscillation amplitude of the
magnetostrictive transducer was kept constant in all experiments at 1.67 m/s (rms). It was
measured by placing a magnetic ring with an inductive coil on the transducer next to its
output surface. Voltage was created in the coil as the transducer oscillated. The amplitude of
this voltage corresponded to the oscillation amplitude and was measured by an oscilloscope.
Prior calibration of this device was performed, in which the vibration amplitude was
measured directly by a microscope.
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 95

Figure 13. Full-wave barbell horn is shown with d1 = d5; kL1 = kL3; kL2 = kL4 = 0.5, along with (a)
the distribution of the oscillatory velocity, V, and strain, e, along the horn; (b) drawing of the horn; (c)
plot of the distribution of the horn‘s parameters.
Table 3

d
1
/d
3
G kL
1
kL
2
kL
5

1.5 2.176 1.383 0.405 2.853
2.0 3.527 1.290 0.693 2.725
2.5 4.918 1.245 0.916 2.640
3.0 6.285 1.224 1.099 2.574
3.5 7.597 1.216 1.253 2.519
4.0 8.834 1.215 1.386 2.470
4.5 9.987 1.217 1.504 2.426
5.0 11.049 1.222 1.609 2.384
Alexey S. Peshkovsky and Sergei L. Peshkovsky 96

Figure 14. Full-wave (a) and half-wave (b) high-gain barbell horns are shown. High vibration amplitude
of the output tip is achieved without having to sacrifice the tip diameter. These particular barbell horns
have output tip diameters of 65 mm and provide ultrasonic amplitudes (a) up to 120 microns peak-to-
peak and (b) up to 80 microns peak-to-peak.
A set of replaceable full-wave barbell horns was constructed to provide the necessary
stepped change in the amplitude of the oscillatory velocity of the output end in contact with
water. The set consisted of nine such horns with different gain factors (greater or smaller than
unity), all of which had equal input and output diameters of 60 mm. Maximum oscillation
velocity of some of these horns reached very large values, close to maximum theoretically
possible for the best titanium alloys. Greatest achieved oscillation velocity was 12 m/s (rms).
Therefore, maximum gain factor for the set was 7.2.
Static pressure in the calorimeter was produced with compressed nitrogen. The
measurements of the resulting temperature of water were performed using a set of
thermocouples. A change in the temperature of water during ultrasonic treatment was not
more than 2 – 5
0
C.
Experimentally measures acoustic energy intensity levels absorbed in the cavitation area
are presented above in Figures 5 and 6. The dispersing effect of acoustic cavitation is shown
in Figure 7.

Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 97

Figure 15. Schematic of acoustic calorimeter is presented. 1-magnetostrictive transducer, 2-replaceable
full-wave barbell horn, 3-external wall of calorimeter, 4-heat insulation gasket, 5-cover with porous
sound-absorber, 6-internal wall of calorimeter, 7-sealing ring, 8-set of thermocouples, 9-gas supply, 10
– microphone, 11-point of control over amplitude of transducer vibrations.
Performance verification of the horns with different gain factors conducted during the
experiments showed that all of them possessed resonance and gain characteristics well
corresponding to the theoretically predicted values. In no case was it necessary to make any
adjustments to the horns after they were originally machined.
The region of acoustic energy intensity with the values above 10
5
W/m
2
is very little
studied, especially from the technological standpoint. The reason for this, in the authors‘
opinion, is that the traditional cone-shaped horns, widely used in ultrasonic technology, are
incapable of providing large total radiation power, since their oscillation amplitudes are
inversely proportional to the areas of their output surfaces. At large gain factors, the output
surface area becomes very small, which complicates the development of sonochemical
reactors capable of processing significant volumes of liquids. Thus, for example, a traditional
stepped horn having an input diameter of 60 mm and a gain factor of 7.2 has the output
diameter of, approximately, 20 mm. Therefore, at the maximum experimentally achieved
acoustic energy intensity of 10
6
W/m
2
, this stepped horn is capable of depositing no more
Alexey S. Peshkovsky and Sergei L. Peshkovsky 98
than 300 W into its liquid load. Our full-wave barbell horn, used in the experiments presented
in this section, on the other hand, delivers, approximately, 2.7 kW of total power, providing a
power transfer efficiency increase by almost an order of magnitude.
3.3. Section Conclusion

Matching a magnetostrictive transducer to water is a matter of selecting the horn type that
fulfills expression (19) at a given gain factor G , and of subsequent calculation of its
resonance dimensions with the use of equations (24). The most powerful horn, among the
designs described above, is full-wave barbell horn, which was chosen for the experimental
investigations. During the experiments, evaluation of a set of such horns with different gain
factors showed that all of them had the resonance and the gain factor characteristics that
corresponded very well to those predicted theoretically. It was also experimentally verified
that matching of the acoustic horns with water at cavitation, according to the theory described
above, is truly established for all values of the output oscillation velocities of the horns.
It should be noted that matching an acoustic transducer to a load using an acoustic horn is
not the only possible method of matching. Another powerful matching factor, which results
from the specific properties of water at cavitation, is the static pressure, p
0
, according to the
expression (11) and the experimental results. It is clear that the best results are obtained when
these two matching techniques are used jointly.
In conclusion, we would like to add that barbell horns also perform well in non-aqueous
liquids and solutions with significant viscosity, and permit building very effective ultrasonic
reactors, suitable for treatment of such liquids, for example oils, epoxy resins, honey, polymer
melts, metal melts, etc.
Photographs presented in Figure 16 illustrate primary (a) and secondary (b) cavitation
zones formed during the operation of full-wave barbell horn having an output diameter of 65
mm providing acoustic energy intensity of 2x10
5
W/m
2
in the primary cavitation zone below
output tip.
In certain applications of powerful ultrasonic systems, however, it is more important to
increase the residence time of the working liquid in the reactor, than to maximize the output
amplitude. This is especially important during preliminary preparation for further high-
amplitude processing, such as during pre-dispersion, pre-emulsification, treatment of high-
viscosity liquids, etc. In these cases, it is convenient to utilize a long spool-shaped barbell
horn, incorporated into a reactor chamber. Figure 17 shows such a horn (a) as well as the
cavitation zones formed by it in a relatively viscous liquid, glycerin (b). This figure shows
that two well developed secondary cavitation zones are formed near the two "necks" of the
long spool-shaped barbell horn, constructed as two spool-shaped barbell horns connected in
series.
In semi-industrial ultrasonic reactor systems with relatively low transducer power (1 - 2
kW), it is convenient to use half-wave barbell horns, shown in Figure 14 (b). These horns are
compact and have minimal losses due to the side-surface radiation.
All photographs shown above were obtained using ultrasonic equipment produced by
Industrial Sonomechanics, LLC. Videos of the corresponding cavitation processes are
available at the company‘s website: http://www.sonomechanics.com.
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 99

Figure 16. Experimentally obtained photographs of well developed stable cavitation zones are shown.
The zones were created in an unrestricted volume of water by a barbell horn, having the following
operational parameters: output tip diameter – 65 mm, ultrasound frequency – 18 kHz, acoustic energy
intensity – 20 W/cm
2
. Part (a) shows the primary cavitation zone under the horn tip; part (b) shows the
secondary cavitation zone produced near the neck of the barbell horn (marked with a white line).














Figure 17. Photograph of a long spool-shaped barbell horn is shown in part (a). Photograph taken
during operation of this horn in glycerin is displayed in part (b), showing multiple secondary cavitation
zones formed near its transitional sections.
Alexey S. Peshkovsky and Sergei L. Peshkovsky 100
4. ULTRASONIC REACTOR CHAMBER GEOMETRY
During a flow-through ultrasonic process, it is important to make sure that all working
liquid is directed through the active cavitation zone, otherwise inhomogeneous processing
may result, leading to a lower-quality product. Eliminating the low cavitation intensity areas
in the reactor also helps increase the power density that the system can deposit into a liquid
load. Optimization of the ultrasonic reactor chamber geometry, therefore, leads to an
improvement in the technological effects obtained during the operation of the reactor.
In a common reactor chamber the treated liquid enters through the inlet at the bottom,
passes through the primary cavitation zone of a horn, Figure 16 (a), flows along the horn's
side surface and comes out through the outlet at the side of the chamber at the top. If a barbell
horn is utilized, there is also a secondary cavitation zone near the transitional sections, as
shown in Figure 16 (b), which accounts for approximately 20 % of the total radiated
ultrasonic power. An optimized reactor chamber design would efficiently direct all treated
liquid through both of these cavitation zones.
It has been explained above that the shape of a well developed cavitation zone formed at
the bottom of a barbell horn resembles an upside-down circular cone. Therefore, it is
beneficial to shape the bottom of the reactor chamber in the same manner, as shown in Figure
18. An approximately 20 % increase in the absorbed acoustic energy can be achieved due to
the presence of a cone insert at the bottom of the reactor chamber, which optimizes the
volume and the shape of the main cavitation zone at the output tip of the barbell horn [2]. To
take the full advantage of the secondary cavitations zone, a liquid deflector ring may be
inserted near the neck of the barbell horn (its second cylindrical section), as shown in Figure
18. Supplying the reactor chamber with both of these features dramatically improves the
homogeneity of ultrasonic exposure of the working liquid and increases the total power
deposition.
5. FINAL REMARKS
Industrial implementation of ultrasonic reactor systems has not reached its full potential.
This is especially true when processes require high ultrasonic amplitudes, for example in
production of nanoemulsions or nanodispersions. On the other hand, a large number of
laboratory studies exist that demonstrate high potential effectiveness of ultrasonic processing
in these and other areas [40, 41].
Since prior to the introduction of barbell horns the ultrasonic amplitude amplification was
commonly done with converging horns, high-amplitude industrial-scale ultrasonic equipment
was not available. Consequentially, transferring the results of many laboratory studies
involving high-amplitude ultrasound to the plant floor has not been possible. Low-amplitude
(below 30 microns peak-to-peak (µ
pp
)) industrial ultrasonic equipment has been around for
several decades. This equipment, however, has had limited capability to translate optimized
ultrasonic processes to commercial scale due to its inability to provide high-intensity
cavitation in large reactor volumes. Additionally, this equipment has generally relied on
piezoelectric transducer designs, which for industrial-scale liquid processing applications
suffer from several important limitations compared with magnetostrictive devices.
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 101

Figure 18. Schematic of an optimized flow-through ultrasonic reactor is presented, where 1 – electro-
acoustical transducer, 2 – barbell horn, 3 – working liquid outlet, 4 – reactor chamber, 5 – upside-down
circular cone insert, 6 – working liquid inlet, 7 – circular reflection surface.
The ultrasonic cavitation theory and main hardware design principles presented in
this chapter provide the background necessary to be able to construct high-capacity industrial
ultrasonic systems with up to 10,000 L/h processing capability, able to operate at extremely
high ultrasonic amplitudes in excess of 150 µ
pp
. Using these systems, any laboratory study
results can be directly implemented on industrial scale by simply increasing the horn tip
diameter and the corresponding reactor volume and boosting the power of the generator and
the transducer. All of the process parameters optimized during the laboratory study
(ultrasonic amplitude, reactor residence time, pressure, etc.) can be retained, while the system
productivity is increased by orders of magnitude.
REFERENCES
[1] S.L. Peshkovskiy, M.L. Friedman, and W.A. Hawkins, Ultrasonic Rod Waveguide-
Radiator. 2004, Industrial Sonomechanics, LLC: U.S. Patent #7,156,201.
[2] S.L. Peshkovsky and A.S. Peshkovsky, High Capacity Ultrasonic Reactor System.
2008, Industrial Sonomechanics, LLC: International Application #PCT/US08/68697.
[3] T.G. Leighton, Bubble population phenomena in acoustic cavitation. Ultrason.
Sonochem., 1995. 2: p. 123.
Alexey S. Peshkovsky and Sergei L. Peshkovsky 102
[4] H.G. Flynn, Physics of acoustic cavitation in liquids, in Physical Acoustics, principles
and methods, W.P. Mason, Editor. 1964, Academic Press: New York and London. p.
78-172.
[5] M.S. Plesset and A. Prosperitty, Ann. Rev. Fluid Mech., 1977. 9.
[6] J.L. Laborde, A. Hita, J.P. Caltagirone, and A. Gerard, Fluid dynamics phenomena
induced by power ultrasounds. Ultrasonics, 2000. 38: p. 297-300.
[7] W. Lauterborn and C.D. Ohl, Cavitation bubble dynamics. Ultrason. Sonochem., 1997.
4(2): p. 65-75.
[8] G. Servant, J.L. Laborde, A. Hita, J.P. Caltagirone, and A. Gérard, Spatio-temporal
dynamics of cavitation bubble clouds in a low frequency reactor: comparison between
theoretical and experimental results. Ultrason. Sonochem., 2001 8(3): p. 163-74.
[9] J. Klíma, A. Frias-Ferrer, J. González-García, J. Ludvík, V. Sáez, and J. Iniesta,
Optimisation of 20 kHz sonoreactor geometry on the basis of numerical simulation of
local ultrasonic intensity and qualitative comparison with experimental results.
Ultrason. Sonochem., 2007 14(1): p. 19-28.
[10] W. Lauterborn, T. Kurz, R. Geisler, D. Schanz, and O. Lindau, Acoustic cavitation,
bubble dynamics and sonoluminescence. Ultrason. Sonochem., 2007 14(4): p. 484-91.
[11] R. Mettin, P. Koch, W. Lauterborn, and D. Krefting. Modeling acoustic cavitation with
bubble redistribution. in Sixth International Symposium on Cavitation, CAV2006.
September 2006. Wageningen, The Netherlands.
[12] G. Servant, J.L. Laborde, A. Hita, J.P. Caltagirone, and A. Gérard, On the interaction
between ultrasound waves and bubble clouds in mono- and dual-frequency
sonoreactors. Ultrason. Sonochem., 2003 10(6): p. 347-55.
[13] R. Mettin, S. Luther, C.D. Ohl, and W. Lauterborn, Acoustic cavitation structures and
simulations by a particle model. Ultrason. Sonochem., 1999 6(1-2): p. 25-9.
[14] S. Luther, R. Mettin, P. Koch, and W. Lauterborn, Observation of acoustic cavitation
bubbles at 2250 frames per second. Ultrason. Sonochem., 2001 8(3): p. 159-62.
[15] J. Appel, P. Koch, R. Mettin, D. Krefting, and W. Lauterborn, Stereoscopic high-speed
recording of bubble filaments. Ultrason. Sonochem., 2004 11(1): p. 39-42.
[16] A. Moussatov, C. Granger, and B. Dubus, Cone-like bubble formation in ultrasonic
cavitation field. Ultrason. Sonochem., 2003. 10: p. 191–195.
[17] A. Moussatov, R. Mettin, C. Granger, T. Tervo, B. Dubus, and W. Lauterborn.
Evolution of acoustic cavitation structures near larger emitting surface. in World
Congress on Ultrasonics, WCU2003. September, 2003. Paris, France.
[18] P. Diodati and G. Giannini, Cavitation damage on metallic plate surfaces oscillating at
20 kHz. Ultrason. Sonochem., 2001 8(1): p. 49-53.
[19] Y.B. Zel‘dovich and Y.P. Raizer, Physics of Shock Waves and High-Temperature
Hydrodynamic Phenomena. 1966, New York: Acad. Press.
[20] R.A. Thuraisingham, Sound speed in bubbly water at megahertz frequencies.
Ultrasonics, 1998. 36(6): p. 767-773.
[21] L. Van Vijngaarden, Annual review of fluid mechanics, in Annual Review Inc. 1972:
Palo Alto. p. 369.
[22] L.D. Rosenberg, High-intensity ultrasonic fields. 1971, New York: Plenum Press.
[23] W. Herrmann, A Constitutive Equation for the Dynamic Compaction of Ductile Porous
Materials. J. Appl. Phys., 1969. 40: p. 2490.
Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation … 103
[24] A.D. Resnyansky and N.K. Bourne, Shock-wave compression of a porous material. J.
Appl. Phys., 2004. 95: p. 1760-1769.
[25] M.G. Salvadori, R. Skalak, and P. Weidlinger, Stress Waves in Dissipative Media.
Transactions New York Academy of Science, Ser. II, 1959. 21(5): p. 427-434.
[26] K. Fukushima, J. Saneyoshi, and Y. Kikuchi, Ultrasonic Transducers, ed. Y. Kikuchi.
1969, Tokyo: Corona Publ. Co.
[27] N.B. Brandt, A.D. Yakovlev, and S.L. Peshkovsky, Russ. Tech. Phys. Let., 1975. 1(10):
p. 460.
[28] R.T. Knapp, J.W. Daily, and F.G. Hammitt, Cavitation. 1970 New York: McGraw-Hill.
[29] P. Chand, C.V. Reddy, J.G. Verkade, and D. Grewell. Enhancing Biodiesel Production
from Soybean Oil using Ultrasonics. in ASABE Paper No. 8. 2008. St. Joseph, MI,
USA.
[30] A.K. Singh, S.D. Fernando, and R. Hernandez, Base-catalyzed fast transesterification
of soybean oil using ultrasonication. Energy and Fuels, 2007. 21: p. 1161-1164.
[31] G. Towerton, The use of ultrasonic reactors in a small scale continuous biodiesel
process. 2007, GandM Global Enterprises Inc.: Amarillo, TX, USA. p. 1-4.
[32] U.S. Bhirud, P.R. Gogate, A.M. Wilhelm, and A.B. Pandit, Ultrasonic bath with
longitudinal vibrations: a novel configuration for efficient wastewater treatment.
Ultrason. Sonochem., 2004. 11: p. 143-147.
[33] E. Eisner, Physical Acoustics, in Methods and Devices, Part B, W.P. Mason, Editor.
1964, Acad. Press: New York.
[34] S. Sherrit, S.A. Askins, M. Gradziol, B.P. Dolgin, X.B.Z. Chang, and Y. Bar-Cohen,
Novel Horn Designs for Ultrasonic/Sonic Cleaning, Welding, Soldering, Cutting and
Drilling. Proceedings of the SPIE Smart Structures Conference, San Diego, CA, 2002.
4701: p. Paper No. 34.
[35] J.W. Rayleigh (Strutt), The Theory of Sound. 1945, New York: Dover Publications.
[36] J.A. Gallego Juárez, G. Rodríguez Corral, E. Riera Franco de Sarabia, C. Campos
Pozuelo, F. Vázquez Martínez, and V.M. Acosta Aparicio, A Macrosonic System for
Industrial Processing. Ultrasonics, 2000. 38: p. 331-336.
[37] Y. Kikuchi, Ultrasonic Transducers, ed. Y. Kikuchi. 1969, Tokyo Corona Publ. Co.
[38] E.A. Neppiras, Measurements in liquids at medium and high ultrasonic intensities.
Ultrasonics, 1965. 3(1): p. 9-17.
[39] L.G. Merkulov and A.B. Kharitinov, Theory and analysis of sectional concentrators.
Sov. Phys. - Acoust., 1959(5): p. 183-90.
[40] J.P. Canselier, H. Delmas, A.M. Wilhelm, and B. Abismaïl, Ultrasound
Emulsification—An Overview. Journal of Dispersion Science and Technology, 2002.
23(1): p. 333 – 349.
[41] T.J. Mason and J.P. Lorimer, Applied Sonochemistry: Uses of Power Ultrasound in
Chemistry and Processing. 2002, Weinheim: Wiley-VCH. 303.
In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 3



SOME APPLICATIONS OF ULTRASOUND
IRRADIATION IN PINACOL COUPLING
OF CARBONYL COMPOUNDS


Zhi-Ping Lin
a
and Ji-Tai Li
b

a
Department of Chemistry and Biology, Baoding University,
Hebei Province, Baoding 071000, P. R. China;
b
College of Chemistry and Environmental Science,
Hebei University, Key Laboratory of Analytical Science
and Technology, Hebei Province,
Baoding 071002, P. R. China
ABSTRACT
Carbon-carbon bond formation is one of the most important topics in organic
synthesis. One of the most powerful methods for constructing a carbon-carbon bond is
the reductive coupling of carbonyl compounds giving 1,2-diols. Of these methods, the
pinacol coupling, which was described in 1859, is still a useful tool for the synthesis of
vicinal diols. 1, 2-Diols obtained in the reaction were very useful synthons for a variety
of organic synthesis, and were also used as intermediates for the construction of
biologically important natural product skeletons and asymmetric ligands for catalytic
asymmetric reaction. In particular, pinacol coupling has been employed as a key step in
the construction of HIV-protease inhibitors.
Generally, the reaction is effected by treatment of carbonyl compounds with an
appropriate metal reagent and/or metal complex to give rise to the corresponding alcohols
and coupled products, The coupling products can have two newly chiral centers formed.
Threo, erythro mixtures of diols are usually obtained from reactions. As a consequence,
efficient reaction conditions have been required to control the stereochemistry of the 1,2-
diols. Recent efforts have focused on the development of new reagents and reaction
systems to improve the reactivity of the reagents and diastereoselectivity of the products.
In some of the described methods, anhydrous conditions and long reaction time are
required to get satisfactory yields of the reaction products, some of the used reductants
are expensive or toxic; excess amounts of metal are needed. Sonication can cause metal
in the form of a powder particle rupture, with a consequent decrease in particle size,
Zhi-Ping Lin

and Ji-Tai Li 106
expose new surface and increase the effective area available for reaction. It was effective
in enhancing the reactivity of metal and favorable for single electron transfer reaction of
the aldehydes or ketones with metal to form diols. Some recent applications of ultrasound
in pinacol coupling reactions are reviewed. The results are mostly from our research
group.
INTRODUCTION
During 1980s, like thermal chemistry, photochemistry, and electrochemistry,
sonochemistry as a new branch of chemistry is a new cross-discipline whose use of
ultrasound to accelerate chemical reactions, improves the chemical production rate. It has
become a frontier area in chemical research, and its development has been brought to the
attention of chemistry academics.
It has been recognized for many years that power ultrasound has a great potential for uses
in a wide variety of processes in the chemical and allied industries. Reported applications
include cleaning, sterilization, flotation, degassing, defoaming, filtration, homogenization,
extraction, crystallization and of course as a stimulus for chemical reaction [1-21].
The technology is expected to bring major changes in pesticides, synthetic drugs, plastics
and the microelectronic devices industry, and has been attracting increasing interest in
chemical and related industries.
Carbon-carbon bond formation is one of the most important topics in organic synthesis.
One of the most powerful methods for constructing a carbon-carbon bond is the reductive
coupling of carbonyl compounds giving olefins and/or 1,2-diols. Of these methods, the
pinacol coupling, which was described in 1859, is still a useful tool for the synthesis of
vicinal diols [22, 23]. The corresponding products of this reaction can be used as
intermediates for the preparation of ketones and alkenes. 1,2-Diols obtained in the reaction
were very useful synthons for a variety of organic syntheses and also used as intermediates
for the construction of biologically important natural product skeletons and asymmetric
ligands for catalytic asymmetric reactions [24].
Particularly, pinacols with a chiral are important raw materials for the synthesis of chiral
natural products and drugs, such as Pradimicinone, |-blockers (S)-Propranolol, leukotriene
antagonist SKF104353, Paclitaxel, and C
2
-symmetric HIV protease inhibitors [25, 26]. The
chiral pinacols have been applied to synthesize chiral diamines, chiral crown ethers, chiral
diphosphine ligands, and especially to synthesize asymmetric catalyst [27]. So, study on the
pinacol synthetic method is very meaningful.
The 1,2-diol unit is one of the most ubiquitous functional groups in nature, and
consequently a lot of methods leading to its synthesis have been developed. Foremost in this
arsenal are the reductive coupling of aldehydes or ketones [22], double-hydroxylation of
olefins [28], ring opening of epoxides [29], reduction of o-hydroxy/alkoxy carbonyls [30] and
alkylation of o-hydroxy/alkoxy carbonyls and so on [31].
Among them, the pinacol-coupling reaction of aldehydes/ketones is the most classical
and effective methods, but also is one of the frequently used methods for the formation of
carbon-carbon bonds in organic reactions [27]. Although 140 years have passed from the first
synthesis of pinacol [32] up to now, the topic is still one of the hottest research fields in
organic synthesis. Generally, the reaction is effected by treatment of carbonyl compounds
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 107
with an appropriate metal reagent and/or metal complex to give rise to the corresponding
coupled product. This reaction is affected by many factors, such as the reductant used, solvent
type, and reaction pH, etc. The coupling products have two chiral centers, threo, erythro
mixtures of diols are usually obtained from reactions, which increases the difficulties to
improve chemoselectivity and stereoselectivity for the synthesis of pinacol. Therefore,
seeking new metal reagents, a new reaction system and new approaches have been the focus
of attention and study. Before the 1970s, the method of synthesis of pinacol was mainly
electrochemical methods, and reductive coupling of aldehydes and ketones induced by alkali
metals such as Na, Mg and other active metals in the non-proton-media. In the last two
decades, the introduction of low-valent transition metal and lanthanoid based reducing
systems, especially those based on titanium, have provided dramatic advances in efficiency
and selectivity. It is now possible to select appropriate conditions for efficient coupling of all
types of carbonyl compounds, often with high chemo-, region- and stereo-selectivity [33].
The formation of 1,2-diol [34] has been attempted using a number of regents such as Mg
[35], Al [36], Ga [37], In [38], Ti [39-68], V [69-72], Cr [73], Mn [74-75], Fe [76-77], Ni
[78], Zn [79-81] and their compounds, rare earth metals Ce [82-83], Sm [84-89], others [90-
92] and their compounds, non-metallic tellurium [93], the organic metal hydride of Tin
(Bu
3
SnH) [94].
In addition to using the reagents above by traditional thermodynamic approach to
synthesis of pinacol, microwave technology in solvent-free conditions [95] can also be used.
Coupling also can be initiated photochemically [96-103], electrochemically [104-105],
ultrasonically [106-110], or with the combination of ultrasound irradiation and
photochemistry or electrochemistry techniques [111-113].
However, in some of the described methods, anhydrous conditions and long reaction time
are required to get satisfactory yields of the reaction products. Some of the used reductants
are expensive and these reactions are often associated with the toxic reagents and heavy
metals, which would lead to economical and environmental concerns.
The coupling products can have two newly formed stereocenters.Threo, erythro mixtures
of diols are usually obtained from reactions. As a consequence, efficient reaction conditions
have been required to control the stereochemistry of the 1,2-diols. Recent efforts have
focused on the development of new reagents and reaction systems to improve the reactivity of
the reagents and diastereoselectivity of the products.
Ultrasound has increasingly been used in organic synthesis in the last two decades.
Applications of sonication achieve a number of beneficial effects, for example, accelerate a
reaction, permit the use of less forcing conditions, reduce the number of steps required—
favouring one-pot syntheses, enhance radical reactions, enhance catalyst efficiency, etc.
Compared with traditional methods, this technique is more convenient. A large number of
organic reactions, such as pinacol coupling reaction [114-140], Biginelli reaction [141-150],
Michael addition [151-155], Knoevenagel condensation [156-163], Claisen-Schmidt
condensation [164-169], Cannizzaro reaction [170], Vilsmeier Haack reaction [171],
Reformatsky reaction [172-174], and many other reactions [175-193], can be carried out in
higher yields, shorter reaction time and milder conditions under ultrasound irradiation.
In this chapter, some recent applications of ultrasound in the synthesis of pinacol were
reviewed, the results are mostly from our research group.


Zhi-Ping Lin

and Ji-Tai Li 108
MECHANISM
As ultrasonic irradiation has been widely employed in chemistry and chemical
technology, a number of exhaustive monographs [194] and reviews [195] have been
published, there is no need for us to expatiate on the topic. However, a short explanation of
current concepts of sonochemistry seems to be useful for introducing the matter of this paper.
Ultrasonic irradiation differs from traditional energy sources in duration, pressure, and
energy per molecule. It is certain that sonochemical effects cannot be caused by direct impact
of the acoustic field on the reacting molecules since the energy of ultrasonic irradiation is too
low to alter their electronic, vibrational, or rotational states. Cavitation is the origin of
sonochemistry. Irradiation of liquids by power ultrasound leads to cavitation phenomena:
microbubbles present in a liquid are submitted to formation, growth, and finally implosion
[3, 19].
Cavitation is the production of microbubbles in a liquid when a large negative pressure is
applied to it. If a sufficiently large negative pressure is applied to the liquid that cavitation
bubbles will form. Once formed, small gas bubbles irradiated with ultrasound will absorb
energy from the sound waves and grow. Once the cavity has overgrown, it can no longer
absorb energy efficiently. The surrounding liquid rushes in, and the cavity implodes. In
succeeding compression cycles these cavities can collapse violently with the release of large
amounts of energy in and around these microbubbles.
The ‗hot-spot‘ theory suggests that temperatures of up to 5000K, pressures of several
thousand atmospheres, lifetime considerably less than a microsecond, and heating and cooling
rates above 10 billion
o
C per second are produced during this collapse. For a rough
comparison, these are, respectively, the temperature of the surface of the sun, the pressure at
the bottom of the ocean, the lifetime of a lightning strike, and a million times faster cooling
that a red hot iron rod plunged into water!
Because of the immense temperatures and pressures and the extraordinary heating and
cooling rates generated by cavitation bubble collapse, ultrasound provides an unusual
mechanism for generating high-energy chemistry.
1. Homogeneous Reactions Involving a Single Liquid Phase

The mechanical and chemical effects of the collapsing bubble will be felt in three distinct
regions: the inside of the bubble; at the interface between the bubble and the bulk liquid; in
the bulk media. High temperatures and pressures generated during collapse in the cavity. Less
forcing conditions pluses shock wave on collapse at the interface. Shock wave on collapse
induces shear forces in the bulk media [3, 19].
2. Heterogeneous Reactions Involving Immiscible Liquids

When the reactions were carried out in immiscible liquids such as water and an organic
solvent, the synthetic chemist will induce those reactions by the use of phase transfer catalyst
(PTC). However, in spite of their potential utility, some of the specialized PTC reagents are
suffer from drawbacks such as expensive and all PTCs are potentially dangerous since they
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 109
can transfer chemicals from water into human tissue. Sonication can be used to produce very
fine emulsions from immiscible liquids because disruption at phase boundary by cavitational
collapse causes emulsification.
3. Heterogeneous Reactions Involving a Solid and a Liquid

Cavitation can effect two types of reaction involving solid/liquid interfaces: (i) in which
powder is a reagent and trapped gas on surface or in defects cause nucleation and cavitational
collapse resulting in fragmentation and (ii) in which solid is a catalyst such as pinacol
coupling reduced by metal and collapse near solid surface in the liquid phase causes microjet
to hit surface.
A general problem during the preparations of organometallic compounds is that the metal
surface is easily ‗poisoned‘ by the presence of moisture and other impurities. Ultrasonic
irradiation has made it possible to prepare some of these reagents even with technical-grade
chemicals, conditions unheard of in classical methodology. Because sonication can cause
particle rupture, with a consequent decrease in particle size and increase in surface area
available for reaction.
The coupling of ketones to give pinacols is a very old, well-established reaction in
organic chemistry. The synthesis of pinacols from carbonyl compounds is generally thought
of as taking place via reduction of the carbonyl to a radical anion, followed by radical
coupling to give a pinacol dianion, which is subsequently protonated by the medium or upon
quenching [136,138].
The reaction is generally thought to proceed via single electron transfer (SET)
mechanism. Coupling is propagated by single-electron reduction of the carbonyl group from
metal reagent and /or metal complex to form a ketyl radical anion (I), which either undergoes
radical-radical coupling (route a), or is further reduced to the corresponding dianion (II) and
then nucleophilically attacks a second carbonyl group (route b), so leading to pinacol
formation, while dianion (2) can be protonated by H
+
to generate alcohol (Scheme 1)

[22,
110]. By far the majority of pinacolic couplings occur via radical-radical coupling and
generally afford a mixture of dl and meso diols [196-197].
H
+
R
R
R
R
O
O
OH
OH
R
R
R
R
H
+
+e
+e
R R
O
.
a
b
R
O
R
R
O
R O
R R
R R
O
.
R
R
R
R
O
O OH
R R
H
+
(I)
(II)

Scheme 1. Mechanism of pinacol coupling
Zhi-Ping Lin

and Ji-Tai Li 110
PINACOL COUPLING UNDER ULTRASOUND
The recent interest in green chemistry has posed a new challenge for organic synthesis in
that new reaction conditions need to be found which reduce the emission of volatile organic
solvents and the use of hazardous toxic chemicals. In this connection, organic reactions in
water or aqueous media have attracted increasing interest currently because of the
environmental issue and understanding biochemical processes. Water offers many practical
and economic advantages as a reaction solvent, including low cost, safe handling and
environmental compatibility. Recently, pinacol coupling reaction in aqueous media has been
described in the literatures [36, 107, 109, 119, 125], however, these methods so far suffer
from harsh reaction and workup conditions, using an excess amount of metal or a long
reaction time.
1. Metal (or Ion) Induced Reductive Coupling of Aromatic Aldehydes and
Ketones in Aqueous Media

In the classic method the reaction of metal induced reductive coupling of aromatic
aldehydes and ketones is usually carried out in organic solvents which are usually flammable,
explosive or hazardous toxic chemicals, and easy to pollute the environment. On the other
hand, the increasing cost in production process is forced to search for environmentally
friendly solvents. In recent years, organic reactions in aqueous solution have attracted
considerable attention. Compared with the organic solvent, water is simple, safe, inexpensive,
and environmentally friendly and so on. The classical active metals used in the reductive
coupling reaction such as Li, Na, etc. due to the role of violent react with water which is very
dangerous. Lim et al. reported the reaction of aromatic aldehydes with indium in aqueous
media using sonication to afford the corresponding diols in moderate to good yield [107]. We
have choosen to examine the potential of Mg, Al, Zn, Mn and other metal in view of their
suitable catalytic activity, cheap and ready availability in pinacol coupling reaction.

1) Zinc Powder Induced Reductive Coupling of Aromatic Aldehydes and Ketones in
Aqueous Media
The Zn-ZnCl
2
reagent is not sensitive to oxygen. In 1990, Tanaka et al. reported that the
reductive coupling of aromatic aldehydes and ketones in Zn-ZnCl
2
aqueous solution, but the
main product is single-molecule alcohols, the pinacol product was isolated as a by-product in
a very low yield [117]. Delair et al. described the pinacol coupling reaction used of Zn-Cu
alloys under ultrasound irradiation and found that ultrasound accelerates considerably the
aromatic aldehydes and ketones‘ conversion in 1989 [118]. Mecarova and Toma described
the pinacol coupling reaction in aqueous media under ultrasound irradiation and found that
ultrasound accelerates considerably the benzaldehydes‘ conversion with zinc powder in 0.1 M
aq. NH
4
Cl [119]. Our laboratory has also reported the pinacol coupling of aromatic aldehydes
and ketones induced by Zn-ZnCl
2
in aqueous THF media under ultrasound irradiation and the
results showed that ultrasound irradiation can not only accelerates considerably the
chemoselectivity of the reactions but also can significantly increase the yield of diol [120]. In
the classical method, 1,2-bisphenyl-1,2-ethanediol and 1,2-bis(p-chlorophenyl)-1,2-ethanediol
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 111
were prepared in only 11% and 16% yield respectively. Whereas under ultrasound irradiation,
they were increased to 49.6% and 51.5% respectively in the same time, 1,2-bis(o,p-
dichlorophenyl)-1,2-ethanediol was up to 77.5% yield in this procedure. Aromatic ketones are
much less efficient for this reaction. Aromatic ketones with electron donating groups such as
m-aminoacetophenone and p-methoxylacetophenone, and steric hindered ketones such as
dibenzyl ketone and benzophenone did not give any pinacol products.
In recent years, catalysts and reagents supported on inorganic substrates have received
increasing attention because of their high level of chemoselectivity and environmental
compatibility as well as simplicity of operation. When certain chemicals are absorbed onto
solid supports their reactivity is enhanced over the reagent itself. Montmorillonite K10 is
known to behave as Bronsted acids in organic reactions. The use of K10 as solid support has
become very useful in synthetic organic chemistry because of its enhanced selectivity due to
its lamellar swelling structure and large surface area. Up to now, the catalyst has been used as
acidic catalyst for many organic reactions. The advantages of the catalyst are easy handing,
chemical inertness, and lower cost, environmentally friendly and easy modification of acidity
by exchanging the cations in the interlayer space. We examined the pinacol coupling
catalyzed by ZnCl
2
supported on Montmorillonite K10 instead of ZnCl
2
, some aromatic
aldehydes such as o,p-dichlorobenzaldehyde, m-chlorobenzaldehyde, cinnamaldehyde and
furfural gave the desired 1,2-diols with 87%, 74%, 75% and 61% yield respectively.
Compared with the reaction catalyzed by ZnCl
2
only, the pinacols yield increased about 10%-
30%, and the supported reagent was very easy separation and recycling [121]. In the present
system, the ratio of dl and meso of the corresponding 1,2-diols is about 1:1. The K10-ZnCl
2

could be recycled for 3 times without significant losing activity.
Pinacol coupling of aromatic aldehydes in aqueous H
2
NSO
3
H or H
3
PO
4
mediated by zinc
powder under ultrasound irradiation could lead to the corresponding pinacols in 14%~88%
yields within 2.5 h. Aromatic aldehydes with electronwithdrawing groups increase the
reactivity. For system Zn-H
2
NSO
3
H(aq., 1N), when the substrates are o-chlorobenzaldehyde,
m-chlorobenzaldehyde and m-bromobenzaldehyde, the corresponding pinacol products were
obtained in 70%, 74% and 63% yield respectively for 2.5 h ultrasound irradiation; while using
Zn-H
3
PO
4
(aq., 3N), the yield of pinacols were 85%, 88% and 79% respectively, which also
indicated that higher meso-stereoisomer can be obtained and higher yield of pinacols also
obtained under system Zn-H
3
PO
4
when compared to those of Zn-H
2
NSO
3
H [122].
If Zn-(COOH)
2
(aq.) instead of H
2
NSO
3
H or H
3
PO
4
during the reactions, high yields of
pinacol could be obtained when o,p-dichlorobenzaldehyde (78%) and p-chlorobenzaldehyde
(65%) as the substrate compared with the reaction using H
2
NSO
3
H or H
3
PO
4
aqueous (the
corresponding yields are 54% and 42% using H
2
NSO
3
H, 42% and 34% using H
3
PO
4
,
respectively) after 2.5 h ultrasound irradiation [123]. Ultrasound irradiation frequency had
little effect on this reaction system. No coupling of m-chlorobenzaldehyde was observed
when Zn powder was replaced by Mg or Al powder.
Zinc is a amphoteric metal,the reductive coupling of aromatic aldehydes in a basic
system such as Zn-NaOH (10% aq.)-MeOH under ultrasonic irradiation was observed. The
results showed that the basic situation not only further improved the pinacols yield of
aromatic aldehydes with electron-withdrawing substituents in the benzene ring, but also
aromatic aldehydes with electron-donating substituents in the benzene ring such as p-
methylbenzaldehyde and p-methoxybenzaldehyde yielded the pinacols in 92% and 80%
Zhi-Ping Lin

and Ji-Tai Li 112
respectively [124]. Compared with the acidic medium, the coupling in basic medium was
significantly improved on the chemoselectivity and shortened the reaction time from 2.5-3 h
to 25-60 min. When piperonaldehyde was used as substrate, the meso-pinacol was obtained
only, while other aldehydes as the substrates, the ratio of dl and meso was about 1:1.

2) Reductive Coupling of Aromatic Aldehydes and Ketones Induced by Magnesium
Powder in Aqueous Media
In 1999, Zhang and Li reported a simple and effective method for pinacol coupling
reactions of various aromatic aldehydes and ketones in aq. NH
4
Cl (0.1 N) mediated by
magnesium with stirring [125]. The yields of pinacols were 56-96%, but it needed a long
reaction time (12-24 h) and the molar ratio of ArCHO:Mg turning as high as 1:20. Mečiarová
et al. [109] studied the influence of reaction time, quality and quantity of magnesium, and
reaction conditions on pinacol coupling of benzaldehyde by Mg-NH
4
Cl (or H
2
O). They
decreased the molar ratio of PhCHO:Mg to 1:10, and found that ultrasound irradiation can
accelerate the pinacolization of benzaldehyde using magnesium turning, the conversion of
benzaldehyde up to 100% determined by
1
H NMR and the corresponding pinacol was
obtained in 95% yield within 90 min. It is clear that the ultrasound can accelerate the metal-
induced pinacolization of benzaldehyde, but the pinacolization of other aldehydes did not
involve in the paper. They proved also that reaction could be carried out in pure water
(without addition of ammonium chloride) in very good yields. Later on they found also that
very good yields of pinacols are formed with zinc powder in aqueous NH
4
Cl, but no reaction,
even under sonication, was observed with iron, nickel and tin powders.
We studied the coupling of aromatic aldehydes induced by magnesium powder in the
NH
4
Cl (0.1M) aqueous within 3 h at room temperature under ultrasonic irradiation. The data
were shown that this system was very effective for the aromatic aldehydes with electron-
donating substituents in the benzene ring such as p-methylbenzaldehyde and p-
methoxybenzaldehyde yielded the pinacols both in 95% and the ratio of dl/meso of
corresponding pinacol were 9/1 and 2/1 respectively. When benzaldehyde and
piperonaldehyde were used as the substrates, the corresponding pinacols were obtained in
75% and 72% respectively, while the ratios of dl/meso were about 1:1 [127].
The pinacol coupling of aromatic aldehydes and ketones was carried out in 20-62% and
10-91% yield respectively with Mg and Mg-MgCl
2
in water under ultrasound irradiation at
r.t. for 3-4 h. For example, 1,2-diphenyl-1,2-ethanediol, 1,2-di(p-methylphenyl)-1,2-
ethanediol and 1,2-di(p-methoxyphenyl)-1,2-ethanediol were obtained with 85%, 90% and
91% yield respectively using Mg-MgCl
2
at r.t for 3 h under ultrasound and higher than those
in stirring condition. Furthermore, when aromatic aldehydes with electron-withdrawing such
as the p-chlorobenzaldehyde, m-chlorobenzaldehyde and furfural were used as the substrates,
the pinacols were obtained in 70%, 65% and 60% respectively, while in Mg-NH
4
Cl the yield
of pinacols decreased dramatically. By comparison, the reaction activity induced by Mg in
pure water significantly lower than in MgCl
2
aqueous [128]. The coupling of aromatic
ketones showed very lower reactivity in the above two systems. While insteaded to Mg-
NH
4
Br (aq.), the coupling of acetophenone was successful coupling in 66% yield for 3 h with
sonication. The ratio of dl and meso of the corresponding 1,2-diols is 71/29, and no alcohol
was found during the reaction. The similar coupling yields of aromatic aldehydes were
obtained in the Mg-MgCl
2
(aq.) syntem, but the meso-isomer was increased [129]. It was
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 113
shown that Lewis acid not only affects the chemoselectivity of the reaction, but also the
diastereoselectivity of the pinacol.
At room temperature, the Mg-MgI
2
system has high chemoselectivity especially for
benzophenone, furaldehyde, α-acetonaphthone and β-acetonaphthone, to give the desired 1,2-
diols with 99%, 96%, 90% and 91% yields respectively within 20-60 min in a mixed solvent
of ether-benzene. The dl/meso ratio of the coupling products of α-acetonaphthone and β-
acetonaphthone were 8/2 and 7/3. We also observed the effect of different frequency of
ultrasound irradiation on this reaction. When the frequency was 25 kHz, the coupling of
benzaldehyde resulted the desired product in 56% yield in ethanol, while under 40 kHz and
59 kHz ultrasound irradiation, the pinacolization were completed with 49% and 35% yields
respectively [130]. It is shown that lower frequency of ultrasound irradiation improved the
result. The reason may be that the lower frequency condition creates the better cavitation.

3) Reductive Coupling of Aromatic Aldehydes and Ketones Induced by Aluminum
Powder in Aqueous Media
Khurana et al. reported pinacol coupling of aromatic aldehydes and ketones promoted by
aluminum in KOH aqueous solution in 1994 and 1996 respectively, and the corresponding
1,2-diols were produced in high yields [131]. But excess amount of alkali (the molar ratio of
substrate /KOH = 1/9) was used during the reaction. In 1999, Mečiarová et al. reported that
benzaldehyde can coupled into pinacol at a lower concentration of KOH aqueous solution
using ultrasonic probes [109]. The reaction time was shortened but the yield did not meet
Khurana‘s result. Furthermore, the yield was determined by
1
H NMR analysis, not the
isolated yield.
Under ultrasound irradiation the pinacol coupling reaction of aromatic aldehydes and
ketones was carried out in 60%-98% yield with aluminum in aqueous NaOH-MeOH at r.t.
within 20-30 min [132]. Among them, benzaldehyde, p-methoxybenzaldehyde and p-
methylbenzaldehyde were reacted smoothly with aluminum in aqueous NaOH-MeOH. The
corresponding pinacol coupling products were obtained in 91%, 89% and 88% yield
respectively, m-chlorobenzaldehyde and p-chlorobenzaldehyde gave nearly quantitative yield
of 1,2-diols. But o,p-dichorobenzaldehyde gives 61% pinacol only. The reason may be that
the steric hindrance around carbonyl group inhibits the coupling during the reaction. When
aromatic ketones such as p-methoxyacetophenone and p-chloroacetophenone were used as the
substrates, less pinacols and more alcohols were obtained, while the reaction with
cinnamaldehyde was unsuccessful in the same conditions.
Metal aluminum has a low first ionization potential (5.986 eV) and the presence of trace
fluoride ion can accelerate corrosion of aluminum. In 2000, Chen et al. reported that the
conversion of benzaldehyde was 100% (measured by
1
H NMR) by stirring for 16 h in the Al-
KF aqueous solution, and yield of pinacol was obtained in 87% [36d]. While under
ultrasound irradiation, benzaldehyde conversion will reach 99% within 1.5 h, 1,2-diphenyl-
1,2-ethanediol yield can reach 82%. But the coupling product of other aromatic aldehyde was
not as good as stirring conditions [198].

Zhi-Ping Lin

and Ji-Tai Li 114
4) Manganese Powder Induced Reductive Coupling of Aromatic Aldehydes and
Ketones in Aqueous Media
The pinacol coupling of aromatic aldehydes was carried out in 40-90% yield with
manganese in aqueous NH
4
Cl at r.t. for 2 h under ultrasound irradiation. The reactions in Mn-
MnCl
2
/THF:H
2
O(1:4) system gave pinacols in 30-95% yield at r.t. for 2-3 h under ultrasound
[133]. Compared with classical method, the main advantages of the present procedure are
shorter reaction time, less reagent quantity and higher yield. For example, 1,2-diphenyl-1,2-
ethanediol, and 1,2-di(p-chlorophenyl)-1,2-ethanediol were prepared previously in 65% and
64% yield respectively using manganese in aqueous NH
4
Cl at r.t. for 16 h, whereas under
ultrasound irradiation, 1,2-diphenyl-1,2-ethanediol and 1,2-di(p-chlorophenyl)-1,2-ethanediol
were obtained in 70% and 90% yield respectively at r.t. for 2 h. Compared with Mn-NH
4
Cl
(aq.)-THF system, the Mn-MnCl
2
(aq.)-THF system can lead to the higher chemoselectivity.
It is indicated that the aromatic aldehydes with electron-withdrawing substituents in the
benzene ring show higher reactivity and higher yield than those electron-donating
substituents. The coupling has lower stereoselectivity in the Mn-MnCl
2
(aq.)-THF system and
the ratio of dl/meso is about 3/2.
The Mn-HOAc-H
2
O system was less effective in pinacol coupling as the above-
mentioned two systems [199].

5) Reductive Coupling of Aromatic Aldehydes Induced by Vanadium (II) in Aqueous
Solution
Vanadium (II) complexes have been recognized to be highly capable of one–electron
reduction, thereby including radical reactions such as reduction of several organic substrates

[200] and pinacol-type reductive coupling [201].

In 1926, Conant reported the dimolecular
reduction of carbonyl compounds by vanadium and chromous salts

[202], but some aromatic
aldehydes were slowly reduced by vanadium salts in the presence of acid, alcohol or acetone.
In 1989, Pedersen reported the stereoselective coupling of two different types of substrates,
yet electronically similar aldehydes employing the well-characterized vanadium (II) complex,
[V
2
Cl
3
(THF)
6
]
2
[Zn
2
Cl
6
]; the major diastereomer in all of the cross coupling reactions is a
threo diol [203]. Hirao reported highly diastereoselective pinacol coupling of secondary
aliphatic aldehydes induced by Cp
2
VCl
3
/R
3
SiCl/Zn [69a]; and using VOCl
3
/Me
3
SiCl/Al
system [69c], six aromatic aldehydes gave desired pinacols in 49%-89% yields, their
diastereoselectivities were high (dl:meso≧9:1).
Pinacol coupling of aromatic aldehydes by aqueous vanadium (II) solution under
ultrasound irradiation at 15-35
o
C can lead to the corresponding pinacols in 78%-93% yields
within 15-30 min. The substituent group in the benzene ring has no significant effection on
the reactivity but the stereoselectivity. For example, when p-methylbenzaldehyde, p-
methoxybenzaldehyde, and piperonaldehyde as substrate, the ratio of dl and meso of 1,2-diols
was dl isomer, 91/9 and 92/8. While benzaldehyde and m-chlorobenzaldehyde as the
substrate, the ratio of dl and meso was about 72/38 and 67/33 respectively [134].
The optimization reaction condition and yield of pinacol coupling in aqueous under
ultrasound irradiation were summarized in Table 1.
Should be clear is that eithor the classical method or ultrasound, Sn can not reduce
aromatic aldehydes and ketones to vicinal diol. When the aldehydes and ketones with nitro-
group in the benzene ring as substrates, there were no pinacol obtained, but the nitro was
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 115
reduced to amino group. The pinacol coupling was difficult to go on under the above
mentioned conditions when the aldehydes and ketones with amino groups in the benzene ring.

Table 1. The optimization reaction condition and yield of pinacol coupling in aqueous
under ultrasound irradiation

Entry ArCHO Met/ (aq.)/ time
Isolated
yield, %
*dl/meso
1 C
6
H
5
CHO Al/NaOH-MeOH(aq.)/20 min 91[132]
VCl
2
/EtOH(aq.)/15 min 91[134] 72/28
Mg/MgCl
2
(aq.)/3 h 85[128] 31/69
2 4-CH
3
OC
6
H
4
CHO Al/NaOH-MeOH(aq.)/20 min 89[132]
Mg/NH
4
Cl(aq.)/3 h 95[127]
VCl
2
/EtOH(aq.)/30 min 89[134] 91/9
Mg/MgCl
2
(aq.)/3 h 91[128] 7/93
3 4-CH
3
C
6
H
4
CHO Al/NaOH-MeOH(aq.)/20 min 88[132] 71/29
Mg/NH
4
Cl(aq.)/3 h 95[127] 90/10
VCl
2
/EtOH(aq.)/30 min 85[134] 100/0
Zn/NaOH-MeOH(aq.)/30 min 92[124] 51/49
Mg/MgCl
2
(aq.)/3 h 90[128] 92/8
4 4-ClC
6
H
4
CHO Al/NaOH-MeOH(aq.)/20 min 98[132] 71/29
VCl
2
/EtOH(aq.)/25 min 92[134]
Zn/NaOH-MeOH(aq.)/30 min 97[124] 43/57
Mn/MnCl
2
/THF(aq.)/2 h

95[133] 50/50
5 3-ClC
6
H
4
CHO Al/NaOH-MeOH(aq.)/20 min 98[132]
VCl
2
/EtOH(aq.)/15 min 86[134] 67/33
Zn/NaOH-MeOH(aq.)/30 min 85[124] 55/45
Mn/MnCl
2
/THF(aq.)/2 h 86[133] 61/39
6 2-ClC
6
H
4
CHO VCl
2
/EtOH(aq.)/15 min 88[134] 61/39
7 2,4-Cl
2
C
6
H
3
CHO Zn/K10-ZnCl
2
(aq.)/THF/3 h 87[121] meso
8 3-BrC
6
H
4
CHO VCl
2
/EtOH(aq.)/15 min 93[134] 37/63
9 piperonaldehyde VCl
2
/EtOH(aq.)/25 min 87[134] 79/21
Zn/NaOH-MeOH(aq.)/40 min 79[124] 0/100
10 furaldehyde Mg-I
2
/ether-benzene/60 min 96[130] 57/43
11 PhCOPh Mg-I
2
/ether-benzene/30 min 99[130]
12 α-acetonaphthone Mg-I
2
/ether-benzene/60 min 90[130] 79/21
β-acetonaphthone Mg-I
2
/ether-benzene/60 min 91[130] 70/30
*dl/meso were determined by
1
H NMR.
2. Reductive Coupling of Aromatic Aldehydes and Ketones Using Low-
Valent Titanium

Low valent titanium is a highly reactive reagent and attracts increasing interest in
carbonyl-coupling reactions. High valent titanium reagent or complexes could be reduced by
some metal to corresponding low valent titanium complexes, which can induce some
aromatic aldehydes and ketones occurred the pinacol coupling reaction. In 1973, Mukaiyama
Zhi-Ping Lin

and Ji-Tai Li 116
firstly reported that TiCl
4
-Zn reduced aromatic aldehydes and ketones to produce the
corresponding 1,2-diols in high yield [135], but the stereoselectivity was not reported. With
improved of the preparation of low-valent titanium, the in-depth study was underwent and
there are many reports on the synthesis of 1,2-diol using low-valent titanium complex in
recent years [22, 39, 42, 43, 51, 136]. However, in spite of their potential utility, some of the
reported methods suffer from drawbacks such as expensive catalysts and critical reduction
conditions.
McMurry et al. [33] reported that coupling reaction induced by low valent titanium gave
pinacols at 0
o
C, but at reflux temperature, it gave alkenes through deoxygenation. In the
presence of ultrasonic irradiation, the coupling was carried out at room temperature, gave
pinacol in high yield, and improved the chemoselectivity and stereoselectivity. Besides, the
competing Cannizzaro reaction, giving alcohol and carboxylic acid, was not observed and
there was also no olefin formation arising from McMurry reactions.

1) Reductive Coupling of Aromatic Aldehydes Induced by TiCl
4
-M (Zn, Mg, Al)-THF
in CH
2
Cl
2

In 2001, Yamamoto et al. reported diastereoselective pinacol coupling of aldehydes
promoted by monomeric titanocene (III) complex Cp
2
TiPh [61]. Five aromatic aldehydes
given desired pinacol in 54-96% yields within 1-4 h. In 2000, Li et al. reported the 1,2-diols
were obtained in pinacol coupling mediated by TiCl
4
-Mg with a high stereoselectivity [42].
These systems of TiCl
4
-THF-Zn, TiCl
4
-THF-Al, TiCl
4
-THF-Mg can quickly reduce a
number of aromatic aldehydes to pinacol with high yields and high stereoselectivity under
ultrasound. Without ultrasound, the pinacols were obtained in lower yield. For example, using
TiCl
4
-THF-Zn under Ar stirring for 30 min, 1,2-diphenyl-1,2-ethanediol was previously
prepared in 57% yield [51]; using TiCl
4
-Et
2
O-Al and stirring for 38 h gave 1,2-diphenyl-1,2-
ethanediol in 50% yield [43]. Whereas under ultrasonication for only 5 min, in the presence
of TiCl
4
-THF-Zn, replacement of Ar by N
2
, 1,2-diphenyl-1,2-ethanediol was obtained in 96%
yield. TiCl
4
-THF-Al system provided 1,2-diphenyl-1,2-ethanediol in 90% yield for 20 min
[137]. Unfortunately, this method applies only to aromatic aldehydes with electron-donating
substituents in the benzene ring.
As shown in Table 2, the type of reduce metal has some effects on the reaction speed,
yield and product stereoselectivity. Al was proven to be more diastereoselective (dl/meso)
than Zn. The reaction in TiCl
4
-THF-Zn reduction system can be carried out in higher yields
and shorter reaction time, but lower stereoselectivity. While in TiCl
4
-THF-Al system, pinacol
coupling can be carried out in higher yields within 15-20 min, and the stereoselectivity was
also improved. Compared with the previous two systems, TiCl
4
-THF-Mg system was not
efficient to the reaction [137].

2) Reductive Coupling of Aromatic Aldehydes Induced by TiCl
3
-M (Al, Mg, Mn, Zn)-
EtOH
In 1982, Clerici et al. reported pinacol coupling of aromatic aldehydes and ketones
promoted by aqueous titanium trichloride in basic media [138]. The reaction was completed
in few minutes, but the reducing power of Ti
3+
/Ti
4+
system is strongly pH dependent, the
method has some limitations with respect to some aromatic aldehydes and ketones.
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 117
Clerici et al. again reported pinacolization of aromatic aldehydes mediated by titanium
trichloride in dichliromethane in 1996 [139]. The reaction was completed in high dl-
stereoselectivity, but aromatic aldehydes bearing an electron-donating group showed lower
reactivity. Recently, we reported the pinacolization mediated by TiCl
4
-M (Zn, Mg, Al)-THF
in CH
2
Cl
2
at room temperature under ultrasound irradiation. Eight pinacols were obtained in
33-98% yield within 4-35 min. All of the results stated above prompted us to study the
possibility of the pinacol coupling of aromatic aldehydes mediated by TiCl
3
-Mn-EtOH,
TiCl
3
-Mg-EtOH, TiCl
3
-Al-EtOH and TiCl
3
-Zn-EtOH systems under ultrasound [140]. The
results were summarized in Table 3.
As shown in the Table 3, the coupling of some aromatic aldehydes was carried out in
good yields and diastereoselectivity using TiCl
3
-M-EtOH under ultrasound irradiation.
Compared with the classic stirring for 30 min in TiCl
3
-CH
2
Cl
2
,

it could smoothly undergo that
the pinacol coupling of aromatic aldehydes carrying electron-withdrawing, and 1,2-diol was
obtained in higher yield in this procedure. Furthermore, aromatic aldehydes carrying electron-
donating substituents could also couple to pinacol in higher yield, which those did not
successed in TiCl
4
-THF-M system, but lower diastereoselectivity than those in latter system.
Improved diastereoselectivity has been observed in our system compared to the
analogous process in THF at room temperature [61]. When p-methylbenzaldehyde, p-
methoxybenzaldehyde as a substrate, the ratio of dl and meso of the 1,2-diols is 74:26 and
72:28 respectively in Yamamoto et al.
,
report. In the TiCl
3
-Al-EtOH system, the ratio of dl
and meso of the corresponding 1,2-diols is 91:9 and 8:92 respectively.

Table 2 The reductive coupling of aromatic aldehydes using TiCl
4
-THF-M (M: Zn、Al
or Mg) at r.t. in CH
2
Cl
2
under ultrasound irradiation

Entry Substrate
Reduction
system
a

Time,min Isolated yield,
%
dl/meso*
a C
6
H
5
CHO A 5 96 76/24
B 20 90 93/7
C 20 68 77/23
b 3-ClC
6
H
4
CHO A 4 98 82/18
B 15 96 97/3
C 30 87 92/8
c 4-ClC
6
H
4
CHO A 4 98 69/31
B 15 98 96/4
C 20 89 85/15
d 2,4-Cl
2
C
6
H
3
CHO A 6 98 51/49
B 25 92 97/3
C 25 84 32/68
e 2-ClC
6
H
4
CHO A 5 97 74/26
B 20 92 34/66
C 20 79 52/48
f 3-BrC
6
H
4
CHO A 5 98 82/18
B 15 95 97/3
C 20 84 90/10
a
A: TiCl
4
-THF-Zn; B: TiCl
4
-THF-Al; C: TiCl
4
-THF-Mg; *dl/meso were determined by
1
H NMR.

Zhi-Ping Lin

and Ji-Tai Li 118
Table 3 The reductive coupling of aromatic aldehydes using TiCl
3
-M (Mn、Mg、Al or
Zn)-EtOH under ultrasound irradiation

Entry Substrate Systems
a
Time, min Isolated
yield, %
dl/meso
*

a C
6
H
5
CHO A 40 64 73/27
B 40 75 68/32
C 60 75 63/37
D 40 89 63/37
b 2-ClC
6
H
4
CHO A 40 56 37/63
B 30 56 27/73
C 45 68 20/80
D 35 88 45/57
c 3-ClC
6
H
4
CHO A 40 67 41/59
B 20 85 28/72
C 40 79 66/40
D 35 92 53/47
d 2,4-Cl
2
C
6
H
3
CHO A 50 86 18/82
B 30 75 20/80
C 30 71 21/79
D 40 79 18/72
e 4-ClC
6
H
4
CHO A 40 69 38/62
B 30 92 25/75
C 30 79 66/34
D 40 92 65/35
f 3-BrC
6
H
4
CHO A 60 63 49/52
B 15 95 44/56
C 35 82 60/40
D 35 91 46/54
g 4-CH
3
C
6
H
4
CHO A 40 70 84/16
B 30 89 63/37
C 80 69 91/9
D 35 87 47/53
h 4-CH
3
OC
6
H
4
CHO A 40 72 74/26
B 40 81 66/34
C 80 62 8/92
D 45 83 60/40
i 3,4-(OCH
2
O)C
6
H
3
CHO A 50 62 89/11
B 15 86 86/14
C 50 69 66/34
D 30 87 66/34
j Furaldehyde B 30 86 55/45
C 50 58 59/41
a
A:TiCl
3
-Mn-EtOH, B:TiCl
3
-Mg-EtOH, C:TiCl
3
-Al-EtOH, D:TiCl
3
-Zn-EtOH; *dl/meso were
determined by
1
H NMR.

Some Applications of Ultrasound Irradiation in Pinacol Coupling… 119
The coupling of some aromatic aldehydes was also carried out in good yield using TiCl
3
-
Al in water under ultrasound irradiation. For example, 1,2-bis(p-methylphenyl)-1,2-
ethanediol was previously prepared in 35% yield using TiCl
3
-CH
2
Cl
2
under stirring for 30
min [139], whereas under ultrasonication, 1,2-bis(p-methylphenyl)-1,2-ethanediol was
obtained with 52% yield. In Bhar and Panja’ [36b] report, 1,2-bis(o-chlorophenyl)-1,2-
ethanediol was prepared in 62% yield using Al-NaOH-H
2
O under stirring for 120 min,
whereas in this procedure, 1,2-bis(o-chlorophenyl)-1,2-ethanediol was obtained with 72%
yield within 45 min. It is noteworthy that the reagents used are readily available inexpensive
and stable to air oxidation, and the method is easier and more convenient compared with
those so far reported.
It was shown that lower frequency of ultrasound irradiation improved the yield of pinacol
coupling. The type of reducing-metal is a very important factor in the reaction, which related
to the reduction of high valent titanium ability of metal. Furthermore, the type of solvent or
ligands has a significant impact on the stereoselectivity of the products.
The following sequence of reaction appears to be a reasonable rationalization for the
formation of the products [136, 138] (Scheme 2, The reductive coupling of aldehydes induced
by TiCl
4
-M). The dl-diastereoselection could be explained by the initial generation of
intermediate radical species whose oxygen atoms of the two ketyl radicals are linked side by
side to the low valent titanium species and their alkyl groups are located anti each other to
minimize the steric interaction. That is dl-pinacols are preferentially formed by an internal
carbon-carbon coupling of 'titanium-bridged' intermediate A which is formed readily due to
the highly coordinating ability of low valent titanium species. In the absence of 'titanium-
bridged', the radicals of intermediate B, for which steric and polar effects appear to be
important, lead predominantly to the meso dimmers.

R H
O
+ + M
R
Ti
O
H
.
O
Ti
.
H
R
Ti-O interaction
R
Ti
O
H
.
O
Ti
.
H
R
intermediate B
"Ti-bridged"
intermediate A
R
R
H
H
OH
HO
R
R
H
H
OH
HO
dl selective
meso selective
TiCl
4

Scheme 2.
Zhi-Ping Lin

and Ji-Tai Li 120
CONCLUSION
Cavitation produces an unusual method for fundamental studies of chemistry and physics
under extreme conditions, and sonochemistry provides a unique interaction of energy and
matter. One may be optimistic that the unusual reactivities caused by ultrasound will find
important industrial application in the years to come.
Ultrasound irradiation as being of great value in pinacol coupling reaction has been
amply demonstrated by the many examples presented in this chapter. It improved the
chemoselectivity significantly of the reactions, but the stereoselectivity of the reaction was
expected to be further improved. The largest current drawback of the reaction is its
mechanism, diastereoselectivity, chiral synthesis and resolution of chiral isomer. As a
consequence, efficient reaction conditions have been required to control the stereochemistry
of the 1,2-diols. Recent efforts have focused on the development of efficient and
environmentally friendly reagents and reaction systems to improve the reactivity of the
reagents and diastereoselectivity of the products. We look forward to increasing the uses for
ultrasound irradiation in organic synthesis reaction.
REFERENCES
[1] Brown, B.; Goodman, J. E. High intensity ultrasonics, Ilife Books Ltd, London, 1965.
[2] El‘Piner, I. E. Ultraound: physical, chemical and biological effects, Consultants
Bureau, New York, 1964.
[3] Suslick, K. S. Ultraound: its chemical, physical and biological effects, VCH, 1988.
[4] Mason, T. J.; Lorimer, J. P. Sonochemistry: theory, applications and uses of ultrasound
in chemistry, Ellis Horwood, 1989.
[5] Chemistry with Ultrasound, Ed. Mason, T. J. Critical Reports in Applied Chemistry No
28, Society for Chemical Industry, 1990.
[6] Advances in Sonochemistry, Volume 1, Ed. Mason, T. J. JAI Press, 1990.
[7] Sonochemistry: the uses of ultrasound in chemistry, Ed. Mason, T. J. Royal Society of
Chemical, 1990.
[8] Ley, S. V.; Low, C. M. R. Ultrasound in Synthesis, Springer-Verlag, 1989.
[9] Rechards, W. T.; Loomis, A. L. J. Am. Chem. Soc. 1927, 49, 3086.
[10] Porfer, C. W.; Young, L. J. Am. Chem. Soc. 1938, 60, 1497.
[11] Renaud, P. Bull. Soc. Chem. Fr. 1950, 1044.
[12] Han, B. H.; Boudjouk, P. J. Org. Chem. 1982, 47, 5030.
[13] Feng R.; Zhao, Y. Y.; Bao, C. G. Ultrason. Sonochem. 1997, 4, 183.
[14] Cognet, P.; Wilhelm, A. M.; Delmas, H.; Lyazidi, H. A.; Fabre, P. L. Ultrason.
Sonochem. 2000, 7, 163.
[15] Singh, J., Kaur; J., Nayyar, S.; Bhandari, M.; Kad G. L. Indian J. Chem. 2001, 40B,
386.
[16] Yadav, S. J.; Reddy, B. V. S.; Reddy, K. B. Raj, K. R.; Prasad, A. R. J. Chem. Soc.
Perkin Trans 1 2001, 1939.
[17] Qin, Z. H.; Chen, F. H.; Xie, Y. Y. Progress In Chemistry 1998, 10(1), 63. (b) Bremner,
D. H. Ultrason. Sonochem. 1994, 1, S119. (c) Boldyrev, V. V. Ultrason. Sonochem.
1995, 2, S143. (d) Price, G. J. Ultrason. Sonochem. 2003, 10, 277.
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 121
[18] Li, J. T.; Zang, H. J. J. Hebei Univ. (Natural Science Edition) 2000, 20, 96. (b) Li, J. T.;
Wang, Y. H. Chem. Reagent (Huaxue Shiji) 1987, 9, 98. (c) Bian, Y. J.; Li, J. T.; Li, T.
S. Chin. J. Org. Chem. 2002, 22, 227.
[19] Mason, T. J. Practical Sonochemistry, Ellis, Horwood Limited, 1991. (b) Mason, T. J.;
Peters, D. Practical Sonochemistry, Second Ed., Ellis Horwood, London, 2002.
[20] Luche, J. L. Synthetic Organic Sonochemistry, Kluwer Academic/Plenum Publishers,
Hingham, 1998. (b) Feng, R.; Li, H. M. Sonochemistry and its application, Science and
Technology Publisher of Anhui, Hefei, 1992.
[21] Mason, T. J. Advance in Sonochemistry, 1990(Vol 1), 1991(Vol 2), 1993(Vol 3),
1996(Vol 4), 1999(Vol 5), 2001(Vol 6).
[22] Robertson, G. M. Pinacol coupling reaction. in Comprehensive Organic Synthesis, Ed.
Trost, B. M.; Fleming, I., Pergamon, New York, Vol.3, p.563-611, 1991.
[23] Rieke, R. D. Kim, S. H. J. Org. Chem. 1998, 63, 5235.
[24] Seyden-Penne, J. Chiral Auxiliaries and Ligands in Asymmetric Synthesis, John Wiley
and Sons, New York, 1995.
[25] (a)Lohray, B. B. Tetrahedron:Asymmetry, 1991, 3, 1317. (b) Nicolaou, K. C.; Liu, J. J.;
Yang, Z; Ueno, H.; Guy, R. K.; Sorensen, E. J.; Claiborne, C. F.; Hwang, C. K.;
Nakada, M.; Nantermet, P. G. J. Am. Chem. Soc. 1995, 117, 634. (c) Shiina, I.;
Nishimura, T.; Ohkawa, N.; Sakoh, H.; Nishimura, K.; Saitoh, K.; Mukaiyama, T.
Chem. Lett. 1997, 419.
[26] Kammermeier, B.; Beck, G.; Holla, W.; Jacobi, D.; Napierski, B.; Jendralla, H. Chem.
Eur. J. 1996, 2, 307. (b) Kammermeier, B.; Beck, G.; Jacobi, D.; Jendralla, H. Angew.
Chem., Int. Ed. Engl. 1994, 33, 685.
[27] Sun, X. L.; Li, X. Y.; Zhang, S. Y. Chemistry (Huaxuetongbao) 1998, 12, 10.
[28] Jacoben, E. N.; Marko, I.; Mungall, W. S.; Schroder, G.; Sharpless, K. B.; J. Am. Chem.
Soc. 1988, 110, 1968. (b) Calo, V.; Nacci, A,; Monopoli, A.; Fanizzi, A. Org. Lett.
2002, 4, 2561. (c) Fisher, A. J.; Kerrigan, F. Synth. Commun. 1998, 28, 2959.
[29] Caron, M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 1557.
[30] Davis, F. A.; Hague, M. S.; Przeslawski, R. M. J. Org. Chem. 1989, 54, 2021.
[31] Dondoni, A.; Fantin, G.; Fogagnolo, M.; Mayo, P. Advances in organic chemistry,
Interscience: New York, 1960, Vol 2, pp 361.
[32] Fittig, R. Ann. 1859, 110, 23.
[33] McMurry, J. E. Chem. Rev. 1989, 89, 1513.
[34] Chatterjee, A. Joshi, N. N. Tetrahedron 2006, 62, 12137.
[35] Zhang, W. C.; Li, C. J. J. Org. Soc., Perkin. Trans. 1 1998, 3131. (b) Gomberg, M.;
Bachmann, W. E. J. Am..Chem. Soc. 1927, 49, 236.
[36] Schreibmann, A. A. P. Tetrahedron Lett. 1970, 4271. (b) Bhar, S.; Panja, C. Green
Chem. 1999, 1, 253. (c) Sahade, D. A.; Kawaji, T.; Sawada, T.; Mataka, S.; Thiemann,
T.; Tsukonok, T.; Tashiro, M. J. Chem. Res., Synop. 1999, 210. (d) Li, L. H.; Chan, T.
H. Org. Lett. 2000, 2, 1129.
[37] Wang, Z. Y.; Yuan, S. Z.; Zha, Z. G.; Zhang, Z. D. Chin. J. Chem. 2003, 21, 1231.
[38] Wang, C.Y.; Pan, Y. J.; Wu, A. X. Tetrahedron 2007, 63, 429.
[39] Dieter, L. Chem. Rev. 1989, 883.
[40] Corey, E. J.; Danheiser, R. L.; Chandrasekaran, S. J. Org. Chem. 1976, 41, 260.
[41] Pierrot, M.; Pons, J. M.; Santelli, M. Tetrahedron Lett. 1988, 29, 5925.
Zhi-Ping Lin

and Ji-Tai Li 122
[42] Li, T. Y.; Wang, L. P.; Zhang, T.; Li, Y. X.; Wang, Z. M. Chem. J. Chin. Univ. 2000,
21, 1391.
[43] Hu,Y. L.; Du, Z. Y.; Wang, J. X.; Xi Y. S.; Gu, S. J. Synth. Commun. 1998, 28, 3299.
[44] Wang, J. X.; Du, Z. Y.; Hu, Y. L. J. Northwest Norm. Univ. (Nat. Sci.) 2000, 36, 46.
[45] Li, T. Y.; Wang, L. P.; Cui, W.; Zhao, J. Z.; Wang, Z. M. Chem. Research Chin. Univ.
2000, 16, 320.
[46] Gansäuer, A.; Bauer, D. J. Org. Chem. 1998, 63, 2070.
[47] Bandini, M.; Cozzi, P. G.; Morganti, S.; Umani-Ronchi, A. Tetrahedron Lett. 1999, 40,
1997.
[48] Li, Y. G.; Tian, Q. S.; Zhao, J.; Feng, Y.; Li, M. J.; You, T. P. Tetrahedron: Asymmetry
2004, 15, 1707.
[49] Dunlap, M. S.; Nicholas, K. M. Synth. Commun. 1999, 29, 1097.
[50] Dunlap, M. S.; Nicholas, K. M. J. Organmet. Chem. 2001, 630, 125.
[51] Li, T. Y.; Cui, W.; Liu, J. G.; Zhao, J. Z.; Wang, Z. M. J Chem. Soc., Chem. Commun.
2000, 139.
[52] Gansauer, A. J. Chem. Soc., Chem. Commun. 1997, 457.
[53] Chatterjee, A.; Bennur, T. H.; Joshi, N. N. J. Org. Chem. 2003, 68, 5668.
[54] Tsuritani, T.; Ito, S.; Shinokubo, H.; Oshima, K. J. Org. Chem. 2000, 65, 5066.
[55] Shimizu, M.; Goto, H.; Hayakawa. R. Org. Lett. 2002, 4, 4097.
[56] Nayak, S. K.; Banerji, A. J. Org. Chem. 1991, 56, 1940.
[57] Rele, S.; Chattopadhyay, S.; Nayak, S. K. Tetrahedron Lett. 2001, 42, 9093.
[58] Balu, N.; Nayak, S. K.; Banerji, A. J. Am. Chem. Soc. 1996, 118, 5932.
[59] Lipski, T. A.; Hilfiker, M. A.; Nelson, S. G. J. Org. Chem. 1997, 62, 4566.
[60] Yamamoto, Y.; Hattori, R.; Itoh, K. J Chem. Soc., Chem. Commun. 1999, 825.
[61] Yamamoto, Y.; Hattori, R.; Miwa, T.; Nakagai, Y.; Kubota, T.; Yamaoto, C.; Okamoto,
Y.; Itoh, K. J. Org. Chem. 2001, 66, 3865.
[62] McMurry, J. E.; Rico, J. G. Tetrahedron Lett. 1989, 30, 1169.
[63] McMurry, J. E.; Siemers, N. O. Tetrahedron Lett. 1993, 34, 7891.
[64] Barden, M. C.; Schwartz, J. J. Am. Chem. Soc. 1996,118, 5484.
[65] Paradas, M.; Campa a, A. G.; Est vez, R. E.; Cienfuegos, L. l.; Jim nez, T.; Robles,
R.; Cuerva, J. M.; Oltra, J. E. J. Org. Chem. 2009, 74, 3616. (b) Bensari, A.; Renaud, J.
L.; Riant, O. Org. Lett. 2001, 3, 3863. (c) Gansäuer, A. Synlett 1997, 363. (d) Oller-
López, J. L.; Campaña, A. G.; Cuerva, J. M.; Oltra, J. E. Synthesis 2005, 15, 26192.
[66] Enders, D.; Ullrich, E. C. Tetrahedron: Asymmetry 2000, 11, 3861.
[67] Hashimoto, Y.; Mizuno, U.; Matsuoka, H.; Miyahara, T.; Takakura, M.; Yoshimoto,
M.; Oshima, K.; Utimoto, K.; Matsubara, S. J. Am. Chem. Soc. 2001, 123, 1503.
[68] Mukaiyama T, Kagayama A, Igarashi K. Chem. Lett. 2000, 336. (b) Matsubara, S.;
Hashimoto, Y.; Okano, T.; Utimoto, K. Synlett 1999, 1411. (c) Duan, X. F.; Feng, J. X.;
Zi, G. F.; Zhang, Z. B. Synthesis 2009, 277. (d) Sana, S. Synlett 2002, 364.
[69] Hirao, T.; Asahara, M.; Muguruma, Y.; Ogawa, A. J. Org. Chem. 1998, 63, 2812. (b)
Hatano, B.; Ogawa, A.; Hirao, T. J. Org. Chem. 1998, 63, 9421. (c) Hirao, T.; Hatano,
B.; Imamoto, Y.; Ogawa, A. J. Org. Chem. 1999, 64, 7665. (d) Xu, X. L.; Hirao, T. J.
Org. Chem. 2005, 70, 8594. (e) Sun, J. T.; Dai, Z. Y.; Li, C. S.; Pan, X.; Zhu C. J. J.
Organometal. Chem. 2009, 694, 3219. (f) Xu, X.; Hirao, T. Synfacts 2005, 340.
[70] Hirao, T.; Hasegawa, T.; Muguruma, Y.; Ikeda, I. J. Org. Chem. 1996, 61, 366.
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 123
[71] Hirao, T.; Takeuchi, H.; Ogawa, A.; Sakurai H. Synlett 2000, 1658.
[72] Konradi, A. W.; Kemp, S. J.; Pedersen, S. F. J. Am. Chem. Soc. 1994, 116, 1316.
[73] SvatoŠ, A.; Boland, W. Synlett 2000, 549. (b) Halterman, R. L.; Porterfield, J. P.;
Mekala, S. Tetrahedron Lett. 2009, 50, 7172. (c) Svato, A.; Boland, W. Synlett 1998,
549.
[74] Li, C. J.; Meng, Y.; Yi, X. H.; Ma, J. H.; Chan, T. H. J. Org. Chem. 1997, 62, 8632.
[75] Li, C. J.; Meng, Y.; Yi, X. H. J. Org. Chem. 1998, 63, 7498.
[76] Inoue, H.; Suzuki, M.; Fujimoto, N. J. Org. Chem. 1979, 44, 1722.
[77] Ito, K.; Nakanishi, S.; Otsuji, Y. Chem. Lett. 1980, 1141.
[78] Shi, L.; Fan, C. A.; Tu, Y. Q.; Wang, M.; Zhang, F. M. Tetrahedron 2004, 60, 2851.
[79] Wang, L.; Sun, X. H.; Zhang, Y. M.; J. Chem. Res., Synop. 1998, 336.
[80] Liu, X.; Zhang, Y. M. Chin. J. Org. Chem. 2003, 23, 92.
[81] Liu, S. M.; Li, J. T.; Bian, Y. J.; Yang, J. H.; Li, T. S. Chin. J. Org. Chem. 2002, 22,
675.
[82] Groth, U.; Jeske, M. Chem.Int. Ed. 2000, 39, 574.
[83] Groth, U.; Jeske, M. Synlett 2001, 129.
[84] Yamada, R.; Negoro, N. Tetrohedron Lett. 1997, 38, 3271. (b) Banik, B. K.; Banik, I.;
Aounallah, N.; Castillo, M. Tetrahedron Lett. 2005, 46, 7065. (c) Aspinall, H. C.;
Greeves, N.; Valla, C. Org. Lett. 2005, 7, 1919. (d) Matsukawa, S.; Hinakubo, Y. Org.
Lett. 2003, 5, 1221.
[85] Ding, Z. B.; WU, S. H. Chin. J. Org. Chem. 1997, 17, 165.
[86] Wang, L.; Zhang, Y. M. Terahedron 1998, 54, 11129. (b) Wang L.; Zhang Y. M. Synth.
Commun. 1998, 28, 3991.
[87] Talukdar, S.; Fang, J. M. J. Org. Chem. 2001, 66, 330.
[88] Nomura, R.; Matsuno, T.; Endo, T. J. Am. Chem. Soc. 1996, 118, 11666.
[89] Taniguchi, N.; Uemura, M. Tetrahedron 1998, 54, 12775.
[90] Hou, Z.; Takamine, K.; Aoki, O.; Shiraishi, H.; Fujiwara, Y.; Taniguchi, H. J. Org.
Chem. 1988, 53, 6077.
[91] Shimada, H.; Qu, J. P.; Matsuzaka, H.; Ishii, Y.; Hidai, M. Chem. Lett. 1995, 671.
[92] Maury, O.; Villiers, C.; Ephritikhine, Michel. Tetrahedron Lett. 1997, 38, 6591.
[93] Khan, R. H.; Mathur, R. K.; Ghosh, A. C. Synth. Commun. 1997, 27, 2193.
[94] Hays, D. S.; Fu, G. C. J. Am. Chem. Soc. 1995, 117, 7283.
[95] Bolourtchian M, Zadmard R, Saidi M. Synth. Commun. 1998, 28, 2017.
[96] Schonberg, A.; Mustafa, A. Chem. Rev. 1947, 40, 181. (b) Moore, W. M.; Hammond,
G. S.; Foss, R. P. J. Am. Chem. Soc. 1961, 83, 2789. (c) Hammond, G. S.; Baker, W. P.;
Moore, W. M. J. Am. Chem. Soc. 1961, 83, 2795.
[97] Pitts, J. N.; Letsinger, R. L.; Taylor, R. P.; Patterson, J. M.; Recktenwald, G.; Maktin,
R. B. J. Am. Chem. Soc. 1959, 81, 1068.
[98] Cohen, S. G.; Parola, A.; Parsons, G. H. Chem. Rev. 1973, 73, 141.
[99] Seeback, D.; Daum, H. J. Am. Chem. Soc. 1971, 93, 2795.
[100] Bradshaw, J. S. J. Org. Chem. 1966, 31, 237.
[101] Stocker, J. H.; Kern, D. H. J. Org. Chem. 1968, 33, 291.
[102] Ji, S. J.; Matsushita, M.; Takahashi, T. T.; Horiuchi, C. A. Tetrahedron Lett. 1999, 40,
6791.
[103] Li, J. T.; Yang, J. H.; Han, J. F.; Li, T. S. Green Chem. 2003, 54, 433.
[104] Stocker, J. H.; Jenevein, R. M. J. Org. Chem. 1968, 33, 294.
Zhi-Ping Lin

and Ji-Tai Li 124
[105] Carbajo, J.; Calvente, J. J.; Andreu, R.; Roldan, E.; Dominguez, M. J. Electroanal.
Chem. 2000, 482, 102.
[106] Zhang, S. M.; Li, H.; Zhang, X. C.; Li, B. Q.; Wu, S. H.; Huang, W. P.; Liu, Z. G.;
Feng, Y. Chin. J. Org. Chem. 2002, 22, 603.
[107] Lim, H. J.; Keum, G.; Kang, S. B.; Chung, B. Y.; Kim, Y. Tetrahedron Lett. 1998, 39,
4367.
[108] Ogawa, A.; Takeuchi, H.; Hirao, T. Tetrahedron Lett. 1999, 40, 7113.
[109] Mečiarová, M.; Toma, Ś. Green Chem. 1999, 1, 257.
[110] Basu, M. K.; Becker, F. F.; Banik, B. K. J. Chem. Research (S) 2000, 406.
[111] Joma, S.; Gaplovsky, A.; Luche, J. L. Ultrason. Sonochem. 2001, 8, 201.
[112] Gaplovsky, A.; Gaplovsky, M.; Toma, S.; Luche, J. L. J. Org. Chem. 2000, 65, 8444.
[113] Cognet, P.; Ghanem-Lakhal, A.; Berlan, J.; Wilhelm, A. M.; Delmas, H.; Fabre, P. L.
Chem. Eng. Sci. 2000, 55, 2571.
[114] Li, J. T.; Yang, J. H.; Li, T. S. Chin. J. Org. Chem. 2004, 24(11), 1340.
[115] Li, J. T.; Wang, S. X.; Chen, G. F.; Li, T. S. Current Organic Synthesis 2005, 2, 4156.
[116] Li, Y. G.; Jiang, C. S.; You, T. P. http://hxtb.icas.ac.cn/col/2001/index.htm 2000-09-
04/2000-11-21.
[117] Tanaka, K.; Kishigami, S.; Toda, F. J. Org. Chem. 1990, 55, 2981.
[118] Delair, P.; Luche, J. L. J. Chem. Soc., Chem. Commun, 1989, 398.
[119] Mečiarová, M.; Toma, Ś.; Babiak, P. Chem. Pap. 2001, 55, 302; Chem. Abstr. 2002,
136, 325277r.
[120] Zang, H. J.; Li, J. T.; Ning, N.; Wei, N.; Li, T. S. Indian J. Chem. 2002, 41B, 1078.
[121] Zang, H. J.; Li, J. T.; Bian, Y. J.; Li, T. S. Chem. J. Inter. 2003, 5, 8.
[122] Yang, J. H.; Li, J. T.; Zhao, J. L.; Li, T. S. Synth. Commun. 2004, 34, 993.
[123] Li, J. T.; Yang, J. H.; Chen, Y. X.; Li, T. S. J. Chem. Research(S) 2004, 494.
[124] Bian, Y. J.; Liu, S. M.; Yang, J. H.; Li, J. T. Chin. J. Synth. Chem. 2004, 12, 429.
[125] Zhang, W. C.; Li, C. J. J. Org. Chem. 1999, 64, 3230.
[126] Bian, Y. J.; Han, X. F.; Liu, S. M.; Li, J. T. Chin. J. Org. Chem., 2003, 23, 1356.
[127] Li, J. T.; Bian, Y. J.; Zang, H. J.; Li, T. S. Synth. Commun. 2002, 32, 547.
[128] Li, J. T.; Bian, Y. J.; Liu, S. M.; Li, T. S. Indian J. Chem. 2004, 42B, 196.
[129] Li, J. T.; Chen, Y. X.; Li, T. S. Synth. Commun. 2005, 35, 2831.
[130] Wang, J. S.; Li J. T.; Lin Z. P.; Li T. S. Synth. Commun. 2005, 35, 1419.
[131] Khurana, J. M.; Sehgal, A. J. Chem. Soc., Chem. Commun. 1994, 571. (b) Khurana, J.
M.; Sehgal, A.; Gogia, A.; Manian, A.; Maikap, G. C. J. Chem. Soc., Perkin Trans.1.
1996, 2213.
[132] Bian, Y. J.; Liu, S. M.; Li, J. T.; Li, T. S. Synth. Commun. 2002, 32, 1169.
[133] Li, J. T.; Bian, Y. J.; Liu, S. M.; Li, T. S. Chin. J. Org. Chem. 2003, 23, 479.
[134] Wang, S. X.; Wang, K.; Li, J. T. Synth. Commun. 2005, 35, 2387.
[135] Mukayama, T.; Sato, T; Hanna. J. Chem. Lett. 1973, 1041.
[136] Mukaiyama, T.; Yoshimura, N.; Igarshi, K.; Kagayama, A. Tetrahedron 2001, 57,
2499.
[137] Li, J. T.; Yang, J. H.; Li, T. S. Chin. J. Org. Chem. 2003, 23, 1428. (b) Li, J. T.; Chen,
Y. X.; Li, T. S. J. Chem. Research(S) 2005, 361.
[138] Clerici, A.; Porta, O. Tetrahedron Lett. 1982, 23, 3517.
[139] Clerici, A.; Clerici, L.; Porta, O. Tetrahedron Lett. 1996, 37, 3035.
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 125
[140] Li, J. T.; Chen, Y. X.; Chang, R. X.; Li, T. S. J. Chem. Res.(S) 2005, 784. (b) Li, J. T.;
Lin, Z. P.; Li, T. S. Ultrason. Sonochem. 2005, 12, 349. (c) Li, J. T.; Lin, Z. P.; Li, T. S.
Synth. Commun. 2004, 34, 4339.
[141] Kappe, C. O. Tetrahedron 1993, 49, 6937.
[142] Li, J. T.; Han, J. F.; Yang, J. H.; Li, T. S. Ultrason. Sonochem. 2003, 10, 119.
[143] Wang, J. S.; Li, J. T.; Lin, Z. P. Lett. Org. Chem. 2006, 3, 523.
[144] Fu, N. Y.; Yuan, Y. F.; Cao, Z.; Wang, S. W.; Wang, J. T.; Peppe, C. Tetrahedron
2002, 58, 4801.
[145] Kumar, H.; Parmar, A. Ultrason. Sonochem. 2008, 15, 129.
[146] Li, J. T.; Han, J. F.; Li, T. S. J. Chem. Res.(S) 2004, 160.
[147] Li, J. T.; Han, J. F.; Lin, Z. P.; Li, T. S. Chin. J. Org. Chem. 2004, 24, 675.
[148] Li, J. T.; Lin, Z. P.; Han, J. F.; Li, T. S. Synth. Commun. 2004, 34, 2623.
[149] Garcia Navio, J. L.; Lorente, A.; Soto, J. L. Heterocycles 1982, 19, 305.
[150] Stefani, H. A.; Oliveira, C. B.; Almeida, R. B.; Pereira, C. M. P.; Braga, R. C.; Cella,
R.; Borges, V. C.; Savegnago, L.; Nogueira, C. W. Eur. J. Medicinal Chem. 2006, 41,
513.
[151] Ji, S. J.; Shen, Z. L.; Gu, D. G.; Wang, S. Y. J. Organometal. Chem. 2004, 689, 1843.
[152] Zhou, W. J.; Ji, S. J.; Shen, Z. L. J. Organometal. Chem. 2006, 691, 1356.
[153] Li, J. T.; Lin, Z. P. Ultrason. Sonochem. 2008, 15, 265.
[154] Li, J. T.; Xu, W. Z.; Chen, G. F.; Li, T. S. Ultrason. Sonochem. 2005, 12, 473.
[155] Reddy, D. B.; Padmavathi, V.; Reddy, M. M. Indian J. Chem. 1992, 31B, 407.
[156] McNulty, J.; Steere, J. A.; Wolf, S. Tetrahedron Lett. 1998, 39, 8013.
[157] Li, J. T.; Zhang, H. J.; Meng, L. H.; Li, L. J.; Yin, Y. H.; Li, T. S. Ultrason. Sonochem.
2001, 8, 93.
[158] Sager, J. M.; Saharia, G. S. J. Ind. Chem. Soc. 1957, 34, 898.
[159] Li, J. T.; Li, T. S.; Li, L. J.; Cheng, X. Ultrason. Sonochem. 1999, 6, 199.
[160] Popp, F. D. J. Org. Chem. 1960, 25, 646.
[161] Wang, S. X.; Li, J. T.; Yang, W. Z.; Li, T. S. Ultrason. Sonochem. 2002, 9, 159.
[162] Xu, W. Z.; Chen, G. F.; Han, J. F.; Li, T. S.; Li, J. T. Chem. Indian. J. 2003, 1, 109.
[163] Jin, T. S.; Ma, Y. R.; Li, T. S. Indian J. Chem. 1999, 38B, 109.
[164] Dippy, J. F. J.; Lewis, R.L. Rec. Trav. Chim. 1937, 56, 1000 (CA: 32, 5215).
[165] Calvino, V.; Picallo, M.; Lopez-Peinado, A. J.; Martin-Aranda, R. M.; Duran-Valle, C.
J. Appl. Surface Sci. 2006, 252, 6071.
[166] Ding, L.; Wang, W.; Zhang, A. Ultrason. Sonochem. 2007, 14, 563.
[167] Toda, F. Tanaka, K. Hamai, K. J. Chem. Soc. Perkin Trans 1 1990, 3207.
[168] Li, J. T.; Chen, G. F.; Wang, J. X.; Li, T. S. Synth. Commun. 1999, 29, 965.
[169] Li, J. T.; Yang, W. Z.; Chen, G. F.; Li, T. S. Synth. Commun. 2003, 33, 2619.
[170] Polackova, V.; Tomova, V.; Elecko, P.; Toma, S. Ultrason. Sonochem. 1996, 3, 15. (b)
Wang, L.; Li, J. T.; Wang, J. S.; Xu, W. Z. Chem. Indian J. 2005, 1, 621. (c) Entezari,
M.H.; Shameli, A.A. Ultrason. Sonochem. 2000, 7, 169.
[171] Ali, M. M.; Sana, S.; Tasneem; Rajanna, K. C.; Saiprakash, P. K. Synth. Commun.
2002, 32, 1351.
[172] Shriner, R. L. Org. React. 1946, 1, 1. (b) Rathke, M. W. Org. React. 1975, 22, 423. (c)
Gensler, W. J. Chem. Rev. 1957, 57, 265. (d) Diaper, D. G. M.; Kuksis, A. Chem. Rev.
1959, 59, 89.
Zhi-Ping Lin

and Ji-Tai Li 126
[173] Becker, D.; Brodsky, N.; Kalo, I. J. Org. Chem. 1978, 43, 2557. (b) Barco, A.; Benett,
S.; Pollini, G. P. J. Org. Chem. 1980, 45, 4776. (c) Klipa, D. K.; Hart, H. J. Org. Chem.
1981, 46, 2815.
[174] Bang, K.; Lee, K.; Park, Y. K.; Lee, P. H. Bull. Korean Chem. Soc. 2002, 23, 1272.
[175] Tu, S. J.; Jiang, H.; Zhuang, Q. Y.; Liao, C. B.; Shi, D. Q.; Wang, X. S.; Gao, Y. Chin.
J. Org. Chem. 2003, 23, 488.
[176] Jin, T. S.; Xiao, J. C.; Wang, S. J.; Li, T. S.; Song, X. R. Synlett 2003, 2001.
[177] Han, J. F.; Li, J. T.; Li, T. S. Chem. Indian J. 2004, 1, 562.
[178] Li, J. T.; Xu, W. Z.; Yang, L. C.; Li, T. S. Synth. Commun. 2004, 34, 4565.
[179] Wang, S. X.; Wang, W.; Li, J. T. E J. Chem. 2005, 2, 121.
[180] Wang, S. X.; Li, Z. Y.; Zhang, J. C.; Li, J. T. Ultrason. Sonochem. 2008, 15, 677.
[181] Jin, T. S.; Xiao, J. C.; Wang, S. J.; Li, T. S. Ultrason. Sonochem. 2004, 11, 393. (b) Jin,
T. S.; Zhang, J. S.; Wang, A. Q.; Li, T. S. Ultrason. Sonochem. 2006, 13, 220.
[182] Abaee, M. S.; Hamidi, V.; Mojtahedi, M. M. Ultrason. Sonochem. 2008, 15, 823.
[183] Leite, A. C. L.; Moreira, D. R. M.; Coelho, L. C. D.; Menezes, F. D.; Brondani, D. J.
Tetrahedron Lett. 2008, 49, 1538.
[184] Mojtahedi, M. M.; Abaee, M. S.; Hamidi, V.; Zolfaghari, A. Ultrason. Sonochem. 2007,
14, 596.
[185] Sreedhar, B.; Reddy, P. S.; Prakash, B. V.; Ravindra, A. Tetrahedron Lett. 2005, 46,
7019.
[186] Li, J. T.; Li, X. L.; Li, T. S. Ultrason. Sonochem. 2006, 13, 200. (b) Li, J. T.; Zhang, X.
H.; Lin, Z. P. Beilstein J. Org. Chem. 2007, 3, 13.
[187] Wang, S. X.; Li, X. W.; Li, J. T. Ultrason. Sonochem. 2008, 15, 33.
[188] Koyama, J.; Sugita, Y. Chem. Pharm. Bull. 1983, 31, 2601.
[189] Peng, Y. Q.; Zhong, W. J.; Song, G. H. Ultrason. Sonochem. 2005, 12, 169.
[190] Tobia, D.; Rickborn, B. J. Org. Chem. 1986, 51, 3849.
[191] Yokoe, I.; Higuchi, K.; Shirataki, Y.; Komatsu, M. Chem. Pharm. Bull. 1981, 29, 894.
[192] Li, J. T.; Liu, X. F. Ultrason. Sonochem. 2008, 15, 330. (b) Li, J. T.; Zhang, X. H.; Lin,
Z. P. Synth. Commun. 2008, 38, 2838. (c) Li, J. T.; Zhai, X. L.; Lin, Z. P.; Zhang, X. H.
Lett. Org. Chem. 2008, 5, 579. (d) Li, M.; Li, J. T.; Sun, H. W. Ultrason. Sonochem.
2008, 15, 37. (e) Li, J. T.; Liu, X. R.; Liu, X. F. Ultrason. Sonochem. 2009, 16, 4. (f)
Song, Y. L.; Li, J. T. Ultrason. Sonochem. 2009, 16, 440. (g) Li, J. T.; Meng, X. T.;
Zhai, X. L. Ultrason. Sonochem. 2009, 16, 590. (h) Li, J. T.; Liu, X. F.; Yin, Y.; Du, C.
Org. Commun. 2009, 2, 1. (i) Li, J. T.; Sun, X. L. Synth. Commun. 2009, 39, 4321.
[193] Li, J. T.; Xu, W. Z.; Zhao, X.; Li, T. S. J. Chem. Res.(S) 2004, 838. (b) Li, J. T.; Yin,
Y.; Li, L.; Sun, M. X. Ultrason. Sonochem. 2010, 17, 11. (c) Li, J. T.; Liu, X. R.; Sun,
M. X. Ultrason. Sonochem. 2010, 17, 55. (d) Li, J. T.; Zhai, X. L.; Chen, G. F.
Ultrason. Sonochem. 2010, 17, 356. (e) Li, J. T.; Sun, M. X. Aust. J. Chem. 2009, 62,
353. (f) Li, J. T.; Li, X. L.; Liu, X. F.; Ma, J. J. Front. Chem. China 2009, 4, 58. (g)
Song, Y. L.; Li, J. T.; Chen, H. J. Chem. Technol. Biotechnol. 2009, 84, 578. (h) Li, J.
T.; Yin, Y.; Meng, X. T. Lett. Org. Chem. 2009, 6, 384.
[194] Suslick, K. S. Ultrasound, its Chemical, Physical and Biological Effects, VCH
Publishers: New York, 1990. (b) Mason, T. J.; Peters, D. Practical Sonochemistry.
Power Ultrasound: Uses and Applications, Ellis Horwood: Chichester, 2002. (c)
Mason, T. J.; Lorimer, J. Applied Sonochemistry: Uses of Power Ultrasound in
Some Applications of Ultrasound Irradiation in Pinacol Coupling… 127
Chemistry and Processing, Wiley-VCH: Weinheim, 2002. (d) Luche, J. L. Synthetic
Organic Sonochemistry, Plenum Press: New York, 1988.
[195] Cravotto, G.; Cintas, P. Chem. Soc. Rev. 2006, 35, 180. (b) Mason, T. J. Chem. Soc.
Rev. 1997, 26, 443.
[196] Kiguchi, T.; Tajiri, K.; Ninomiya, I.; Naito, T. Tetrahedron Lett. 1995, 36, 253.
[197] Kammermeier, B.; Beck, G.; Jacobi, D.; Jendrella, H. Angew, Chem. 1994, 106, 719.
(b) Reetz, M. T.; Griebenow, N. Liebigs Ann. 1996, 335. (c) Hays, D. S.; Fu, G. C. J.
Am. Chem. Soc. 1995, 117, 7283. (d) Naito, T.; Tajiri, K.; Harimoto, T.; Ninomiya, I.
Tetrahedron Lett. 1994, 35, 2205.
[198] Li, J. T.; Chen, Y. C.; Lin, Z. P.; Li, T. S. Chin. J. Org. Chem. 2005, 25, 1583.
[199] Bian, Y. J.; Zhao, Y. J.; Li, M. X.; Li, J. T. Chin. J. Org. Chem. 2004, 24, 828.
[200] Ho, T. L.; Henninger, M.; Olah, G. A. Synthesis 1976, 815. (b) Olah, G. A.; Arvanaghi,
M.; Prakash, G. K. S. Synthesis 1980, 220. (c) Inokuchi, T.; Kawafuchi, H.; Torii, S. J.
Org. Chem. 1991, 56, 4983. (d) Hirao, T.; Hirano, K.; Hasegawa, T.; Ohshiro, Y.;
Ikeda, I. J. Org. Chem. 1993, 58, 6529.
[201] Takahara, P. M.; Freudenberger, J. H.; Konradi, A. W.; Pedersen, S. F. Tetrahedron
Lett. 1989, 30, 7177. (b) Konradi, A. W.; Pedersen, S. F. J. Org. Chem. 1990, 55, 4506.
(c) Park, J.; Pedersen, S. F. J. Org. Chem. 1990, 55, 5924. (d) Annunziata, R.; Cinquini,
M.; Cozzi, F.; Giaroni, P.; Benaglia, M. Tetrahedron 1991, 47, 5737. (e) Raw, A. S.;
Pedersen, S. F. J. Org. Chem. 1991, 56, 830. (f) Kempf, D. J.; Sowin, T. J.; Doherty, E.
M.; Hannick, S. M.; Codavoci, L.; Henry, R. F.; Green, B. E.; Spanton, S. G.; Norbeck,
D. W. J. Org Chem. 1992, 57, 5692. (g) Konradi, A. W.; Pedersen, S. F. J. Org. Chem.
1992, 57, 28. (h) Kraynack, E. A.; Pedersen, S. F. J. Org. Chem. 1993, 58, 6114.
[202] Conant, J. B.; Cutter, H. B. J. Am. Chem. Soc. 1926, 48, 1016.
[203] Freudenberger, J. H.; Konradi, A. W.; Pedersen, S. F. J. Am. Chem. Soc. 1989, 111,
8014.
In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 4



ULTRASOUND AND HYDROPHOBIC
INTERACTIONS IN SOLUTIONS


Ants Tuulmets, Siim Salmar and Jaak Järv
Institute of Chemistry, University of Tartu, Ravila 14A, 50411
Tartu, Estonia
ABSTRACT
Sonochemistry and solution chemistry have been explicitly brought together by
analyzing the effect of ultrasound on kinetics of ester hydrolysis and benzoin
condensation, measured by the authors, and similar kinetic data for the solvolysis of tert-
butyl chloride, compiled from literature. For the first time the power ultrasound, reaction
kinetics and linear free-energy relationships were simultaneously exploited to study ionic
reactions in water and aqueous-organic binary solvents and the importance of
hydrophobic ground-state stabilization of reagents in aqueous solutions was discussed.
This approach has opened novel perspectives for wider understanding of the effect of
sonication on chemical reactions in solution, as well as on solvation phenomena in
general.
1. INTRODUCTION
Because ultrasound promotes or accelerates a wide range of chemical and physical
processes [1-4], it has been used for a variety of purposes in areas as diverse as surface
cleaning, food technology, medical diagnostics and therapy, sewage treatment and chemical
synthesis. The latter applications, commonly described by the term ―sonochemistry ‖, have
proven to be invaluable and unique tools for making nanomaterials [5], in green technologies
[6], and certainly in organic synthesis [4,7,8].
As many homogeneous and heterogeneous reactions are initiated or accelerated by
ultrasound through generation of free radicals, which give rise to chain reactions [1,4], this
mechanism has been canonized in sonochemistry, and homogeneous ionic reactions have long
been confined to a marginal place in this vast domain of chemical reactivity. However, more
Ants Tuulmets, Siim Salmar and Jaak Järv 130
recent applications of quantitative methods like reaction kinetics and the linear free-energy
analysis (also known as ―correlation analysis‖), have lead to a better understanding of
sonochemical effects also in ionic reactions, as well as in the solvation phenomena taking
place in binary solvents in general.
In parallel to the analysis of sonication effects in kinetic data and their reliability,
measured in aqueous-organic binary solvents, the physical meaning of thermodynamic
activation parameters and other relevant issues will be discussed in this chapter.
Sonochemically investigated reactions implicated in this work as model processes are
solvolysis of tert-butyl chloride, acid-catalyzed, neutral, or base-catalyzed hydrolysis of
esters, and the benzoin condensation of benzaldehyde. These model processes have been
kinetically studied in water (if possible) and in aqueous-organic solvent mixtures involving
various alcohols and 1,4-dioxane as co-solvents.
Many of the conclusions reviewed in this chapter reach out beyond the conventional
sonochemistry actually contributing to solution chemistry and physical organic chemistry.
Among the most significant inferences from the results of these investigations, the
paramount importance of hydrophobic ground-state stabilization of reagents in aqueous
solutions, taking place independent of the reaction mechanism has to be stressed, an effect
mostly overlooked in conventional analysis of solvent effects [9]. An experimental
demonstration of formerly predicted ultrasonic retardation of reactions, reluctantly accepted
by the sonochemical community, provided a conclusive evidence for occurrence of
homogeneous ionic sonochemical reactions in the bulk solution instead of the cavitation
bubbles as commonly believed.
2. CURRENT VIEWS OF THE SONOCHEMISTRY IN SOLUTIONS
It is certain that sonochemical effects cannot be caused by direct impact of the acoustic
field on the reacting molecules, since the energy of ultrasound is too low to alter their
electronic, vibrational, or rotational states [1-4]. Therefore most often the effect of ultrasound
has been explained by the "hot spot" theory that assumes the involvement of cavitation
bubbles [10]. The nucleation, growth and collapse of these bubbles constitute the cavitation
phenomenon. According to the "hot spot" theory, each cavitation bubble acts as a localized
micro-reactor in which high temperatures and pressures are generated, reaching several
thousand degrees and hundreds atmospheres, thus effectively concentrating within "hot spots"
the diffuse energy of sound wave [1-3]. As the nearly adiabatic bubble collapse will thus
enhance molecular energy by almost nine orders of magnitude, it is no wonder that ultrasound
can affect chemical reactions.
The sonochemical process is usually thought to be localized either inside the cavitation
bubble or in the liquid shell surrounding it, or in both simultaneously. A general model
developed by Reisse et al. [11] considers the cavitating liquid as heterogeneous: each
collapsing bubble, acting as a closed microreactor, presents a physical environment that is
quite different from that of the bulk liquid phase.
Sonochemistry in solutions has been often rationalized in terms of this theory: solvents
that are volatile enough can be vaporized into the bubble where they will undergo pyrolytic
cleavage to form radicals or excited chemical species. These may induce subsequent reactions
Ultrasound and Hydrophobic Interactions in Solutions 131
with less volatile substrates at the bubble shell or, perhaps most frequently, in the bulk
medium.
Ionic reactions are extremely rare in the gas phase because separated ions are unstable
when not solvated. In other words, the dissociation of a molecule into ions is a process of
very low probability in the gas phase. Even chemical reactions where the activated complexes
are characterized by high dipole moments are uncommon in gas phase chemistry. Thus it is
hardly possible to conceive a neat heterolytic reaction in the gas phase of the bubble.
However, such reactions can take place in the liquid shell.
It is important to mention that intense shock waves form upon the collapse of cavitation
bubbles causing various mechanical actions. These are the mainstays of the explanation of
sonochemical effects on heterogeneous processes leading to enhanced reaction rates and
yields, which, however, often do not differ from those obtained by the use of a high-speed
stirrer [12].
Chemical effects of ultrasound will only occur if a particular reaction is the sonication
sensitive step of the process or when the active species released from cavitational collapse
participate as reaction intermediates. Luche et al [13] have distinguished sonochemical
applications resulting from "true" or "false" effects. The former are real chemical effects
induced directly by cavitation ("true sonochemistry"), while the latter can be mainly ascribed
to the mechanical impact of bubble collapse. A set of empirical rules has been established by
Luche [4,13]. While Rules II and III concern heterogeneous reactions, the Rule I states that
homogeneous reactions activated by sonication are those proceeding via radical or radical-ion
intermediates. Thus, according to Luche, homogeneous ionic reactions should not be affected
by sonication.
However, examples of ultrasonic acceleration of homogeneous ionic reactions had been
reported already before formulation of the Rules. Although they provided a challenging
puzzle, little attention was paid to them by sonochemists until recently, perhaps because these
reactions do not profit from the use of sonication in comparison with synthetically important
ones.
3. IONIC REACTIONS ACCELERATED BY ULTRASOUND
Following the current principles of sonochemistry (vide supra), it can be concluded that
an ionic reaction which is not switchable to a radical pathway, should not be susceptible to
ultrasound effect. However, several examples of homogeneous polar reactions accelerated by
ultrasound have been found, mostly hydrolysis and solvolysis reactions that have been
kinetically investigated for sonication effects. In the first paper of this kind [14], published
already in 1953, the acid-catalyzed hydrolysis of ethyl acetate in aqueous solution was
studied. The sonication effect was small but exceeded the experimental error.
Later, the acid-catalyzed hydrolysis of methyl acetate has been investigated by three
groups [15-17]. In all these works similar experimental conditions were used and the kinetics
was followed by titration of the formed acid. The reaction was performed in water without
sonication and under sonication and also in a water-acetone binary solvent [17]. The
sonication effect was from low to moderate, the rate enhancement not exceeding 60%.
Under conditions affording more pronounced sonication effects, a many-fold acceleration
of the acid-catalyzed hydrolysis of ethyl acetate in water was attained at 22 kHz [18].
Ants Tuulmets, Siim Salmar and Jaak Järv 132
However, detailed investigations revealed sonication effects not exceeding 30% in water
medium [19-21].
Still lower acceleration effect (14-15 %) by ultrasound has been reported for the alkaline
hydrolysis of 4-nitrophenyl esters of several aliphatic carboxylic acids in a water-acetonitrile
mixture [22]. Kinetics of this reaction was followed by spectrophotometric monitoring of 4-
nitrophenol formation. Similarly, for the base-catalyzed hydrolysis of 4-nitrophenyl acetate in
water accelerations in a range 10 to 12% were found [23]. Moderate sonication accelerations
were found over the 4-13 pH range for the hydrolysis of phthalic acid esters in aqueous
solution [24].
In contrast to these findings, an ultrasonic acceleration by two orders of magnitude was
reported by Hua et al. [25] for the hydrolysis of 4-nitrophenyl acetate in aqueous solution
over the pH range of 3-8 at 20 kHz. However, the reliability of their experimental procedure
has been questioned and just a moderate ultrasonic acceleration of the reaction was found by
Ando et al [26]. Later on, the comparative use of titanium and quartz immersion horns for
sonication [23] enabled rationalization of the sonication effects reported by Hua et al.
Evidently the large sonication accelerations observed were not merely caused by direct effects
of ultrasound but also involved a considerable contribution from catalytic effects probably
due to metal traces from titanium horns [23].
It is remarkable that only negligible to small sonication effects have been found in water
or in mixtures with organic solvents of low ability to form hydrogen bonds.
In contrast to this large sonication effects up to 20 times were observed for the solvolysis
reaction of 2-chloro-2-methylpropane (tert-butyl chloride) in ethanol-water [27-30],
isopropanol-water [28] and tert-butanol-water [28] mixtures by Mason‘s group. (Scheme 1,
a). Kinetics of the solvolysis was followed conductometrically. Surprisingly, the effect of
ultrasound showed nonlinear dependences on the composition of aqueous binary mixtures.
For example, at 10°

C the solvolysis rate in 20 wt% of ethanol in the presence of ultrasound
was twice that in the absence of irradiation, whereas at 40% and 60% of ethanol the rate
increases were six- and 20-fold, respectively. The solvolysis of 1-bromo-1-phenylethane in
alcohol-water mixtures has been studied by another group [31] and also an ultrasonic
acceleration of the reaction was observed, however, the stereoselectivity was unaffected in all
cases.
Kinetic investigations of sonication effects in water-organic binary mixtures were
recently reopened by our group [19-21,23,32-35]. The acid-catalyzed hydrolysis of alkyl
esters (Scheme 1, b) in water-ethanol and in water-1,4- dioxane binary mixtures were studied
in these works [19-21,32,35]. Also the base-catalyzed hydrolysis of 4-nitrophenyl acetate
(Scheme 1, c) [23] as well as the benzoine condensation of benzaldehyde in water and in
ethanol-water binary mixtures [33,34] were investigated for sonication effects.
Results of this extensive research allowed to draw a number of important conclusions
about the mechanism of sonication effects for homogeneous ionic reactions as well as on the
nature of solvation phenomena in aqueous-organic systems. The most important results
concern the hydrophobic interactions in solutions and their role in determining the reactivity
in solutions.
Ultrasound and Hydrophobic Interactions in Solutions 133
C H
3
C
CH
3
CH
3
Cl
CH
3
C
+
C H
3
CH
3
Cl
O H
2
C H
3
C
CH
3
CH
3
OH
O H
3
+
C H
3
C
O
OR
OH
C C H
3
OR
O H
2
+
C H
3
C
O
OH ROH H
+
H
+
O H
2
C H
3
C
O
NO
2
O
O
C
O H O
C H
3
NO
2
C H
3
C
O
O
OH
NO
2
OH
+ +
,
+ +
+
a)
b)
c)

Scheme 1. a) Solvolysis of 2-chloro-2-methylpropane, b) acid-catalyzed hydrolysis of an alkyl acetate,
c) base-catalyzed hydrolysis of 4-nitrophenyl acetate.
4. WATER AND HYDROPHOBIC INTERACTIONS
Water occupies a special place in chemistry because of its role as the solvent for all of the
chemical reactions of life. Water is also a desirable solvent for industrial chemical reactions
for reasons of cost, safety, and environmental concerns [6,36]. Moreover, this interest arises
from the fact that reactivity of some compounds benefit from the unique properties of water,
resulting inter alia from hydrophobic interactions to which species are subjected when
dissolved in water [37-39].
Although water is not frequently the solvent of choice because it is a poor solvent for
nonpolar compounds, solubility of these compounds in water can be improved by additions of
miscible with water organic solvents. This largely expands the range of feasible reactions.
Among such additives the lower alcohols distinguish in all aspects as green solvents.
Solvation of reactants is one of the most important factors governing the rates of polar
reactions [9]. In binary solvents this dependence is complicated by the occurrence of
preferential solvation. This means that the composition of the solvation shell around reacting
species is different from that of the bulk solvent. In solvents that can form hydrogen bonds
the structure of the medium is also of great importance [40]. This seems to be the main reason
why quantitative solvent effects on organic reactivity have been extensively studied mainly
for pure solvents, and great numbers of correlation equations have been suggested for
description of these effects [9]. Alongside of this mainstream, investigations into solvent
effects in binary solvents, including water-solvent mixtures, have lead to results not as
ambiguous if compared with those for pure solvents [41].
Clearly, involvement of water in a binary mixture brings forth a number of specific
interactions with the co-solvent, including the hydrophobic interaction. The hydrophobic
Ants Tuulmets, Siim Salmar and Jaak Järv 134
interaction is the tendency of apolar species to aggregate in aqueous solutions to reduce their
contact surface with water [37-39]. Hydrophobic interactions between apolar molecules or
apolar parts of molecules in water are important noncovalent driving forces for inter- and
intramolecular binding and assembling processes, taking place in aqueous chemistry and
biochemistry [36-39]. In aqueous systems these interactions can strongly influence chemical
equilibria and reaction rates [37-39,42,43]. In the hydrolysis of esters enforced hydrophobic
interactions stabilize the ground state and make the ester less reactive [42-44]. On the other
hand, the Diels-Alder reaction and the benzoin condensation are dramatically accelerated
because of the packing of hydrophobic surfaces of the reagents in the transition state when the
reaction is carried out in water rather than in organic solvents [37,45,46].
Solute-solvent and solute-solute interactions have attracted interest of investigators for a
long time. Since the pioneering work from the Engberts and Blandamer group [47] on
quantitative interpretation of the co-solute-induced rate effects, many papers about reactions
in mixed aqueous solvents have appeared (for reviews see, e.g. Refs [38] and [39]). However,
the most definite results have been obtained for water-rich media, i.e. at concentrations of co-
solvents about few mole percents. At lower concentrations of water, complications of
different origin have been met (see, e.g. [44]).
Attempts to describe the solvent effects in binary solvents have been done also by means
of empirical multiparameter correlation equations [9] or basing on simplified solvent
exchange models concerning the solvation shell of a solute [41,48]. Thermodynamic
considerations [40] and several theoretical calculations, e.g. of the Kirkwood-Buff integral
functions [49] have shown that many binary mixtures are micro-heterogeneous, consisting of
microdomains composed of organic solvent molecules surrounded by water, and of water
solvated by the organic solvent.
These ideas have been well supported by recent spectroscopic, X-ray diffraction, and
mass spectrometric investigations of alcohol-water solutions [50-52]. It has been concluded
that small additions of ethanol in the range of 0<X
E
<0.08 (X
E
is the ethanol mole ratio) exert
a strong structure-making effect accompanied by an increase in the self-association of water
molecules. Indeed, the partial molar volume of ethanol is a minimum at X
E
= 0.08 [53], and
the excess solvatochromic parameters distinctly show an enhancement in the structure of
water in this region [54]. Further additions of the alcohol begin to prevent water from
organizing into three-dimensional structures. The structural behavior of these solutions is
strongly modified at X
E
>0.15. In this region a large number of ethanol-water bonds are
formed and water-water bonds are broken. The resulting structure is described by a cluster
model, envisaging a stacked ethanol core and a thin water shell. The region shifts to lower
alcohol contents for more hydrophobic alcohol-water mixtures. On the contrary, in aqueous
methanol the cluster region stretches at X
MeOH
> 0.4 [52], however, in an alcohol-water
mixture, concentrated in regard of the alcohol, most of the water molecules exist as clusters in
the alcohol medium [55].
Although hydrophobic interactions can be studied by a large variety of experimental and
computational techniques, the determination of chemical reactivity has an important position
among them [38,39,45,46]. Further we show that application of power ultrasound to kinetic
investigations into polar homogeneous reactions revealed important features of hydrophobic
interactions in solutions.
Ultrasound and Hydrophobic Interactions in Solutions 135
5. SONOCHEMICAL EFFECTS IN REACTION KINETICS
A comprehensive investigation of sonication effects on polar homogeneous reactions was
first performed by Mason‘s group [27-30]. An unexpectedly complicated dependence of the
sonication effect (k
son
/k) on the composition of alcohol-water binary solvents was found for
the solvolysis reaction of tert-butyl chloride. The authors supposed that the application of
ultrasound to the reaction disrupted the binary solvent structure, thus permitting a better
solvation of the substrate and resulting in enhanced reaction rates.
That pioneering work inspired us to extend the investigation to a mechanistically
different reaction, viz. to the acid-catalyzed hydrolysis of esters in aqueous binary mixtures to
elucidate more details of the sonication effect on polar reactions. Whereas in the case of tert-
butyl chloride the matter of sonication-induced radical processes can still be raised, it is
almost excluded when alkyl esters are used. Furthermore, experiments carried out in 1 M HCl
solutions prevent possible pH changes due to water sonolysis or nitrogen oxidation products
[56,57].
For the acid-catalyzed hydrolysis of ethyl acetate we observed a similar trend to the work
of Mason on the dependence of the sonication effect on ethanol-water solvent composition
(see, e.g. Figure 1). These results initially led us to think that sonication effects were merely
related to perturbation of the solvent system. However, on replacing ethyl acetate with more
hydrophobic esters, we observed a dramatic change in the dependence of the sonication effect
on solvent composition, which obliged us to revise our early point of view. Solute-solvent
interactions in these complicated systems proved to be particularly important in clarifying the
matter [21,34].
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
X

k
s
o
n
/
k
n
o
n

Figure 1. Rate inhancements induced by ultrasonic irradiation in water-organic binary solvents (X -
molar fraction of the organic component in the mixture).
□ - acid-catalyzed hydrolysis of ethyl acetate in 1,4-dioxane -water mixtures at 18 °C [21]
○ - acid-catalyzed hydrolysis of ethyl acetate in ethanol-water mixtures at 18 °C [20]
● - solvolysis of tert-butyl chloride in ethanol-water mixtures at 20 °C [29]
Ants Tuulmets, Siim Salmar and Jaak Järv 136
For the effect of ultrasound on the rate of the reaction in ethanol-water and 1,4-dioxane-
water mixtures, non-linear dependences involving extreme points were found (Figure 1).
Because many physicochemical properties of binary systems depend on the composition
nonlinearly, it should be clearly determined how much of the ultrasonic energy is absorbed by
the system at any component ratio to ensure a confident interpretation of the results.
Several methods are available to estimate the amount of ultrasonic power entered into a
sonochemical reaction [3,58]. Many authors have suggested determining the thermal effect of
ultrasound as a means of obtaining the effective power. This is based on the assumption that
almost all the cavitational energy produces heat, and thus the output power can be obtained
via calorimetry. The other method involves a chemical dosimeter, which monitors the
sonochemical generation of a chemical species. The yields of the reaction after an adequate
sonication time are regarded as a measure of the power of the ultrasound.
Although chemical dosimetry is generally believed to be the most straightforward method
for determination of the ultrasonic power in a sonochemical reaction, it cannot be applied to
binary solvent systems, because the reaction rate as well as the ultrasonic acceleration
depends on the solvent composition. However, many authors

[59-62] have shown that the
results from a chemical dosimeter were directly and linearly related to the calorimetrically
determined ultrasonic power. In addition, it is important to notice that a chemical dosimeter
may not describe the true acoustic power, but describes the sonochemical efficiency for the
reaction induced under certain experimental conditions [62].
Ultrasonic power determinations were performed in the 0-60 wt.% region of ethanol-
water and 1,4-dioxane-water binary mixtures (For details see [21]). It appears that the
calorimetric sonication effect depends insignificantly on the solvent composition (Figure2).
The power of ultrasound in this system did not exceed 1.6% relative to that for pure water and
thus remained within the experimental error limits. Similar results were obtained for the 1.4-
dioxane-water system [21].

0 10 20 30 40 50 60 70
37
38
39
40
41
42
wt% EtOH
P

(
W
)

Figure 2. Ultrasonic power in a 500 cm3 calorimeter filled with water or ethanol-water mixtures.
If the assumption that almost all the cavitational energy produces heat that is measurable
via calorimetry is valid, it follows that at least for the solvent systems under consideration the
solvent properties show an insignificant effect on the number of cavitational events as well as
the cavitational intensity. This result is somewhat unexpected in the context of the complexity
Ultrasound and Hydrophobic Interactions in Solutions 137
and microheterogenity of alcohol-water binary systems. However, our results indicate that
dependences of the ultrasonic rate enhancement on solvent composition do describe changes
in the sonochemical efficiency.
Data for the hydrolysis of ethyl acetate and for the solvolysis of tert-butyl chloride
(Figure 1) show a distinct maximum in the region about 50 wt. % of ethanol. Mason et al.
[29,30] have pointed out a coincidence of the maximum in their data with the maxima found
in the viscosity, enthalpy of mixing and sound absorbtion versus solvent composition curves
[40]. These properties of the binary liquid mixture show the existence of a structurally critical
region at 0.2-0.3 mol fraction (40-50 wt.%) of ethanol. This is also reflected in the volumes of
activation ΔV
#
. All the available data for a variety of solvolysis reactions in ethanol-water
mixtures show a decrease in ΔV
#
when passing from water to ethanol-water mixtures and a
minimum in the region between 0.2 and 0.3 mol fraction of the alcohol [63].
Recent spectroscopic, X-ray diffraction and mass spectrometric investigations [50-52]
have shed light on the structure of ethanol-water solutions (see previous section). Based on
these findings the application of ultrasound to the reaction would, by disrupting the binary
solvent structure, result in the enhanced rates of reaction. However, solute-solvent
interactions in these complicated systems can be particularly important, since the replacement
of ethyl acetate by more hydrophobic esters changed beyond recognition the dependence of
the sonication effect on the solvent composition (Section 7).
Engberts, Blandamer et al. [38,64,65] have developed a versatile quantitative approach to
reactions in binary solvent systems including ester hydrolyses based on an idea about
equilibrium formation of encounter complexes between reactants and hydrophobic co-
solvents. The more hydrophobic the reagents and the co-solvents, e.g. alcohols, the more
extensively the reagents are included in the encounter complexes and thus rendered
unreactive. From the rate constants for the neutral hydrolysis of 4-methoxyphenyl-2,2-
dichloroalkanoates in dilute aqueous solutions of short- chain alcohols, the molar energies of
hydrophobic interactions between the components of the solutions have been estimated to be
as small as 1 kJ or less [65]. Nevertheless, two-fold and greater rate decreases in solutions
that are about 2 mol % in alcohol and 10
-5
M in ester were plausibly assigned to hydrophobic
interactions.
Kinetic sonication data for the hydrolysis in the 1,4-dioxane-water solvent system are
usefully complementary to the reasonings above (Figure 1). It has been pointed out that the
structure enhancement of long-range order in water-alcohol systems appears to be absent in
mixtures of dioxane and water

[66,67]. Moreover, in solutions ranging from pure water up to
0.2 mole fraction, dioxane gradually breaks down the structure of water [68].
Consequently, in the region beyond 5 mol % of dioxane (Figure 1), the sonication effect
can be attributed to the breakdown of ester-1,4-dioxane encounter complexes, the efficiency
of irradiation decreasing with an increase in the content of the hydrophobic co-solvent in the
mixture.
In contrast to the sonication effects and despite considerable changes in the solvent
structure, rate constants for the hydrolyses without ultrasonic irradiation decrease slightly and
monotonously with increasing organic co-solvent content. The same was observed for the
solvolysis of tert-butyl chloride in ethanol-water mixtures. Winstein and Fainberg

[69] have
shown that the activation free energy of tert-butyl chloride solvolysis increases smoothly with
increasing ethanol content, while the enthalpy and entropy of activation show mirror-imaged
extremes in the region of 15 mol % of ethanol. This is also the region of the maximum
Ants Tuulmets, Siim Salmar and Jaak Järv 138
solvation energy of the initial reagent, tert-butyl chloride [70]. A similar compensation effect
has been observed for the hydrolysis of ethyl acetate in water-DMSO and water-acetone
systems [71].
Thus, ultrasonication is able to reveal subtle interactions and particular effects of entropic
or enthalpic origin, which remain hidden in conventional kinetics.
6. MODE OF ACTION OF ULTRASOUND ON REACTIONS IN SOLUTIONS
From mean velocities for the first half-lives of reactions without sonication and under
ultrasound, the sonochemical efficiency of our experimental equipment was estimated to be
1.3 × 10
-9
molJ
-1
for the hydrolysis of butyl acetate in 40 wt.% 1,4-dioxane and 2 × 10
-9
molJ
-1

for ethyl acetate in 50 wt.% ethanol [21].
These numbers are comparable with those reported for OH radical formation in water (3
× 10
-10
molJ
-1
) [72], the sonolysis of 4-nitrophenylacetate (5.7 × 10
-9
molJ
-1
) [73], KI
oxidation (6 × 10
-9
molJ
-1
) [62], and Fricke dosimeter (3 × 10
-10
molJ
-1
) [62]. This
comparability is somewhat amazing because all these data are related to radical formation or
degradation reactions, i.e. to high-energy processes, while in our case only weak interactions
in the solution are perturbed by the irradiation. This means that similar molar efficiency is
apparently associated with a lower energetic efficiency in the case of these polar reactions.
Hence, the question, of how ultrasound acts upon homogeneous ionic reactions still needs to
be answered.
Cavitation is now generally accepted as the origin of the chemical effects of ultrasound.
The sonochemical reaction is thought to occur in the cavitation bubble or in its immediate
vicinity (see Section 2). Extremely harsh conditions are produced by the collapse of a
cavitation bubble. Under these conditions standard solvents are in the supercritical state, thus
providing a promoting medium for certain reactions

[25,74].
Three regions in which a reaction can take place exist in a cavitating liquid: the gaseous
phase inside the bubble, the limit shell around it, and the bulk solution [11,74,75]. Therefore,
a cavitating reaction medium is considered to be a pseudo-heterogeneous system. This is the
concept that sound energy is focused in small regions and is not able to process into the rest
of the material, and thus its effect is felt only at certain points in the medium.
If the sonochemical acceleration or promotion of a non-radical reaction occurs
exclusively in the cavitational sites of the reaction medium as generally expected (see Section
2), the rate of a first-order reaction under sonication can be expressed as follows:

v = k
son,obs
c = k
silent
c + xk°
son
c,

where x is the fraction of the reaction medium under perturbation by cavitation at any
instant, and k°
son
is the rate constant of the reaction inside the cavitational site.
It should be noticed that the observed rate of the reaction consists of the rate in
cavitational sites and of the rate in bulk solution presumably not affected by sonication.
The intrinsic sonochemical rate constant, i.e. that for the reaction inside the cavitational
sites, can thus be calculated as:

Ultrasound and Hydrophobic Interactions in Solutions 139
.
,
x
k k
k
silent obs son
o
son
÷
=


While the observed sonochemical acceleration is

,
,
silent
obs son
obs
k
k
a =


the intrinsic sonochemical acceleration is

. 1
1
,
|
|
.
|

\
|
÷ = =
silent
obs son
silent
o
son o
k
k
x k
k
a


Whereas rate constants k
son,obs
and k
silent
can be routinely determined, the values for x are
not available in most cases. However, void fractions of 10
-4
[76] or 2.9 × 10
-5
to 4.2 × 10
-5

[77] have been calculated for water under sonication. Actually, the active volume including
the shell around the bubble may be greater, e.g. Hua et al.[25] used a heat-transfer model for
the estimation of the lifetime and spatial extent of alleged supercritical water (SCW) during
the cavitational bubble collapse. A value for x, equal to 1.5 × 10
-3
in pure water was proposed
[25].
Thus, depending on how rigorous conditions the reaction requires, x can take different
values, however, it should not exceed 10
-3
. In other words, 0,1% of the reaction solution or
less is under cavitation simultaneously.
This means that the intrinsic ultrasonic acceleration a° required to produce an observed
rate enhancement (a
obs
) by a factor of two is about 10
3
times or more. In other words, the
reaction located in the cavitational sites has to proceed up to several thousands times faster
than in the bulk solution. Such rate enhancements have been reported for only a few reactions
and require substantial changes in solvent properties [9]. On the contrary, quenching of a
reaction in the cavitation zone leads to a rate decrease by 0.1% or less and therefore cannot be
ascertained experimentally.
Although the intrabubble gas phase is an inconceivable site for ionic reactions to proceed,
the liquid shell, particularly in the supercritical state, can provide a favorable medium for
reactions. However, the low density, low polarity and cluster formation indigenous to
supercritical water [78] counteract ester hydrolysis reactions. The bubble-bulk interface can
also be a site of accumulation for hydrophobic molecules

[72-74], however, estimated
concentration limits of species are far too low to provide the required rate enhancements.
Moreover, the observed sonication effect increases in the opposite direction to the
hydrophobicity of the esters (see next section).
Although an extension of the linear Arrhenius equation up to the supercritical water or
hot-spot region temperatures may be acceptable in the case of cleavage or degradation
reactions, the same approach is not valid for extremely solvation-dependent solvolysis or
Ants Tuulmets, Siim Salmar and Jaak Järv 140
hydrolysis reactions. Moreover, the occurrence of high-temperature zones in cavitating
solution provides no adequate explanation of the observed effects in polar reactions because
the absence of a sonication effect for a reaction with a positive activation energy has been
documented [26] and has also been found in our work [21].
From the definition of the activation volume of the reaction,

,
ln
RT
V
dP
k d
T
#
A
÷ =
|
.
|

\
|


the acceleration caused by pressure can be calculated. Assuming an activation volume equal
to –20 cm
3
mol
-1
, the rate of the reaction can be doubled by applying a pressure of 800 atm to
the reaction solution at the standard temperature. At higher temperatures, e.g. in the cavitation
bubbles, considerably greater pressure must be applied. If the reaction is accelerated only at
cavitational sites with x = 0.001, then the same rate increase can be attained under a pressure
greatly exceeding 7500 atm, which is hardly accessible even in the hot spots. Thus, also the
kinetic pressure effects should be ruled out.
It follows, that the observed acceleration ratios for polar homogeneous reactions,
particularly those for ester hydrolyses, cannot be accounted for directly by the phenomena
occurring in the cavitation bubbles. It seems to be necessary to take into consideration the
bulk solution or at least an essential part of it.
Evidently, ultrasonic waves passing through the medium cause changes in the
translational energy of species. The same may occur because of shock waves produced by
collapsing cavitational bubbles in the medium. An acoustically induced motion of the water
of crystallization in the crystal lattices leading to changes in the melting points of compounds
has been pointed out [79]. The perturbation of normal molecular motion in the liquid phase by
ultrasound has been detected through its effects on NMR spin-lattice relaxation times

[80,81].
From NMR-spectra, it has been found that the introduction of 20 kHz ultrasound to a liquid
sample induces conformational changes to appropriate constituent molecules of the sample

[81]. It has been accepted for a long time that the equilibria involving aggregates present in
solution are perturbed by pressure changes produced by sound waves

(for recent reviews see
[82]) and that extensively exploited relaxation processes in liquids are caused by the re-
establishment of the equilibria perturbed by sound waves

[83,84]. Our results corroborate this
concept pointing at a highly probable action of ultrasound in the bulk solution.
However, current results do not permit to discern the true acoustic-field effects from
those caused by pressure waves due to the cavitation phenomena. In many cases, the indirect
contribution of cavitation is evident, since the efficiency of ultrasound increased when
hydrolysis was performed under argon [2-4,18,25] or decreased with elevation of the reaction
temperature

[2-4].
7. INFERENCES FROM SONICATION EFFECTS
Our approach to a better understanding of solvent effects stemmed from the study of
kinetic sonication effects in aqueous binary solvents. We were able to relate ultrasonic
Ultrasound and Hydrophobic Interactions in Solutions 141
acceleration of ester hydrolysis to a perturbation by power ultrasound of hydrophobic solute-
solvent interactions.
As discussed in Section 5, these kinetic data were in line with the current idea of the
structure of ethanol-water solutions. According to it (see section 4), in mixtures with X
EtOH
>
0.15 a large number of ethanol-water hydrogen bonds are formed at the expense of water-
water bonds, a result that led to a cluster model envisaging a stacked ethanol core and a thin
water shell. This model allowed a straightforward interpretation of our results: a hydrophobic
reagent could be hidden inside the clusters and thus made unavailable for the reaction. If such
interaction with the hydrophobic interior of the cluster can be overcome by ultrasound, the
reaction will be accelerated accordingly.
In our recent study

[21] ethyl, n-propyl and n-butyl acetates were used as probes of
reagent inclusion within the clusters. In fact the sonication effects (k
son
/k) for hydrolysis,
determined in the X
EtOH
> 0.15 range, matched in reverse order the hydrophobicity of the
esters. Sonication had the smallest effect in the case of butyl acetate, the substrate that should
be most powerfully trapped within the clusters.
We were able to conclude that the regular decrease in the rate of ester hydrolyses in
ethanol-water mixture was mainly due to hydrophobic interactions, i.e. to ground-state
stabilization by this solvent system [21,34].
A logical inference from the results of kinetic sonication experiments with esters was that
ultrasound would decrease, rather than increase, the rate of reactions promoted by
hydrophobic interactions, similar to the Diels-Alder reaction, the benzoin condensation, etc.

[37-39]. As early as in 1997 we have predicted an ultrasonic retardation for chemical
reactions [85], an effect that has so far been ignored in the sonochemical literature.
It cannot be excluded that some researchers have encountered the same phenomena,
however taking it for an experimental error or discarding as nonsense. Therefore we consider
the rationalization of the sonochemical retardation of the reaction rate as particularly
important.
Our choice for the model reaction was the benzoin condensation of benzaldehyde [33,34],
a reaction of well established mechanism [86] (Scheme 2), investigated in detail for the
hydrophobic effects by Breslow et al. [45,87].
It has been shown

[45,46] that hydrophobic packing of reactants in the transition state
promotes the benzoin condensation. In the rate-determining step of the reaction two benzene
rings become stacked, an interaction that in an aqueous solvent is favored by a hydrophobic
effect. In ethanolic solutions stacking effects should be greatly reduced; as a matter of fact the
reaction is much slower than it is in water [87].
As expected, the reaction was slowed down by ultrasound in pure water and in ethanol-
water mixtures up to an ethanol content of 45 wt % (X
EtOH
= 0.25, Figure 3).
The good linear fit of these data to second-order kinetics proves that ultrasound affects
the rate-limiting condensation step of the reaction exclusively. Sonochemical degradation of
benzaldehyde would have led to an apparent acceleration of the reaction instead of the
observed retardation. A loss of benzoin by decomposition could lower the apparent reaction
rate; in this case however a curvature of the second-order kinetic plot should be observed.
Moreover, GLC analysis of solutions of benzaldehyde and benzoin in the absence of catalyst
did not reveal any degradation products after they had been sonicated longer than required by
kinetic experiments. If the reaction was switched to a chain mechanism under sonication, no
Ants Tuulmets, Siim Salmar and Jaak Järv 142
rate reduction could be observed and unexpected by-products should have appeared.
However, this was not the case.

C-
CN
OH
C
O
H
o
+
Ph C
O
H
C
-
N
Ph C
-
OH
CN
Ph C
O
H
+
C
-
N -
+
Ph C
O
Ph C
OH
H
A
B

Scheme 2. Mechanism of the benzoin condensation of benzaldehyde (A); stacking of the benzene rings
in the rate-determining step (B).
The retardation effect of ultrasound was most pronounced in pure water and gradually
decreased with increasing ethanol content up to about X
EtOH
= 0.25 (Figure 3), when
sonication turned to a promoting factor. The last finding can be interpreted in terms of the
structure of aqueous ethanol binary system. Additions of ethanol up to 25 mol% modify the
structure but evidently do not entirely prevent the favorable hydrophobic effects which are
disturbed by ultrasound.
Ethanol clusters in this region and more extensively in that of higher X
EtOH
bring about
different consequences at different ethanol concentrations. The condensation reaction is
favoured when ethanol clusters host complexes of the reagents. On the other hand, if ethanol
clusters host single reagent molecules, the reaction is slowed down. These effects obviously
compete with one another; the small accelerating effect of ultrasound for X
EtOH
> 0.20
indicates the prevalence of the latter.
The observed statistically significant decrease of the rate of benzoin condensation means
that the reaction was quenched in 20 % of the total volume of water solution, or was hindered
in a larger part of the solution. This provides a direct and unambiguous evidence for the
occurrence of non-radical sonochemical processes in the bulk solution of homogeneous
systems, i.e. outside of cavitational sites (see the discussion in Section 6).
Apart from this fundamental conclusion, kinetic investigations into the sonochemical
effect in water-organic binary mixtures led to an important generalization which can be called
the Fourth Rule of sonochemistry (a sequel to the Rules by Luche [4,13]): if sonication breaks
down stabilization of the encounter complexes between reagents, it decreases the reaction
rate; on the contrary, if sonication perturbs the solvent stabilization of the initial state of the
reagents, it accelerates the reaction.
Ultrasound and Hydrophobic Interactions in Solutions 143
0.0 0.1 0.2 0.3 0.4
0
2
4
6
8
without sonication
under ultrasound
X
EtOH
k
I
I
I
×

1
0
3

Figure 3. Plot of third-order rate constants, k
III
(L
2
mol
-2
s
-1
) for the benzoin condensation of
benzaldehyde vs ethanol content in the aqueous solution under ultrasound and without sonication at 65
°C catalyzed with KCN [33,34].
8. SOME QUANTITATIVE CONSIDERATIONS
8.1. LFE Analysis

It has been concluded that in aqueous-organic binary solvents the sonochemical effect in
ionic reactions may be related with the destruction of hydrophobic solute-solvent interactions
[21,23]. However, the conclusion has been a qualitative deduction based on the observed
sonication effects in reaction kinetics (Section 7). To obtain a quantitative proof of this
conclusion the sonication effects were further related to the Hansch-Leo hydrophobicity
parameter log P [34,88], where P is the partition coefficient of the substrate between 1-
octanol and water [89,90], and the data were subjected to the linear free energy analysis (the
correlation analysis) [91,92].
In Figure 4 the linear free energy (LFE) relationships show how the kinetic sonication
effect for ester hydrolyses are related to the hydrophobic interaction of reagents with the
Ants Tuulmets, Siim Salmar and Jaak Järv 144
solvent system. The plot in Figure 4A represents the relationship at X
EtOH
= 0.28 in the region
of ethanol clusters, providing a convincing quantitative proof of the conclusions made
intuitively above. Plotting of sonication effects at X
EtOH
= 0.04 and 0.09 against
hydrophobicity parameters (Figure 4B) reveals also linear relationships.
The LFE test indicates that the mechanism of the sonication effect is the same for 4-
nitrophenyl acetate and the alkyl acetates independent on the hydrolysis reaction mechanism,
in this particular case the base-catalyzed vs acid-catalyzed reactions. In light of the sonication
effects one can admit now that independent on the reaction mechanism the esters interact
similarly with the solvent system. Subsequently it can be concluded that the regular decrease
of the rate of ester hydrolysis with the increasing content of the alcohol in aqueous binary
solvents is mainly caused by hydrophobic interactions, i.e. by the ground-state stabilization
by the solvent system. Likewise this reaffirms conclusions made by other groups for water-
rich solvent systems [38,39,47].

0.5 1.0 1.5 2.0
0.0
0.1
0.2
0.3
0.4
0.5
EtOAc
PrOAc
BuOAc
0.0
0.1
0.2
0.3
0.4
0.5
EtOAc
PrOAc
BuOAc
X
EtOH
= 0.28 L
o
g

(
k
s
o
n
/
k
n
o
n
)
4-NO
2
PhOAc
4-NO
2
PhOAc
A
B
X
EtOH
= 0.04
X
EtOH
= 0.09
Log P
L
o
g

(
k
s
o
n
/
k
n
o
n
)

Figure 4. Linear Free Energy Relationships between sonication effects for ester hydrolyses and the
hydrophobicity parameter (log P) for the substrates. Acid-catalyzed hydrolysis of ethyl, n-propyl, and
n-butyl acetate; base-catalyzed hydrolysis of 4-nitrophenyl acetate. Data from Refrs. [21], [23], and
[35], normalized for sonication intensities. A - X
EtOH
= 0.28, B - X
EtOH
= 0.04 and 0.09.
Ultrasound and Hydrophobic Interactions in Solutions 145
In the region X
EtOH
< 0.15 (e.g., Figure 4B) the order of the sonication effects is reverse
to that found for the region of clusters. Such dependence of sonication effects was related to
the weak solvation of esters in this region. Obviously, an enforced cluster formation occurs
when a hydrophobic substrate is introduced to a solvent system not comprising common
alcohol-water clusters. Undoubtedly, these clusters or encounter complexes are weaker than
the clusters present in the region X
EtOH
> 0.15. Thus, a greater hydrophobicity of the substrate
leads to stronger solvation and consequently to the decreased reactivity. However, ultrasound
breaks down the weak hydrophobic interactions almost entirely, thus providing paradoxically
large sonication effects for more hydrophobic esters.
Recent experimental data [35] corroborated this conclusion straightforwardly. The
neutral hydrolysis of 4-nitrophenyl chloroacetate was studied. While the observed rate of the
hydrolysis decreased in the presence of 1 mol% of aliphatic alcohols and this effect was
parallel with the increasing hydrophobicity of the co-solvents, the rate constants were not
different under ultrasound (Figure 5). Thus, the dependence of the apparent sonication effect
upon co-solvent hydrophobicity (Figure 6) was similar to the plot shown in Figure 4B. In
other words, the applied acoustic power appeared to destroy completely the ester-cosolvent
encounter complexes, regardless of hydrophobicity of these compounds.


Figure 5. Diagrammatic representation of rate constants for the neutral hydrolysis of 4-nitrophenyl
chloroacetate without sonication and under ultrasound at 20 °C [35]. The alcohols were present as co-
solvents in 1 mol% amount. The initial concentration of the ester was 10
-5
M. The ultrasonic power at
25 kHz was 8.1 W/100 mL.
Ants Tuulmets, Siim Salmar and Jaak Järv 146
0 1 2 3 4 5
1.0
1.2
1.4
1.6
1.8
The number of carbon atoms in the alcohols
k
s
o
n
/
k
n
o
n

Figure 6. Sonication effects for the hydrolysis of 4-nitrophenyl chloroacetate vs the number of carbon
atoms in the alcohols used as co-solvents in 1 mol% amount.
It is noteworthy that extrapolation of the dependences in Figure 5 and 6 to the point for
methanol predicts a very small sonication effect close to that found in pure water. However,
this is not too surprising if the similarity between water and methanol is considered.
8.2. Solvolysis of Tert-Butyl Chloride

Solvolysis of tert-butyl chloride, investigated by Mason‘s group under sonication [27-
30], has important theoretical implications for understanding both solvation phenomena and
sonication effects. The authors clearly concluded that ultrasound caused perturbation of
molecular interactions taking place in the reacting system [30].
Now a more detailed interpretation of the results can be developed. The solvolysis of tert-
butyl chloride is accelerated in polar and protic solvents, as these stabilize the dipolar
transition state. However, in water the reaction is much faster than would be expected on the
basis of the polarity and hydrogen-bonding ability of water. Abraham et al. [93] showed that
owing to the hydrophobic character of the reagent its ground state is destabilized in water in
comparison to other polar protic solvents. Addition of ethanol to the solvent system causes an
effective hydrophobic stabilization of the ground state leading to a dramatic decrease of the
reaction rate (Figure 7).
The sonication effects for tert-butyl chloride solvolysis confirm the suggestions above. In
Figure 7 the data compiled from literature are compared with reaction rates under sonication,
obtained by extrapolation to the zero degree (0
o
C) of Arrhenius plots from the paper by
Mason et al. [29]. The sonication effects are large and increase with the increasing ethanol
content in the binary solvent.
Ultrasound and Hydrophobic Interactions in Solutions 147
0.0 0.2 0.4 0.6
-7
-6
-5
-4
-3
-2
X
EtOH
L
o
g

k

Figure 7. A compilation of literature data [94] for the solvolysis of tert-butyl chloride in aqueous
ethanol at 0 °C. Vertical arrows indicate the rate enhancement by sonication extrapolated from Mason‘s
kinetic data [29].
However, the reaction rate under ultrasound depends only slightly on the solvent
composition, which indicates that sonication suppresses hydrophobic ground-state
stabilization leaving little play for speculations on medium polarity effects. Extrapolation of
sonication data to pure water results in an almost negligible sonication effect, in accordance
with the highly destabilized ground state of tert-butyl chloride in water (vide supra).
It is remarkable that sonication-accelerated rate constants in Figure 7 mainly fall into the
range corresponding to lower ethanol content without sonication. Similarly, the rate constants
determined at 25 °C correspond to those found at 0 °C for considerably lower ethanol content
(Figure 8) As far as the temperature effect on reaction rates in condensed media comprises
inter alia changes in the solvation of reagents, both sonication and temperature effects can be
assigned to the shifts of solvation equilibria in the reaction system. Indeed, El Seoud [41] has
concluded that hydrogen bonding of water with the substrate ground state is less susceptible
to temperature increase than that of the organic component. This leads to a measurable
depletion of the organic co-solvent in the substrate solvation shell as a function of increasing
temperature.
The moderate influence of ultrasound on the reaction at 20 °C (Figure 1) thus cannot be
explained in conventional terms of solvent vapor pressure, but should be considered as an
evidence of a large difference in solvation at these temperatures. Moreover, Lorimer and
Mason [30] failed in establishing a distinct relationship between the reaction rate under
sonication and the solvent vapor pressure in this experiment. In some way or another (cf.
Section 6), sonication leads to a rise in the effective temperature of the species in solution,
resulting either in solvent structure break or in shift of the solvation equilibria.
This conclusion seems to be supported by the thermodynamic parameters of activation
for hydrolyses reactions. For the acid-catalyzed hydrolysis of methyl acetate only a little
variation in the activation energy was produced by the use of ultrasound. However, the
Arrhenius plots showed notably different intercept values for the irradiated and non-irradiated
reactions [15, 95] (Figure 9).
Ants Tuulmets, Siim Salmar and Jaak Järv 148
0.0 0.2 0.4 0.6
-7
-6
-5
-4
-3
-2
-1
25
o
C
0
o
C
X
EtOH
L
o
g

k

Figure 8. Rate data for the solvolysis of tert-butyl chloride in aqueous ethanol at 0 °C and 25 °C [94].
For the meaning of dotted lines see Text.
30 32 34 36 38
-8
-7
-6
-5
-4
-3
without sonication
under ultrasound
10
4
/ T
L
n

k

Figure 9. Arrhenius plots for the hydrolysis of methyl acetate. Data from [15].
Ultrasound and Hydrophobic Interactions in Solutions 149
Explanations of the sonochemical effect based on the shift of the frequency factor in the
Arrhenius equation under sonication have been suggested [15, 30, 95]. However, the reported
changes in thermodynamic activation parameters under sonication may largely be artifacts,
because in their calculation sums of rate constants (k
nonson
+ Δk
son
) appear under logarithm.
Indeed, if these are expanded into a logarithmic series we have

....
2
2
ln ) ln( ln +
A +
A
+ = A + =
son nonson
son
nonson son nonson son
k k
k
k k k k


Limiting the sum to the first two terms we obtain

nonson son
nonson son
nonson son
k k
k k
k k
+
÷
+ ~
) ( 2
ln ln


and if the sonication effect is small the difference in the frequency factor is

1
) ( 2
÷ ~
+
÷
~ A
nonson
son
nonson son
nonson son
k
k
k k
k k
A
,

with practically no difference of activation energy for the sonicated and non-sonicated
reaction, as was actually observed [15, 95].
However, if Δk
son
>> k
nonson
, which is the case for the data from Mason‘s group

[30], the
calculated activation parameters can reflect the real proportions. For the solvolysis of tert-
butyl chloride under sonication the values obtained for the activation entropy are largely
negative (Table 1). The most substantial decrease observed was nearly 500 J mol
-1
K
-1
in 60
wt% ethanol.

Even if some systematic error could be suspected in such large numbers, the
established trend in the data indicates a large electrostriction effect in the activation process
inherent for polar reactions in low-order media. Because ultrasound cannot affect the
transition state, these activation entropy values reflect a great disorder in the solvation of the
ground state brought about by ultrasound.

Table 1. Activation energies and entropy values for the solvolysis of tert-butyl chloride
in ethanol-water mixtures under sonication [30].

Ethanol
( wt%)
E
son
(kJ mol
-1
)
∆S

son
(J mol
-1
K
-1
)
20 62 -75
30 30 -193
40 10 -270
50 -21.6 -386
60 -49.5 -491

Ants Tuulmets, Siim Salmar and Jaak Järv 150
In contrast to the hydrolysis reactions [15, 95], a notable decrease in the observed
activation energy for solvolysis of tert-butyl chloride was found under sonication (Table 1).
For systems with higher ethanol content the decrease resulted in negative activation energies.
This appearance is reminiscent of those found for reactions of low intrinsic activation energy
whose mechanism comprises pre-equilibria that can account for the negative ΔH

obs
values
[96-99]. In such cases, if log k
obs
= log K + log k, and since -ΔH
o
> ΔH

it appears that

∆H

obs
= ∆H
o
+ ∆H

< 0.

The formal analogy between those processes and that under consideration stems out of
the similar procedure for determination of the activation energy. Since the reacting system
(M) undergoes a perturbation prior to the reaction,

M + AH
M* products,


the activation energy determined from the dependence of log k
obs
vs 1/T, appears as

E
a =
∆∆H + ∆H

.

Whereas the sonication effect diminishes with the increasing temperature, the amount of
acoustic energy absorbed by the reacting system accordingly decreases. Therefore ∆∆H < 0
which in some cases results in E
a
< 0.
9. THE SOLVENT STRUCTURE AND SONICATION EFFECTS
The rate of solvolysis of tert-butyl chloride in a binary solvent is nonlinear but smooth in
respect of the solvent composition and therefore does not reflect known features of the
solvent structure, e.g. those in aqueous alcohols. However, log k values of tert-butyl chloride
solvolysis in water-methanol and water-ethanol solutions plotted against each other (Figure
10A) show a distinct deviation of points in the region of
O H
2
X between 0.45 and 0.85. This
is just the region of cluster formation in aqueous ethanol found by physical investigations
[50-52]. In aqueous methanol the cluster formation is much weaker and can be observed only
at
O H
2
X < 0.6. As we have shown [21], the clusters are able to seize the reagent molecules
rendering them less reactive.
It was instructive to superpose kinetic sonication effects from the work by Mason‘s group
[29] on the graph. In Figure 10A arrows represent kinetic sonication effects in water-ethanol
solution at the same temperature. Evidently ultrasound breaks down the hydrophobic solvent
clusters and thus brings the solvation patterns of reagents closer to each other in the solvent
systems. It is not clear whether more intensive sonication would further shift the points in
Figure 10A; however, feeble sonication effects in aqueous methanol can be expected (see
Section 8.1). Nevertheless, available experimental data reflect well the impact of the
hydrophobicity driven solvent structure in aqueous binary solvents.

Ultrasound and Hydrophobic Interactions in Solutions 151
-6 -5 -4 -3 -2
-6
-5
-4
-3
-2
-6
-5
-4
-3
-2
A
B
Log k (H
2
O - EtOH)
L
o
g

k

(
H
2
O
-
M
e
O
H
)
L
o
g

k

(
H
2
O

-

d
i
o
x
a
n
e
)

Figure 10. Plot of log k for the solvolysis of tert-butyl chloride [69] A - in water-methanol and water-
ethanol binary mixtures, B - in water-1,4-dioxane and water-ethanol mixtures. The straight lines were
plotted to guide the eye and represent ideal solvation of the reagents. In A arrows represent kinetic
sonication effects in water-ethanol solution at the same temperature from Ref [29]. In B arrows
represent expected sonication effects in 1,4-dioxane-water solution.
Using the same approach as above, data for the tert-butyl chloride solvolysis in water-
1,4-dioxane and water-ethanol solutions were plotted in Figure 10B. In this case a deviation
in the opposite direction can be observed. Not much is known about the structure of water-
1,4-dioxane mixtures, however, it has been pointed out that the structural enhancement of
long range order in water-alcohol systems appears to be absent in mixtures of 1,4-dioxane and
water [66,67]. Moreover, in solutions ranging from pure water up to 0.2 mol fraction, 1,4-
dioxane gradually breaks down the structure of water [68]. Evidently, the solvent-structural
effects on the reactivity operating in water-1,4-dioxane mixtures are opposite to and exceed
those in the water-ethanol solvent system. As a result, somewhat unexpected deviations seen
in Figure 10B appear.
Sonication effects on the solvolysis of tert-butyl chloride in water- 1,4-dioxane mixtures
have not been determined, however, one can speculate upon two available facts. First, in
water-ethanol mixtures sonication effects for the solvolysis and for acid-catalyzed hydrolysis
of ethyl acetate show very similar dependences on composition of the solvent being small in
the region up to 15 mol% of the alcohol [21,30] (Figure 2). Second, rate of the acid-catalyzed
hydrolysis of ethyl acetate in water-1,4-dioxane solution exhibits remarkable susceptibility to
sonication just in this region [21]. Consequently, if the latter is valid also for the solvolysis
reaction, sonication effects would be significant for the reaction in the water-1,4-dioxane
solution shifting the points in Figure 10B upwards and thus reducing the differences between
the straight line and the experimental curve.

Ants Tuulmets, Siim Salmar and Jaak Järv 152
10. THE DOMINO EFFECT IN UNDERSTANDING OF SOLVATION
PHENOMENA
The progress in understanding of solvation phenomena in ethanol-water binary mixtures
attained through the LFE-analysis of sonication data (Section 8.1) allows us to expand the
analysis to different reactions in various water-organic solvents [100].
For rate data processing, the free-energy relationship can be used in the form

log k = C
sim
log k
st
+ b,

where C
sim
is the similarity coefficient [92] and k
st
is the rate constant of the standard reaction,
the solvolysis of tert-butyl chloride in this case.
Rate constants of reactions in aqueous organic binary solvents were correlated with those
for the solvolysis of tert-butyl chloride in the same solvents. Relying on principles of the
LFE-analysis, the solute-solvent interactions for the standard process and for the process
under consideration must be closely related [9]. In reverse, if the LFE relationship holds,
similarity between the solute-solvent interactions is greatly plausible.
Correlations found were good to excellent for binary solvents, ranging from water-rich
systems up to mixtures with prevailing organic co-solvent. Numerical values of the similarity
coefficients reflect the susceptibility of reaction rates to changes in the solvent composition
relative to the solvolysis of tert-butyl chloride in the same binary solvent.
The most impressive conclusion from the results was the fact that good correlations had
been found for such definitely different reactions as ester hydrolyses, various reactions with
ionic and non-ionic reactants, a Menshutkin reaction and S
N
2 replacements included. It is
remarkable that all these reactions provided linear relationship with kinetic data for tert-butyl
chloride solvolysis, an S
N
1 reaction, in a wide range of the co-solvent content. Thus, it can be
inferred that independent of substrate and the reaction mechanism, the nature of this
phenomenon is caused by hydrophobic interactions of reagents with the aqueous reaction
medium.
It has to be mentioned that the similarity determination procedure has some similarity to
correlations with the well known Y values by Grunwald and Winstein [101]:

Y = log k
t-BuCl
(solvent) - log k
t-BuCl

(80 vol% EtOH-H
2
O).

However, the approach of this work [100] was more straightforward because only the
values for log k
t-BuCl
in different solvents were involved as standard systems, and these plots
clearly point to the prevalent contribution of hydrophobic interactions in water-organic binary
systems. This means that the Y parameters, as derived by using the log k values in water-
ethanol mixture, should also contain this influence. The latter aspect has, however, never been
discussed before.


Ultrasound and Hydrophobic Interactions in Solutions 153
CONCLUSION
Application of quantitative methods, including kinetic measurements and correlation
analysis, to the study of homogeneous ionic reactions under sonication in aqueous and
aqueous-organic solutions has opened new perspectives for better understanding of the
mechanism of these reactions and solvation phenomena in general. Quantitative correlation of
kinetic sonication effects with substrate hydrophobicity has shed more light on details of the
solvation of reagents in aqueous-organic binary solutions. Therefore ultrasound may now
become a useful tool for physico-chemical investigations to reveal subtle hydrophobic
interactions that remain hidden in conventional kinetic analysis.
An analysis of sonication data has revealed that independent of the reaction mechanism
the decrease in reaction rate with increasing content of hydrophobic co-solvent is mainly due
to the ground-state stabilization of reagents and this phenomenon is largely of hydrophobic
origin. Following this concept, if ultrasonication suppresses the hydrophobic stabilization of
reagents, it accelerates the reaction. On contrary, if ultrasonication perturbs the stabilization
of encounter complexes between the reagents, sonication hinders the reaction. Notably, the
first experimental evidence of this phenomenon has been obtained.
The detailed knowledge about the mechanism of ultrasonic acceleration and retardation
of reactions can be useful for chemical technology, based on application of aqueous solvent
systems as ―green‖ media. The same conclusion can be drawn for biotechnology, if control of
chemical modification of proteins is needed in water-based media. Moreover, the capability
of ultrasound to control reactions by affecting weak interactions between reacting species in
water solutions also indicates that the impact of ultrasound on living organisms may have
much more complex nature than the physical and chemical destructive effects caused by
cavitation phenomena.
In summary, many of the conclusions drawn so far reach beyond the conventional
sonochemistry, giving for the first time some more information about solution chemistry and
physical organic chemistry. In this way, investigations into homogeneous polar reactions have
provided clear evidence that sonochemistry is not merely a random method for the
improvement of reaction yields by few percentage or a tool for sludge degradation in the
sewage industry. It is a useful probe for solution chemistry that can reveal information not
easily obtained by any other method.
REFERENCES
[1] Suslick, K. S. Ultrasound, its Chemical, Physical and Biological Effects; VCH
Publishers: New York, 1990.
[2] Mason, T. J.; Peters, D. Practical Sonochemistry. Power Ultrasound: Uses and
Applications; Ellis Horwood: Chichester, 2002.
[3] Mason, T. J.; Lorimer, J. Applied Sonochemistry: Uses of Power Ultrasound in
Chemistry and Processing; Wiley-VCH: 2002.
[4] Luche, J. L. Synthetic Organic Sonochemistry; Plenum Press: New York 1998.
[5] Gedanken, A. Ultrason. Sonochem. 2007, 14, 418-430.
[6] Mason, T. J.; Cintas, P. In Handbook of Green Chemistry; Clark, J.; Macquarrie, D.;
Eds.; Blackwell: Oxford, 2002.
Ants Tuulmets, Siim Salmar and Jaak Järv 154
[7] Mason, T. J. Chem. Soc. Rev. 1997, 26, 443-451.
[8] Cravotto, G.; Cintas, P. Chem. Soc. Rev. 2006, 35, 180-196.
[9] Reichard, C. Solvents and Solvent Effects in Organic Chemistry; 3rd Ed.; VCH:
Weinheim, 2003.
[10] Noltingk, B. E.; Neppiras, E. A. Proc. Phys. Soc. 1950, 63B, 674-685.
[11] Reisse, J.; Caulier, T.; Dekerckheer. C.; Kegelaers, Y.; Segebarth, N.; Bartik, K. In
Sonochemistry and Sonoluminescence; Crum, L. A.; Ed.; Kluwer Acad. Publ.:
Dordrecht, 1999; p.205-224.
[12] Kegelaers, Y.; Eulaerts, O.; Reisse, J.; Segebarth, N. Eur. J. Org. Chem. 2001, 19,
3683-3688.
[13] Luche, J. L.; Einhorn, C.; Einhorn, J.; Sinisterra-Gago, J. V. Tetrahedron Lett. 1990,
31, 4125-4128.
[14] Thompson, D.; Vilbrand, F. C.; Gray, W. C. J. Acoust. Soc. Am. 1953, 25, 485-490.
[15] Chen, N.; Kalback, W. M. Ind. Eng. Chem. Fundam. 1967, 6, 175-178.
[16] Fogler, S.; Barnes, D. Ind. Eng. Chem. Fundam. 1968, 7, 222-226.
[17] Couppis, E. C.; Klinzing, G. E. AIChE J. 1974, 20, 485-491.
[18] Tuulmets, A.; P.Raik, P. Ultrason. Sonochem. 1999, 6, 85-87.
[19] Tuulmets, A.; Salmar, S.; Talu, L. International Conference and Exhibition on
Ultrasonics (ICEU-99); New Delhi, December 24, 1999; Conference Papers; Vol. 2,
320-323.
[20] Tuulmets, A.; Salmar, S, Ultrason. Sonochem. 2001, 8, 209-212.
[21] Tuulmets, A.; Salmar, S.; Hagu, H. J. Phys. Chem. B 2003, 107, 12891-12896.
[22] Kristol, D. S.; Klotz, H.; Parker, R. C. Tetrahedron Lett. 1981, 22, 907-908.
[23] Salmar, S.; Cravotto, G.; Tuulmets, A.; Hagu, H. J. Phys. Chem. B 2006, 110, 5817-
5821.
[24] Yim, B.; Nagata, Y.; Maeda, Y. J. Phys. Chem. A 2002, 106, 104-107.
[25] Hua, I.; Höchemer, R. H.; Hoffmann, M. R. J. Phys. Chem. 1995, 99, 2335-2342.
[26] Ando, T.; Fujita, M.; Kimura, T.; Kondo, Y. J. Org. Chem. 1998, 63, 6048-6049.
[27] Lorimer, J. P.; Mason, T. J. J. Chem. Soc. Chem. Commun. 1980, 1135-1136.
[28] Mason, T. J.; Lorimer, J. P.; Mistry, B. P. Tetrahedron Lett. 1982, 23, 5363-5364.
[29] Mason, T. J.; Lorimer, J. P.; Mistry, B. P. Tetrahedron 1985, 41, 5201-5204.
[30] Lorimer, J. P.; Mason, T. J.; Mistry, B. P. Ultrasonics 1987, 25, 23-28.
[31] Broekaert, L.; Reisse, J. Abstracts 4th Meeting Eur. Soc. Sonochemistry, 18-22 Sept.
1994; Blankenberge, Belgium; 49.
[32] Hagu, H.; Salmar, S.; Tuulmets, A. Proc. Estonian Acad. Sci. Chem. 2002, 51, 235-239.
[33] Hagu, H.; Salmar, S.; Tuulmets, A. Ultrason. Sonochem. 2007, 14, 445-449.
[34] Tuulmets, A.; Hagu, H.; Salmar, S.; Cravotto, G.; Järv, J. J. Phys. Chem. B 2007, 111,
3133-3138.
[35] Piiskop, S.; Hagu, H.; Järv, J.; Salmar, S.; Tuulmets, A. Proc. Estonian Acad. Sci.
Chem. 2007, 56, 199-206.
[36] Breslow, R. In Green Chemistry; Anastas, P. T.; Williams, T. C.; Eds.; Oxford Press:
New York, 1983; Ch. 13.
[37] Breslow, R. In Organic Reactions in Water; Lindström, V. M.; Ed.; Blackwell
Publishers: Oxford, 2007; 1-28.
[38] Blokzijl, W.; Engberts, J. B. F. N. Angew. Chem. Int. Ed. Engl. 1993, 32, 1545-1579.
[39] Otto, S.; Engberts, J. B. F. N. Org. Biomol. Chem. 2003, 1, 2809-2820.
Ultrasound and Hydrophobic Interactions in Solutions 155
[40] Franks, F.; Ives, D. J. G. Quart. Rev. 1966, 20, 1-44.
[41] El Seoud, O. A. Pure Appl. Chem. 2007, 79, 1135-1151.
[42] Lindström, V. M. Chem. Rev. 2002, 102, 2751-2772.
[43] Li, C. Chem. Rev. 2005, 105, 3095-3166.
[44] Rispens, T.; Caballeiro-Lago, C.; Engberts, J. B. F. N. Org. Biomol. Chem. 2005, 3,
597-602.
[45] Breslow, R.; Groves, K.; Mayer, M. U. Pure Appl. Chem. 1998, 70, 1933-1938.
[46] Breslow, R. J. Phys. Org. Chem. 2006, 19, 813-822.
[47] Blokzijl, W.; Engberts, J. B. F. N.; Jagen, J.; Blandamer, M. J. J. Phys. Chem. 1987, 91,
6022-6027.
[48] Connors, K. A. In Handbook of Solvents; Wypych, G.; Ed.; Chem Tec Publishing:
Toronto, 2001; 281-303.
[49] Blandamer, M.J.; Burgess, J.; Engberts, J. B. F. N.; Warrick, P. Jn. J. Mol. Liq. 1992,
52, 15-39.
[50] Nishi, N.; Takahashi, S.; Matsumoto, M.; Tanaka, A.; Muraya, K.; Takamuku, T.;
Yamaguchi, T. J. Phys. Chem. 1995, 99, 462-468.
[51] Egashira, K.; Nishi, N. J. Phys. Chem. B 1998, 102, 4054-4057.
[52] Wakisaka, A.; Komatsu, S.; Usui, Y. J. Mol. Liq. 2001, 90, 175-184.
[53] Franks, F.; Johnson, H. H. Trans. Faraday Soc. 1962, 58, 656-661.
[54] Buhvestov, U.; Rived, F.; Ràfols, C.; Bosch, E.; Rosés, M. J. Phys. Org. Chem. 1998,
11, 185-192.
[55] Dixit, S.; Crain, J.; Poon, W. C. K.; Finney, J. L.; Soper, A. K. Nature 2002, 416, 829-
832.
[56] Suslick, K. S. Science 1990, 247, 1439-1445.
[57] Huang, J. L.; Feng, R.; Zhu, C. P.; Chen, Z. H. Ultrason. Sonochem. 1995, 2, 93-97.
[58] Berlan, J.; Mason, T. J. Adv. Sonochem. 1996, 4, 1-73.
[59] Mason, T. J.; Lorimer, J. P.; Bates, D. M.; Zhao, Y. Ultrason. Sonochem. 1994, 1, 91-
95.
[60] Ratoarinoro; Contamine, F.; Wilhelm, A. M.; Berlan, J.; Delmas, H. Ultrason.
Sonochem. 1995, 2, 43-47.
[61] Kimura, T.; Sakamoto, T.; Leveque, J. M.; Sohmiya, H.; Fujita, M.; Ikeda, S.; Ando, T.
Ultrason. Sonochem. 1996, 3, 157-161.
[62] Koda, S.; Kimura, T.; Kondo, T.; Mitome, H. Ultrason. Sonochem. 2003, 10, 149-157.
[63] Asano, T.; Le Noble, W. J. Chem. Rev. 1978, 78, 407-489
[64] Engberts, J. B. F. N.; Blandamer, M. J. J. Phys. Org. Chem. 1998, 11, 841-846.
[65] Buurma, N. J.; Pastorello, L.; Blandamer, M. J.; Engberts, J. B. F. N. J. Am. Chem. Soc.
2001, 123, 11848-11853.
[66] Franks, F. In Physico-Chemical Processes in Mixed Aqueous Solvents; Franks, F.; Ed.;
Heinemann: London, 1967.
[67] Hammes, G. G.; Knoche, W. J. Chem. Phys. 1966, 45, 4041- 4048.
[68] Feakins, D.; O´Neill, R. D.; Waghorne, W. E. J. Chem. Soc. Faraday Trans. I 1983, 79,
2289-2298.
[69] Winstein, S.; Fainberg, A. H. J. Am. Chem. Soc. 1957, 79, 5937- 5950.
[70] Arnett, E. M.; McKelvey, D. R. J. Am. Chem. Soc. 1965, 87, 1541-1553.
[71] Tommila, E.; Murto, M. L. Acta Chem. Scand. 1963, 17, 1957-1970.
Ants Tuulmets, Siim Salmar and Jaak Järv 156
[72] Mark, G.; Tauber, A.; Laupert, R.; Schuchmann, H. P.; Schulz, D.; Mues, A.; von
Sonntag, C. Ultrason. Sonochem. 1998, 5, 41-52.
[73] Tauber, A.; Schuchmann, H. P.; von Sonntag, C. Chem. Eur. J. 1999, 5, 2198-2202.
[74] Henglein, A. Adv. Sonochem. 1993, 3, 17-83.
[75] Riesz, P. Adv. Sonochem. 1991, 2, 23-64.
[76] Burdin, F.; Tsochatzidis, N. A.; Guiraud, P.; Wilhelm, A. M.; Delmas, H. Ultrason.
Sonochem. 1999, 6, 43-51.
[77] Birkin, P. R.; Leighton, T. G.; Power, J. F.; Simpson, M. D.; Vinçotte, A. M. L.;
Joseph, P. F. J. Phys. Chem. A 2003, 107, 306-320.
[78] Brennecke, J. F.; Chateauneuf, J. E. Chem Rev. 1999, 99 , 433-452.
[79] Homer, J.; Howard, M. J.; Gooda, S. C. Ultrason. Sonochem. 1995, 2, 71-74.
[80] Homer, J.; Patel, S. V. J. Chem. Soc. Faraday Trans. 1990, 86, 215-216.
[81] Homer, J.; Paniwnyk, L.; Palfreyman, S. A. Adv. Sonochem. 1996, 4, 75-99.
[82] Cravotto, G.; Cintas, P. Chem. Soc. Rev. 2009, 38, 2684-2697.
[83] Eigen, M.; Kurtze, G.; Tamm, K. Z. Electrochem. 1953, 57, 103-118.
[84] Eigen, M.; Discuss. Faraday Soc. 1954, 17, 194-205.
[85] Tuulmets, A.; Ultrason. Sonochem. 1997, 4, 189-193.
[86] March, J. Advanced Organic Chemistry; 4th Ed.; Wiley: New York, 1992; 969-970.
[87] Kool, E. T.; Breslow, R. J. Am. Chem. Soc. 1988, 110, 1596-1597.
[88] Tuulmets, A.; Järv, J.; Salmar, S.; Cravotto, G. J. Phys. Org. Chem. 2008, 21, 1002-
1006.
[89] Hansch, C. Acc. Chem. Res. 1969, 2, 232-239.
[90] Hansch, C.; Leo, A.; Hoekman, D. Exploring QSAR: Hydrophobic, Electronic, and
Steric Constants; ACS: Washington DC, 1995.
[91] Shorter, J. Correlation Analysis in Organic Chemistry; Clarendon Press: Oxford, 1973.
[92] Williams, A. Free Energy Relationships in Organic and Bio-Organic Chemistry; RSC:
Cambridge, 2003.
[93] Abraham, M. H.; Gullier, P. L.; Naschzadeh, A.; Walker, R. A. C. J. Chem. Soc. Perkin
Trans. 2 1988, 9, 1717-1724.
[94] Palm, V. A.; Ed.; Tables of Rate and Equilibrium Constants of Heterolytic Organic
Reactions; Publ. House VINITI: Moscow, 1977; Vol. 3(1).
[95] Lorimer, J. P. In Sonochemistry: The Uses of Ultrasound in Chemistry; Mason, T.J.;
Ed.; RSC: Cambridge, 1990; Ch. 2, 9-26.
[96] Singh, T. D.; Taft, R. W. J. Am. Chem. Soc. 1975, 97, 3867-3869.
[97] Nagy, O. B.; Reuliaux, V.; Bertrand, N.; van der Mensbrugghe, A.; Leseul, J.; Nagy, J.
B. Bull. Soc. Chim. Belg. 1985, 94, 1055-1074.
[98] Talvik, A. T.; Tuulmets, A.; Vaino, E. J. Phys. Org. Chem. 1999, 12, 747-750.
[99] Tuulmets, A.; Talvik, A. T. ACH-Models in Chem. 2000, 137, 111-119.
[100] Tuulmets, A.; Järv, J.; Tenno, T.; Salmar, S. J. Mol. Liq. 2009, 148, 94-98.
[101] Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846-854.

Reviewed by Professor Timothy J. Mason
Director of the Sonochemistry Centre
Faculty of Health and Life Sciences
Coventry University, UK
In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 5



SYNTHETIC METHODOLOGIES
USING SONINCATION TECHNIQUES


Ziyauddin S. Qureshi, Krishna M. Deshmukh
and Bhalchandra M. Bhanage
1

Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg,
Matunga, Mumbai-400 019. India
ABSTRACT
Ultrasound generates cavitation, which is "the formation, growth, and implosive
collapse of bubbles in a liquid. Cavitation collapse produces intense local heating (~5000
K), high pressures (~1000 atm), and enormous heating and cooling rates (>109 K/sec)"
and liquid jet streams (~400 km/h), which can be used as a source of energy for a wide
range of chemical processes. This review will concentrate on theory, reactions and
synthetic applications of ultrasound in both homogeneous liquids and in liquid-solid
systems. Some recent applications of ultrasound in organic synthesis, such as, Suzuki
reaction, Sonogashira reaction, Biginelli reaction, Ullmann coupling reaction,
Knoevenagel condensation, Claisen-Schmidt condensation, Reformatsky reaction,
Bouveault reaction, Baylis-Hillman reaction, Michael addition, Curtius rearrangement,
Diels-Alder reaction, Friedal-Craft acylation, Heck reaction, Mannich type reaction,
Pechmann condensation and effect of ultrasound on phase transfer catalysis, oxidation-
reduction reactions, ionic liquids and photochemistry are reviewed. Ultrasound found to
provide an alternative to traditional techniques by means of enhancing the rate, yield and
selectivity to the reactions.
INTRODUCTION
Chemicals reactions are typically performed using conventional thermal energy sources
such as oil baths, sand baths and heating jackets. These sources can develop temperature

1
Tel.: +91 22 24145616; fax: +91 22 24145614, Email address: bhalchandra_bhanage@yahoo.com;
bmb@udct.org.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 158
gradient within the sample. In addition to this over heating, which occurs many times can lead
to product, substrate and reagent decomposition. Owing to these, there are various constraints
for use of conventional energy sources for organic reactions. Hence, increasing efforts have
been made during the last decades to replace conventional energy sources with other non-
conventional techniques such as Ultrasound and Microwaves. The non-conventional sources
often have upper hand in terms of selectivity, reaction time and operational simplicity. For
instance, many reactions can be made to go completion at ambient temperature under
ultrasound irradiation. Sonochemistry is the study of the effect of ultrasound on chemical
reaction [1-5]. On the basis of the frequency, sound is divided into three ranges (Figure 1).
Thus, ultrasound is defined as any sound a frequency beyond the level to which human
ear can respond, i.e. 20 KHz. The sound audible to the human ear falls between 16 Hz (cycles
per second) to 18 KHz and it has no effect on chemical reactions. Ultrasound is again divided
into two regions namely, high frequency ultrasound having frequency in the range of 1-10
MHz and power ultrasound with frequencies between 20-100 MHz. the upper limit of
ultrasound frequency is one which is not sharply defined but is taken to be 5 MHz for gases
and 500 MHz for liquid and solids.
The use of ultrasound within this frequency range may be divided broadly into two areas.
The first area may involve low amplitude (higher frequency) propagation, which is concerned
with the effect of the medium on the wave and is commonly referred to as low power or
higher frequency ultrasound. It is used in the medicinal scanning, chemical analysis and the
study of relaxation phenomenon. The second area involve high energy (low frequency) wave
known as power ultrasound, which is between 20-100 KHz used for cleaning, plastic welding
and more recently to effect the chemical reactivity [1]. The application of high frequency
ultrasound concerned essentially with the measurement of degree to which the sound is
absorbed as it passes through medium.

Infrasound: Frequencies below 10 Hz fall in the category of infrasound.
Sonic: The human hearing range (10 Hz-18 KHz) and is termed as sonic range.
Ultrasonic: Frequencies greater than 20 KHz are called ultrasonic waves.
Figure 1. Ultrasound range diagram.
Synthetic Methodologies Using Sonincation Techniques 159
This effect is known as ‗attenuation‘. High frequency ultrasound is used in medicine for
fetus imaging, in under water range finding (SONAR) and in non-destructive testing of metals
for flaws. For chemist, ultrasound is a form of energy that would be considered for the
acceleration of chemical reactions.
In many chemical reactions, both homogeneous and heterogeneous applications of
ultrasound is known to increases the reaction rates, change in chemical reaction pathway and
assist in conducting the reaction under less severe conditions. There are a few examples of
reactions which occur only upon irradiation with ultrasound.
Most modern ultrasonic devices rely on transducer which use the inverse effect i.e.
production of an electrical potential across the opposite faces. If the potential is alternated at a
high frequency, the crystal converts the electrical energy into the sound energy [6]. Different
types of transducers are used for generating ultrasound waves. These are piezoelectric,
magnetostrictive, mechanical, electromagnetic, electrostatic and miscellaneous which
includes thermal, chemical and optical transducers Figure 2.


Figure 2. The energy transformation chain in an ultrasonic apparatus.

Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 160
Ultrasonic waves can be focused, reflected and refracted, but they require a medium of
elastic properties for propagation. When these waves propagate, particles in the elastic
medium oscillate and transfer the energy through the medium in the direction of prppagation.
The marked effect of ultrasound actually arises from the way in which sound propagates
through the medium. In solid, both longitudanl and transverse waves can be transmitted
where as in gas and liquids only longitudinal waves can be transmitted. In liquids,
longitudinal vibrations of molecule generate compressions and rarefactions, i.e. alternating
zone of high pressure and low pressure. The low pressure gives rise to formation of cavities
or bubbles which expand and finally, during the compression phase collapse violently
generating shock waves. The phenomenon of bubble formation and collapse is generally
known as cavitation and is generally responsible for most of the ultrasonic physical and
chemical effects in solid/liquid or liquid/liquid.
Cavitation: The principle phenomenon behind all the effect of ultrasound is cavitation.
First reported in 1895 [7], cavitation is defined as phenomenon of formation, growth and
eventual collapse of small bubbles within a liquid [8-9]. A cavity or bubble is grown by
reducing the ambient pressure by static or dynamic means. The word formation is also refers
to the excitation of the cavities or microbubbles that are already present in the medium under
the influence of the pressure variation. Cavitation is classified in many ways. The one which
is based on the method of its generation is given below.

1. Acoustic cavitation: In this cavitation the growth of the cavity is induced by the
pressure variation by the passage of ultrasound.
2. Hydrodynamic cavitation: This type of cavitation is induced by pressure variation in
the system by changing the flow geometry of the flow system. This can be achieved
by passing the fluid through a reducing cross-section, like a venture or an orifice.
3. Optic cavitation: This cavitation is produced by passing photons of high intensity
light (laser), rupturing the liquid bonds.
4. Particle cavitations : It is produced by bombarding a liquid with high intensity
particles, like proton, rupturing the liquid of the four types listed above, only acoustic
cavitation and hydrodynamic cavitation have the potential for commercially
exploitation. In the present work, acoustic cavitation has been used to carry out
organic reactions.

Since liquids are not elastic, successive cycles of compression and rarefaction lead to
non-uniform translational motion of individual molecules within the solution, which enhance
the rate of the transport processes. As the power is increased, more efficient mixing is
typically observed. In addition, applied above a critical intensity, ultrasonic irradiation can
also induce oxidation and other chemical reactions.
Factors affecting cavitation:

a) Frequency of ultrasound: Using moderate power, any common liquid (generally
water) can be made to undergo cavitation in the frequency range of 20-50 KHz which
is usually to carry out sonochemical reactions. In a sonochemical reaction, as the
frequency of irradiation is increased, more power is required to maintain an
equivalent amount of cavitation in a liquid. In a high frequency region, the cavitation
is difficult as the rarefaction and compression cycles are so rapid, that sufficient time
Synthetic Methodologies Using Sonincation Techniques 161
is not available to pull the molecule of the liquid part, thereby generating the bubble
and further growth of it.
b) Intensity of ultrasound (power input): As the intensity of sonication is increases,
sonochemical effect increases due to increase in the amplitude of vibration of the
source of ultrasound. But, due to certain factors, such as damage to the transducer,
loss in efficiency of the transfer of the power from the source to the medium and
formation of more number of bubbles, which collapse to form stable bubbles
ultrasonic energy input to the system, can not increase. These may dampen the
passage of sound energy through the liquid and also remove many of the smaller
bubbles, which would have collapsed to give sonochemical effects. Luche has
illustrated the importance of the use of proper intensity (power) [10].

Now a days, ultrasonic bath and ultrasonic probe/horn are the most commonly used
source of ultrasonic irradiation in the chemical laboratory Figure 3.


a b
Figure 3. (a) Ultrasonic bath (b) Ultrasonic probe.
There are three different types of reactions susceptible to sonochemical enhancement.

1) Homogeneous sonochemistry: homogeneous systems that proceed via radical or
radical-ion intermediates. This implies that sonication is able to affect reactions
proceeding through radicals and, furthermore, that it is unlikely to affect ionic
reactions. In the case of volatile molecules, the bubbles (or cavities) are believed to
act as a microreactor; as the volatile molecules enter the microbubbles and the high
temperature and pressure produced during cavitation break their chemical bonds,
short-lived chemical species are returned to the bulk liquid at room temperature, thus
reacting with other species. Compounds of low volatility, which are unlikely to enter
bubbles and thus be directly exposed to these extreme conditions, still experience a
high energy environment resulting from the pressure changes associated with the
propagation of the acoustic wave or with bubble collapse (shock waves);
alternatively, they can react with radical species generated by sonolysis of the
solvent.
2) Heterogeneous sonochemistry (liquid–liquid or solid–liquid systems): heterogeneous
systems that proceed via ionic intermediates. Here, the reaction is influenced
primarily through the mechanical effects of cavitation, such as surface cleaning,
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 162
particle size reduction, and improved mass transfer. When cavitation occurs in a
liquid near a solid surface, the dynamics
3) of cavity collapse change dramatically. In homogeneous systems, the cavity remains
spherical during collapse because its surroundings are uniform (Figure 4a). Close to a
solid boundary, cavity collapse is very asymmetric and generates high-speed jets of
liquid (with velocities of approximately 400 Km/h; Figure 4b). These jets hit the
surface with tremendous force. This process can cause harsh damage at the point of
impact and produce newly exposed highly reactive surfaces.
4) Sonocatalysis (overlap homogeneous and heterogeneous sonochemistry):
heterogeneous reactions that include a radical and ionic mechanism. Radical
reactions will be chemically enhanced by sonication, but the general mechanical
effect described above may very well still apply. If radical and ionic mechanisms
lead to different products, US should favor the radical pathway, potentially leading to
a change in the nature of the reaction products.


Figure 4. (a) Cavitation bubble in a homogeneous system; (b) cavitation bubble in a heterogeneous
system.
ULTRASOUND IN ORGANIC SYNTHESIS:
The application of ultrasound in organic synthesis has gained considerable attention in
recent years and several organic transformations are effected using ultrasound. It has been
observed that they reduce the reaction temperature and higher reaction rates can be achieved
at ambient conditions. Some of important contributions are summarized bellow.
Suzuki Reaction

The Suzuki reaction is one of the most studied carbon-carbon bond forming reaction and
useful for the synthesis of several symmetrical/unsymmetrical biaryls (Scheme. 1) [11].
Couple of the methods has been reported for Suzuki reaction under ultrasound and microwave
irradiation [12-13].

B(OH)
2
H
3
CO
Br
H
3
CO +
Pd, base
Solvent
)))

Scheme. 1. Ultrasound-assisted Pd catalyzed Suzuki–Miyaura cross-coupling reaction.
Synthetic Methodologies Using Sonincation Techniques 163
Palladium (0)-catalyzed cross-coupling reactions between potassium aryl- and
inyltrifluoroborate salts and aryl- and vinylic tellurides proceeds readily to afford the desired
stilbenes in good to excellent yields (Scheme. 2) [14-16]. Stilbenes containing a variety of
functional groups can be prepared.

R
X Te R
1
R
X R
2
R
R
2
R
R
2
R
2
R
2
BF
3
K, Pd(PPh
3
P)
4
Ag
2
O, Et
3
N, MeOH
)))
+
+

Scheme 2. Cross-coupling reaction between potassium organotrifluoroborate salts and the
organotellurium compounds.
Reaction of 3-bromo-4-hydroxycoumarin with aryl boronic acid under high-intensity
ultrasound with Pd/C heterogeneous catalyst was carried out. 3-Arylation with the Suzuki
procedure had failed, exclusively affording the homocoupling products, symmetric biaryls
(Scheme. 3) [17]. Besides offering a number of operational advantages, the use of HIU
broadens the field of application for the Suzuki reaction.

O O
OH
Br
O O
OH
O O
OH
Ar
Ar-Ar
Ar-B(OH)
2

Scheme 3. Suzuki homocoupling of arylboronic acids in the presence of 3-bromo-4-hydroxycoumarin.
Sonogashira Coupling

Srinivasan et al. have reported firstly a copper-, ligand- and amine-free one-pot synthesis
of benzo[b]furans via palladium acetate catalyzed tandem Sonogashira coupling-5-endo-dig-
cyclization under ultrasonic irradiation at ambient temperature (Scheme. 4) [18].

OH
I
Ph
O
Ph
Pd(OAc)
2
, Base
Solvent, )))
+

Scheme. 4. Synthesis of 2-substituted benzo[b]furan/nitro benzo[b]furan under ultrasonic irradiation.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 164
Similar concept was applied for ligand-, copper-, and amine-free one-pot synthesis of 2-
substituted indoles via Sonogashira coupling 5-endo-dig cyclization (Scheme. 5) [19].

NHTs
I
Ph
N
Ts
Ph
Pd(OAc)
2
, Base
Solvent, )))
+

Scheme. 5. Synthesis of indole derivatives under ultrasonic irradiation.
Biginelli Reaction

The Biginelli reaction was first described more than a century ago, as a one-pot
multicomponent reaction providing low yield (20-50%) of the product [20]. Biginelli reaction
is a condensation of 1,3-dicarbonyl compounds with aldehydes and urea or thiourea in the
presence of a catalytic amount of an acid (Scheme. 6).

R
1
R
2
O O
R
3
H
O
H
2
N NH
2
X
N
H
NH
R
1
R
3
R
2
O
X
+
+
X = O, S

Scheme 6. Biginelli reaction
The product dihydropyrimidinones (DHPMs) are serving as skeleton in many natural or
synthetic biologically active materials and its derivatives are applied in various
pharmaceuticals and biochemicals fields (Figure 6) [21-23].

O
Et
N
H
N
H
O
O
H
N
O
NH
2
NH
2
OH
N
H
O
Me
X
-
+
Crambescidin 800
( )
12

Synthetic Methodologies Using Sonincation Techniques 165
OH
C
2
H
5
O O
HN NH
S
Monastrol

Figure 5. Some biologically active DHPMs.
Dihydropyrimidin-2-ones (thiones) (DHPM) were also recently prepared under
ultrasound irradiation in solvent-free conditions [24]. The Biginelli reaction was catalyzed by
HCl (1 mol %) or trifluoroacetic acid (5 mol %) and completed within 15–45 min in reactions
involving urea and 60–90 min in reactions involving thiourea. Srinivasan and co-workers [25]
discovered that Biginelli reactions can also be performed in the absence of any catalyst. The
reaction between aldehydes, ethyl acetoacetate and urea or thiourea was carried out in 1-n-
butylimidazolium tetrafluoroborate [Hbim]BF
4
, a non-volatile ionic liquid, in the presence of
sonic waves in a very short reaction time. DHPM(s) were easily isolated and in a high yield,
by simple dilution and filtration procedure. The aqueous filtrate was then distilled to remove
water and leave behind quantitative yields of [Hbim]BF
4
. The recovered ionic liquid could be
reused in the same reaction at least three times without decrease in yield. Based on the
spectral data, the authors were able to postulate that the ionic liquid plays an important role in
this multicomponent reaction, acting as an inherent Brønsted acid.
Li and co-workers [26-27] used ultrasound to promote the Biginelli reaction between
aldehydes, β-keto esters, and urea to obtain DHPM in good to excellent yields. The reaction
was catalyzed by aminosulfonic acid or iodine and, in both cases; the reaction was very
tolerant of aromatic aldehydes carrying either electron-withdrawing or electron-donating
substituents. However, when aliphatic aldehydes were employed, the iodinecatalyzed reaction
was not very successful.
Yadav and co-workers [28] showed that ceric ammonium nitrate (CAN) can also be used
as a catalyst in ultrasound promoted Biginelli reaction. The reaction was carried out in
methanol under ultrasonic waves. Heteroaryl, aromatic (electron poor or electron rich),
aliphatic, and α,β-unsaturated aldehydes were used and, in all cases, compounds were
obtained in high yields and with high purity. The authors suggest a radical mechanism for the
reaction, in which a single-electron transfer from CAN to the β-keto esters and latter radical
adds to the imine intermediate.
DHPM(s) have been produced by utilization of inexpensive ammonium chloride as a
mediator of the reaction under ultrasound irradiation [29]. The Biginelli reaction was carried
out in methanol and irradiated for 3–5 h in a cleaning bath. The antioxidant activity of these
DHPM(s) was evaluated, and some of these compounds exhibited strong activity against lipid
peroxidation induced by Fe and EDTA.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 166
Ullmann Coupling Reaction

The Ullmann condensation between 2-chlorobenzoic acid and 2-aminopyridine
derivatives using ultrasound has been described [30-31]. The reaction was carried out in the
presence of anhydrous potassium carbonate and copper powder using DMF as solvent
(Scheme 7). In comparison with conventional conditions (stirring for 6 h at reflux
temperature), the ultrasound irradiated reaction demonstrated a shorter reaction time (20 min)
and greater yields

N
R
1
R
2
H
2
N
R
5
R
4
R
3
Cl
OH
O
N
N
O
R
1
R
2
R
3
R
4
R
5
Cu, K2CO3, DMF
)))
+

Scheme 7. Ultrasound mediated Ullmann condensation between 2-chlorobenzoic acid and 2-
aminopyridine derivatives.
Mason and group reported ultrasound assisted methods for Ullmann coupling reaction of
halonitro benzene in presence of copper powder which enhances the reaction reactivity to a
50 fold [32-33]. Ultrasonic irradiation of a mixture of picryl bromide and copper powder at or
below room temperature result in the formation of hexanitrobiphenyl (I) or a 1,3,5-
trinitrobenzene/picric acid mixture, depending on the solvent and relative amounts of picryl
bromide and copper [34].

NO
2
O
2
N
NO
2
NO
2
NO
2
NO
2
(I)
Applications of ultrasound in the Ullmann reaction were successfully employed for the
synthesis of several N-arylanthranilic acids [35], diaryl ethers [36] and substituted [37]
quinazolin-12-ones by using copper catalyst.


Synthetic Methodologies Using Sonincation Techniques 167
Knoevenagel Condensation

Application of ultrasound has been found to greatly assist the Knoevenagel aldol
condensation reaction of activated methylenes with aromatic aldehydes under mild conditions
(Scheme 8) [38]. The outcome of the ultrasound-promoted reaction depends upon the
electronic nature of the aromatic aldehyde, the solvent employed and the addition of acids,
bases or ammonium salts.

Ar
NO
2
OH
R RCH
2
NO
2
ArCHO
R-C-CH
2
CO
2
H
O
Ar
NO
2
R
Ar R
O
R = OH, alkyl, aryl

Scheme 8. Knoevenagel aldol condensation reaction of activated methylenes with aromatic aldehydes.
Whereas condensation of ketones with ethylcynoacetate catalyzed by ammonium acetate-
acetic acid and alkaline-promoted clays (Li
+
- and Cs
+
-exchanged saponites) results in ethyl
alkylidene α cyanoacetate in 31-89% and 97% yields respectively under ultrasound irradiation
(Scheme 9) [39-40].

R
1
O
R
2
CN
CO
2
Et
CN
CO
2
Et R
2
R
1
NH
4
OAc / AcOH
40-50
o
C, )))

Scheme 8. Condensation of ketones with ethylcynoacetate catalyzed by ammonium acetate-acetic acid
and alkaline-promoted clays.
Surfactant ethyltrioctylammonium chloride (Aliquat 336) [41] and KF-Al
2
O
3
[42]
assisted Knoevenagel condensation of active methylene compounds with arylaldehydes were
also effectively catalyzed under ultrasound.

Claisen-Schmidt condensation

Chalcones are important intermediates in the synthesis of many potential anti-
inflammatory and cancer chemopreventive agents [43]. They are commonly synthesized via
the Claisen-Schmidt condensation between acetophenone and benzaldehyde (Scheme 10).


Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 168
CHO C
O
H
3
C
R R
C
H
CH
C
O
Base
+

Scheme 10. Claisen-Schmidt condensation between benzaldehyde and acetophenone to yield the
chalcone.
Improved synthesis of chalcones under ultrasound irradiation were successfully catalyzed
by alumina-supported potassium fluoride [44], barium hydroxide [45-46], basic activated
carbons (Na and Cs-Norit) [47], KF-Al
2
O
3
[48-49]. In order to develop a greener protocol
Martin et al. developed a green, solvent free procedure for the preparation of chalcones using
a new type of amino grafted zeolites under ultrasound activation [50].
Reformatsky Reaction

Bartsch and co-workers [51] have reported the synthesis of β-lactams 15 via the US-
promoted Reformatsky reaction using ‗not activated‘ zinc dust and a catalytic amount of
iodine. The reactions were subjected to high-intensity ultrasound (HIU) from a direct
immersion horn. A previous work [52] also demonstrated the formation of β-lactams, but
under low intensity ultrasound (LIU). However, in this case the zinc dust was activated by
washing with nitric acid in order to achieve high yields. The reactions were performed in a
cleaning bath in the presence of catalytic I
2
in dioxane and products were obtained in 70–95%
yields. Under these conditions the formation of β-amino esters was not observed.
Comparing this work with that described by Bartsch and coworkers [51], the importance
of the intensity of ultrasound in sonochemistry becomes clear; zinc activation was not
necessary in HIU, however, inactivated zinc leads to an almost 50% reduction in yield using
LIU. Another remarkable difference between the uses of different intensity US is the reaction
time; in HIU, the reaction requires only 5 min, while 4–10 h is necessary in LIU (Scheme 11).

Ar
2
N
Ar
1
BrH
2
C-CO
2
Et
N
O
Ar
1
Ar
2
i
i: Zn "activated", I
2
(cat), LIU, 4-10 hr
+

(Scheme 11).
β-Hydroxy esters were prepared via Reformatsky reaction by sonication technique using
different metals such as Indium [53], zinc dust with catalytic amount of iodine [54-56].


Synthetic Methodologies Using Sonincation Techniques 169
Bouveault Reaction

Alkyl, cycloalkyl, and aryl halides were converted to corresponding aldehydes in high
yield by irradiation with ultrasound in the presence of Li and DMF. As ultrasonic irradiation
of Butyl bromide in DMF containing Li sand at 40 kHz for 5 h gave 88% pentanal [57].
Einhorn and coworker studied the effect of solvent on Bouveault reaction [58] from
DMF, N-(2-Dimethylamino-ethyl)-N-methyl-formamide, and 4-methyl-1-piperazinecarbo-
xaldehyde and the effect of THF, tetrahydropyran, and Et
2
O under ultrasonic irradiation
effect. In the case of Et
2
O, the results were strongly dependent on the wave frequency. Thus,
PrBr and DMF in THF containing Li sonicated for 10 min at 50 KHz gave 81% PhCHO.
Baylis–Hillman Reactions

Fernando et al. studied the effect of ultrasound radiation on Baylis–Hillman reaction with
several aldehydes (aromatics and aliphatics) and different α,β-unsaturated reactants [59]. For
all aldehydes tested, the utilization of ultrasound sources augmented the reaction rate and the
chemical yields. The use of ultrasound with 1,4-diazabicyclo[2.2.2]octane [DABCO]) is
much more effective for catalyzing a Baylis–Hillman (Scheme 12).

EWG
R H
O
R
EWG
OH
N
N
EWG = CO
2
R, CN, CHO, COCH
3
, SO
2
Ph
)))
Baylis-Hillman adduct

Scheme 12. Formation of α-methylene-β-hydroxy compounds by the Baylis–Hillman reaction.
Michael Addition Reaction

Ceric ammonium nitrate efficiently catalyzes the Michael addition of indole to α,β-
unsaturated carbonyl ketones by means of alkylation of indole under ultrasonic irradiation to
afford the corresponding adduct in excellent yields (Scheme 13) [60]. Interestingly it was
observed that substitution on the indole nucleus occurred exclusively at the 3-position, and N-
alkylation products have not been observed.

N
H
R
1
R
2
O
R
1
R
2
O
HN
CAN / )))
r.t.
+

Scheme 13. Ultrasound assisted Michael addition of indole with α,β unsaturated carbonyl compounds
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 170
Curtius Rearrangement

Vommina and co-worker [61] reported the synthesis and isolation of isocyanates of
Fmoc-amino acids by means ultrasonications as Curtius rearrangement and their utility for the
synthesis of dipeptidyl ureas (Scheme 14).

HN C
N
3
R H
O
Fmoc-
Fmoc- HN NCO
R H
Toluene, )))
15-20 min.

(Scheme 14)
Diels-Alder Reaction

Ultrasound irradiation accelerates hetero Diels-Alder reactions between 1-
dimethylamino-1-azadienes and electron-deficient dienophiles [62]. Besides the lower
reaction times and increased yields, other advantages of the sonicated reactions are the
possibility of isolating previously unknown adducts due to the milder reaction conditions and,
in some cases, the decrease in side reactions.
Martin et al. [63] studied the insights reaction mechanism for Diels-Alder cycloadditions
of masked o-benzoquinones with furans by means of thermal and sonochemical aspects.
Friedel–Crafts Acylation

The Friedel–Crafts acylation of 2-methoxynaphthol is generally carried out by using
highly polluting acids such as HF, AlCl
3
, BF
3
which are used in more than stoichiometric
quantities and are neutralized at the end creating large quantities of waste, corrosion problems
and hazard. To overcome these disadvantageous Yadav et al. reported the use of acid treated
clays such as K-10, Filtrol-24 and cation exchange resins such as Amberlyst-36, Amberlyst-
15 and Indion-130 as catalysts at 25
o
C (Scheme 15) [64]. In the presence of ultrasound, the
activities were found to increase by more than a factor of 3 in the case of large porous resins
than the clays. The selectivity to 1-acyl-2-ethoxynaphthalene was found to remain the same.
Utrasonics did not promote isomerisation or direct conversion to 6-acyl-2-
methoxynaphthalene.

O
O
O
OCH
3 OCH
3
O OCH
3
CH
3
COOH
+
+
Catalyst

Scheme 15. Acylation of 2-methoxynaphthalene with acetic anhydride.
Synthetic Methodologies Using Sonincation Techniques 171
Acylation reactions of various aromatic and heterocyclics were successfully done with
pivaloyl chloride in the presence of catalytic amtount of iodine [65], without any added
solvent and at room temperature giving excellent yields of the respective pivalophenones in a
short reaction time.
Heck Reaction

Samant et al. reported the Low temperature recyclable catalyst for Heck reactions using
ultrasound [66]. The Heck reaction of iodobenzene with methyl acrylate in NMP as a solvent
has been studied using Pd/C as a catalyst in the presence of ultrasound at room temperature.
(Scheme 16) It was observed that ultrasound increases the rate of the reaction and reaction
only takes place in the presence of ultrasound.

I
CH
2
=CHCOOCH
3
Et
3
N
CH=CHCOOCH
3
+
NMP, Pd/C

Scheme 16. Heck reaction of iodobenzene with methyl acrylate using Pd/C in the presence of
ultrasound.
Zhang and co-worker reported an aqeous Heck reaction by Pd(0) nanoparticles under
ultrasonic irradiation at the ambient temperature (25 °C) [67]. It was found that catalyst for
the reaction palladium forms nanoparticles in-situ can be recycled. Furthermore, the Heck
reaction under such mild and environmentally friendly conditions offers excellent
regioselectivity of para- over ortho-substitution in phenyl iodides especially with electron-
donating groups.
Mannich-Type Reaction

Zeng et al. for the first time reported the one-pot three-component Mannich-type
reactions of aldehydes with ketones and amines using sulfamic acid as an efficient,
inexpensive, non-toxic and recyclable green catalyst ultrasound irradiation [68]. This
ultrasound protocol has advantages of high yield, mild condition, no environmental pollution,
and simple work-up procedures. Most importantly, β-aminocarbonyl compounds with ortho-
substituted aromatic amines are obtained in acceptable to good yields by this methodology.
Pechmann Condensation

Ultrasound was found to synergistically accelerate the Pechmann condensation of phenol
with β-ketoesters in the presence of bismuth (III) chloride [69]. In the absence of ultrasound,
under the same conditions, the reaction was found to be slow. Thus, the reaction can be
carried out in the presence of ultrasound at room temperature (28-30 °C), with a considerable
reduction of reaction time, with high yield and high purity of coumarins.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 172
Allylation of Aldehydes and Ketones

The allylation reactions of aromatic aldehydes and ketones using SnCl
2
-H
2
O under
ultrasound irradiation at room temperature gave homoallyl alcohols in 21-84% yield within 5
h, whereas the same system desired 24 h for completion. Compared with traditional stirring
methods, ultrasonic irradiation is more convenient and efficient [70].
Epoxidation Reaction

Ultrasound-assisted epoxidation of cyclohexene [71], α,β-unsaturated ketones [72] and
unsaturated fatty esters [73] were successfully carried out with oxygen on ultrasound air-lift
loop reactor, hydrogen peroxide and m-chloroperoxybenzoic acid (MCPBA) respectively.
This general and selective protocol is relatively fast and is applicable to a wide variety of
substrates.
Effect of Ultrasound and Phase Transfer Catalysis

The rate of reacting two immiscible reactants is low because of poor mass transfer. To
increase the reaction rate, strong agitation is essential. Phase ransfer catalyst (PTC) is of help
in such cases. It transfers the active species from one phse to the other. Ultrasound produces
either extremely fine emulsion of immiscible liquids or assists mass transfer and surface
activation (in solid/liquidsystem). These factors enhance PTC catalyzed heterogeneous
reactions or even replace PTC. A number of such reactions are reported.
Ultrasound accelerates the reaction of oxime with dichloromethane in the presence of
sodium hydroxide in combination with benzyldimethyltetradecylammonium chloride as a
PTC to give methylene dioxime (Scheme 17) [74].

R
1
R
2
NOH
CH
2
Cl
2
R
1
R
2
N O CH
2
+
NaOH/PTC
)))
2

(Scheme 17)
Wang studied the effect of different quaternary ammonium salts with potassium
hydroxide in a synthesis of 4-ethoxynitrobenzene by nucleophilic substitution reaction of p-
chloronitrobenzene with ethanol (Scheme 18) [75], ultrasound is found to enhance the
reaction with quarternary ammonium salt, as compared to the reaction carried out under silent
condition.
Synthetic Methodologies Using Sonincation Techniques 173
NO
2
Cl
EtOH KOH
PTC
NO
2
Et
H
2
O KCl
+ +
)))
+ +

(Scheme 18)
Ultrasound along with microwave has been used for the synthesis of ethers through
Williamson synthesis reaction, which usually involves the employment of organic solvent or
PTC for several hours. The simultaneous use of ultrasound and microwave irradiation
(SUMI) results in reduction or reaction time with good yield of the desire product without
using (Scheme 19) PTC [76].

Ar-OH R-Cl Ar-O-R +
R = benzyl, aryl
NaOH / H
2
O
SMUI
60-150 S
SMUI: Simultaneous microwave
and ultrasound irradiation

(Scheme 19)
Ultrasound accelerates the Cannizzaro reaction of 4-chlorobenzaldehyde under PTC,
using benzyl triethylammounium chloride as PTC to give 4-chlorobenzoic acid [77]. Perfume
material 2-naphthyl ether is synthesized in high yield and better purity by means of the
ultrasound-PTC method [78]. Vegetable oils can be saponified by sonically using aqeous
KOH and various PTCs at room temperature [79]. It is observed that heterogeneous liquid-
liquid phase saponification of vegetable oils is remarkably accelerated by ultrasound.
Formation of benzoylbenzyl cyanided and benzoic acid from benzyl cyanide and potassium
superoxide in the presence of 18-crown-6 and ultrasound is reported [80].
The application of ultrasound to the N-alkylation of a variety of amines (indole,
carbazole, Ph
2
NH) by alkyl halides under phase transfer conditions (polyethylene glycol
Methyl ether and alkylammonium compounds as catalysts) leads to a decrease in the time
required to effect reaction [81].
Ultrasound in Oxidation and Reduction Reaction

Ultrasonic irradiation of a biphasic system consisting of substrate, CH
2
Cl
2
, H
2
O, CH
3
CN,
NaIO
4
and catalytic amounts of RuCl
3
.nH
2
O, accelerated the oxidation reaction of aromatic
and heteroaromatic compounds to afford the desired products in good yields [82]. In the
presence of ultrasound various mono-, di-, and -unsaturated cyanides were reduced with
Cu-Al alloy in NaOD-D
2
O and THF to the corresponding deuteriated aliphatic amines, such
as nonylamines, Putrescine, and 1,6-hexanediamine, in high deuterium content [83].
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 174
Zinc reduction of -unsaturayed ketones in acetic acid has been efficiently
accomplished under sonochemical conditions [84]. Different -enone systems give two kinds
of products: olefins and allylic alcohols. Regio- and stereoselectivities are reported. Thus, a
mixture of enones I (R
1
= H, Cl, R
2
= OAc, R
3
= H; R
1
= R
3
= H, R
2
= Ac; R
1
= H, R
2
R
3
= O)
and Zn-AcOH was sonicated 15 min at 15° C to give ~quantity yields of reduced products
II as 5 :5 epimers.
O
R
1
Me
Me
R
2
R
3
Me
H
R
1
I
II


Similarly, under ultrasonic irradiation deoxygenation of 3-oxosteroids I (X = O) with zinc
dust in acetic acid or acetic acid-water give rise to 90% androstanol I (X = H
2
), a new
Clemmensen-type reduction [85].
X
Me
Me
OH
H
I

Sonication in Ionic Liquids (IL)

Ionic liquids (IL) are consisting of complex cations, usually imidazolium, pyridinium or
phosphonium cations and complex anions having negligible vapour pressure. Although the
correlation between vapour pressure and cavitational energy is not straightforward, rate of the
sonochemical reaction can be increased, within the limits by lowering the vapour pressure of
the solvent. It is extremely difficult to induce cavitation in an IL; however the reactant could
enter the cavitation bubbles or the superheated liquid shell surrounding it, to undergo strong
cavitational effect.
The ultrasound assisted preparation of several 1-butyl-3-methylimidazolium and
pyridinium cations salts (BF
4
, PF
6
, CF
3
SO
3
and BPh
4
) ionic liquids (ILs) was carried out [86-
89]. The reaction yield increased, the reaction time decreased dramatically, and the quality of
the products improved. A short and simple method is used to recover the ILs without a
purification step.
Ionic liquids have favorable intrinsic properties that make them of interest as solvents for
various chemical reactions. The same properties that make the liquids effective solvents also
Synthetic Methodologies Using Sonincation Techniques 175
make them interesting liquids for studies involving sonochemical, acoustic cavitation, and
sonoluminescence. Recent interest in using ultrasound to accelerate chemical reactions
conducted in ionic liquids necessitates an understanding of the effects of acoustic cavitation
on these solvents [90].
A few coupling reactions have so far been achieved ubder sonication in ILs, such as 1,3-
di-n-butylimidazolium tetrafluroborate or bromide [bmim][BF
4
]. Suzuki reaction gives good
yield in an ultrasonic bath (50 KHz) under argon atmosphere at room temperature in an IL
and methanol as a co-solvent [91]. The ligands are not required and chlorobenzene could be
also taken as a substrate under these conditions. Sonochemical Heck reaction of aryl halides
and acrylate is carried out in IL with ultrasound to give the corresponding products (Scheme
20) [92].

X
COOR COOR
IL
)))
+
X = Halogen

(Scheme 20)
Pei and co-worker reported the synthesis of 3-naphthylcyclohexene by the Heck reactions
[93] of bromonaphthalene and naphthyl triflates with cyclohexene catalyzed by palladium and
nickel complex (promoted by ultrasonic and microwave in ionic liquid of [bmim][BF
4
]) with
high yield and good regioselectivity. This method has advantages of environmentally benign,
generality, simplicity and potential for recycling of ionic liquid and catalyst.
Potential of an inexpensive IL in catalyzing a rearrangement with ultrasound has also
been shown in the rearrangement of cyclopropyl carbinol derivatives to give aryl substituted
trans-conjugated butadienes (Scheme 21) [94]. This procedure offers marked improvements
such as operational simplicity, stereoselectivity (exclusively trans) and high yield of products,
considerably low reaction time and mild reaction conditions.

Ph R
OH
Ph
R
IL
)))

(Scheme 21)
Moreover, in recent years ultrasonic irradiation in an IL has been used for
multicomponent synthesi of dihydropyrimidones [95], acetylation of alcohol [96], nitration of
phenols with para-selectivity [97], in the direct halogenations of alcohols with ter-butyl
halides [98] and synthesis of 4-azalactones [99].


Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 176
Ultrasound and Photochemistry

Ultrasound considerably enhances and simplifies photochemical reaction of
cyclohexanone with cyclohexene [100]. The Paterno-Bachi reaction of acetone with ethyl
vinyl ether is enhanced by ultrasound and yields a different ratio of cis/trans oxetanes under
sonication by comparison with the silent reaction. Sonication appears to affect the first
reaction by homogenization of excited intermediates and by quenching the excited triplet state
at the second reaction.
The combination of ultrasound and photochemistry has been used for the oxidation of
unsymmetrical 1,4-dihydropyridines to the pyridine derivatives [101]. An ultrasonic probe of
24 kHz frequency and an Hg-lamp of 100 W have been used for this study. The effects of
parameters such as ultrasonic intensity, the presence of oxygen, argon atmospheres and also
the separate usage of one of these irradiation sources have been studied. Whereas sonication
of these compounds alone did not result in their oxidation, the use of ultrasound increases the
rate of photooxidation. The presence of oxygen decreases or increases the rate of reaction,
depending on the type of excited state of 1,4-dihydropyridines involved in the reaction.
Miscellineous

Bhanage and co-workers effectively demonstrated a simple and convenient methodology
for the regioselective nitration of phenols using dil. HNO3 as nitrating agent under sonication
(Scheme 22) [102]. The protocol eliminates the use of any additive and requires lower
concentration of HNO3 (9%). The effect of various reaction parameters such as agitation
speed, solvent, phase hold-up ratio, substrate concentration, HNO3 concentration and
temperature on the reaction system was studied. The present methodology shows a
considerable enhancement in the reaction rate along with improved para-selectivity compared
with the reactions performed under silent conditions. The kinetic analysis of nitration of
phenol both with and without sonication was studied by studying reaction parameters such as
substrate and HNO3 concentration. The increased rate of reaction and selectivity are
explained on the basis of ultrasonically generated cavitational effects.

OH
HNO
3
))))))
R
OH
NO
2
R
R
OH
NO
2
+
TBAB, 25
o
C
+
R=CH
3
, Cl

Scheme 22. Ultrasound assisted nitration of phenol to o-nitrophenol using phase transfer catalyst.
Similar type of work eas reported by Kamal and group which uses nitric acid/zinc
chloride for the nitration of phenols under ultrasonic conditions [103].
Synthetic Methodologies Using Sonincation Techniques 177
The effect of cavitating ultrasound was studied, in heterogeneous aqeous hydrogenation
of cis-2-buten-1-ol and cis-2-penten-1-ol to obtain trans-2-buten-1-ol and trans-2-penten-1-ol
and saturated alcohols (1-butanol and 1-pentanol, respectively), using a com. Pd black
catalyst (Scheme 23) [104].

OH
H
2
OH
HO
HO
trans-2-buten-1-ol
trans-2-penten-1-ol
cis-2-penten-1-ol
cis-2-buten-1-ol
Pd black

(Scheme 23)
The hydrogenation, employing hydrogen gas, of cinnamaldehyde was performed using
Pd-black and Raney Ni catalysts at 298 ± 3 K in a water-cooled (jacketed) reaction vessel
[105]. Comparing the ultrasound-assisted and blank (stirred) experiments revealed that a
higher maximum relative concentration of the intermediate benzenepropanal was formed in
the ultrasound experiments compared to the stirred experiment. The activity of the ultrasound
experiments compared to blank was 9-fold and 20-fold greater for the Pd-black and Raney Ni
catalysts, respectively.
Bhanage and co-workers reported a simple and convenient methodology for selective
sulfonation of aromatic compounds using sulfuric acid under sonication (Scheme 24) [106].
The present methodology shows a considerable enhancement in the reaction rate along with
improved selectivity compared with the reactions performed under silent conditions. The
effect of various parameters such as agitation speed, sulfuric acid concentration, and
temperature on reaction system has been investigated and is explained on the basis of
ultrasonically generated cavitational effects.

SO
3
H
+ Conc. H
2
SO
4
)))))
25
o
C
R
R

R = H, CH
3
, OCH
3
, -X, Ar etc
Scheme 24. Sulfonation of aromatic compounds under sonication.
Application of ultrasound shows significant rate enhancement for the synthesis of β-
enamino nitriles in the presence of base (Scheme 25) [107]. The role of various homogeneous
and heterogeneous bases/solvents was also studied for the reaction, and potassium t-
butoxide/t-Bu alc combination was found to give the best result at room temperature.

Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 178
CN
R
t-BuOK
t-BuOH
R
CN
H
2
N
R
1
+ R
1
CH
2
CN
R= (a) -H (b) -CH
3
(c) -Cl
R
1
=(a) -H (b) -Br (c) -Ph (d) -CH
2
OCH
3
1 3 2
)))

Scheme 25. Ultrasound assisted synthesis of |-Enaminonitriles
Naphthols were selectively coupled under sonication using Fe
+3
impregnated pillared
Montmorillonite K-10 and TBHP as an oxidant. Considerable enhancement in the reaction
rate was observed under sonication as compared to the reaction performed under silent
condition (Scheme 26) [108].


Scheme 26. Symmetrical coupling of naphthalene.
Furthermore, in recent years effect of ultrasonic irradiation is found to be very important
tool in several organic reactions such as synthesis of diethyl ether without catalyst [109],
preparation of phenylalkyl ethers and phenyl esters from benzenediazonium [110], synthesis
of 1,5-bis(nitroaryl)-1,4-pentadien-3-ones[111], conversion of azides to carbamates and
sulfonamides using Fe:NH
4
Cl [112], synthesis of symmetrical vicinal diamines [113],
synthesis of imines [114], synthesis of propargylamines [115], synthesis of functionalized
arylacetylenes [116], one pot synthesis of α-amino phosphonates [117], cleavage of epoxides
with aromatic amines [118], ultrasound and microwave assisted bromination reactions of
substituted alkyl aromatics with N-bromosuccinimide [119], O-alkylation of 5-
hydroxychromones [120], synthesis of benzaldehyde from benzyl alcohol using H
2
O
2
[121],
N-alkylation and N-acylation of 2,4-dinitrophenylamine [122], synthesis of N-
alkoxyphthalimides [123], N-alkylation of imidazole [124], N-Alkylation of acetanilide [125],
synthesis of N-alkoxyphthalimides [126].
CONCLUSION
This Review summarized the recent developments in the area of Sonochemistry:
Reactions and Synthesis, and applications. Sonochemistry is an expanding field of study that
continues to thrive on outstanding laboratory results that have even more significance with
Synthetic Methodologies Using Sonincation Techniques 179
the availability of the types of scale-up systems used in processing. Compared with the past,
there is now far greater contact and cooperation between the scientific disciplines interested
in the effects of cavitation. The future of sonochemistry is therefore bright, both from the
point of view of a greater interest in the fundamental principles of its action and in the
development of international programmes in applied research and technology.
REFERENCES
[1] Mason, T. J., Lorimer J. P. (2002). Applied Sonochemisrty, The Uses of Ultrasound in
Chemistry and Processing. Weinheim, Wiley-VCH Verlag Gmbh.
[2] Luque de Castro, M. D., and Priego-Capote, F. (2007). Ultrasound-assisted preparation
of liquid samples. Talanta, 72, 321-334.
[3] Bonrath, W., and Schmidt, R. (2005). Ultrasound in synthetic organic chemistry.
Advances in Organic Synthesis, 1, 81-117.
[4] Davidson, R. S., Safdar, A., Spencer, J. D., and Robinson, B. (1987). Applications of
ultrasound to organic chemistry. Ultrasonics, 25, 35-39.
[5] Li, J. T., Wang, S. X., Chen, G. F., and Li, T. S. (2005). Some applications of
ultrasound irradiation in organic synthesis. Current Organic Synthesis, 2, 415-436.
[6] Mason, T. J. (1991). Practical Sonochemistry, Users Guide to Application to Chemistry
and Chemical engineering. NY, Ellis Horwood Limited.
[7] Thornycroft, J., and Barnaby, S. (1895). Torpedo-Boat Destroyers (Including Appendix
and Plate at Back of Volume). Proceeding Institution of Civil Engineering, 122, 51-69.
[8] Gogate, P. R., and Pandit, A. B. (2003). Some aspects of the design sonochemical
reactors. Ultrasonics Sonochemistry, 10, 325-330.
[9] Ashokkumar, M., Lee, J., Kentish, S., and Grieser, F. (2007). Bubbles in an acoustic
field: An overview. Ultrasonics Sonochemistry, 14, 470-475.
[10] Desouza-barboza, J. C., Petrier, C., and Luche, J. L. (1988). Ultrasound in organic
synthesis. 13. Some fundamental aspects of the socochemical Barbier reaction. Journal
of Organic Chemistry, 53, 1212-1218.
[11] de Souza A. L. F., da Silva, L. C., Oliveira, B. L., and Antunes, O. A. C. (2008).
Microwave- and ultrasound-assisted Suzuki–Miyaura cross-coupling reactions
catalyzed by Pd/PVP. Tetrahedron Letters 49 3895–3898.
[12] Zhang, J., Yang, F., Ren, G., Mak, T. C.W., Song, and Wu M. Y. (2008). Ultrasonic
irradiation accelerated cyclopalladated ferrocenylimines catalyzed Suzuki reaction in
neat water. Ultrasonics Sonochemistry, 15, 115–118.
[13] Polackova, V., Hutka, M., and Toma, S. (2005). Ultrasound effect on Suzuki reactions.
1. Synthesis of unsymmetrical biaryls. Ultrasonics Sonochemistry, 12, 99–102.
[14] Guadagnin, R. C., Suganuma, C. A., Singh, F. V., Vieira, A. S., Cella, R., and Stefani
H. A. (2008). Chemoselective cross-coupling Suzuki–Miyaura reaction of (Z)-(2-
chlorovinyl)tellurides and potassium aryltrifluoroborate salts. Tetrahedron Letters, 49,
4713–4716.
[15] Cella, R., and Stefania, H. A. (2006). Ultrasound-assisted synthesis of Z and E stilbenes
by Suzuki cross-coupling reactions of organotellurides with potassium
organotrifluoroborate salts. Tetrahedron, 62, 5656–5662.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 180
[16] Rodrigo, C., Orfao, A. T. G., and Stefani, H. A. (2006). Palladium-catalyzed cross-
coupling of vinylic tellurides and potassium vinyltrifluoroborate salt: synthesis of 1,3-
dienes. Tetrahedron Letters, 47, 5075-5078.
[17] Cravotto, G., Giovanni, P., Stefano, T., Gian, M. N., and Andrea, P. (2005). The Suzuki
homocoupling reaction under high-intensity ultrasound. Ultrasonics Sonochemistry, 12,
91–94.
[18] Palimkar, S. S., More, V. S., and Srinivasan, K. V. (2008). Ultrasound promoted
copper-, ligand- and amine-free synthesis of benzo[b]furans/nitro benzo[b]furans via
Sonogashira coupling-5-endo-dig-cyclization. Ultrasonics Sonochemistry, 15, 853–862.
[19] Palimkar, S. S., Kumar, P. H., Lahoti, R. J., and Srinivasan, K. V. (2006). Ligand-,
copper-, and amine-free one-pot synthesis of 2-substituted indoles via Sonogashira
coupling 5-endo-dig cyclization. Tetrahedron, 62, 5109–5115.
[20] Biginelli, P. (1893). Synthesis of 3,4-dihydropyrimidin-2(1H)-ones. Gazzetta Chimica
Italiana, 23, 360-416.
[21] Rovnyak, G. C., Kimball, S. D., Beyer, B., Cucinotta, G., Dimarco, J. D., Gougoutas, J.,
Hedderg, A., Malley, M., MacCarthy, J. P., Zhang, R., and Moreland, S. (1995).
Calcium entry blockers and activators: Conformational and structural determinants of
dihydropyrimidine calcium channel modulators. Journal of Medicinal Chemistry, 38,
119-129.
[22] Atwal, K. S., Rovnyak, G. C., Kimball, S. D., Floyd, D. M., Moreland, S., Swanson, B.,
Gougoutas, S. J., Schwartz, J., Amillie, K. M., and Malley, M. F. (1990).
Dihydropyrimidine calcium channel blockers. II. 3-Substituted-4-aryl-1,4-dihydro-6-
methyl-5- pyrimidinecarboxylic acid esters as potent mimics of dihydropyridines.
Journal of Medicinal Chemistry, 33, 2629-2635.
[23] Atwal, K. S., Swanson, B. N., Unger, S. E., Floyd, D. M., Moreland, S., Hedderg, A.,
and O‘Reilly, B. C. (1991). Dihydropyrimidine calcium channel blockers 3.3-
Carbamoyl-4-aryl-1,2,3,4-tetrahydro-6-methyl-5-pyrimidinecarboxylic acid esters as
orally effective antihypertensive agents. Journal of Medicinal Chemistry, 34, 806-811.
[24] Singh, K., Singh, S., and Kaur, P. (2006). Efficient preparation of Biginelli compounds.
An comparative study of sifferent reaction techniques. Letters in Organic Chemistry, 3,
201-203.
[25] Gholap, A. R., Venkatesan, K., Daniel, T., Lahoti, R. J., and Srinivasan, K. V. (2004).
Ionic liquid promoted novel and efficient one pot synthesis of 3,4-dihydropyrimidin-
2(1H)-ones at ambient temperature under ultrasound irradiation. Green Chemistry, 6,
147-150.
[26] Li, J. T., Han, J. F., Yang, J. H., and Li, T. S. (2003). An efficient synthesis of 3,4-
dihydropyrimidin-2-ones catalyzed by NH2SO3H under ultrasound irradiation.
Ultrasonics Sonochemistry, 10, 119-122.
[27] Wang, J. S., Li, J. T., and Lin, Z. P. (2006). Iodine catalyzed synthesis of 3,4-
dihydropyrimidin-2(1H)-ones under ultrasound irradiation. Letters in Organic
Chemistry, 3, 523-525.
[28] Yadav, J. S., Subba Reddy, B. V., Bhaskar Reddy, K., Raj, K. S., and Prasad, A. R.
(2001). Ultrasound-accelerated synthesis of 3,4-dihydropyrimidin-2(1H)-ones with
ceric ammonium nitrate. Journal of Chemical Society, Perkin Transaction, 1, 1939-
1941.
Synthetic Methodologies Using Sonincation Techniques 181
[29] Stefani, H. A., Oliveira, C. B., Almeida, R. B., Pereira, C. M. P., Braga, R. C., Cella,
R., Borges, V. C., Savegnago, L., and Nogueira, C. W. (2006). Dihydropyrimidin-
2(1H)-ones obtained by ultrasound irradiation: a new class of potential oxidant agents.
Europen Journal of Medicinal Chemistry, 41, 513-518.
[30] Docampo, M. L., and Pellon, R. F. (2003). Synthesis of 11H-Pyrido[2,1-b]quinazolin-
11-one and derivatives using ultrasound irradiation. Synthetic Communications, 33,
1777-1781.
[31] Pellon, R. F., Docampo, M. L., Kunakbaeva, Z., Gomez, V., and Castro-Velez, H.
(2006). Synthesis of 9-Methyl-11H-Pyrido[2,1-b]quinazolin-11-one using the Ullmann
condensation. Synthetic Communications, 36, 481-485.
[32] Lindley, J., Lorimer, J. P., and Mason, T. J. (1986). Enhancement of an Ullmann
coupling reaction induced by ultrasound. Ultrasonics, 24, 292-293.
[33] Lindley, J., Mason, T. J., and Lorimer, J. P. (1987). Sonochemically enhanced Ullmann
reactions. Ultrasonics 25, 45-48
[34] Nelson, K. A., and Adolph, H. G. (1991). Ullmann reaction of picryl bromide in the
presence of ultrasound. Synthetic Communications, 21, 293-305.
[35] Hanoun, J. P.; Galy, J. P.; and Tenaglia, A. (1995). A convenient synthesis of N-
arylanthranilic acids using ultrasonics in the Ullmann-Goldberg condensation. Synthetic
Communications, 25, 2443-2448.
[36] Smith, K.; and Jones, D. (1992). A superior synthesis of diaryl ethers by the use of
ultrasound in the Ullmann reaction. Journal of the Chemical Society, Perkin
Transactions 1: Organic and Bio-Organic Chemistry, 4, 407-408.
[37] Pellon, R. F., Docampo, M. L., and Fascio, M. L. (2007). Mild method for Ullmann
reaction of 2-chlorobenzoic acids and aminothiazoles or aminobenzothiazoles under
ultrasonic irradiation. Synthetic Communications, 37, 1853-1864.
[38] James, M., Jennifer, A., Steere and Sonja W. (1998). The Ultrasound Promoted
Knoevenagel Condensation of Aromatic Aldehydes. Tetrahedron Letters, 39, 8013-
8016.
[39] Li, J. T., Zang, H. J., Meng, L. H., Li, L. J., Yin, Y. H., and Li, T. S. (2001). Syntheis of
ethyl alkylidene α-cyanoacetates under ultrasound irradiation. Ultrasonics
Sonochemistry, 8, 93-95.
[40] Martın-Aranda, R. M., Ortega-Cantero, E., Rojas-Cervantes, M. L., Vicente-Rodrıguez,
M. A. and Banares-Munoz, M. A. (2005). Ultrasound-activated Knoevenagel
condensation of malononitrile with carbonylic compounds catalysed by alkaline-doped
saponites. Journal of Chemical Technology Biotechnology, 80, 234–238.
[41] Vanden Eynde, J. J., Mutonkole, K., and Van Haverbeke, Y. (2001). Surfactant-assisted
organic reactions in water. Effect of ultrasound on condensation reactions between
active methylene compounds and arylaldehydes. Ultrasonics sonochemistry, 8, 35-39.
[42] Li, J. T., Chen, G. F., Wang, S. X., He, L., and Li, T. S. (2005). Synthesis of
(Arylmethylene)malononitriles Catalyzed by KF-Al2O3 under Ultrasound. Australian
Journal of Chemistry, 58, 231-233.
[43] Won, S. J., Liu, C. T., Tsao, L. T., Weng, J. R., Ko, H. H., Wang, J. P., and Lin, C. N.
(2005). Synthetic chalcones as potential anti-inflammatory and cancer chemopreventive
agents. European Journal of Medicinal Chemistry, 40, 103-112.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 182
[44] Jin, H., Xiang, L., Wen, F., Tao, K., Liu, Q., and Hou, T. (2008). Improved synthesis of
chalconoid-like compounds under ultrasound irradiation. Ultrasonics Sonochemistry,
15, 681-683.
[45] Fuentes, A., Marinas, J. M., and Sinisterra, J. V. (1987). Catalyzed synthesis of
chalcones under interfacial solid-liquid conditions with ultrasound. Tetrahedron
Letters, 28, 4541-4544.
[46] Xin, Y., Zang, Z. H., and Chen, F. L. (2009). Ultrasound-Promoted Synthesis of 1,5-
Diarylpenta-2,4-dien-1-ones Catalyzed by Activated Barium Hydroxide. Synthetic
Communications, 39, 4062-4068.
[47] Calvino, V., Picallo, M., Lopez-Peinado, A. J., Martin-Aranda, R. M., and Duran-Valle,
C. J. (2006). Ultrasound accelerated Claisen-Schmidt condensation: A green route to
chalcones. Applied Surface Science, 252, 6071-6074.
[48] Li, J. T., Yang, W. Z., Wang, S. X., Li, S. H., abd Li, T. S. (2002). Improved synthesis
of chalcones under ultrasound irradiation. Ultrasonics Sonochemistry, 9, 237-239.
[49] Li, J. T., Yang, W. Z., Chen, G. F., Li, T. S. (2003). A facile synthesis of α,α'-
bis(substituted benzylidene)cycloalkanones catalyzed by KF/Al2O3 under ultrasound
irradiation. Synthetic Communications, 33, 2619-2625.
[50] Elizabeth, P. R., Rosa, M. M. A., Carlos, J. D. V., Willma, N. L., Zhang, X. F., and
King, L. Y. (2006). Sonocatalysis in solvent free conditions: An efficient eco-friendly
methodology to prepare chalcones using a new type of amino grafted zeolites. Catalysis
Today, 114, 183–187.
[51] Ross, N. A., MacGregor, R. R., and Bartsch, R. A. (2004). Synthesis of β-lactams and
β-aminoesters via high intensity ultrasound-promoted Reformatsky reactions.
Tetrahedron, 60, 2035-2041.
[52] Bose, A. K., Gupta, K., and Manhas, M. S. (1984). β-Lactum formation by ultrasound-
promoted Reformatsky type reaction. Journal of Chemical Society, Chemical
Communication, 86-87.
[53] Phil, H. L., Keukchan, B., Kooyeon, L., Sung, S. Y., and Sukbok, C. (2001). Ultrasound
promoted synthesis of β-hydroxyesters by Reformatsky reaction using indium metal.
Synthetic Communications, 31, 3781–3789.
[54] Ross, N. A., and Bartsch, R. A. (2003). High-intensity ultrasound-promoted
Reformatskii reactions. Journal of Organic Chemistry, 68, 360-366.
[55] Ross, N. A., Bartsch, R. A., and Marchand, A. P. (2003). High-intensity ultrasound-
promoted Reformatsky reactions of pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-
dione. ARKIVOC, 12, 27-30.
[56] Han, B. H., and Boudjouk, P. (1982). Organic sonochemistry. Sonic Acceleration of the
Reformatsky Reaction. Journal of Organic Chemistry, 47, 5030-5032.
[57] Petrier, C., Gemal, A. L., and Luche, J. L. (1982). Ultrasounds in organic synthesis. 3.
A simple, high yield modification of the Bouveault reaction. Tetrahedron Letters, 23,
3361-3364.
[58] Einhorn, J., and Luche, J. L. (1986). Ultrasound in organic synthesis. 9. Further results
for the Bouveault reaction. Tetrahedron Letters, 27, 1791-1792.
[59] Fernando, C., Wanda, P. A., Demetrius, V., Cristiano, R. M., Elizandra, C. S. L.,
Rodrigo, C. R., Gabriel, P. C. S., and Cesar, H. P. (2002). Ultrasound in Baylis–
Hillman reactions with aliphatic and aromatic aldehydes: scope and limitations.
Tetrahedron, 58, 7437–7447.
Synthetic Methodologies Using Sonincation Techniques 183
[60] Ji, S. J., and Wang, S. Y. (2003). Ultrasound-accelerated Michael Addition of Indole to
α,β-Unsaturated Ketones Catalyzed by Ceric Ammonium Nitrate (CAN). Synlett, 13,
2074–2076.
[61] Suresh Babu, V. V., Kantharaju, and Subramanyam, J. T. ( 2005). Curtius
rearrangement using ultrasonication: Isolation of isocyanates of Fmoc-amino acids and
their utility for the synthesis of dipeptidyl ureas. International Journal of Peptide
Research and Therapeutics, 11, 131–137.
[62] Villacampa, M., Perez, J., Avendano, C., and Menendez, J. C. (1994). Ultrasound
assisted Diels-Alder reactions of 1-azadienes with "normal" electronic demand.
Tetrahedron, 50, 10047-10054.
[63] Martın, A., Reyes, B., Noemi, C., Pedro, C., Michael, B. H., Jose, L. J., Mark, E. L.,
and Juan, C. P. (2003). Thermal and Sonochemical Studies on the Diels-Alder
Cycloadditions of Masked o-Benzoquinones with Furans: New Insights into the
Reaction Mechanism. Journal of Organic Chemistry, 68, 7193-7203.
[64] Yadav, G. D., and Mujeebur Rahuman, M. S. M. (2003). Synergism of ultrasound and
solid acids in intensification of Friedel–Crafts acylation of 2-methoxynaphthalene with
acetic anhydride. Ultrasonics Sonochemistry, 10, 135–138.
[65] Gopalakrishnan, G., Anandhi, S., and Narasimhan, N. S. (1996). Facile synthesis of
pivalophenones by an ultrasound assisted iodine catalyzed Friedel-Crafts acylation
reaction. Indian Journal of Chemistry, Section B: Organic Chemistry Including
Medicinal Chemistry, 35, 1197-1198.
[66] Ambulgekar, G. V., Bhanage, B. M., and Samant, S. D. (2005). Low temperature
recyclable catalyst for Heck reactions using ultrasound. Tetrahedron Letters, 46, 2483–
2485.
[67] Zhang, Z., Zha, Z., Gan, C., Pan, C., Zhou, Y., Wang, Z., and Zhou, M. M. (2006).
Catalysis and Regioselectivity of the Aqueous Heck Reaction by Pd(0) Nanoparticles
under Ultrasonic Irradiation. Journal of Organic Chemistry, 71, 4339-4342.
[68] Zeng, H., Li, H., and Shao, H. (2009). One-pot three-component Mannich-type
reactions using sulfamic acid catalyst under ultrasound irradiation. Ultrasonics
Sonochemistry, 16, 758-762.
[69] Patil, S., Bhat, R., Raje, V., and Samant, S. (2006). Ultrasound-assisted Pechmann
condensation of phenols with β-ketoesters to form coumarins, in the presence of
bismuth (III) chloride catalyst. Synthetic Communications, 36, 525-531.
[70] Bian, Y. J., Xue, W. L., and Yu, X. G. (2009). The allylation reactions of aromatic
aldehydes and ketones with tin dichloride in water. Ultrasonics Sonochemistry, 17, 58-
60.
[71] Zhang, P., Yang, M., and Lu, X. (2007). Epoxidation of cyclohexene with oxygen in an
ultrasound air-lift loop reactor. Chinese Journal of Chemical Engineering, 15, 196-199.
[72] Pillai, U. R., Endalkachew, S. D., and Varma, R. S. (2003). Ultrasound-assisted
epoxidation of olefins and α,β-unsaturated ketones over hydrotalcites using hydrogen
peroxide. Synthetic Communications, 33, 2017-2027.
[73] Lie, K. J., Marcel, S.F., and Lam, C.K. (1995). Ultrasound-assisted epoxidation reaction
of long-chain unsaturated fatty esters. Ultrasonics Sonochemistry, 2, S11-S14.
[74] Li, J. T., and Li, X. L. (2007). An efficient and practicl synthesis of methylene dioximes
by combination of ultrasound and phase transfer catalyst. Ultrasonics Sonochemistry,
14, 677-679.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 184
[75] Wang, M. L., and Rajendran, V. (2007). Ethoxylation of p-chloronitrobenzene using
phase-transfer catalyst by ultrasound irradiation–A kinetic study. Ultrasonics
Sonochemistry, 14, 368-374.
[76] Peng, Y., and Song, G. (2002). Combine microwave and ultrasound assisted
Williamson ether synthesis in the absence of phase transfer catalysts. Green Chemistry,
4, 349-351.
[77] Polackova, V., Tomova, V., Elecko, P., and Toma, S. (1996). Ultrasound-promoted
Cannizzaro reaction under phase-transfer catalyst. Ultrasonics Sonochemistry, 3, 15-17.
[78] Qiao, Q., Yu, D., Zhang, Q., and Wei, J. (1997). Chemical Abstract, 14, 32.
[79] Bhatkhande, B. S., and Samant, S. D. (1998). Ultrasound assisted PTC catalyzed
saponification of vegetable oils using aqeous alkali. Ultrasonics Sonochemistry, 5, 7-
12.
[80] Yim, E. S., Park, M. K., and Han, B. H. (1999). Effect of ultrasound on the formation of
α–benzoyl benzyl cyanide from benzyl cyanide and alkylphenyl ketone from α–
alkylbenzyl cyanide by potassium superoxide in the presence of crown ether.
Ultrasonics Sonochemistry, 6, 105-109.
[81] Stephen, D. R., Patel, A. M., Safdar, A., and David, T. (1983). The application of
ultrasound to the N-alkylation of amines using phase-transfer catalysis. Tetrahedron
Letters, 24, 5907-5710.
[82] Tabatabaeian, K., Mamaghani, M., Mahmoodi, N. O., Khorshidi, A. (2007). Ultrasonic-
assisted ruthenium-catalyzed oxidation of aromatic and heteroaromatic compounds.
Catalysis Communications, 9, 416-420.
[83] Tsuzuki, H., Harada, T., Mukumoto, M., Mataka, S., Tsukinoki, T., Kakinami, T.,
Nagano, Y., and Tashiro, M., (1996). Ultrasound-assisted reduction of cyanides to
deuteriated aliphatic amines. Journal of Labelled Compounds and
Radiopharmaceuticals, 38, 385-93.
[84] Salvador, J. A. R., Sa e Melo, M. L., Neves, A. S. Campos. (1993). Ultrasound assisted
zinc reactions in synthesis. 1. Efficient reduction of enones. Tetrahedron Letters, 34,
357-60.
[85] Salvador, J. A. R., Sa e Melo, M. L., and Neves, A. S. Campos. (1993). Ultrasound
assisted zinc reactions in synthesis. 2. A new Clemmensen-type reduction. Tetrahedron
Letters, 34, 361-362.
[86] Namboodiri, V. V., and Varma, R. S. (2002). Solvent-Free Sonochemical Preparation
of Ionic Liquids. Organic Letters, 4, 3161-3163.
[87] Leveque, J. M., Luche, J. L., Petrier, C., Roux, R., and Bonrath, W. (2002). An
improved preparation of ionic liquids by ultrasound. Green Chemistry, 4, 357-360.
[88] Oxley, J. D., Prozorov, T., and Suslick, K. S. (2003). Sonochemistry and
Sonoluminescence of Room-Temperature Ionic Liquids. Journal of the American
Chemical Society, 125, 11138-11139.
[89] Zhao, S., Zhao E., Shen, P., Zhao, M., and Sun, J. (2008). An atom-efficient and
practical synthesis of new pyridinium ionic liquids and application in Morita-Baylis-
Hillman reaction. Ultrasonics Sonochemistry, 15, 955-959.
[90] Flannigan, D. J., Hopkins, S. D., and Suslick, K. S. (2005). Sonochemistry and
sonoluminescence in ionic liquids, molten salts, and concentrated electrolyte solutions.
Journal of Organometallic Chemistry, 690, 3513-3517.
Synthetic Methodologies Using Sonincation Techniques 185
[91] Rajgopal, R., Jarikote, D. V., and Srinivasan, K. V. (2002). Ultrasound promoted
Suzuki cross-coupling reactions in ionic liquid at ambient condiments. Chemical
Communications, 616-617.
[92] Deshmikh, R. R., Rajgopal, R., and Srinivasan, K. V. (2001). Ultrasound promoted C-C
bond formation: Heck reaction at ambient conditions in room temperature ionic liquids.
Chemical Communications, 1544-1545.
[93] Pei, W., and Shen, C. (2006). Heck arylation of cyclohexene-promoted by ultrasonic
and microwave in ionic liquid. A novel method of the synthesis of 3-
naphthylcyclohexene. Chinese Chemical Letters, 17, 1534-1536.
[94] Ranu, B. C., Banerjee, S., and Das, A. (2006). Catalysis by ionic liquids: cyclopropyl
carbonyl rearrangements catalyzed by [pmim]Br under organic solvent free conditions.
Tetrahedron Letters, 47, 881-884.
[95] Gholap, A. R., Venkatesan, K., Daniel, T., Lahoti, J., and Srinivasan, K. V. (2004).
Ionic liquid promoted novel and efficient one pot synthesis of 3,4-dihydropyrimidin-2-
(1H)-ones at ambient temperature under ultrasound irradiation. Green Chemistry, 6,
147-150.
[96] Gholap, A. R., Venkatesan, K., Daniel, T., Lahoti, J., and Srinivasan, K. V. (2003).
Ultrasound promoted acetylation of alcohols in room temperature ionic liquid under
ambient conditions. Green Chemistry, 5, 693-696.
[97] Rajgopal, R., and Srinivasan, K. V. (2003). Ultrasound promoted para-selective
nitration of phenols in ionic liquid. Ultrasonics Sonochemistry, 10, 41-43.
[98] Ranu, B. C., and Jana, R. (2005). Direct halogenations of Alcohols and their derivatives
with ter-butyl halides in the ionic liquid [pmim]Br under sonication condition – A
novel, and green methodology. European Journal of Organic Chemistry, 2005, 755-
758.
[99] Heravi, Mohammad R. P. (2009). Erlenmeyer synthesis of azlactones by sonochemical
reaction in ionic liquids. Journal of the University of Chemical Technology and
Metallurgy, 44, 86-90.
[100] Anton, G., Jana, D., Stefan, T., and Robert, K. (1997). Ultrasound effects on
photochemical reactions, Part l" photochemical reactions of ketones with alkenes.
Ultrasonics Sonochemistry, 4, 109-115.
[101] Memarian, H. R., and Masumeh, A. S. (2007). Ultrasound-assisted photochemical
oxidation of unsymmetrically substituted 1,4-dihydropyridines. Ultrasonics
Sonochemistry, 15, 110-114.
[102] Nandurkar, N. S., Bhor, M. D., Samant, S. D., and Bhanage, B. M. (2007). Ultrasound-
Assisted Regioselective Nitration of Phenols Using Dilute Nitric Acid in a Biphasic
Medium. Industrial and Engineering Chemistry Research, 46, 8590-8596.
[103] Ahmed, K., Ashwini, K., Arifuddin, M., and Midoux, P. (2004). An efficient and facile
nitration of phenols with nitric acid/zinc chloride under ultrasonic conditions.
Ultrasonics Sonochemistry, 11, 455–457.
[104] Disselkamp, R. S., Denslow, K. M., Hart, T. R., White, J. F., and Peden, C. H. F.
(2005). The effect of cavitating ultrasound on the aqueous phase hydrogenation of cis-
2- buten-1-ol and cis-2-penten-1-ol on Pd black. Applied Catalysis, A: General, 288,
62-66.
Ziyauddin S. Qureshi, Krishna M. Deshmukh and Bhalchandra M. Bhanage 186
[105] Disselkamp, R. S., Hart, T. R., Williams, A. M., White, J. F., and Peden, C. H. F.
(2004). Ultrasound-assisted hydrogenation of cinnamaldehyde. Ultrasonics
Sonochemistry, 12, 319-324.
[106] Qureshi, Z. S., Deshmukh, K. M., Jagtap, S. R., Nandurkar, N. S., and Bhanage, B. M.
(2008). Ultrasound assisted regioselective sulfonation of aromatic compounds with
sulfuric acid. Ultrasonics Sonochemistry, 16, 308-311.
[107] Jagtap, S. R., Bhanushali, M. J., Nandurkar, N. S., and Bhanage, B. M. (2007).
Ultrasound-assisted synthesis of β-enaminonitriles in the presence of base. Synthetic
Communications, 37, 2253-2258.
[108] Malhari, D. B., Nitin, S. N., Mayur, J. B., and Bhalchandra, M. B. (2008).Ultrasound
promoted selective synthesis of 1,10-binaphthyls catalyzed by Fe impregnated pillared
Montmorillonite K10 in presence of TBHP as an oxidant. Ultrasonics Sonochemistry,
15, 195–202.
[109] Xu, H., Liao, W. M., and Li, H. F. (2007). A mild and efficient ultrasound-assisted
synthesis of diaryl ethers without any catalyst. Ultrasonics Sonochemistry, 14, 779-782.
[110] Olah, G., and Wu, A. H. (1991). Synthetic methods and reactions. 160. Preparation of
phenylalkyl ethers and phenyl esters from benzenediazonium tetrafluoroborate with
alkoxytrimethylsilanes and trimethylsilyl esters. Synthesis, 3, 204-206.
[111] Ding, L., Wang, W. and Zhang, A. (2007). Synthesis of 1,5-bis(nitroaryl)-1,4-
pentadien-3-ones under ultrasound irradiation. Ultrasonics Sonochemistry, 14, 563-567.
[112] Chandrasekhar, S., and Narsihmulu C. (2000). Direct conversion of azides to
carbamates and sulfonamides using Fe: NH4Cl: effect of sonication. Tetrahedron
Letters, 41, 7969–7972.
[113] Qiang, G. R., Wu, X. M., Wang, Q., and Pei, W. (2007). Ultrasonicwave-assisted
tandem-reaction for synthesis of symmetrical vicinal diamines. Chinese Chemical
Letters, 18, 1469-1470.
[114] Guzen, K. P., Guarezemini, A. S., Orfao, A. T. G., Cella, R., Pereira, C. M. P., and
Stefani, H. A. (2007). Eco-friendly synthesis of imines by ultrasound irradiation.
Tetrahedron Letters, 48, 1845-1848.
[115] Sreedhar, B., Reddy, P. S., Prakash, B. V., and Ravindra, A. (2005). Ultrasound-
assisted rapid and efficient synthesis of propargylamines. Tetrahedron Letters, 46,
7019-7022.
[116] Stefani, H. A., Cella, R., Doerr, F. A., de Pereira, C. M. P., Gomes, F. P., and Zeni, G.
(2005). Ultrasound-assisted synthesis of functionalized arylacetylenes. Tetrahedron
Letters, 46, 2001-2003.
[117] Xia, M., and Lu, Y. D. (2006). Ultrasound-assisted one-pot approach to α-amino
phosphonates under solvent-free and catalyst-free conditions. Ultrasonics
Sonochemistry, 14, 235-240.
[118] Kamal, A., Adil, S. F., and Arifuddin, M. (2005). Ultrasonic activated efficient method
for the cleavage of epoxides with aromatic amines. Ultrasonics Sonochemistry, 12, 429-
431.
[119] Heropoulos, G. A., Cravotto, G., Screttas, C. G., and Steele, B. R. (2007). Contrasting
chemoselectivities in the ultrasound and microwave assisted bromination reactions of
substituted alkyl aromatics with N-bromosuccinimide. Tetrahedron Letters, 48, 3247-
3250.
Synthetic Methodologies Using Sonincation Techniques 187
[120] Mason, T. J., Lorimer, J. P, Turner, A. T., and Harris, A. R. (1988). Ultrasonically
assisted O-alkylation reactions of 5-hydroxychromones. Journal of Chemical Research,
Synopses, 2, 80-81.
[121] Mahamuni, N. N., Gogate, P. R., and Pandit, A. B. (2006). Ultrasonic Synthesis of
Benzaldehyde from Benzyl Alcohol Using H2O2: Role of Ultrasound. Industrial and
Engineering Chemistry Research, 45, 98-108.
[122] Khalaj, A., Doroudi, A., Adibpour, N., and Araghi, G. M. (2009). N-alkylation and N-
acylation of 2,4-dinitrophenylamine by ultrasound irradiation. Asian Journal of
Chemistry, 21, 997-1001.
[123] Wang, S. X., Li, X. W., and Li, J. T. (2008). Synthesis of N-alkoxyphthalimides under
ultrasound irradiation. Ultrasonics Sonochemistry, 15, 33-36.
[124] Lopez-Pestana, J. M., Avila-Rey, M. J., and Martin-Aranda, R. M. (2002). Ultrasound-
promoted N-alkylation of imidazole. Catalysis by solid-base, alkali-metal doped
carbons. Green Chemistry, 4, 628-630.
[125] Huang, K., Ji, X., and Liu, H. (1993). N-Alkylation of acetanilide under ultrasonic
irradiation. Yingyong Huaxue, 10, 105-106.
[126] Wang, S. X., Li X. W., and Li, J. T. (2008). Synthesis of N-alkoxyphthalimides under
ultrasound irradiation. Ultrasonics Sonochemistry, 15, 33-36.

In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 6



SONOCHEMOTHERAPY AGAINST CANCERS


Tinghe Yu
1
1, 2
and Yi Zhang
2

1 Institute of Life Science, Chongqing Medical University,
Chongqing 400016, China
2 Laboratory of Biomedical Ultrasonics,
Institute of Women and Children‘s Health,
West China Second University Hospital,
Sichuan University, Chengdu 610041, China
ABSTRACT
Sonochemotherpy is the use of ultrasound to enhance anticancer agents. Preclinical
trials have manifested this modality is effective against cancers including chemoresistant
lesions. Sonochemotherapy is a target therapy, in which cavitation plays the leading role.
Making the occurrence and level of cavitation under control improves the safety and
therapeutic efficacy. Sonosensitizers and microbubbles enhance cavitation, being a
measure to adjust the level of cavitation. Free radicals due to cavitation have the
potentials of restructuring a molecule and changing the conformation; thus the molecular
structure and anticancer potency of a cytotoxic agent must be investigated, especially
when sonosensitizer and microbubble are employed. A potential clinical model for
investigating sonochemotherapy is the residual cancer tissues when performing palliative
high intensity focused ultrasound treatment.
INTRODUCTION
Adverse events and the development of chemoresistance are the main barriers to clinical
applications of chemotherapy against tumors. Techniques, which potentiate anticancer agents
and decrease their toxicities to noncancerous tissues as well, are therefore urgently needed.
As a non-ionizing mechanical wave, ultrasound has a better tissue penetration and can be
focused on the predetermined volume within the body without harming overlying tissues.

1 Correspondence: Institute of Life Science, Chongqing Medical University, Chongqing 400016, China; E-mail:
yutinghe@hotmail.com.
Tinghe Yu and Yi Zhang 190
Ultrasound issues in structural and functional changes in exposed tissues and the insonation
level must be determined according to the therapeutic goal [1]. Biological responses due to
ultrasound result from thermal and nonthermal (mechanical effect and cavitation) effects, and
there are considerable differences between tissue types and between individuals [2, 3]. When
the temperature is <50 °C, this modality is ultrasonic hyperthermia. Ultrasonic hyperthermia
can enhance anticancer drugs, i.e., ultrasonic thermochemotherapy [2]. This technique will
not be discussed in this chapter, since it is actually thermochemotherapy. High intensity
focused ultrasound (HIFU) also employs heat, which leads to a temperature of above 56 °C in
few seconds. HIFU results in immediately coagulative necrosis, and has been used to ablate
solid tumors [3]. Therapeutic applications of nonthermal effects, especially cavitation, have
been investigating.
Sonochemotherapy is the use of ultrasound to enhance anticancer chemicals against
cancers [4]. This technique is once considered as ultrasound-mediated drug delivery, as
insonation facilitates the transmembrane transportation of drug molecules [5, 6]. However,
recent data have manifested that some events cannot be interpreted with the increase of
intracellular drug accumulation [2]. Sonochemotherapy is still at the preclinical stage despite
those stirring findings, which confuses scientists. Thus, this paper concentrates on the
limitations of this modality, and then possible solutions including personal perspectives are
brought forward.
AN OVERVIEW OF SONOCHEMOTHERAPY
Sonochemotherapy is the use of ultrasound to enhance anticancer agents [4]. This
modality equipotentially deactivates cancer cells with a lower dose of antitumor drug
compared with conventional chemotherapy; toxicities to normal tissues are decreased as well.
Cytotoxicity occurs only in the lesion via focusing ultrasound beams at the predetermined
volume. Thus, sonochemotherapy realizes a targeted therapy. The excellent tissue penetration
of ultrasound suggests that this technique can be applied for a lesion located deeply.
The dose-anticancer effect curve parallels the dose-toxicity curve in conventional
systemic chemotherapy. Sonochemotherapy leads to a left-shift of the dose-effect curve and a
right-shift of the dose-toxicity curve (Figure 1). Sonochemotherapy is a targeted therapy,
which is realized via releasing anticancer drugs into the lesion directly thus deactivating
cancer cells efficiently. Adjacent noncancerous tissues are therefore exposed to a very low
dose decreasing toxicities. Consequently, sonochemotherapy indicates higher therapeutic and
safe indexes.


Sonochemotherapy Against Cancers 191

Figure 1. Dose-anticancer effect and dose-toxicity curves in conventional chemotherapy (Left) and
sonochemotheapy (Right). Two curves are parallel in conventional chemotherapy. In
sonochemotherapy, the level of a cytotoxic agent is increased and confined within the lesion. These
lead to the deactivation of cancer cells directly and efficiently. Surrounding normal tissues are therefore
exposed to a much lower dose of anticancer drug. Thus, the dose-effect curve shifts left and the dose-
toxicity curve shifts right in sonochemotherapy compared with systemic chemotherapy.
Sonochemotherapy is a targeted therapy.
Sonochemotherapy here employs nonthermal effects of ultrasound. The use of ultrasound
increases the intracellular drug accumulation, which is usually mediated by cavitation [2, 5,
6]. Cavitation, the formation and/or activity of gas-filled bubbles in insonated medium, results
in localized high temperature (10
4
-10
6
K) and high pressure (10
4
atmospheres). Such an
extreme condition leads to the formation of free radicals, microstreaming and microjetting
[5]. Those active species damage tissues, and shear forces resulted from microstreaming and
microjetting distort surrounding objects. These permeabilize cell membrane including pore
formation, thus facilitating the influx. The level of cavitation depends on the intensity,
frequency and exposure duration. A higher intensity and lower frequency favor the
occurrence of cavitation, and cavitation increases with prolonging exposure duration.
Cavitation in vitro can be adjusted by varying the physical acoustic parameters. The tissue
property is the biological determinant for cavitation. In vivo cavitation depends on both
ultrasound and tissues. The cavitation threshold, viz. the minimal intensity to trigger
cavitation, is low in loose and porous tissues, and is high in dense ones. The behavior of
ultrasound in tissues is so complex that it is difficult to predict/modulate cavitation in vivo.
Some agents, such as microbubbles and sonosensitizers, serve as cavitation nuclei decreasing
the threshold intensity in vitro and in vivo [2, 5]. Overpressure suppresses the expansion of
bubbles thus being a measure to inhibit cavitation, but this technique cannot be applied in vivo
[7]. Sonodynamic therapy (SDT) is also mediated by free radicals attributable to ultrasonic
cavitation, which differs from sonochemotherapy on the role of insonation (Tab. 1).


Toxicity
Anticancer effect
Dose
E
f
f
i
c
i
e
n
c
y


Anticancer effect
Toxicity
Dose
E
f
f
i
c
i
e
n
c
y


Tinghe Yu and Yi Zhang 192
Table 1. Comparison of sonodynamic therapy and sonochemotherapy

Initiator Promoter
Sonodynamic therapy Ultrasound Sonosensitizer
Sonochemotherapy Anticancer drug Ultrasound

The increase of intracellular drug level does not occur sometimes, but a better anticancer
effect occurs [8]. This is because ultrasound has the potential of sensitizing cells. Insonated
cells are prone to being deactivated by other cytotoxic factors. Ultrasonic sensitization is one
of the reasons why the dose-anticancer effect curve in sonochemotherapy shifts left. The
addition of ultrasound lowers the thresholds for both apoptosis and necrosis [2]. Some cells
directly befallen necrosis when exposed to sonochemotherapy, which will be deactivated via
apoptosis pathway while exposed to an anticancer drug alone. This leads to an interesting
phenomenon in sonochemotherapy--the rate of cell death increases with increasing drug level
but with only a slight gain in the rate of cell apoptosis [9, 10]. Survival curves of human
ovarian cancer cells subjected to sonochemotherapy were evaluated with the ―target‖ model
in radiation biology (S=1-(1-Exp(-D/D
0
)
N
)), where S was the survival rate, and D
0
and N
were cell-specific intrinsic parameters determining the sensitivity to a cytotoxic factor.
Insonation alone had no cytotoxicity, but changed both D
0
and N [11]. This might be the
mechanism for ultrasonic sensitization.
That sonochemotherapy directly induces cell necrosis is a specific advantage.
Malfunction of apoptosis leads to chemotherapy resistance. One of strategies to overcome
chemoresistance is to deactivate cells independent of apoptosis [12]. This suggests that
sonochemtherapy can be developed to treat refractory lesions.
The Present Status

Not all antitumor drugs can be applied for sonochemotherapy, and not all cancers respond
to this modality [2]. Those anticancer agents and human cancer types with better therapeutic
outcomes are briefly summarized in Tab. 2.
Sonochemotherapy is effective against chemoresistant cancers. Adriamycin-resistant
human ovarian carcinoma cells SKOV
3
/ADR were exposed to ultrasound (0.24 MHz, 5.76
W/cm
2
) after adriamycin administration. Sonochemotherapy resulted in a lower surviving rate
compared with adriamycin. If cells were pretreated with 1 μg/ml verapamil for 24 h and then
subjected to sonochemotherapy, the deactivation rate was increased further [9]. The finding
suggests a measure for refractory cancers, i.e., the combination of a chemical modifier and
insonation. A chemical modulator cannot be clinically adopted just because the dose required
to overcome chemoresistance is beyond body tolerance. The use of ultrasound makes it
possible to decrease the dose of a modulator to a safe level. Adriamycin resistance usually
results from the overexpression of P-glycoprotein (P-gp), an ATP-depended membrane
transport protein, which pumps out intracellular drug molecules. A P-gp modulator
overcomes chemoresistance via down-regulating gene expression and quenching/inhibiting
enzyme [26, 27].

Sonochemotherapy Against Cancers 193
Table 2. A summarization of human cancer types and anticancer drugs, which have a
better response to sonochemotherapy

Anticancer agent Cancer Frequency
(Hz)
Intensity
(W/cm
2
)
Ref
In vitro
ADR Leukemia (HL-60) 80 k 3.6 13
Ovary (3AO) 0.24 M 5.12 8
Ovary (SKOV
3
/ADR)* 0.24 M 5.76 9
Breast (MCF-7WT) 1.765 M 0.25 14
Lymphoma (U937) 1.0 0.3, 0.5 15
ADR micelle P105 Leukemia (HL-60) 80 k 3.6 13
Ovary (A2780/ADR)* 69 k 3.2 16
DDP Uterine cervix (Hela) 28 k 17
Ovary (COC1/DDP)* 0.8 M 2.0 18
Ovary (HO-8910) 0.8 M 2.0 19
Ovary (HO-8910PM) 0.8 M 2.0 19
MMC Uterine cervix (Hela) 28 k 16
Ara C Leukemia (HL-60) 48 k 0.3 20
5-FU Breast (MCF-7) 3.0 M 3.0 21
Paclitaxel Ovary (HO-8910) 0.8 M 2.0 19
Ovary (HO-8910PM) 0.8 M 2.0 19
In vivo
ADR Ovary (SKOV
3
/ADR)* 0.24 M 7.84 22
Liposome-encapsulated
ADR
Colon (WiDr) 20 k 3.16 23
ADR micelle P105 Ovary (A2780) 1 M 1.2 24
5-FU Colon (KM20)* 20 k 25
Plutogel-encapsulated 5-
FU
Colon (WiDr) 20 k 3.16 25
ADR: Adriamycin, DDP: Cisplatin, MMC: Mitomycin, Ara C: Cytosine Arabinoside, 5-FU: 5-
Fluorouracil. * Chemoresistant cancer.

Reverse transcription-polymerase chain reaction assay did not support the hypothesis that
ultrasound inhibited the gene expression of P-gp in SKOV
3
/ADR cells [10]. Verapamil
competitively inhibits P-gp thus reducing the efflux, and ultrasound enhances the influx.
These increase both the intracellular adriamycin level and the retention. Anticancer effect is
therefore enhanced. In vivo investigations confirmed the effect of sonochemotherapy against
chemoresistant ovarian cancers, in that a smaller tumor volume was detected [22]. Cisplatin
resistance is the other type of chemoresistance, where a higher capacity of DNA repair plays
the leading role. Single cell comet electrophoresis assay (SCGE) revealed severer DNA
breaks in cells subjected to sonochemotherapy, compared with cisplatin alone [19].
Tinghe Yu and Yi Zhang 194
Encapsulated adriamycin micelle P105 has been used in sonochemotherapy.
Investigations on human leukemia cell line HL-60, ovarian cancer cell line A2780 and its
chemoresistant subclone A2780/MDR, have demonstrated that the cytotoxicity of
encapsulated drug was stronger than that of free molecule [13, 16, 24]. Ultrasound enhances
the release of drug from micelles and the uptake of cells. The release of drug from P105
comprises four phases, i.e., micelle destruction, destruction of cavitation nuclei, reassembly
of micelle, and reencapsulation of adriamycin [28]. The recapsulation indicates the reuse of
drugs. Those drug molecules, which are not driven into cells, will be released into the cancer
tissues in following sonication cycles. Ultrasound (20 kHz, 3.16 W/cm
2
in continuous wave)
enhanced liposome-encapsulated adriamycin (3 mg/kg or 6 mg/kg, i.p.) and Plurogel-
encapsulated 5-FU (100 mg/kg or 200 mg/kg, i.p.) against human colon cancers WiDr
transplanted in nude mice, in that tumor growth was delayed [23]. Considering a better
tolerance, sonochemotherapy with liposome-encapsulated drugs can be especially developed
for patients with poor health conditions.
The Present Limitations and Possible Solutions

Low-level ultrasound is preferred for sonochemotherapy; it can be performed
conveniently. Ultrasonic thrombolysis employing low-level ultrasound and cavitation has
been clinically introduced [29]. However, sonochemotherapy is still at an early stage.
Miller and Dou reported that high amplitude ultrasound (1.35 MHz, 5 MPa with 1 ms
burst, and ultrasound was emitted at a rate of 1 Hz) enhanced lung metastasis of melanoma
B16-D5, and cavitation was considered as the mechanism [30]. Cavitation detaches cancer
cells from the primary focus releasing them into circulation, the first step of metastasis.
Interestingly, cavitation also plays an important role in HIFU but clinical investigations have
not confirmed that metastasis is enhanced [3]. There must be some puzzles beyond the
present horizon. The level of cavitation increases with increasing intensity and prolonging
exposure duration. The cavitation threshold in vivo is actually low, 80 mW/cm
2
at 0.75 MHz
induces detectable cavitation in limb of a guinea pig [31]. HIFU therapy employs an intensity
of above 1000 W/cm
2
, and is lengthy. Such a manner favors the occurrence of cavitation.
Theoretically, HIFU may lead to a higher rate of metastasis compared with low-level
ultrasound, but this is not the fact. Metastasis is a very complex process through a serial of
programmed events [32]. Intravasation of cancer cells does not indicate a spread necessarily.
The phenotype of metastasis is cell-specific; cancers with a high potential are prone to
metastasis. We therefore assume that the difference between low- and high-intensity
ultrasound results from the metastatic potantial of cancer cells; insonation is not the initiator
but only a promoter. If this is confirmed, a cancer with highly metastatic potential is a
contraindication to ultrasonic therapy. Effects of sonochemotherapy on adhesion, migration
and invasion were investigated in human ovarian cancer cells HO-8910PM, a subline with
highly metastatic potential. All of them were inhibited by insonaton and lower rates occurred
when applying sonochemptherapy, indicating that cancer spread was not stimulated. A low
level of paclitaxel produced no cytotoxicity, but inhibited cell migration and invasion, being a
potential measure to prevent cancer metastasis during ultrasonic therapy [19].
Only partial cancer types respond to sonochemotherapy [2]. However, those human
cancer types have not been screened systemically. Arthur et al manifested that human bladder
Sonochemotherapy Against Cancers 195
cancer cells TCC-SUP, T24 and RT4 poorly responded to sonochemotherapy with
doxorubicin [33]. Thus, sonochemotherpy cannot be employed for those cancer types.
Designing ultrasonic devices with a low-intensity output is not a challenge. However,
there is no a commercially clinical instrument for sonochemotherapy. In ultrasonic
thrombolysis, the intensity varies from <720 mW/cm
2
to 35 W/cm
2
[34]. Sonochemotherapy
might also work under a wide range of acoustic intensity.
Cavitation is the mediator of sonochemotherapy. The occurrence and level of cavitation
in vivo should therefore be under control. In vivo cavitation is usually determined by detecting
passive cavitation. Free radicals attributable to cavitation are involved in sonochemotherapy.
Thus, those reactive radicals in tissues need to be measured. The cavitation level depends on
the intensity, frequency and insonatime time. Therapeutic ultrasound works in the range of
non-linear acoustics, and there are drastic differences between tissue types and between
individuals. Thus, it is difficult to control cavitation in vivo via just adjusting the acoustic
parameters. Employing other techniques might be a solution.
Polystyrene nanoparticles (with diameters of 100 nm and 280 nm) decrease the cavitation
threshold. In nude mice bearing KM20 colon cancers, 100-nm particles and 5-fluorouracil (5-
FU, 90 mg/kg) were injected before 20 kHz ultrasound irradiation. This modality resulted in
an enhanced antitumor effect, in that the cancer volume was reduced compared with that
attributable to 5-FU alone [25]. Microbubbles enhance ultrasonic cavitation, and can be used
for sonochemotherapy. Potential techniques include (i) anticancer agents are encapsulated
into/coupled with microbubbles, (ii) cytotoxic drugs and microbubbles are co-used, and (iii)
micelles containing anticancer chemicals are combined with microbubbles [2]. 5-FU, Optison
(microbubble agent for contrast ultrasonography), and ultrasound (3.0 MHz, 3.0 W/cm
2
) were
combined to deactivate human breast carcinoma cells MCF-7. The combination of Optison
and ultrasound induced immediate cell death, and cell deactivation more depended on 5-FU
after 24 h. With insonation (50 % duty cycle), there was a synergism between 5-FU (10
μg/ml) and Optison (10 %); however, cell deactivation attributable to 5-FU decreased with
increasing concentration of Optison without insonation [21]. Watanabe et al manifested that
ultrasound enhanced cisplatin against HT29-luc xenografts in the presence of microbubbles
[35]. These data confirm the role of cavitation in sonochemotherapy.
Sonosensitizers favor ultrasonic cavitation suggesting a measure for sonochemotherapy,
i.e., ―sonosensitizer-anticancer drug-ultrasound‖. Free radicals are generated when activating
the sonosensitizer. The level of cavitation is under control via adjusting the dose of
sonosensitizer. The alternative is that an anticancer agent is linked to a sonosensitizer.
Insonation is performed when the fusion molecule reaches the target lesion. Cavitation is
therefore confined to a definite volume, improving the therapeutic precision and efficiency.
Developing a drug responding to ultrasound specifically improves the safety and therapeutic
effects.
Microbubbles can be applied for aforementioned technique, i.e., the combination of
sonosensitizer, microbubble, antitumor drug and insonation. Sensitizers and cytotoxic agents
are encapsulated into microbubbles, and ultrasound is used to destruct microbubbles when
entering into the lesion. Anticancer agents are therefore released into cancer tissues directly.
The influx of anticancer drugs is facilitated as sensitizers and microbubbles enhance
cavitation permeabilizing cell membrane. Alternatively, micelles containing sonosensitizers
and anticancer chemicals are co-administrated with microbubbles. Microbubble-enhanced
Tinghe Yu and Yi Zhang 196
cavitation accelerates the release of anticancer drugs and sonosensitizers from micelles, and
permeabilizes cancer cells as well.
In ―sonosensitizer-anticancer drug-ultrasound‖ and ―sonosensitizer-microbubble-
anticancer drug-ultrasound‖ modalities, the cavitation level can be adjusted by modulating the
dose of sonosensitizer and/or microbubble, while the insonation level is set at the threshold to
activate sensitizers/microbubbles. These techniques realize targeted cavitation in vivo.
Sonochemotherapy can be guided and monitored with ultrasound images. A device
integrated a diagnostic ultrasound unit with a therapeutic ultrasound one should be developed
to perform sonochemotherapy. Ultrasonography is a rapid imaging technique, so treatment
can be monitored in real time.
Sonosensitizers and microbubbles intensify acoustic cavitation. Sonochemistry
attributable to cavitation can decompose chemicals, restructure molecules, change
conformations, and increase the rate of chemical reactions [36-38]. Thus, the molecular
structure and anticancer potency of an anticancer agent must be investigated, especially when
sonosensitizers and microbubbles are used. On the other hand, some drugs, such as
cyclophosphamide (CTX) and ifosfamide (IFO), must be catalyzed in tissues producing active
forms. The rate of catalysis may be accelerated by cavitation, which increases the yield of
active forms resulting in better therapeutic outcomes. Effects of cavitation on the structure
and function of proteins need to be investigated when employing an antibody-linked
anticancer drug for sonochemotherapy. The denaturation of antibodies nullifies the affinity to
cancer cells.
Inducing apoptosis is involved in sonochemotherapy. Cytochrome C-mediated apoptosis
has been understood, in which the release of cytochrome C from mitochondria initiates the
cascade of cell suicide. As an indicator of permeabilization of outer membrane (a preparation
for releasing cytochrome), swollen mitochondria occur frequently [39, 40]. Apoptotic bodies
were detected in COC1/DDP cells after exposed to nonlethal insonation. However, the level
of cytochrome C in cytosol was decreased, and mitochondrial tumefaction only occurred in
some cells [41]. The data suggests that non-mitochondria apoptosis pathways participate in
ultrasound-induced cell apoptosis.
When chemoresistant cancers SKOV
3
/ADR were treated with sonochemotherapy,
necrosis was detected in the center of cancer tissues [22]. The finding suggests that
sonochemotherapy may impair microcirculation in cancers. Vascular endothelial growth
factor (VEGF), a pivotal cytokine for angiogenesis, was decreased by ultrasound (10 MHz, 40
W/cm
2
) either in cancer tissues or in serum [42]. VEGF is also involved in the formation of
metastatic lesions, and is a target for cancer treatment [43]. These suggest that ultrasound may
not stimulate the cancer spread.
Sonochemotherapy is an adjuvant therapy, which is performed after surgical debulking to
deactivate residual and chemoresistant cells. This technique will change the clinical practice
when chemotherapy becomes a radical cure for cancers. The development of this modality
also relies on the understanding of biological effects induced in tissues, and the advancement
of ultrasonic devices.


Sonochemotherapy Against Cancers 197
The Interaction between an Anticancer Drug and Insonation

The interaction between a cytotoxic drug and ultrasound in sonochemotherapy has not
been understood; it is not clear whether ultrasound synergizes or just adds a drug. We
evaluated the interactions in human ovarian cancer cells HO-8910 and HO-8910PM.
Insonation efficiently enhanced a combined chemotherapy. Combination indexes showed a
synergism or an addition when applying cisplatin, and a synergism, an addition or an
antagonism when using paclitaxel. Cell type was an important determinant for
sonochemotherap; sonochemotherapy realized a specific effect via a synergism and mediated
another specific response via an addition, for a specific cell type [19]. Sonochemotherapy
should not be applied when there is an antagonism. The data indicate the cell death (tumor
inhibition) rate may not reflect the panorama of the effects of sonochemotherapy. How many
fold the dose of an anticancer drug can be decreased in sonochemtherapy needs to be
investigated in following trials.
Exploring Sonochemotherapy from HIFU Therapy

HIFU treatment opens a window to investigating sonochemotherapy. The focal region
comprises 84 % and 71 % energies emitted from the transducer, when defined as -6 dB and -3
dB, respectively [44]. Such a high intensity induces a temperature of >56 °C thus ablating
tissues within the focus. Tissues outside the focus are therefore exposed to a limited
ultrasonic energy. Cavitation can still be triggered in those areas, as the threshold intensity is
low. HIFU is a palliative therapy sometimes (only segmental lesions are ablated). If those
cases receive anticancer drugs, residual cancer tissue may be a clinical model to explore
sonochemotherapy (Figure 2).


Figure 2. A clinical model for exploring sonochemotherapy. During HIFU therapy, ultrasonic energies
emitted from the therapeutic transducer are efficiently delivered into the focal tissues, resulting in
immediately coagulative necrosis. Tissues outside the focus are therefore exposed to a limited
ultrasonic intensity thus producing slight thermal effects, but cavitation can also be induced. When
HIFU is used as a palliative treatment, residual cancer tissues open a window to evaluating
sonochemotherapy.
Tinghe Yu and Yi Zhang 198
SUMMARY
Sonochemotheapy is a promising modality against cancers, including refractory lesions.
This modality is at the preclinical stage yet. Ultrasonic cavitation plays the leading role in
sonochemotherapy. Making the occurrence and level of cavitation under control improves the
safety and efficiency. The use of sonosensitizer/microbubble enhances cavitation, and can
also adjust cavitation in vivo. The molecular structure and anticancer potency of a cytotoxic
drug must be investigated when combining anticancer agents, sonosensitizers and
microbubbles. The interaction between an anticancer agent and ultrasound in
sonochemotheray must be understood. Residual cancer tissues after palliative HIFU treatment
open a window to evaluating sonochemotherapy.
ACKNOWLEDGMENTS
The work in our laboratory is supported with grants from the Natural Science Foundation
of China (10774198) and the Natural Science Foundation Project of Chongqing (CSTC
2009BA5049).
REFERENCES
[1] Yu, T; Wang, Z; Mason, TJ. A review of research into the use of low level ultrasound
in cancer therapy. Ultrason. Sonochem. 2004, 11, 95-103.
[2] Yu, T; Li, S; Zhao, J; Mason, TJ. Ultrasound: a chemotherapy sensitizer. Technol.
Cancer Res. Treat. 2006, 5, 51-60.
[3] tar Haar, G. Therapeutic application of ultrasound. Prog. Biophys. Mol. Biol. 2007, 93,
111-129.
[4] Yu, T; Zhou, S; Zhang, J. Ultrasonic therapy for gynecologic tumors. J. Minim.
Invasive Gynecol. 2008, 15, 667-672.
[5] Paliwal, S; Mitragotri, S. Ultrasound-induced cavitation: applications in drug and gene
delivery. Expert Opin. Drug Deliv. 2006, 3, 713-726.
[6] Reddy, LH. Drug delivery to tumours: recent strategies. J. Pharm. Pharmacol. 2005,
57, 1231-1242.
[7] Bailey, MR; Couret, LN; Sapozhnikov, OA; Khokhlova, VA; ter Haar, G; Vaezy, S;
Shi, XG; Martin, R; Crum, LA. Use of overpressure to assess the role of bubbles in
focused ultrasound lesion shape in vitro. Ultrasound Med. Biol. 2001, 27, 695-708.
[8] Yu, T; Wang, Z; Jiang, S. Potentiation of cytotoxicity of adriamycin on human ovarian
cancer cell line 3AO by low-level ultrasound. Ultrasonics 2001, 39, 307-309.
[9] Yu, T; Hu, K; Bai, J; Wang, Z. Reversal of adriamycin resistance in ovarian carcinoma
cell line by combination of verapamil and low-level ultrasound. Ultrason. Sonochem.
2003, 10, 37-40.
[10] Yu, T; Huang, X; Hu, K; Bai, J; Wang, Z. Mechanisms of reversal of adriamycin
resistance in human ovarian carcinoma cell line by ultrasound. Int. J. Gynecol. Cancer
2004, 14, 76-81.
Sonochemotherapy Against Cancers 199
[11] Yu, T; Xiong, Z; Chen, S; Tu, G. The use of models in ―target‖ theory to evaluate the
survival curves of human ovarian carcinoma cell line exposure to adriamycin combined
with ultrasound. Ultrason. Sonochem. 2005, 12, 345-348.
[12] Agarwal, R; Kaye, SB. Ovarian cancers: strategies for overcoming resistance to
chemotherapy. Nat. Rev. Cancer 2003, 3, 502-516.
[13] Munshi, N; Rapoport, N; Pitt, WG. Ultrasonic activated drug delivery from pluronic P-
105 micelles. Cancer Lett. 1997, 118, 13-19.
[14] Harrison, GH; Balcer-Kubiczek, EK; Eddy, HA. Potentiation of chemotherapy by low-
level ultrasound. Int. J. Radiat. Biol. 1991, 59, 1453-1466.
[15] Yoshida, T; Kondo, K; Ogawa, R; Feril, LB; Zhao, QL; Watanabe, A; Tsukada, K.
Combination of doxorubicin and low-intensity ultrasound causes a synergistic
enhancement in cell killing and an additive enhancement in apoptosis induction in
human lymphoma U937 cells. Cancer Chemother. Pharmacol. 2008, 61, 559-567.
[16] Rapoport, N. Combined cancer therapy by micellar-encapsulated drug and ultrasound.
Int. J. Pharm. 2004, 277, 155-162.
[17] Takada, E; Sunagawa, M; Ohdaira, E; Ide, M. Ultrasonic effect on anti-cancer drugs.
In: Proceedings of World Congress on Ultrasonics. Yokohama, Japan, 1997, p. 400-
401.
[18] Yu, T; Yang, Y; Liu, S; Yu, H. Ultrasound increases DNA damages attributable to
cisplatin in cisplatin-resistant human ovarian cancer cells. Ultrasound Obstet Gynecol
2009, 33, 355-359.
[19] Zhou, S; Yu, T; Zhang, J; Liu, S; Huo, Y; Zhang, Y. Sonochemotherapy inhibits the
adhesion, migration and invasion of human ovarian cancer cells with highly metastatic
potential. Ultraschall Med. 2010, 31 in press Doi: 10.1055/s-0028-1110020
[20] Tachibana, K; Uchida, T; Tamura, K; Eguchi, H; Yamashita, N; Ogawa, K. Enhanced
cytotoxicity of Ara-C by low intensity ultrasound to HL-60 cells. Cancer Lett. 2000,
149, 189-194.
[21] Chumakova, OV; Liopo, AV; Evers, BM; Esenaliev, RO. Effect of 5-fluorouracil,
Optison and ultrasound on MCF-7 cell viability. Ultrasound Med. Biol. 2006, 32, 751-
758.
[22] Yu, T; Huang, X; Hu, K; Bai, J; Wang, Z. Treatment of transplanted adriamycin-
resistant ovarian cancers in mice by combination of adriamycin and ultrasound
eExposure. Ultrason. Sonochem. 2004, 11, 287-291.
[23] Myhr, G; Moan, J. Synergistic and tumour selective effects of ahemotherapy and
ultrasound treatment. Cancer Lett. 2006, 232, 206-213.
[24] Rapoport, NY; Christensen, DA; Fain, HD; Barrows, L; Gao, Z. Ultrasound-triggered
drug targeting of tumors in vitro and in vivo. Ultrasonics 2004, 42, 943-950.
[25] Larina, IV; Evers, BM; Ashitkov, TV; Bartels, C; Larin, KV; Esenaliev, RO.
Enhancement of drug delivery in tumors by using interaction of nanoparticles with
ultrasound radiation. Technol. Cancer Res. Treat. 2005, 4, 217-226.
[26] Cascorbi, I. Role of pharmacogenetics of ATP-binding cassette transporters in the
pharmacokinetics of drugs. Pharmacol. Ther. 2006, 112, 457-473.
[27] Modok, S; Mellor, HR; Callaghan, R. Modulation of multidrug resistance efflux pump
activity to overcome chemoresistance in cancer. Curr. Opin. Pharmacol. 2006, 6, 350-
354.
Tinghe Yu and Yi Zhang 200
[28] Stevenson-Abouelnasr, D; Husseini, GA; Pitt, EG. Further investigation of the
mechanism of doxorubicin release from P105 micelles using kinetic models. Colloids
Surf. B Biointerfaces 2007, 55, 59-66.
[29] Eggers, J; Seidel, G; Koch, B; Konig, IR. Sonothrombolysis in acute ischemic stroke
for patients ineligible for rt-PA. Neurology 2005, 64, 1052-1054.
[30] Mille, DL; Dou, C. The potential for enhancement of mouse melanoma metastasis by
diagnostic and high-amplitude ultrasound. Ultrasound Med. Biol. 2006, 32, 1097-1101.
[31] ter Haar, GR; Daniels, S. Evidence for ultrasonically induced cavitation in vivo. Phys.
Med. Biol. 1981, 26, 1145-1149.
[32] Mehlen, P; Puisieux, A. Metastasis: a question of life or death. Nat. Rev. Cancer 2006,
6, 449-458.
[33] Arthur, C; Flaig, T; Su, LJ; Denney, R; Barnes, F; Glodé, LM. The effect of ultrasonic
irradiation on doxorubicin-induced cytotoxicity in three human bladder cancer cell
lines. Ultrasonics 2007, 46, 68-73.
[34] Pfaffenberger, S; Devcic-Kuhar, B; Kastl1, SP; Huber, K; Maurer, G; Wojta, J;
Gottsauner-Wolf, M. Ultrasound thrombolysis. Thromb. Haemost. 2005, 94, 26-36.
[35] Watanabe,Y; Aoi, A; Horie, S; Tomita, N; Mori, S; Morikawa, H, Matsumura Y;
Vassaux, G; Kodama1, T. Low-intensity ultrasound and microbubbles enhance the
antitumor effect of cisplatin. Cancer Sci. 2008, 99: 2525-2531.
[36] Kardos, N; Luche, JL. Sonochemistry of carbohydrate compounds. Carbohyd. Res.
2001, 332, 115-131.
[37] Mason, TJ. Sonochemistry and sonoprocessing: the link, the trends and (probably) the
future. Ultrason. Sonochem. 2003, 10, 175-179.
[38] Cravotto, G; Cintas, P. Power ultrasound in organic synthesis: moving cavitational
chemistry from academia to innovative and large-scale applications. Chem. Soc. Rev.
2006, 35, 180-196.
[39] Jiang, X; Wang, X. Cytochrome C-mediated apoptosis. Ann. Rev. Biochem. 2004, 73,
87-106.
[40] Martinou, JC; Green, DR. Breaking the mitochondrial barrier. Nat. Rev. Mol. Cell Biol.
2001, 2, 63-67.
[41] Yu, T; Huang, X; Jiang, S; Hu, K; Kong, B; Wang, Z. Ultrastructure alterations in
adriamycin-resistant and cisplatin-resistant human ovarian cancer cell lines exposed to
nonlethal ultrasound. Int. J. Gynecol. Cancer 2005, 15, 462-467.
[42] Yang, X; Bai, J; Yu, T; Wang, Z; Li, Q. Effects of high intensity focused ultrasound on
vascular endothelial growth factor in melanoma bearing mice. Technol. Cancer Res.
Treat. 2004, 3, 499-503.
[43] Kilarski, WW; Bikfalvi, A. Recent developments in tumor angiogenesis. Curr. Pharm.
Biotechnol. 2007, 8, 3-9.
[44] ter Haar, GR. Therapeutic and surgical applications. In: Hill, CR; Bamber, JC; ter Haar
GR eds. Physical Principles of Medical Ultrasonics (2nd Ed). West Sussex: John Wiley
and Sons Ltd; 2004, p. 407-456.

In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 7



APPLICATION OF ULTRASOUND FOR WATER
DISINFECTION PROCESSES


Vincenzo Naddeo, Milena Landi and Vincenzo Belgiorno
Department of Civil Engineering, University of Salerno,
Fisciano SA, Italy
SONOCHEMICAL EFFECTS IN WATER TREATMENT
Ultrasound (US) is a sound wave of a frequency greater than the superior audibility
threshold of the human hearing. Sonochemistry is the application of ultrasound in chemistry.
It became an exciting new field of research over the past decade. Some applications date back
to the 1920s (Harvey and Loomis, 1929). The 1950s and 1960s subsequently represented the
first extensive sonochemical research years and significant progresses were made throughout
them. Then it was realized that ultrasound power has a great potential for uses in a wide
variety of processes in the chemical and allied industries (Brown and Goodman, 1965;
El‘Pilner, 1964). In these early years, experiments were often performed without any real
knowledge of the fundamental physical background about the US action. The situation
changed in the 1980s when a new surge of activity started and the use of US as a real tool in
chemistry began. It was in 1986 that the first ever international symposium on Sonochemistry
was held at Warwick University U.K. (Mason and Peters, 2002).
Therefore, ultrasound are considered as an novel alternative technologies able to reduce
the total processing cost while maintaining or enhancing product quality in an
environmentally benign manner. Cavitation, indeed, offers immense potentiality for
intensification of physical or chemical processing in an energy-efficient manner (Gogate and
Kabadi, 2008).
Today, we know that the reason why ultrasound power can produce chemical effects is
through the phenomenon of cavitation. Cavitation is the production of microbubbles in a
liquid that are formed when a large negative pressure is applied to it (Mason and Peters,
2002).
Compression and rarefaction waves rapidly move through the liquid media. If the waves
are sufficiently intense they will break the attractive forces in the existing molecules and
Vincenzo Naddeo, Milena Landi and Vincenzo Belgiorno 202
create gas bubbles. As additional ultrasound energy enters the liquid, the gas bubbles grow
until they reach a critical size. Once gas bubbles have reached the critical size, they will either
implode or collapse (Neppiras, 1980; Dehghani, 2005).
High power ultrasound produces strong cavitation in aqueous solutions causing shock
waves and reactive free radicals (e.g.,

OH, HO

2
and O

) through the violent collapse of the
cavitation bubble. These effects should contribute to the physical disruption of microbial
structures and inactivation as well as the decomposition of toxic chemicals (Furuta et al.,
2004).
Sonochemical benefits are caused by chemical and physical effects that arise from
ultrasonic cavitations.
CHEMICAL EFFECTS
The chemical effects of ultrasonic cavitation are caused by the formation of hydroxyl and
hydrogen radicals in the collapsing cavities (Makino et al., 1982). Radicals react with each
other and with solutes present in the liquid medium.
Sonochemical reactions in a cavitating liquid occur in three regions, the gas inside a
cavity, the interface between a gas cavity and a liquid and the bulk liquid (Él'piner, 1959;
Suslick et al., 1986). Figure 1 shows a diagram of these three regions in a cavitating liquid,
where sonochemical reactions and processes take place.


Figure 1. Schematic diagram of the three regions in a cavitating liquid in which the chemical reactions
take place.

Application of Ultrasound for Water Disinfection Processes 203
High temperatures and pressures occur inside the collapsing gas bubble, according to the
hot spot theory (Noltingk and Neppiras, 1950). They both cause the thermal dissociation of
water vapour into hydroxyl HO
-
and hydrogen radicals H
-
. These radicals have been
identified by reaction with spin trapping compounds (Makino et al., 1982; Makino et al.,
1983). Hydroxyl and hydrogen radicals in the gas cavities react either with other radicals
producing water, hydrogen peroxide and hydrogen gas, as shown in Figure1a, or with other
gaseous components such as volatile organic solutes (Sehgal et al., 1982; Todd, 1970).
The second region where sonochemical reactions take place is at the interface between
the hot gas cavities and the bulk liquid. Large temperature and pressure gradients exist in this
region (Riesz and Kondo, 1992). The formation of H
2
O
2
, H
2
O and H
2
, as shown in Figure 1b,
also occur at the interface between the hot gas cavity and the bulk liquid.
Sonochemical reactions take place also in bulk liquid solution (Figure 1c) at ambient
temperature (Riesz et al., 1990). Radicals produced in collapsing gas cavity (a) and gas/liquid
interface (b) diffuse into this region and react with non-volatile solutes with kinetics similar to
that observed in aqueous radiation chemistry (Riesz et al., 1990; Sehgal et al., 1982).
Gutiérrez and co-workers estimated that less than 10 % of the hydroxyl and hydrogen radicals
formed in the gas cavity reach the bulk solution (Gutiérrez et al., 1991). Products, such as
hydrogen peroxide, from radical reactions occurring in the first two regions also diffuse into
this region and undergo secondary reactions.
Early ultrasonic investigations showed that the nature of a gas present during sonication
affected the sonochemical reactions. Weissler and co-workers found that the amount of iodine
liberated from a potassium iodide solution was dependent on the gas (air, oxygen, nitrogen,
helium or carbon dioxide) that was present during sonication (Weissler et al., 1950). Parke
and Taylor found that hydrogen peroxide formation differed when different gases (oxygen,
argon or nitrogen) were present during sonication (Parke and Taylor, 1956).
PHYSICAL EFFECTS
Sonochemical applications, such as catalysis, cleaning, emulsification and
depolymerization, are possible due to the physical effects of ultrasound. These effects, like
the chemical effects of ultrasound, are caused by the collapse of cavities in a liquid under the
action of a sound wave. The two important mechanisms responsible for the effects of
cavitation in solid-liquid mixtures are microjet impact and shock wave damage (Suslick et al.,
1990). These phenomena will occur when a cavitation bubble collapses near a solid surface,
asymmetric cavitaty collapse (Figure 2). During a collapse a cavity deformation is self-
reinforcing and at the same time a stream of fast-moving liquid directed towards the solid
surface is generated (Olson and Hammitt, 1969; Suslick et al., 1990). It is called microjet.
The speed of microjets is estimated to be around 100 m/s (Suslick et al., 1990). The
impact of microjets on a solid surface causes localised erosion or pitting. Ultrasonic pitting
has been recorded photographically (Numachi, 1965; Olson and Hammitt, 1969). The surface
area of a solid is increased and new surface material is exposed.
Shock waves formation also occurs during cavity collapse (Boudjouk, 1986). Shock
waves break apart loosely aggregated particles along existing cracks (increasing the surface
area) and remove loosely adhering particles to a solid surface (Crawford, 1963).
Vincenzo Naddeo, Milena Landi and Vincenzo Belgiorno 204

Figure 2 Schematization of asymmetric cavity collapse in bulk solution and microjet and shock wave
formation.
Reaction products are thus removed from a solid surface, leaving the surface clean and
available for further reaction (Mason, 1999). Turbulent flow and shock waves produced by
intense ultrasound cause small metal particles to collide with sufficiently high speed so as to
induce melting at the point of collision (Suslick et al., 1990).
The following paragraph overview several studies on the use of ultrasound to treat
several types of microorganisms in various aqueous matrices.
ULTRASOUND FOR WATER DISINFECTION
Ultrasound environmental applications include many processes on drinking water,
wastewater, sludge, waste, contaminated site remediation and air. Disinfection is one of the
applications of ultrasound at both drinking water and wastewater treatments.
It is well known that chlorination is the most common method for water disinfection. It is
also well known that during this process, however, chlorine and its compounds react with
some organic matter to form unwanted by-products, hazardous to human health, known as
DBPs (Disinfection By Products). In more countries very stringent limits for chlorination by-
products such as trihalomethanes were set for wastewater reuse. In accord with this, the use of
alternative oxidation/disinfection systems should be evaluated as possible alternative to
chlorine. Recently ultrasound were found to be effective for wastewater disinfection. An
alternative to chlorination is the use of multiple disinfectants which can enhance inactivation
of pathogens and reduces the chlorination by-products (i.e. trihalomethanes and haloacetic
acids).
Ultrasound is able to inactivate bacteria and de-agglomerate bacterial clusters through
both physical and chemical effects. Indeed, cavitation bubbles produce enough energy to
mechanically weaken or disrupt bacteria or biological cells through essentially these two
processes listed hereafter (Joyce et al., 2003a; Von Sonntag, 1986; Oyane, 2009; Furuta et al.,
2004).

- Formation of mechanical forces due to surface resonance of the bacterial cell.
Pressures and pressure gradients, resulting from the collapse of gas bubbles, get
bacterial solution in or near bacterial cell walls. Bacterial cell damage results from
mechanical stress, over a period of time, which depends on frequency (Furuta et al.,
Application of Ultrasound for Water Disinfection Processes 205
2004). As a effect of cavitation there is micro-streaming, that occurs within bacterial
cells, induces shear forces breaking bacterial agglomerates up into a greater number
of individual bacteria (bacterial splitting) (Oyane I., 2009).
- Formation of radicals (

OH and

H) during cavitation in the aqueous medium
generates a chemical attack. These radicals attack the chemical structure of bacterial
cell walls and weaken cell walls to the point of disintegration (Von Sonntag, 1986).
Hydrogen peroxide, which is a strong bactericide, is among final products of water
sonochemical degradation (Hua and Thompson, 2000).

The overall effect of applying ultrasound is thus the result of a competition between these
two processes in a water solution.
Disinfection efficiency is also strongly influenced by both irradiation time and intensity.
Generally, disinfection performances are in direct ratio to time and intensity. Sometimes it
may happen that low frequencies apparently provide to a higher performance at first (Figure
2). In these cases even if we have the same number of colonies at t
0
, more colonies could be
found at high intensities at short sonication time. This happen because for high frequencies
the splitting is higher. These is one limit that cannot be clear with used analytical methods.
Sonication alone can provide powerful disinfection. However, to achieve high
performances in a shorter time, using only ultrasound is necessary to use high ultrasonic
intensities.
Most studies focus on the inactivation of Escherichia coli in various aqueous matrices
(Table 1). E. coli inactivation exhibits pseudo-first order behaviour (Hua and Thompson,
2000; Oyane et al., 2009). Hua and Thompson (2000) investigated the effect of ultrasound at
a frequency of 20 kHz for E. coli inactivation. They observed that the extent of inactivation
increased with increasing intensity and became about 2.8 Log after 60 min at the highest
density of 470 W/L. Furuta et al. investigated the inactivation of E. coli along with hydrogen
peroxide formation due to water sonolysis in order to correlate the level of H
2
O
2
formation to
the extent of inactivation (Furuta et al., 2004). A 27.5 kHz horn type sonicator was used
whose operation was based on the ―squeeze-film effect‖ (i.e. the film is defined as the space
between the end of the probe of the sonicator and the bottom of the reactor) and the maximum
power of this sonicator was 42 W/mL. When the amplitude on the vibration face was 3µm,
inactivation was 6 Log at room temperature. They observed that the ultrasonic shock wave
was more important in killing microorganisms rather than the indirect effect of

OH radicals
formed by ultrasonic cavitation. Ultrasound waves at a frequency of 42 kHz were used to treat
aqueous suspensions of E. coli in the study by Dehghani (2005); the author reported a 2.7 Log
inactivation at a power density of 0.12 W/mL and a sonication of 90 min.
Ultrasound performances increase with smaller treatment volumes. Indeed the better
result was obtained by Furuta and co-workers that worked with a ―squeeze film‖ ultrasonic
system (Furuta et al., 2004).
It should be noted that, in almost all studies reviewed, the used systems are low
frequencies systems. However, it has been generally observed that these low frequency
technologies achieve the best performances concern to microorganisms inactivation.
Indeed, it can be said that less resistant microorganisms are Escherichia coli and Total
coliform, these showed the higher inactivation percentages.
Vincenzo Naddeo, Milena Landi and Vincenzo Belgiorno 206
Several types of reaction systems have been employed for ultrasound disinfection studies
and these are discussed in detail in recent reviews (Gogate, 2007; Gogate and Pandit, 2004),
while they are schematically shown in Figure 3. In brief, the ultrasonic probe is suitable to
treat relatively small volumes of water with the ultrasound irradiation being localized around
the emitting horn and not distributed as in the case of ultrasonic bath, plug-flow reactor and
the flow cell. The plug-flow reactor consists of immersed ultrasound transducers unlike the
bath where the transducers are not in direct contact with the liquid phase; moreover, it can
treat larger volumes than the probe or the bath. On the other hand, the flow cell is a unique
system that works under pressure and the water inside is sonicated all around.
There is a drive towards the use of ultrasound in disinfection as an adjunct to other
techniques because some microorganisms are becoming resistant to existing disinfection
techniques involving biocides, ultraviolet light, and heat treatment. In this view, recent studies
have dealt with the use of low frequency ultrasound (in the range 20–40 kHz) alongside
ozone (Belgiorno et al., 2007), ultraviolet irradiation (Naddeo et al., 2007), hydrodynamic
cavitation (El‘Piner, 1964), electrolysis (Brown and Goodman, 1965), chlorination (Mason
and Peters, 2002; Mason, 1976; Asher, 1987), and heterogeneous catalysts (i.e. activated
carbon, ceramic, zinc, and titanium dioxide) (Hoyler and Luke, 1994; Richards and Loomis,
1927), and reported that enhanced disinfection efficiencies could be achieved with the
combined treatments. Process efficiency may also be dictated by operating conditions such as
ultrasound intensity, frequency, and conduct time as well as the water matrix (i.e. pH,
alkalinity, suspended solids, dissolved gases) (Hua and Thompson, 2000; Madge and Jensen,
2002; Joyce et al., 2003; Dadjour et al., 2006; Antoniadis et al., 2007).
The following paragraph overview several studies on the use of ultrasound to treat
several types of microorganisms in various aqueous matrices.


Figure 2. Example about as analytical methods affect bacterial measurements (t0<t1<t2)

Application of Ultrasound for Water Disinfection Processes 207
Table 1. Summarizes studies on the inactivation of various microorganisms induced by
ultrasound irradiation as the sole disinfectant; relevant operating conditions and
efficiencies are quoted

Microorganism
Frequency

Density
[W/mL]
Ultrasonic
system
Sonication
time
[min]
Efficiency Reference
Bacillus
subtilis
L 0.24 Probe 15 C
Joyce et al.,
2003
Escherichia
coli
L 0.47 Probe 60 C
Hua and
Thompson,
2000
L 42 Probe** 3 A
Furuta et al.,
2004
L 0.12 Bath 90 A
Dehghani,
2005
L 45 Probe 20 A
Antoniadis et
al., 2007
L 0.005 Reactor 30 B
Naddeo et al.,
2009
Pseudomonas
aeruginosa
H 15 Bath 15 C
Phull et al.,
1997
Saccharomyces
cerevisiae
L 0.16 Probe** 10 C
Tsukamoto et
al., 2004
Total coliforms
L 2.4 Probe 15 C
Jyoti and
Pandit, 2004
L 0.06 Bath 15 C
Jyoti and
Pandit, 2004
L 0.005 Reactor 30 B
Naddeo et al.,
2009


Figure 3. Ultrasonic systems typically used for sonochemical treatment
Vincenzo Naddeo, Milena Landi and Vincenzo Belgiorno 208
ULTRASOUND USED IN COMBINATION WITH ULTRAVIOLET
Some authors have proposed a combined use with ultraviolet using cavitation for
disinfection as a pre-treatment rather than as a combined treatment. On the other hand,
Naddeo and co-workers (2009) found that the effectiveness of chlorination significantly
improves in combination with ultrasound.
A patent was granted to University of Salerno for the combined treatment of ultrasound
and ultraviolet for wastewater disinfection. A study was carried out for testing the
simultaneous combination of UV and US in terms of bacteria inactivation at pilot-scale.
The pilot plant was composed of two reactors (US–UV reactor and UV reactor) and set
up for use at the wastewater treatment plant (WWTP) of Mercato San Severino (Salerno,
Italy). Reactor 1 (US–UV reactor, Figure 4) was composed of ultrasonic transducer TD-US
1400 (CEIA S.p.A., Italy) at low frequency (39 kHz), variable power from 350 to 1400W and
two low pressure UV-C lamps (Trojan Technologies, Canada) of 150W each. Reactor 2 (UV
reactor) was composed of only two low pressure UV-C lamps (PROCOM s.r.l., Italy) of
200W each. In both reactors, a volume of 80L has been designed for disinfection zone. The
tests were carried out to evaluate the inactivation of two type of bacteria: Escherichia coli and
Total coliform.
An important enhancement of UV disinfection ability has been observed in presence of
US, especially. Sonication effects also increase the UV disinfection efficiency in terms of
reduction of big particles and cleaning lamps.
The tests were conducted with wastewater characterized by low transmittance, where
generally UV disinfection was not suitable. Instead, this innovative combined treatment is
able to guarantee high performances also with low transmittance wastewater. An important
enhancement of UV disinfection ability has been observed in presence of US, especially.
Sonication effects also increase the UV disinfection efficiency in terms of reduction of big
particles and cleaning lamps. What is more, the analyses show the effects of solar radiation on
UV lamps fouling formation and the specific possibility to remove fouling by US.
Thus the combined process US–UV can be considered as a valuable alternative to
conventional oxidation/disinfection processes when less expensive solutions such as
chlorination cannot be applied because of very stringent limits set by regulations (e.g.
trihalomethanes). Indeed, the combined process US–UV allowed decreasing the E. coli
colonies under 10 CFU/100mL wastewater reuse Italian limit) with a retention time of 15min.
The tests showed the influence of ultrasound on lamps fouling formation. In fact, while
during the tests, the lamps in UV reactor were becoming dirtier day by day, in US–UV reactor
the UV lamps were perfectly clean even after three days of treatment (Figure 2). The US
cleaning effects was guaranteed by the collapse of cavitation bubbles which produce liquid
jets on the lamps‘ surface. In this way, the US breaks the cake layer on the lamps making the
UV beans emission achievable in wastewater. US irradiation in combined process has a
double key role; US increase the disinfection performance not only by its disinfection power
but also by providing the constant cleaning of the UV lamps, guaranteeing constant
disinfection performances.
The advanced ultrasound disinfection (US–UV), applied under such conditions, may be
an effective technique in all WWTP where the wastewater reuse is an important
integrative/alternative resource for not drinking purposes. Nonetheless, further studies should
Application of Ultrasound for Water Disinfection Processes 209
be performed to evaluate better the disinfection effectiveness on a different bacteria species
and in continuous operation, subsequently in terms of formation of unknown ultrasound
disinfection by-products (UDBPs).

Figure 4. Schematic longitudinal section of the US-UV reactor (Reactor 1).
REFERENCES
Antoniadis, A.; Poulios, I.; Nikolakaki, E. and Mantzavinos, D. (2007). Sonochemical
disinfection of municipal wastewater. Journal of Hazardous Materials 146, 492–495.
Asher, R.C. (1987). Ultrasonics in chemical analysis. Ultrasonics. 25(1), 17-19.
doi:10.1016/0041-624X(87)90004-7
Belgiorno, V.; Rizzo, L.; Fatta, D.; Della Rocca, C.; Lofrano, G.; Nikolaou, A.; Naddeo, V.
and Meric, S. (2007). Review on endocrine disrupting-emerging compounds in urban
wastewater: occurrence and removal by photocatalysis and ultrasonic irradiation for
wastewater reuse. Desalination. 215, 166-176.
Brown, B., Goodman, J.E., 1965. High Intensity Ultrasonics. Iliffe Books Ltd, London.
Crawford, A.E., 1963. A practical introduction to ultrasonic cleaning. Ultrasonics. 1(2), 65-
69.
Dadjour M.F., Ogino C., Matsumura S., Nakamura S., Shimizu N. (2006) Disinfection of
Legionella pneumophila by ultrasonic treatment with TiO2, Water Res. 40, 1137–1142.
Dehghani, H.M., 2005. Effectiveness of Ultrasound on the Destruction of Escherichia coli.
American Journal of Environmental Sciences. 1(3), 187-189.
El‘Pilner, I.E., 1964. Ultrasound, physical, chemical and biological effects. Consultants
Bureau: New York.
Furuta, M., Yamaguchi, M., Tsukamoto, T., Yim, B., Stavarache, C.E., Hasiba, K., Maeda,
Y., 2004. Inactivation of Escherichia coli by Ultrasonic irradiation. Ultrasonics
Sonochemistry. 11, 57-60. doi:10.1016/S1350-4177(03)00136-6
Gogate, P. (2007). Application of cavitational reactors for water disinfection: Current status
and path forward. Journal of Environmental Management 85, 801–815.
Vincenzo Naddeo, Milena Landi and Vincenzo Belgiorno 210
Gogate P. R. and Pandit A. B. (2004) Sonochemical reactors: scale up aspects. Ultrasonics
Sonochemistry 11, 105–117.
Gutiérrez, M., Henglein, A., Ibañez, F., 1991. Radical scavenging in the sonolysis of aqueous
solutions of I
-
, Br
-
, and N
3-
. Journal of Physical Chemistry. 95(15), 6044-6047.
Harvey E.N., Loomis A.L., 1929. The destruction of luminous bacteria by high frequency
sound waves. J. Bacteriol. 17, 373-379.
Hua, I. and Thompson, J.E. (2000). Inactivation of Escherichia coli by Sonication at discete
ultrasonic frequencies. Wat. Res. 34(15), 3888-3893. doi:10.1016/S0043-1354(00)00121-
4
Hoyler, B.S. and Luke, S.P. (1994). Ultrasound in the process industries. Engineering Science
and Education Journal. 3(3), 119-122. doi:10.1049/esej:19940309
Joyce, E., Phull, S.S., Lorimer, J.P. and Mason, T.J. (2003). The development and evaluation
of ultrasound for the treatment of bacterial suspensions. A study of frequency, power and
sonication time on cultured Bacillus species. Ultrasonics Sonochemistry. 10, 315-318.
doi:10.1016/S1350-4177(03)00101-9
Madge B.A. and Jensen J.N. (2002). Disinfection of wastewater using a 20-kHz ultrasound
unit, Water Environ. Res. 74, 159–169.
Makino, K., Mossoba, M.M., Riesz, P., 1982. Chemical effects of ultrasound on aqueous
solutions. Evidence for HO
*
and H
*
by spin trapping. Journal of the American Chemical
Society. 104(12), 3537-3539.
Makino, K., Mossoba, M.M., Riesz, P., 1983. Chemical effects of ultrasound on aqueous
solutions. Formation of hydroxyl radicals and hydrogen atoms. Journal of Physical
Chemistry. 87(8), 1369-1377.
Mason, W. P. (1976). Sonics and ultrasonics: early history and applications, IEEE
Transactions on Sonics and Ultrasonics, SU-23(4), 224-232.
Mason, T. J., 1999. Ultrasound in environmental protection - An overview. Ultrasound in
Environmental Engineering. Sanitary Engineering. 25, 1-9. doi:10.1016/S0041-
624X(01)00081-6
Mason, T.J. and Peters, D. (2002) Practical Sonochemistry: Power Ultrasound and
Applications, 2
nd
ed. Chichester. p. 151 England: Horwood Publishing Series in Chemical
Science.
Naddeo, V., Belgiorno, V. and Napoli, R.M.A. (2007) Behavior of natural organic mater
during ultrasonic irradiation. Desalination. 10, 175-182. doi:10.1016/j.desal.2006.05.042
Naddeo V., Landi M, Belgiorno V. and Napoli R.M.A. (2009). Wastewater disinfection by
combination of ultrasound and ultraviolet irradiation. Journal of Harardous Materials. 168
(2-3), 925-929. doi:10.1016/j.jhazmat.2009.02.128
Neppiras, E.A., 1980. Acoustic Cavitation. Phys. Rep. 61, 159-251. doi:10.1016/0370-
1573(80)90115-5
Noltingk, B.E., Neppiras, E.A., 1950. Cavitation produced by ultrasonics. Proceedings of the
Physical Society of London, Section B. 63, 674-685.
Numachi, F., 1965. An experimental study of accelerated cavitation induced by ultrasonics.
Journal of Basic Engineering. (December), 967-976.
Olson, H.G., Hammitt, F.G., 1969. High-speed photographic studies of ultrasonically induced
cavitation. Journal of the Acoustical Society of America. 46(5), 1272-1283.
Oyane I., Takeda T., Oda Y., Sakata T., Furuta M., Okitsu K., Maeda Y. and Nishimura R.
(2009). Comparison between the effects of ultrasound and gamma-rays on the
Application of Ultrasound for Water Disinfection Processes 211
inactivation of Saccharomyces cerevisiae: analyses of cell membrane permeability and
DNA or RNA synthesis by flow cytometry. Ultrasonics Sonochemistry. Accepted
manuscript. doi:10.1016/j.ultsonch.2009.01.001
Phull, S.S., Newman, A.P., Lorimer, J.P., Pollet, B. and Mason T.J. (1997). The development
and evaluation of ultrasound in the biocidal treatment of water. Ultrasonics
Sonochemistry. 4, 157-164. doi:10.1016/S1350-4177(97)00029-1
Richards, W.T. and Loomis, A.L. (1927). The chemical effects of high frequency sound
waves. A preliminary survey. Journal of the American Chemical Society. 49(12), 3086-
3100.
Riesz, P., Kondo, T., 1992. Free radical formation induced by ultrasound and its biological
implications. Free Radical Biology and Medicine. 13(3), 247-270.
Riesz, P., Kondo, T., Krishna, C.M., 1990. Sonochemistry of volatile and non-volatile solutes
in aqueous solutions: e.p.r. and spin trapping studies. Ultrasonics. 28(5), 295-303.
Sehgal, C., Yu, T.J., Sutherland, R.G., Verrall, R.E., 1982. Use of 2,2-diphenyl-1-
picrylhydrazyl to investigate the chemical behaviour of free radicals induced by
ultrasonic cavitation. Journal of Physical Chemistry. 86(15), 2982-2986.
Suslick, K.S., Doktycz, S.J., Flint, E.B., 1990. On the origin of sonoluminescence and
sonochemistry. Ultrasonics. 28(5), 280-290. doi:10.1016/0041-624X(90)90033-K
Todd, J.H., 1970. Measurement of chemical activity of ultrasonic cavitation in aqueous
solutions. Ultrasonics. 8(4), 234-238.
Tsukamoto I., Yim B., Stavarache C.E., Furuta M., Hashiba K. and Maeda Y. (2004).
Inactivation of Saccharomyces cerevisiae by ultrasonic irradiation. Ultrasonics
Sonochemistry 11, 61–65
Von Sonntag, C. (1986). Disinfection by free-radicals and UV-radiation. Water Supply. 4, 9-
10.
In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 8



USE OF ULTRASONICATION IN THE PRODUCTION
AND REACTION OF C
60
AND C
70
FULLERENES


Anne C. Gaquere-Parker
1
and Cass D. Parker
2

1
Chemistry Department, University of West Georgia,
2
Chemistry Department, Clark Atlanta University, Atlanta, GA 30314
ABSTRACT
In this chapter, the use of ultrasounds on fullerenes (C
60
and C
70
) and fullerene
derivatives is described. The focus is on the articles reporting the ultrasound-promoted
treatment of these nanoparticles written in English. The ultrasound-enhanced synthesis
and chemical modification of fullerenes are detailed. The improvement obtained by
sonicating the reaction mixtures while carrying out traditional organic reactions is
discussed. This includes many types of reactions, such as oxidation, cycloaddition,
reduction and amination. Also the ultrasound-enhanced crystallization of fullerenes,
producing fullerites, and the formation of colloids when the fullerenes are sonicated in
various solvent mixtures are detailed, providing the role of ultrasound in these processes.
INTRODUCTION
Since its discovery, fullerene represents a most unusual molecule to understand and has
fascinating potentials. The physical and electronic properties of the molecules have lead to a
number of potential applications in the biochemical and medicinal fields. Fullerenes have
biological activities that are inherent in the nature of the molecule. In addition, the physical
and chemical properties of fullerenes show promise in optics and nanodevice applications. To
achieve some of the potential biochemical and medicinal applications one must overcome the
low solubility of the fullerenes. To achieve increased solubility, fullerenes are derivatized to
methanofullerenes or fulleroids. To achieve functionalization of fullerenes sonochemistry has
shown extreme promise in producing sufficient quantities of the methanofullerenes and other
fullerene derivatives. The high temperature and pressure within the cavitation bubble provides
an unusual chemical environment that is much suited to fullerenes chemical modification. In
Anne C. Gaquere-Parker and Cass D. Parker 214
this chapter we discuss the application of ultrasounds (sonochemistry) in the chemical
modification of fullerenes.
SONOSYNTHESIS OF FULLERENES AND FULLERENE DERIVATIVES
Ultrasound has been used in the production of C60 on a very limited basis. Katoh et al.
[1] reported the production of C60 using ultrasounds. In their paper they reported the
production of C60 using benzene as the starting material (Figure 1).
They conducted ultrasonic irradiation using a MST, UH-600 ultrasonic homogenizer
equipped with a 20 mm in diameter titanium tip at a frequency of 20 kHz and 600 watts.
During irradiation argon gas was bubbled through the benzene starting material in an open
vessel. Production of C
60
was noted to occur after 1 hour of irradiation. Irradiation continued
for 12 hours. The material was separated and verified using high performance liquid
chromatography and fast atom bombardment mass spectrometry via the 720 m/z nominal
mass.
One of the earliest applications of sonochemical modification of fullerene was in the
synthesis of C
60
H
2
by Mandrus et al. [2]. They reported the production of C
60
H
2
using a 20-
kHz titanium horn operating at 30 ± 5 watts (Figure 2).

)))), 0
o
C, 12 h.

Figure 1. Sonosynthesis of C
60
from benzene.

)))), 25
o
C, 2-4 h.
H
H
Hydrogens are placed on the [6,6]junction,
although it is not specified in the article.

Figure 2. Sonosynthesis of C60H2 from C60.
The solvent chosen for the synthesis of C
60
H
2
was decahydronaphthalene.
Decahydronaphthalene was chosen as a solvent for several reasons; sonochemistry of
decahydronaphthalene is well understood, fullerenes are soluble in it, and it produces highly
energetic cavitation bubbles due to its low vapor pressure. Ultrasonic irradiation of C
60
in
decahydronaphthalene produced a brown precipitate that was analyzed using high resolution
mass spectrometry and HPLC. The material obtained produced was shown to contain the
Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 215
C
60
H
2
moiety conclusively based on the intensity of the 722 m/z peak that exceeded the
expected intensity of the C
60
isotopic ratio for
13
C
2
12
C
58
+
and subsequent deuterium
experiments. As an additional confirmation of the production of the C
60
H
2
, the sonochemical
reaction of C
60
was conducted in deuterated decahydronaphthalene. The result provided
support for the production of C
60
H
2
with the detection of the C
60
HD
+
ion observed at 723 m/z.
This surprising result was characterized as arising from the rapid H/D exchange prior to mass
analysis. The source of the H was determined to be from moisture in the air or residual
sources that contacted surfaces of glassware or the mass spectrometer probe itself. The most
surprising result of their work was that only the C
60
H
2
molecule was observed. It was
concluded however, that the results fit with several observations; 1) molecular H
2
and smaller
alkenes are produced during sonolysis of alkanes, 2) such products are consistent with the
Rice radical chain mechanism of pyrolysis and 3) the intensity of cavitational collapse
increases with the lower vapor pressure of the solvent, which increases the sonochemical rate.
It still is not clear why only C
60
H
2
was produced. The concluding factor is that it involves a
secondary reaction arising from the production of atomic hydrogen during sonolysis of the
solvent and reaction with the C
60
fullerene.
In addition to the production of C
60
H
2
, the use of ultrasounds to produce
methanofullerenes derivatives have been reported, [3,4]. The methanofullerenes consist of a
bridging methyl group between two fullerene units using the [6,6]-[6,6] (Figure 3), or [6,6]-
[6,5] or [6,5]-[6,5] bonding scheme.
The methanofullerene dimer, C
121
(C
60
CC
60
) and C
122
(C
60
C
2
C
60
) were first synthesized
thermolytically and photolytically by Dragoe et al.

[5]. The carbene adds across a [6,6] bond
of the C
60
or the [6,5] which is across an annulene bond of the C
60
. Yinghuai and Yinghuai et
al. [3,4] report the synthesis of the methanofullerenes in ionic liquids (ILs) using ultrasonic
irradiation. The results of the synthesis were compared to thermolysis and photolysis
synthesis of the same compounds. In the sonochemical synthesis of methanofullerene, the
methanofullerene derivatives C
60
(CCl
2
), C
60
(CBr
2
), C
60
(CI
2
) and C
121
were synthesized by
reacting the corresponding haloform, CHCl
3
, CHBr
3
or CHI
3
, with fullerene in the presence
of base at 50 kHz for two or three days at 298K.


Figure 3. [6,6]-[6,6] Methanofullerene.
Anne C. Gaquere-Parker and Cass D. Parker 216
CHX
3
/ NaOH
IL, ))))
X
X
X
X
Mg or Zn, C
60
IL, ))))
X = Cl, Br or I
a.
b.

Figure 4. a: Synthesis of a dihalogeno methanofullerene. b. Synthesis of C121.
In each case the corresponding methanofullerene derivatives, C
60
(CCl
2
), C
60
(CBr
2
),
C
60
(CI
2
), were obtained with good yields in yields ranging from 55 – 84% in the ILs (Figure
4a). Once isolated the dihalomethanofullerenes were reacted with fullerene in the presence of
magnesium under similar conditions. Yields for the sonochemical synthesis of C
121

methanofullerene dimer was on the order of 55 - 84% for using dichloro-, dibromo-, and
diiodo-methanofullerene. The yields of the methanofullerenes derivatives were compared
using different reaction media and solvents. Yields were significantly higher in the ionic
liquid media, 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF
4
], 1-butyl-3-
ocylimidazolium tetrafluoroborate [OMIM][BF
4
] and 1-butyl-3-methylimidazolium
hexafluorophosphate [BMIM][PF
6
] than when conducted in the solvent THF. (Figure 4 b).
In comparison to the thermolytic and photolytic synthesis pathways, the sonochemical
synthesis was found to produce only one of the previously reported methanofullerene
derivatives. Sonochemical synthesis produced exclusively the [6,6] methanofullerene dimer.
This is in direct contrast to the photolytic or thermolytic synthetic routes that produces a
combination of the [6,6]-[6,6], or [6,6]-[6,5] or [6,5]-[6,5] methanofullerene derivative [5]. In
the closely related work, Yinghaui et al. reported the reaction of diiodomethane or 7,7-
dibromobicyclo [4,1,0] heptanes with fullerene in the presence of Zn or Mg respectively
under ultrasound in ILs to produce the corresponding methanofullerene as shown in the
following scheme with very good yields (Figure 5).

Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 217
Zn, CH
2
I
2
IL, ))))
Mg, IL, ))))
Br
Br

Figure 5. Synthesis of methanofullerenes from C
60
in ionic liquids.

Benzene, 5h, RT, ))))
Oxidation conditions
3-Chloroperoxybenzoic acid
4-Methyl morpholine-N-oxide
CrO
3
, CS
2
, acetone
KHSO
5
, H
2
O, 18-crown-6
O
C
60
O
C
60
or
or
or

Figure 6. Epoxidation of C60 in benzene.
Another area of significant interest is the sonochemical functionalization of fullerenes in
the synthesis of aromatic amines to produce monosugar derivatives. This work has been
conducted on a large part by the research work of Ko and is summarized here. The earliest
published report is the synthesis of fullerene oxides using various oxidants under ultrasound
irradiation conditions. They reported the synthesis of epoxylated fullerenes, C
60
(O)
n
, with n
ranging from 1-3 and C
70
(O)
n
, n from 1-2 [6,7,8]. Four different oxidizing agents were used,
3-chloroperoxy benzoic acid, 4-methyl morpholine N-oxide, chromium (VI) oxide and
oxone® monopersulfate KHSO
5
(Figure 6).
Anne C. Gaquere-Parker and Cass D. Parker 218
Yields were not reported, however, 3-chloroperoxy benzoic acid and 4-methyl
morpholine N-oxide were able to produce the epoxide with n ranging from 1-3 under
ultrasound conditions. The latter two, chromium (VI) oxide and oxone® monopersulfate were
not successful for the production of n>1 of the fullerene epoxide. Ultrasound conditions for
the synthesis were not reported. In their follow up report on the epoxidation of fullerene C
70

by the above oxidants, it is noted that the reactions were carried out using a horn type
sonicator operated at 20 kHz and at 750 watts [7]. The horn tip was 13 mm in diameter. The
reactions were carried out for 5 hours in air at room temperature. This work provides
evidence that reaction times are shortened using ultrasonic irradiation with much higher
yields and that mechanism involved for formation for the epoxides is non-thermal. In the case
of oxidation using 4-methyl morpholine N-oxide to oxidize C
70
no reaction occurred in the
absence of ultrasound. The results strongly suggests that epoxidation under ultrasound is
viable and efficient for electron rich olefins and fullerenes. The proposed mechanism of
epoxidation of C
70
fullerene under ultrasound is through a nucleophilic attack to a [6-6] bond
followed by heterolytic cleavage of the O-O bond. The epoxidation of C
60
fullerene was
expanded to include several amine N-oxides. Under ultrasound irradiation fullerene C
60
was
found to be oxidizable by 3-picoline N-oxide, isoquinoline N-oxide, pyridine N-oxide hydrate
or quinoline N-oxide to the fullerene epoxide, C
60
(O)
n
, where n = 1-2 or n=1, depending on
the amine N-oxide (Figure 7) [8].
In a separate report, Ko reported the synthesis of fullerene oxides using metal
hexacarbonyl complexes under ultrasounds [9]. In this method, fullerene C
70
, in hexane is
subjected to ultrasounds in the presence of a metal carbonyl complex (M(CO)
6
, M = Cr, Mo
or W) for 24 hours in air at 25-43°C. This method produced fullerene epoxides of the nature
C
70
O
n
, with n = 1-2. The oxidation by ultrasonic irradiation may proceed by nucleophilic
attack on the [6-6] bond in the fullerenes as noted previously. These methods provide an easy
process to obtain fullerene epoxides that can be easily modified to produce a number of
interesting fullerene molecules. As an indicator, Ko utilized fullerene epoxides in the reaction
with aromatic amines under ultrasounds [10]. In this report, C
70
O
n
was reacted with 3-
nitroaniline, 4-isopropylaniline, or 4-nitroaniline in the presence of FeCl
3
in tetrahydrofuran
(THF) to produce aminofullerenols under ultrasonic irradiation (Figure 8). The
aminofullerenols were confirmed by MALDI-TOF-MS and UV-visible spectrophotometry.

THF, 24h, RT, ))))
Oxidation conditions
3-Picoline-N-oxide
Pyridine-N-oxide
Quinoline-N-oxide
Isoquinoline-N-oxide
O
C
60
O
C
60
or
or
or
Figure 7. Epoxidation of C60 in THF.
Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 219
OH
NHR
O
FeCl
3
, THF, )))), 24 h
O
2
N
NO
2
RNH
2
R =

Figure 8. Amination of C70 epoxide with three aniline derivatives.
Ko has also undertaken the sonochemical synthesis of glycosyls fullerenes, C
60
and C
70

[11,12]. The interests in these materials are their potential medicinal applications due to the
solubility of such materials and possible biological activities. The glycosyls fullerenes are
prepared via a cycloaddition by reacting C
60
or C
70
with 2‘-azidoethyl per-O-acetylglycoside
of interest at a 1:1 ratio in benzene under ultrasounds for 2 days at room temperature, as
shown in the scheme below (Figure 9).
An ultrasound horn sonicator was used operating at a frequency of 20 kHz and 750 watts.
The resulting glycosyl fullerene derivatives were isolated using flash chromatography and
analyzed using FAB-MS,
1
H and
13
C NMR, FT-IR and UV-vis spectrophotometry. The
characterization results strongly support the production of the closed [5,6] and [6,6]
monoadducts. No evidence of the open [5,6] or open [6,6] isomer formation was observed. In
addition, no evidence was present for the formation of the bis-adduct formation under
ultrasounds. Although produced in very small yields, <5%, ultrasound provides a simple and
direct method for the production of the glycosyl mono-adducts.
SONOCHEMISTRY APPLIED TO FULLERENES AND CARBON
NANOTUBES MODIFICATION, SEPARATION AND PURIFICATION
Ultrasounds have potential applications in the production of fullerenes and carbon
nanotubes. In the following applications a careful distinction is made between the use of
―horn type‖ and ―bath‖ ultrasonic devices. Horn type typically operates at a higher power
level and induces a higher level of mechanical damage during processing. Bath type
ultrasonic devices operate a lower power level, but are very much capable of activating or
accelerating a reaction.
Anne C. Gaquere-Parker and Cass D. Parker 220
N
sugar
sugar
N
3
benzene, ))))
RT, 2 days
O
O
OAc
AcO
AcO
AcO
O
O
OAc
AcO
AcO
AcO
OAc
O
O
OAc
AcO
AcO
OAc
AcO
O
O
AcO
OAc
O
O
OAc
AcO
AcO
O
O
OAc
AcO
OAc
2,3,4,6-tetra-O-Acetyl-alpha-D-mannopyranoside 2,3,4,6-tetra-O-Acetyl-beta-D-galactopyranoside
2,3,4,6-tetra-O-Acetyl-beta-D-glucopyranoside 2,3,4-tri-O-Acetyl-beta-D-xylopyranoside
octa-O-Acetyl-beta-D-maltopyranoside
Sugars derivatives are listed below:

Figure 9. Synthesis of glycosyls fullerenes.
One the earliest reports for the isolation and characterization of fullerenes using
ultrasounds was published by Diack et al. [13]. They reported the purification by the use of
ultrasonic bath at room temperature followed by a one step non-aqueous reversed phased
chromatography process using octadecyl silica as the stationary phase and n-hexane as the
mobile phase. Characterization was determined using mass spectrometry and UV-visible
spectroscopy. Diack et al. compared the use of THF and boiling toluene as solvents during the
ultrasound ―bath‖ treatment of the impure material. The extraction involves dispersion of the
soot samples in THF and submission to the ultrasonic bath for 20 minutes. The material is
then filtered and washed until the filtrate is clear. The washing and filtrate are combined and
Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 221
placed into a rotary evaporator to remove the solvent. Benzene is added to aid in the removal
of residual moisture from the THF. The extract is recovered using methylene chloride and
dried under vacuum. For separation of the fullerenes from the extract a 25 cm, 4.6 mm id
preparative column was used. The column was packed with 8.9 µm IMPAQRG 2010
C18silica. The extract was dissolved in methylene chloride, injected on the column and eluted
with n-hexane at a flow rate of 1.0 mL per minute. Analysis of the collected fractions shows
clearly that C
60
and C
70
could easily be separated at a fairly high purity, along with traces of
higher mass fullerenes such as C
76
, C
78
, C
82
and C
84
.
Using a very different approach, Gasgnier and Petit used ultrasound to increase the purity
of a fullerene extract mixture [14]. In their procedure a fullerene sample of an approximate
composition of 80/20 of C
60
/C
70
and higher fullerenes and C
60
-solvates were dispersed in
dodecane (fullerenes are weakly soluble in this solvent). Using a double walled container for
water bath temperature control at 300-310 K, the solution was subjected to ultrasounds from a
horn type sonicator operating at 20 kHz and 180 W/cm
2
for seven hours. After sonication, the
solvent was removed by drying and the resulting residue analyzed using XRD. The resulting
pattern for the material collected after sonication had the corresponding diffraction lines of
fcc C
60
. Based on the XRD results the conversion of the starting material to C
60
fullerene was
90% or greater. The use of microwave was compared to the ultrasound method for the same
starting material with a conversion rate of greater than 95% within 2 minutes. Alternate
starting materials showed very little change when subjected to ultrasounds, however, those
same were convertible to a higher purity C
60
when subjected to microwaves.
Minato et al. were able to reproducibly grow C
60
fullerene nanotubes by the modification
of liquid-liquid interfacial precipitation method [15]. In their procedure they utilized
ultrasonic dispersion upon the addition of isopropyl alcohol to successfully grow C
60

fullerene nanotubes from a C
60
solution in pyridine. Solutions were maintained at 10°C
during the crystal growth process. Through the use of ultrasonic pulverization,
recrystallization and crystal growth they were able to produce C
60
nanotubes of different
morphologies (Figure 10). They report the production of open and closed end C
60
nanotubes
of various sizes ranging from several hundred nanometers to several micrometers (Figure 11).
The importance of their work is that the nanotubes grown can easily be redissolved such that
the C
60
nanotubes could be used as a template or a reaction vessel for encapsulated materials.


Figure 10. (a) Photograph of C
60
nanotubes grown by forming liquid–liquid interface between pyridine
saturated with C
60
and isopropyl alcohol and (b) optical photomicrograph of C
60
nanotubes. Reprinted
from [15], Copyright (2005), with permission from Elsevier.
Anne C. Gaquere-Parker and Cass D. Parker 222

Figure 11. Transmission electron microscope image of a C60 nanowhisker with partly dissolved
textures at the ends. Reprinted from [15], Copyright (2005), with permission from Elsevier.
Miller et al. used liquid-liquid interfacial precipitation to grow C
60
nanotubes of
diameters reaching 300 nm[16]. The method employed is a modification of the Miyazawa‘s
technique, addition of a ninefold volume excess of isopropanol to a C
60
solution prepared in
pyridine. Nucleation in their study was initiated at 2° C, the solution shaken after 24 hrs, and
crystal growth continued for several days at 2° C. In their study the sonochemical stability of
the tubes grown was studied by sonicating in a bath for up to 60 seconds. The tubes showed
no sonochemical stability. Damage was observed as early as after 5 seconds of sonication, as
observed by optical microscopy and AFM. After 30 seconds of sonication in a bath type
sonicator the tube structure was mostly compromised leaving very small fragments. As the
nanotubes are held together by weak van der Waals forces between the C
60
fullerenes, the
nanotubes are easily broken by the force incurred during sonochemical processes.
GROWTH OF C
60
FULLERITE CRYSTALS USING ULTRASOUNDS
The potential of growing macroscopic C
60
crystals has been of considerable interest in
recent history. Most of the early approaches involved the vapor phase synthesis at high
temperature under high vacuum. This method produces high quality crystals, however it is an
expensive approach with limited availability of the specialized equipment. Gupta et al. [17]
reported on the ultrasound induced growth of C
60
single crystals of mm size overnight. As
noted by Miller [16], they found that the crystals are bonded together entirely through van der
Waals forces. The crystals produced are extremely brittle. The method developed by Gupta et
al. is very straightforward; pure KBr powder is filled into a glass cylinder to a depth of ~5
mm, to this added C
60
, after which sufficient benzene is added to give a C
60
concentration of 2
mg C
60
/ml benzene. The beaker is ultrasonically treated to dissolve the C
60
into the benzene.
After dissolution of C
60
sonication is continued for several more hours. The benzene is then
allowed to evaporate overnight at room temperature yielding partially or fully grown C
60

single crystals. The crystals were characterized using X-ray diffraction analysis (Figure 12).
Peaks noted from the diffraction pattern were narrow, indicating good crystallinity, with a
calculated fcc lattice parameter of a=14.17±0.2 Å. SEM pictures show some KBr particles
(Figure 13 a and b) which can be washed with water. EDX spectrum shows one single peak,
confirming the high purity of the crystals (Fig 13.c). The C
60
single crystals were reported to
be very brittle, probably due to structural defects or their van der Waals bonding, which both
prevent the motion of dislocations. Such fragility is not reported when the fullerites are
produced at high temperature, which can be explained by the incorporation of carbon in the
crystal. This novel technique allows the production of large size C
60
fullerites in an easy and
very inexpensive way.
Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 223

Figure 12. X-ray diffraction patterns of (a) original C60 powder and (b) C60 fullerites. Reprinted from
[17], Copyright (2006), with permission from Elsevier.


Figure 13. (a, b) SEM images of the C60 fullerites and (c) EDX spectra of the C60 fullerites. Reprinted
from [17], Copyright (2006), with permission from Elsevier.
Anne C. Gaquere-Parker and Cass D. Parker 224
Shul‘ga et al. [18] used ultrasound in the preparation of C
60
fullerite by a precipitation
method using a different solvent than Gupta [17]. Shul‘ga was attempting to reduce the size
of the C
60
crystallite and make an amorphous form of the C
60
fullerite. In their procedure a
C
60
solution is prepared, using toluene, chlorobenzene or 1,2-dichlorobenzene as the solvent,
sonicated by an ultrasound horn operating at 35 kHz and 200 watts for 5 minutes to
completely dissociate the C
60
. To the solution is added a five-fold excess of isopropanol and
sonicated for an additional 60 minutes. In their work they noted that ultrasounds produce very
little effect on the size of the crystallite in the fcc phase of the fullerite prepared regardless of
the solvent used. They did find that the parameter a of the fcc lattice was significantly smaller
for the samples subjected to sonication than those that were not subjected to ultrasound. They
concluded that sonication promotes the degasification of the solvent that can be captured
during the crystallization process, decreasing therefore the concentration of gases in the
crystal. As a result the fcc lattice of the fullerite is smaller.
COLLOID PRODUCTION
In a different approach to the use of ultrasounds, Todorovic-Markovic et al. used
ultrasound for the preparation of colloidal C
60
that were characterized by atomic force
microscopy [19]. They prepared C
60
or C
84
colloidal suspension by ultrasound dispersion of
fullerenes in THF for 10 days. This solution was filtered through a .45 µm PTFE filter. The
solution is then purged using argon and to it is added an equal volume of MiliQ water at a rate
of 2 L/min under continuous ultrasounds. The THF is then evaporated using a rotary
evaporator at 45°C. Concentration of the fullerenes-based colloids was determined by drying
completely the suspension and reconstituting in xylene before submitting it to an additional
two hours of sonication. The absorption of the resulting solution was measured
spectrophotometrically and the concentration determined using from a calibration curve.
FTIR and atomic force microscopy were used to characterize the colloids. FTIR clearly shows
the presence of C
60
and C
84
fullerenes colloids. In addition, their results show that THF forms
a shell around the nanocrystals formed during sonication. AFM was used to characterize the
particle size of the fullerenes in THF. The results show a reduction in particle size with
increased sonication time. Particle size of the colloids before sonication was determined to be
between 80-90 nm for C
60
and 95 nm for C
84
, with a solvent layer of approximately 31 nm
thick of THF (Figure 14 a). Particle size for the C
60
was reduced from an average of 1.312 µm
to 90.33 nm when exposed to ultrasounds for four days and ten days respectively (Figure 15 a
and b). Similarly C
84
particles size decreased from

240 to 170 nm under the same conditions.
The nanocrystal structure of C
84
can be seen clearly (Figure 14 b and c).
Andrievsky et al. [20] prepared aqueous colloidal solutions of fullerenes in a totally
different manner. In their procedure a fullerene solution in toluene, .2 mg per mL, is mixed
with deionized water and subjected to ultrasounds for several hours until the toluene was
completely evaporated from the solution. This solution was then filtered through a .22 µm
filter resulting in a transparent, but brightly brownish orange solution. The solution was
opalescent suggesting a colloidal solution of ≤.2 µm in diameter. Loss of fullerene was
determined as the final solution was estimated to have a concentration of 5 µg/mL.
Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 225



Figure 14. Top view AFM images of nC84 colloid recorded in (a) wave, (b) 2D phase and (c) 3D phase
modes. Mica was used as a substrate. Reprinted from [19], Copyright (2008), with permission from
Elsevier.


Figure 15. AFM images of C
60
dissolved in THF within four (a) and (b) ten days. Mica was used as a
substrate. Reprinted from [19], Copyright (2008), with permission from Elsevier.
The mass spectrum of the final solution clearly shows the presence of the C
60
and C
70

fullerene with no evidence of fullerene modification chemically.
The goal of this study was to prepare soluble fullerene solutions to study their interaction
with water and the biological activity of fullerenes in such a media. Such a solution was
Anne C. Gaquere-Parker and Cass D. Parker 226
easily prepared by the use of ultrasounds to give a finely dispersed colloidal suspension of
high stability. Mass spectrometric analysis of the colloidal suspension indicates no
admixtures are formed during ultrasound irradiation. Stabilization of the fullerene colloids is
derived from fullerene-water interaction via the inclusion of fullerenes into the water structure
and formation of clathrate-like networks of water molecules around the fullerenes and
aggregates which is stabilized by the low mobility of the fullerenes. In addition, they
proposed that the electronic properties of the fullerenes may lead to donor-acceptor and
charge-transfer interactions that promote weak water-fullerene interactions. Such interactions
have been stated previously to explain the unusual properties of the fullerenes in other
solvents.
Andrievsky [21] continued their study of ultrasound produced colloidal solutions of
fullerenes in water (FWS) by electron microscopy to determine the structure of the colloidal
suspension. The FWS prepared by ultrasounds are stable for up to 18 months. Using a
suspension method for the preparation of samples for TEM analysis they were able to obtain
electron micrographs of the colloidal particles (Figure 16).
The results were compared to similarly prepared C
60
solution prepared in benzene. The
results showed that the C
60
FWS particles consists of sphere shaped aggregates of 7-72 nm in
size. This result is the proof of an ultramicroheterogeneous and polydispersed C
60
hydrosol.
Electron diffraction results show the crystal-like character of primary aggregates of C
60
. The
results of their study show that the C
60
FWS to be a molecular-colloid system containing
hydrated single fullerene molecules and fractal clusters.
Ko et al. utilized a different approach to preparing water soluble C60 [22] and C
70
[23]

fullerenes under ultrasounds. They report the reaction of C
60
or C
70
under ultrasounds
with a mixture of sulfuric and nitric acid that give rise to a water soluble C
60
or C
70
fullerene.
Employing a horn type sonicator, operating at 20 kHz and 750 watts, 20 mg of the fullerene is
added to 10.0 mL of a concentrated sulfuric acid/nitric acid (3:1, v/v ratio) and reacted under
ultrasounds for 3 days in air at 25-43°C. The resulting solution is neutralized with NaOH
producing a brownish-orange solid and evaporated to retrieve the solid material. The resulting
solids were analyzed using MALDI-TOF MS and the C
60
was also analyzed using
13
C-NMR.


Figure 16. TEM of fullerene C
60
coagulates. Reprinted from [21], Copyright (1999), with permission
from Elsevier.
Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 227
The MS results show the prerequisite molecular ion of C
60
at m/z 720.3285 and C
70
at
840.000 (Figure 17).


Figure 17. MALDI–TOF mass spectrum of a water-solubilized fullerene C
70
. Reprinted from [23],
Copyright (2006), with permission from Elsevier.
In contrast to Andrievsky et al. [20], Ko et al. [22,23] noted the degradation of the C
60

and C
70
moiety in their mass spectral results arising from a Am/z of 24 mass units starting
with the parent peak ion. In their study a water soluble fullerene could be prepared under
similar chemical reaction conditions without ultrasound albeit the reaction time was longer
than three days. They proposed a water soluble species of the nature [C
60
@(H
2
O)
n
] [22] and
[C
70
@(H
2
O)
n
] [23] for the fullerenes. They reported a similar conclusion as Andrievsky [20]
based on published results of the study of fullerenes as to the properties of the colloidal
fullerenes.
CONCLUSION
The use of ultrasounds in the synthesis and production of fullerenes derivatives and
nanomaterials offers two major advantages; speed and specificity. The articles cited in this
chapter clearly show the advantages of using ultrasound for the synthesis of fullerene
derivatives that cannot be synthesized easily by conventional methods. In the case of
methanofullerenes not only was speed and specificity noted, solvent effects under ultrasounds
also led to a significant increase in yield paving the way for synthesizing additional fullerene
derivatives. Ultrasound was also noted be useful in the production of colloidal suspensions
and large crystals of fullerenes that will facilitate the study of fullerene interactions in the
environment and production of new materials.


Anne C. Gaquere-Parker and Cass D. Parker 228
REFERENCES
[1] Katoh, R.; Yanase, E.; Yokoi, H.; Usuba, S.; Kakudate, Y.; Fujiwara, S. Ultrason.
Sonochem. 1998, 5, 37-38. Possible new route for the production of C
60
by ultrasound.
[2] Mandrus, D.; Kele, M.; Hettich, R. L.; Guiochon, G.; Sales, B. C.; Boatner, L.A. J.
Phys. Chem. B 1997, 101, 123-128. Sonochemical Synthesis of C
60
H
2
.
[3] Yinghuai, Z.; J. Phys. Chem. Solids 2004, 65, 349-353. Application of ultrasound
technique in the synthesis of methanofullerene derivatives.
[4] Yinghaui, Z.; Bahnmueller, S.; Chibun, C.; Carpenter, K.; Hosmane, N. S; Maguire, J.
A., Tetrahedron Lett. 2003, 44, 5473-5476. An effective system to synthesize
methanofullerenes: substrate-ionic liquid-ultrasonic radiation.
[5] Dragoe, N.; Tanibayashi, S.; Nakahara, K.; Nakao, S.; Shimotani, H.; Xiao, L.;
Kitazawa, K.; Achiba, Y.; Kikuchi, K.; Nojima, K. Chem. Commun., 1999, 85-86.
Carbon allotropes of dumbbell structure: C
121
and C
122
.
[6] Ko, W.; Baek, K., Phys. Solid State 2002, 44, 424-426. The Oxidation of Fullerenes
(C
60
, C
70
) with Various Oxidants under Ultrasonication.
[7] Ko, W.; Baek, K., Ultrasonics 2002, 39, 729-733. The oxidation of fullerene [C
70
] with
various oxidants by ultrasonication.
[8] Ko W.; Nam J.; Hwang S., Ultrasonics 2004, 42, 611-615. The oxidation of fullerene
[C
60
] with various amine N-oxides under ultrasonic irradiation
[9] Ko, W.; Park, Y., Elastomer 2005, 40, 174-180. Sonochemical synthesis of fullerene
oxides [C
70
O
n
] (n=1-2) using metal hexacarbonyl complexes M(CO)
6
(M=Cr, Mo, W)
under air Atmosphere.
[10] Ko, W.; Park, B.; Lee, Y. Elastomer 2008, 43, 31-38. Sonochemical reaction of
fullerene oxides, [C
70
(O)
n
](n>1) with aromatic amines.
[11] Yoon, S.; Hwang, S.; Ko, W. J. Nanosci. Nanotechnol. 2008, 8, 3136-3141.
Sonochemical reaction of fullerene [C
60
] with several 2‘-azidoethyl per-O-acetyl
glycosides.
[12] Yoon, S.; Hwang, S.; Ko, W. Colloids and Surf., A 2008, , 313-314, 304-307. Synthesis
of glycosyls fullerene [C
70
] under ultrasonic irradiation.
[13] Diack, M.; Hettich, R. L.; Compton, R. N.; Guiochon, G. Anal. Chem. 1992, 64, 2143-
2148. Contribution to the isolation and characterization of buckminsterfullerenes.
[14] Gasgnier, M.; Petit, A. Mater. Res. Bull. 1998, 33, 1427-1432. Crystallographic data for
ultrasound-and microwave-treated fullerene C
60
.
[15] Minato, J.; Miyazawa, K.; Suga, T. Sci. Technol. Adv. Mater. 2005, 6, 272-277.
Morphology of C
60
nanotubes fabricated by the liquid-liquid interfacial precipitation
method.
[16] Rauwerdink, K.; Liu, J.; Kintigh, J.; Miller, G. P. Microsc. Res. Tech. 2007, 70, 513-21.
Thermal, sonochemical, and mechanical behaviors of single crystal [60] fullerene
nanotubes.
[17] Gupta, V.; Scharff, P.; Miura, N. Mater. Lett. 2006, 60, 3156-3159. Ultrasound induced
growth of C
60
fullerites over KBr.
[18] Shul‘ga, Y. M.; Baskakov, S.A.; Martynenko, V.M,; Petinov, V. I.; Razumov, V.F.;
Shchur, D.V. Russ. J. Phys. Chem. 2006, 80, 654-658. Effect of ultrasound treatment of
C
60
solutions on the crystalline structure of precipitated fullerite.
Use Of Ultrasonication in the Production and Reaction of C60 and C70 … 229
[19] Todorovic-Markovic, B.; Jovanovic, S.; Jokanovic, V.; Nedic, Z.; Dramicanin, M.;
Markovic, Z. Appl. Surf. Sci. 2008, 255, 3283-3288. Atomic force microscopy study of
fullerene-based colloids.
[20] Andrievsky, G. V.; Kosevich, M. V.; Vovk, O. M.; Shelkovsky, V. S.; Vashchenko, L.
A. J. Am. Chem. Soc. 1995, 107, 1281-1282. On the production of an aqueous colloidal
solution of fullerenes.
[21] Andrievsky, G.V.; Klochkov, V.K.; Karyakina, E.L.; Mchedlov-Petrossyan. N.O.
Chem. Phys. Lett. 1999, 300, 392-396. Studies of aqueous colloidal solutions of
fullerene C
60
by electron microscopy.
[22] Ko, W.; Heo, J.; Nam, J.; Lee, K. Ultrasonics 2004, 41, 727-730. Synthesis of a water-
soluble fullerene [C
60
] under ultrasonication.
[23] Ko W.; Park Y.; Jeong M. Ultrasonics 2006, 44, e367-9. Preparation of a water-soluble
fullerene [C
70
] under ultrasonic irradiation.

In: Sonochemistry: Theory, Reactions, Syntheses … ISBN: 978-1-61728-652-0
Editor: Filip M. Nowak © 2010 Nova Science Publishers, Inc.






Chapter 9



APPLICATION OF ULTRASOUNDS TO
CARBON NANOTUBES


Anne C. Gaquere-Parker
1
and Cass D. Parker
2

1
Chemistry Department, University of West Georgia,
2
Chemistry Department, Clark Atlanta University, Atlanta, GA 30314


ABSTRACT

In this chapter, the use of ultrasounds on carbon based nanotubes is reviewed with a focus
on the English written articles. The synthesis of carbon nanotubes and their surface
modification such as oxidation and covalent functionalization under ultrasounds are reported.
The synthesis of hybrid nanocomposite materials where carbon nanotubes are added as a
reinforcement agent via ultrasound-induced assembly is not described in this chapter. A
detailed survey of the literature concerning the purification and separation of carbon
nanotubes under ultrasounds is provided. The effect of sonication on carbon nanotubes
suspensions which covers aqueous and organic solutions in the presence of surfactants is
discussed with an emphasis being placed on the effect that ultrasounds have on non-covalent
interactions between the carbon nanotubes and the components of the suspensions. The effect
of ultrasounds on the physical properties of the carbon nanotubes, especially the introduction
of wall defects is analyzed. Finally the advantages and shortcomings of sonochemistry
described in this chapter are summarized, showing a possible trend in the direction of future
research in this field.


INTRODUCTION
Ultrasounds can act in three ways on liquids: cavitation process, localized hot spots, and
radical formation. This chapter first reviews the use of high intensity ultrasound for the
synthesis of carbon nanotubes. The ultrasonic spray method is not described in this chapter
but can be found in the literature [1], [2], [3]. Single wall carbon nanotubes have a high
Anne C. Gaquere-Parker and Cass D. Parker 232
surface energy and in order to minimize that energy, carbon nanotubes form bundles and
multi wall carbon nanotubes can be entangled during the synthesis process, therefore
dispersion problems which cannot be solved by simple agitation are encountered for both
kinds of nanotubes. Carbon nanotubes can be mechanically separated during sonication, and
this has been used for purification and for the formation of dispersions as described in this
chapter. Functionalization of the nanotubes using ultrasounds is also an important feature,
since it affects their physical properties. The sonochemical preparation of polymer
nanocomposites through dispersions has been reviewed recently [4] and is not be described in
this chapter. Cavitation can cause defects in solids and the damage caused by ultrasounds to
carbon nanotubes is reported here. Finally, the applications combining the use of ultrasounds
and carbon nanotubes are presented.


SONOCHEMICAL PRODUCTION OF CARBON
NANOTUBES

Katoh et al. [5] reported results of the sonication of chlorobenzene and o-dichlorobenzene
in the presence of solid metallic particles that have a diameter under 200 m. ZnCl
2
, Zn,
ZnO, Ni, and NiCl
2
were tested. Sonication of liquid chlorobenzene and benzene without
solid particles or in the presence of Ni, NiCl
2
and ZnO yielded a polymer and graphitic
particles (Figure 1.a.). When ZnCl
2
was added, carbon nanotubes were obtained (Figure 1.b.).
The authors suggest that the polymer obtained from the sonication of the halogenated
aromatic compound is annealed during the heterogeneous process, which is due to the high
rate of collisions of the relatively small particles in the mixture. Similar results were obtained
when o-dichlorobenzene was sonicated in the presence of ZnCl
2
and Zn.

b.
Figure 1: a. TEM image of the product after ultrasound irradiation of dichlorobenzene with Ni. b. TEM
image of the product after ultrasound irradiation of clearly shows that annealing of the product proceeds
dichlorobenzene with ZnCl
2
. Reprinted from [5], Copyright (1999), with permission from Elsevier.
Jeong et al. [6], [7] reported results of the sonication of ferrocene and p-xylene in the
presence of silica powder under ambient conditions. The process provided single wall carbon
nanotubes without the production of multi wall carbon nanotubes. The presence of silica was
crucial in obtaining the carbon nanotubes, as it may serve as a nucleation site. Ferrocene is
Application of Ultrasounds to Carbon Nanotubes 233
decomposed by the ultrasounds into fine iron particles that are the catalytic site for the growth
of the single wall carbon nanotubes, as well. Since no multi wall carbon nanotubes were
observed, the formation of larger iron particles is unlikely to have occurred. The authors
suggest that the action of the ultrasounds not only decomposes the ferrocene and the p-xylene
to provide the iron and the carbon sources, but also to provide the energy necessary to
synthesize the carbon nanotubes. Under traditional conditions, high energy systems such as
high temperature, high vacuum, or arc discharge are required for the formation of carbon
nanotubes. With ultrasounds, ambient conditions are successfully used, potentially leading to
the large scale synthesis of carbon nanotubes.
In 2008, Manafi et al. [8] synthesized multi wall carbon nanotubes from a mixture of
dichloromethane, lithium and cobalt chloride in a basic aqueous solution at room temperature
in an ultrasonic bath, followed by 24 hours in a 160
o
C oven. The overall yield of nanotubes
was 70%, with amorphous carbon and carbon nanoparticles accounting for the remainder of
the carbon. Raman spectroscopy shows two peaks at 1586 and 1340 cm
−1
(Figure 2),
corresponding to the vibration of sp
2
-bonded carbon atoms in a 2D hexagonal lattice and of
carbon atoms with dangling bonds in poorly ordered carbon, respectively. The ratio of these
peaks, in the range of G/D=65/35, indicates that the carbon nanotubes exhibit a rather
defective structure. The use of ultrasounds allows the formation of these multi wall carbon
nanotubes with this morphology whereas similar experiments conducted without ultrasonic
pre-treatment led to larger and shorter nanotubes and nanoparticles. It is believed that the
sonication step is an important step to generate the multi wall carbon nanotubes before the
heat treatment. The nanotubes were 2-5 m long with a 60±20 nm diameter with a ring shape
as seen by transmission electron microscopy (TEM) (Figure 3).


Figure 2. Raman spectrum Reprinted from [8], Copyright (2008), with permission from Elsevier.
Anne C. Gaquere-Parker and Cass D. Parker 234

Figure 3. High resolution TEM image of MWCNTs. Reprinted from [8], Copyright (2008), with
permission from Elsevier.
Ring formation has been described more recently for single wall carbon nanotubes by
Martel et al. [9]. They sonicated single wall carbon nanotubes in a mixture of sulfuric acid
and hydrogen peroxide for several hours at 40-50
o
C, filtered and resuspended the
nanoparticles in 1,2-dichloroethane using sonication. TEM and atomic force microscopy
(AFM) images revealed the formation of rings and ropes under these oxidative conditions.
The yield depends on the sonication duration as well as the concentration of hydrogen
peroxide. The oxidation step helps reduce the amount of metal catalyst as well amorphous
carbon particles. Single wall carbon nanotubes are cut during the oxidation process, leading to
carboxylated ends. Through van der Waals attraction, the tubes curl together to form rings.
The effect of the ultrasounds is to provide the energy activation necessary for the ring
formation, the carbon nanotubes being at the bubble-liquid interface would be bent
mechanically during bubble collapse. Komatsu et al. [10] also reported the formation of
toroidal aggregates of single wall carbon nanotubes after ultrasonic treatment in
tetrahydrofuran, chloroform and n-heptane, with n-heptane providing the highest purity in
toroidal nanotubes (Figure 4).


Figure 4. TEM images of toroidal aggregates of SWCNTs. Reprinted from [10], Copyright (2006), with
permission from Elsevier.
Li et al. [11], [12] sonicated chlorinated hydrocarbons (CH
2
Cl
2
, CHCl
3
and CH
3
I) in the
presence of silicon nanowires to obtain multi wall carbon nanotubes and other carbon
nanoparticles such as onion-like carbon nanotubes. The silicon nanowires were pre-treated
with HF to ensure an active surface and the absence of oxide layers. Sonication ensured a
Application of Ultrasounds to Carbon Nanotubes 235
greater yield of nanotubes and nanoonions. The authors suggest a reaction between the Si-H
and the C-Cl bonds from the chloroform, forming C-H units able to polymerize forming
hydrogenated graphite sheets. These sheets wrap around the silicon template leading to the
formation of hydrogenated carbon nanotubes, which upon further sonication are removed
from the silicon templates and are dehydrogenated. Ultrasounds promote the heterogeneous
reaction between the silicon nanowire and the hydrocarbon material in solution as well as the
demolding of the products from the silicon nanowires.
Wang et al. [13] cut graphene oxide nanosheets into smaller hydroxylated analogues of
naphthalene, anthracene and pyrene after 10 minutes of sonication in nitric acid at room
temperature. Dehydration of the hydroxylated analogues under acidic condition and
subsequent recomposition eventually led to the formation of fullerenes and carbon nanotubes.
Upon increasing the temperature, different results were obtained. At 60
o
C only fullerene-like-
particles were obtained, and at 70
o
C, only polyaromatic amorphous carbon was detected.
Since cavitation efficiency is known to decrease at a higher temperature, the temperature
study showed the true sonochemical effect in the synthesis process. It is interesting to note
that Li et al. [14] reported sonicating carbon black in deionized water in an ultrasonic bath for
44 hours under ambient conditions produced carbon nanosheets but no carbon nanotubes.
This result shows the probable need for acidic and oxidative conditions as used by Wang [13].


PURIFICATION OF CARBON NANOTUBES

Very few articles deal with the purification of carbon nanotubes directly. Very often
articles refer to the dispersion of carbon nanotubes which upon centrifugation can lead to
purer samples. In this section articles dealing with the purification of the carbon nanotube
samples are described, whereas the latter part of this chapter will discuss dispersions.
In 1998, Dujardin et al. [15] synthesized what they called single shell nanotubes by the
laser-oven ablation method and purified them by sonicating the raw sample in nitric acid in a
sonication bath at room temperature, before refluxing the mixture for 4 hours. They obtained
purified nanotubes which do not show any distortion in the TEM images suggesting that little
oxidative damage had occurred on the walls as is usually observed with multi shell nanotubes.
Unfortunately no explanation is provided regarding the use of the ultrasounds in the first step.
The same year, Shelimov et al. [16] reported the ultrasonically assisted filtration of single
wall carbon nanotubes from soot obtained by a laser vaporization process. The sample is
dispersed in methanol and the ultrasounds generated by a horn inserted in the filtration funnel
help the filtration process by maintaining the particles in suspension, preventing the formation
of a ―cake‖ on the filter. Because the author is aware that sonication can lead to damage to the
walls, they refluxed without sonicating the purified single wall carbon nanotubes in nitric acid
for 18 hours. The TEM pictures show untangled bundles of the carbon nanotubes, with no
multi wall carbon nanotube or amorphous carbon. The authors suggest the first sonication
step created defects in the walls which were easily oxidized and cut during the nitric acid
treatment. However no experiment was carried out without the sonication to verify that
hypothesis. Also they report that the filtration process assisted by sonication is not enough to
cut the carbon nanotubes and that a longer sonication time with an acidic treatment is
necessary to seriously shorten the carbon nanotubes. Finally, only the outer nanotubes in the
Anne C. Gaquere-Parker and Cass D. Parker 236
single wall carbon nanotubes bundles are believed to incur damages, leaving inner carbon
nanotubes with little or no damage.
In 2002, Thien-Nga et al. [17] purified single wall carbon nanotubes by mixing the
impure particles with ZrO
2
and CaCO
3
in an ultrasonic bath. The ferromagnetic impurities
were removed from the nanoparticles and then trapped by magnets. In this case the
mechanical action of the ultrasounds provides an effective mixing of the slurry, while the
metal particles are being removed in what the authors called a ―snooker‖ process.
More recently in 2005, Li et al. [18] purified soot obtained from arc discharges samples,
which usually contain a significant amount of impurities along with single wall carbon
nanotubes (amorphous carbon, metallic catalyst and multi wall graphite nanoparticles). He
dispersed the sample by sonicating in an aqueous solution of sodium dodecyl sulfate (SDS)
for two hours. Further oxidation and acidic treatment were carried out. The overall process
led to a removal of 45% of the weight of the original sample. The ultrasounds helped detach
the impurities from the single wall carbon nanotubes, before the oxidative and acidic
processes removed the remaining impurities, as clearly seen in the scanning electron
microscopy (SEM) images, Figure 5a and 5b.


Figure 5: SEM images of (a) cloth-soot and (b) purified SWNT. Reprinted from [18], Copyright (2005),
with permission from Elsevier.

DISPERSIONS OF CARBON NANOTUBES UNDER
ULTRASOUNDS

Dispersion of carbon nanotubes obtained in neat organic solvents are first described, then
in aqueous solutions with surfactants and finally after acidic treatment.
Liu et al. [19] reported the stable dispersion of single wall carbon nanotubes by
sonicating them in N,N-dimethylformamide (DMF) or N-methyl pyrrolidinone (NMP) for 15
hours. AFM shows tube lengths of approximately 1m, evidence that the tubes were cut.
However, because the tubes underwent acidic treatment prior to sonication, it is hard to
determine when and how the cutting process occurred. AFM imaging also showed that the
tubes are not bundled any longer and are individualized, providing suspensions which
remained stable for several months. However, Ausman et al. [20] while reporting the effect of
various solvents on the stability of single wall carbon nanotubes disagree with the fact that
dispersions in DMF or NMP are stable suspensions for months but do aggregate within a few
Application of Ultrasounds to Carbon Nanotubes 237
days. Landi et al. [21] studied the effect of several alkyl amide solvents on the dispersion of
single wall carbon nanotubes using sonication as part of the dispersing process in N,N-
dimethylacetamide (DMA), N,N-dimethylpropanamide and N,N-diethylacetamide. UV-Vis
spectroscopy was used to assess the dispersion capability of each solvent, with DMA yielding
the largest absorbance and the most well resolved spectrum. They also reported that the
dispersions were stable only for days up to a week depending on the concentration. They
verified that DMA did not undergo any chemical change during the sonication process,
rationalizing the dispersion ability of the amides as a combination of stacking, high
polarity and appropriate geometry.
Niyogi et al. [22] dispersed single wall carbon nanotubes in o-dichlorobenzene and DMF
at ambient temperatures using a sonication bath. During sonication, the carbon nanotubes
undergo degradation and are coated with a polymer, resulting from the decomposition and
polymerization of o-dichlorobenzene. DMF did not undergo any chemical change during this
treatment and the carbon nanotubes show no sign of degradation in the absence of o-
dichlorobenzene. When o-dichlorobenzene is sonicated prior to the addition of the carbon
nanotubes an insoluble polymer is generated that cannot disperse the carbon nanotubes.
Similarly, if as little as 1% ethanol is used to inhibit the polymerization, no stable dispersion
is obtained. It is concluded that the process creates a polymer that adheres to the surface of
the nanotubes in an irreversible process. Although the exact mechanism is not known, it is
possible that the polymerization reaction is terminated by the presence of the carbon
nanotubes, with the polymers immobilized on them.
Ganter et al. [23] led another study on the dispersion of single wall carbon nanotubes in
various organic solvents: DMA, TMMA (N,N,N,N-tetramethylmalonamide), o-
dichlorobenzene and 1-chloronaphtalene. He monitored the effect of ultrasounds on the single
wall carbon nanotubes extinction coefficients using optical absorption spectroscopy. He
attributed a decrease of the single wall carbon nanotubes extinction coefficients with the
chlorinated solvents to the formation of a sonopolymer as Niyogi [22] described with o-
dichlorobenzene. The decrease observed with TMMA as a solvent was attributed to a
preferred orientation of the solvent molecules along the axial direction of the carbon
nanotubes, leading to a greater dielectric screening than with DMA. When samples were
sonicated for longer periods of time, the spectra obtained with the carbon nanotube dispersed
in alkyl amides did not show any change. However the formation of a sonopolymer from both
chlorinated solvents was shown. Sonication of the solvent without carbon nanotube led to
polymer formation as well, confirming Nioygi‘s results. Stirring the mixtures for 3 days in the
absence of sonication did not lead to a stable dispersion. This result provides further evidence
that the formation of the sonopolymer in situ is necessary to obtain a stable dispersion.
Finally Raman spectroscopy data showed that the single wall carbon nanotubes were only
minimally damaged during the dispersion process with the alkyl amides, making this family
of solvents appropriate for future work. Similar results were obtained when single wall carbon
nanotubes were dispersed in N-methylpyrrolidinone (NMP) using ultrasounds [24]. No
explanation is provided as to the efficacy of this solvent that led to the formation of stable
dispersions over several days. Raman spectroscopy was used to show that no damage was
detected on the tubes during the dispersion process. Kim et al. used ultrasounds when
dispersing single wall carbon nanotubes in NMP with the presence of a thiophene based
oligomer [25]. Although the study uses ultrasounds, their direct effect was not studied. N,N-
dimethylacetamide (DMAc) was used a solvent in the dispersion of single wall carbon
Anne C. Gaquere-Parker and Cass D. Parker 238
nanotubes with added polyimides as dispersants by Delozier et al. [26]. The sample was
sonicated before and after addition of the polyimides. Sonicating before the addition of the
polyimide led to suspensions where single wall carbon nanotubes chunks were seen as
suspended agglomerates. Only 3 of the polyimides tested would lead to a homogenous
suspension without any visible agglomerates, these were obtained from the polymerization of
2,7-diamino-9,9‘-dioctylfluorene with either 3,3‘,4,4‘-oxydiphtalic anhydride, or 3,3‘,4,4‘-
biphenyltetracarboxylic dianhydride or pyromellitic dianhydride. The results are explained by
the ability of these specific polyimides to adopt the right geometry and wrap around the single
wall carbon nanotubes to prevent their re-aggregation.
Chen et al. used ultrasounds for the synthesis of polymer grafted single wall carbon
nanotubes [27]. By sonicating methyl methacrylate (MMA) and single wall carbon nanotubes,
the authors acknowledge a sonochemical effect as follows: MMA monomers are thermally
decomposed during the cavitation into radicals while defects are created on the nanotubes,
leading after collision of the radicals and the nanotubes to the polymerization of MMA on the
tube surface. These PolyMMA-grafted single wall carbon nanotubes are soluble upon mild
sonication in traditional organic solvents such as THF, toluene, chloroform, dichloromethane.
Li et al. [28] studied the use of a horn sonication for the grafting of multi wall carbon
nanotubes using polyvinyl pyrrolidinone, a water-soluble polymer. IR spectra show the
grafted polymer on the tubes. Variation of the sonication time allows control over the
molecular weight of the polymer grafted onto the tubes. Molar mass of the polymer decreases
rapidly at first and levels off a minimum mass when sonication was performed from 5 to 80
minutes. It is believed that an increase in sonication time degrades the polymer grafted onto
the tube. The grafting mechanism is reported to be a radical one, where radicals are formed
during sonication and are trapped by the tubes. They also monitored the disentanglement of
the tubes as well as their shortening during the process by TEM. The length of the grafted
tubes is shorter than the ungrafted ones, showing the ability of the ultrasounds to cut the
tubes. Also seen in the TEM pictures, very few open tubes are found on the pristine nanotubes
whereas many open end tubes can be found on the grafted ones, again supporting the cutting
(Figure 6). The polymer is believed not to be wrapped around the tubes through van der
Waals forces but to be covalently linked, as dispersions of the pre-formed polymer with the
tubes did not lead to stable dispersions. This technique provided stable dispersions thanks to
the grafting of a water-soluble polymer and also to the shortening of the tubes.
Giordani et al. [24] sonicated single wall carbon nanotubes in NMP with a tip sonicator
for 2 minutes and then in a bath for 4 hours, and again with a tip for one minute. Dilutions
and centrifugations followed to reach a final concentration decreasing from 0.125 to 0.04
mg/L. The suspensions are stable for at least 17 days. AFM was used to monitor the size of
the bundle overtime showing no re-aggregation during this period in agreement with the lack
of sedimentation observed by absorbance at 650 nm. Raman spectroscopic data shows that no
damage was done to the nanotubes during the sonication process as well as the presence of
individual nanotubes. This paper reinforces the previously published data that amides are
good solvents to achieve stable suspensions without any surfactant.
Single wall carbon nanotubes were efficiently dispersed in ethylene glycol under horn
sonication by Amrollahi et al. [29]. The settling time was studied as a function of sonication
duration, showing a correlation of longer sonication time to the longer settling time. The
authors suggest that debundling of the nanotubes from closely packed to loosely packed to
individual particles as the explanation for this observation which was corroborated by the
Application of Ultrasounds to Carbon Nanotubes 239
TEM images. Similarly the thermal conductivity of the solution increased with longer
sonication time. The authors were able to correlate an increase in thermal conductivity to the
loosening of the carbon nanotubes clusters as well.


Figure 6. TEM images of (a), (b) original MWCNTs and (c), (d), (e), (f) PVP grafted MWCNTs.
Reprinted from [28], Copyright (2009), with permission from Elsevier.
The use of gum Arabic by Bandyopadhyaya et al. proved to be effective for the
dispersion of an aqueous solution of entangled ropes of single wall carbon nanotubes under
mild oxidation and sonication conditions [30]. The Arabic gum, a water soluble
polysaccharide used as a surfactant, was adsorbed onto the carbon nanotubes, which disrupted
the inter-tube interactions. The carbon nanotubes wrapped by the gum Arabic were
debundled, as their polymer chains tend to repulse each other under given solvent conditions.
Unfortunately the authors do not explain the effect of the ultrasounds in the process.
During a study of the fluorescence of single wall carbon nanotubes dispersions in
aqueous solution with sodium dodecyl sulfate (SDS) as an ionic surfactant in a flow-through
ultrasonication unit, Strano et al. [31] suggested that the ultrasonic process creates gaps at the
ends of the carbon nanotube bundles, which become available for interaction with the
surfactant. Surfactant adsorption and diffusion propagates these gaps in an ―unzippering‖
process. The equilibrium between the individualized nanotubes and the bundles is reversible
and stable and depends on the SDS concentration. Raman spectroscopy data showed no
increase in the D-band, indicating few or no defects were introduced in the carbon nanotubes.
This eliminates not only the possibility of damage from the sonication process but also of a
covalent interaction between the surfactant and the nanotubes. Grossiord et al. [32] also
studied the ―unzippering‖ process of single wall carbon nanotubes in an aqueous solution of
SDS. Using HiPCO nanotubes, 130 minutes of sonication with the horn are needed to
completely exfoliate the carbon nanotubes, leaving only individual carbon nanotubes as seen
by cryo-TEM. These results were also corroborated in the UV-Vis spectroscopy study, which
showed the maximum absorbance of the solution corresponds to the maximum exfoliation of
the carbon nanotubes observed by cryo-TEM. Finally the authors warned of the effect of the
Anne C. Gaquere-Parker and Cass D. Parker 240
mode of synthesis of carbon nanotubes. Because van der Waals interactions are lessened by
impurities, carbon nanotubes with less impurity take longer to debundle. Monitoring the
debundling process by UV-Vis spectroscopy allows one to stop the sonication when the
maximum absorbance possible has been reached as unnecessary damage could occur to the
carbon nanotubes beyond that point.
Paredes et al. [33] reported the combined use of tip and bath sonication of single wall
carbon nanotubes in an aqueous solution of sodium dodecyl benzene sulfonate (SDBS).
SDBS allows the dispersion of the tubes while minimizing the damage to the walls and their
shortening. Tip sonication was performed first and after centrifugation, bath sonication was
performed for a few minutes to several hours. After the tip sonication, AFM images showed
individual nanotubes (50% of all objects) and bundles. The bath sonication that followed led
to individualized tubes (80%). The tube lengths had a mean value of 820 (± 556) nm and then
770 (±572) nm after tip and bath sonication respectively. The mild sonication bath treatment
allows for the debundling without tube cutting because the suspension is already made of
well-dispersed bundles and not entangled bundles of tubes. UV-Vis data were also collected
to monitor the sedimentation rate and showed that little re-aggregation took place over the
course of several months.
Geckeler et al. [34] studied the effect of lysozyme as a surfactant on the debundling of
single wall carbon nanotubes. The dispersion obtained after sonication with a probe for 30
minutes was reported stable for 9 months. The ultrasounds debundled the carbon nanotubes
by overcoming van der Waals attractions, which provided the opportunity for the lysozyme to
adhere to the carbon nanotubes, making them well dispersed in the solution. The dispersion is
explained by the repulsive forces between the positive charges of the protein at that pH (6.5),
whereas increasing the pH from 8.5 to 11 provoked the aggregation of the carbon nanotubes.
However a higher pH (>11) produced a dispersion again due to the ionization of the
carboxylic acids into carboxylates, leading to electrostatic repulsive forces again.
Bottini et al. [35] used mercaptopropyltrimethoxysilane as a surfactant for the dispersion
of aqueous solutions of single wall carbon nanotubes obtained after 30 minutes of sonication
at room temperature. They concluded that mild sonication alone was not sufficient to disperse
the tubes in solution and did not introduce damage to the carbon nanotubes but was necessary
for the surfactant to adhere to the carbon nanotubes surfaces.
Gladchenko et al. [36] studied the sonication of single wall carbon nanotubes with DNA
buffered at pH 7 for 30 minutes using a tip sonicator. The dispersions were stable for months.
In order to estimate the damage done by the ultrasounds, they performed gel electrophoresis.
The DNA was fragmented down to 2.3 x 10
3
base pairs as early as within the first 4 minutes
of sonication. By the end of the 30 minutes, the DNA fragments length was less than 500 base
pairs. The DNA was more sensitive to degradation that the nanotubes, yielding to single and
double strand DNA fragments. The authors report the wrapping of untwisted single strand of
DNA onto the carbon nanotubes during the sonication process, which explains the stability of
the suspension over months.
Ciofani et al. [37] dispersed multi wall carbon nanotubes using Pluronic F127
(polyoxyethylene-polyoxypropylene co-polymer, Figure 7) as a non-ionic surfactant in a bath
sonicator.

Application of Ultrasounds to Carbon Nanotubes 241
O
O
O
OH H
a a
b

Figure 7. Pluronic F127.
The process was monitored using UV-Vis spectroscopy in the 200-1200 nm region, since
van Hove singularities are observed for individual nanotubes but not for bundles. The authors
used the ―unzippering‖ model, although the surfactant did not participate in electrostatic
repulsions as previously described, but steric repulsions since it is not ionic. It took 2 hours of
sonication to achieve a plateau corresponding to the maximum absorbance and therefore
maximum degree of dispersion achievable under these conditions. Increasing the
concentration of Pluronic F127 does not increase the maximum degree of dispersion by much
(from 70 to 90 µg/mL ranging Pluronic concentration from 0.05% to 0.5%). In addition to the
shearing effect of the ultrasounds which breaks the bundles and allows the surfactant to
adhere to the walls, the higher temperatures also improved the dispersion due to increased
enthalpic energy. The suspensions were stable for many weeks after preparation. When the
tubes were heated at 70
o
C for up to 8 hours and then sonicated in the same conditions as
described above, a significant increase in the dispersion was observed. The heating and the
stirring pre-treatment did not really accelerate the reaction but were important for the
debundling of the agglomerates that could not be broken under the effects of ultrasounds
only. As a result, heating and sonicating doubled the concentration of the dispersion
compared to sonicating only.
Lopez-Pastor et al. [38] reported the sonication of single wall carbon nanotubes in an
ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) and subsequent analysis by
capillary electrophoresis. When the nanotubes were mixed in the ionic liquids, aggregates
were observed under optical microscope, showing the need for ultrasounds for dispersing.
Under the conditions of the experiments, (power density varying from 46 to 460 W/cm
2
, tip
sonicator, used with a cycle for 2 to 40 minutes), Raman spectroscopy revealed an increase
G/D ratio, with the D band corresponding to sp
3
-hybridized carbons present as impurities and
single wall carbon nanotubes defects. This shows the carbon nanotubes have been purified
during the process, but when harsher conditions (higher power density) are used, single wall
carbon nanotubes degradation was observed. The authors concluded that a power density of
63 W/cm
2
for 5 minutes was enough to obtain appropriate ionic liquid-single wall carbon
nanotubes dispersions. Further experiments involved adding an aqueous solution of SDS to
the dispersions, which dissolves the ionic liquid whereas sonication ensures the efficient
encapsulation of the nanotubes in micelles.
Kumar et al. [39] sonicated in a bath single wall carbon nanotubes in nitric acid for 2
hours at room temperature before refluxing the dispersion for an additional 2 hours. IR
spectroscopy analysis showed the presence of carboxylate groups due the oxidative action of
the nitric acid. Less degradation was observed in this study compared to their previous study
[40], although the oxidative conditions seem harsher in the second study. The most damage
observed in the first study could be explained by the amount of residual catalyst from the
carbon nanotubes synthesis (HiPco) being less, 2% wt versus 35% wt, using less nitric acid
Anne C. Gaquere-Parker and Cass D. Parker 242
and leaving more nitric acid to react with the nanotubes. The authors studied the effect of
sonication on the carbon nanotubes and found limited side-wall damage under these
conditions. The nitric acid treated nanotubes were dispersed easily in ethanol or butanol (or
their mixtures with toluene or xylene) due to the hydrogen bonding of the carboxylic acid
groups with the hydroxyl groups of the alcohols. The pristine nanotubes were soluble in
toluene and xylene but not in the alcohols or their mixtures. The presence of carboxylic acids
groups on acid-treated carbon nanotubes, as well as carbonyl and hydroxyl groups has been
confirmed by Yue-Feng et al. [41] when studying the influence of an electric field on the
dispersion of carbon nanotubes. An aqueous solution of original carbon nanotubes and acid
treated carbon nanotubes (with a mixture of sulfuric and nitric acids) was sonicated and
submitted to a 25V DC electric field. SEM images showed that the better dispersions were
obtained when both sonication and an electric current were applied on the acid treated
nanotubes. This effect was not observed on the original nanotubes. IR spectroscopy revealed
the presence of the oxygenated groups mentioned above which are necessary for an effective
dispersion regardless of the use of external devices such as ultrasounds and an electric field.
In his study on the analysis of nanocomposites of multi wall carbon nanotubes and
polycarbonate, Li et al. [42] boiled multi wall carbon nanotubes in a mixture of nitric and
sulfuric acid before dispersing them in water using an ultrasonic bath. The SEM images
showed that the nanotubes were fragmented and stacked loosely without any compact
agglomerates. The authors suggest that the behavior of the acid treated multi wall carbon
nanotubes is due to their many defects, making them easily broken.
Kim et al. [43] refluxed multi wall carbon nanotubes with sulfuric and nitric acid at 60
o
C
for 24 hours before sonicating for 8 hours in alcohols. The dispersions were monitored by IR
spectroscopy and using a turbiscan. IR data showed the presence of phenols groups on the
pristine nanotubes and the introduction of carboxylic acid groups after treatment. The length
of the tubes observed after treatment decreased by a factor of 4 when compared to the
untreated tubes. After 120 hours, no precipitate appeared in the vials, whereas the non acid-
treated carbon nanotubes precipitated rapidly in ethanol. The stability of the carbon nanotubes
came from the oxygen groups introduced on the tubes, forming interactions with methanol,
ethanol and iso-propanol.
Nadler et al. [44] compared the effect of bath ultrasounds for up to 16 hours on aqueous
solutions of pristine multi wall, single wall and hydroxylated multi wall carbon nanotubes and
SDS. TEM pictures were taken and the disc centrifuge method was used to monitor particle
sizes. Regardless of the nanotubes studied, the size analysis showed a bimodal distribution,
where the mass fraction above 0.1 µm decreased until a mono-modal distribution was reached
after 16 hours (Figure 8).
The density function maximum decreased from 1.8 µm for one minute of sonication to
300 nm at 4 hours. The maximum density function below 0.1 µm remained at an equivalent
spherical diameter of 30-40 nm. The fraction below 0.1 µm consisted of exfoliated nanotubes
whereas the fraction above represented the agglomerates. When the authors compared the
results of sonication with the results of ball milling, ultrasounds were the most efficient at
completely achieving the debundling of the nanotubes, although some individual breakage is
to be expected.

Application of Ultrasounds to Carbon Nanotubes 243
0.8
0.6
0.4
0.2
0.0
-0.2
1 0.1 0.01 d [µm]
q
3
(d)
[ - ]
1min
5min
15min
30min
1h
2h
4h
8h
16h

Figure 8: q
3
(d) particle size density function by mass (area normalised) of Baytubes in aqueous
dispersion sonicated for different processing times. Reprinted from [44], Copyright (2008), with
permission from Elsevier.
Margrave et al. [45] reported the efficient dispersion of fluorinated single wall carbon
nanotubes in alcohol obtained by bath sonicating for 10 minutes. The solutions were reported
to be metastable for up to a week, depending on the solvents tested: methanol, ethanol, 2,2,2-
trifluoroethanol, 2-propanol, 2-butanol, n-pentanol, n-hexanol, cyclohexanol and n-heptanol,
with 2-propanol and 2-butanol as the best solvents tested. However sonication could not
achieve the solubilization of the fluorinated nanotubes in water, diethylamine, acetic acid or
chloroform, although chloroform somewhat solvated the tubes. Analysis of the fluorinated
tubes after 2 hours of sonication showed a loss of fluorine but they remained solvated. On the
contrary, when C
4.4
F(OCH
3
)
0.25
were obtained after reaction of the fluorinated nanotubes with
sodium methoxide under ultrasounds, the tubes precipitated out of solution.


ULTRASOUND-INDUCED DAMAGE ON CARBON
NANOTUBES

The first article on possible damages done by ultrasounds on carbon nanotubes was
published by Lu et al. in 1996 [46]. Sonication with a horn in dichloromethane at 0
o
C for up
to 20 minutes introduced defects revealed by TEM imaging. They reported a thinning of the
outer graphitic layers similar to ones observed during oxidation processes. The extent of the
damages to the nanoparticles depended on the solvent with lesser effects observed in water or
ethanol. Raman spectroscopy was used to assess the damage by looking at the G band and the
D band, respectively 1585 cm
-1
and 1286 cm
-1
, with the ratio of the two bands corresponding
to the amount of defects observed by TEM. In addition, they monitored the broadening of the
peak g = 2000 in ESR as a tool to assess the increase in defects. The broadening could be
linked to the disturbance in the graphene layers and to the change in the conduction band
Anne C. Gaquere-Parker and Cass D. Parker 244
energy levels. The appearance of a peak at g = 1991, whose intensity increased with
sonication time, may come from dangling bonds. It is concluded that prolonged sonication
leads to the formation of amorphous carbon from the nanotubes and nanoparticles.
When Hilding et al. [47] monitored tube lengths with SEM during the sonication of multi
wall carbon nanotubes in toluene in an ultrasonic bath, a shortening by as much as 65%
during the first five minutes from 50 to 16 µm was observed. An additional 20 minutes were
needed to cut the tubes down to 6.5 µm, because shorter tubes are harder to break than longer
ones. Similar results were obtained when the same experiments were repeated with a
sonication horn.
Liu et al. [48] formed fullerene pipes by sonication of single wall carbon nanotubes in a
mixture of nitric and sulfuric acids at 40
o
C. The combination of the ultrasounds and oxidation
led to the cutting of the single wall carbon nanotubes ropes into thinned ropes and individual
nanotubes. Liu et al. in a later article [49] improved the oxidation conditions to cut and purify
single wall carbon nanotubes in three steps: nitric acid refluxing, followed by sonication in
the presence first of Triton at pH 10 and then of sulfuric acid and (NH
4
)
2
S
2
O
8
(to form a very
strong oxidizer H
2
SO
5
), then a high temperature treatment with ammonia, known to recover
the single wall carbon nanotubes structure. The nitric acid treatment did not lead to any
noticeable length shortening but some wall damages. The ultrasounds in combination with the
in-situ generated H
2
SO
5
led to significant damages through tube shortening, with a uniform
final length of 1 µm (the beginning length was several to several hundreds of µm). This
purification technique allows for the removal of undesirable carbon nanoparticles such as
multi wall carbon nanotubes which have more wall defects and therefore are more sensitive to
these harsh conditions and can be removed completely from the sample.
Monthioux et al. [50] reported the damaging effect of ultrasounds on acid pre-treated
single wall carbon nanotubes suspended in DMF using TEM. Single wall carbon nanotubes
were unexpectedly found to be sensitive to DMF. Defects in the tubes prior to sonication in
DMF create side-openings in the walls, enabling DMF to interact with the tubes and possibly
increase the amount of damage. However the authors were able to remove the wall defects by
thermal annealing at high temperature. Similarly, Furtado et al. [51] studied the effect of
ultrasounds on the single wall carbon nanotubes during their debundling in DMF. They
showed that the damage is due to the experimental conditions of acid treatment that the tubes
undergo prior to sonication in DMF. They found no evidence that ultrasounds created more
defects. The sonication was carried out for 4 hours with either DMF or NMP. When treating
the single wall carbon nanotubes with HCl or HNO
3
, the ones treated with HNO
3
always
showed more defects in Raman spectroscopy, with carboxylic groups found on the wall
surface. Defects were also detected even with diluted nitric acid. The authors showed that the
acid treated single wall carbon nanotubes could form stable dispersions in DMF or NMP with
sonication for weeks, whereas skipping the acid treatment could not produce a stable
dispersion. This was explained by a weak charge transfer between the DMF and the
nanotubes and a reduction of van der Waals interactions within the bundles due to the acid
treatment. Smaller diameter bundles were obtained in the HNO
3
/DMF combination compared
to HCl/DMF or HCl/NMP. Tubes are functionalized by the nitric acid process with functional
groups such as COOH that are better able to interact with DMF and in turn lead to better
dispersions and smaller bundles. Raman spectroscopy also shows more defects in that case,
due to the introduction of the oxidized groups. When the tubes were annealed, they did not
disperse as well in the amide solvents. Finally the authors reported that the extent of the
Application of Ultrasounds to Carbon Nanotubes 245
length cutting depends on the oxidative process used in the acid treatment, which creates wall
defects prone to subsequent ultrasound cutting.
Koshio et al. [52], [53] observed the formation of ragged single wall carbon nanotubes
produced by sonication in a chlorobenzene solution of polymethylmethacrylate (Figure 9) in
an ultrasonic bath and then with a sonication tip.

C
C OCH
3
O
CH
3
CH
2
n
n=5000

Figure 9: Polymethylmethacrylate.
After heating in a furnace to remove all carbon impurities like chlorobenzene, amorphous
carbon, fullerene and carbon nanocapsules, SEM images were taken (Figure 10).


Figure 10. High magnification TEM of r-SWCNT. Reprinted from [52], Copyright (2001), with
permission from Elsevier.
The single wall carbon nanotubes were short, appeared worm-eaten and were named
ragged single wall carbon nanotubes. They displayed an unusual thermal stability, with
degradation starting above 800
o
C. During the ultrasound treatment, the ragged tubes had
reactive dangling bonds ready to react with the fragments obtained from the degradation of
PMMA. This process started at defectives sites on the tubes and was propagated along the
walls during the process. Roughly 1 to 3 defect sites per 1 nm length were estimated. Later
on, Koshio et al. [54] used ragged single wall carbon nanotubes to synthesize fullerenes upon
pyrolysis. When the ragged single wall carbon nanotubes were heated in a sealed tube at
1200
o
C none remained, only leaving a deposit. Solubilization of the deposit in toluene gave a
Anne C. Gaquere-Parker and Cass D. Parker 246
purple solution, which after mass spectrometry analysis revealed the presence of fullerene C
60

and C
70
and traces of some higher fullerenes such as C
76
, C
78
and C
84
. The amount of C
70
was
about 30% of C
60
. When a similar experiment was performed without ultrasound treatment of
the nanotubes, fullerenes were not detected after heat treatment. The authors concluded that
defects in the ragged single wall carbon nanotubes make them susceptible to decomposition
and the material easily recomposes into C
2
fragments during pyrolysis, eventually leading to
the formation of fullerenes.
The study of single wall carbon nanotubes in chlorobenzene by Koshio [52], [54] led
Zhang et al. [55] to perform TEM and thermogravimetric analysis (TGA) on samples coming
from the sonication of the acid-treated single wall carbon nanotubes in chlorobenzene. Three
kinds of single wall carbon nanotubes were detected: an amorphous-like material on both the
inside and outside of the walls, one with similar residue inside the walls and the third one did
not show any amorphous-like material. IR spectroscopy revealed the amorphous like material
consisted of hydrocarbons from the degradation of chlorobenzene. The exact nature of the
interaction between the single wall carbon nanotubes and the amorphous-like material was
not discussed.
Heller et al. [56] reported an effective method for the cutting of single wall carbon
nanotubes. Sonication of the tubes in a sodium cholate hydrate with a horn sonicator was
followed by centrifugation, additional sonication and gel electrophoresis. The samples
showed a systematic increase in the migration of the particles with the sonication duration.
Since gel electrophoreses migration is based on the particles length the shortest nanotubes
migrate faster than longer ones and the results showed that sonication cut the nanotubes in
proportion of the sonication time. Similar results were obtained when other ionic surfactants
were used (SDS and Triton X-100), showing that the cutting was independent of the
surfactant used. Raman spectroscopy was also used to determine the diameter of the
nanotubes. The results showed not only that the length was cut but also the diameter of the
bundles was diminished in the process. The cutting process is diameter selective and the
mechanism of the diameter-dependent cutting process is still under investigation. This work
could eventually lead to a process were nanotubes of specific length and diameter could be
prepared and isolated in a controlled way. Arnold et al. [57] suspended single wall carbon
nanotubes in sodium cholate as well with a sonicator tip and monitored the samples with
AFM, IR and UV-Vis spectroscopy. They postulated that the cavitation process cuts the tubes
into smaller parts and that there is a critical length below which tubes cannot be cut any
longer. They reached that point in their experiment after 40 minutes of sonication for a
median nanotubes length of 200 nm.
Wang et al. [58] used Pluronic P123 (Figure 11), an amphiphilic triblock copolymer:
poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) as a dispersant for the
preparation of stable single wall carbon nanotubes dispersions.
CH
2
CH
2
CH
2
CH
2
CH
2
O O O CH
CH
3
n
n p

Figure 11. Pluronic P123.
Application of Ultrasounds to Carbon Nanotubes 247
The authors treated the tubes under very oxidative conditions with sonication and
monitored the results using electron microscopy (Figure 12). They used a ―piranha‖ solution
which consists of concentrated sulfuric acid and 30% hydrogen peroxide. They attributed the
damages and cutting of the tubes to these harsh oxidative conditions, which are known to
attack defective sites of the nanotubes that are created by the ultrasounds.


Figure 12. TEM images of (a) the as-produced SWNTs dispersed in EtOH; (b) the piranha-treated
SWNTs dispersed in DMF; (c) the NH
3
-treated SWNTs dispersed in water. HRTEM image of (d) the
NH
3
-treated SWNTs dispersed in water. Reprinted from [58], Copyright (2006), with permission from
Elsevier.
Multi wall carbon nanotubes were shortened efficiently by sonication in DMF in a
sonication bath for various time lengths by Park et al. [59]. This process was compared to the
oxidative action of a mixture of sulfuric and nitric acids on nanotubes. The mean length of the
sonicated nanotubes was shorter than the acid treated ones, but the length distribution was
narrower in the previous case. Although more cutting was reported with the ultrasounds, less
wall damage was simultaneously observed.
The use of phosphomolybdic acid is reported by Warakulwit et al. [60] to cut multi wall
carbon nanotubes. TEM was used to monitor the length shortening which was dependent on
the sonication duration. The mild oxidative conditions allowed the discrimination between the
various carbon particles, oxidizing the ones with more defects at a faster rate than the ones
with less. This could not only limit damage to the nanotubes but also induce cutting in a
controlled manner. Also in search for mild oxidation conditions for multi wall carbon
nanotubes, Liu et al. [61] oxidized multi wall carbon nanotubes with a combination of
ultrasounds and ammonium persulfate. TEM indicated the shortening of the tubes into a
bimodal distribution: at 370 nm and 930 nm, respectively with thin and thick diameters,
making the tubes well dispersed in water. IR spectroscopy results indicated the introduction
of carboxylic acid groups on the surface as noted in previous reports, increasing the level of
dispersion. Luong et al. [62] tested the effect of another mild oxidant, ceric sulfate on single
and multi wall carbon nanotubes in the presence of ultrasounds. Although the treatment lasted
Anne C. Gaquere-Parker and Cass D. Parker 248
for only 2 to 5 hours with a 0.1 N of cerium sulfate, considerable structural damage was
observed on the single wall carbon nanotubes after only 15 minutes of sonication. Length
shortening of the nanotubes and the appearance of amorphous carbon was observed on the
TEM images. After 5 hours of treatment no tubes could be found. By comparison, nanotubes
sonicated for 5 hours in DMF showed no evidence of damage. Similar results were obtained
when multi wall carbon nanotubes were sonicated with ceric sulfate. The thinning of the tubes
exposed thin inner tubes to sonication and induced further damage. Tubes were degraded into
graphite or even amorphous carbon. Comparative sonication in DMF did not lead to any
damage on the multi wall carbon nanotubes, but sonication for 24 hours in ethanol resulted in
carbon fibers. XPS was used to assess the chemical oxidation. Carbonyl stretching was
observed and some mild defects were found on the tubes sonicated in DMF. Raman
spectroscopy also confirmed that no significant damage was introduced under these
conditions. However a complete disappearance of the radial breathing modes at 150-300 cm
-1
,
a decrease of the tangential G-band at 1580 cm
-1
and an increase in the disorder induced D-
band at 1325 cm
-1
, corroborated the results of the TEM imaging. In conclusion single wall
carbon nanotubes were converted into amorphous non conducting carbon nanoparticles,
whereas multi wall carbon nanotubes were converted into graphitic or amorphous carbon
nanoparticles that retained some conductivity.


SONOCHEMICAL FUNCTIONALIZATION OF CARBON
NANOTUBES

Several articles reported the use of ultrasounds prior to the chemical functionalization.
Chen et al. [63] used ultrasounds to create an emulsion between water and chloroform
containing single wall carbon nanotubes and triethylbenzylammonium chloride as a phase
transfer catalyst, prior to adding the sodium hydroxide for the cyclopropanation reaction.
Although the reaction was successful, it could not be attributed to the ultrasounds which were
stopped when the base was added. Similarly, Saini et al. [64] reacted fluorinated single wall
carbon nanotubes with alkylithium with sonication as part of the procedure. However, even
though the substitution reaction was successful, there was no discussion of the role of the
ultrasounds in the study. Kovtyukhova et al. [65] performed the oxidation of single wall
carbon nanotubes with ultrasounds and an acidic treatment as well as the use of potassium
permanganate. TEM images showed the presence of nanotubes decorated with fragments of
oxidized and broken tubes. Raman and IR spectroscopy results were consistent with the
presence of carboxylic acid, carbonyl and hydroxyl functional groups, however the role of the
oxidative action of the ultrasounds was not assessed. Chen et al. [66] reacted a carboxylated
single wall carbon nanotubes obtained through acid treatment and ultrasounds with
octadecylamine, forming the corresponding octadecylammonium single wall carbon
nanotubes-carboxylate zwitterion. Once again, no effect or study on the use of ultrasounds
was indicated.
A number of articles reported the use of ultrasounds and their effect on the chemical
functionalization of the carbon nanotubes. Kaempgen et al. [67] studied the conductivity of
single wall carbon nanotubes as a function of the treatment with nitric acid and ultrasounds
Application of Ultrasounds to Carbon Nanotubes 249
using a tip sonicator. Carbonyl, hydroxyl, carboxylic acid groups were observed by IR
spectroscopy. A sonication time of 3 minutes provided maximum conductivity which then
dropped below the initial value. This was explained by a trade-off between doping of semi-
conducting single wall carbon nanotubes and scattering of the charge carriers when the
functional groups were introduced: doping took place during the first 3 minutes followed by a
breakdown of the crystal structure. Longer reaction times, up to 60 minutes, led only to
increased degradation and formation of amorphous carbon as monitored by AFM imaging.
Zhang et al. [68] functionalized single wall carbon nanotubes using ultrasounds. They
reported the need to use ultrasounds in order to obtain a good dispersion, leaving individual
nanotubes ready to react. Ultrasounds were also needed to initiate the reaction between the
nanotubes and SU-8. SU-8 is a polymeric epoxy resin dissolved in an organic solvent along
with a photoacid generator. The epoxy resin shown in Figure 13 consists of repeating novolac
glycidyl ether units. The oxidation process of the single wall carbon nanotubes with
potassium permanganate was not conducted using ultrasounds, however the initial mixture
was sonicated for mixing purposes only. The subsequent reaction between the hydroxylated
nanotubes and SU-8 was sonicated. The authors reported the need of acidic conditions and
sonication for the reaction to take place, without providing more explanation.

O
CH
2
HC
O
H
2
C
CH
2
C H
3
C CH
3
O
CH
2
HC
H
2
C
O
O
CH
2
HC
O
H
2
C
CH
2
C H
3
C CH
3
O
CH
2
HC
H
2
C
O
O
CH
2
HC
O
H
2
C
CH
2
C H
3
C CH
3
O
CH
2
HC
H
2
C
O
O
CH
2
HC
O
H
2
C
C H
3
C CH
3
O
CH
2
HC
H
2
C
O

Figure 13. Epoxy resin SU-8, based novolac glycidyl ether groups.
Ren et al. [69] deposited metallic nanoparticles on multi wall carbon nanotubes by
sonicating and drying a suspension of carbon nanotubes and Pt, Pd or CoPt
3
. TEM pictures
showed clearly the metallic nanoparticles on the outer surface of the nanotubes. The
ultrasounds ensured a good dispersion of the carbon nanotubes and the nanoparticles, which
stayed in a well dispersed state during the evaporation process. The authors also noted that
any surfactant remaining from the synthesis of the carbon nanotubes should be removed
Anne C. Gaquere-Parker and Cass D. Parker 250
because they prevented the metallic nanoparticles from being uniformly deposited on the
nanotubes.
The deposition of metallic particles on multi wall carbon nanotubes has also been
realized by Qiu et al. [70]. Acid treated tubes were sonicated in the presence of tin (II)
chloride (SnCl
2
)

using a tip sonicator. Nanosize particles of tin were obtained and most of the
carbon nanotubes were decorated with these crystalline tin particles, without any SnCl
2
or
SnO present. Drying and sonicating the decorated carbon nanotubes did not change their
morphology as seen in the TEM micrographs, showing the strength of the bonds between the
tin particles and the carbon nanotubes. However there was no evidence of the presence of tin
inside the carbon nanotubes, either because the size of the tin and carbon nanotubes were not
compatible for such an interaction or the open end of the tubes was blocked by a tin particle.
The authors applied this technique using iron pentacarbonyl Fe(CO)
5
instead of SnCl
2
and
found multi wall carbon nanotubes decorated with iron nanoparticles, although amorphous in
nature. This evidence suggests a clear mechanistic difference between the formation of
crystalline nanoparticles of tin and iron.
Xing [71] used a sonochemical process for the acid treatment of carbon nanotubes before
platinum deposition. Multi wall carbon nanotubes were sonicated in a bath with sulfuric and
nitric acids at 60
o
C for 2 hours. The deposition of uniformly dispersed nanoparticles on
sonochemically treated nanotubes was due to the uniformity of the functionalization during
the sonication, since it prevents the tubes from forming aggregates. When the same
experiment was conducted without ultrasounds, the platinum nanoparticles were bigger in
size and not as well dispersed. Moreover ultrasounds allowed for a higher loading of Pt
nanoparticles on the tubes as it produced more functional groups able to interact with the Pt.
The authors did not describe the nature of these groups being formed. Xing et al. [72]
reinvestigated the process of sonochemical oxidation of multi wall carbon nanotubes and
identified the functional groups present on the oxidized nanotubes as a function of sonication
duration. Progressive appearance of carbonyl and C-O groups and then COO groups are
indicated by XPS results, with maximum oxidation reached in 4 hours. Pt nanoparticle
binding on functionalized multi wall carbon nanotubes was performed by Hull et al. [73] by
pre-treating the tubes with nitric and sulfuric acids and sonicating for 2 hours. Increasing the
sonication time to 4 hours did not result in better results as significant damages had occurred.
However one hour of sonication was found not to be enough because the carbon nanotubes
surfaces did not appear to be sufficiently functionalized for a stable platinum-tube interaction.
IR spectroscopy data showed the presence of the carbonyl band and a C-O group.
Sonochemical oxidation produced hydroxyl, carbonyl, C-O-C and –COO
-
groups with little or
no COOH present. Platinum will bind to these groups according to the two possible structures
shown below in Figure 14.
Worsley et al. [74] published a comparative study of stirring and sonicating during the
functionalization of carbon nanotubes using a Bingel reaction. The procedure consisted of:
sonicating/or stirring single wall carbon nanotubes in o-dichlorobenzene, 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) and diethylbromomalonate for 19 hours. Scanning
tunneling microscopy (STM) images showed that the stirred reaction did not produce
debundled carbon nanotubes, leading to varying degrees of functionalization on the tubes
throughout the bundles. Sonicating for 19 hours produced a very high degree of
functionalization. This was explained by the fact that sonication increased the energy of the
reactants, hence increasing the probability of reaction between the tube and the malonate. In
Application of Ultrasounds to Carbon Nanotubes 251
addition, sonication can debundle the tubes leading to a more uniform functionalization. The
authors did not exclude the possible presence of a sonopolymer derived from o-
dichlorobenzene as previously reported [22], yet they did not detect any trace of the
sonopolymer. This was explained by the washing of the samples with dimethylsulfoxide,
probably washing away the sonopolymer as well.

C C
O
O
Pt
C
O O
Pt
a b

Figure 14. Pt-coordination to the functional groups.
Yang et al. [75] dispersed multi wall carbon nanotubes in deionized water using a
sonication bath. They reported an increase in dispersion as a function of sonication time.
Unsonicated nanotubes could not be dispersed in water, 2 minutes of sonication resulted in
some dispersion but 45 minutes formed a dispersion that was stable for at least 3 weeks. No
oxidizing agent was used during the sonication process. The nanotubes were deposited onto a
gold surface and SEM pictures taken. The nanotubes showed significant changes in
morphology. The interaction of the carbon nanotubes and gold are related to the wettability of
the nanotubes and increases with sonication time as early as 2 minutes. Such interaction is
stronger than inter-tube interaction as manifested by cracks in the carbon nanotubes layer
rather than a loss of carbon nanotubes adhesion to the gold surface. Unsonicated carbon
nanotubes did not interact with gold and could be easily washed from the surface of gold with
water, whereas sonicated ones cannot. No or little damage and no shortening were observed
by SEM, XPS or Raman spectroscopy analysis of the tubes when sonicated in water after 2
hours. IR spectroscopy did reveal some changes in the nanotubes upon sonication. The
presence of aliphatic C-H bonds was observed before sonication and disappeared during
sonication. Peaks corresponding to hydroxyl groups, carbonyl and carboxyl groups appeared
as sonication continues. This was most likely due to the oxidation of the already existing C-H
bonds on the outer walls. This oxidation could explain the increased wettability of the tubes
and their increased dispersion in water. This method seemed to be a promising technique as
little or no damage was reported to the tubes.
Goyanes et al. [76] studied the influence of the type of acid used and sonication time
when performing the carboxylation of multi wall carbon nanotubes. The acids used were
either nitric acid or a mixture of nitric and sulfuric acid. The sonication time was varied from
2, 4 and 6 hours at 30
o
C. The carbon nanotubes were used as received and it was determined
that carboxylic acid groups were present on the tubes prior to acid treatment. Treatment in
acidic mixture for 2 hours was reported to modify the open ends of the nanotubes without
altering the sidewalls. Therefore the new C-O groups were located at the open end of the
tubes (Figure 15). A longer sonication time shortened and eventually destroyed the walls of
Anne C. Gaquere-Parker and Cass D. Parker 252
the nanotubes as seen on the AFM images (Figure 16). Once bond symmetry is disrupted
within the nanotubes, adjacent carbons increase in reactivity resulting in the entire nanotubes
being oxidized.
Liu et al. [77] reported the functionalization and shortening of single wall carbon
nanotubes using peroxy-organic acids such as m-chloroperbenzoic acid (MCPBA), 2-bromo-
2-methylperpropionic acid (BMPPA), after 12 hours of sonication. In a previous study [78],
they reported the treatment of single wall carbon nanotubes with per-trifluoroacetic acid and
the covalent bonding of trifluoroacetic groups on the single wall carbon nanotubes. The tubes
were also shortened, small bundles and individual tubes were obtained, which provided stable
dispersions in water, DMF and ethanol. Treatment with MCPBA and BMPPA led to similar
results. Oxidation products were obtained with the presence of epoxide, carboxylic acid and
ester groups as confirmed by Raman and IR spectroscopy. After the epoxidation of the
nanotubes, the opening of the epoxide led to reaction with the organic acids producing
hydroxyl and ester groups. TGA was used to determine the degree of functionalization with
the following order: MCPBA > PTFAA > BMPPA. The milder strength of BMPPA was also
noted when AFM images were taken, showing that the first two peroxy organic acids
shortened the tubes length, whereas BMPPA introduced only very little or no damage.
Chang et al. [79] sonicated with a probe double wall carbon nanotubes in o-
chlorobenzene using an azobis-type radical initiator. The authors used ultrasounds to
debundle the tubes making them well separated and available for the subsequent radical
attack from the thermal decomposition of the radical initiators. The authors did not mention
the potential role of the ultrasounds on the radical pathway. The authors compared the
reaction with and without the use of ultrasounds and observed a great improvement in the
degree of functionalization when ultrasounds were used. The presence of carboxylic acids
groups was shown by XPS as the major functional group present, although some peaks were
assigned to carbonyl, nitrile and amide groups. It is important to consider the nature of the
radical initiators to understand the presence of some of the groups reported, i.e. 4,4‘-azobis(4-
cyanopentanoic acid); 2,2‘-azobis[2-methyl-N-(2-hydroxyethyl)propianamide], 2,2‘-azobis(2-
methylpropionamidine) hydrochloride, 2,2‘-azobis[2-(2-imidazolin-2-yl)propane] and 1,1‘-
azobis(cyclohexane-1-carbonitrile). Adhesion of PtRu nanoparticles also demonstrated the
functionalization of the surface by carboxylic acid groups. The authors expanded the work to
single wall carbon nanotubes and multi wall carbon nanotubes without providing details but
demonstrating the feasibility of this work to other types of nanotubes.


Figure 15. Schematic representation of the attack to the MWCNTs during the oxidation process.
Reprinted from [76], Copyright (2006), with permission from Elsevier.
Application of Ultrasounds to Carbon Nanotubes 253



Figure 16. Images of MWCNTs: (a) as-received; (b) treated with HNO
3
; treated with HNO
3
/H
2
SO
4
for:
(c) 2 h; (d) 4 h and (e) 6 h (left/right: height/phase). Reprinted from [76], Copyright (2006), with
permission from Elsevier.
Anne C. Gaquere-Parker and Cass D. Parker 254

Figure 17. Settling behavior of SWCNTs suspension with US only treatment and O
3
/US treatment.
Experimental conditions: [SWCNTs] = 200 ppm, ozone mass rate = 0.14 g/min; pH=3.0; temperature =
23
o
C. Reprinted from [80], Copyright (2008), with permission from Elsevier.
Li et al. [80] carried out the oxidation reaction of single wall carbon nanotubes using
ozone in a sonication bath at room temperature. They compared the action of ultrasounds
only, ozone only and the two combined together and analyzed the results by XPS, light
scattering, zeta potential and turbidity measurements. When ultrasounds alone were used, no
stable dispersion was formed after sonication was stopped. Using ozone and ultrasounds
provided stable suspensions even after sonication had ceased (Figure 17).
The length of the tubes initially at 1200 nm was measured of ultrasonic treatment with or
without ozone, with a length after 24 hours of respectively 150 nm and 300 nm. The final
length for the combined technique was reached after only 7 hours of treatment. The turbidity
showed that sedimentation was slower to occur when the combination of techniques had been
used. However the zeta potential provided similar results for both cases, showing no
significant difference in terms of zeta potential between the ozone treatments and the ozone
and ultrasounds treatment. The two treatments seemed to share the same reaction pathways
(Figure 18) but with a greater reaction rate for the combined one. XPS results confirmed the
presence of carbonyl, hydroxyl and carboxylic acid groups. It is concluded that the
ultrasounds created defects on the walls which led to further oxidation and also the high
temperatures resulting from cavitation enhanced the overall reaction rate.
C C
O
3
OH
.
O
.
/
C C
OH HO
O
OH
O
O
3
OH
.
O
.
/

Figure 18. Reaction pathway.
You et al. [81] used ultrasounds in a sonication bath as a way to assemble multi wall
carbon nanotubes based gels. The ultrasounds dispersed the nanotubes bundles in DMF
before facilitating the assembly of poly(amidoamine) functionalized nanotubes via hydrogen
bonds (Figure 19). Hyper branched poly(amidoamine) (HPAA) are grafted onto multi wall
carbon nanotubes during this process. HPAA has a great ability to assemble via hydrogen
bonds and to form gel under an external stimulus. Ultrasounds were found to accelerate the
Application of Ultrasounds to Carbon Nanotubes 255
gelling process of multi wall carbon nanotubes and HPPA dispersed in a solution of
poly(amidoamine) in DMF. The ultrasound induced the assembly of hyper branched
poly(amidoamine) functionalized multi wall carbon nanotubes with linear poly(amidoamine)
into a gel, because the ultrasounds disrupted the carbon nanotubes interactions, dispersing the
bundles and stretching the polymer functional groups on the surface of the tubes, thus
increasing the potential for interaction between the polymers and the nanotubes. Vigorous
stirring and microwave could not initiate the gel formation but could revert it back to its
original state, which could in turn be sonicated to lead to a gel again. The gels were sensitive
to acids hydrolysis under ultrasounds, probably because of acid catalyzed breaking of the
hydrogen bonds after the protonation of the amine groups.
MWCNT
N
O
N
N
NH
O
NH
O
N
H
N
H
O
O
MWCNT
N
H
O
N
H
N
H
O
O
N
N
MWCNT
1. HNO
3
2. AEPZ, EDC
AEPZ: 1-(2-aminoethyl) piperazine
MBA: N,N'-methylene bisacrylamide
EDC: 1-Ethyl-3-[3-dimethylaminopropyl]
carbodiimide hydrochloride
MWCNT
N
O
N
NH
2
MWCNT
N
H
O
N
NH
+
+

Figure 19. Amidoamine functionalized nanotubes.

Anne C. Gaquere-Parker and Cass D. Parker 256
COMBINED USE OF CARBON NANOTUBES AND
ULTRASOUNDS FOR ENVIRONMENTAL APPLICATIONS

Very few applications where carbon nanotubes and ultrasounds are combined have been
reported and interestingly all investigate the use of multi wall carbon nanotubes and
ultrasounds for environmental remediation purposes.
Zhao et al. [82] used carbon nanotubes as a trap for pyridine in water. Multi wall carbon
nanotubes were treated with nitric acid, heat, ultrasounds and polyvinyl alcohol and used as
adsorbents for the removal of pyridine. The adsorption capacity increased in going from the
pristine multi wall carbon nanotubes to the multi wall carbon nanotubes sonicated in nitric
acid, whereas the multi wall carbon nanotubes heated in nitric acid showed an intermediate
lower value, respectively 3.8 mg g
-1
, 4.36 mg g
-1
, and 4.28 mg g
-1
, tested with a pyridine
concentration of 80 mg l
-1
. As expected the surface area and the amount of suspended
nanotubes increased during the acid treatment. Data also showed that further treatment of the
acid treated multi wall carbon nanotubes with polyvinyl alcohol decreased the adsorption
capability of the tubes. The authors attributed the increase in pyridine adsorption to an
increase in surface area and pore volume, due to the fracture where the defects were located
on the carbon nanotubes.
The field of sonophotocatalysis has been widely investigated in the past few years [83,
84, 85], but only one article reports the use of carbon nanotubes as part of the process.
Traditionally the photodegradation of a pollutant dissolved in an aqueous solution is enhanced
through the use of UV light and ultrasounds using titanium dioxide TiO
2
as a catalyst, with a
great synergistic effect. Wang et al. [86] reported for the first time the use of a multi wall
carbon nanotube titanium dioxide composite (CNT-TiO
2
) as the catalyst in the
sonophotodegradation of methyl orange. They compared its catalytic activity to P25, a
titanium dioxide catalyst traditionally used for such experiments. P25 is a combination of two
crystalline phases of TiO
2
, anatase and rutile in a 3:1 proportion. X-Ray diffraction on CNT-
TiO
2
identified the crystalline nature of the titanium dioxide to be anatase. A TEM picture of
the catalyst CNT-TiO
2
is shown below in Figure 20.


Figure 20. TEM image of CNT-TiO
2
composite material. Reprinted from [86], Copyright (2008), with
permission from Elsevier.
Application of Ultrasounds to Carbon Nanotubes 257
The degradation of methyl orange for 60 minutes showed a 66% removal rate in the case
of sonophotocatalysis, 44% for photocatalysis and 9% for sonocatalysis. Also the kinetic
results obtained with CNT-TiO
2
as a catalyst were twice as high as P25 under
sonophotocatalysis (Figure 21). Unfortunately the authors did not provide any explanation for
these results and it would have been interesting to compare the specific surface area of the
two catalysts.


Figure 21. Reaction kinetic plots of MO degradation. Reprinted from [86], Copyright (2008), with
permission from Elsevier.
Yu et al. [87] studied the adsorption of benzoic acid from an aqueous solution using multi
wall carbon nanotubes, treated with nitric acid and ultrasounds. This treatment raised the
oxygen contents of the multi wall carbon nanotubes surface and increased the specific surface
area. A high adsorption of benzoic acid was observed, which was explained via electrostatic
interaction between the nanotubes and the benzoic acid. The authors claimed the surface of
the nanotubes had no functional groups, but only a considerable amount of chemisorbed
oxygen. However no IR or Raman spectroscopy was provided in this article in support of this
statement which is in direct contrast of other researchers conclusions as discussed above in
this chapter.


CONCLUSION

Ultrasounds have been widely used with carbon nanotubes. Synthesis, purification,
chemical functionalization and applications of sonochemistry applied to carbon nanotubes
have been reviewed in this chapter with a large part reserved to the formation of stable carbon
nanotubes dispersions. Ultrasounds have been shown to promote the chemistry of carbon
nanotubes by debundling them, allowing them to react with the components in solution either
in a covalent way or through van der Waals interactions. It is widely accepted that ultrasounds
Anne C. Gaquere-Parker and Cass D. Parker 258
are necessary to individualize the nanotubes. Acid treatment of carbon nanotubes is the most
common reaction performed. It introduces oxygenated groups on the nanotubes which can
interact with the solvent or surfactants forming stable dispersions or with metallic
nanoparticles yielding decorated nanotubes. Structural defects on the carbon nanotubes walls
are reported as a result of the chemical modification under harsh conditions and can hinder
the use of ultrasounds with carbon nanotubes. However mild experimental conditions
combined with careful monitoring of the progress of the damages can be combined to allow a
greater development of the sonochemistry of carbon nanotubes.


REFERENCES


[1] Skrabalak, S.E. ; Suslick, K.S. J. Am. Chem. Soc, 2006, 128, 12642-12643. Porous
carbon powders prepared by ultrasonic spray pyrolysis.
[2] Khatri, I.; Soga, T.; Jimbo, T.; Adhikari, S.; Aryal, H.; Umeno, M. Diamond Relat.
Mater. 2009, 18, 319-323. Synthesis of single walled carbon nanotubes by ultrasonic
spray pyrolysis method.
[3] Skrabalak, S. E. Phys. Chem. Chem. Phys. 2009, 11, 4930-4942. Ultrasound synthesis
of carbon materials.
[4] Zhang, K.; Park, B.; Fang, F.; Choi, H. Molecules 2009, 14, 2095-2110 Sonochemical
preparation of polymer nanocomposites.
[5] Katoh, R,; Tasaka, Y,; Sekreta, E.; Yumura, M.; Ikazaki, F.; Kakudate, Y.; Fujiwara, S.
Ultrason. Sonochem. 1999, 6, 185-187. Sonochemical production of a carbon
nanotube.
[6] Jeong, S.; Ko, J.; Park, J.; Park, W. J. Am. Chem. Soc. 2004, 126, 15982-15983. A
Sonochemical route to single-walled carbon nanotubes under ambient conditions.
[7] Srinivasan, C. Current Science 2005, 88 12-13. A sound method for synthesis of single-
walled carbon nanotubes under ambient conditions.
[8] Manafi, S.; Nadali, H.; Irani, H.R. Mater. Lett. 2008, 62, 4175-4176. Low temperature
synthesis of multi-walled carbon nanotubes via a sonochemical /hydrothermal method.
[9] Martel, R.; Shea, H. R.; Avouris, P. J. Phys. Chem. B 1999, 103, 7551-7556. Ring
formation in single-wall carbon nanotubes.
[10] Komatsu, N.; Shimawaki, T.; Aonuma, S.; Kimura; T. Carbon 2006, 44, 2093-2095.
Ultrasonic isolation of toroidal aggregates of single-walled carbon nanotubes.
[11] Li, C.P.; Teo, B.K.; Sun, X.H.; Wong, N.B.; Lee, S.T.; Teo, B.K. Chem. Mater. 2005,
17, 5780. Hydrocarbon and carbon nanostructures produces by sonochemical reactions
of organic solvents on Hydrogen-passivated silicone nanowires under ambient
conditions.
[12] Sun, X.H.; Li, C.P.; Wong, N.B.; Lee, C.S.; Lee, S.T.; Teo, B.K. J. Am. Chem. Soc.
2002, 124, 14856. Templating effect of hydrogen-passivated silicon nanowires in the
production of hydrocarbon nanotubes and nanoonions via sonochemical reactions with
common organic solvents under ambient conditions.
Application of Ultrasounds to Carbon Nanotubes 259
[13] Wang, S.; Tang, L., Bao, Q.; Lin, M.; Deng, S.; Goh, B.; Loh, K. J. Am. Chem. Soc.
2009, 131, 16832-16837. Room-temperature synthesis of soluble carbon nanotubes by
the sonication of graphene oxide nanosheets.
[14] Li, Q.; Zhang, X.; Wu, G.; Xu, S.; Wu, C. Ultrason. Sonochem. 2007, 14, 225–228.
Sonochemical preparation of carbon nanosheet from carbon black.
[15] Dujardin, E.; Ebbesen, T. W.; Krishman, A.; Treacy, M. M. J. Adv. Mater. 1998, 10,
611-613. Purification of single-shell carbon nanotubes.
[16] Shelimov, K. B.; Esenaliev, R. O.; Rinzler, A. G.; Huffman, C. B.; Smalley, R. E.
Chem. Phys. Lett. 1998, 282, 429-434. Purification of single-wall carbon nanotubes by
ultrasonically assisted filtration.
[17] Thien-Nga, L.; Hernadi, K.; Ljubovic´, E.; Garaj, S.; Forro´, L.; Nano Lett. 2002, 2,
1349-1352. Mechanical purification of single-walled carbon nanotube bundles from
catalytic particles.
[18] Li, J.; Zhang, Y. Physics E 2005, 28, 309-312. A simple purification for single-walled
carbon nanotubes.
[19] Liu, J.; Casavant, M. J.; Cox, M.; Walters, D.A.; Boul, P.; Lu, W.; Rimberg, A.J.;
Smith, K.A.; Colbert, D. T.; Smalley, R. E. Chem. Phys. Lett. 1999, 303, 125-129.
Controlled deposition of individual single-walled carbon nanotubes on chemically
functionalized templates.
[20] Ausman, K. D.; Piner, R.; Lourie, O.; Ruoff, R. S.; Korobov, M. J. Phys. Chem. 2000,
104, 8911-8915. Organic solvent dispersions of single-walled carbon nanotubes:
toward solutions of pristine nanotubes.
[21] Landi, B. J.; Ruf, H. J.; Worman, J. J.; Raffaelle, R. P. J. Phys. Chem. B 2004, 108,
17089-17095. Effects of alkyl amide solvents on the dispersion of single-wall carbon
nanotubes.
[22] Niyogi, S.; Hamon, M.A.; Perea, D. E.; Kang, C.B.; Zhao, B.; Pal, S.K.; Wyant, A. E.;
Itkis, M. E.; Haddon, R.C. J. Phys. Chem. B 2003, 107, 8799-8804. Ultrasonic
dispersions of single-walled carbon nanotubes.
[23] Ganter, M. J.; Landi, B. J.; Worman, J. J.; Schauerman, C. M.; Cress, C. D.; Raffaelle,
R. P. Mater. Chem. Phys. 2009, 116, 235-241. Variation of single wall carbon
nanotube dispersion properties with alkyl amide and halogenated aromatic solvents.
[24] Giordani, S.; Bergin, S.; Nicolos, V.; Lebedkin, S.; Blau, W.J.; Coleman, J.N.Phys.
Stat. Sol. 2006, 243, 3058-3062. Fabrication of stable dispersions containing up to 70%
individual carbon nanotubes in a common organic solvent.
[25] Kim, K.; Yoon, S.; Choi, J.; Lee, J.; Kim, B.; Kim, J.; Lee, J.; Paik, U.; Park, M.; Yang,
C.; An, K.; Chung, Y.; Lee, Y. Adv. Funct. Mater. 2007, 17, 1775-1783. Design of
dispersants for the dispersion of carbon nanotubes in an organic solvent.
[26] Delozier, D. M.; Watson, K. A.; Smith, Jr., J. G.; Clancy, T. C.; Connell, J. W.
Macromolecules 2006, 39, 1731-1739. Investigation of aromatic / aliphatic polymides
as dispersants for single wall carbon nanotubes.
[27] Chen, W.; Tao, X. Mater. Res. Soc. Symp. Proc. 2006, 920, 0920-S02-02. Ultrasonic-
induced functionalization and solubilization of carbon nanotubes for potential
nanotextiles applications.
[28] Li, Q.; Ma, Y.; Mao, C.; Wu, C. Ultrason. Sonochem. 2009, 16, 752-757. Grafting
modification and structural degradation of multi-walled carbon nanotubes under the
effect of ultrasonics sonochemistry.
Anne C. Gaquere-Parker and Cass D. Parker 260
[29] Amrollahi, A.; Hamidi, A. A.; Rashidi, A.M. Nanotechnology 2008, 19, 1-8. The
effects of temperature, volume fraction and vibration time on the thermo-physical
properties of a carbon nanotube suspension (carbon nanofluid).
[30] Bandyopadhyaya, R.; Nativ-Roth, E.; Regev, O.; Yerushalmi-Rozen, R. Nano Lett.
2002, 2, 25-28. Stabilization of individual carbon nanotubes in aqueous solutions.
[31] Strano, M. S.; Moore, V. C.; Miller K.; Allen, M. J.; Haroz, E. H.; Kittrell, C., Hauge,
R. H.; Smalley, R. E. J. Nanosci. Nanotechnol. 2003, 3, 81-86. The role of surfactant
adsorption during ultrasonication in the dispersion of single-walled carbon nanotubes.
[32] Grossiord, N.; Regev, O.; Loos, J.; Meuldijk, J.; Koning; C. E. Anal. Chem. 2005, 77,
3135-5135. Time-dependent study of the exfoliation process of carbon nanotubes in
aqueous dispersions by using UV-Visible spectroscopy.
[33] Paredes, J.I.; Burghard, M. Langmuir 2004, 20, 5149-5152. Dispersions of individual
single-walled carbon nanotubes of high length.
[34] Nepal, D.; Geckler, K. E. Small 2006, 2, 406-412. pH-Sensitive dispersion and
debundling of single-walled carbon nanotubes: lysozyme as a tool.
[35] Bottini, M.; Magrini, A.; Rosato, N.; Bergamaschi, A.; Mustelin, T. J. Phys. Chem. B
2006, 110, 13685-8. Dispersion of pristine single-walled carbon nanotubes in water by
a thiolated organosilane application in supramolecular nanoassemblies.
[36] Gladchenko, G. O.; Karachevtsev, M.V.; Leontiev, V.S.; Valeev, V.A.; Glamazda, A.
Yu; Plokhotnichenko, A.M; Stephanian S.G. Mol. Phys. 2006, 104, 3193-3201.
Interaction of fragmented double-stranded DNA with carbon nanotubes in aqueous
solution.
[37] Ciofani, G.; Raffa,V.; Pensabene, V.; Menciassi, A.; Dario, P. Fullerenes Nanotubes
Carbon Nanostruct. 2009, 17, 11-25. Dispersion of multi-walled carbon nanotubes in
aqueous Pluronic F127 solutions for biological applications.
[38] Lopez-Pastor, M.; Dominguez-Vidal, A.; Ayora-Canada, M. J.; Simonet, B. M.; Lendi,
B.; Valcarcel, M. Anal. Chem. 2008, 80, 2672-2679. Separation of single-walled
carbon nanotubes by use of ionic liquid-aided capillary electrophoresis.
[39] Lee G., Kumar, S. J. Phys. Chem. B 2005, 109, 17128-17133. Dispersion of nitric
acid-treated SWNTs in organic solvents and solvent mixtures.
[40] Zhang, X., Sreekumar, T.V., Liu T., Kumar S., J. Phys. Chem. B 2004, 108, 16435-
16440. Properties and structure of nitric acid oxidized single wall carbon nanotube
films.
[41] Yue-Feng, Z.; Chan, Z.; Jing-Dong, W.; Lei, S.; Ji, L. J. Dispersion Sci. Technol. 2006,
27, 371-375, Influence of electric field on dispersion of carbon nanotubes in liquids.
[42] Li, Z. F.; Luo, G. H.; Zhou, W. P.; Wei, F.; Xiang, R.; Liu, Y. P. Nanotechnology
2006, 17, 3692-3698. The quantitative characterization of the concentration and
dispersion of multi-walled carbon nanotubes in suspension by spectrophotometers.
[43] Kim, H.; Kang, M.; Park, W.; Kim, D.; Jin, H. Mod. Phys. Lett. B 2008, 22, 2493-
2501. Dispersity and stability measurement of functionalized multiwalled carbon
nanotubes in alcohols.
[44] Nadler, M.; Mahrholz, T.; Riedel, U.; Schilde, C.; Kwade, A. Carbon 2008, 46, 1384-
1392. Preparation of colloidal carbon nanotube dispersions and their characterization
using a disc centrifuge.
Application of Ultrasounds to Carbon Nanotubes 261
[45] Margrave, J.L.; Mickelson, E. T.; Chiang, I. W.; Zimmerman, J. L.; Boul, P. J. Lozano,
J.; Lui, J.; Smalley, R.E.; Hauge, R.H. J. Phys. Chem. 1999, 103, 4318-4322.
Solvation of fluorinated single-wall carbon nanotubes in alcohol solvents.
[46] Lu, K. L; Iago, R. M.; Chen, Y. K; Green, M. L.H.; Harris, P. J. F.; Tsang, S.C. Carbon
1996, 34, 814-814. Mechanical damage of carbon nanotubes by ultrasound.
[47] Hilding, J.; Grulke, E. A,; Zhang, Z. G.; Lockwood, F. J. Dispersion Sci. Technol.
2003, 24, 1-41. Dispersion of carbon nanotubes in liquids.
[48] Lui, J.; Rinzler, A. G. ; Dai, H.; Hafner, J. H.; Bradley, R. K.; Boul, P. J.; Lu, A.;
Iverson, T.; Shelimov, K.; Huffman, C. B. ; Rodriguez-Macias, F.; Shon, Y.; Lee, T. R.;
Colbert, D. T.; Smalley, R. E.; Science 1998, 280, 1253-1256. Fullerene pipes.
[49] Liu, Y.; Gao, L.; Sun, J.; Zheng, S.; Jiang, L.; Wang, Y.; Kajiura, H.; Li, Y.; Noda, K.
Carbon 2007, 45, 1972-1978. A multi-step strategy for cutting and purification of
single-walled carbon nanotubes.
[50] Monthioux, M.; Smith, B.W.; Burteaux, B.; Claye, A.; Fischer, J. E.; Luzzi, D.E.
Carbon 2001, 39, 1251-1272. Sensitivity of single-wall carbon nanotubes to chemical
processing: an electron microscopy investigation.
[51] Furtado, C. A.; Kim, U. J.; Gutierrez, H. R.; Pan, L.; Dickey, E. C.; Eklund, P. C. J.
Am. Chem. Soc. 2004, 126, 6095-6105. Debundling and dissolution of single-walled
carbon nanotubes in amide solvents.
[52] Koshio, A.; Yudasaka, M.; Iijima, S. Chemical Physics Letters 2001, 341, 461-466.
Thermal degradation of ragged single-wall carbon nanotubes produced by polymer-
assisted ultrasonication.
[53] Koshio, A.; Yudasaka, M.; Zhang, M.; Iijima, S. Nano Lett. 2001, 1, 361-363. A
simple way to chemically react single-wall carbon nanotubes with organic materials
using ultrasonication.
[54] Koshio, A.; Yudasaka, M.; Ozawa, M.; Iijima, S. Nano Lett. 2002, 2, 995-997.
Fullerene formation via pyrolysis of ragged single-wall carbon nanotubes.
[55] Zhang, M.; Yudasaka, M.; Koshio, A.; Iijima, S. Chem. Phys. Lett. 2002, 364, 420-
426. Thermogravimetric analysis of single-wall carbon nanotubes ultrasonicated in
monochlorobenzene.
[56] Heller, D. A.; Mayrhofer, R. M.; Baik, S.; Grinkova, Y. V.; Usrey, M. L.; Strano, M. S.;
J. Am. Chem. Soc. 2004, 126, 14567-14573. Concomitant length and diameter
separation of single-walled carbon nanotubes.
[57] Arnold, K.; Hennrich, F.; Krupke, R.; Lebedkin, S.; Kappes, M.M.; Phys. Status Solidi
B 2006, 243, 3073-3076. Length separation studies of single walled carbon nanotube
dispersions.
[58] Wang, Y.; Gao, L.; Sun, J.; Liu, Y.; Zheng, S.; Kajiura, H.; Li, Y.; Noda, K.; Chem.
Phys. Lett. 2006, 432, 205-208. An integrated route for purification, cutting and
dispersion of single-walled carbon nanotubes.
[59] Park, H.; Park, M.; Chang, J. Y.; Lee, H. Nanotechnology 2008, 19, 1-7. The effect of
pre-treatment methods on morphology and size distribution of multi-walled carbon
nanotubes.
[60] Warakulwit, C.; Majimel, J.; Delville, M.; Garrigue, P.; Limtrakul, J.; Kuhm, A. J.
Mater. Chem. 2008, 18, 4056-4061. Controlled purification, solubilization and cutting
of carbon nanotubes using phosphomolybdic acid.
Anne C. Gaquere-Parker and Cass D. Parker 262
[61] Liu, P.; Wang, T. Appl. Phys. A 2009, 97, 771-775. Ultrasonic-assisted chemical
oxidative cutting of multiwalled carbon nanotubes with ammonium persulfate in neutral
media.
[62] Luong, J. H. T.; Hrapovic, S.; Liu, Y.; Yang, D.; Sacher, E.; Wang, D.; Kingston, C. T.;
Enright, G. D.; J. Phys. Chem. B 2005, 109, 1400-1407. Oxidation, deformation, and
destruction of carbon nanotubes in aqueous ceric sulfate.
[63] Chen, Y.; Haddon, R.C.; Fang, S.; Rao, A.M.; Eklund, P.C.; Lee, W.H.; Dickley, E.C.;
Grulke, E.A.; Pendergrass, J.C.; Chavan, A.; Haley, B.E.; Smalley, R.E. J. Mater. Res.
1998, 13, 2423-2431. Chemical attachment of organic functional groups to single-
walled carbon nanotube material.
[64] Saini, R. K.; Chiang, I. W.; Peng, H.; Smalley, R.E.; Billups, W. E.; Hauge, R. H.;
Margrave, J. L. J. Am. Chem. Soc. 2003, 125, 3617-3621. Covalent sidewall
functionalization of single wall carbon nanotubes.
[65] Kovtyukhova, N. I.; Mallouk, T. E.; Pan, L.; Dickey, E. C. J. Am. Chem. Soc. 2003,
125, 9761-9769. Individual single-walled nanotubes and hydrogels made by oxidative
exfoliation of carbon nanotube ropes.
[66] Chen, J.; Rao, A. M.; Lyuksyutov, S.; Itkis, M. E.; Hamon, M. A.; Hu, H.; Cohn, R. W.;
Eklund, P. C.; Colbert, D. T.; Smalley, R. E.; Haddon, R. C. J. Phys. Chem. B 2001,
105, 2525-2528. Dissolution of full-length single-walled carbon nanotubes.
[67] Kaempgen, M.; Lebert, M.; Haluska, M.; Nicoloso, N.; Roth, Siegmar; Adv. Mater.
2008, 20, 616-620. Sonochemical optimization of the conductivity of single-wall
carbon nanotube networks.
[68] Zhang, N.; Xie, J.; Guers, M.; Varadan, V. K. Smart Mater. Struct. 2003, 12, 260-263.
Chemical bonding of multiwalled carbon nanotubes to SU-8 via ultrasonic irradiation.
[69] Ren, G.; Xing, Y. Nanotechnology 2006, 17, 5596-5601. Deposition of metallic
nanoparticles on carbon nanotubes via a fast evaporation process.
[70] Qui, L.; Pol, V. G.; Wei, Y.; Gedanken, A. New. J. Chem. 2004, 28, 1056-1059.
Sonochemical decoration of multi-walled carbon nanotubes with nanocrystalline tin.
[71] Xing, Y. J. Phys. Chem. 2004, 108,19255-19259. Synthesis and electrochemical
characterization of uniformly-dispersed high loading Pt nanoparticles on
sonochemically-treated carbon nanotubes.
[72] Xing, Y.; Li, L.; Chusuei, C. C.; Hull, R. V. Langmuir 2005, 21, 4185-4190.
Sonochemical oxidation of multiwalled carbon nanotubes.
[73] Hull, R. V.; Li, L.; Xing, Y.; Chusuei, C. C. Chem. Mater. 2006 18, 1780-1788. Pt
nanoparticle binding on functionalized multiwalled carbon nanotubes.
[74] Worsley, K. A.; Moonoosawmy, K. R.; Kruse, P. Nano Lett. 2004, 4, 1541-1546. Long-
range periodicity in carbon nanotube sidewall functionalization.
[75] Yang, D.; Rochette, J.; Sacher, E. J. Phys. Chem. 2005, 109, 7788-7794.
Functionalization of multiwalled carbon nanotubes by mild aqueous sonication.
[76] Goyanes, S.; Rubiolo, G.R.; Salazar, A.; Jimeno, A.; Corcuera, M. A.; Mondragon, I.
Diamond Relat. Mater. 2007, 16, 412-417. Carboxylation treatment of multiwalled
carbon nanotubes monitored by infrared and ultraviolet spectroscopes and scanning
probe microscopy.
[77] Liu, M.; Yang, Y.; Zhu, T.; Liu, Z. J. Phys. Chem 2007, 111, 2379-2385. A general
approach to chemical modification of single-walled carbon nanotubes with peroxy
organic Acids and its application in polymer grafting.
Application of Ultrasounds to Carbon Nanotubes 263
[78] Liu, M.; Yang, Y; Zhu, T.; Liu, Z., Carbon, 2005, 43, 1470-1478. Chemical
modification of single-walled carbon nanotubes with peroxytrifluoroacetic acid.
[79] Chang, J.; Wu, H.; Hwang, G.; Su, T. J. Mater. Chem. 2008, 18, 3972-3976.
Ultrasonication-assisted surface functionalization of double-walled carbon nanotubes
with azobis-type radical initiators.
[80] Li, M.; Beebe, T. P.; Huang, C.P. Carbon 2008, 46, 466-475. Oxidation of single-
walled carbon nanotubes in dilute aqueous solutions by ozone as affected by ultrasound.
[81] You, Y.; Yan J.; Yu, Z., Cui, M.; Hong, C.; Qu, B. J. Mater. Chem. 2009, 19, 7656-
7660. Multi-responsive carbon nanotube gel prepared via ultrasound-induced
assembly.
[82] Zhao, B.; Liang, H.; Han, D.; Qui, D.; Chen, S. Sep. Sci. Technol. 2007, 42, 3419-3427.
adsorption of pyridine from aqueous solution by surface treated carbon nanotubes.
[83] Adewuyi, Y..; Environ. Sci. Technol. 2005, 39, 8557-8570. Sonochemistry in
environmental remediation. 2. Heterogeneous sonophotocatalytic oxidation processes
for the treatment of pollutants in water.
[84] Gogate, P.R.; Pandit, A.B.; AIChE Journal, 2004, 50, 1051-1079. Sonophotocatalytic
reactors for wastewater treatment: A critical review.
[85] Joseph, C.; LiPuma G.; Bono, A.; Krishnaiah, D. Ultrason. Sonochem. 2009, 16, 583-
589. Sonophotocatalysis in advanced oxidation process: A short review.
[86] Wang, S.; Gong, Q.; Liang, J. Ultrason. Sonochem. 2008, 16, 205-208.
Sonophotocatalytic degradation of methyl orange by carbon nanotube/ TiO2 in aqueous
solutions.
[87] Kotel, L.Y.; Brichka, A.V.; Brichka, S.Y. Russ. J. Appl. Chem. 2009, 82, 569-573.
Adsorption properties of modified multilayer carbon nanotubes with respect to benzoic
Acid.











INDEX


A
absorption, 11, 20, 21, 82, 83, 224, 237
absorption spectra, 11
absorption spectroscopy, 237
acetate, 12, 17, 21, 22, 24, 25, 46, 52, 56, 131,
132, 133, 135, 137, 138, 141, 144, 147, 148,
151, 163, 167
acetic acid, 167, 174, 243
acetone, 18, 114, 131, 138, 176
acetonitrile, 132
acetophenone, 112, 167, 168
acetylation, 175, 185
acetylene, 33, 57
acidic, 4, 111, 112, 235, 236, 248, 249, 251
acidity, 111
acoustic, vii, viii, 1, 2, 36, 49, 63, 64, 65, 66, 67,
68, 69, 70, 72, 73, 74, 75, 76, 77, 78, 79, 80,
81, 82, 83, 84, 85, 86, 87, 88, 91, 94, 96, 97,
98, 99, 100, 101, 102, 108, 130, 136, 140, 145,
150, 160, 161, 175, 179, 191, 195, 196
acoustic waves, 66, 68, 83
acoustical, 66, 101
acrylate, 35, 171, 175
ACS, 156
activated carbon, 168, 206
activation, 130, 137, 140, 147, 149, 150, 168,
172, 234
activation energy, 140, 147, 149, 150
activation entropy, 149
activation parameters, 130, 149
acute ischemic stroke, 200
acylation, ix, 157, 170, 178, 183, 187
additives, 12, 27, 133
adriamycin, 192, 193, 194, 198, 199, 200
adsorption, 9, 60, 239, 256, 257, 260, 263
AFM, 222, 224, 225, 234, 236, 238, 240, 246,
249, 252
Ag, 8, 10, 11, 16, 25, 26, 27, 28, 31, 36, 50, 51,
55, 56, 57
agent, ix, x, 4, 5, 7, 20, 22, 23, 31, 46, 47, 48, 60,
176, 189, 191, 193, 195, 196, 198, 231, 251
agents, vii, ix, 3, 12, 21, 48, 167, 180, 181, 189,
190, 191, 192, 195, 198, 217
aggregates, 18, 21, 22, 23, 28, 30, 140, 226, 234,
241, 250, 258
AIBN, 31
air, 9, 14, 15, 16, 17, 18, 20, 25, 33, 36, 41, 42,
46, 48, 79, 84, 119, 172, 183, 203, 204, 215,
218, 226, 228
alcohol, 10, 35, 109, 112, 114, 116, 132, 134,
135, 137, 144, 145, 151, 175, 178, 221, 243,
256, 261
alcohols, viii, 105, 110, 113, 130, 133, 137, 145,
146, 150, 172, 174, 175, 177, 185, 242, 260
Alcohols, 185
aldehydes, ix, 106, 110, 111, 112, 113, 114, 115,
116, 117, 118, 119, 164, 165, 167, 169, 171,
172, 182, 183
aliphatic amines, 173, 184
alkali, 20, 107, 113, 184, 187
alkaline, 6, 7, 9, 21, 38, 47, 132, 167, 181
alkaline hydrolysis, 132
alkanes, 215
alkenes, 32, 106, 116, 185, 215
alkylation, 106, 169, 173, 178, 184, 187
alkylation reactions, 187
alloys, 83, 96, 110
alpha, 36, 55, 58, 60
alternative, ix, 157, 195, 201, 204, 208
ambient air, 14, 20, 41, 46
ambient pressure, 9, 160
amide, 18, 53, 237, 244, 252, 259, 261
amine, 38, 163, 164, 180, 218, 228, 255
amines, 171, 173, 178, 184, 186, 217, 218, 228
Index 266
amino, 27, 56, 60, 115, 168, 170, 178, 182, 183,
186
amino acid, 27, 56, 170, 183
amino acids, 27, 56, 170, 183
amino groups, 115
ammonia, 12, 29, 38, 244
ammonium, 17, 19, 22, 30, 32, 33, 45, 112, 165,
167, 169, 172, 180, 247, 262
ammonium chloride, 112, 165
ammonium salts, 167
amorphous, 10, 25, 31, 33, 36, 51, 57, 60, 224,
233, 234, 235, 236, 244, 245, 246, 248, 249,
250
amorphous carbon, 233, 234, 235, 236, 244, 245,
248, 249
amphoteric, 111
amplitude, viii, 19, 26, 63, 67, 70, 71, 75, 84, 85,
86, 87, 94, 96, 97, 98, 100, 101, 158, 161, 194,
200, 205
anaerobic, 15
anatase, 18, 256
angiogenesis, 196, 200
aniline, 32, 33, 43, 219
anionic surfactant, 45
annealing, 16, 36, 39, 40, 232, 244
antagonism, 197
antagonist, 106
anthracene, 235
antibacterial, 29, 31, 56
antibody, 196
anticancer, vii, ix, 189, 190, 191, 192, 193, 195,
196, 197, 198
anti-cancer, 199
anticancer drug, 190, 191, 192, 193, 195, 196,
197
antihypertensive agents, 180
antioxidant, 165
antitumor, 190, 192, 195, 200
apoptosis, 192, 196, 199, 200
apoptosis pathways, 196
application, vii, ix, 2, 25, 49, 52, 53, 56, 57, 121,
134, 135, 137, 153, 158, 162, 163, 173, 184,
198, 201, 214, 260, 263
aqueous solution, ix, 3, 4, 6, 7, 8, 10, 11, 14, 16,
17, 18, 20, 21, 22, 24, 25, 27, 28, 32, 33, 34,
35, 40, 42, 45, 50, 51, 110, 113, 129, 130, 131,
132, 134, 137, 143, 202, 210, 211, 233, 236,
239, 240, 241, 242, 256, 257, 260, 263
aqueous solutions, ix, 3, 8, 11, 20, 21, 27, 33,
129, 130, 134, 137, 202, 210, 211, 236, 240,
242, 260, 263
aqueous suspension, 19, 205
argon, 3, 4, 11, 15, 26, 29, 36, 38, 140, 175, 176,
203, 214, 224
aromatic compounds, 177, 186
aromatics, 169, 178, 186
Arrhenius equation, 139, 149
aspect ratio, 4, 41, 44
assumptions, 69, 78
atmosphere, 11, 17, 24, 25, 26, 27, 30, 33, 36,
175
atomic force, 224, 234
atomic force microscopy, 224, 234
atomic force microscopy (AFM), 234
atoms, 6, 119, 146, 210, 233
ATP, 192, 199
Au nanoparticles, 3
availability, 84, 110, 179, 222
B
Bacillus, 207, 210
Bacillus subtilis, 207
bacteria, 29, 204, 205, 208, 209, 210
bacterial, 204, 205, 206, 210
bacterial cells, 205
band gap, 12, 20, 21, 30, 44
behavior, 17, 26, 38, 72, 78, 134, 191, 242, 254
Belgium, 154
benzene, 35, 111, 112, 113, 114, 115, 116, 141,
142, 166, 214, 217, 219, 222, 226, 232, 240
binding, 12, 35, 134, 199, 250, 262
binding energies, 35
binding energy, 12
biochemistry, 134
biodiesel, 103
biological activity, 225
biological coating, 18
biotechnology, 36, 153
bismuth, 19, 20, 55, 61, 171, 183
bladder, 194, 200
bladder cancer, 195, 200
bonding, 146, 147, 215, 222, 242, 262
bonds, 20, 106, 134, 141, 160, 233, 235, 244,
245, 250, 251, 254
boundary conditions, 89, 91
bromination, 178, 186
bubble, viii, 2, 31, 49, 63, 65, 66, 67, 68, 69, 70,
71, 72, 73, 75, 76, 78, 82, 83, 102, 108, 130,
131, 138, 139, 160, 161, 162, 202, 203, 213,
234
bubbles, vii, ix, 1, 2, 49, 66, 67, 68, 72, 73, 74,
75, 76, 77, 78, 81, 83, 102, 108, 130, 131, 140,
157, 160, 161, 174, 191, 198, 202, 204, 208,
214
Index 267
Bubbles, 2, 179
bulk crystal, 23
by-products, 142, 204, 209
C
calcination temperature, 22, 24
calcium, 30, 40, 180
calcium channel blocker, 180
calibration, 94, 224
calorimetry, 73, 136
Canada, 208, 260
cancer, ix, 167, 181, 189, 190, 191, 192, 193,
194, 195, 196, 197, 198, 199, 200
cancer cells, 190, 191, 192, 194, 195, 196, 197,
199
cancer treatment, 196
capillary, 241, 260
Carbon, viii, 33, 43, 58, 59, 105, 106, 219, 228,
231, 232, 258, 260, 261, 263
carbon atoms, 146, 233
carbon dioxide, 203
carbon materials, 258
carbon nanotubes, x, 34, 35, 43, 59, 219, 231,
232, 233, 234, 235, 236, 237, 238, 239, 240,
241, 242, 243, 244, 245, 246, 247, 248, 249,
250, 251, 252, 254, 256, 257, 258, 259, 260,
261, 262, 263
Carbon nanotubes, 232
carbonates, 24
Carbonyl, 105, 248, 249
carboxyl, 251
carboxyl groups, 251
carboxylates, 240
carboxylic, 22, 38, 116, 132, 240, 242, 244, 247,
248, 249, 251, 252, 254
carboxylic acids, 132, 240, 242, 252
carboxylic groups, 244
carburization, 34
carcinoma, 192, 195, 198, 199
catalysis, vii, ix, 2, 3, 22, 42, 44, 157, 184, 196,
203
catalyst, 9, 10, 18, 28, 35, 36, 43, 51, 55, 56, 106,
107, 108, 109, 111, 141, 163, 165, 166, 171,
172, 175, 176, 177, 178, 183, 184, 186, 234,
236, 241, 248, 256, 257
catalytic activity, 9, 28, 35, 110, 256
catalytic effect, 132
catalytic properties, 61
cathode, 34, 53
cavities, 75, 108, 160, 161, 202, 203
C-C, 185, 235
cell, 6, 64, 191, 192, 193, 194, 195, 196, 197,
198, 199, 200, 204, 205, 206, 211
cell death, 192, 195, 197
cell killing, 199
cell line, 194, 198, 199, 200
cell lines, 200
cellulose, 46
ceramic, 206
ceramics, 2, 49
cerium, 58, 248
cervix, 193
chalcogenides, vii, 2, 44, 47
channels, 16
chemical bonds, 161
chemical interaction, 26
chemical oxidation, 248
chemical properties, 213
chemical reactions, ix, 2, 106, 129, 130, 131, 133,
141, 158, 159, 160, 174, 196, 202
chemical reactivity, 129, 134, 158
chemicals, 109, 110, 111, 190, 195, 196, 202
chemiluminescence, 61
chemopreventive agents, 167, 181
chemoresistance, 189, 192, 193, 199
chemoresistant, ix, 189, 192, 193, 194, 196
chemotherapy, 189, 190, 191, 192, 196, 197, 198,
199
China, 105, 126, 189, 198
chiral, viii, 105, 106, 107, 120
chiral center, viii, 105, 107
chloride, ix, 7, 11, 129, 130, 132, 135, 137, 146,
147, 148, 149, 150, 151, 152, 167, 171, 172,
173, 176, 183, 185, 221, 233, 248, 250
Chloride, 146
chlorinated hydrocarbons, 234
chlorination, 204, 206, 208
chlorobenzene, 175, 224, 232, 245, 246, 252
chloroform, 9, 234, 235, 238, 243, 248
chromatography, 219, 220
chromium, 217, 218
circulation, 3, 194
cis, 16, 176, 177, 185
cisplatin, 193, 195, 197, 199, 200
Claisen, ix, 107, 157, 167, 168, 182
classical, 57, 67, 78, 106, 109, 110, 114
cleaning, 45, 46, 84, 106, 129, 158, 161, 165,
168, 203, 208, 209
cleavage, 9, 130, 139, 178, 186, 218
clouds, 102
cluster model, 134, 141
clusters, 11, 12, 39, 60, 134, 141, 142, 144, 145,
150, 204, 226, 239
CNTs, 34, 35
Index 268
Co, 10, 24, 51, 103
CO2, 9, 28
coatings, 18
cobalt, 233
coil, 87, 94
coliforms, 207
collisions, 232
colloidal particles, 226
colloids, x, 213, 224, 226, 229
colon, 194, 195
colon cancer, 194, 195
combustion, 15, 28, 56
components, x, 64, 65, 83, 137, 203, 231, 257
composites, 28, 29, 30, 56, 57, 58
composition, 16, 19, 36, 132, 133, 135, 136, 137,
147, 150, 151, 152, 221
compounds, vii, viii, 47, 61, 105, 106, 107, 109,
114, 133, 140, 145, 163, 164, 165, 167, 169,
171, 173, 176, 180, 181, 182, 184, 200, 203,
204, 209, 215
concentration, 5, 8, 9, 12, 14, 19, 20, 22, 23, 27,
36, 43, 67, 68, 69, 79, 113, 139, 145, 176, 177,
195, 222, 224, 234, 237, 238, 239, 241, 256,
260
condensation, ix, 107, 129, 130, 132, 134, 141,
142, 143, 157, 164, 166, 167, 168, 171, 181,
182, 183
condensed media, 147
conducting polymers, 43
conductivity, 32, 35, 57, 73, 239, 248, 262
configuration, 103
Congress, 102, 199
construction, viii, 73, 76, 78, 85, 88, 105, 106
control, viii, ix, 2, 37, 51, 56, 97, 105, 107, 120,
153, 189, 195, 198, 221, 238
conversion, 9, 14, 31, 40, 76, 110, 112, 113, 170,
178, 186, 221
conversion rate, 221
cooling, ix, 2, 87, 108, 157
copolymer, 21, 23, 246
copper, 22, 24, 29, 54, 55, 60, 163, 164, 166, 180
copper oxide, 29
core-shell, 10, 11, 36, 38, 39, 40, 51, 58
correlation, 130, 133, 134, 143, 153, 174, 238
correlation analysis, 130, 143
corrosion, 8, 113, 170
coupling, vii, viii, ix, 105, 106, 107, 109, 110,
111, 112, 113, 114, 115, 116, 117, 118, 119,
120, 121, 157, 162, 163, 164, 166, 175, 178,
179, 180, 181, 185
covalent, x, 231, 239, 252, 257
covalent bond, 252
covalent bonding, 252
critical value, 76
cross-sectional, 84, 88
crystal growth, 221, 222
crystal lattice, 140
crystal structure, 249
crystalline, 4, 6, 7, 15, 24, 25, 36, 41, 45, 48, 50,
59, 60, 228, 250, 256
crystallinity, 3, 17, 222
crystallites, 28
crystallization, x, 16, 18, 106, 140, 213, 224
crystals, 5, 8, 23, 36, 40, 222, 227
CTAB, 3, 4, 17, 22, 40, 45, 46
cyanide, 173, 184
cycles, 48, 108, 158, 160, 194
cyclodextrin, 5, 48, 60
cyclohexane, 252
cyclohexanol, 243
cyclohexanone, 176
cyclophosphamide, 196
cysteine, 30
cytochrome, 196
cytokine, 196
cytometry, 211
cytosol, 196
cytotoxic, ix, 189, 191, 192, 195, 197, 198
cytotoxic agents, 195
cytotoxicity, 192, 194, 198, 199, 200
D
decomposition, 15, 16, 18, 20, 34, 36, 40, 42,
141, 158, 202, 237, 246, 252
deduction, 143
defects, x, 109, 231, 232, 235, 238, 239, 241,
242, 243, 244, 246, 247, 254, 256, 258
definition, 140
deformation, 85, 203, 262
degradation, 10, 18, 22, 24, 31, 66, 138, 139, 141,
153, 205, 227, 237, 240, 241, 245, 246, 249,
257, 260, 261, 263
Degussa, 18
density, 33, 68, 72, 73, 75, 76, 77, 78, 79, 86,
100, 139, 205, 241, 242, 243
depolymerization, 203
deposition, 55, 56, 84, 100, 250, 259
derivatives, x, 35, 164, 166, 175, 176, 181, 185,
213, 215, 216, 217, 219, 227, 228
destruction, 71, 143, 194, 210, 262
diagnostic ultrasound, 196
diamines, 106, 178, 186
Diamond, 258, 262
dichloroethane, 234
dienes, 180
Index 269
diffraction, 17, 61, 221, 222, 226, 256
diffusion, 2, 67, 68, 72, 239
dimer, 215, 216
dimethylformamide, 42, 236
dimethylsulfoxide, 251
dipole, 131
dipole moment, 131
dipole moments, 131
discontinuity, 67, 71, 73
discrimination, 247
disinfection, 204, 205, 206, 208, 209, 210
dispersion, 14, 28, 31, 57, 72, 81, 82, 91, 98, 220,
221, 224, 232, 235, 236, 237, 239, 240, 241,
243, 244, 247, 249, 251, 254, 259, 260, 261
dissociation, 23, 131, 203
distilled water, 14, 46
distribution, vii, 1, 5, 7, 9, 10, 12, 18, 21, 29, 31,
34, 36, 38, 66, 68, 69, 71, 72, 77, 91, 92, 93,
95, 242, 247, 261
divergence, 81
DMF, 42, 43, 166, 169, 236, 237, 244, 247, 248,
252, 254
DNA, 193, 199, 211, 240, 260
DNA damage, 199
DNA repair, 193
donor, 22, 226
dopant, 43
doped, 17, 18, 20, 22, 29, 41, 42, 43, 44, 53, 54,
56, 181, 187
doping, 2, 18, 53, 249
drug delivery, 24, 190, 199
drugs, 106, 192, 194, 195, 196, 199
drying, 18, 221, 224, 249
durability, 27
duration, 19, 108, 191, 194, 234, 238, 246, 247,
250
E
E. coli, 205, 208
earth, 17, 24, 42, 54, 55, 107
Education, 210
electric conductivity, 35
electric current, 242
electric energy, 83
electric field, 242, 260
electrical power, 88
electrocatalyst, 51
electrochemistry, 44, 106, 107
electromagnetic, 20, 159
electron, ix, 106, 109, 111, 112, 114, 116, 117,
165, 170, 171, 218, 222, 226, 229, 247, 261
electron microscopy, 226, 229, 233, 236, 247,
261
electrophoresis, 193, 240, 241, 246, 260
emission, 17, 20, 22, 40, 41, 110, 208
employment, 173
emulsification, 55, 72, 98, 109, 203
emulsion polymerization, 58
emulsions, 109
encapsulated, 30, 31, 32, 193, 194, 195, 199, 221
encapsulation, 31, 241
energy density, 33
energy parameters, viii, 63, 64
England, 210
entanglement, 5
entropy, 137, 149
entropy of activation, 137
environment, 17, 49, 73, 75, 110, 161, 213, 227
environmental protection, 210
Epoxidation, 172, 183, 217, 218
epoxides, 106, 178, 186, 218
epoxy, 98, 249
equilibrium, 68, 70, 71, 77, 79, 137, 239
equilibrium state, 70, 79
erosion, 72, 82, 203
Escherichia coli, 29, 205, 207, 208, 209, 210
ESR, 243
ester, ix, 30, 129, 134, 137, 139, 140, 141, 143,
144, 145, 152, 252
esters, 130, 132, 134, 135, 137, 139, 141, 144,
145, 165, 168, 172, 178, 180, 183, 186
Estonia, 129
ET, 109
etching, 39, 40
ethanol, 8, 9, 16, 17, 24, 31, 34, 38, 40, 46, 50,
52, 113, 132, 134, 135, 136, 137, 138, 141,
142, 143, 144, 146, 147, 148, 149, 150, 151,
152, 172, 237, 242, 243, 248, 252
Ethanol, 52, 142, 149
ethers, 106, 166, 173, 178, 181, 186
ethyl acetate, 56, 131, 135, 137, 138, 151
ethylene, 4, 6, 7, 10, 11, 24, 38, 46, 47, 48, 238,
246
ethylene glycol, 4, 6, 7, 10, 11, 24, 38, 46, 47, 48,
238
ethylene oxide, 246
ethylenediamine, 47
Euro, 181
excitation, 20, 22, 44, 160
exfoliation, 239, 260, 262
experimental condition, 19, 41, 131, 136, 244,
258
exposure, 100, 191, 194, 199
external magnetic fields, 27
Index 270
extinction, 237
extraction, 106, 220
extrapolation, 146
F
fabrication, 2, 3, 49, 51, 55, 57, 60
family, 42, 85, 237
fatigue, 64, 85, 86, 91, 94
ferromagnetic, 16, 17, 38, 58, 236
fibers, 29, 56, 248
film, 36, 205
films, 35, 60, 260
filtration, 106, 165, 235, 259
flow, viii, 15, 38, 63, 64, 66, 70, 71, 74, 75, 83,
100, 101, 160, 204, 206, 211, 221, 239
flow rate, 221
fluid, 102, 160
fluid mechanics, 102
fluorescence, 239
fluoride, 14, 113, 168
fluorinated, 243, 248, 261
focusing, viii, 63, 71, 72, 82, 190
formaldehyde, 18, 28
formamide, 169
fouling, 208
fractal cluster, 226
fracture, 256
fragility, 222
fragmentation, 109
France, 102
free energy, 137, 143
free radical, 129, 191, 202, 211
free radicals, 129, 191, 202, 211
free-radical, 211
FTIR, 30, 40, 224
FT-IR, 219
fuel, 9, 10, 49
fuel cell, 9, 10, 49
fullerene, x, 213, 214, 215, 216, 217, 218, 219,
221, 224, 225, 226, 227, 228, 229, 235, 244,
245, 246
fullerenes, vii, x, 213, 214, 217, 218, 219, 220,
221, 222, 224, 225, 226, 227, 229, 235, 245
Fullerenes, 213, 214, 219, 228, 260
functional changes, 190
functionalization, x, 213, 217, 231, 248, 250,
252, 257, 259, 262, 263
G
gadolinium, 20
gamma-ray, 210
gas, vii, 2, 9, 14, 38, 49, 52, 66, 67, 68, 69, 70,
71, 72, 73, 75, 76, 77, 78, 81, 82, 83, 97, 108,
109, 131, 139, 160, 177, 191, 202, 203, 204,
214
gas diffusion, 72
gas phase, vii, 2, 49, 131, 139
gases, 71, 158, 203, 206, 224
gel, 22, 240, 246, 254, 263
gel formation, 255
gene, 192, 193, 198
gene expression, 192, 193
generalization, 142
generation, viii, 2, 63, 119, 129, 136, 160
Georgia, 213, 231
glass, 14, 18, 222
glucose, 4, 5, 6
glycerin, 98, 99
glycerol, 47
glycol, 4, 6, 10, 11, 20, 21, 26, 27, 46, 48, 173
glycosaminoglycans, 40, 58
glycosides, 228
gold, 3, 4, 5, 10, 12, 26, 27, 32, 50, 51, 57, 251
gold nanoparticles, 4, 5, 10, 50, 57
graphite, 81, 82, 235, 236, 248
groups, 22, 30, 34, 38, 106, 111, 115, 119, 131,
144, 163, 171, 241, 242, 244, 247, 248, 249,
250, 251, 252, 254, 255, 257, 258, 262
growth, vii, ix, 1, 2, 3, 6, 12, 17, 27, 37, 41, 43,
47, 49, 50, 51, 52, 59, 68, 74, 75, 76, 108, 130,
157, 160, 161, 194, 196, 200, 221, 222, 228,
233
growth factor, 196, 200
growth mechanism, 12, 59
growth temperature, 17
H
H
2
, 9, 174, 203, 215, 253
HA, 30, 56, 199
halogenated, 232, 259
HDPE, 56
health, 194, 204
hearing, ix, 158, 201
heat, 15, 16, 18, 24, 25, 34, 86, 97, 136, 139, 190,
206, 233, 246, 256
heating, ix, 17, 22, 24, 54, 66, 72, 108, 157, 241,
245
heavy metal, 107
heavy metals, 107
hematite, 15, 16, 52
heptane, 234
Index 271
heterogeneous, 129, 130, 131, 134, 138, 159,
161, 162, 163, 172, 173, 177, 206, 232, 235
heterogeneous systems, 161
hexafluorophosphate, 216
hexagonal lattice, 233
hexane, 218, 220
high intensity ultrasound, 182, 231
high pressure, ix, 2, 157, 160, 191
high resolution, 214
high temperature, 2, 34, 49, 82, 130, 161, 191,
213, 222, 233, 244, 254
high-speed, 66, 102, 131, 162
HIV, viii, 105, 106
homogeneity, 28, 64, 100
hot spots, 2, 49, 130, 140, 231
House, 156
HPLC, 214
HPM, 165
HR, 29, 199
HRTEM, 13, 26, 39, 41, 45, 247
human, ix, 109, 158, 192, 193, 194, 195, 197,
198, 199, 200, 201, 204
hybrid, x, 32, 57, 231
hydrate, 7, 47, 218, 246
hydro, 35, 43, 178, 187, 234, 246
hydrocarbon, 43, 235, 258
hydrocarbons, 43, 246
hydrodynamic, 81, 160, 206
hydrogels, 262
hydrogen, 2, 5, 18, 34, 40, 43, 53, 57, 132, 133,
141, 146, 147, 172, 177, 183, 202, 203, 205,
210, 215, 234, 242, 247, 254, 258
hydrogen atoms, 210
hydrogen bonds, 132, 133, 141, 254
hydrogen gas, 177, 203
hydrogen peroxide, 5, 18, 53, 172, 183, 203, 205,
234, 247
hydrogenation, 10, 32, 35, 57, 177, 185, 186
hydrolysis, ix, 18, 21, 38, 52, 129, 130, 131, 132,
133, 134, 135, 137, 138, 139, 140, 141, 144,
145, 146, 147, 148, 150, 151, 255
hydrophilicity, 31
hydrophobic, vii, ix, 129, 130, 132, 133, 134,
135, 137, 139, 141, 142, 143, 144, 145, 146,
147, 150, 152, 153
Hydrophobic, 129, 133, 134, 156
hydrophobic interactions, vii, 132, 133, 134, 137,
141, 144, 145, 152, 153
hydrophobicity, 139, 141, 143, 144, 145, 150,
153
hydrothermal, 258
hydroxide, 12, 30, 61, 168, 172, 248
hydroxides, 12, 22
hydroxyapatite, 30, 40, 58, 59
hydroxyl, 2, 19, 202, 203, 210, 242, 248, 249,
250, 251, 252, 254
hydroxyl groups, 242, 251
hydroxylation, 106
hydroxypropyl, 18, 53, 60
hyperthermia, 190
hypothesis, 193, 235
I
id, 141, 221, 241, 251
illumination, 24
images, 4, 5, 11, 13, 15, 20, 23, 26, 27, 28, 29,
35, 38, 39, 40, 41, 42, 45, 196, 223, 225, 234,
235, 236, 239, 240, 242, 245, 247, 248, 250,
252
imaging, 24, 159, 196, 236, 243, 248, 249
immersion, 132, 168
immobilization, 27, 56, 57
implementation, viii, 63, 64, 100
impurities, 109, 236, 240, 241, 245
in situ, 30, 32, 58, 60, 237
in vitro, 191, 198, 199
in vivo, 191, 194, 195, 196, 198, 199, 200
inactivation, 202, 204, 205, 207, 208, 211
Indian, 49, 120, 124, 125, 126, 183
indication, 81
indigenous, 139
indium, 17, 53, 60, 110, 182
indole, 164, 169, 173
induction, 199
industrial, viii, 18, 63, 64, 83, 84, 91, 94, 98, 100,
101, 120, 133
industrial application, 91, 94, 120
inflammatory, 167, 181
inhibitors, viii, 105, 106
inorganic, 2, 25, 29, 40, 57, 111
insertion, 2, 56
insulation, 97
integration, 69
interaction, 10, 11, 30, 66, 102, 119, 120, 133,
141, 143, 197, 198, 199, 225, 239, 246, 250,
251, 255, 257
interactions, vii, x, 30, 132, 133, 134, 135, 137,
138, 141, 143, 144, 145, 146, 152, 153, 197,
226, 227, 231, 239, 240, 242, 244, 255, 257
interface, 108, 139, 202, 203, 221, 234
intrinsic, 3, 25, 138, 139, 150, 174, 192
Investigations, 194
iodine, 165, 168, 171, 183, 203
Iodine, 180
Index 272
ionic, ix, 5, 7, 14, 18, 50, 52, 53, 57, 60, 129,
130, 131, 132, 138, 139, 143, 152, 153, 157,
161, 162, 165, 174, 175, 184, 185, 215, 216,
217, 228, 239, 240, 241, 246, 260
ionic liquids, ix, 157, 174, 175, 184, 185, 215,
217, 241
ionization, 113, 240
ions, 3, 6, 10, 11, 17, 21, 22, 23, 27, 45, 47, 48,
131
IR, 200, 238, 241, 242, 246, 247, 248, 249, 250,
251, 252, 257
IR spectra, 18, 238
IR spectroscopy, 241, 242, 246, 247, 248, 249,
250, 251, 252
Iran, 1
iron, 15, 16, 25, 36, 37, 38, 39, 52, 108, 112, 233,
250
isolation, 77, 170, 220, 228, 258
isothermal, 77
Italy, 201, 208
J
Japan, 199
Japanese, 21, 34
Jun, 55
Jung, 12, 51, 52
K
KBr, 222, 228
ketones, ix, 106, 109, 110, 112, 113, 114, 115,
116, 167, 169, 171, 172, 174, 183, 185
kinetics, ix, 2, 75, 129, 130, 131, 138, 141, 143,
203
KOH, 20, 113, 173
Korean, 126
L
laboratory studies, vii, 63, 88, 100
lactams, 168, 182
lamellae, 59
lamellar, 111
Langmuir, 50, 51, 56, 60, 260, 262
lanthanide, 21, 22, 40, 41, 59
lanthanum, 61
lattice, 17, 20, 222, 224, 233
Legionella, 209
Legionella pneumophila, 209
lesions, ix, 189, 192, 196, 197, 198
lifetime, 108, 139
ligand, 22, 61, 163, 164, 180
ligands, viii, 27, 48, 105, 106, 119, 175
light scattering, 14, 254
limitation, 84
limitations, vii, viii, 1, 63, 87, 92, 94, 100, 116,
182, 190
linear, ix, 44, 66, 129, 130, 136, 139, 141, 143,
152, 195, 255
linear dependence, 136
lipid, 165
lipid peroxidation, 165
liposome, 194
liquid chromatography, 214
liquid interfaces, 109
liquid phase, 32, 75, 76, 109, 130, 140, 173, 206
liquids, viii, ix, 63, 64, 72, 83, 97, 98, 102, 103,
108, 140, 157, 160, 172, 174, 184, 185, 215,
217, 231, 241, 260, 261
lithium, 34, 57, 233
London, 102, 120, 121, 155, 209, 210
low-intensity, 66, 195, 199
low-level, 194, 198, 199
low-temperature, 35, 59
luminescence, 17, 23, 59
lymphoma, 199
lysozyme, 240, 260
M
maghemite, 27, 56
magnesium, 19, 22, 112, 216
magnetic, 3, 8, 17, 24, 26, 27, 31, 32, 36, 38, 56,
57, 94
magnetic field, 26, 27, 31, 38
magnetic properties, 17, 24, 26, 31, 32, 36
magnetic resonance, 24
magnetic resonance imaging, 24
magnetite, 16, 25, 26, 27, 38, 52, 55
magnetization, 25, 26, 36, 38, 55
manganese, 17, 33, 34, 53, 57, 114
Manganese, 16, 114
mass spectrometry, 214, 220, 246
mass transfer, 162, 172
matrix, 27, 31, 32, 51, 206
MDR, 194
measurement, 38, 49, 82, 94, 158, 260
measures, 96
mechanical behavior, 228
mechanical energy, 83
mechanical stress, 64, 83, 85, 204
media, 9, 44, 67, 107, 108, 110, 116, 134, 147,
149, 153, 201, 216, 225, 262
Index 273
medical diagnostics, 129
medicine, 159
melanoma, 194, 200
melting, 26, 31, 140, 204
membrane permeability, 211
mercury, 19, 47, 53, 60
mesoporous materials, 2
metal carbides, vii, 2
metal hydroxides, 22
metal ions, 11, 23, 27
metal nanoparticles, 3, 27, 56, 57
metal oxide, vii, 2, 32, 35
metal oxides, vii, 2
metals, vii, 2, 3, 8, 27, 56, 107, 110, 159, 168
metastasis, 194, 200
metastatic, 194, 196, 199
methanol, 9, 10, 26, 27, 32, 134, 146, 150, 151,
165, 175, 235, 242, 243
methyl group, 215
methyl methacrylate, 35, 238
methylene, 18, 167, 169, 172, 181, 183, 221
methylene chloride, 221
mice, 194, 195, 199, 200
micelles, 194, 195, 199, 200, 241
microbial, 202
microcirculation, 196
microemulsion, 55
microorganisms, 31, 204, 205, 206, 207
microscope, 94, 222, 241
microscopy, 222, 224, 226, 229, 234, 247, 250,
261, 263
microspheres, 12, 38, 51
microstructures, 14
microwave, 54, 56, 60, 107, 162, 173, 175, 178,
184, 185, 186, 221, 228, 255
microwaves, 221
migration, 194, 199, 246
mirror, 137
mitochondria, 196
mitochondrial, 196, 200
mixing, 137, 160, 236, 249
MMA, 35, 238
mobility, 226
modalities, 196
modality, ix, 189, 190, 192, 195, 196, 198
models, 66, 87, 134, 199, 200
modulus, 36, 85
moieties, 30
moisture, 109, 215, 221
molar ratio, 5, 6, 8, 9, 20, 21, 32, 112, 113
molar volume, 134
mole, 9, 134, 137
molecular structure, ix, 189, 196, 198
molecular weight, 238
molecules, vii, 1, 2, 5, 17, 108, 130, 134, 139,
140, 142, 150, 160, 161, 190, 192, 194, 196,
201, 213, 218, 226, 237
molybdenum, 19
monomer, 6, 31, 32, 43
morphological, 45, 46, 56
morphology, vii, 1, 2, 3, 7, 8, 10, 11, 12, 14, 15,
16, 19, 21, 36, 37, 41, 42, 43, 44, 52, 55, 56,
233, 250, 251, 261
movement, 66, 69, 70, 73, 75, 76, 78, 81
MS, 27, 218, 219, 226, 227
multidrug resistance, 199
multiwalled carbon nanotubes, 34, 260, 262, 263
N
nanobelts, 4, 5, 48, 50, 60, 61
nanocapsules, 245
nanocatalyst, 35
nanocomposites, vii, 2, 10, 25, 27, 29, 31, 32, 34,
35, 54, 56, 57, 242
Nanocomposites, 25, 27, 30
nanocrystal, 42, 224
nanocrystalline, 18, 24, 36, 50, 52, 53, 54, 55, 58,
60, 61, 262
nanocrystals, 6, 7, 12, 16, 18, 21, 22, 23, 25, 31,
40, 42, 47, 55, 58, 60, 61, 224
Nanocrystals, 54
nanocubes, 17, 46, 60
nanofibers, 43, 44, 59
nanomaterials, 2, 49, 60, 129, 227
nanometer, 24, 28, 51
nanometers, 48, 221
nanoribbons, 14
nanorods, 3, 4, 6, 8, 12, 13, 18, 20, 21, 23, 24, 28,
36, 40, 41, 42, 46, 47, 48, 50, 51, 52, 53, 55,
58, 59, 60, 61
nanosheets, 40, 235, 259
nanostructured materials, 2
nanostructures, 3, 7, 8, 10, 12, 13, 14, 22, 41, 42,
43, 44, 46, 48, 50, 51, 53, 59, 60, 61, 258
Nanostructures, 46, 59
nanotechnology, vii, 1
nanotube, 7, 34, 35, 43, 58, 235, 237, 239, 256,
258, 259, 260, 261, 262, 263
nanotube films, 260
nanowires, 7, 12, 14, 43, 46, 50, 60, 234, 258
Nanowires, 52, 59
naphthalene, 178, 235
natural, viii, 29, 105, 106, 164, 210
Nd, 21, 40, 41, 54
neck, 99, 100
Index 274
necrosis, 190, 192, 196, 197
New York, iii, iv, 63, 102, 103, 120, 121, 126,
153, 154, 156, 209
Ni, 24, 52, 59, 107, 155, 177, 232
nickel, 112, 175
nitrate, 6, 7, 10, 18, 22, 25, 29, 48, 50, 165, 169,
180
nitric acid, 168, 176, 185, 226, 235, 241, 242,
244, 247, 248, 250, 251, 256, 257, 260
nitrobenzene, 27
nitrogen, 24, 48, 79, 96, 135, 203
NMR, 112, 113, 115, 117, 118, 140, 219, 226
NO, 14, 35, 52
noble metals, 3, 27, 56
non-destructive, 159
non-thermal, 218
non-uniform, 72, 160
normal, 17, 78, 79, 80, 81, 94, 140, 183, 190, 191
normal conditions, 81
novel materials, 49
nucleation, 17, 21, 23, 27, 38, 43, 45, 109, 130,
232
nuclei, 2, 6, 27, 68, 72, 74, 75, 76, 191, 194
nucleus, 16, 26, 31, 70, 169
numerical analysis, 66
O
octane, 169
o-dichlorobenzene, 232, 237, 250
oil, 9, 24, 103, 157
oils, 98, 173
olefins, 106, 174, 183, 218
oligomer, 237
olive, 18
onion, 234
optical, 3, 23, 44, 60, 159, 221, 222, 237, 241
optical microscopy, 222
optical properties, 23, 60
optical storage, 44
optics, 3, 42, 213
optimization, viii, 64, 114, 115, 262
optoelectronic, 3, 44, 49
optoelectronic devices, 44
optoelectronics, 42
organic matter, 204
organic solvent, 43, 108, 110, 130, 132, 133, 134,
152, 173, 185, 236, 237, 238, 249, 258, 259,
260
organic solvents, 43, 110, 132, 133, 134, 152,
236, 237, 238, 258, 260
organometallic, 109
Organometallic, 184
oscillation, 70, 72, 76, 94, 96, 97, 98
ovarian cancer, 192, 193, 194, 197, 198, 199, 200
ovarian cancers, 193, 199
overtime, 238
oxidants, 217, 218, 228
oxidation, ix, x, 9, 10, 15, 18, 19, 34, 36, 51, 57,
119, 135, 138, 157, 160, 173, 176, 184, 185,
204, 208, 213, 218, 228, 231, 234, 236, 239,
243, 244, 247, 248, 249, 250, 251, 252, 254,
262, 263
oxidation products, 135
oxidative, 234, 235, 236, 241, 245, 247, 248, 262
oxidative damage, 235
oxide, 14, 15, 16, 19, 20, 29, 33, 34, 37, 52, 53,
57, 58, 61, 217, 218, 234, 235, 246, 259
oxide nanoparticles, 16, 29, 52, 53
oxides, 2, 9, 12, 15, 19, 20, 217, 218, 228
oxygen, 9, 33, 50, 110, 119, 172, 176, 183, 203,
242, 257
P
paclitaxel, 194, 197
PAHs, 35
palladium, 6, 27, 34, 50, 57, 163, 171, 175
palliative, ix, 189, 197, 198
PANI, 32, 33, 35, 43, 44
parameter, 66, 143, 144, 222, 224
particles, vii, 1, 3, 4, 5, 7, 10, 11, 12, 15, 17, 18,
19, 20, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33,
36, 37, 38, 43, 47, 48, 51, 54, 57, 58, 70, 81,
160, 195, 203, 204, 208, 222, 224, 226, 232,
233, 234, 235, 236, 238, 246, 247, 250, 259
pathways, 196, 216, 254
patients, 194, 200
Pb, 19, 21, 22, 23, 24, 45, 46, 47, 48
PbS, 44, 45, 46, 60
PCT, 101
periodicity, 262
permeability, 211
permeabilization, 196
permit, viii, 64, 66, 83, 85, 98, 107, 140
peroxide, 18, 205, 234
perturbation, 135, 138, 140, 141, 146, 150
perturbations, 69
pesticides, 106
P-glycoprotein, 192
pH, 3, 4, 17, 20, 21, 23, 27, 34, 35, 41, 46, 48, 50,
107, 116, 132, 135, 206, 240, 244, 254, 260
pH values, 23
pharmaceuticals, 164
pharmacogenetics, 199
pharmacokinetics, 199
Index 275
phase-transfer catalysis, 184
phenol, 171, 176
phenotype, 194
phenyl esters, 178, 186
phosphate, 30, 31, 40, 56
phosphonates, 178, 186
phosphors, 54
photocatalysis, 18, 209, 257
photocatalysts, 53
Photocatalytic, 18
photochemical, 22, 176, 185
photodegradation, 256
photographs, 66, 98, 99
photoluminescence, 17, 23, 40, 42, 51, 53, 57
Photoluminescence, 22
photolysis, 215
photonic, 36
photonic crystals, 36
photons, 160
photooxidation, 176
photovoltaic, 44
physical environment, 130
physical properties, vii, x, 1, 231, 232, 260
physicochemical, 136
physicochemical properties, 136
physics, 120
piezoelectric, 83, 84, 100, 159
planar, 4, 67, 85, 88
plastic, 38, 42, 158
plastics, 84, 106
platinum, 10, 11, 28, 29, 32, 38, 51, 57, 250
PMMA, 30, 56, 245
polarity, 139, 146, 147, 237
pollutant, 20, 256
pollutants, 263
pollution, 171
poly(vinylpyrrolidone), 4, 6
polyacrylamide, 31, 56
polyaniline, 32, 43, 44, 57, 59
polycarbonate, 242
polycrystalline, 23, 35, 41
polycyclic aromatic hydrocarbon, 35
polyethylene, 6, 11, 21, 46, 48, 173
polyimide, 238
polyimides, 238
polymer, 11, 23, 31, 32, 44, 46, 47, 48, 57, 61,
98, 232, 237, 238, 239, 240, 255, 258, 261,
263
polymer chains, 31, 239
polymer melts, 98
polymer nanocomposites, 232, 258
polymerase, 193
polymerase chain reaction, 193
polymeric materials, 2, 14
polymerization, 31, 32, 44, 56, 57, 237, 238
polymerization temperature, 44
polymers, 2, 11, 43, 44, 47, 48, 49, 53, 237, 255
polymethylmethacrylate, 30, 245
polypropylene, 57
polysaccharide, 239
polystyrene, 31
polyvinyl alcohol, 256
polyvinylpyrrolidone, 60
poor, 133, 165, 172, 194
poor health, 194
population, 65, 101
pore, 16, 28, 191, 256
pores, 16, 28, 29, 75
porosity, 56
porous, 14, 28, 29, 31, 42, 51, 52, 57, 75, 97, 103,
170, 191
potassium, 10, 163, 166, 168, 172, 173, 177, 179,
180, 184, 203, 248, 249
powder, viii, 9, 18, 19, 24, 25, 26, 43, 47, 48, 53,
55, 60, 61, 82, 105, 109, 110, 111, 112, 166,
222, 223, 232
powders, 18, 21, 24, 47, 53, 54, 55, 112, 258
power, viii, ix, 2, 3, 5, 7, 9, 10, 12, 14, 25, 31, 33,
34, 38, 42, 44, 46, 57, 64, 83, 84, 85, 86, 87,
88, 94, 97, 98, 100, 101, 102, 106, 108, 116,
129, 134, 136, 141, 145, 158, 160, 161, 201,
202, 205, 208, 210, 219, 241
PPO, 23
precipitation, 22, 40, 59, 221, 222, 224, 228
pressure, 2, 9, 17, 49, 68, 69, 70, 71, 72, 73, 75,
76, 77, 78, 79, 80, 81, 86, 87, 94, 96, 98, 101,
108, 140, 147, 160, 161, 174, 191, 201, 203,
204, 206, 208, 213, 214
pristine, 29, 31, 238, 242, 256, 259, 260
probability, 131, 250
probe, 9, 24, 42, 43, 48, 153, 161, 176, 205, 206,
215, 240, 252, 263
production, vii, 1, 12, 18, 100, 106, 108, 110,
159, 201, 214, 215, 218, 219, 221, 222, 227,
228, 229, 232, 258
propagation, 67, 69, 158, 160, 161
propane, 252
property, iv, 14, 57, 60, 191
Propranolol, 106
propylene, 246
protease inhibitors, viii, 105, 106
protection, 210
protein, 192, 240
protocol, 24, 168, 171, 172, 176
pseudo, 138, 205
Pseudomonas, 207
Index 276
Pseudomonas aeruginosa, 207
PT, 173
PTCs, 108, 173
PTFE, 224
pure water, 18, 43, 112, 136, 137, 139, 141, 142,
146, 147, 151
purification, x, 174, 220, 231, 232, 235, 244, 257,
259, 261, 262
PVP, 4, 6, 10, 31, 46, 47, 179, 239
pyrene, 235
pyrolysis, 3, 215, 245, 258, 261
pyromellitic dianhydride, 238
Q
QSAR, 156
quantum, 40, 44, 48, 61
quantum dot, 61
quantum yields, 40
quaternary ammonium, 172
quaternary ammonium salts, 172
R
radiation, 17, 30, 35, 49, 64, 66, 67, 77, 79, 81,
83, 85, 91, 92, 94, 97, 98, 169, 192, 199, 203,
208, 211, 228
radical formation, 2, 138, 211, 231
radical mechanism, 165
radical reactions, 107, 114, 203
radius, 2, 44, 68, 69, 70, 73
Raman, 31, 233, 237, 238, 239, 241, 243, 244,
246, 248, 251, 252, 257
Raman spectra, 31
Raman spectroscopy, 233, 237, 239, 241, 243,
244, 246, 248, 251, 257
range, ix, 3, 7, 8, 9, 10, 14, 17, 18, 19, 20, 23, 25,
29, 31, 36, 42, 69, 70, 79, 88, 129, 132, 133,
134, 137, 141, 147, 151, 152, 157, 158, 159,
160, 195, 206, 233, 262
rare earth, 17, 24, 55, 107
Rayleigh, 68, 69, 72, 78, 82, 103
reactant, 22, 174
reactants, 12, 47, 133, 137, 141, 152, 169, 172,
250
reaction mechanism, 47, 130, 144, 152, 153, 170
reaction medium, 138, 152
reaction rate, vii, 1, 19, 47, 49, 131, 134, 135,
136, 141, 142, 146, 147, 152, 153, 159, 162,
169, 172, 176, 177, 178, 254
reaction temperature, 17, 34, 44, 140, 162
reaction time, viii, 105, 107, 110, 112, 113, 114,
116, 158, 165, 166, 168, 170, 171, 173, 174,
175, 218, 227, 249
reactivity, viii, 105, 106, 107, 111, 112, 114, 117,
120, 129, 132, 133, 134, 145, 151, 158, 166,
252
reagent, viii, 22, 23, 105, 107, 109, 110, 111,
114, 115, 138, 141, 142, 146, 150, 158
reagents, viii, ix, 8, 105, 107, 108, 109, 111, 119,
120, 129, 130, 134, 137, 142, 143, 147, 150,
151, 152, 153
recrystallization, 221
recycling, 111, 175
refractory, 192, 198
regioselectivity, 171, 175
relationship, 73, 80, 88, 144, 147, 152
relationships, ix, 80, 129, 143
relaxation, 55, 140, 158
relaxation process, 140
relaxation processes, 140
relaxation time, 140
relaxation times, 140
reliability, 85, 130, 132
remediation, 204, 256, 263
resistance, 192, 193, 198, 199
resolution, 33, 120, 214, 234
restructuring, ix, 189
retardation, 71, 130, 141, 142, 153
rhodium, 34
rings, 141, 142, 234
RNA, 211
room temperature, 6, 9, 17, 20, 21, 35, 38, 46, 61,
79, 112, 113, 116, 117, 161, 166, 171, 172,
173, 175, 177, 185, 205, 218, 219, 220, 222,
233, 235, 240, 241, 254
room-temperature, 14
Royal Society, 120
ruthenium, 7, 10, 11, 50, 51, 184
rutile, 18, 53, 256
S
Saccharomyces cerevisiae, 207, 211
safety, vii, ix, 1, 133, 189, 195, 198
salt, 7, 40, 172, 180
salts, 114, 163, 172, 174, 179, 184
sample, 17, 21, 24, 36, 38, 42, 77, 140, 158, 221,
235, 236, 238, 244
sand, 157, 169
saturation, 25, 26, 35, 36, 85
scanning electron microscopy, 236
scattering, 14, 249, 254
SCW, 139
Index 277
SDBS, 240
SDS, 5, 7, 10, 11, 31, 32, 42, 236, 239, 241, 242,
246
SDT, 191
search, 110, 247
sedimentation, 238, 240, 254
selected area electron diffraction, 8, 35
selecting, 88, 98
selectivity, ix, 9, 10, 28, 107, 111, 157, 158, 170,
175, 176, 177
SEM, 5, 13, 15, 19, 29, 37, 41, 222, 223, 236,
242, 244, 245, 251
semiconductor, 18, 44
semiconductors, 2, 12, 44
sensors, 9, 20, 49
separation, x, 56, 111, 221, 231, 261
series, ii, 25, 42, 79, 91, 98, 149
serum, 14, 52, 196
serum albumin, 14, 52
shape, vii, 1, 2, 3, 4, 10, 12, 21, 36, 40, 46, 51,
66, 72, 77, 84, 87, 100, 198, 233
shear, 108, 191, 205
Shell, 10, 36, 40
shock, vii, viii, 2, 49, 63, 67, 71, 72, 73, 75, 78,
81, 83, 108, 131, 140, 160, 161, 202, 203, 204,
205
shock waves, 67, 72, 73, 131, 140, 160, 161, 202,
204
silica, 38, 40, 43, 51, 220, 232
silicon, 43, 234, 258
silver, 7, 8, 10, 25, 26, 29, 31, 32, 50, 51, 55, 56,
57, 58, 60
similarity, 146, 152
simulation, 66, 102
simulations, 102
single crystals, 40, 222
single walled carbon nanotubes, 258
single-crystalline, 41, 50, 59
single-wall carbon nanotubes, 258, 259, 261
SiO2, 38, 39, 40, 58
sites, 2, 9, 31, 34, 38, 138, 139, 140, 142, 245,
247
sludge, 153, 204
Sm, 21, 40, 41, 54, 107
snooker, 236
sodium, 5, 10, 14, 22, 24, 32, 33, 42, 45, 172,
236, 239, 240, 243, 246, 248
sodium dodecyl sulfate (SDS), 32, 236, 239
sodium hydroxide, 172, 248
solar, 18, 44, 208
solar cell, 18, 44
solar cells, 18, 44
solubility, 133, 213, 219
solvation, ix, 129, 130, 132, 133, 134, 135, 138,
139, 145, 146, 147, 149, 150, 151, 152, 153
solvent molecules, 134, 237
solvents, ix, 7, 47, 110, 129, 130, 133, 134, 135,
137, 138, 140, 143, 144, 145, 146, 150, 152,
174, 177, 216, 220, 226, 236, 237, 238, 243,
244, 259, 261
sonodynamic therapy, 192
soot, 220, 235, 236
sound speed, 67, 78
spatial, 66, 67, 72, 73, 77, 139
species, 3, 15, 23, 29, 119, 130, 131, 133, 134,
136, 139, 140, 147, 153, 161, 172, 191, 209,
210, 227
specific surface, 18, 20, 28, 34, 257
specificity, 227
spectrophotometric, 132
spectrophotometry, 218, 219
spectroscopy, 16, 220, 237, 239, 241, 242, 244,
246
spectrum, 11, 20, 35, 40, 222, 225, 227, 233, 237
speed, 26, 38, 66, 67, 78, 86, 102, 116, 131, 162,
176, 177, 203, 204, 210, 227
spheres, 39, 40, 45, 58
spin, 140, 203, 210, 211
spindle, 14, 15, 21, 22, 23, 43, 52
stability, 21, 35, 48, 67, 222, 226, 236, 240, 242,
245, 260
stabilization, ix, 6, 129, 130, 141, 142, 144, 146,
147, 153
stabilize, 134, 146
Staphylococcus, 29
Staphylococcus aureus, 29
steric, 111, 113, 119, 241
storage, vii, 2, 24, 44, 49
storageError! Bookmark not defined. media, 44
strain, 17, 91, 92, 93, 95
strains, 89, 91
strategies, 192, 198, 199
streams, ix, 157
strength, 36, 64, 66, 67, 68, 76, 83, 85, 86, 91, 94,
250, 252
stress, 83, 85, 86, 88, 204
stretching, 248, 255
stroke, 200
strontium, 25, 55
structural defect, 222
structural defects, 222
substitution, 169, 171, 172, 248
substitution reaction, 172, 248
substrates, 13, 111, 112, 113, 114, 131, 144, 172
sulfate, 10, 19, 32, 42, 236, 239, 247, 262
sulfonamides, 178, 186
Index 278
sulfur, 27, 30, 40, 56
sulfuric acid, 177, 186, 226, 234, 242, 244, 247,
250, 251
Sun, 52, 53, 54, 58, 59, 60, 121, 122, 123, 126,
184, 258, 261
supercritical, 138, 139
superoxide, 173, 184
supramolecular, 48, 61, 260
surface area, vii, 1, 18, 20, 22, 27, 34, 54, 97,
109, 111, 203, 256
surface energy, 232
surface modification, x, 231
surfactant, 4, 10, 17, 21, 31, 41, 42, 45, 54, 238,
239, 240, 241, 246, 249, 260
surfactants, x, 10, 231, 236, 246, 258
surgical, 196, 200
survival, 192, 199
survival rate, 192
surviving, 192
susceptibility, 151, 152
suspensions, x, 210, 227, 231, 236, 238, 241, 254
swelling, 111
SWNTs, 247, 260
symmetry, 76, 252
synergistic, 199, 256
synergistic effect, 256
systems, vii, viii, ix, 2, 63, 64, 84, 85, 91, 98,
100, 101, 105, 107, 112, 114, 116, 117, 120,
132, 134, 135, 136, 137, 138, 142, 144, 150,
151, 152, 153, 157, 161, 162, 174, 179, 204,
205, 206, 207, 233
T
tar, 198
TCC, 195
technology, 24, 81, 97, 106, 107, 108, 129, 153,
179
Tehran, 1
tellurium, 6, 47, 50, 107
TEM, 4, 6, 8, 10, 11, 13, 15, 16, 20, 23, 25, 26,
27, 28, 30, 32, 33, 34, 35, 36, 37, 38, 39, 40,
41, 42, 44, 45, 226, 232, 233, 234, 235, 238,
239, 242, 243, 244, 245, 246, 247, 248, 249,
250, 256
temperature dependence, 25
temperature gradient, 158
tensile, 66, 67, 68, 76
tensile strength, 66, 67, 68, 76
TEOS, 38
tetrahydrofuran, 7, 9, 218, 234
TGA, 246, 252
therapeutic goal, 190
therapy, ix, 129, 189, 190, 191, 192, 194, 196,
197, 198, 199
thermal decomposition, 36, 252
thermal degradation, 31
thermal energy, 36, 157
thermal load, 83
thermal stability, 35, 48, 245
thermal treatment, 42
thermodynamic, 107, 130, 147, 149
thermodynamic parameters, 147
thermogravimetric, 246
thermogravimetric analysis, 246
thermolysis, 215
thin film, 17, 30
three-dimensional, 134
threshold, ix, 67, 75, 76, 77, 80, 81, 87, 191, 194,
195, 196, 197, 201
time periods, 24
tin, 6, 19, 34, 50, 57, 112, 183, 250, 262
tin oxide, 19, 34, 57
TiO
2
, 18, 53, 209, 256, 257, 263
tissue, 109, 189, 190, 191, 195, 197
titanium, 18, 25, 36, 43, 46, 48, 53, 94, 96, 107,
115, 116, 117, 119, 132, 206, 214, 256
Titanium, 36, 58, 115
titanium dioxide, 18, 53, 206, 256
Tokyo, 103
tolerance, 192, 194
toluene, 18, 36, 220, 224, 238, 242, 244, 245
total energy, 67
toxic, viii, 105, 107, 110, 171, 202
toxicities, 189, 190
toxicity, 190, 191
trans, 16, 175, 176, 177
transcription, 193
transducer, viii, 63, 64, 65, 83, 84, 85, 86, 87, 88,
94, 97, 98, 100, 101, 159, 161, 197, 208
transesterification, 103
transfer, viii, ix, 20, 63, 64, 98, 106, 108, 109,
157, 160, 161, 165, 172, 173, 176, 183, 184,
226, 244, 248
transference, viii, 64, 85, 86
transition, 31, 72, 74, 75, 81, 83, 107, 134, 141,
146, 149
translational, 140, 160
transmission electron microscopy, 233
transparency, 82
transparent, 7, 14, 224
transport, 160, 192
transport processes, 160
transportation, 190
treatment methods, 261
trifluoroacetic acid, 165, 252
Index 279
tumor, 193, 194, 197, 200
tumor growth, 194
tumors, 189, 190, 198, 199
tumour, 199
tumours, 198
tungstates, 24
tungsten, 34, 57
tungsten carbide, 34, 57
tunneling, 250
Turbulent, 204
two-dimensional, 47, 48, 56, 59
U
UK, 156
ultrasonic vibrations, 83
ultrasonic waves, 10, 14, 19, 43, 140, 158, 165
ultrasonography, 195
ultraviolet, 206, 208, 210, 263
ultraviolet irradiation, 206, 210
uniform, vii, 1, 15, 29, 35, 38, 40, 44, 47, 49, 51,
72, 85, 160, 162, 244, 251
urea, 22, 25, 42, 164, 165
UV, 18, 20, 24, 54, 208, 209, 211, 218, 219, 220,
237, 239, 240, 241, 246, 256, 260
UV light, 24, 256
UV-radiation, 211
UV-Visible spectroscopy, 260
V
vacuum, 38, 221, 222, 233
values, 23, 64, 71, 72, 73, 75, 76, 78, 79, 80, 82,
83, 87, 88, 94, 96, 97, 98, 139, 147, 149, 150,
152
van der Waals, 222, 234, 238, 240, 244, 257
van der Waals forces, 222, 238
vanadium, 14, 15, 52, 114
vanadium oxides, 15
vapor, viii, 2, 63, 147, 214, 222
variation, 91, 147, 160
vascular endothelial growth factor, 200
vegetable oil, 173, 184
velocity, 67, 68, 69, 70, 72, 73, 75, 76, 77, 78, 79,
80, 81, 82, 85, 86, 91, 92, 93, 95, 96
vibration, 64, 67, 84, 85, 87, 89, 91, 94, 96, 161,
205, 233, 260
violent, 110, 202
viscosity, 98, 137
visible, 20, 21, 53, 54, 65, 238
VOCl3, 114
volatility, 77, 161
W
wastewater, 103, 204, 208, 209, 210, 263
wastewater treatment, 103, 204, 208, 263
water clusters, 145
water vapour, 203
water-soluble, 229, 238
wave number, 89
weak interaction, 138, 153
workers, 47, 165, 168, 176, 177, 203, 205, 208
X
xenografts, 195
XPS, 31, 35, 248, 250, 251, 252, 254
X-ray analysis, 11
X-ray diffraction, 48, 134, 137, 222, 223
X-Ray diffraction, 256
XRD, 14, 18, 19, 27, 30, 40, 55, 221
xylene, 43, 224, 232, 242
Y
yield, ix, 2, 36, 57, 110, 111, 112, 113, 114, 115,
116, 117, 118, 119, 157, 164, 165, 168, 169,
171, 172, 173, 174, 175, 182, 196, 227, 233,
234, 235
yttria-stabilized zirconia, 28
Z
zeolites, 168, 182
zeta potential, 254
zinc, 12, 24, 55, 110, 111, 112, 168, 174, 176,
184, 185, 206
Zinc, 22, 55, 110, 111, 174
zirconia, 28, 29, 56
zirconium, 31, 56
Zn, 12, 13, 22, 24, 107, 110, 111, 114, 115, 116,
117, 118, 174, 216, 232
ZnO, 12, 13, 14, 28, 29, 51, 52, 56, 232
ZnO nanorods, 12, 13, 28, 51, 52
ZnO nanostructures, 12, 13, 14, 51

CHEMICAL ENGINEERING METHODS AND TECHNOLOGY

SONOCHEMISTRY: THEORY, REACTIONS, SYNTHESES, AND APPLICATIONS

No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in rendering legal, medical or any other professional services.

CHEMICAL ENGINEERING METHODS AND TECHNOLOGY
Additional books in this series can be found on Nova‘s website under the Series tab.

Additional E-books in this series can be found on Nova‘s website under the E-books tab.

CHEMICAL ENGINEERING METHODS AND TECHNOLOGY

SONOCHEMISTRY: THEORY, REACTIONS, SYNTHESES, AND APPLICATIONS

FILIP M. NOWAK
EDITOR

Nova Science Publishers, Inc.
New York

Copyright © 2010 by Nova Science Publishers, Inc.
All rights reserved. No part of this book may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying, recording or otherwise without the written permission of the Publisher. For permission to use material from this book please contact us: Telephone 631-231-7269; Fax 631-231-8175 Web Site: http://www.novapublishers.com NOTICE TO THE READER The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained in this book. The Publisher shall not be liable for any special, consequential, or exemplary damages resulting, in whole or in part, from the readers‘ use of, or reliance upon, this material. Any parts of this book based on government reports are so indicated and copyright is claimed for those parts to the extent applicable to compilations of such works. Independent verification should be sought for any data, advice or recommendations contained in this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage to persons or property arising from any methods, products, instructions, ideas or otherwise contained in this publication. This publication is designed to provide accurate and authoritative information with regard to the subject matter covered herein. It is sold with the clear understanding that the Publisher is not engaged in rendering legal or any other professional services. If legal or any other expert assistance is required, the services of a competent person should be sought. FROM A DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS. LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA Sonochemistry : theory, reactions, syntheses, and applications / [edited by] Filip M. Nowak. p. cm. Includes index. ISBN 978-1-62100-147-8 (eBook) 1. Sonochemistry. I. Nowak, Filip M. QD801.S665 2009 660'.2842--dc22 2010025362

Published by Nova Science Publishers, Inc.  New York

Krishna M. F. Gaquere-Parker and Cass D. Bhanage Sonochemotherapy Against Cancers Tinghe Yu and Yi Zhang Application of Ultrasound for Water Disinfection Processes Vincenzo Naddeo. Gaquere-Parker and Cass D. Deshmukh and Bhalchandra M. Ghasemi Industrial-Scale Processing of Liquids by High-Intensity Acoustic Cavitation: The Underlying Theory and Ultrasonic Equipment Design Principles Alexey S. Parker Application of Ultrasounds to Carbon Nanotubes Anne C. Qureshi. Peshkovsky and Sergei L.CONTENTS Preface Chapter 1 Sonochemistry: A Suitable Method for Synthesis of NanoStructured Materials M. Siim Salmar and Jaak Järv Synthetic Methodologies Using Sonincation Techniques Ziyauddin S. Mousavi and S. Peshkovsky Some Applications of Ultrasound Irradiation in Pinacol Coupling of Carbonyl Compounds Zhi-Ping Lin and Ji-Tai Li Ultrasound and Hydrophobic Interactions in Solutions Ants Tuulmets. Parker vii 1 Chapter 2 63 Chapter 3 105 129 157 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Chapter 8 189 201 213 231 265 Chapter 9 Index . Milena Landi and Vincenzo Belgiorno Use Of Ultrasonication in the Production and Reaction of C60 and C70 Fullerenes Anne C.

.

metal carbides. Sonochemistry uses the ultrasonic irradiation to induce the formation of particles with smaller size and high surface area. During the ultrasonic irradiation. but the growth of the number of researches and published articles in the field of sonochemistry during the recent years shows a large interest and attempt to apply sonochemistry in nanotechnology. size and properties. This chapter is planned to deal with the application of sonochemistry for the synthesis of various nano-structured materials such as metals. The effect of different ultrasonic parameters on the prepared structures including their size. ultrasound irradiation in pinacol coupling of carbonyl compounds. Chapter 1 . This book reviews research data in the study of sonochemistry including the application of sonochemistry for the synthesis of various nanostructured materials. purity and some other chemical and physical properties of such produced materials has been the scope of the researchers recently. Because of its importance. and high purity of prepared nano-sized materials are some of the main advantage of sonochemistry. The implosive collapse of the bubbles generates a localized hotspot or shock wave formation within the gas phase of the collapsing bubbles (The hot-spot theory).PREFACE The study of sonochemistry is concerned with understanding the effect of sonic waves and wave properties on chemical systems. as well as the use of ultrasound to enhance anticancer agents in sonochemotherapy and the ultrasound-enhanced synthesis and chemical modification of fullerenes. Also. growth and implosive collapse of bubbles in a liquid. e.A multitude of useful physical and chemical processes promoted by ultrasonic cavitation have been described in laboratory studies. catalysis. narrow size distribution. Rapid reaction rate. size. sonochemistry has experienced a large promotion in various fields concerned with production of new nano-structured materials and improvement of their properties during the recent years. sonochemistry has been employed extensively in the synthesis of nano-structured materials. some applications of prepared nano-materials are introduced. biosensor and electrooxidation. ultrasound and hydrophobic interactions in solutions. chalcogenides and nanocomposites with unique properties. Chapter 2 . Sonochemistry uses the powerful ultrasound irradiation (20 kHz to 10 MHz) to induce chemical reaction of molecules. Industrial-scale . controllable reaction conditions. electrochemical energy storage. the acoustic cavitations will occur which consist of the formation. metal oxides. The improvement of shape.Recently.g. However. simplicity and safety of the technique as well as the uniform shape. morphology and properties are investigated. it has encountered limitations in the case of production of some nano-materials with specific morphology.

2-diols. These horns are key to industrial implementation of high-power ultrasound because they permit producing extremely high ultrasonic amplitudes. erythro mixtures of diols are usually obtained from reactions. owing to the formation of a spherical micro-shock wave inside each vapor-gas bubble. and makes it possible to explain some newly discovered properties of acoustic cavitation that occur at extremely high intensities of ultrasound. the pinacol coupling. In some of the described methods. The coupling products can have two newly chiral centers formed. Recent efforts have focused on the development of new reagents and reaction systems to improve the reactivity of the reagents and diastereoselectivity of the products. It was effective in enhancing the reactivity . which provide the impedance matching and can help achieving the transference of all available acoustic energy from transducers into the liquids.  detailed theory of matching acoustic impedances of transducers and cavitating liquids in order to maximize the ultrasonic power transfer efficiency. and were also used as intermediates for the construction of biologically important natural product skeletons and asymmetric ligands for catalytic asymmetric reaction. Generally. One of the most powerful methods for constructing a carbon-carbon bond is the reductive coupling of carbonyl compounds giving 1. been hindered by several technological limitations. 2-Diols obtained in the reaction were very useful synthons for a variety of organic synthesis. 1. In particular.  calculation methodology of ―barbell horns‖. however. efficient reaction conditions have been required to control the stereochemistry of the 1. excess amounts of metal are needed. followed by a detailed description of "shockwave model of acoustic cavitation". which was described in 1859. Conditions which must be fulfilled to ensure effective and continuous operation of an ultrasonic reactor system are provided in this chapter. expose new surface and increase the effective area available for reaction. specifically focusing on:  electromechanical transducer selection principles.2-diols. Nowak implementation of high-intensity ultrasound has. Of these methods. which shows how ultrasonic energy is absorbed in the cavitation region. some of the used reductants are expensive or toxic. with a consequent decrease in particle size. anhydrous conditions and long reaction time are required to get satisfactory yields of the reaction products. making it difficult to directly scale up ultrasonic systems in order to transfer the results of the laboratory studies to the plant floor. Chapter 3 .viii Filip M. the reaction is effected by treatment of carbonyl compounds with an appropriate metal reagent and/or metal complex to give rise to the corresponding alcohols and coupled products. Threo. while the output horn diameters and the resulting liquid processing capacity remain very large. is still a useful tool for the synthesis of vicinal diols. After the theoretical background is laid out.Carbon-carbon bond formation is one of the most important topics in organic synthesis. fundamental practical aspects of industrial-scale ultrasonic equipment design are provided. Sonication can cause metal in the form of a powder particle rupture.  operation principles and calculation methodology of high-amplitude acoustic horns used for the generation of high-intensity acoustic cavitation in liquids. As a consequence.  optimization of the reactor chamber geometry. High-capacity flow-through ultrasonic reactor systems required for commercial-scale processing of liquids can only be properly designed if all energy parameters of the cavitation region are correctly evaluated. pinacol coupling has been employed as a key step in the construction of HIVprotease inhibitors.

It became an exciting new field of research over the past decade. yield and selectivity to the reactions. Some applications date back to the 1920s. especially when sonosensitizer and microbubble are employed. The results are mostly from the author research group. Ultrasound found to provide an alternative to traditional techniques by means of enhancing the rate. The 1950s and 1960s subsequently represented the first extensive sonochemical research years and significant progresses were made throughout them. Michael addition. In these early years. Free radicals due to cavitation have the potentials of restructuring a molecule and changing the conformation. thus the molecular structure and anticancer potency of a cytotoxic agent must be investigated.Sonochemotherpy is the use of ultrasound to enhance anticancer agents. Knoevenagel condensation. Pechmann condensation and effect of ultrasound on phase transfer catalysis. Friedal-Craft acylation. Ullmann coupling reaction. Sonochemistry is the application of ultrasound in chemistry.Ultrasound (US) is a sound wave of a frequency greater than the superior audibility threshold of the human hearing. experiments were often performed without any real knowledge of the fundamental physical background about the US action. Some recent applications of ultrasound in pinacol coupling reactions are reviewed. Mannich type reaction.Ultrasound generates cavitation. ionic liquids and photochemistry are reviewed. The situation changed in the 1980s when a new surge of activity started . Preclinical trials have manifested this modality is effective against cancers including chemoresistant lesions. Baylis-Hillman reaction. and similar kinetic data for the solvolysis of tert-butyl chloride. Sonosensitizers and microbubbles enhance cavitation.Preface ix of metal and favorable for single electron transfer reaction of the aldehydes or ketones with metal to form diols. This review will concentrate on theory. which can be used as a source of energy for a wide range of chemical processes. Claisen-Schmidt condensation. as well as on solvation phenomena in general. Heck reaction. Making the occurrence and level of cavitation under control improves the safety and therapeutic efficacy. compiled from literature. Curtius rearrangement. For the first time the power ultrasound. A potential clinical model for investigating sonochemotherapy is the residual cancer tissues when performing palliative high intensity focused ultrasound treatment. Cavitation collapse produces intense local heating (~5000 K). Some recent applications of ultrasound in organic synthesis. growth. Biginelli reaction. reaction kinetics and linear free-energy relationships were simultaneously exploited to study ionic reactions in water and aqueous-organic binary solvents and the importance of hydrophobic ground-state stabilization of reagents in aqueous solutions was discussed. Sonochemotherapy is a target therapy. Bouveault reaction. and implosive collapse of bubbles in a liquid. reactions and synthetic applications of ultrasound in both homogeneous liquids and in liquid-solid systems. and enormous heating and cooling rates (>109 K/sec)" and liquid jet streams (~400 km/h). This approach has opened novel perspectives for wider understanding of the effect of sonication on chemical reactions in solution. which is "the formation. in which cavitation plays the leading role. such as.Sonochemistry and solution chemistry have been explicitly brought together by analyzing the effect of ultrasound on kinetics of ester hydrolysis and benzoin condensation. measured by the authors. Sonogashira reaction. Chapter 5 . Diels-Alder reaction. Chapter 4 . Chapter 7 . Reformatsky reaction. being a measure to adjust the level of cavitation. Then it was realized that ultrasound power has a great potential for uses in a wide variety of processes in the chemical and allied industries. oxidation-reduction reactions. Suzuki reaction. high pressures (~1000 atm). Chapter 6 .

The effect of sonication on carbon nanotubes suspensions which covers aqueous and organic solutions in the presence of surfactants is discussed with an emphasis being placed on the effect that ultrasounds have on non-covalent interactions between the carbon nanotubes and the components of the suspensions. producing fullerites.In this chapter. Nowak and the use of US as a real tool in chemistry began. providing the role of ultrasound in these processes. Chapter 9 . such as oxidation. and the formation of colloids when the fullerenes are sonicated in various solvent mixtures are detailed. The effect of ultrasounds on the physical properties of the carbon nanotubes. especially the introduction of wall defects is analyzed. the use of ultrasounds on carbon based nanotubes is reviewed with a focus on the English written articles. The improvement obtained by sonicating the reaction mixtures while carrying out traditional organic reactions is discussed. This includes many types of reactions. It was in 1986 that the first ever international symposium on Sonochemistry was held at Warwick University U. Chapter 8 . cycloaddition. . Finally the advantages and shortcomings of sonochemistry described in this chapter are summarized.K. The synthesis of hybrid nanocomposite materials where carbon nanotubes are added as a reinforcement agent via ultrasound-induced assembly is not described in this chapter.x Filip M. A detailed survey of the literature concerning the purification and separation of carbon nanotubes under ultrasounds is provided. The synthesis of carbon nanotubes and their surface modification such as oxidation and covalent functionalization under ultrasounds are reported. The ultrasound-enhanced synthesis and chemical modification of fullerenes are detailed. showing a possible trend in the direction of future research in this field. the use of ultrasounds on fullerenes (C60 and C70) and fullerene derivatives is described.In this chapter. The focus is on the articles reporting the ultrasoundpromoted treatment of these nanoparticles written in English. reduction and amination. Also the ultrasound-enhanced crystallization of fullerenes.

Tarbiat Modares University. Box 14115175. mfmousavi@yahoo.ac. The University of Qom. Sonochemistry uses the ultrasonic irradiation to induce the formation of particles with smaller size and high surface area [1]. sonochemistry has been employed extensively in the synthesis of nanostructured materials.In: Sonochemistry: Theory. Tehran. growth and implosive collapse of bubbles in a liquid. Tarbiat Modares University. However. .: +98 21 82883474/9. Department of Chemistry. Rapid reaction rate. Ghasemi Department of Chemistry. Mousavi1 and S. Because of its importance. the acoustic cavitations will occur which consist of the formation. controllable reaction conditions. Chapter 1 SONOCHEMISTRY: A SUITABLE METHOD FOR SYNTHESIS OF NANO-STRUCTURED MATERIALS M. purity and some other chemical and physical properties of such produced materials has been the scope of the researchers recently [2]. narrow size distribution.F. and high purity of prepared nano-sized materials are some of the main advantage of sonochemistry. Iran 1 ABSTRACT Recently. size and properties. but the growth of the number of researches and published articles in the field of sonochemistry during the recent years shows a large interest and attempt to apply sonochemistry in nanotechnology. Reactions. During the ultrasonic irradiation. fax: +98 21 82883455. simplicity and safety of the technique as well as the uniform shape. Sonochemistry uses the powerful ultrasound irradiation (20 kHz to 10 MHz) to induce chemical reaction of molecules. M. sonochemistry has experienced a large promotion in various fields concerned with production of new nano-structured materials and improvement of their properties during the recent years. Tehran. Mousavi. Syntheses … ISBN: 978-1-61728-652-0 Editor: Filip M. Qom.F. size. The implosive collapse of the bubbles generates a localized hotspot or 1 Corresponding author. F. Mousavi). it has encountered limitations in the case of production of some nano-materials with specific morphology.com (M. P.O. Nowak © 2010 Nova Science Publishers. The improvement of shape. Iran Tel. Iran 2 Department of Chemistry. Inc. E-mail addresses: mousavim@modares.ir.

metal carbides. .2 M. alloy.g. Bubbles undergo the formation. Also. The dissolved gas. named hot spots. Also. a number of book chapter and reviews have been published 4. Bubble growth occurs through the diffusion of solute vapor into the bubble. A bubble can be included evaporated water molecules and dissolved gas molecules. The collapsing bubbles provide reaction sites. e. morphology and properties are investigated. At this sites. metal oxides. A number of factors can influence on cavitation efficiency and the properties of the products. Mousavi and S. some applications of prepared nano-materials are introduced. 1. Sonochemical synthesis of different types of nanostructured materials consisted of metals and their oxides. Also a review articles was published by Gedanken in 2004 entitled ―Using sonochemistry for the fabrication of nanomaterials‖ focused on the typical shape of products obtained in sonochemistry [1]. In this chapter. temperature of the bulk solution. and radical formation. growth. shock wave generation. F. and type of solvent are all important factors that control the yield and properties of the synthesized materials. INTRODUCTION When ultrasound radiations interact with molecules. The size of a bubble depends on ultrasonic frequency and intensity. semiconductors. and implosive collapse in a liquid under ultrasonic irradiation. catalysis. Mastai and A. Sonochemistry arises from acoustic cavitations. The effect of different ultrasonic parameters on the prepared structures including their size. Y. chemical reactions can be initiated. Sonochemistry is an interesting research area deal with the processes occurs during the application of powerful ultrasound (20 KHz–10 MHz). Ghasemi shock wave formation within the gas phase of the collapsing bubbles (The hot-spot theory) [3]. In the field of sonochemistry. The fast kinetics of such process can hinders the growth of nuclei produced during the collapse of bubbles. chalcogenides and nanocomposites with unique properties. This chapter is planned to deal with the application of sonochemistry for the synthesis of various nano-structured materials such as metals. electrochemical energy storage. organic molecules in solution can form organic radicals with a reducing ability. Bubbles collapse occurs in very short time (nanosecond) and cooling rate of 1011 K/s is obtained. Another review articles also published dealt with insertion of nanoparticles into mesoporous materials [5] and the sonochemical doping of various nanoparticles into ceramics and polymers [6]. we will present a literature survey on the various inorganic. Gedanken reviewed articles in the field of sonochemistry published before 2004 in a chapter of book entitled ―Sonochemistry and Other Novel Methods Developed for the Synthesis of Nanoparticles‖ [2]. organic/inorganic and inorganic/inorganic systems more recently have been synthesized by using ultrasonic method from January 2004 to January 2010s. sonolysis of water molecules to hydrogen radicals (H•) and hydroxyl radicals (OH•) is occurred which is responsible to sonochemical reaction. When the bubble size reaches to a radius down to several µm. ultrasonic power and frequency. This may be the reason of formation of nanostructured materials. biosensor and electrooxidation. the bubbles collapse provides extreme conditions of transient high temperature(as high as 5000K) and high pressure (up to ~1800 atm) within the collapsing bubbles. carbon carbonic and polymeric materials and their nanocomposite have received much attention in recent years.

optoelectronic. They can be obtained form sonication of solution containing related metal ion in the absence and presence of capping agents. pyrolysis radicals and unstable products are formed via pyrolysis of . and catalysis. 200 kHz. electronics. CTAB and AgNO3 act as effective capping agents for the shape controlled growth of gold seeds. etc. During the reaction. 200 W) of gold ions in aqueous solution (60 mL) containing of HAuCl4 and CTAB including 1.1.0 mM) and 240 μL of ascorbic acid (0.5 nm in 20 mM 1-propanol. and magnetic devices. 2. Pt. shape. In reaction 3. optical. SYNTHESIS OF NANOMETALS Intensive works on metal nanostructures such as noble metals (Au.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 3 2. and crystallinity of nanometals. pyrolysis radicals and unstable products. Pd) with various size and morphology have been achieved due to their potential applications in the fabrication of electronic. Okitsu et al reported the synthesis of Au nanoparticles and investigate the dependence of sonochemical reduction rate of Au(III) to Au nanoparticles in aqueous solutions containing 1-propanol as accelerator and their particle size to the ultrasound frequency so that the highest reduction rate was at 213 kHz in the range of 20 to 1062 kHz [7].2 mL of AgNO3 (4.5 [8]. This group also synthesized Gold nanorods by using sonochemical reduction (frequency. it can be possible to tune the intrinsic properties of a metal nanostructure. Au (III) is immediately reduced to Au (I) by reaction with the ascorbic acid. In the presence of ultrasonic. The average size of Au particles was 15. Gold Gold and other noble metal nanoparticles have been extensively considered in recent years because of their potential applications in optics. the following reactions are proposed: H 2O ))) H   OH   CTAB  OH  ( H  )  H 2 O( H 2 ) + reducing species (1) (2) (3) (4) (5) (6) CTAB  H 2 O  pyrolysis radicals and unstable products Au   M  Au 0  H   M  nAu 0  ( Au 0 ) n Au 0  ( Au 0 ) n  ( Au 0 ) n1 Where M corresponds to various reducing species.050 M) with pH 3. With controlling size. power. The solution was purged with argon for 15 min and then sonicated in a water bath (at 27 ºC) by a water circulation system.

0. 30-40 nm planar dimensions. most of the particles formed had a spherical shape with a smaller particle size than those formed in the lower pH solutions. (d) pH 7. the surfactant poly(vinylpyrrolidone). At pH 7. and (e) pH 9. irregular shaped gold nanoparticles were formed.5. At pH 9.4 M. The size of the sonochemically formed gold nanorods was less than 50 nm. From the obtained results. it was clear that the size and shape of the sonochemically formed gold nanoparticles are dramatically dependent on the pH value of the solution (Figure 1). (b) pH 5. Ethylene glycol.8 without ultrasonic irradiation. F.5. (f) TEM image of gold nanoparticles formed in pH 9. Figure 1.7. Ghasemi CTAB and water. (c) pH 6. . Based on the obtained results.8. Single-crystalline gold nanobelts have been prepared sonochemically from aqueous solution of HAuCl4 in the presence of α-D-glucose. reported the synthesis of single-crystal Au nanoprisms with triangular or hexagonal shape. under ambient conditions (Figure 2). and 6-10 nm thickness from solution of HAuCl4 and PVP in ethylene glycol solution [9]. Li et al. and their average aspect ratio decreased with increasing pH of the solution.7. it was demonstrated that longer gold nanorods would be obtained if the synthesis was performed in solution with acidic pH.8 after 180 min irradiation under argon. Mousavi and S. TEM images of gold nanorods and nanoparticles formed in different pH solutions of (a) pH 3. a biological directing agent. and ultrasonic irradiation play important roles in the formation of Au nanoprisms.

When its concentration was as low as 0. Small gold nanoparticles size of 2.05 M. A sonochemical method in preparation of gold nanoparticles capped by thiolfunctionalized ionic liquid (TFIL) in the presence of hydrogen peroxide as a reducing agent reported by Jin et al.d) high-magnification SEM images of as-synthesized gold nanobelts. Park et al. [HAuCl4]=50 mgmL-1. ultrasound time=1 h.b) SEM images and c. .3 nm can be synthesized when ultrasound irradiation applied to a solution with the molar ratio of Au/S = 1:2 for 12 h.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 5 Figure 2. Nanobelts have thickness of approximately 10 nm. a. showed the effects of concentration of stabilizer (sodium dodecylsulfate: SDS) and ultrasonic irradiation power on the formation of gold nanoparticles (Au-NPs) [11]. In the dilute solution. Authors also showed that only spherical particles with a diameter of approximately 30 nm were obtained in the presence of β-cyclodextrin. [α-D-glucose]= 0. the glucose can not provide effective coverage or passivation of gold facets. The formation of gold nanobelts depends on the concentration of α-D-glucose. It was mentioned that ultrasound irradiation can enhance the entanglement and rearrangement of the α-D-glucose molecules on gold crystals.7±0.2 m. The multiple shapes and size distribution of Au-NPs are observed by different ratio of Au (III) ion/SDS and ultrasonic irradiation power. only gold particles with a size of approximately 40 nm were obtained [10]. It was demonstrated that the molar ratio of gold atom in chloroauric acid to thiol group in TFIL (Au/S) has great effects on the particles size and distribution of gold nanoparticles. The gold nanobelts have a width of 30–50 nm and a length of several micrometers with highly flexibility. [12].

and have 30–60 nm in diameter with 200–300 nm in length.CP) for 2 h treatment in an ultrasonic bath [14]. In the reaction a solution of SnCl2 in ethylene glycol was exposed to highintense ultrasound irradiation. 2. It has been shown by TEM that the increase of the Pd (II)/PVP molar ratio from 0. 0. The following mechanism was proposed: H 2 O )))) OH   H   HOCH2 CH 2 OH  OH  (OH  )  HOCH2 C  HOH  H 2 O( H 2 ) nPd ( II )  2nHOCH2 C  HOH  nPd (0)  2nHOCH2 CHO  nH  (7) (8) (9) The coordination of the PVP carbonyl group to the palladium atoms causes to the stabilization of the Pd nanoparticles in ethylene glycol. are also found in the products. . For the highest Pd (II)/PVP value. Tellurium Crystalline tellurium nanorods and nanorod branched structures are successfully prepared at room temperature via an ultrasonic-induced process in alkaline aqueous solution containing tellurium nitrate.13 ×10-3 to 0.53 × 10-3. consisting of several nanorods. no reduction of tin ions occurs even at temperatures as high as 500 ºC in a closed cell. In the absence of the high-intensity ultrasonic irradiation.6 M. the color of the solutions turned from the initial pale yellow to a dark brown. The as-obtained nanorods are single crystalline with [0 0 1] growth orientation. the reduction reaction leads to the unexpected smallest aggregated nanoparticles. F. 3. The crystallized metallic tin nanorods have diameters of 50– 100 nm and lengths of up to 3 µm were synthesized.4. Ghasemi 2. 2. D-glucose and polyethylene glycol (PEG-400. Some branched architectures. Mousavi and S. The formation of the branched structures is suggested to be the result of multi-nuclei growth in monomer colloid. Tin Metallic tin nanorods were synthesized by a sonochemical method employing the polyol process [15]. A yellow sol was produced and was kept in darkness for 24 h to allow the growth of Te nanocrystals.53 ×10-3 decreases the number of palladium nanoparticles with a slight increase in particle size.2. During the ultrasonic irradiation of the palladium (II) nitrate mixture. Palladium Nemamcha et al reported the sonochemical synthesis of stable palladium nanoparticles by ultrasonic irradiation of palladium (II) nitrate solution in ethylene glycol and in the presence of poly(vinylpyrrolidone) (PVP) for 180 min [13].

2. Silver (10) Dendritic silver nanostructures were formed by means of ultrasonic irradiation[19] of an aqueous solution of silver nitrate with isopropanol as reducing agent and PEG400 as disperser for 2 h. power.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 7 2. Germanium Wu et al. The solution was added dropwise to the corresponding selenious acid solution. At the same time. An optimum reduction rate was determined in the frequency range 213–355 kHz. Selenium Single crystalline trigonal selenium (t-Se) nanotubes with diameters of less than 200 nm and nanowires with diameters of 20-50 nm have been synthesized by the reduction of H2SeO3 in different solvents with a sonochemical method [18]. . The sonochemical reduction rate has been found to influence by ultrasound frequency. the anhydrous salt is added to form a transparent ionic solution in THF. and time).g. The effects of different ultrasound frequencies in the range 20–1056 kHz were investigated. etc.6.. reported a method based on ultrasonic solution reduction of GeCl4 by metal hydride (LiAlH4 and NaBH4) or alkaline (N2H4·H2O) in tetrahydrofuran (THF) and in ambient condition [17]. The germanium nanocrystals have narrow size distribution with average grain sizes ranging from 3 to 10 nm. Octanol was used as capping agent. 2.5. The morphology of the products depends on the reaction conditions including ultrasonic parameters (e. The Ru particles have diameters between 10 and 20 nm. to form solutions. ultrasound was preceded to the solution. and solvent.7. The rate of Ru (III) reduction by the sonochemical method is very slow. Selenium nanotube and nanowire formation involved several stage: H 2 SeO3  N 2 H 4 ))) Spherical (  Se) ))) Spherical  like(t  Se)   ))) Nanowires (t  Se)  2. To prevent the formation of GeO2 formed in the presence of water. Ruthenium Ruthenium nanoparticles have been prepared by sonochemical reduction of a ruthenium chloride solution in 0.1 M perchloric acid containing propanol and SDS for almost 13 h [16]. frequency. and the ultrasonic time is 30-60 min.8. Hydrazine hydrate was dissolved in ethylene glycol. aging time. water.

Ghasemi Figure3. The side branches of the dendritic silver are constructed of well crystallized small nanorods (Figure 3). magnetic and corrosion-resistant properties. Bimetallic nanoalloys show different .8 M.0 M isopropanol and 0. 4. Mousavi and S. 3. including electronic. Only silver spheroidal nanoparticles were obtained at the beginning of the reaction but silver dendrites were observed with 1 h sonication. the concentration of Ag+ and the molar ratio of PEG to AgNO3 are parameters can influence the morphology of silver nanostructured. TEM image of a silver dendritic nanostructures obtained with ultrasonic irradiation of the aqueous solutions of 0. The irradiation time. These dendritic nanostructures transform to hexagonal compact crystals after 6 h later. catalytic.01 M PEG400 for 2 h . F. highly monodispersed Ag nanoparticles (NPs) were prepared by a sonochemical reduction in which Ag+ in an ethanol solution of AgNO3 was reduced by ultrasound irradiation in the presence of benzyl mercaptan without the additional step of introducing other reducing reagents or protective reagents [20]. In another work. The selected area electron diffraction (SAED) image of dendritic silver nanostructures has single crystal nature with cubic phase and the side branch direction assembles along <011> direction. The low molar ratio of PEG400 to AgNO3 (1:4 ~ 1:1) result in the formation of silver dendritic nanostructures but the molar ratio of 10:1 will cause to formation of silver nanoparticles (in the range of 40–100 nm ) instead of dendritic nanostructures. Nanoalloy materials can exhibit many novel properties. The sonochemical method has been used as a new technique for preparing alloy nanoparticles.04 M AgNO3. SYNTHESIS OF METALLIC NANOALLOYS The nanoalloys are formed when two or more kinds of metals are melted together.

the concentration of ethanol and the concentration of citric acid affect the size distribution of the Pd–Sn nanoparticles.5 were synthesized and its response toward the electrochemical oxidation of CO and CH3OH in 0. The Pd in Pd–Sn nanoparticles is mostly in the metallic form. Pt-Ru Nanoparticle bimetallic electrocatalysts with XRu ≈0. Pt provides sites for C-H bond cleavage and CO adsorption.1 and XRu ≈ 0. The average size of Pd–Sn nanoparticles thus prepared was about 3–5 nm. Then 0.3. They show that when the ultrasonic power was increased from 700 to 1000 Wcm-2. and Ru activates water to produce reactive oxides that enable conversion of carbon containing fragments to CO2.2. Sn–Bi Sn–Bi alloy nanoparticles were prepared by sonicating bulk Sn–Bi alloy directly in paraffin oil under ambient pressure and room temperature [21]. Pd–Sn Kim et al. The product was centrifuged after cooled to room temperature and washed with chloroform and dried to get some grayblack powder. Korzeniewski et al. The initial concentrations of Pd and Sn and their molar ratio. .1. 3. In Pt-Ru catalyst.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 9 properties such as high catalytic activity and catalytic selectivity in comparison with the corresponding monometallic counterparts so that they can be used as catalysts and gas sensors.5 g bulk Sn–Bi alloy was added to 30 ml paraffin oil in a horniness test tube and the system was irradiated for two hours at 1000Wcm−2 with a high intensity ultrasonic probe. Syntheses were carried out in tetrahydrofuran (THF) containing Ru3+ and Pt4+ in a fixed mole ratio of either 1:10 or 1:1 using high-intensity sonochemistry. 3. prepared Pd–Sn nanoparticles from aqueous ethanol solution of Pd(NH4)2Cl4 and SnCl2 in the presence of citric acid by applying ultrasonic irradiation and investigate the Pd–Sn nanoparticles for the oxygen reduction reaction (ORR) in alkaline media [22]. 3. They also show that the sonication time had little impact on the size of the nanoparticles.1 M H2SO4 was investigate [24]. Twenty grams Sn and 30 g Bi were melted together in a vessel to obtain the bulk Sn–Bi alloy. Pt-Ru Bimetallic catalysts comprised of Pt and Ru (Pt-Ru) are important in the development of low temperature (<~120 ºC) H2-air and direct methanol fuel cells. prepared Pt-Ru nanoparticles with diameters in the range of 2–6 nm as catalyst materials to investigate the electrochemical oxidation of CH3OH and CO [23]. the size distribution reduced from 60-80 nm to 10-25 nm.

PVP (MW =55000) is used as the stabilizer. 200 mM propanol. A potassium tetrachloroplatinate (K2PtCl4) solution containing 8 mM SDS. 3.6. When 1mg/mL of polyvinyl-2-pyrrolidone. and 0. F. . Ghasemi 3. TEM image of the nanoparticles showed that the ruthenium formed a layer around the platinum particles and Pt-Ru core-shell particles in the range of 5-10 nm were formed (Figure 4).4. poly(ethylene glycol). while the thickness of the ruthenium shell was estimated to be between 2 and 3 nm.10 M. respectively. Multiangular Au-Ag nanocomposites of larger size appeared after ultrasonic irradiation of the gold-silver mixture in the presence of poly (vinyl pyrrolidone) in ethylene glycol due to the capping effect and the relatively low rate of degradation of PVP. Uniformly distributed gold-silver with round shapes was resulted after sonication in poly (ethylene glycol). Au/Pd 28 and Pt-Ru [29]. 3. the RuCl3 solution was added to the Pt colloidal solution and sonication continued. Au-Ag Au-Ag nanoalloys were prepared sonochemically form solution containing gold nanoparticles and silver nitrate in the presence of different surfactant (sodium borohydride in water. sodium dodecyl sulfate in water or propanol) [26]. During liquid-phase cinnamaldehyde (CMA) hydrogenation. Pt-Ru has been used as a methanol oxidation catalyst in direct methanol fuel cells (DMFC). With SDS. A sequential sonolysis method was used to synthesis of Pt-Ru core shell (Pt@Ru) structure [29]. Co-B Uniform spherical Co-B amorphous alloy nanoparticles were prepared by ultrasoundassisted reduction of Co(NH3)2+6 with BH−4 in aqueous solution which the particle size distribution was controlled by changing the ultrasound power and the ultrasonication time [25]. Bimetallic Nanoparticles with Core-Shell Morphology Sonochemically assisted synthesis of bimetallic nanoparticles with core-shell morphology have been reported for materials such as Co/Cu [27].5. worms or netlike gold-silver nanostructures obtained after 1 h of ultrasonic irradiation of AgNO3 in propanol and water. the RuCl3 solution was added to the Pt colloidal solution and sonication continued. When all of the Pt (II) has been reduced. the as-prepared Co-B catalyst exhibited much higher activity and better selectivity to cinnamyl alcohol (CMO) than the regularCo-B in the absence of ultrasonic waves. when all of the Pt (II) was reduced. The platinum particle sizes are ~7 nm. poly(vinyl pyrrolidone) in ethylene glycol. Mousavi and S. It was suggested that the degradation of the surfactants occurred during the ultrasonic treatment and allowed modification of the shape of gold nanoparticles in their interaction with silver ions. Monodisperse gold-silver nanocomposite of triangular or polygonal structure was obtained with reduction of the silver by NaBH4 on the gold surface in the presence of ultrasonic irridation.1 M HClO4 were sonicated to reduce the Pt (II) to colloidal Pt (0) during 3h at 20 °C. the formation of colloidal platinum is very rapid and become complete within 1 h of sonication. At the end of 1 h.

Curve a shows the absorption spectrum of PtCl4 2. Vinodgopal et al used a sequential reduction method to prepare PtRu core-shell nanoparticles but Anandan and his coworker prepared Au-Ag bimetallic nanoparticles by the sonochemical co-reduction of Au(III) and Ag(I) ions in aqueous solutions containing polyethylene glycol (0. As mentioned above. (b) Absorption spectra Pt-Ru nanoparticles.in 200 mM propanol. The average diameter of the bimetallic clusters prepared by the simultaneous reduction is about 20 nm.1 M HClO4. The stabilizing polymers can coordinate to metal ions before the reduction. 0.solution was sonicated for 4 h. Figure 4b shows the change in absorption spectra of the colloidal solutions with time.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 11 Figure 4: (a) TEM of Pt-Ru nanoparticles synthesized by sonocation of a solution containing 1 mM PtCl4 2. This interaction between the polymer and the metal ions lead to the formation of smaller size core- .1 wt %) and ethylene glycol (0.1 M) [30]. Curve e shows the absorption spectrum immediately upon addition of the ruthenium chloride. and 8 mM SDS followed by the reduction of 1 mM RuCl3 under argon atmosphere. The total time of sonication was 7h at 213 kHz. The RuCl3 solution was added after the PtCl4 2. The TEM images showed ultrasmall 2 nm sized particles without core-shell morphology and only the presence of bimetallic ruthenium and platinum was confirmed by energy-dispersive X-ray analysis of the TEM. Only one prominent peak at 400 nm appears in the curve indicating an instantaneous partial reduction of Ru (III) upon addition to the solution.solution at time t = 0 and continuing through the addition of the RuCl3 and its reduction.

triethyl citrate was added to the mixture of zinc acetate dihydrate solution (90 mL) and ammonia– water (10 mL). Ghasemi shell nanoparticles with a narrow size distribution. ZnO ZnO is one of the most important multifunctional semiconductors with wide direct energy band gap of 3. Sonochemical synthesis of ZnO nanostructures with different shapes such as nanowires. concentration of reactants. the ultrasonically assisted synthesis of metallic oxides and hydroxides has been considered by some of researchers. F. The effects of various parameters on the morphology of ZnO nanostructures were investigated. They also suggested that the formation of core-shell morphology is most likely due to the difference in the reduction rates of the individual metal ions and the involvement of a polymer-Ag ion complex. nanorods [33]. For the synthesis of ZnO nanoflowers and nanospheres. nanodisks. 4. Triethyl citrate was used as an additional chemical additive to synthesize ZnO nanodisks. nanotubes. needleshape [34]. In the case of ZnO nanospheres. nanocups. and nanospheres in a horn-type reaction vessel using an ultrasonic technique at a power of 50 W (intensity of 39. sonication time and additives are dominant factor affect on preparation of different morphology of ZnO.1. nanosheet [36] and Hollow ZnO microspheres [37]. METAL OXIDE During the last years. ZnO nanostructure with morphologies such as flower-like clusters [31]. 4. ammonia–water (28–30 wt %) solution were used as hydroxide anion precursors. Jung et al fabricated ZnO nanorods. some of them are investigated in the following paragraph. The growth rate of the ZnO crystal along the [0001] direction decreases dramatically due to the addition of triethyl citrate. For the production of ZnO nanorods and ZnO nanocups. The kind of hydroxide aniongenerating agents. different concentration of Zn(NO3)2 and hexamethylenetetramine (HMT. trigonal-shaped [35]. (CH2)6N4 as well as different sonication time (30 min for nanorods in comparison with 2h for nanocups) were used. Due to their importance in various area of science. ZnO nanocrystals grow preferentially along the [0001] direction to form nanorods.12 M. Mousavi and S.5 W/cm2) and frequency of 20 kHz (Figure 5) [38]. An increase in ultrasonication time provides such energy indicates to the reaction System that hinders the ZnO nanorod growth. nanoparticles have been considers by some of authors. nanoflowers. The sonochemical growth mechanism of ZnO nanostructures was suggested by authors as follows: (CH 2 ) 6 N 4  6H 2 O  4 NH 3  6HCHO  NH 3  H 2 O  NH 4  OH  (11) (12) . Gold ions are firstly reduced under the sonochemical conditions followed by the reduction of Ag+ ions on the surface of the gold particles.37 eV and large exciton binding energy (about 60 meV). cauliflower-like [32].

The same authors presented in another paper a sonochemical method for fabricating vertically aligned ZnO nanorods arrays on various substrates such as a large-area Zn sheet. (i. (Insets: HRTEM image) . (a.f) Nanodisks.b) Nanorods. (g.   (15) Figure 5.d) Nanocups. (e. (c. h) Nanoflowers. j) Nanospheres. Si .Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 13 (13) (14) Zn 2  4OH   Zn(OH ) 2 4 Zn(OH ) 2 ))) ZnO  H 2 O  2OH   4 3  Zn 2  2  O2 ))) ZnO  O2  2 The sonolysis of water produces O2 radicals in solution. SEM (left) and TEM (right) images of ZnO nanostructures.

high performance NO2 gas sensor [43].5 mmol) and sodium fluoride (NaF. F. Some of authors used ultrasonic irradiation to fabricate well-defined dentritic ZnO nanostructures in a room-temperature ionic liquid [41]. The effect of ultrasonic irradiation time on conversion process of Cu(OH)2 to CuO was investigated. A template-free.46 g.2. An increase in the scattered light signals of V2O5 bundles were observed by the addition of BSA. 2. 0. The nano-disks are 260–400 nm across the edges and 290–430 nm across the vertices[40]. 0.14 M. and flexible polymeric materials. sonochemical route to prepare porous hexagonal ZnO nano-disks has been developed by Bhattacharyya and Gedanken. in an aqueous solution under ambient conditions [39]. CuO The synthesis of one-dimensional (1D) Cu(OH)2 nanowires [45] in a aqueous solution of CuCl2 and NaOH was done under ultrasound irradiation with 40 kHz ultrasonic waves at the output power of 100% at 70 ºC for 5-60 min. A color change of the product from the pale-blue to the black was observed in the range of 15 to 45 min of irradiation implied the gradual conversion of Cu(OH)2 to CuO. V2O5 A sonochemical method has been developed to preparation self-assemble V2O5 nanowires with spindle-like morphology (Figure 6). finally. 4. Cu(OH)2 nanowires integrated into nanoribbons. The enhanced RLS intensity at 468 nm of V2O5 bundles-BSA varies linearly with the concentration of BSA in the range from 0. 3D nanostructures disrupted and transformed into 3D CuO microstructures. The XRD analyses of the products confirmed the conversion process. Mousavi and S.21 g. transparent glass.5 to 20 µg mL-1. The morphology of products is highly depends on time of ultraonication. The CuO microstructures showed better electrochemical property than Cu(OH)2. a sensitive resonance light scattering (RLS) method was developed to detect bovine serum albumin (BSA) based on the ultrasonically V2O5 bundles [46].3. Also. then parts of nanoribbons crosswise grew to form 3D Cu(OH)2 nanostructures. Ghasemi wafer. It was demonstrated that the ultrasound plays two roles besides dispersion: shortening the conversion time from Cu(OH)2 to CuO and inducing the formation of 3D CuO microstructures. Under continuous ultrasonic irradiation. 5 mmol) were dissolved in 50 mL of distilled water in a 100-mL round-bottom flask and exposed to high-intensity ultrasound irradiation (20 kHz. Vanadium oxide (V2O5. 100 W/cm2) under ambient air for 2 h. gas sensitivity to NO [44]. The organization of 1D V2O5 nanostructured subunits into spindle -like V2O5 bundles was occurred Each bundles composed of several tens of homogeneous nanowires with diameters of 3050 nm and lengths of 3-7 µm. . Synthesis of self-assembled nanorod vanadium oxide bundles by sonochemical technique were reported by a Malaysian group [47]. 4. The ZnO nanostructures have been used to sensing etanol [42].

FE-SEM images of the V2O5 bundles with spindle-like morphology (a) low-magnification SEM image of V2O5 bundles. well defined shapes and smaller size nanorod vanadium oxide bundles were obtained with higher ultrasound irradiation times. Vanadium oxide bundles showed higher activity to anaerobic oxidation of n-butane than the bulk material.5 mL) in 40 mL of hexadecane was irradiated by a high-intensity ultrasound horn (operated at 20 kHz and 50 W/cm2 at 20 °C for 3 h under argon flow).1 g) (4. The high-surface-area iron shells rapidly oxidize in contact with air and release such heat that ignites the carbon particles. . Mössbauer spectra confirm the presence of hematite as the only iron species. The morphologies of the nanorod vanadium oxides are depended on the time of sonication so that a uniform.4. The combustion of the nanosized carbon particles generates enough heat to crystallize the iron oxide shells to hollow cores α-Fe2O3 (Figure 7). A mixture of Spherical carbon nanoparticles (0.12 nm diameter) and Fe(CO)5 (0. 4. the sonication of precursor solution in the absence of carbon nanoparticles produce agglomerated nanoparticles of ~ 6 nm.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 15 Figure6. The decomposition of Fe(CO)5 form high-surface-area iron shells around the core carbon nanoparticles. Under the same condition. Iron oxide Suslick and Bang used carbon nanoparticles as a spontaneously removable template for synthesis of crystalline hollow hematite (α-Fe2O3) [48]. (b) low-magnification TEM image.

The size of MnO2 incorporated in CMK-3 is between 0. used an FeCl2 ethanol–water mixed solvent and a 2 N NaOH aqueous solution to from a Fe(OH)2 precipitate. KMNO4 reduce to MnO2. Manganese Oxide An ultrasonic technique was used to prepare MnO2 nanoparticles inside the pore channels of ordered mesoporous CMK-3 [51]. Another work has been reported to sonochemically synthesis of monodispersed magnetit nanoparticles [49]. In the pores.0 nm. CMK-3 with 20 wt. Dang et al.16 M. Mousavi and S. . Any organic residues were completely removed by annealing the as-produced hollow hematite at 450 °C for 2 h under air.5 nm and 3.5. TEM image and EDS (energy dispersve X-ray spectroscopy) reveal that the morphology and composition of the hollow hematite remained unchanged after the heat-treatment. the hollow hematite nanoparticles are weakly ferromagnetic down to 5 K. Monodisperse iron oxide nanoparticles with 5–20 nm can be synthesized by an inexpensive and simple ultrasonic-assisted method at low temperature [50]. MnO2 nanoparticles were anchored in pores of carbon CMK-3. Also. after the react solution was refluxed at this temperature. Ultrasonic technique controls the amount of loading MnO2 inside CMK-3. The hollow hematite nanoparticles shows hysteresis loops for at 5 and 298 K. It was demonstrated that the formation of magnetite was accelerated in ethanol–water solution in the presence of ultrasonic irradiation. This is based on the decomposition of iron pentacarbonyl in cis–trans decalin. The Fe(OH)2 precipitate was irradiated by an ultrasonic horn in air at 50 ºC to synthesize magnetite nanoparticles. % loading of MnO2 inside CMK-3 produced an improved discharge capacity of 223 mAhg-1 at 1 Ag-1. (a) Bright-field and (b) dark-field TEM image of nanosized hollow hematit. monodisperse γ-Fe2O3 nanocrystals were obtained. They found that ultrasonic irradiation could greatly enhance the crystallization of iron oxide nucleus at 190 °C. Ghasemi Figure 7. 4. F.

60 ml water was added and pH of solution was adjusted to 10 by adding NH4OH. In2O3 The synthesis of monodispersed In2O3 nanoparticles and doped with rare earth ions ((Eu3+ and Dy3+)) is another work considered to investigate their photoluminescence properties [56]. Kumar et al. It was shown that the rate of the sonochemical reduction of MnO4. Mn3O4 nanoparticles were prepared by reacting MnCl2 and NaOH in water at room temperature through a sonochemical method.2 [53]. .6. In(OH)3 nanocubes are obtained in the range of 30-35 nm. Then. the In2O3 diffraction peaks broads with respect to diffraction peaks of undoped In2O3. The effect of H2O2 formed in the sonolysis of water on the rates of reduction of MnO4.5–5. It was shown that reveal the size and the crystallinity of Mn3O4 nanoparticles depends on the growth temperature so that the smaller the average diameter and the poorer the crystallinity of Mn3O4 nanoparticles was observed at lower reaction temperature. A similar strain causes to the low emission intensity in the In2O3 doped Eu3+ particles. With Eu3+/Dy3+ incorporation. After 1 h sonication.was investigated [54].5 nm range.36 g cetyltrimethyl ammonium bromide (CTAB). The magnetic properties of the samples showed that Mn3O4 nanoparticles exhibited ferromagnetic behavior at low temperature (40 K). under air at room temperature resulted in In(OH)3 nanoparticles.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 17 Colloidal Mn3O4 nanoparticles with diameters of about 5-10 nm has been pepared by an ultrasonic-assisted method in the absence of any additional nucleation and surfactant at normal temperature and pressure [52]. The sonochemical preparation of MnO2 was reported through the reduction of MnO4.in water under Ar atmosphere. Eu3+/Dy3+ has gone into the In2O3 lattice and lattice undergoes distortion.depend on the amount of sonochemically formed H2O2 molecules. 4. The In2O3 nanoparticles were formed by heating the In(OH)3 nanoparticles in furnace under air at 350 °C for 1 h. prepared sonochemically a highly dispersed and non-agglomerated α-MnO2 nano-needles of dimensions 20–30 nm from aqueous solution consisting of manganese Mn(acetate)3 and LiOH with a pH value of 7. emission peaks around 460 nm (blue) and two relatively less intense peaks centered around 548 nm (yellow) and 618 nm (orange) were observed possibly due to the presence of shallow defect levels in the annealed samples. they were transformed into phase-pure LiMn2O4 nanoparticles of about 50 to 70 nm size in diameter. In2O3 doped Dy3+ nanoparticles did not show any luminescence due to the highly strained and distorted environment around the dysprosium ions in the In2O3 lattice.5–5. To a solution of indium ethoxide. in 20 ml ethanol containing 0.5 nm was coated onto the surface of Mn3O4 under the same sonochemical conditions and the LiOH-coated Mn3O4 particles sample was heated at the relatively low temperature of 300–500 °C. operated at 20 kHz and 220 W for 20 min [55]. Also. A thin film of the LiOH with the thickness of about 4. With Eu3+/Dy3+ incorporation. In(OEt)3. the LiMn2O4 nanoparticles were also prepared. On exciting at 235 nm. The thickness of coated LiOH on Mn3O4 obtained from the reaction ratio of 3:1 between LiOH and Mn3O4 was about 4. by heating LiOH-coated Mn3O4 particles at the relatively low temperature of 300–500 °C for 1 h. The irradiation of solution with a high-intensity (100 W/cm2) ultrasonic radiation operating at 20 kHz.

3 eV. and 1200 W/cm2 at 50% efficiency) for 45 min.0 g) and 30% hydrogen peroxide solution (30 mL) were mixed into a glass reactor and suspension was treated under ultrasonic irradiation for 4. prepared the mesoporous TiO2 nanorods using industrial bulk Ti powder [59]. The sonication promoted the hydrolysis of TBOT. The as prepared materials contained numerous irregular olive-like nanorods aggregates. A white powder was obtained after washing and drying. The products showed higher photocatalytic activity to toluene than Degussa P25 TiO2. Mesopore TiO2 prepared by ultrasonic method showed better photocatalytic activities than the samples prepared by conventional hydrolysis method. Zhou reported the preparation of nanocrystalline mesoporous Fe-doped TiO2 powders red by the ultrasonic-induced hydrolysis reaction of tetrabutyl titanate (Ti(OC4H9)4) in a ferric nitrate aqueous solution [61]. Guo et al. TiO2 TiO2 is an important semiconductor for a broad range of applications. The spherical shaped TiO2 particles have a small size (~5 nm) with narrow size distribution. solar cells. Ghasemi 4.3 mm diameter Ti-horn. Crystalline anatase TiO2 nanoparticles was synthesized from titanium tetraisopropoxide in the ionic liquid 1-(3-hydroxypropyl)-3-methylimidazolium-bis(trifluoromethan esulfonyl)amide by ultrasound assisted synthesis [60]. The nanorods were 8–12 nm in width and 15–100 nm in length. prepared mixed-crystal TiO2 powder with high sonocatalytic activity under ultrasonic irradiation in hydrogen peroxide solution [58]. TBOT was added dropwise to 40 ml pure water in a 100 ml beaker. such as hydrogen production. The photocatalytic activities of Fe-doped TiO2 powders were investigated by the photocatalytic oxidation of acetone in air. This powder was heat-treated at 400 °C for 40 min. The as-prepared products by the ultrasonic method were composed of anatase and brooktie phases Photocatalytic decomposition was investigated for formaldehyde and acetone. . The high activities of the Fe-doped TiO2 powders was observed due to synergetic effects of Fe-doping and large specific surface area of catalyst. Wang et al. Pulse irradiation was done with a high intensity ultrasonic horn (6. TiO2 nanoparticles have high surface area of 177m2 g−1 with bandgap of 3. F. The sonocatalytic degradation of methylene blue in aqueous solution was investigated under ultrasonic irradiation in the presence of treated mixed-crystal TiO2 powder. ultrasonic wave is on for 2 s followed by 2 s off during the whole reaction. 20 kHz. Mousavi and S.0 h. The spherical TiO2 nanocrystals have good photocatalytic activity in the degradation of methylorange. crystallization of TiO2 and formation of mesopore TiO2. biological coatings and photocatalysis [57] Mesoporous titanium dioxide nanocrystalline powders were synthesized by ultrasonicinduced hydrolysis reaction of tetrabutyl titanate (Ti(OC4H9)4 . TBOT). In pulse technique.7. The XRD and the FT-IR spectra of treated mixed-crystal showed both nano-sized rutile phase and anatase phase TiO2 powders. It was shown by the UV–vis spectra that the methylene blue in aqueous solution can be obviously degraded under ultrasonic irradiation in the presence of treated mixed-crystal TiO2 powder.18 M. Effect of different parameters such as heat-treated temperature and heat-treated time on degredation of methylen blue was studied. The nano-sized rutile phase TiO2 powder (10.

instead of the lead precursor β-PbO. It was found that the applied ultrasonic wave determines the particle size.8. PbO2 Our research group synthesized β-PbO2 nano-powder by the ultrasonic irradiation of an aqueous suspension of dispersed β-PbO (Pure yellow orthogonal phase). 4. β-PbO was not oxidized under these conditions. magnesium oxide66.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 19 4.9. It was observed that the use of Pb(NO3)2. . the increased concentration of hydroxyl radical facilitated the oxidation of βPbO to PbO2 under ultrasonic irradiation. Figure 8. lead oxide [64 65]. even with an increase in the duration of ultrasonication. mercury oxide [68]. molybdenum oxide [67]. only a fraction of the lead oxide was converted to lead dioxide. When the reaction mixture was stirred instead of ultrasonically irradiated. reaction rate and composition of products were investigated. temperature and ultrasonic wave amplitude on the morphology. In the presence of ammonium peroxydisulfate. resulted in the formation of PbSO4. in the presence of ammonium peroxydisulfate as an oxidant [62].2 g β-PbO and 5 g (NH4)2S2O8 at 60 ºC and ultrasonic amplitude of 84µm (Diffrent magnification). When ultrasonic waves were applied to β-PbO particles. The XRD results reveal that only β-PbO2 is formed under optimum conditions. Other Metallic Oxide Other metallic oxides such as bismuth oxide [63]. Thus. In fact. SEM of lead dioxide (β-PbO2) samples prepared from a solution containing 0. as precursor. a proper oxidant is necessary to convert β-PbO to PbO2. The effect of pararmeters such as oxidant concentration. PbO2 samples prepared under optimized experimental conditions have lead dioxide particles in the range of 50–100 nm. The reaction rate increased with an increase in temperature and ammonium peroxydisulfate concentration. only mechanical milling occurred and the particles were cracked. which precipitated out at the end of the reaction. Tungsten oxide [69] and tin oxide[70] have been synthesized by sonochemistry methods in the past several years. and lead sulfate was the main reaction product. the oxidation process should be initiated with β-PbO.

THE SONOCHEMICAL SYNTHESIS OF MIXED OXIDES Mixed Oxides such as aluminates. The as-prepared BiVO4 .7 m2 g-1 of commercial CeO2. Eu3+/Tb3+. The CeO2 nanotubes were obtained only at concentration higher than 5 M KOH. To a solution of Ce(NO3)3 containing 1 g of PEG600. and triple (Eu3+/Dy3+/Tb3+) doped Gd2O3 (gadolinium oxide) nanoparticles were prepared via a sonochemical technique [74]. electrooptic and electromagnetic devices because of their prominent properties. Zhang et al proposed a sonochemical method to synthesis of Polycrystalline CeO2 nanorods with 5-10 nm in diameter and 50-150 nm in length at room temperature [73]. After that. manganates and etc. Tb3+). aqueous solutions of Bi(NO3)3 and NH4VO3 were mixed together in 1:1 molar ratio and exposed to high-intensity ultrasound irradiation for 60 min. TEM images of the CeO2 showed nanorods with the clear (111) and (220) lattice fringes with the interplanar spacing of 0. respectively. Dy3+/Tb3+). The CeO2 nanotubes had diameters of 10–15nm and length of 150–200 nm. 5. Miao et al. The particles sizes were in the range of 15 to 30 nm. double(Eu3+/Dy3+. 50 nm and samples exhibited surface areas of ca. The UV-vis absorption spectrum of the CeO2 nanorods exhibits a strong absorption band at the UV region due to the charge transfer transitions from O 2p to Ce 4f bonds.19 nm.16 m2/g. A facile sonochemical approach has been developed for the synthesis of BiVO4 photocatalyst by Zhou and his coworkers.005 g/mL) was added gradually (5 mL/min) under ultrasonication for ~1 h at room temperature until the pH value was 10. The triple doped samples showed multicolor emission on single wavelength excitation. Rare-Earth Oxide Wang et al. have been found many applications in sensors.31 and 0. In 2007. In the absence of PEG. 4. MVO4 Much of work on metal vanadate is focused on bismuth vanadate (BiVO4) because BiVO4 has been recently recognized as a strong photocatalyst for water water decomposition and organic pollutant decomposing under visible light irradiation due to its narrow band gap 75. The average crystal size of as-prepared BiVO4 particles is ca.5 m2 g-1 in comparison with 5. The BET specific surface area of CeO2 nanorods was calculated 154. F. Dy3+. Nanoparticles of the single (Eu3+. Polyethylene glycol (PEG) was used as a structure-directing agent. molybdates. The sonochemical method is one of the simple route have been used during the last years to prepare nanostructure mixed oxides. 5. They also showed that when 3 M KOH aqueous solutions is used.20 M. succeed to synthesis of CeO2 nanotubes by a sonochemical method under ambient air in alkali aqueous solution without any template [72]. Mousavi and S. the agglomerated nanoparticles was formed instead nanorods. In a typical preparation. NaOH solution (0.1. Ghasemi 4. only rod-like assemblies composed of CeO2 nanoparticles with the size of 5 nm were appeared. in 2002 used a sonochemical method to prepare CeO2 nanoparticles [71].10.

Each particles (as aggregates) are composed of smaller nanoparticles of 10-20 nm. Lu) nanoparticles had been prepared from an aqueous solution of Ln(NO3)3 and NH4VO3 without any surfactant under ultrasonic irradiation[77]. Ce. Ti ions dissolve form the Ti-based sol to form Ti(OH)62. PbTiO3. Nd. BaTiO3. The pH value was adjusted to about 7 by NH3. 20 kHz) for 30 min in ambient condition.45 eV. Nd. The nanosized BiVO4 exhibited excellent visible-light-driven photocatalytic efficiency for degrading Rhodamine B (RhB) with good stability.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 21 nanocrystals had strong absorption in visible light region with an obvious blue-shift compared with that of the bulk sample.octahedron and the nucleation of BaTiO3 occurs around the Ti-based sol. It is thought that under ultrasonic irradiation. developed a sonochemical method for the synthesis of spherical BaTiO3 nanoparticles by sonicating a strong alkaline solution including BaCl2 and TiCl4 [81]. Sm. Yb. When the RhB solution was irradiated with visible-light (λ > 420 nm) in the presence of calcinated well-crystallized BiVO4 sample. Pr. Er. 5. The sonochemical synthesis of Lanthanide orthovanadates RVO4 ( R = La. The as-formed LnVO4 particles have a spindle-like shape with an equatorial diameter of 30-70 nm and a length of 100-200 nm. MTiO3 The metal tiatanates. tetrabutyl titanate Ti(OBu)4 as precursors via ultrasound irradiation. 600W. They . It was observed that the morphology of the LnVO4 nanoparticles was affected strongly by ultrasonic irradiation. Ultrasound influences the synthesis of BaTiO3 particles mainly through acceleration the dissolution of Ti ion from Ti-based sol and the nucleation of BaTiO3 particles. 2. 60 nm. Ho. Eu. They used ultrasonic irradiation to form narrow size distribution of aggregated particles. The formation of BaTiO3 particles was reported by a Japanese group [80]. Dy. An aqueous solutions of Bi(NO3)3 and NH4VO3 in 1:1 molar ratio as well as polyethylene glycol (1 g) was exposed to high-intensity ultrasonic irradiation (6 mm diameter Ti-horn. used polyethylene glycol (PEG 20000) as surfactant[76]. about 95% of RhB was degraded after being irradiated for 30min and the spectral maximum shifted from 552 to 500 nm. The lanthanide orthovanadate LnVO4 (Ln = La. This method caused to formation of the aggregation of the original 5–10 nm BaTiO3 particles. Xu et al. Sm.2. nanospindles of GdVO4 and nanoparticles of other orthovanadates were obtained. With the surfactant PEG. BiVO4 nanocrystals showed high photocatalytic activities to decolorization of methyl orange under visible light (λ > 400 nm). The band gap was estimated to be ca. When the P123 surfactant was used. Shang et al. Ti-based sol forms by the hydrolysis of TiCl4 in Ba2+ aqueous solution. Nanosized BiVO4 consisted of small nanoparticles with the size of ca. and PbTiO3 have been reported to be synthesized by sonochemical methods [79]. nanorods of NdVO4. the Lanthanide orthovanadates with nanorod shape was observed. Ce. Tb. Wang and his coworker prepared PbTiO3 fine powders with narrow size distribution (40–60 nm) by a sol-gel method with lead acetate Pb(OCOCH3)2. Eu and Gd) was reported in the presence of Polyethylene glycol (PEG-900) and amphiphilic triblock copolymer Pluronic P123 as structure-directing agents at room temperature [78]. Gd. Tm.

and urea. Spinel copper aluminate (CuAl2O4) nanoparticles were prepared by sonicating an aqueous solution of copper nitrate. The doped samples showed multicolor emission on single wavelength excitation.3. The BET surface area of CuAl2O4 anoparticles was about 110 m2 g−1. MWO4 PbWO4 nanostructures with different morphologies. 5. MAl2O4 (M = Cu. In the presence of . has been also prepared by sonochemical methods [82]. aluminium nitrate. containing the metal hydroxides and ammonium nitrate. The photochemical catalysis degeneration of methyl orange on CuAl2O4 noparticles as photocatalyst was investigated under the irradiation of 125W Hg lamp (λ > 400 nm). While with nitrates/acetates a gel is obtained after sonication. To explain what has been occurred in the reaction vessel. alkoxides and aluminium nitrates/magnesium acetates in the presence and absence of cetyl trimethyl ammonium bromide (CTAB). In the case of alkoxides precursors the as-made product is a mixture of hydroxides of aluminium and magnesium. Tb3+. and after heating at 500 ºC pure MgAl2O4 phase was not obtained [84]. Heating at 500 ºC transforms the as-made products into MgAl2O4 spinel phase with the surface area of 267 m2/g. capable of coordinating to several metal centers. Two kinds of precursors were used. spindle-like. The rate of the methyl orange degradation was measured to be as high as 98% in 2 h. The reaction was carried out under ultrasound irradiation at 80 ºC for 4 h and a calcination temperature of 900 ºC for 6 h.22 M. and dot-shaped.to form Pb-NTA complex. incorporating carboxylic acid groups and one N-donor atom. Zinc Aluminate ZnAl2O4 and Zinc Gallate ZnGa2O4 doped with Mn2+ and some of lanthanide ions such as Dy3+. Mousavi and S. such as polyhedral. High surface area MgAl2O4 has been synthesised by a sonochemical method. Zn and Mg). the CTAB reduces the formation of large stable aggregates. This group also synthesizes the SrTiO3 nanoparticles with the same sonochemical method. the precursor formed nanosized CuAl2O4 particles with an average size of 17nm. The mechanism of the formation of PbWO4 nanocrystals is probably related to the coordination of Pb2+ and NTA3. In the case of nitrates/acetates precursors.4. Ghasemi showed that the reactant concentration influence the particle size. 5. MAl2O4 Metal aluminate. it was suggested that PbNTA complex is formed due to coordination of Pb2+ and NTA3-. F. have been synthesized via a mild sonochemical route from an aqueous solution of lead acetate and sodium tungstate (Na2WO4) in the presence of complexing reagent nitrilotriacetate acid (NTA) [86]. Upon heating at 900 ◦C for 6 h. Eu3+ were synthesized through a sonochemical process 85. Photoluminescence studies were done on prepared samples. They reported another work that investigate the effect of processing conditions on preparation of nanosized copper aluminate (CuAl2O4) spinel using Cu(NO3)2 and Al(NO3)3 as starting materials and urea as a precipitation agent at a concentration of 9 M [83]. H3NTA is a precursor of a multidentate organic ligand (NTA3-).

When pH was lower than 5. In another work. spindle-like. At the pH > 11. Pb(OH)x2-x.0 are polyhedrons with dimension of (400-500) nm × (600-700) nm. Room-temperature photoluminescence of PbWO4 nanocrystals showed green emissions at 480-500 nm with different luminescence intensity. (b) 7. 20.0.0.0. i. Pb2+ ions in the solution are easily attracted on the micellar surfaces by forming Pb-(PEO-PPO-PEO) units and provide nucleation domains for the subsequent reaction between Pb2+ and WO42. 60 W/cm2). and H3NTA were 20.0. The optical properties of these PbWO4 nanocrystals differ from those of the bulk crystals. NTA3.(EO20PO70EO20) as a structure directing agent [87]. the dissociation of the complex was occurred and PbWO4 was formed. . and dot-shaped morphologies were obtained with controlling the pH value and the amount of complexing reagent. polyhedral. At the pH value was decreased of 7. and (c) 5. nitrilotriacetic acid exists as NTA3. The concentration of polymer had vital role in preparation of PbWO4. and 40 mM.and the predominant species in solution remains a 1:1 complex of PbNTA-. A pH range of 5-9 is optimal. another complex. NTA3. The mechanism is summerised as follow: PbNTA  Pb 2   NTA3 2 Pb 2   WO4   PbWO4 (16) (17) Different shapes of PbWO4 nanocrystals. the homogeneous spindle-like nanorods with diameters of 50-60 nm at the center and lengths of about 200-250 nm (Figure 9b) was obtained. Figure 9c shows the dotshaped product prepared with a pH value of 5. prepared nanosized lead tungstate (PbWO4) hollow spindles via a sonochemical process by using triblock copolymer Pluronic P123. The average size of these polycrystalline particles is about 10 nm.e. PbWO4 hollow spindles can be formed by templating the P123 micellar aggregates induced by the ultrasonic irradiation. Geng et al. The initial concentrations of Pb2+.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 23 ultrasound irradiation (20 kHz.0.to form PbWO4 nanoparticles. TEM images of samples prepared at pH values of (a) 9. Figure 9. With pH decreasing.would exist as HxNTAx-3 and its complexing ability with metal ions would therefore decrease. Figure 9a shows that the products prepared at pH 9. WO42-.would partly combine H+ in the solution. Under pH 7-9. Hollow PbWO4 nanospindles were obtained in the polymer concentration of 4 gL-1. respectively. was formed instead of PbWO4 due to the strong complexing ability between Pb2+ and OH-.

Sr and Ca. Cu and Zn)) such as copper ferrite (CuFe2O4) [92] and zinc ferrite (ZnFe2O4) [93a] were reported. Ghasemi The same procedure was used to preparation of ZnWO4 nanorods [88]. Ferrites with formula MFeO3 also were reported. 20mL ethanol and 200mL deionized and Ultrasound irradiation was applied to solution by a highintensity ultrasonic probe. The small amount of oil present on the surface of the as-synthesized ferrite sample was removed by heat treatment at 350 °C for 3 h. Mousavi and S. The photocatalytic activity of ZnWO4 in degradation of rhodamine-B (RhB) under 365nm UV light illumination was investigated.24 M. magnetic resonance imaging. F.5 ± 5. 4.3 nm for M = Ba. An aqueous solution of sodium tungstate (Na2WO4) was slowly added to a solution of zinc acetate. reported the preparation of nanosized BiFeO3 powders by sonochemical technique [94]. The as-synthesized sample consisted of crystalline zinc ferrite particles with an average diameter of ~4 nm and the heat-treated ferrite particles (350 °C for 3 h) with ~12 nm.1 ± 3. The particle sizes were 29. Tb and Eu) were prepared by Sivakumar et al. Also.1 and 13. Spherically α-Bi2Mo3O12 powder was dissolved in pyridine and sonicated at 30–40°C under nitrogen atmosphere. respectively. Ferrites Ferrites are widely used in ferrofluid technology. Metal tungstates (MWO4.05 ± 2. 5. M = Ba. 250 W/cm2.68 nm for PbMoO4 and PbWO4.0 ± 10. . 8. Ni. Sivakumar et al. Bismuth molybdate (α-Bi2Mo3O12 phase) nanorods were synthesized by pyridine intercalative sonochemical method [91].4. 6. The magnetic properties of different orthoferrites were reported. The diameter of the α-Bi2Mo3O12 nanorods were about 10 nm and length in few hundreds of nanometer to μm after sonicating in pyridine for 6 h. A distinct advantage of the sonochemical method is the preparation of nanocrystalline orthoferrites at a remarkably reduced calcination temperature. The synthesis of spinel ferrites MFe2O4 ((M = Mn.5. Das et al. and 10 h). drug delivery and data storage. respectively. using Fe(CO)5 and rare earth carbonates precursor through sonochemical method [95].6. The controlled heating of pyridine-intercalated nanorods to 450 °C was resulted in a-Bi2Mo3O12 phase nanorods free of pyridine. 20 kHz. Sr and Ca) were synthesized using the corresponding M(NO3)2 and Na2WO4 in ethylene glycol by ultrasonic irradiation [89]. Er. 3 g P123.22 nm and 21. 18.09 ± 5. ZnWO4 nanorods were successfully synthesized via powerful ultrasonic irradiation. for varying time periods (2. 5. Co. Nanocrystalline rare earth orthoferrites MFeO3 (M=Gd. [93b] used a ultrasound assisted emulsion (consisting of rapeseed oil and aqueous solution of Zn2+ and Fe2+ acetates) and evaporation protocol to synthesize zinc ferrite (ZnFe2O4) nanoparticles (Figure 10). Their average sizes of round shaped nanoparticles of metal tungstates were 42. MoO4 Lead molybdate (PbMoO4) and lead tungstate nanoparticles were synthesized from solution of Pb(NO3)2 and Na2MO4 dissolved in 50 ml ethylene glycol by applying ultrasound waves for 1 h [90].

1. Stoichiometric amounts of SrCO3 and Fe(CO)5 was dissolved in decalin and irradiated with ultrasound (using the titanium horn tip with power of 29. The resultant precursor was then calcined at 900°C for 14 h in air atmosphere. The magnetization vs. Same authors reported a sonochemical method for preparation of strontium hexaferrite by a sonochemical method employing Fe(CO)5 and SrCO3 [96]. 6. 6. TEM of as-prepared and heat-treated ZnFe2O4 nanocrystals (scale bar is 20 nm). which is lower than the conventional solid-state reaction (1300°C). Metal Oxide-Metal (Oxide) Nanocomposite Perkas and et al. . The crystalline size of silver nanoparticles was calculated as 50 nm and magnetite nanoparticles ~ as 10 nm. temperature pattern exhibits strong temperature dependence over a range of 300–800 K probably due to the presence of single-domain nanoparticles and consequent superparamagnetism.7W/cm2) in an air atmosphere at 0°C for 4 h to get the strontium hexaferrite powder. A SrCO3 hexagonal rod was synthesized using strontium nitrate and urea in the presence of ultrasonic irradiation. Ag-Fe3O4 composite was well arranged in the series of chains (Figure 11 a and b). used sonochemical irradiation of iron (II) acetate aqueous solution in presence of silver nanopowder to deposite magnetite nanoparticles on silver nanocrystals [97]. NANOCOMPOSITES Sonochemistery is one of the techniques have been used to synthesis different categories of nanocomposites such as inorganic/inorganic and inorganic/organic materials [97].Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 25 Figure 10. The Hc value remains more or less temperature independent over the 20–300K range. It was suggested that the application of ultrasound on the Fe(CO)5 generates amorphous Fe2O3. SrFe12O19 exhibited an intrinsic coercivity field (Hc) of ~4600 Oe and a saturation magnetization (Ms) of ~60 emu/g at 20 K and ~32 emu/g at 300 K. The amorphous Fe2O3 was then dispersed or coated on SrCO3 during the ultrasound irradiation.

Gold could contribute to changes in the surface states and magnetic properties. also synthesized gold-magnetite nanocomposite materials via sonochemical methods (Figure 12) [98]. diethylene glycol (100 μL).1 mM HAuCl4 (aq) containing methanol (100 μL). It was suggested that local melting of silver occur when the magnetite nucleus is thrown at the silver surface by high speed sonochemical microjets and this is probably the phenomenon causes the anchoring of magnetite to the nanosilver surface. The solution was then sonicated in a jacketed. The coercivity of the treated magnetite was 75 Oe.2 wt% of the nanocomposite is corresponded to Fe3O4 and its magnetization would be about 35 Emu/g Fe3O4. . it most considered that only 5. Mousavi and S. The gold–magnetite nanocomposite material was pulled against the wall of the test tube by the magnet. Pradhan et al. water cooled (20 C) reaction vessel under an argon atmosphere for 10 min at 50% amplitude using an ultrasonic processor. Magnetite nanoparticles (1 mg suspended in 100 μL of methanol) with diameter of ca. or oleic acid (100 μL) as solvent modifiers sparged with argon during the experiment [99]. Ghasemi Figure 11. The characterization of the product reveals the presence of two phases of the silver and the magnetite without any chemical interaction between them. 30 nm were added to a 50 mL solution of 0. The changes in magnetic properties are likely due to changes in the surface characteristics of the magnetite. The total saturation magnetization of the composite is rather low – 1. However.26 M. The resulting solution was then transferred into a test tube and kept in front of a magnet. (a) initial nanosilver powder (b) TEM images of Ag–Fe3O4 composite obtained by sonochemical method and (C) HRTEM image of Ag–Fe3O4 composite. F. while the gold–magnetite nanocomposite material exhibited a coercivity of 200 Oe. The AgFe3O4 nanocomposite showed superparamagnetic behavior in a magnetic field.8 Emu/g.

The Ag nanoparticles were incorporated in a mesoporous structure of γ-Al2O3 upon calcination of product under Ar atmosphere at 700 °C for 4 h. Then. which prepared the magnetically retrievable palladium/Maghemite nanocomposite catalysts by sonochemical reduction method [101]. The as prepared product consisted of Ag nanoparticles dispersed in the bayerite [Al(OH)3]/boehmite [AlO(OH)] matrix. Mizukoshi et al. and uniformly immobilized on the surface of the maghemite. Mizukoshi et al. TEM images showed that the diameters noble metal particles depended upon the concentration of PEG-MS. Ptand Pd) on the surface of maghemite with irradiation of aqueous solutions containing noble metal ions (HAuCl4. substantially smaller gold particles were observed. also introduced Au/γ-Fe2O3 composite nanoparticles which could selectively adsorb sulfur-containing amino acids [102]. The noble metal ions were reduced by the effects of ultrasound. grey particles are magnetite. Adsorbed amino acids were successfully manipulated by applying all external magnetic fields. Dark particles are gold.7 wt % Ag nanoparticles. The average diameter of immobilized Au was 7–13 nm. H2PtCl6). Also. XRD patterns of prepared nanocomposites showed peaks originated from 111 planes of noble metals with peaks of maghemite. For a nanocomposite containing 3. during sonication. but not upon the maghemite concentration. reported immobilization of noble metal nanoparticles (Au.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 27 Figure 12. the capping ligands can be removed and cause a change in the surface charge or magnetic domains. TEM images of gold–magnetite nanocomposite material formed by sonication of magnetite in aqueous HAuCl4 with added (a) methanol (b) oleic acid additives. Another work was reported by Mizukoshi et al. and the diameters of Pd and Pt were several nm. the growth of noble metal nuclei were continuing on the surface of the maghemite. Nanocomposites of Ag nanoparticles/mesoporous γ-Al2O3 were synthesized by sonochemical method [103]. Such a catatalyst show high catalytic activities for the reduction of nitrobenzene and could be readily retrieved by magnets and verified the durability of the catalytic performance. pH of the solution and the concentration of noble metal ions. polyethyleneglycol monostearate (PEG-MS). Na2PdCl4. The additives were also found to change the gold particle loading and the Fe/Au ratio in the composite materials. It was suggested that the nucleation of noble metal occurred in the homogeneous bulk solution and then the nuclei were immobilized on the surface of the Maghemite. and magnetic maghemite nanoparticles [100]. With oleic acid added. and the Fe/Au ratio was intermediate between that of the materials prepared with methanol and diethylene glycol. the BET surface area is more than that of γ-Al2O3 because the Ag nanoparticles remained on the .

and also increased the diameter of the pores of mesoporous alumina. and formaldehyde in a aqueous solution 105. TEM of 3Y-TZP porous nano-aggregates impregnated with 1. the specific surface area. ZnO nanorod/Ag nanoparticle composites was synthesized by ultrasonic irradiation of a mixture of ZnO nanorods. Ghasemi surface of mesoporous alumina whereas for 10. With low temperature sintering (1150 °C for 30 h). The best results with 100% selectivity to CO2 at the lowest temperature were achieved with the Pt catalysts sonochemically incorporated into the mesoporous CeO2 support previously synthesized by the ultrasound method. The observed changes could be attributed to incorporation of the metallic Pt particles in the CeO2 interparticle volume.28 M. F. Ag(NH3)2+. TEM images of ZnO/Ag composites reveal that the ZnO nanorods are coated with spherical Ag nanoparticles with a mean size of several tens nanometer and fcc structure. Ultrasonic technique causes to the homogeneity and better dispersion of the Pt in CeO2 support. the primary crystallites with an average size of ~5nm are aggregated and nanoaggregates with a mean aggregate size of 20–40 nm are formed. pore volume and size of the CeO2 support decreased.5 wt % Ag nanoparticles. The sonochemically synthesized Pt (Pd) nano-particles (~2 nm) were impregnated into zirconia (3 mol% yttria-stabilized zirconia. the Ag nanoparticles blocked the pores. The catalytic activity of these catalysts was higher than that of the Pt catalysts on the CeO2 support prepared by the classic incipient wetness.5 wt. It was demonstrated that the higher the dispersion of the CeO2 support and the Pt phase. As shown in Figure 13. Mousavi and S.impregnation method. In this case.% of platinum. Pt/CeO2 nanoparticles have excellent properties in EA combustion at low temperature. 3Y-TZP) nano-aggregates (20–45 nm) (Figure 13) 106. Insertion of Pt nanoparticles into Mesoporous (MSP) CeO2 reported by an ultrasoundassisted reduction procedure [104]. Figure 13. the better the catalyst properties. it can be possible to produce the Pt–3Y-TZP . With incorporation of highly dispersed Pt into the CeO2 (MSP) by the sonochemical method. the BET surface area decreased.

Organic-Inorganic Nanocomposite The sonochemical assisted syntheses of organic-inorganic nanocomposites have been prepared by some researchers[108]. Bhattacharyya and Gedanken reported [107] the preparation of γ-Al2O3-doped porous ZnO nanocomposite by sonochemistry. Figure 14. The antibacterial effect is due to the copper oxide nanoparticles. silver nitrate. The antibacterial activities of the CuO-fabric composite were tested against Escherichia coli (Gram negative) and Staphylococcus aureus.5–2 wt. Copper oxide nanoparticles (~ 10–15 nm) were synthesized and subsequently deposited on the surface of cotton fabrics using ultrasound irradiation. CuO nanoparticles can generate some active species that are responsible for damaging the bacteria's cells. Natural Fibers Perelshtein et al prepared CuO-cotton nanocomposite and investigate its antibacterial activity [108].Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 29 and Pd–3Y-TZP (0. (Inset: magnified image (×100. The nanoparticles of γ-Al2O3 partially or fully block the pores of porous ZnO.2. silver nanoparticles were deposited on the surface of natural wool fibers under ultrasonic irradiation [109]. 6. (a) HR-SEM images of pristine cotton fabric coated with CuO nanoparticles (magnification ×20.000). and ammonia in an aqueous medium for 120 min under an argon .1. In a similar work. % of platinum) nano-composites with uniform distribution of the Pt (Pd) grains (in the range of 20–60 nm) and with a zirconia average grain size of 120 nm. 6. The sonochemical irradiation of slurry containing wool fibers.000) of the nanoparticles coated the fiber). (Gram positive) cultures.2.

Figure 15.2.55 eV. The precursors of the HA and commercial PMMA in 2-butanone were placed simultaneously in a reactor under ultrasonic radiation at 20 kHz. TEM bright field image of PMMA/ HA composites. The FTIR spectra showed the interactions between the ester group of PMMA and the phosphates groups of HA. 25 and 35 min. Silver adhere strong to the wool through the interaction of silver with sulfur moieties related to the cysteine group. Composite materials were obtained from the in situ synthesis of hydroxyapatite (HA) in dissolved PMMA. Polymeric Based Nanocomposites 6. for periods of 15. forming ‗‗pockets‘‘ of the composite material (Figure 15). studied the preparation of composite materials based on PMMA with nanometric hydroxyapatite (Ca10(PO4) 6(OH)2) under ultrasonic radiation for different times [111].30 M. 6. ammonium phosphate [(NH4)2HPO4] and calcium hydroxide [Ca(OH)2] were used as precursors. Ghasemi atmosphere yielded a silver-wool nanocomposite. In the synthesis of Hydroxyapatite (HA).1 Poly(Methylacrylate) and Poly(Methylmethacrylate) Preparation of ceria nanoparticles embedded in polymethylmethacrylate (PMMA) has been reported by means of sonochemistry [110]. but larger aggregates of 50-100 nm were also observed. XRD results show the formation of . An average size of the ceria is found to be similar to 5 nm by XRD and TEM measurements. In Ceria–PMMA composite. Parra et al. Hydroxyapatite particles encapsulated in a thin film of PMMA. the band gap found is 3. The average silver particle size was 5-10 nm. F.2.2. Mousavi and S.2.

The nanoparticles are spherical and their size was in the range of 20 to 80 nm. It was observed that in the presence of the surfactant.5–0. polystyrene particles are covered with some small silver beads (because of their high hydrophilicity) and complete encapsulation does not occur. The conversion of monomer can reach about 70% in 3. a homogeneous distribution of silver nanocrystals with 50 nm in size and a relatively high silver content (0. Polystyrene Polystyrene (PS)/Fe3O4 nanocomposite were prepared with miniemulsion polymerization of styrene in the presence of Fe3O4 nanoparticles under ultrasonic irradiation [113]. The peaks observed in the energy region of the Ag 3d transition are symmetric and centered at 367.6 wt % Ag) was formed on the PP beads surface. with poly(Nvinyl pyrrolidone) (PVP) as stabilizer and 2. 6. The appearance of the high-intensity bands characteristic of pristine carbon at ~1344 and 1580 cm-1 in the Raman spectra of silver coated PP for after coating PP with nanosilver was caused by the localized melting of the polymer at their points of contact with silver nanoparticles. PS/Fe3O4 emulsion and nanocomposite exhibit magnetic properties and can be separated from the magnetic emulsion by an external magnetic field. XPS studies also showed the presence of Ag (0) in silver-coated polymer PP.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 31 HA in the amorphous PMMA matrix. sonochemically prepared polyacrylamide and gamma-zirconium phosphate (Zr-P) nanocomposites by intercalative polymerization 112. Kai et al.0 h. It was suggested that microjets formed during the bubble collapsing can throw the silver nucleus to the polymer‘s surface and cause to local melting of the PP at the collision sites.9 and 373. At collision sites. In another paper. The appearance of broad peak in XRD implies nanometric crystal size of HA. When bare nano-silver particles without pretreatment are introduced into the polymerization medium. The monomer conversion and polymerization increased when nanosilver particles was added to reaction vessel. With PVP.0 h. the thermal degradation of polymer chains cause to the formation of a small amount of pure carbon. wang et al.2.2. no silver bead is detected on the whole surface of the samples and the nano-silver particles are encapsulated in the polystyrene particles. Each (PS)/Fe3O4 nanoparticles and PS latex with no encapsulated Fe3O4 nanoparticles were found in PS/Fe3O4 magnetic emulsion. SDS.3.9 eV. 6. PVP prevent the agglomeration of the reduced silver nanoparticles. In another reported work.2.2. Antimicrobial test show that the beads of the silver PP composite have high antibacterial activity against microorganisms. proposed a method based on sonochemistry to prepare silver/PS nanocomposite [114]. The preparation of Ag/PS nanocomposite was achieved by dispersion polymerization of styrene in a water–ethanol (1/6 wt/wt) solution.2. . Polypropylene Deposition of silver nanoparticles on porous Polypropylene (PP) polymer was investigated by an ultrasound-assisted reduction of AgNO3 in the presence of poly(vinyl pyrrolidone) (PVP) as stabilizing agent [115].2'-azobisizobutyronitrile (AIBN) as initiator in the presence of nano-silver particles under ultrasonic irradiation with a power output of 300 W at 20 kHz for 3.

polyaniline/Au 120.4. TEM of Au-NPs show small Au-NPs dispersed in PPy matrix and the average diameter of Au-NPs/PPy are 15 nm (Figure 16). TEM image of (a) Au-NPs/PPy (b) Pt-NPs/PPy nanocomposite prepared by ultrasonic irradiation for 4 h. Figure 16. Conducting Polymer Among conductive polymer. The conductivity and magnetic properties of the PANI/Fe3O4 composite can be controlled by the Fe3O4 content so that with increasing the Fe3O4 content. Ghasemi 6.2. The authors also investigated the effect of poly(N-vinyl-2-pyrrolidone) as a stabilizer in preparation of Au-NPs/PPy (Figure 16 b) 117. The decrease of the conductivity is raised from the addition of nonconducting Fe3O4 nanoparticles. .2. PANI deposited on the surfaces of the Fe3O4 particles and all Fe3O4 nanoparticles was encapsulated with PANI.and Pt-NPs) and polypyrrole (PPy) were prepared by a sonochemical method. The maximaum conductivity of PANI was obtained with 2:1 molar ratios of oxidant to aniline. in which metal ion and pyrrole monomer in an aqueous solution were reduced and oxidized. Same authors also preapared polypyrrole-encapsulated platinum nanoparticles (PPy/PtNPs) by a sonochemical synthesis and used it as catalysts for the liquid phase hydrogenation of substituted alkenes in methanol or methanol/water mixtures 118. The ultrasonically synthesis of PANI/Fe3O4 nanocomposite was reported with in situ polymerization of aniline in the initially neutral medium and in the presence of Fe3O4 nanoparticles and oxidant. Colloidal dispersions of hybrid nanocomposite composed of gold and platinum nanoparticles (Au. polyaniline/Y2O3 121 and polyaniline/Fe3O4 122 have been synthesis with the aid of ultrasonic irradiation. respectively. The nanocomposites of polyaniline/silver 119. polypyrrole and polyaniline have been used to prepare nanocomposite with different materials such as nobel metal and metal oxide [116]. Fe3O4 nanoparticles were dispersed on the nanoscale by ultrasonic irradiation and the polymerization of aniline was begun by the addition of an oxidant. F.32 M. by ultrasonic irradiation in the presence of sodium dodecyl sulfate (SDS). a decrease in the conductivity and an increase in the magnetic properties of the PANI/Fe3O4 composite were observed. Mousavi and S. ammonium persulfate (APS).

used sonochemical method to synthesized amorphous manganese oxide and acetylene black (HSMO/AB) [124]. phosphoric acid (H3PO4). ammonium peroxydisulfate (APS).65 g of acetylene black (AB) was irradiated with ultrasound (600W of total power and 100 kHz in frequency) was for 6 h in air atmosphere. respectively. The thickness of the amorphous substance varied from 1 to 10 nm. sodium.20 g of NaMnO4 was dissolved in 750 ml of deionized water and 0. Carbonaceous Nanocomposite Kawaoka et al. and manganese.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 33 Polyaniline (PANI) nanotubes containing Fe3O4 nanoparticles were also synthesized under ultrasonic irradiation of the aqueous solutions of aniline. At operating voltage of 2. A solution containing 1. 6. the power and energy density are 20 kW kg-1 and 90 Wh kg-1. The capacity of the HSMO/AB nanocomposite tested under large current density. Energy dispersive spectrometer (EDS) analysis showed that the amorphous substance was composed of Carbon. is 185 mAh g-1. The acetylene black particles were homogeneously coated with amorphous manganese oxide with ca. oxygen. . and the quantitative amount of Fe3O4 123.5 V. It was suggested that AB particles were coated with the amorphous phase of hydrated sodium manganese Oxide (HSMO). Figure 17. 10 A g1. 35 nm in diameter (Figure 17).3. Low-resolution TEM of HSMO/AB nanocomposite.

Pd/C. They investigated the electrochemical properties of WC1−x/Pt/MWNT nanocomposite especially for the hydrogen oxidation reaction (HOR). They optimized the synthesis conditions. When a Pd-loaded GKB (Graphitic Ketjen Black). Cao et al used the sonochemical method to prepare mesoporous carbontin oxide (SnO2) nanocomposite [126]. a part of the deposit reacts with the Pd nanoparticles forming a Pd–W alloy which showed much lower HOR activity than non-alloy Pd nanoparticles. Nanocomposite based on carbon nanotube has been considered by some researchers during last years[128].5 (0. After preparation β-WC/Pd/C nanoparticles.1 M RhCl3 aqueous solution and 40 mg of borane morpholine complex (C4H12BNO) and sonication was continued for another 20 min. The conventional synthesis method such as carburization of tungsten oxide precursors cannot generate such high temperatures and most of studies on tungsten carbides have been restricted to W2C or α-WC whereas nanoparticles of β-WC can be synthesized by a sonochemical reaction method due to extreme conditions generated by this method. such as the reaction temperature and pH and specific surface area of the carbon. As shown in Figure 18. Jang et al also used the similar ultrasonic method to prepare composite of Pt and WC1−x nanoparticles supported on multiwalled carbon nanotube (MWNT). a nanocomposite composed of Pd and β-WC nanoparticles was obtained by a sonochemical decomposition of W(CO)6 followed by heat-treatment. rhodium (Rh) nanoparticles with an average diameter of 2. Also. The prepared tungsten carbide–palladium nanocomposites with different amount of W were examined as hydrogen oxidation reaction (HOR) catalysts. F. TEM image of sonochemical synthesized CNT/Rh nanocomposite is shown in Figure 18. They showed that the use of a carbon with a higher specific surface area caused to the higher specific capacity and lower capacity drop. Ghasemi This Japanese group also published another article in which the preparation of manganese oxide/carbon nanocomposite was described [125]. For this purpose. it was shown that without sonication and functionalized MWNTs. . 20 mg of carboxylate-functionalized MWNTs were dissolved in 20 mL ethanol. and the solution was sonicated for 1 h. The manganese oxide/carbon nanocomposite was used as the cathode material of a high-power lithium-ion battery. It was discussed that when too excessive W was deposited. Borane morpholine complex has a milder reducing ability compared with NaBH4 and produce Rh nanoparticles with a narrow size distribution. The well-dispersed CNT solution was added to a solution with 400 µL of 0. In other work. This is an evidence of preference of sonochemistry to other conventional methods.7 nm is deposited uniformly on multiwalled carbon nanotubes (MWNTs). Jang et al prepared nanocomposites between β-WC (also known as WC1−x ) and Pd nanoparticles supported on carbon [127]. By varying the amount of W(CO)6 in the sonochemical reaction. was used as the support. two samples with different W-contents denoted as β-WC(12)/Pd/C and β-WC(39)/Pd/C were synthesized. well-dispersed small metallic nanoparticles cannot be formed and deposited on CNTs. obtained by reducing PdCl2 with NaBH4 in the presence of GKB. The carboxylate groups of functionalized MWNTs (acid washed) provide sites for anchoring the metallic nanoparticles. stable above 2785 ◦C. Mousavi and S. β-WC is a high temperature phase. The synthesis of carbon nanotube (CNT)-supported Rh nanoparticles was reported by a sonochemical method [129]. The resulting nanocomposite is consist of SnO2 with 3 nm in size dispersed on ordered mesoporous carbon.34 M.

Results show that complete ring saturation of polycyclic aromatic hydrocarbons (PAHs) can be achieved under mild hydrogenation conditions using the Rh/MWNT. It was shown that the MWNT/PANI nanocomposites causes enhanced electric conductivity and thermal stability in comparison with pure PANI. The catalytic activity of the Rh/MWNT catalyst is much higher compared with a commercially available Rh nanocatalyst.2 ±0. Zhang et al. the smooth. The selected area electron diffraction (SAED) pattern shows a ring pattern corresponding to the face-centered cubic polycrystalline structure of CeO2. Then. Polyaniline/CNT and poly (methyl methacrylateco-n-butyl acrylate) (P(MMA-BA))/ carbon nanotubes (CNTs) are example of such nanocomposites. Also. Firstly. Furthermore. Sonochemistry can be used to synthesize the metal oxide and carbon nanotube nanocomposite. some of articles were focused on preparation of Polymer/CNT nanocomposites with sonochemistry [131].Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 35 Figure 18. The catalytic activities of the Rh/MWNT catalyst were investigated for hydrogenation of neat benzene and benzene derivatives in comparison with commercially available Rh nanocatalysts at low-temperature. TEM of CNT/CeO2 composite shows many tiny interconnected grains with average grain size of 4 nm. The final pH value was 10. CeO2 was deposited on CNT with slowly addition of NaOH aqueous solution to above solution. respectively. uniform. CNT was dispersed in a 0.1 eV related to BEs of Rh(3d5/2) and Rh(3d3/2). used a simple sonochemical route to prepare CNT/CeO2. of Rh(0). The EDX analysis also showed that the mass of Rh in the composite was 11. TEM images of CNT-supported Rh nanoparticles prepared with sonochemical method. and flexible P(MMA-BA)/CNTs composite films were prepared from the composite .1 wt %.2 and 312.05 g/mL Ce(NO)3 alcohol aqueous solution (Valcohol:Vwater = 1:1) with high-intensity ultrasonic radiation at room temperature [130]. The XPS spectrum of the Rh/MWNTs shows binding energies (BEs) at 307.

10 nm were uniformly deposited on the surface of α-Bi2Mo3O12 nanorods. NANOMATERIALS WITH CORE-SHELL MORPHOLOGY Nanostructured materials with core-shell morphology can find many applications in areas such as photonic crystals. Ghasemi emulsion [132]. Aluminum-oleic acid core-shell nanoparticles have been synthesized using the titaniumcatalyzed thermal decomposition of Alane N.05 A m1).4.06) and good. 200 nm) in pyridine.4 M toluene solution in which the thermal energy was supplied via acoustic cavitation [135]. TEM of the second sample prepared with the concentration of 11. Other Nanocomposite Ghule et al. soft magnetic properties (coercive field HC = 0. The aluminum-oleic acid core-shell nanoparticles prepared with 3. Nanocrystalline particles have a core-shell structure where a coating of Fe3C and carbon protects the body-centered cubic Fe in the core from oxidation. Material obtained under appropriate conditions possesses a high saturation magnetization close to that of bulk iron (Ms/M0 = 0. The iron nanoparticles are coated by a crystalline shell with a thickness of about 5 nm. To prepare Ag/Bi2Mo3O12 nanocomposite. 100 nm diameter) was prepared by ultrasonication of preformed α.Bi2Mo3O12 spherical nanoparticles (ca.8 mM oleic acid have spherical nanoparticles with an average size of ~30 nm and a size distribution estimated at 20-70 nm. Titanium (IV) isopropoxide was the catalyst of reaction.4 mM oleic acid showed spherical nanoparticles of a . a mixture of alpha-Bi2Mo3O12 nanorods and Ag2O in pyridine was irradiated by ultrasonic wave. F. Tensile tests of film suggest that with the modulus and the yield strength of composite film increased with increasing in the CNTs content. 20-40 nm and 20-100 nm and with round shape morphology. α-Bi2Mo3O12 nanorods (ca.N-dimethylethylamine in a 0.1.50-0. The size of the particles. their composition and magnetic properties could be controlled by changing the sonication conditions and annealing temperature. 6.36 M. Mousavi and S. Particles annealed at 700 °C are composed mainly of tetragonal and round particles. catalysts. Particles heated at 300 and 400 °C have narrow range distribution ca. and biotechnology [134. Calcination of sample at 450 °C produces pyridine-free α-Bi2Mo3O12 nanorods with deposited Ag nanoparticles.97-1. Nanoparticle with Metal Core Nikitenko et al prepared the air-stable Fe/Fe3C nanocrystalline particles have by sonicating of Fe(CO)5 in diphenylmethane solutions under argon and subsequently annealing the as prepared amorphous products in an inert atmosphere for 2 h. Silver nanoparticles with an average size of ca.] In the following paragraph some of nanoparticls with core shell morphology are reviewed. An increase in the annealing temperature to 800 °C causes the formation of hexagonal and tetragonal particles. reported the synthesis of Ag/Bi2Mo3O12 nanocomposite by ultrasonic method [133]. 7. 7.

which have been sonochemically synthesized for 4 h: (a) SEM image. . Trioctylphosphine (TOP) (as P source) is used to react with iron pentacarbonyl for the formation of iron phosphide and trioctylphosphine oxide (TOPO) is used to control the size and growth morphology of resulting materials. reported the sonochemically synthesis of Fe3O4–FeP core–shell nanoparticles with Fe3O4 core of 5–10 nm and FeP shell of 2–3 nm [136]. Oleic acid may act to cap the surface of the growing nanoparticles. Nanoparticles with Metal Oxide Core Hu et al.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 37 much smaller diameter with an average size of ~5 nm with a size distribution of 2-15 nm. They also reported the preparation of FeP hollow nanoparticles with outer-diameter of 5–10 nm and inner-diameter of 3–8 nm (Figure 19). 7. (b) TEM image. Characterization of core–shell Fe3O4–FeP particles. thus limiting particle size.2. Figure 19. The TOPO/TOP mixture was sonicated under aerobic condition in a sealed bottle at 65–70 ºC in water bath.

forms a densely packed shell with uniform coating.05 M HCl was rapidly injected via a fine plastic tube to 40 mL of 2 M ammonia solution containing 0. F. which is smaller than 760 Oe of sample FeP.0-3.01 M of hydrazine under power ultrasound at 30-32 °C in an argon flow. Silica microspheres were modified with a two layer polyelectrolyte of aqueous poly (ethyleneimine) and poly (acrylic acid). To prepare FePt/ZnS/SiO2 core-shell. and then FePt nanoparticles nucleate on the ZnS shell.010 g of modified SiO2 in 12 mL of ethylene glycol was sonicated for about 10 min and platinum (II) acetylacetonate (Pt(acac)2) (0. report a rapid sonochemical synthesis of monodisperse nonaggregated Core shell Fe3O4@SiO2 magnetic nanoparticles (NPs) 137. The sonochemical preparation of FePt/SiO2 and FePt/ZnS/SiO2 core-shell was demonstrated by Wang et al (Figure 20) 138. In the case of FePt/SiO2.5 nm after 3 h of ultrasonic treatment. 2Fe( III )  Fe( II )  8OH   Fe3O4  8H 2 O (18) Fe3O4 NPs have smaller size and a narrow size distribution (4-8 nm) than the silent reaction. A freshly prepared mixture of 1.0 kOe. High speed of sonochemical coating prevents the magnetite from oxidizing. 0. . the low temperature measurement shows that the coercivity reaches 500 Oe.5 kOe at room temperature when annealed under a high vacuum at 400 °C for 20 min and 600 °C for 10 min. Ghasemi The core–shell Fe3O4– FeP particles and FeP hollow nanoparticles showed the M–H loop at room temperature and low temperature under magnetic field up to 7 T. magnetic FePt nanoparticles with size of 3-5 nm. FePt/SiO2 core-shell particles exhibit coercivity of 3.5 nm after 1 h of sonication to 3. Fe3O4 is magnetically a much soft material. For the core–shell sample.5 mmol FeCl3 and 0. Fe3O4@SiO2 NPs prepared with sonochemistry exhibit a higher magnetization value than that for NPs obtained under silent conditions.108 g of Fe(acac)3 were then added into the mixture and sonication was continued for 2-4 h under an Ar gas flow. at 10 K with coercivity ranging from 200 Oe for 4 nm to 450 Oe for 16 nm nanoparticles. respectively. Nanoparticle with Sio2 Core Morel et al. Silica shell thickness of Fe3O4@SiO2 magnetic nanoparticles increase with sonication time. The reaction is accelerated many-fold in the presence of a 20 kHz ultrasonic field. The M–H curve shows a soft ferromagnetic behavior. It was demonstrated that the amine and carboxylic functional groups in the polyelectrolyte layer provided nucleation sites for FePt nanoparticles. the coercivity of the FePt/ZnS/SiO2 core-shell sample annealed at 530 °C is 12.5 and 12. Sonication of Fe3O4 NPs suspension in alkaline ethanol-water solutions of tetraethyl orthosilicate (TEOS) cause to hydrolysis of TEOS and Fe3O4 NPs coated with silica are prepared. Mousavi and S. the increasing of Fe3O4 results in a decreasing of coercivity. The Fe3O4 NPs were prepared by coprecipitation of Fe(III) and Fe(II) in alkaline solutions in the presence of ultrasonic irridation.060 g) and iron acetylacetonate (0. the unmodified silica was precoated with ZnS.078 g of Fe(acac)2 or 0. The thickness of ZnS shell and FePt shell on FePt/ZnS/SiO2 is ~30 nm and ~15 nm.38 M. TEM images shows an increase in the silica shell thickness is from 1. 7.0 -1.3. It was seen that.75 mmol FeCl2 in 5 mL of 0.

. Figure 21. (c) FePt/ZnS/SiO2 (inset. (d) HRTEM of FePt and ZnS nanoparticles on the shell .Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 39 Figure 20. (a) TEM of sonochemically prepared hollow MoO3 nanospheres after HF etching of MoO3/SiO2 (before thermal annealing) (b) After thermal annealing at 350 °C. the thickness of ZnS shell and FePt shell is ~30 nm and ~15 nm. TEM images of fcc phase FePt core-shell spheres: (a) average size ~240 nm FePt/SiO2 using Fe(III)(acac)3 as iron precursor. and SAED pattern of FePt shows fcc phase). respectively). (b) HRTEM image of dense 3-5 nm FePt clusters on the FePt/SiO2 shell (inset: ~120 nm FePt/SiO2 using Fe(II)(acac)2 as iron precursor.

CdTe/CdS nanocrystals show bright emission with an obvious red shift of spectra. Pr. Mousavi and S. HAP). TEM images showed that nanoparticles with short rod-like shape with 20–50 nm length and 12–25 nm width or spherical shape with 10–25 nm were obtained. Gd. F. 961. Hydroxyapatite (Ca10(PO4)6(OH)2. In comparison with the original CdTe nanocrystals.4.40 M. . Nanosized. Ce. XRD results also proved the appearance of HAp phases. reported the preparation of lanthanide orthophosphate LnPO4 (Ln = La. the prime constituent of tooth and bone mineral was synthesized sonochemically from aqueous solution of Ca(H2PO4)2 and glycosaminoglycans (GAGs) with adding saturated Ca(OH)2 aqueous solution [142]. Ho) nanoparticles via ultrasonic irradiation of inorganic salt aqueous solution under ambient conditions [144]. The FTIR spectrum show the characteristic bands for PO43.1. Sm. 8. Dy. Hollow shells of the MoS2 and MoO3 were obtained with washing the MoS2. and 1108 cm-1. Ghasemi Dhas and Suslick reported the synthesis of MoS2/SiO2 and MoO3/SiO2 core shell materials uniform coating using sonochemical method 139. Chalcogenide Core-Shell Ultrasonic irradiation was employed to aqueous synthesis of CdTe/CdS core-shell nanocrystals by using preformed TG-capped CdTe nanocrystals as template cores and thiourea as the sulfur source [140].appear at 472. The resultant coreshell nanocrystals presented dramatically improved photoluminescence (PL) quantum yields (QYs). leading to the formation of gradient CdS shell on CdTe cores. 22) The SAED pattern indicates that the nanorods are single crystals. The mixture was irradiated for different time (0. 7. Tb. Eu. CaHPO4) with orderly layered structure assembled by nanosheets was synthesized from solution containing Ca(NO3)2 and NaH2PO4 in the presence of cetyltrimethylammonium bromide (CTAB) by a sonochemical method [141]. 601. The internal structure of these platelike formations consists of specifically oriented and laterally connected HAp nanorods with a length of about 500 nm and a diameter of about 100 nm (Fig . 1032. platelike hydroxyapatite (HAp) was synthesized using a homogeneous precipitation method under ultrasound irradiation[143]. It was found that ultrasound facilitated the decomposition of thiourea. Thermal annealing of MoO3/SiO2 at 450 °C before HF etching was caused to conversion of hollow MoO3 spheres to truncated cubic hollow crystals (Figure 21). Metal Phosphate Monetite (anhydrous calcium hydrogen phosphate. 10 times higher than the original nanocrystals. 583. OTHER NANOMATERIAL 8.or MoO3-coated silica with 10% HF in aqueous ethanol.5 h. Nd. Yu et al. The thicknesses of the nanosheets are 100-200 nm with the lateral sizes of about 2 μm. 3 h and 5 h) by an ultrasonic cleaner at 40 kHz and 250 W.

The BiPO4 nanorod have singlecrystalline nature with a preferential growth oriented along the (001) crystalline plane. Nanorods have diameters of 40-60 nm and lengths of 25µm. It was demonstrated that the synthetic parameters such as pH of solution and sonication time effect on morphology of BiPO4. Figure 23. which shows a large aspect ratio of 50-80 (Figure 23). BiPO4 nanorods were successfully synthesized via a sonochemical method without any surfactant under ambient air [145]. Eu. Sm. TEM images show that the hexagonal structured lanthanide orthophosphate LnPO4 (Ln = La. Gd) products have nanorod bundles morphology.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 41 Figure 22. Nd. Dy. Uniform BiPO4 nanorods with a large aspect ratio could . (b) TEM image and SAED pattern recorded on a single BiPO4 nanorod. Ho) samples prepared under the same experimental conditions are composed of nanoparticles. (a) TEM and (b) SAED pattern of a single nanorod of Hap. Pr. They also prepared Eu3+-doped LaPO4 samples and investigated their photoluminescent properties. HRTEM micrographs and SAED results show that LnPO4 nanostructures are polycrystalline in nature. Eu3+-doped LaPO4 exhibit an orange– red emission. Ce. while the tetragonal LnPO4 (Ln = Tb. (a) SEM images of BiPO4 nanorods.

Subsequently. Thermal treatment of MnCO3 samples prepared without surfactant and in the presence of AOT produced a nanoporous cubic Morphology. Then. CdCO3 147 and CeCO3OH [148]. The morphology of the product could be affected by the volume ratios of water/DMF in initial solutions. Metal Fluoride BaF2 nanocrystals doped with 5. Ghasemi only be obtained when the pH of reaction system was adjusted at range of 0. To prepare Dumbbell-like YF3 nanostructures. The assemblies were porous and constructed of ca. The ellipsoidal morphology of sample prepared in the presence of SDS was retained after decomposition of MnCO3 to Mn2O3. Metal Carbonate Sonochemistry has been used to prepared various type of nanostructure metal carbonate such as BaCO3[146].N-dimethylformamide (DMF) was added to the above solution (water/DMF ratio of 5/15). Y2O3 was dissolved in 10% dilute HNO3.[149] reported the sonochemical preparation of MnCO3 submicrocubes and highly oriented MnCO3 nanocrystal assemblies with an ellipsoidal morphology.0 mL N.5-1. TEM images of sample show a series of dumbbells each comprised of abundant nanorods. 8. A thermal treatment of MnCO3 at 600 °C in air produces nanoporous Mn2O3. 15. . optoelectronics. 5 nm nanocrystals. Rare-earth fluorides with controllable shapes and sizes have attracted intense research interest due to their particular photoluminescence properties and potential applications in optics. Table 1 summarizes the observed morphology depended on water/DMF ratio. In the presence of AOT as a surfactant. MnCO3 submicrocubes with sizes of about 500 nm were observed which is significantly smaller than those prepared without using AOT. The aqueous solution containing MnCl2 and urea was sonicated with an ultrasonic probe immersed directly in solution (operate at 20 kHz. The reaction was repeated in the presence of aerosol OT (AOT) and SDS (sodium dodecyl sulfate).3. F.0 mol% Eu3+ (BaF2:Eu3+) nanospheres [151] EuF3 nanoflower [152] and Dumbbell-like YF3 nanostructures [153] are metal fluorides family were prepared by ultrasonic-assisted method. 8. EuF3 nanoflower prepared through the reaction of Eu(NO3)3 and KBF4 under mild ultrasonic irradiation. Mousavi and S. highly oriented ellipsoidal assemblies were observed. In the presence of SDS.2.42 M. ~ 80 W/cm2) at 80 °C for 90 min [150]. the mixed system was transferred into a 50 mL plastic flask and irradiated by ultrasonic wave with 40 kHz and ultrasonic power of 100% (200 W) at 65 °C for 2 h. biological labeling and catalysis. The morphologies of the products is the result of the sensitive influence of the pH on the solute concentrations ([Bi3+] and [HnPO4(3-n)-]). NH4F (3 mmol) was added under stirring. Yang et al.

01 mol %). 8. . Also. p-xylene and ferrocene provide carbon source for SWCNT growth and silica powder acted as a nucleation site for SWCNT growth. and CH3I on hydrogen-passivated silicon nanowires (SiNWs) as templates under ambient conditions [155]. nanofibers are formed. reported a sonochemically method to prepare SWCNT. Single-Walled Carbon Nanotube (SWCNT) Jeong et al. Ferrocene is decomposed during sonication and provide Fe nanoparticles as catalyst for nanotube growth. Li et al. CH2Cl2. the morphology does not change markedly. A solution of ferrocene and p-xylene was mixture with silica powder (diameters of 2-5 mm) and irradiated with ultrasonic waves by a 1/2-in. It was demonstrated that different dopant acids produced PANI nanotubes (Figure 24) and nanofibers with similar morphology. the concentration ratio of [dopant acid]/[aniline] effect the morphology of polyaniline nanostructures. After the volume ratio was decreased to 10/10. It was found that high-purity SWCNTs were obtained at relatively low concentration of ferrocene (0.4.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials Table 1. PANI nanotubes and nanofibers doped with different mineral (HNO3. nanotubes could be observed but with high concentration of dopant acid. morphology of YF3 as function of Water/DMF ratio Water/DMF ratio 20/0 (pure water) 15/5 10/10 5/15 0/20 (pure DMF) Morphology of YF3 nanostructures spindle-like (particles with about 350 nm in length) spindle-like rod-like dumbbell-like near-spherical 43 When the volume ratio of water/DMF was decreased to 15/5. HClO4) and organic acid (camphorsulfonic acid) were synthesized under ultrasonic irradiation [156]. Also. HF solution was used to remove silica particles at end of reaction. At low concentration of dopant acid. Silica powder was broken into small pieces during the sonication. the spindle-like particles with the thin in two ends and the thick in middle had converted into morphology. 8. When reaction was completed in pure DMF (0/20). H3PO4. titanium tip 200-W probe pulsed 65% under ambient conditions for 20 min [154]. Further decreasing the volume ratio of water/DMF to 5/15 produces particles. Polyaniline PANI is one of the most important conducting polymers. the as-prepared product was composed of a great number of nanoparticles with a mean diameter of ~30 nm. Ammonium peroxydisulfate was used to oxidize aniline monomer. reported the synthesis of new hydrocarbons (hydrocarbon nanotubes and nanoonions) and carbon nanostructures (carbon nanotubes and nano-onions) via the sonochemical reactions of organic solvents such as CHCl3.5.

Also. The effect of various parameters such as ultrasonic power. Also.41 eV at 300 K) and a larger excitation Bohr radius of 18 nm.4 eV and has received considerable attention in solar cells. TEM of PANI nanotubes synthesized under ultrasonic irradiation doped by perchloric acid. Se-2. and reaction temperature was investigated on morphology of polymer. . reported the chemically synthesized polyaniline nanofiber via ultrasonic irradiation [157]. selenides and tellurides are considered. for example the polymer prepared at 50 kHz showed the highest uniformity and smoothest surfaces. photo-electrochemistry and biological labeling.e. CdS is one of the most important II–IV group semiconductors with narrow band gap of 2. catalysis. In next section. and Te-2) of metal have semiconductive properties and found extensive applications in various fields such as non-linear optic detectors. quantum size effect semiconductor. photovoltaic solar cells and optical storage media. Mousavi and S.6. F. Metal Chalcogenides Sonochemistry provide a facile synthetic method to prepare nanostructures of metal chalcogenides.44 M. Chalcogenides (S-2. the polymers prepared at higher frequencies showed higher purity. HgS 159. MoS2 [160]. In2S3 [162]and CuS [163]. metal sulfides. Ghasemi Figure 24. whereas longer nanofibers with larger aspect ratios were obtained at a higher polymerization temperature. 8. The length or aspect ratio of PANI nanofibers decreased with increasing ultrasonic power.Ag2S [161]. 8.1. Among various types of metal sulfide CdS and PbS have been explored extensively because of its unique properties 164. Lead sulfide (PbS) is an important π–π semiconductor with small bulk band gap (0. frequency. It was found that increase of ultrasonic power (up to 250 W) or the reaction temperature (up to 75°C) produce PANI nanofibers with more uniform diameters.6. various types of nanochalcogenides i. optoelectronic devices. Li et al. Metal Sulfides Various types of metal sulfides have been synthesized based on ultrasonic techniques such as ZnS [158].

The shells of the hollow spheres estimated to be around 20 nm and are composed of small PbS nanoparticles with diameters of about 12 nm. The adsorbed ions provide nucleation domains for the subsequent reaction between Pb2+ and H2S to form PbS nanoparticles. It was suggested that DBS has the tendency to selfaggregation and to form vesicles with different sizes under the ultrasound wave. which directly determine the diameters of the spheres.4 µm in width and 3. reported the preparation of PbS hollow nanospheres with diameters of 80-250 nm through a surfactant-assisted sonochemical route (Figure 25). (a) TEM and (b) HRTEM images of the PbS hollow spheres. well-crystalline PbS rods with of 0. and sodium dodecylbenzenesulfonate (DBS) were transferred to a ultrasonic cleaning bath (49 Hz. the surface of spheres has negative charge and Pb2+ ions are easily attracted on the vesicle surfaces.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 45 Wang et al. The formation process of PbS nanoparticles is suggested as follows: H 2O ))) H   OH   2H   RS  H 2 S  R ( RS  CH 3CSNH 2 ) (19) (20) (21) (22) S 2  Pb 2   PbS  nPbS  ( PbS )n The sonochemical process produces H2S gradually. 50W) and sonicated for 4 h. Moreover. In the absence of surfactant only irregular PbS rods were observed.5-7 µm in length were observed.3-0. Table 2 and 3 summarize some of synthetic parameters and morphological structure of PbS and CdS. . Figure 25. An aqueous solution containing Pb(CH3COO)2. when cetyltrimethyl ammonium bromide (CTAB) was used as surfactant. respectively. which avoids the rapid reaction and causes that PbS nanoparticles grow on the surface of spheres. As DBS is an anionic surfactant. thioacetamide (TAA).

100 W) under ambient air Different morphologic al shapes depend on solvent type [165] PbCl2 Water. The conditions of preparation of CdS nanostructures Metal sources solvent Sulfur sources template or structure directing agent Hydroxyethyl cellulose (Mw. CdSO4 H2O and (CH3)2 CHOH H2O Na2S2O3 40-kHz ultrasonic wave at 100W output power at room temperature CdCl2 Na2S CdCl2 H2O Na2S Cadmium acetate H2O Na2S Pulse sonication (ton=6s. 50 W) for 2 and 4 h ultrasonic cleaning bath ( 40kHz 250 W) for 40 min at 40 and 70 °C High-intensity ultrasound irradiation (50 kHz. pH=7 Na2S2O3 EDTA as complexing agent Nanobelts [166] Pb(CH3COO)2 Water Thioacetamide CTAB nanocubes. nanorods and nanotubes Dentritic and star like Nanostructur es [167] Pb(CH3COO)2 Water Thioacetamide Nitrilotriacetic acid as capping agent [168] Pb(NO3)2 Water Thioacetamide Polyethylene glycol-6000 as a kind of capping polymer Nanorods [169] Table 3. 123. 40Wcm-1 for 4 h at room temperature ultrasonic cleaning bath (49 Hz. 350 W) at room temperature at different ultrasonic irradiation time Nanoparticles . Mousavi and S. Pb(CH3COO)2 ethanol. 20 kHz. Ghasemi Table 2. nanowires and dendritic-like shape Nanoparticles (3-5 nm) Hollow nanoparticle chains Nanoparticles [170] [171] [172] [173] . distilled water.46 M.000) Polyvinylpyrr olidone K30 (PVP) Polyacrylica mide Amino-acid histidine (as chelating agent) Ultrasonic parameters Morphology (Size) Ref. ethylene glycol and polyethylene glycol-200 Thiourea - high-intensity ultrasound irradiation under ambient air for 30 min titanium horn. 100 W. F. toff=14s). no. for 30 min to 2 h CdCl2 solution was added into the Na2S solution within 5 min under ultrasonic condition Sonochemical bath (33 kHz. The conditions of preparation of PbS nanostructures Metal sources solvent Sulfur sources template or structure directing agent Ultrasonic parameters Morphology (Size) Ref. 20 KHz. no.

When PVP was added into EG.6. decreasing the activity of Bi3+ ions in the solution and hindering the formation of Bi2Te3.6. Zheng et al. or EG containing certain amount of polyvinyl pyrrolidone (PVP. 8. PVP could adsorb onto the faces of the nanoflakes and hinder their growth. Metal Telluride Metal tellurides are another category of metal chalcogenides that sonochemistry have been used extensively to prepare them [174]. using Te powder and Bi(NO3)3 in the mixed solvent of glycerol and water or ethylene glycol (EG). have been synthesized using a thermal gradient approach and by sonochemical irradiation [182]. The prepared powders consist of granular and flake nanoparticles. K-30) [176]. HgSe. but few instances have been reported for nano structures coordination polymers. Bi2Se3.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 47 8. Metal Selenide Some of metal selenide have been recently synthesized are Ag2Se.3. The size of the particles are about 10~20 nm. Hedge balls nano-structure of a new Pb(II) two-dimensional coordination polymer. resulting in the formation of nanoflakes with smaller size. EDTA form complex compounds with Bi3+ ions. Also. The ultrasonic irradiation accelerates the reaction rate due to the mechanochemical effects of ultrasound waves and cause to formation of relatively small and uniform nanocrystals.is produced in the disproportionation of Te in alkaline solution react with Bi(III) to give out Bi2Te3. {3-Hpyc =3-pyridinecarboxylic acid}.7. prepared Nanocrystalline Bi2Te3 by sonochemical methods at 70 °C using Te and BiCl3 as the reactants and NaBH4 as the reductant [175]. Bi2Te3 hexagonal nanoflakes with controllable edge length ranging from ~150 nm to as small as ~10 nm were synthesized via an ultrasonic-assisted disproportionation route. Table 4 present some of works focused on metal selenides and summarized their synthetic parameters under ultrasonic irradiation. Mercury telluride (HgTe) nanorods (with diameters of ~15 nm and lengths of up to 200 nm) and nanoparticles were synthesized via sonochemical method from mercury perchlorate hydrate and tellurium powder in an ethylenediamine solvent system in the presence of 1thioglycerol as a complexing agent. CdSe. Some papers have been reported by Morsali and co-workers. Coordination Polymers The ultrasonic method is also expected to be useful. The size of the Bi2Te3 nanoflakes changed when using different solvents. The reaction mechanism may be as followed: 2 3Te  6OH   2Te2   TeO3   3H 2O (23) (24) 2Bi 3  3Te2   Bi2Te3 Te2. 8. . [Pb(3-pyc)(N3)(H2O)]n (1). It was observed that the addition of EDTA suppressed the formation of pure Bi2Te3 phase.2. the size of the nanoflakes decreased.

pH=10 Na2SeSO3 β-cyclodextrin Hollow spherical CdSe quantum dot assemblies Bi2Se3 nanobelts (8– 10nm in thickness. air and nitrogen.678(4. no.322(μ-I)2I5. A new nanostructured Bi(III) supramolecular compound. Calcination under air produces nano-sized particles of PbO. AgNO3 Water Se powder Ag2Se Nanoparticles [177] Hg(Ac)2 polyol solvent such as ethylene glycol. results in nano-structures Bi2O3 and BiI3. Some others coordination polymers from La (II) [184]. 4.4΄-Hbipy)1.678]•(4. 75 W/cm2) under ambient conditions for 20 min. citric acid or KSCN as complexing agents Metal sources solvent Selenium sources Ultrasonic parameters Pulse sonication with Ti-horn at 500 W. and several micrometers in length) [179] BiCl3 Water H2SeO3 - High-intensity ultrasound (59 kHz. Mousavi and S. 20–80 nm in width.4΄-bipyridine } was synthesized by a sonochemical method [183]. Morphology (Size) Ref. Ghasemi Table 4.4΄-bipy)} (1). Pb(II) 187 with different ligands and morphologies have been prepared.4΄Hbipy)0. The conditions of preparation of MeS nanostructures template or structure directing agent NH3. F. {Bi2(4. (time of irradiation in every reaction was 50 working cycles ton= 60 s and toff=10 s) Pulse sonication with a high-intensity ultrasonic probe Tihorn. 60 W/cm2) for 1h Bi2Se3 nanoparticles [181] Single-crystal X-ray diffraction of compound 1 shows a two-dimensional polymer with the coordination number seven for Pb(II) ions. Mn(II) [185]. 20 kHz. 80 W/cm2)( ton= 27 s and toff=3 s) High-intensity ultrasonic titanium horn (20 KHz. . 45 W) for 15 h at 25 °C [180] Bismuth nitrate Water. diethylene glycol and polyethylene glycol 200 Se powder - Taper shaped HgSe nanorods [178] CdCl2 Water. pH=11 Na2SeSO3 EDTA as complexing agent High-intensity ultrasonic probe 20 kHz. Calcinations of compound 1 under two different atmospheres. Bi(III) [186].48 M.4΄-bipy = 4. Reduction of the particle size of the supramolecular compound to a few dozen nanometers results in a lower thermal stability when compared to single crystalline samples.

Gedanken. [3] [4] [5] [6] . Y. Landau. V. L. 418-430. N. and high purities. 1. The Chemistry of Nanomaterials: Synthesis. J.. (a) Rao. Gedanken. 52-55. Also. Sonochem. Sonochemistry have been proven to be a useful route for the preparation of novel materials with unusual structures and properties which found their application in various technological applications such as sensors. L. REFERENCES [1] [2] Gedanken. Ultrason... American Scientific: 2004. Ed. and implosive collapse of bubbles in the liquid medium. Mastai. D. 11 (2).. Cheetham. controllable reaction conditions. In The Chemistry of Nanomaterials. ACKNOWLEDGMENTS The authors gratefully acknowledge M. Using sonochemistry for the fabrication of nanomaterials. A.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 49 CONCLUSION The sonochemistry is a new area of research has been considered during last years because of its simplicity and possibility of operating under ambient conditions. Sonochemistry and Other Novel Methods Developed for the Synthesis of Nanoparticles. 2 Volumes WILEY-VCH Weinheim.. A. Sonochem.. M. A. A.. Rao. 2004. 2005. R. optoelectronic device.. 63 (1). N. Vradman. Also. sonochemistry provide easy conditions for synthesize of some materials that other methods can not able to operate at these conditions. Soc. Indian Ceram. A. 47-55.. 137. M. M. growth. M. N. The advantages of this method include a rapid reaction rate.. These local hot spots produce high temperature (~ 5000 K) and pressure (~1800 K) which provide a unique environment for the growth of materials with novel structures. fuel cells and energy storage device and etc. R. C.. 434 (7029). The Sonochemical Insertion of Nanomaterials into Mesostructures. A. the cooperation of M. Y. Yousef Elahi for her assistance in preparation of this chapter. 2004. Kiani. Rao. Herskowitz. S. Doping nanoparticles into polymers and ceramics using ultrasound radiation. K. Flannigan. 2007. Koltypin. Plasma formation and temperature measurement during single-bubble cavitation.. (b) Manoharan. Bagheryan is acknolewdeged.. Besson. 10. 2006. 14 (4). A. C. Sonochemical Synthesis of Nanomaterials. Ultrason. Nature 2005. A. narrow size distributions. and the ability to form materials with uniform shapes. The chemical effect of ultrasonic irradiation arises from the acoustic cavitation which is the formation. S.. Trans. The implosive collapse of the bubbles generates local hot spots or shock wave formation within the gas phase of the collapsing bubble. Suslick. Gedanken.. M. K. Vol. S.. Abbasi and Z. Properties and Applications. Vol. Perkas.. photocatalyst. p 67-82.

J. L.. Wu... P. G. H. Li. L. Liu. I. 2006. K.. Z. 62 (14). 237-241. X. X. K. J.. Cryst. One-Pot Synthesis of Gold Nanorods by Ultrasonic Irradiation: The Effect of pH on the Shape of the Gold Nanorods and Nanoparticles. Sonochemical synthesis of highly monodispersed and size controllable Ag nanoparticles in ethanol solution.. 2005. J. Y.. Int. W. 32 (8). B 2005. Langmuir 2009... 109 (44). Ultrasound-assisted synthesis of nanocrystalline ZnS in the ionic liquid BMIM center dot BF4.. Y. Z. M. Phys. K... Ashokkumar. 12 (4). Alloys Compd. X.. Cryst. 110 (1). M. Jiang.. 383-387. K. Y. M... Shi. Nemamcha. 45 (7). B 2006. F.. 3412-3418. Z.. Grieser. 25 (14).. Kim. F. Qiu. T. Lett. 295 (1).. K. Z. L. Grieser. J. W. Ultrasonically induced Au nanoprisms and their size manipulation based on aging. Li. H. B. T.. Zhu.. Osaka. J. Synthesis of Pd-Sn nanoparticles by ultrasonic irradiation and their electrocatalytic activity for oxygen reduction. Z... 7786-7790. Vinodgopal. L. Fuchigami. P. Chem... L... C. X.. Single crystalline trigonal selenium nanotubes and nanowires synthesized by sonochemical process. Res. W. L. Wang. P. 5 (3).. Chu. Wang. C.. Chen. 709-715. B. J. Li. 60 (21-22). J. Pol. 1546-1552. D. L. T. Li.. 243-247. A:Physicochem. Chem. D. Eng. H. Y.. Ultrasonic-induced growth of crystalline tellurium nanorods and related branched structures. Ghasemi Okitsu. Acta 2009. Rehspringer. Intermed. J.. J. Growth 2006.. Zhou. Jiang. Zhou. 2005.. Sonochemical formation of single-crystalline gold nanobelts. Du. V.. Angew. 20673-20675. Sonochem. Mousavi and S. Synthesis of multiple shapes of gold nanoparticles with controlled sizes in aqueous solution using ultrasound. T. 21932195. Li. K... W.. S. N. J. 2009. Phys. M. J. 2008. J. Lett. 2006. H. Sonochemical synthesis of ruthenium nanoparticles. Cai. F. 911-916. Li. Hu.-E. Y.. Atobe.. Liu. Colloid Surf.. W.. Sonochem. J. M. Chen. Y. Chem. Sharyo. W. Wang. Xie. G. Zhang. Wang. Electrochim. H. E. 394 (1-2). L.. C. Zhu. Phys.. Qin. H.. R. Y. Z.. F. Aspects 2007. Ashokkumar.. Han. 1116-1119. Yu. W. 2006. L. Tang. Shao. Chem.. 2005... Edit.. G. J. Li. Khatmi. F.. Synthesis of tin nanorods via a sonochemical method combined with a polyol process. 282-285. Growth Des. 2764-2766.. Ultrason.. [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] . Q. G. Wang. A. Xu.. P. Calderon-Moreno.50 [7] [8] M. L. S.... 2006. 110 (4). Ultrason.. Guo. Wu. Li. M. B 2006. W.. 747-751... H. J. Yang. Zhang. Park. 69-74.. 366-370. P.. Mater. Li. Ultrason. Gold nanoparticles prepared by sonochemical method in thiol-functionalized ionic liquid... H. Synthesis of palladium nanoparticles by sonochemical reduction of palladium(II) nitrate in aqueous solution. J. Mater. M.. Nishimura. 16 (6). Z. Yang. Jin. Synthesis of dendritic silver nanostructures by means of ultrasonic irradiation. X. Zhang.. Y. M. Gedanken. A novel route to prepare and characterize Sn-Bi nanoparticles. Sonochem. S. B. J. Hao. A. F. Liu. 302 (1-3). Okitsu. Tian.. Yin. Park. He. Sonochemical synthesis of gold nanoparticles: Effects of ultrasound frequency. 54 (12).. 13 (3). Chem. J... Momma. L. Zhang.

G. J. 459 (1-2). Tao.. R. Using sonochemistry for the fabrication of hollow ZnO microspheres. 2008. H.. Li. Growth Des. Zhao. Xiao. J. Tan.. Zhu. Oh..... L18-L22. Z. S197-S200. Mohaierani. 284-287. S. 2009... Y. L. Ultrason. Casadonte. Li. J. Zhou. [35] Zhang. S. Selective-area growth of ZnO nanorod arrays via a sonochemical route. Fan. Grieser.. 573 (1). [29] Vinodgopal.. T. A.. 301-307.. M. 2010... M. 7622-7626. 246 (2).. Structural analysis of sonochemically prepared Au/Pd nanoparticles dispersed in porous silica matrix. Seino. Alloys Compd. S. Park. X. X. Ansari. D. Rivera. 1623-1629. M. Mater. 2462-2468. Tanabe. [38] Jung. [33] (a) Zhang. 38493852. Bull. H. 2008. [37] Jia.. Taghavi. O.. R. C. 40 (9). Appl.. 2005. He. H. Dai. Ultrason. Vijayaraghavan.. 9 (3.. 796-800. Lett. A. Sci. Wu. G. 249-254. Kim. S.. 62 (21-22). Sonochemically prepared platinum-ruthenium bimetallic nanoparticles.. Phys. J. K. K. 110 (9). S. . Lee. [28] (a) Nakagawa. J. Qin. Ashokkumar. S. W. 253 (18). Ultrasonic induced photoluminescence decay in sonochemically obtained cauliflower-like ZnO nanostructures with surface 1D nanoarrays. Effect of basicity on the morphologies of ZnO produced using a sonochemical method. 22 (25).. Shin.. [27] Jia. H. F. Cryst. S.. Surf. M. Q. S. Zhang... Ultrason. Catal. H. Yamamoto... [32] Mazloumi. S. S.. H. 15102-15105. Niu... W. C 2008. R..... A. Smotkin.. Langmuir 2006. 2007. W. Park. 2005. H. Korzeniewski. [24] Basnayake. F.. A. 2008. 265-269.. Surf. Y. Room temperature synthesis of needle-shaped ZnO nanorods via sonochemical method. S. S. [26] Radziuk. H.. Zhang. Current Applied Physics 2006.Sonochemistry: A Suitable Method for Synthesis of Nano-Structured Materials 51 [23] Korzeniewski. 112 (7). Jeong. S. L. 6 (4). 2005. [25] Li.. [31] Thongtem. K.. Phuruangrat. E.. H. H. M.. (b) Jung. Ashokkumar. C. Okitsu.. Jeong... Sadrnezhaad. Mater. M. [36] Xiao. Basnayake. R... Chen. H. P. D. Kang... M.. H. S.. H. Shchukin.. 11-14. Y. Katar. L. Q. X. S. Y. Sonochemical synthesis of ZnO nanosheet.. Sonochem. S.... 3673-3675.. R. E. C. Z.. Low-temperature synthesis and shape c