Download textbook Nanocomposites Nanophotonics Nanobiotechnology And Applications Selected Proceedings Of The Second Fp7 Conference And International Summer School Nanotechnology From Fundamental Research To Innovation ebook all chapter pdf

Nanocomposites Nanophotonics
Nanobiotechnology and Applications

Selected Proceedings of the Second
FP7 Conference and International
Summer School Nanotechnology From
Fundamental Research to Innovations
August 25 September 1 2013 Bukovel
Ukraine 1st Edition Olena Fesenko
Visit to download the full and correct content document:
https://textbookfull.com/product/nanocomposites-nanophotonics-nanobiotechnology-a
nd-applications-selected-proceedings-of-the-second-fp7-conference-and-international
-summer-school-nanotechnology-from-fundamental-research-to-innovation/
Springer Proceedings in Physics
Volume 156
For further volumes:

http://www.springer.com/series/361
Olena Fesenko • Leonid Yatsenko
Editors
Nanocomposites, Nanophotonics,
Nanobiotechnology, and
Applications
Selected Proceedings of the Second FP7
Conference and International Summer School
Nanotechnology: From Fundamental
Research to Innovations, August
25–September 1, 2013, Bukovel, Ukraine
2123
Editors
Olena Fesenko Leonid Yatsenko
National Academy of Sciences of Ukraine National Academy of Sciences of Ukraine
Institute of Physics Institute of Physics
Kiev Kiev
Ukraine Ukraine
ISSN 0930-8989 ISSN 1867-4941 (electronic)

ISBN 978-3-319-06610-3 ISBN 978-3-319-06611-0 (eBook)
DOI 10.1007/978-3-319-06611-0
Springer Cham Heidelberg New York Dordrecht London
Library of Congress Control Number: 2014945121
© Springer International Publishing Switzerland 2015

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the
material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,
broadcasting, reproduction on microfilms or in any other physical way, and transmission or information
storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology
now known or hereafter developed. Exempted from this legal reservation are brief excerpts in connection
with reviews or scholarly analysis or material supplied specifically for the purpose of being entered and
executed on a computer system, for exclusive use by the purchaser of the work. Duplication of this
publication or parts thereof is permitted only under the provisions of the Copyright Law of the Publisher’s
location, in its current version, and permission for use must always be obtained from Springer. Permissions
for use may be obtained through RightsLink at the Copyright Clearance Center. Violations are liable to
prosecution under the respective Copyright Law.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
While the advice and information in this book are believed to be true and accurate at the date of publication,
neither the authors nor the editors nor the publisher can accept any legal responsibility for any errors or
omissions that may be made. The publisher makes no warranty, express or implied, with respect to the
material contained herein.
Printed on acid-free paper
Springer is part of Springer Science+Business Media (www.springer.com)

Preface
This book presents a selection of the latest developments in nanotechnology and

nanomaterials. It features articles written by lecturers and young scientists from
Europe, in particular from Ukraine, who participated in the Second International
Summer School “Nanotechnology: From Fundamental Research to Innovations,”
held in Bukovel, Ukraine from August 25 to September 1, 2013 within the frame-
work of the FP7 project Nanotwinning. This International Summer School provided
early-career scientists the opportunity to participate in a series of lectures on the
emerging fields of nanoscience and nanotechnology. The goal of the Second Inter-
national Summer School was to familiarize young scientists with actual research
and problems of application in this area and to promote the future implementation
of nanotechnology in innovative development to meet public needs. The First Sum-
mer School, held in 2012, received positive feedback from international experts and
sparked interest in the media, with mentions on the Ukrainian Channel 5 programs
“Window to Europe” and “Intellect.UA,” the TBi Ukrainian TV program “Today,”
and on the Tonis national TV Channel program “Social Pulse,” as well as in Viche
magazine and the scientific journal World of Physics. International Summer School
was hosted by the Institute of Physics of NAS of Ukraine in conjunction with its
Nanotwinning project partners: University of Tartu (Estonia), European Profiles
A.E. (Greece), University of Turin (Italy), and Pierre and Marie Curie University
(France).
The beginning of the twenty-first century witnessed tremendous breakthroughs
in nanoscience and nanotechnology. Today, nanotechnology is used in computer
technology and electronics; the aerospace, chemical, and construction industries;
medicine and pharmacology; and in the manufacture of new unprecedented ma-
terials. The present volume surveys some of the latest advances in the field and
points the way to exciting future investigations and applications. The book chapters
cover such currently important topics as microscopy of nanostructures; nanocom-
posites; nanostructured interfaces and surfaces; nanooptics; nanoplasmonics; and
enhanced vibrational spectroscopy. The book demonstrates that researching nanocar-
bons, nanosilicon, biomolecular nanostructures, and their applications is a very
interesting and exciting area of modern science, which will certainly attract the
attention of scientists and engineers for many years to come.
v
vi Preface
The book is divided into four sections: Part I: Nanocomposites and Nanos-
tructures; Part II: Nanophotonics; Part III: Nanobiotechnology; and Part IV:
Application.
An overview of the chapters is provided below. The reader is recommended to
read the following descriptions first, as they provide insights into the book’s contents
and the results presented.
Part I: Nanocomposites and Nanostructures
In Chap. 1 (Dodziuk) endohedral fullerene complexes involving C60 , C70 , and C50 H10
nanotubes, especially those containing small molecular guests, are reviewed and
calculations of their stability presented. Chapter 2 (Nykyforchyn) focuses on the
improvement of certain physical and mechanical properties of surface layers of en-
gineering steels by severe thermal–plastic deformation treatment using high-speed
friction and simultaneous rapid cooling in a special medium. The authors of Chap. 3
(Korol) consider a gapped graphene superlattice (SL) constructed in accordance with
the Fibonacci rule. Chapter 4 (Cravanzola) focuses on the characteristics and electri-
cal conductivity mechanisms of carbon nanotubes and expanded graphite. Chapter 5
(Beresnev) presents nanocomposite (Zr-Ti-Cr-Nb)N coatings with high hardness and
thickness around 8.5 μm which allows their use as protective coatings for cutting
tools. In Chap. 6 (Savchenko), the luminescent spectra of obtained metallocom-
plexes in solid state are investigated and analyzed. In Chap. 7 (Vretik) possible
morphological changes on a poly(methacrylamidoaryl methacrylate) surface before
and after irradiation with polarized UV-light were investigated. Chapter 8 (Orel)
presents research into the nonlinear magnetic properties magneto-mechano-chemical
nanocomplex synthesized from magnetite and antitumor antibiotic doxorubicin.
Chapter 9 (Bellel) describes the electrochemical preparation process of magnesium-
based nanocomposites on a metallic cathode. Chapter 10 (Ulyanova) focuses
on preparation processes of SiO2 –Al2 O3 –TiO2 composite materials doped with
nanostructured fibrous powders γ- and α-Al2 O3 .
Part II: Nanophotonics
Chapter 11 (Donets) presents technological aspects of corrosion resistant steels sur-

facing by intense relativistic electron beams. Chapter 12 (Chrzanowska) reviews
the consequences of the presence and amount of water on the silicon based parts
of nanodevices such as AFM tips. Chapter 13 (Uklein) examines the structural and
optical characterization of the (Y3Al5 O12 , YAG) ceramics prepared by high-pressure
low-temperature technique. The authors of Chap. 14 (Raczyński) interpret the be-
havior of homocysteine molecules in the pure clusters and in the clusters with carbon
nanotube, by qualitative interpretation of physical observables and snapshots of in-
stantaneous configurations. Chapter 15 (Sumarokov) examines the heat capacity of
1D chains of atom/molecule adsorbates in the grooves of c-SWNT bundles.
Preface vii
Part III: Nanobiotechnology
Chapter 16 (Martseniuk) is devoted to the analysis of properties of water, diffused in

the layered compounds SrFe2As2 and FeTe0,8 S0,2 . The aim of Chap. 17 (Pavlovich) is
to study the effect of gold nanoparticles on morphological and functional characteris-
tics of SPEV cells. Chapter 18 (Shcherbak) focuses applications of nanomaterials in
rational gene pool preservation technology. In Chap. 19 (Christophorov) the author
describes the basis and development of the concept of dynamic molecular self-
organization, a model he first introduced more than 20 years ago when searching
the most adequate approach to analyzing the functioning of biomolecules, in partic-
ular, proteins–enzymes. Chapter 20 (Burlaka) presents applications of CNT-based
strategies for improved efficacy, reproducibility, accuracy, and speed in gene transfer
in plants. In Chap. 21 (Chevichalova) the authors present the result of investigations
on the effect of platinum nanoparticle aggregations on the vital activity of a variety
of cancer cells.
Part IV: Applications
Chapter 22 (Kucherenko) describes urease-based conductometric biosensors that

were created using a non-typical method of urease immobilization via adsorption
on micro- and nanoporous particles. Chapter 23 (Bażela) presents the results of
investigations into the effect of particle size on the magnetic properties of RMnO3
(R = Pr, Nd and Tb) using magnetometric and X-ray and neutron diffraction methods.
Chapter 24 (Nichkalo) reviews investigations of silicon nanowire formation via a
combination of LPCVD and wet etching methods on Si substrate using gold films
as mask. In Chap. 25 (Draidi) the authors develop a precision MESFET model
for transconductance variation based on gate length and voltage and resistance and
voltage. Chapter 26 (Shalaeva) discusses the nanocrystalline structure formation
mechanism of quasi-one-dimensional nanostructured aggregates ZnO and Zn–O–C
used as photocatalysts and the effect of thermolysis condition on the formation of
textured structure in these aggregates. Chapter 27 (Boudine) focuses on the study
of spin-polarized transport in semiconductors as new type of current transmission
in semiconductor devices. In the chapter, the authors present a two-degree model
for a so-called SPINFET transistor. Chapter 28 (Protsenko) is devoted to the strain
properties of multilayer thin-film materials based on metals. Chapter 29 (Gudyma)
is devoted to an analysis of spin-crossover system dynamics using both an Ising-like
mechanoelastic model and a macroscopic phenomenological model.
Contents
Part I Nanocomposites and Nanostructures

1 Endohedral Fullerene Complexes. Which and How Many Small
Molecules Can Be Inserted into Fullerenes and a Carbon Nanotube? 3
Helena Dodziuk
2 Physical and Mechanical Properties of Surface Nanocrystalline

Structures Generated by Severe Thermal-Plastic Deformation . . . . . 31
Hryhoriy Nykyforchyn, Volodymyr Kyryliv and Olga Maksymiv
3 Energy Spectra of the Fibonacci Superlattice Based

on the Gapped Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
A. M. Korol and V. M. Isai
4 Carbon-Based Piezoresistive Polymer Composites . . . . . . . . . . . . . . . . 51

Sara Cravanzola, Federico Cesano, Lucia Muscuso,
Domenica Scarano and Adriano Zecchina
5 Structure and Physical and Mechanical Properties of Nanocomposite

(Zr-Ti-Cr-Nb)N and (Ti-Zr-Al-Nb-Y)N Coatings, Obtained by
Vacuum-Arc Evaporation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
V. M. Beresnev, I. N. Torianyk, A. D. Pogrebnjak, O. V. Bondar,
M. Bilokur, O. V. Sobol, D. A. Kolesnikov, S. V. Lytovchenko
and P. V. Turbin
6 New Nanosized Systems Based Lanthanide Diketonate Complexes

for OLEDs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
I. A. Savchenko, A. S. Berezhnytska, N. B. Ivakha and E. K. Trunova
7 Poly(Methacrylamidoaryl Methacrylate)’s Surface Morphology . . . . 95

Lyudmyla O. Vretik, Valentyna V. Zagniy, Olena A. Nikolaeva,
Volodymyr G. Syromyatnikov and Polina V. Vakuliuk
ix
x Contents
8 Investigation of Nonlinear Magnetic Properties Magneto-Mechano-

Chemical Synthesized Nanocomplex from Magnetite and Antitumor
Antibiotic Doxorubicin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
V. E. Orel, A. D. Shevchenko, A. Y. Rykhalskiy, A. P. Burlaka,
S. N. Lukin and I. B. Schepotin
9 Electrochemical Elaboration of Nano Powders Based

on Magnesium and Lithium for Solid Hydrogen Storage . . . . . . . . . . . 111
M. Sahli and N. Bellel
10 Heat-Resistant SiO2 –Al2 O3 –TiO2 Ceramics with Nanostructured

Alumina Filler and Their Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
T. M. Ulyanova, N. P. Krutko, P. A. Vitiaz, L. V. Ovseenko
and L. V. Titova
Part II Nanophotonics
11 Technological Aspects of Corrosion-Resistant Steels Surfacing by

Intense Relativistic Electron Beams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
V. V. Belozerov, S. E. Donets, V. F. Klepikov, V. F. Kivshik,
V. V. Lytvynenko, Yu. F. Lonin, A. G. Ponomarev and V. T. Uvarov
12 An Ellipsometric Model for Establishing Thickness of Thin Water

Nanolayers on the Silicon Wafers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Agnieszka Chrzanowska, Piotr Fornal, Natalia Nosidlak, Gabriela
Lewińska, Edyta Oziȩbło and Jerzy Sanetra
13 The Effect of Sintering Temperature on Linear and Nonlinear

Optical Properties of YAG Nanoceramics . . . . . . . . . . . . . . . . . . . . . . . . 147
V. Ya. Gayvoronsky, A. S. Popov, M. S. Brodyn, A. V. Uklein,
V. V. Multian and O. O. Shul’zhenko
14 Impact of Carbon Nanotube on Homocysteine Clusters:

MD Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
Przemysław Raczyński, Krzysztof Górny and Zygmunt Gburski
15 Heat Capacity of 1D Chains of Atom/Molecule Adsorbates in the

Grooves of c-SWNT Bundles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
V. V. Sumarokov, M. I. Bagatskii and M. S. Barabashko
Part III Nanobiotechnology
16 About Some Physical Properties of Water in Nanosystems and the

Possible Mechanism of Superconductivity Induction by Water in
Compounds SrF e2 As2 and F eT e0,8 S0,2 . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Ludmila Stepanovna Martseniuk, Aleksandr Stepanovich Martseniuk
and Michail Vasilievich Kurik
Contents xi
17 Effect of Gold Nanoparticles on Proliferative Properties

of SPEV Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
E. V. Pavlovich and N. A. Volkova
18 Nanobiotechnologies in the System of Farm Animals’

Gene Pool Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
S. I. Kovtun, N. P. Galagan, O. V. Shcherbak, N. Y. Klymenko
and O. S. Osypchuk
19 Proteins as Nanomachines: Hysteretic Enzymes Revisited . . . . . . . . . . 223

Leonid N. Christophorov
20 Application of Carbon Nanotubes for Plant Genetic Transformation 233

Olga M. Burlaka, Yaroslav V. Pirko, Alla I. Yemets
and Yaroslav B. Blume
21 Platinum Nanoparticles with Adsorptive Layer of Chlorella vulgaris

Polysaccharides Inactivate Tumor Cells of Ascitic Ehrlich Carcinoma,
Ovarian Cancer and Leukemia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
V. R. Estrela-Llopis, A. V. Chevichalova, N. A. Tregubova,
E. D. Shishko and P. M. Litvin
Part IV Applications
22 Biosensors Based on Urease Adsorbed on Nickel, Platinum,

and Gold Conductometric Transducers Modified with Silicalite
and Nanozeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
Ivan S. Kucherenko, Oleksandr O. Soldatkin, Berna Ozansoy Kasap,
Burcu Akata Kurç, Volodymir G. Melnyk, Lyudmila M.
Semenycheva, Sergei V. Dzyadevych and Alexei P. Soldatkin
23 Magnetic Properties of Nanoparticle RMnO3 (R = Pr, Nd, and Tb)

Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
Wiesława Bażela, Andrzej Szytuła, Stanisław Baran, Bogusław Penc,
Marcin Dul, Ryszard Duraj, Zinaiida Kravchenko, Eduard Zubov,
Konstantin Dyakonov, Jens-Uwe Hoffmann, Tommy Hofmann,
Andreas Hoser and Volodymyr Dyakonov
24 Technological Approaches for Growth of Silicon Nanowire Arrays . . 301

Anatoly Druzhinin, Anatoly Evtukh, Ihor Ostrovskii, Yuriy
Khoverko, Stepan Nichkalo and Stanislav Dvornytskyi
25 Influence of Physical Parameters on the Transconductance gm of

Channel for the Component Submicron . . . . . . . . . . . . . . . . . . . . . . . . . 309
M. Draidi, M. Zaabat and A. Boudine
xii Contents
26 Structural, Optical, and Photocatalytic Properties of Quasi-One-

Dimensional Nanocrystalline ZnO, ZnOC:nC Composites, and
C-doped ZnO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
E. V. Shalaeva, O. I. Gyrdasova, V. N. Krasilnikov, M. A.
Melkozerova, I. V. Baklanova and L. Yu. Buldakova
27 Two-Dimensional Spin-FET Transistor . . . . . . . . . . . . . . . . . . . . . . . . . . 337

A. Boudine, L. Kalla, K. Benhizia, M. Zaabat and A. Benaboud
28 Future Strain Properties of Multilayer

Film Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
Serhyi I. Protsenko, Larysa V. Odnodvorets and Ivan Yu. Protsenko
29 Kinetics of Nonequilibrium Transition in Spin-Crossover Compounds 375

Iurii Gudyma, Cristian Enachescu and Artur Maksymov
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
Contributors
M. I. Bagatskii B.Verkin Institute for Low Temperature Physics and Engineering

of the National Academy of Sciences of Ukraine, Kharkov, Ukraine
I. V. Baklanova Institute of Solid State Chemistry UB RAS, Ekaterinburg, Russian
Federation
M. S. Barabashko B.Verkin Institute for Low Temperature Physics and Engineering
Stanisław Baran M. Smoluchowski Institute of Physics, Jagiellonian University,
Kraków, Poland
Wiesława Bażela Institute of Physics, Cracow University of Technology, Kraków,
Poland
N. Bellel Physics Energy Laboratory, Physics Department, Constantine University,
Constantine, Algeria
V. V. Belozerov National Technical University “KhPI”, Ministry of Education and
Science of Ukraine, Kharkiv, Ukraine
A. Benaboud Active Devices and Materials Laboratory, Faculty of Exact Sciences
and Nature and Life Sciences, Larbi Ben M’hidi University, Oum El Bouaghi, Algeria
K. Benhizia Université Constantine, Constantine, Algérie
V. M. Beresnev Karazin Kharkiv National University, Kharkiv, Ukraine
A. S. Berezhnytska V. I. Vernadsky Institute of General and Inorganic Chemistry
NASU, Kiev, Ukraine
M. Bilokur Sumy National University, Sumy, Ukraine
Yaroslav B. Blume Institute of Food Biotechnology and Genomics, National
Academy of Sciences of Ukraine, Kyiv, Ukraine
O. V. Bondar Sumy National University, Sumy, Ukraine
xiii
xiv Contributors
A. Boudine Faculty of Exact Sciences and Natural and Life Sciences, Active De-
vices and Materials Laboratory, Larbi Ben M’hidi University, Oum El Bouaghi,
Algeria
M. S. Brodyn Institute of Physics NASU, Kiev, Ukraine
L. Yu. Buldakova Institute of Solid State Chemistry UB RAS, Ekaterinburg,
Russian Federation
A. P. Burlaka R.E. Kavetsky Institute of Experimental Pathology, Oncology and
Radiobiology/45, Kyiv, Ukraine
Olga M. Burlaka Institute of Food Biotechnology and Genomics, National
Federico Cesano Department of Chemistry, NIS (Nanostructured Interfaces and
Surfaces), Centre of Excellence and INSTM Centro di Riferimento, University of
Torino, Torino, Italy
A. V. Chevichalova F. D. Ovcharenko Institute of Biocolloid Chemistry, Ukrainian
National Academy of Sciences, Kyiv, Ukraine
Leonid N. Christophorov Bogolyubov Institute for Theoretical Physics, NAS
Ukraine, Kiev, Ukraine
Agnieszka Chrzanowska Institute of Physics, Kraków University of Technology,
Kraków, Poland
Sara Cravanzola Department of Chemistry, NIS (Nanostructured Interfaces and
Helena Dodziuk Institute of Physical Chemistry, Polish Academy of Sciences,
Warsaw, Poland
S. E. Donets Institute of Electrophysics and Radiation Technologies, National
Academy of Sciences of Ukraine, Kharkiv, Ukraine
M. Draidi Faculty of Exact Sciences and Natural and Life Sciences, Active Devices
and Materials Laboratory, Larbi Ben M’hidi University, Oum El Bouaghi, Algeria
Anatoly Druzhinin Lviv Polytechnic National University, Lviv, Ukraine
Marcin Dul Institute of Physics, Cracow University of Technology, Kraków, Poland
Ryszard Duraj Institute of Physics, Cracow University of Technology, Kraków,
Poland
Stanislav Dvornytskyi Lviv Polytechnic National University, Lviv, Ukraine
Konstantin Dyakonov A. F. Ioffe Physico-Technical Institute RAN, St.-Petersburg,
Russia
Contributors xv
Volodymyr Dyakonov A. A. Galkin Donetsk Physico-Technical Institute, National

Academy of Sciences of Ukraine, Donetsk, Ukraine
Institute of Physics, PAS, Warszawa, Poland
Sergei V. Dzyadevych Laboratory of Biomolecular Electronics, Institute of Molec-
ular Biology and Genetics, National Academy of Sciences of Ukraine, Kyiv,
Ukraine
Institute of High Technologies, Taras Shevchenko National University of Kyiv, Kyiv,
Ukraine
Cristian Enachescu Alexandru Ioan Cuza University of Iasi, Iasi, Romania
V. R. Estrela-Llopis F. D. Ovcharenko Institute of Biocolloid Chemistry, Ukrainian
Anatoly Evtukh V.E. Lashkaryov Institute of Semiconductor Physics NAS of
Ukraine, Kyiv, Ukraine
Piotr Fornal Institute of Physics, Kraków University of Technology, Kraków,
Poland
N. P. Galagan O.O. Chuiko Institute of Surface Chemistry, National Academy of
Science of Ukraine, Kiev, Ukraine
V. Ya. Gayvoronsky Institute of Physics NASU, Kiev, Ukraine
Zygmunt Gburski Institute of Physics, University of Silesia, Katowice, Poland
Krzysztof Górny Institute of Physics, University of Silesia, Katowice, Poland
Iurii Gudyma Chernivtsi National University, Chernivtsi, Ukraine
O. I. Gyrdasova Institute of Solid State Chemistry UB RAS, Ekaterinburg, Russian
Federation
Jens-Uwe Hoffmann Helmholtz-ZentrumBerlin für Materialien und Energie
GmbH, Berlin, Germany
Tommy Hofmann Helmholtz-ZentrumBerlin für Materialien und Energie GmbH,
Berlin, Germany
Andreas Hoser Helmholtz-ZentrumBerlin für Materialien und Energie GmbH,
Berlin, Germany
V. M. Isai National University for Food Technologies, Kiev, Ukraine
N. B. Ivakha V. I. Vernadsky Institute of General and Inorganic Chemistry NASU,
Kiev, Ukraine
L. Kalla Active Devices and Materials Laboratory, Faculty of Exact Sciences and
Nature and Life Sciences, Larbi Ben M’hidi University, Oum El Bouaghi, Algeria
xvi Contributors
Berna Ozansoy Kasap Central Laboratory, Middle East Technical University,

Ankara, Turkey
Yuriy Khoverko Lviv Polytechnic National University, Lviv, Ukraine
V. F. Kivshik Institute of Electrophysics and Radiation Technologies, National
V. F. Klepikov Institute of Electrophysics and Radiation Technologies, National
N. Y. Klymenko O.O. Chuiko Institute of Surface Chemistry, National Academy
of Science of Ukraine, Kiev, Ukraine
D. A. Kolesnikov Belgorod State National University, Belgorod, Russia
A. M. Korol National University for Food Technologies, Kiev, Ukraine
Laboratory on Quantum Theory, Linköping, Sweden
S. I. Kovtun Biotechnology laboratory, Institute of Animal Breeding and Genetics,
National Academy of Agrarian Science of Ukraine, Kiev, Ukraine
V. N. Krasilnikov Institute of Solid State Chemistry UB RAS, Ekaterinburg,
Russian Federation
Zinaiida Kravchenko A. A. Galkin Donetsk Physico-Technical Institute, National
N. P. Krutko Institute of General and Inorganic Chemistry of NAS of Belarus,
Republic of Belarus
Ivan S. Kucherenko Laboratory of Biomolecular Electronics, Institute of Molec-
ular Biology and Genetics, National Academy of Sciences of Ukraine, Kyiv,
Ukraine
Institute of Biology, Taras Shevchenko National University of Kyiv, Kyiv, Ukraine
Burcu Akata Kurç Central Laboratory, Middle East Technical University, Ankara,
Turkey
Micro and Nanotechnology Department, Middle East Technical University, Ankara,
Turkey
Michail Vasilievich Kurik Institute of physics NAS Ukraine, Kiev, Ukraine
Volodymyr Kyryliv Karpenko Physico-Mechanical Institute of NASU, Ukraine
Gabriela Lewińska Institute of Physics, Kraków University of Technology,
Kraków, Poland
P. M. Litvin V. E. Lashkarev Institute of Semiconductor Physics, Ukrainian
Contributors xvii
Yu. F. Lonin National Science Center Kharkov, Institute of Physics and Technology,
National Academy of Sciences of Ukraine, Kharkov, Ukraine
S. N. Lukin R.E. Kavetsky Institute of Experimental Pathology, Oncology and
Radiobiology/45, Kyiv, Ukraine
S. V. Lytovchenko Karazin Kharkiv National University, Kharkiv, Ukraine
V. V. Lytvynenko Institute of Electrophysics and Radiation Technologies, National
Olga Maksymiv Karpenko Physico-Mechanical Institute of NASU, Ukraine
Artur Maksymov Chernivtsi National University, Chernivtsi, Ukraine
Aleksandr Stepanovich Martseniuk National University of Food Technology,
Kiev, Ukraine
Ludmila Stepanovna Martseniuk Institute of Nuclear Researches NAS Ukraine,
Kiev, Ukraine
M. A. Melkozerova Institute of Solid State Chemistry UB RAS, Ekaterinburg,
Russian Federation
Volodymir G. Melnyk Department of Electrical and Magnetic Measurements,
Institute of Electrodynamics, National Academy of Sciences of Ukraine, Kyiv,
Ukraine
V. V. Multian Institute of Physics NASU, Kiev, Ukraine
Lucia Muscuso Department of Chemistry, NIS (Nanostructured Interfaces and Sur-
faces), Centre of Excellence and INSTM Centro di Riferimento, University of Torino,
Torino, Italy
Stepan Nichkalo Lviv Polytechnic National University, Lviv, Ukraine
Olena A. Nikolaeva Macromolecular Chemistry Department, Taras Shevchenko
National University of Kyiv, Kyiv, Ukraine
Natalia Nosidlak Institute of Physics, Kraków University of Technology, Kraków,
Poland
Hryhoriy Nykyforchyn Karpenko Physico-Mechanical Institute of NASU,
Ukraine
Larysa V. Odnodvorets Department of Applied Physics, Sumy State University,
Sumy, Ukraine
V. E. Orel National Cancer Institute/33/43, Kyiv, Ukraine
Ihor Ostrovskii Lviv Polytechnic National University, Lviv, Ukraine
O. S. Osypchuk Biotechnology laboratory, Institute of Animal Breeding and
Genetics, National Academy of Agrarian Science of Ukraine, Kiev, Ukraine
xviii Contributors
L. V. Ovseenko Institute of General and Inorganic Chemistry of NAS of Belarus,

Republic of Belarus
Edyta Oziȩbło Institute of Physics, Kraków University of Technology, Kraków,
Poland
E. V. Pavlovich Department for Cryobiology of Reproduction System, Institute for
Problems of Cryobiology and Cryomedicine, Natl. Acad. of Sci. of Ukraine, Kharkiv,
Ukraine
Bogusław Penc M. Smoluchowski Institute of Physics, Jagiellonian University,
Kraków, Poland
Yaroslav V. Pirko Institute of Food Biotechnology and Genomics, National
A. D. Pogrebnjak Sumy National University, Sumy, Ukraine
A. G. Ponomarev National Science Center Kharkov, Institute of Physics and
Technology, National Academy of Sciences of Ukraine, Kharkov, Ukraine
A. S. Popov Institute of Physics NASU, Kiev, Ukraine
Ivan Yu. Protsenko Department of Applied Physics, Sumy State University, Sumy,
Ukraine
Serhyi I. Protsenko Department of Applied Physics, Sumy State University, Sumy,
Ukraine
Przemysław Raczyński Institute of Physics, University of Silesia, Katowice,
Poland
A. Y. Rykhalskiy National Cancer Institute/33/43, Kyiv, Ukraine
M. Sahli Physics Energy Laboratory, Physics Department, Constantine University,
Constantine, Algeria
Jerzy Sanetra Institute of Physics, Kraków University of Technology, Kraków,
Poland
I. A. Savchenko National Taras Shevchenko University of Kyiv, Kyiv, Ukraine
Domenica Scarano Department of Chemistry, NIS (Nanostructured Interfaces and
I. B. Schepotin National Cancer Institute/33/43, Kyiv, Ukraine
Lyudmila M. Semenycheva Department of Electrical and Magnetic Measure-
ments, Institute of Electrodynamics, National Academy of Sciences of Ukraine,
Kyiv, Ukraine
E. V. Shalaeva Institute of Solid State Chemistry UB RAS, Ekaterinburg, Russian
Federation
Contributors xix
O. V. Shcherbak Biotechnology laboratory, Institute of Animal Breeding and

Genetics, National Academy of Agrarian Science of Ukraine, Kiev, Ukraine
A. D. Shevchenko G.V. KurdyumovInstitute for Metal Physics/36, Kyiv, Ukraine
E. D. Shishko R. E. Kavetsky Institute of Experimental Pathology, Oncology and
Radiobiology, Ukrainian National Academy of Sciences, Kyiv, Ukraine
O. O. Shul’zhenko V. N. Bakul Institute for Superhard Materials NASU, Kiev,
Ukraine
O. V. Sobol Kharkiv polytechnical institute, National Technical University, Kharkiv,
Ukraine
Alexei P. Soldatkin Laboratory of Biomolecular Electronics, Institute of Molecular
Biology and Genetics, National Academy of Sciences of Ukraine, Kyiv, Ukraine
Ukraine
Oleksandr O. Soldatkin Laboratory of Biomolecular Electronics, Institute of
Molecular Biology and Genetics, National Academy of Sciences of Ukraine, Kyiv,
Ukraine
Ukraine
V. V. Sumarokov B.Verkin Institute for Low Temperature Physics and Engineering
Volodymyr G. Syromyatnikov Macromolecular Chemistry Department, Taras
Shevchenko National University of Kyiv, Kyiv, Ukraine
Andrzej Szytuła M. Smoluchowski Institute of Physics, Jagiellonian University,
Kraków, Poland
L. V. Titova Institute of General and Inorganic Chemistry of NAS of Belarus,
Republic of Belarus
I. N. Torianyk Karazin Kharkiv National University, Kharkiv, Ukraine
N. A. Tregubova R. E. Kavetsky Institute of Experimental Pathology, Oncology
and Radiobiology, Ukrainian National Academy of Sciences, Kyiv, Ukraine
E. K. Trunova V. I. Vernadsky Institute of General and Inorganic Chemistry NASU,
Kiev, Ukraine
P. V. Turbin Karazin Kharkiv National University, Kharkiv, Ukraine
A. V. Uklein Institute of Physics NASU, Kiev, Ukraine
T. M. Ulyanova Institute of General and Inorganic Chemistry of NAS of Belarus,
Republic of Belarus
xx Contributors
V. T. Uvarov National Science Center Kharkov, Institute of Physics and Technology,

National Academy of Sciences of Ukraine, Kharkov, Ukraine
Polina V. Vakuliuk Nature Department, Institute of Chemistry, National University
“Kyiv-Mohyla Acadamy”, Kyiv, Ukraine
P. A. Vitiaz Institute of General and Inorganic Chemistry of NAS of Belarus,
Republic of Belarus
N. A. Volkova Department for Cryobiology of Reproduction System, Institute for
Problems of Cryobiology and Cryomedicine, Natl. Acad. of Sci. of Ukraine, Kharkiv,
Ukraine
Lyudmyla O. Vretik Macromolecular Chemistry Department, Taras Shevchenko
Alla I. Yemets Institute of Food Biotechnology and Genomics, National Academy
of Sciences of Ukraine, Kyiv, Ukraine
M. Zaabat Faculty of Exact Sciences and Natural and Life Sciences, Active Devices
and Materials Laboratory, Larbi Ben M’hidi University, Oum El Bouaghi, Algeria
Valentyna V. Zagniy Macromolecular Chemistry Department, Taras Shevchenko
Adriano Zecchina Department of Chemistry, NIS (Nanostructured Interfaces and
Eduard Zubov A. A. Galkin Donetsk Physico-Technical Institute, National
Part I
Nanocomposites and Nanostructures
Chapter 1
Endohedral Fullerene Complexes. Which and
How Many Small Molecules Can Be Inserted
into Fullerenes and a Carbon Nanotube?
Helena Dodziuk
1.1 Introduction
The discovery of C60 1 [1–3] (Fig. 1.1) and its studies abound in sudden twists like a
detective story. The first fullerene endohedral complexes were observed in the same
year when C60 was discovered [4]. Few years later, an “application rush” begun with
proposals of exciting, strange, and unrealized fullerene applications [5] until today.
In spite of the lack of massive commercialized applications of endohedral fullerene
complexes, this is a rapidly developing domain, which was recently reviewed by the
groups of Cong [6], Lu [7], and Popov [8]. These reviews were almost exclusively
devoted to a very specific type of the complexes, i.e., endohedral metallofullerenes
(EMFs). On the other hand, our review on the endohedral fullerene complexes involv-
ing small guests and in-out isomerism in perhydrogenated fullerenes [9] published
three years ago calls for an update although one of its main conclusions that, in
spite of numerous claims (see, for instance, [10–14]) fullerene cages cannot serve
for hydrogen storage, is valid. Therefore, this report is devoted mainly to the recent
results in the modeling of the endohedral fullerenes stability.
Predicting properties of the endohedral fullerene complexes is a difficult task in
view of their size and complexity. Taking into account properly dispersive interac-
tions (describing nonbonding attraction) is a difficult task. In addition, for the polar
guests there is a strong interaction of the guest with electrons of the host. Numer-
ous calculations on the endohedral complexes involving hydrogen were published
with the number of the molecules inserted into the cage ranging from 0 [15] to 28
[11, 12]. The first Cioslowski’s work of 1991 [15] yielded instability of one hydrogen
molecule inside C60 since the simple Hartree–Fock model with a very small basis
set which could be applied at that time did not describe properly small but numerous
stabilizing nonbonding interactions. On the other hand, simple model considera-
tions taking into account the C60 diameter, van der Waals radii of the hydrogen and
H. Dodziuk ()
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52,
01-224 Warsaw, Poland
e-mail: dodziuk10@vp.pl
O. Fesenko, L. Yatsenko (eds.), Nanocomposites, Nanophotonics, 3

Nanobiotechnology, and Applications, Springer Proceedings in Physics 156,
DOI 10.1007/978-3-319-06611-0_1, © Springer International Publishing Switzerland 2015
4 H. Dodziuk
H H H
H H H
1 2 3 4
H N O
C
H O N H
H
5 6 7 8
O
O H
H
H H
N
9 10
N N
11
12
Fig. 1.1 Formulae 1–12

1 Endohedral Fullerene Complexes. Which and How Many Small . . . 5
C 60 C 70 C 76
Ih D 5h Td D2
C 80
Ih C 2V C 2V ' D2
D3 D 5d D 5h
Fig. 1.2 IPR isomers of C60 , C70 , C76 and C80
carbon atoms and H–H bond length show unequivocally that the complexes with
two or more H2 molecules inside the fullerene cannot be stabilized. On the other
hand, our simple molecular mechanics calculations on the complexes formed by C60
1, C70 2, two isomers of C76 , five isomers of C78 , and 7 isomers of C80 [16] (see
Fig. 1.2 for the formulae) with one to four hydrogen molecules inside revealed in
an agreement with a later experimental finding [17] that H2 @C70 3 prevails in the
mixture with 2H2 @C70 4; interestingly although partially accidentally, and experi-
mentally determined 3:4 as 96:4 [17] corresponds to the earlier calculated difference
of 1.8 kcal/mol [18]). The prediction of the same study that 3H2 molecules should
be stable inside some isomers of C80 has not yet been proven experimentally. The
symmetry adapted perturbation theory (SAPT) calculations [19, 20] for complexes
involving one or two H2 5, CO 6, N2 7, HCN, H2 O 8, H2 S, CO2 , NH3 , CH4 , C2 H2 ,
H2 CO, and CH3 OH guest molecules in C60 and C70 , of which only few have been
6 H. Dodziuk
detected, will be discussed and those on the recently synthesized C50 H10 chair nan-
otube and its complexes with H2 , N2 , CO, HCN, H2 O, CO2 , CS2 , H2 S, NH3 , C2 H2 ,
CH4 , CH3 CN, CH3 OH, CH3 CCN, 2–butyne, methyl halides, or noble gas atoms in-
side [21]. In addition, the molecular dynamics simulations on the C50 H10 nanotube
complexes will be presented. Both methods yielded a very good agreement between
the results obtained and a few available experimental data.
1.2 Nontrivial Fullerene Discovery
Science is often presented to students as a fully logical structure, impersonal, and

devoid of emotions. Among other, centuries-long discussion on the nature of light,
whether it consists of waves or particles in which not the facts but Newton authority
was decisive for more than one hundred years, is a good example of the serendipitous
development of this domain. Fullerene history is of course much shorter but it also
abounds in exciting moments. A structure of such a high, Ih , symmetry was drawn by
Leonardo da Vinci and Dürer ([22] and the references cited therein). Interestingly,
a possibility of existence of a molecule of such a high symmetry was denied in
1945 by Herzberg [23] who was later awarded the Nobel Prize. Then, C60 was
predicted independently in 1970 by Japanese scientists [23] and in 1973 by Russian
computational chemists [24]. Next, the MS signal of C60 was observed and even
published, but went unnoticed [25] in 1984, and a year later, Kroto, Smalley, and Curl
with collaborators published their correctly interpreted observation of the strong MS
C60 signal [3]. For this discovery, they were honoured with the Nobel Prize in 1996.
Interestingly, until the Krätschmer et al. paper on fullerene purification [26], very
small amount of the fullerene available for studies did not enable to prove its proposed
structure. The proof came from the single 13 C NMR signal which was only possible
for the very high symmetry of the molecule [27]. Similarly, the NMR study enabled
first, although not very accurate determination of the fullerene bond lengths [28],
since, in view of the tumbling of the almost spherical C60 at room temperature, X-ray
analysis yielded only the molecular radius and the distance between the molecules
in the crystal. Of course, the full X-ray structure determination at 110 K [29] yielded
much more accurate values than the NMR one.
The first endohedral fullerene complex was observed very soon after the C60 dis-
covery [4] (a compendium of atoms that have been inserted until 2007 is given in
http://homepage.mac.com/jschrier/endofullerenes_table.html). However, similar to
catenanes 13, rotaxanes 14, knots 15, and Möbious strips 16 shown in Fig. 1.3, the
endohedral fullerene complexes have been analyzed as objects of nontrivial topology
only in the works of our group [9, 18, 30–32]. For this, the definition of molecules
with nontrivial topological properties had to be extended allowing for a bond defor-
mation only to such an extent that it does not break [30]. The endohedral fullerene
complexes are the fullerenes that have atoms, ions, and molecules inside the cage.
In the nomenclature used in supramolecular chemistry, the fullerene cage plays a
role of the host, H, while what is inside is treated as a guest, G, and the complex is
denoted as G@H. The detected complexes include not only H2 @C70 3, 2H2 @C70
4 [17], H2 @C60 5 [33], HD@C60 [34], D2 @C60 [35], CO@C60 6 [36],13 CO@C60
13 14 15 16
Fig. 1.3 Schematic formulae of catenane 13, rotaxane 14, knot 15, and Möbius strip 16
[37], N2 @C60 7 [37, 38], and N2 @C70 [37], H2 O@C60 8 [39] but also 2H2 O@C120
9 [40], two C60 –C60 dimers containing an isolated nitrogen atom like 10 [41, 42],
the dimer in which each cage contains an isolated nitrogen atom have also been re-
ported 11 [43], and an analog containing nitrogen isotopomers [44]. Specific nested
(onion-like) fullerenes reported C60 @C240 12, C240 @C540 and C60 @C240 @C540 (the
outer shell of the latter two were most probably incorrectly described as C560 ) [45],
while nested fullerenes with hundreds of fullerene layers were reported long before
the fullerene discovery [46].
As briefly discussed in Sect. 1.5, inserting an atom, a molecule or an ion into a
molecular cage can lead to spectacular changes of the host and/or guest properties.
It can even stabilize a nonisolated pentagon rule (IPR) fullerene isomer [47–52] or
another short-lived species [53] or change the fullerene symmetry upon the guest
inclusion [54], as shown in case of Y@C82 .
It should be stressed that although C60 is the most common fullerene, it does not
form numerous endohedral complexes because of its small internal cavity. As pointed
out independently by Patchkovskii and Thiel [55] and Dodziuk et al. [16], to obtain
endohedral complexes with fairly large guest molecules suitable for applications one
has to master the synthesis and purification of much larger fullerenes.
The stupendous isolation of atomic nitrogen in the C60 cage [38, 56, 57] and in
one [41, 42] or two [43] cages of the C60 –C60 dimer, H2 O without any hydrogen
bonds in one C60 cage [39] and in each cage of the C60 –C60 dimer [40], diatomic van
der Waals molecules of noble gases He2 in the C60 [58] and C70 [58, 59] cages as
well as Ne2 in C70 1 [60] and simultaneous insertion of helium and nitrogen atoms
inside C60 and C70 [61] or helium and neon atoms inside C70 [37] illustrate radical
changes in the guests’ properties due to its encapsulation into the fullerene cage.
Other examples of exotic, short-lived species stabilized in “molecular flasks” are
briefly reviewed by Dodziuk [62, 63].
Today, the endohedral fullerene complexes are studied by several groups not only
because of their exciting properties but also in view of their future applications.
The applications in medicine have been reviewed by Dellinger et al. [64], Nitta
group [65], and Bakry and coworkers [66]. With a metal guest, so called EMFs
can be metal, small-gap semiconductors, or insulators depending upon the fullerene
8 H. Dodziuk
size and the kind and number of encapsulated metal atoms. Interestingly, they form
unusual salts since the metallic guest transfers its electron(s) to the cage. Thus, one
has to destroy the cage for the salt decomposition. EMFs are applied in medicine,
(among others as radiotracers [67], MRI contrast agents [68, 69], drugs [70] (in
particular, HIV-1 protease inhibitors [71])) in electronics [72–76], (in particular, as
single-molecule transistor for quantum computing [77–79]), in photovoltaics [80],
and in the solar cells [80, 81]. Noteworthy, the application of so-called peapods that
is carbon nanotubes filled with endohedral fullerenes encapsulating metal atoms in
the latter devices seems promising [82].
1.3 Types of Endohedral Fullerene Complexes
As mentioned above, due to its small size only few endohedral complexes of C60
are known. The first observation of fullerene complexes was published as early as
in 1985 [4], the same year in which C60 itself has been detected. Depending on the
guest character, the endohedral fullerenes can have an atom(s) or molecule(s) inside
their cages and the guest can be metal or not. It can even be tritium [53] or muonium
[83]. A special class of the complexes are multishell-nested fullerenes that span the
structures having from two [45] to even hundreds of fullerene cages buried inside
one another [46].
The complexes are often so stable that they undergo several chemical reactions
and their numerous derivatives have been synthesized [81, 84–88]. Noteworthy, the
guest can influence the shape of the host cage. To our best knowledge, no endohedral
fullerene complex with an isolated hydrogen atom as the guest has been detected.
However, as mentioned earlier, Cross et al. reported a tritium guest inside C60 [53].
Contrary to organic molecules with distinct topological properties such as cate-
nanes 13, rotaxanes 14, knots 15 and Möbius strip 16 (schematically shown in
Fig. 1.2), the endohedral fullerene complexes 3–12 are not obtained by taking ad-
vantage of the preorganization phenomenon [9, 89] or dynamic covalent chemistry
[90–92]. They are manufactured by applying completely different procedures. Those
having metal cations inside are obtained in an arc reactor or via laser evaporation dur-
ing the process of fullerene formation [93, 94], while the ones with noble gas guests
are produced by heating fullerenes in the nobel gas atmosphere at high pressure using
Krätschmer–Huffmann procedure [95]. The endohedral fullerene complexes of few
simple molecules inside the fullerene cage were obtained mainly by so-called molec-
ular surgery approach consisting in making a hole in the cage chemically, inserting
a guest inside the cage (for instance, one [96] or two [17] hydrogen molecules), and
closing the hole chemically. On the other hand, different nitride cluster fullerenes,
like Sc3 N@C80 [97], were obtained by a reactive gas addition to the cooling gas of
the arc burning process [98]. It should be stressed that the main effort in studying en-
dohedral fullerene complexes seems to be focused on group 2 and 3 metallofullerenes
involving Sc, Y, La, Ca, Sr, Ba, and lanthanide (Ce–Lu) metallofullerenes [99] for
which exciting applications are expected.
Few, but very exciting, proposals of application of endohedral complexes have
been published soon after the C60 discovery [5]. One of them consisted in using
an endohedral fullerene with a door enabling the guest drug escape in appropriately
controlled conditions, another in using the perfluorinated C60 F60 as an ideal lubricant
or the solid C60 with intercalated alkali metals as superconductors. None of them
have been realized until now. The fall of the perfluorinated fullerene proposal was
spectacular. The molecule was synthesized [100] but was unstable and on air it
decomposed with the HF, the strongest acid, formation.
Few studies were devoted to the degree of isolation of the endohedral guest by
the fullerene cage. Measurements of the triplet lifetime or EPR indicated that the
interaction of the H2 molecular guest with the cage walls is too weak to be determined
but, on the other hand, there is a significant interaction between singlet molecular
oxygen (1 O2 ) and the incarcerated H2 or D2 guest [101]. A quantum chemical study
by Varadvaj and Varadvaj [102] indicates that, although the guest water molecule
inside the C60 cage does not form usual O–H. . . H hydrogen bonds, its hydrogen
and oxygen atoms interact with the host carbon atoms, thus it is not fully isolated in
H2 O@C60 8. The recent obtaining of the latter complex [39] and that of two H2 O in
both cages of the C60 –C60 dimer 9 [40] resulted in several physicochemical studies
of these systems [86, 103–105]. Similarly, availability not only of the C60 and C70
complexes with H2 but also of those with HD and D2 allowed one to study their
subtle properties [34, 106, 107]. In addition, interconversion of para and ortho H2
inside fullerenes was demonstrated [108, 109].
Until now, very few fullerenes applications have been commercialized. The idea of
using fullerenes for hydrogen storage also looked promising. However, as mentioned
above placing H2 molecules inside the cage seems impractical for such a purpose
since, even if we do not bother for a moment how to put hydrogen inside, one has to
destroy the cage irreversibly to release it. Some other possibilities, e.g., enhancing
exohedral hydrogen binding electrochemically, or by forming composites either by
placing a metal cation inside the fullerene cavity, or by coating fullerene with Ca
have been proposed [110–114] but their feasibility for practical uses is still unclear.
1.3.1 Fullerenes with Noble Gas Atoms and Molecules as Guests
Individual He, Ne, Ar, and Kr atoms are inserted into C60 and C70 cages by the
fullerene manufacturing in the nobel gas atmosphere [95, 115]. Interestingly, He
and Kr were also detected in higher fullerenes having up to 400 carbon atoms [116].
Cross et al. studied a possibility of inserting another noble gas atom into He@C60
[58]. The observation of two He atoms [117] inside C60 and two He or two Ne atoms
[59] or a mixed guest 3 He22 Ne inside C70 at a close distance [37] raised the question
of the possibility of the existence of a noble gas two-atomic molecule, Ng2 . Krapp
and Frenking carried out elaborated analysis of the Ng2 @C60 [118] using density
functional theory (DFT) with BP86 functional, ab initio methods at MP2 and SCS-
MP2 levels topped with the charge and energy partitioning and topological analysis
of the electron density using Atoms in Molecules (AIM) method. They concluded
that He2 and Ne2 guests in C60 form weakly bound van der Waals complexes and
stated “The Ng–Ng and Ng–C interactions interactions could also be considered as
10 H. Dodziuk
genuine chemical bonds”. Similarly, in Xe2 @C60 both Xe–Xe distance lower than
that in Xe2 (2.494 Å versus 2.746 Å) and the charge transfer from xenon to the cage
q+ q−
Xe2 @C60 (typical for the strong electron acceptors) indicate that the Xe–Xe bond
is genuine. It remains to wait to be able to observe complexes of higher noble gases
with C60 and study their properties.
Simultaneous insertion of helium and nitrogen atoms inside C60 and C70 [61]
raises the question on the character of He to nitrogen bonding in these systems.
In addition to studies of Ar@C60 and Xe@C60 , Amusia et al. carried out
calculations of generalized oscillator strength for nested endohedral fullerenes
A@CN1 @CN2 with N2 N1[119].
In general with very few exceptions, this mini review is devoted to studies of
small molecules inside fullerene cages in which only stabilization energies, that is,
the enthalpic increment to the complex stability is calculated. The results obtained
for the complexes of noble gas atoms with the C50 H10 nanotube on the basis of the
SAPT calculations will be given here since they include also the entropic term and
allowed Dodziuk and Korona [21] to estimate the temperature at which the complexes
decompose. The negative values of interaction energy showed stabilization at T = 0
K due to the attractive E2 disp , E2 ind , and E1 elst terms (Table 1.1). Further analysis
including zero-point vibrational energies and entropic terms allowed them to estimate
temperature for which the complex Ng@C50 H10 becomes stable at 1 atm showing
that the complexes with the Kr and Xe atoms as guests should be stable at room
temperature. In the Scott group [120], the work is in progress to check this prediction.
1.3.2 Endohedral Metallofullerenes
EMF are endohedral fullerene complexes with metals as molecular guests. In these
complexes, the metal atom looses electrons which are accepted by the fullerene cage.
Thus, they represent a quite unusual group of salts since their decomposition into the
cation and anion requires the cage destruction. As mentioned earlier, EMFs are most
thoroughly studied endohedral fullerene complexes since they are relatively easily
obtained and promise applications, among other in medicine [67–70], photovoltaic
[75, 80], and electronics [72–79]. Several reviews of EMFs [6–8, 121–124] appeared.
Thus, an extension covering EMF with molecular guests requires only brief update.
Combining Echegoyen and coworkers [124] and Popov et al. [8] works, we divide
endohedral metallofullerenes into four groups:
a. Mono–di, and trimetallic classical EMFs (M@C2n , M2 @C2n , M3 @C2n , M =
metal and 60 ≤ 2n ≥ 138) including mainly alkali metal and alkali earth metal
atom(s), transition metals, lantanides, iron, cobalt, and uranium. The largest
endohedral fullerenes involved include M@C94 –C3v (134) (M = Ca, Tm, Sm)
[125, 126], Sm2 @C104 -D3d (822) [127], the second largest dimetallofullerenes
isolated to date La2 @C138 [128] and Dy2 C100 and trimetallic Dy3 C100 [98]. Rare
trimetallic EMF of Sm3 @Ih -C80 was recently detected [129].
1
Table 1.1 SAPT interaction energy Eint and its components, zero-point vibrational energies ZPVE, free Gibbs energy for standard conditions for the en-
capsulation reaction Ng + C50 H10 → Ng@C50 H10 , G298.15 , thermal vibrational correction u298.15 , and estimated temperature TG=0 for which the complex
Ng@C50 H10 becomes thermodynamically stable at 1 atm for the complexes of C50 H10 nanotube with the noble gas guest Ng atoms at minimum geometry
1 1 2 2 2 2
Guest Eint Eelst Eexch Eind Eexch−ind Edisp Eexch−disp δEHF ZPVE G298.15 u298.15 TG=0
He −1.14 −0.57 2.45 −0.20 0.19 −3.07 0.20 −0.16 0.60 4.70 1.25 40
Ne −1.83 −1.89 5.98 −2.41 2.61 −6.60 0.68 −0.20 0.25 3.69 1.54 90
Ar −6.79 −4.01 11.12 −4.78 4.65 −15.20 1.84 −0.41 0.32 0.56 1.48 270
Kr −8.23 −11.41 26.52 −16.96 15.46 −27.61 4.73 1.03 0.33 0.03 1.47 300
Xe −8.72 −17.43 38.47 −30.10 26.23 −35.72 7.03 2.80 0.31 −0.32 1.49 310
All energies expressed in kcal/mol
Endohedral Fullerene Complexes. Which and How Many Small . . .
11
Another random document with
no related content on Scribd:
There they found Laddie wide awake, sitting in the assembly room
of the station house, while several officers, who were on reserve
duty, were laughing and joking with him.
“He’s far from being asleep,” said Mr. North.
“I should say so!” agreed Mr. Bunker. “Laddie boy, what in the
world are you doing down here?” he asked the little fellow.
“I came down to find out about a riddle,” he answered.
“And he’s had us all guessing riddles ever since he walked in here
about an hour ago,” chuckled the police sergeant in charge of the
station. “He’s a great boy!”
“I didn’t perzactly come down here to ask riddles,” said Laddie.
“But I wanted to make up a riddle about a policeman to ask Farmer
Joel when I got to the farm, and I had to see a police station inside to
make up the riddle.”
“Well, did you make the riddle up?” asked the sergeant, with
another laugh. Life at the station was very often dull, and the men on
duty welcomed any little change.
“Yes, I got a riddle,” Laddie announced. “’Tisn’t very good, but
maybe I can think of a better one after a while. This is it. Why is a
police station like a candy shop?”
“Ha! Ha!” laughed the sergeant. “That may be a riddle, but I can’t
see it. Nothing could be more different than a candy store and this
police station.”
“Yes, there’s something alike in each of them,” went on Laddie.
“Do you all give up?” he asked. “Can you tell why a police station is
like a candy shop?”
“Is it because when people are brought here they have to stick?”
asked Adam.
“Ha! Ha! That’s pretty good!” laughed the sergeant. “I’d never think
of that myself! Pretty good! A police station is like a candy shop
because people have to stick here! And it’s true! They do have to
stick if we arrest them and put them in a cell. And if there’s sticky
candy on the floor of a candy shop they’d stick there. Pretty good!”
“No, that isn’t the reason,” said Laddie. “Listen. I’ll tell you. A police
station is like a candy shop because it’s full of sticks. Sticks, you
know—the policemen’s clubs. They’re like sticks of candy, you
know!”
“Ha! Ha!” laughed the sergeant again. “That’s pretty good! I must
remember that to tell the captain. Well, good night to you,” he added,
as Mr. Bunker led Laddie out, thanking the sergeant and his men for
having entertained and kept the little boy.
On the way home in the automobile Mr. Bunker said Laddie should
not have slipped off and gone down the street to the police station
without telling some one about it.
“We were all worried, Laddie,” went on his father.
“I’m sorry,” the little fellow said. “I won’t do it again. But I got to
thinking I could make up a good riddle about a policeman, and I
thought it would be better if I could see one before I made the riddle,
so I just went.”
“Well, it’s a pretty good riddle—I’ll say that,” chuckled Adam North.
“Maybe you can make up some about the farm when you get there.
Farmer Joel likes jokes and riddles.”
“I’ll make up a lot of them for him,” kindly offered Laddie, as if he
had a stock of riddles constantly on hand and could turn them out at
a moment’s notice.
“Oh, Laddie, you bad boy, where have you been?” asked his
mother when he reached home.
When they told her his riddle about the police station and candy
shop, she could not help laughing.
A few days after this everything was ready for the start to Farmer
Joel’s. Mr. Bunker had arranged to leave his real estate business in
charge of his men at the office, and Mrs. Bunker prepared to close
the house, taking Norah with her to cook at the farm.
The children’s clothing had been packed in valises and trunks, and
piled in the big auto truck which was filled with straw to make a
comfortable resting place for the six little Bunkers on their forty-mile
trip.
As I have told you, the children and their father would ride in the
big truck with Adam, and Mrs. Bunker would follow with Norah in the
touring car, the children’s mother doing the driving.
All was one grand excitement in the home of the six little Bunkers
when the morning came on which they were to leave for the farm.
Every one seemed to be talking at once, and certainly the children,
Violet especially, never seemed to have asked so many questions
before.
Laddie, too, was on the alert. He was working on a new riddle. He
spoke of it to Russ.
“It’s about a tree,” said Laddie.
“Oh, I know that old riddle,” Russ said. “You mean why is a tree
like a dog? Because it has a bark.”
“No, it isn’t that one,” Laddie said eagerly. “This is a new riddle.
Now I have it! What’s the difference between a tree and a bird? Can
you answer that?”
“Let me see now,” murmured Russ, who wanted to please his little
brother. “The difference between a bird and a tree. Well, one flies
and the other doesn’t.”
“Nope!” cried Laddie. “I’ll tell you. A tree leaves in the spring and a
bird leaves in the fall. See what I mean? A tree leaves in the spring
—the leaves come out. But a bird leaves in the fall. The bird leaves
the North and flies down South where it’s warm.”
“I don’t think that’s a very good riddle,” said Russ.
“Well, maybe I can think of a better one after a while,” Laddie
remarked cheerfully. He certainly was good-natured.
Now that the time of going to the farm had arrived, Violet was
eager to find out all about the animals. She fairly pestered Adam with
wanting to know things. She asked:
“How many chickens are there? How many cows? Did you ever
count the bees?”
“Count the bees? Good land, no!” laughed Adam. “There’s millions
of ’em and they never keep still long enough to be counted. Besides,
if I tried they might sting me.”
“Well,” said Vi, “are there any——”
“Violet, get in the truck and sit still,” ordered her mother firmly, and
Violet obeyed.
Everything was ready for the start. Mr. Bunker was counting the
children and the trunks and the satchels, to make sure none was
missing, when Rose asked:
“Where’s Margy?”
“Here she comes,” said Russ, as he noticed his little sister
appearing around the corner of the house.
“What in the world is she carrying?” asked Mr. Bunker.
And well might he inquire. For Margy was half dragging half
carrying a large pasteboard box which seemed alive, for it swayed
from side to side and seemed about to leap away.
“Margy, what have you there?” called her father.
Before she could answer the box gave a sudden lurch to one side,
Margy lost her balance, and down she went on the path in a heap,
the box tumbling over and over as if it had suddenly come to life.
What could it be?
CHAPTER VI
SOMETHING IN THE STRAW
Five little Bunkers, with their father, their mother, Norah, and Adam
North looked at one little Bunker in a queer plight. That one little
Bunker was Margy.
After her fall Margy rolled along the path a short distance, for she
was a round little girl, quite chubby and, as her father often said,
“about as broad as she was long.”
As Margy rolled along, the box she had been carrying also rolled.
There was nothing very strange in Margy’s rolling over and over
after a tumble. She often did that. So did the other little Bunkers. So,
also, do you if you are little and fat.
There was also nothing very strange in the box, which Margy had
been carrying, rolling over. That is, there would not have been
anything strange if the box had just rolled in one direction.
But it did not. It rolled this way and that way and the other way and
then it rolled this way again, in such a strange manner that Russ
cried:
“What in the world can be in that box to make it go that way?”
“It’s just as if it was alive!” said Rose.
“Maybe it’s a riddle!” suggested Laddie.
Mrs. Bunker had gone to Margy to pick her up. Beyond a scratch
or two and some bruises, together with some dust on her dress,
Margy was unharmed. She was used to cuts and bruises, so these
did not much matter. Nor did the dust.
Russ ran to pick up the queer, rolling box, calling out:
“What’s in it, Margy?”
Before she could answer there came from within the box, the
cover of which was fitted tightly on, a little yipping whine and bark.
“Oh, it’s a dog!” cried Mun Bun. “I want to see the dog!”
“Dog!” exclaimed Violet. “It must be a terribly little dog to be in a
box like that.”
“Margy, what have you in the box?” asked her father, as Russ was
trying to take off the cover.
“It’s a—now—a puppy!” answered Margy.
“A puppy!” cried the other five little Bunkers, while Margy’s mother
asked:
“Where did you get the puppy, Margy?”
“I went over to Tommy Baker’s house. His dog has some little
puppies, and I took one and put it in this box ’cause I want to take a
puppy with me to the farm,” Margy answered.
The others laughed.
By this time Russ had managed to get the cover off the box, and a
cute little puppy stuck his head out, and, with his tongue, began
licking Russ’s hands. I suppose that was the puppy’s way of telling
how glad he was to get out of the box.
“Oh, isn’t he sweet!” cried Rose.
“Could we keep him?” begged Violet.
“I love him an’ he’s my puppy!” announced Margy.
“Well, the next time you love a puppy don’t shut him up in a box
without any air, and don’t drop him so the box rolls and he turns
somersaults,” advised Daddy Bunker. “Russ, you run back to Mr.
Baker’s with the little dog, and tell him Margy didn’t really mean to
take it.”
“Oh, Daddy! can’t I keep it?” begged Margy.
“No, dear. It belongs to Tommy Baker. You’ll find animals enough
out at Farmer Joel’s, anyway,” said her mother, as Russ started back
with the puppy in his arms.
For a moment it seemed as if Margy would cry, but Mun Bun kept
her tears back by saying:
“It was awful funny when he did roll over and over in the box. I like
a puppy to do that!” And when the others laughed at Mun Bun’s
funny way of saying this, Margy also laughed.
Russ came running back, having left the puppy with the others, a
last look was taken around the house to see that all was in good
order, and then Mrs. Bunker and Norah started off in the touring car
and Daddy and Adam North started in the big straw-filled truck with
the six little Bunkers.
“Oh, this is great! It’s going to be lots of fun!” exclaimed Russ, as
they rumbled along.
“I hope there’s a big, old-fashioned kitchen at Farmer Joel’s,” said
Rose. “Mother said I might help her with the baking of cake and
pies.”
“Well, I’ll help with the eating,” laughed Russ. “I hope there’s a
brook on the farm. I want to make a water wheel and build a little toy
mill that the water wheel will turn.”
“I’ll help you,” offered Laddie, as Russ whistled merrily.
The way to Cedarhurst where Farmer Joel lived was along a
pleasant road, and the children, sitting on the straw in the big truck,
enjoyed looking out through openings in the canvas sides.
“Did we bring anything to eat?” asked Vi, after a few miles had
been journeyed.
“No, daddy said we were going to stop in Westfield for our lunch,”
explained Rose. “We are going to meet mother there and all eat
together in a restaurant.”
“Oh, that’ll be fun!” declared Vi.
“It would be more fun if we could camp beside the road, make a
fire and cook something,” suggested Russ.
“If I had a gun I could shoot something and we could cook that,”
cried Laddie.
“Pooh! What could you shoot? A bear?” asked his twin sister.
“No,” he drawled. “But maybe I could shoot a chicken.”
“If you did the farmer that owned it would have you arrested,”
declared Russ. “I guess it will be better for us to eat in the
restaurant.”
Adam North, who sat up in the front seat with Daddy Bunker,
suddenly turned the truck off to one side of the road and brought the
big machine to a stop.
“Oh, are we there already?” cried Rose, leaping up from the straw
where she had been sitting beside Russ.
“Are we at Farmer Joel’s?” asked Violet eagerly.
“I want to wide on a horsie!” demanded Mun Bun.
“No, we aren’t there yet,” answered Adam. “But I need some water
in the radiator of the auto, so I’ll just stop here and get some. There’s
a farmer here whom I know.”
“May we get out?” asked Russ, for he thought perhaps they might
not stop long enough for this.
“Oh, yes, get out and stretch your legs,” his father told him.
“I’ll wait here five or ten minutes and cool down the engine,” added
Adam.
With whoops and shouts of delight the six little Bunkers piled out
of the truck and ran up and down the road. The machine had come
to a stop with the open rear end close to a wooden platform, which
was just as high as the floor of the big car. From the platform a flight
of steps led to the ground, and the Bunker children got out on this
platform and so descended.
“What’s this for?” asked Violet, with her usual way of starting
questions.
“This,” her father told her, “is a milk platform.”
“What’s a milk——” began Vi, but her father held up his hand.
“I’ll tell you all about it, and then you won’t have to ask any more
questions,” he said, with a smile. “This platform is built for the farmer
to set his cans of milk on. It is made high, so it is easy to roll the
cans of milk from the platform into the wagon. The milk is collected
by a big wagon, or auto truck, from the cheese factory. Many farmers
around here sell their milk and cream to the cheese factory, and
these platforms are built to make the work easier.”
“Oh,” murmured Violet. She had never had so many questions
answered before without her asking any, and she was in rather a
daze.
“Now run along and play with the others,” her father told her, for
the five little Bunkers were wandering about, looking at things around
the farmhouse.
Mr. Armstrong owned the place, and he came out to shake hands
with Mr. Bunker and Adam North, telling the latter to take as much
water as he needed for the thirsty automobile.
Mrs. Armstrong invited the children in and gave them some
cookies and glasses of milk.
“Aren’t you afraid you’ll spoil your appetites for dinner by eating
now?” asked Daddy Bunker. “It’s eleven o’clock, and we’ll have lunch
about noon.”
“I guess I can eat again,” said Russ.
“So can I.” “And I!” cried the others.
“Bless their hearts!” laughed the motherly Mrs. Armstrong.
While the auto engine was cooling the children ran about and
played tag. Rose thought perhaps her mother and Norah might come
past in the touring car, but Adam said they had probably taken a
shorter way, over a back road.
“I couldn’t go that way because the truck is so heavy,” he
explained. “I have to stick to the hard highways. But we’ll meet your
mother in Westfield.”
“Oh, come on out and see what I found!” cried Margy, running
around the corner of the house.
“What is it?” asked Mun Bun.
“A lot of little pigs in a pen, and they squeal like anything!” Margy
answered.
“Oh, I want to see the pigs! Maybe I can make up a riddle about
’em!” cried Laddie.
There was a rush for the pen, and the children had fun watching
the little pigs stumble about, rooting with their pink noses in the dirt
of their pen for something to eat.
But now the engine was cool enough to travel on, and Mr. Bunker
called the children to come back. Russ was the first to reach the
machine, running up the platform steps ready to help his smaller
brothers and sisters if they needed it.
He peered inside the truck, thinking perhaps the straw would need
spreading out again in a smooth layer, and, as he did so, he started
back in surprise.
“What’s the matter?” asked Rose, who had followed him.
“There’s something in there—in the straw,” whispered Russ.
“You mean one of the children?” asked Rose, for thus she often
spoke of her smaller brothers and sister.
“No, it—it looks like some animal,” said Russ. “Look!”
Rose looked and saw a dark object—clearly an animal—moving
about in the straw.
“Oh, maybe it’s a bear!” she cried.
CHAPTER VII
AT FARMER JOEL’S
Four other little Bunkers were hurrying up the platform steps to get
into the auto truck when Rose and Russ made this discovery of a
strange animal in the straw.
The first impulse of Rose was to run from the animal that, she half
thought, might be a bear that had wandered in from the woods not
far away and had found the warm straw a good place in which to
sleep. The next thought Rose had was for her smaller brothers and
sisters.
Daddy Bunker and Adam North were up near the front of the truck,
getting ready to take their seats, for the engine was now cool and the
radiator filled with fresh water.
Russ had the same idea as had Rose—the desire to save his
brothers and sisters from harm. Seeing them coming up the platform
steps he cried:
“Keep back! Keep back! Don’t come up here!”
“What’s the matter?” asked Laddie.
“There’s something in the straw,” Russ answered.
“It’s an animal!” added Rose. “A big animal!”
“Oh, I want to see it!” cried Mun Bun. “I like animals! Maybe we
can have a circus—this is like a circus wagon!”
The big truck certainly was. But Rose did not intend to have Mun
Bun or the other small ones rush into danger. She stood on the milk
platform at the top of the steps, holding out her hands.
“You mustn’t go in there where the animal is!” cried Rose. “Russ,
can’t you do something?” and her voice was shrill with excitement.
“I’ll get a stick—a stone—something——” panted Russ.
Just then from inside the truck came a stamping sound, as if the
animal were kicking about. At the same time a loud cry echoed.
“What’s the matter?” asked Daddy Bunker, coming back from the
front end of the truck.
At the same time Mr. Armstrong, the farmer, hurried out of a side
gate, calling:
“Did any of you see a little colt? He got out of the pasture, and I
don’t want him to run away. He’s valuable and he may get hurt.”
Before any one could answer the sound of neighing came from
inside the truck, and then Russ knew it was made by the animal he
and Rose had seen standing in the straw.
“Ha! That sounds like my colt!” said Farmer Armstrong.
“It is!” shouted Russ, with a laugh. “He’s in the auto. I’ll get him
out.”
The oldest Bunker boy started to go inside the auto truck, whence
came the neighing, stamping sound of the little horse. But Mr.
Armstrong called out:
“No, lad, don’t go in there. He might kick you. Not that he’s ugly,
but he’s in a strange place, and if you go in he might think you meant
to harm him. Better let me do it. I know how to handle that colt.”
The six little Bunkers, with their father and Adam North, stood at
one side to allow Mr. Armstrong to enter the truck. In he went,
speaking soothing words to the little colt.
“Oh, ho, Bonnie Boy! So you thought you’d hide away and go with
the six little Bunkers, did you? None of that! We want you to stay on
our farm! So you tried to hide in the straw, did you, Bonnie Boy?
Well, come out and I’ll give you a lump of sugar.”
And out of the truck, onto the milk platform, walked Mr. Armstrong,
leading by his halter the colt Bonnie Boy, as he was named.
“Oh, isn’t he sweet?” cried Violet. “How old is he and where is his
mother and has he any brothers and sisters and——”
“Careful, Vi!” laughingly called her father. “Mr. Armstrong isn’t used
to having so many questions fired at him at once.”
“Oh, I don’t mind,” laughed the good-natured farmer. “But this is
the only little colt I have, and his mother is down in the south
pasture. Now you can pet him if you want to,” he added to the
children. “He won’t kick when he’s outside here where he can see
who is near him.”
Up on the platform, around Bonnie Boy, crowded the six little
Bunkers, and the colt rubbed his velvet-like nose against them and
whinnied softly.
“And to think I took him for a bear!” laughed Rose, as she stroked
the glossy neck of the colt.
“Well, he did look like one,” declared Russ.
“Did he walk up the steps?” asked Violet. “I don’t see how he
could.”
“Oh, he’s a great little colt,” said Mr. Armstrong proudly. “He does
all sorts of tricks. One day he got out of the pasture and walked right
into the kitchen where my wife was making a cake. She thought I
was coming in with my big boots on, so she didn’t turn around, and
the colt put his nose on the back of her neck. She—Ha! Ha! She
thought I was kissing her. Oh, ho! ho!” and the farmer laughed
heartily.
Then he led Bonnie Boy down the steps, the little colt making no
trouble at all about treading on them. He was taken back to the
pasture where his mother was waiting for him, doubtless wondering
what had become of him. It was found that there was a break in the
fence, just large enough for the colt to squeeze through, but not
large enough for his mother, or she would have followed him.
The colt had wandered about, coming up to the rear of the house,
and had then made his way to the front, going up the steps of the
milk platform, and so into the big straw-filled truck, which, perhaps,
he thought was a new kind of barn.
“Well, now we’d better be traveling,” said Mr. Bunker, when the
little colt was taken away. “We don’t want to be late in meeting
mother in Westfield.”
Once again the six little Bunkers were on their way.
They were soon at Westfield, a small country town, and when the
big truck drew up in front of the only restaurant in the place there
was the touring car, with Mrs. Bunker and Norah sitting in it, waiting.
“We got here first, and we would have been here before but I had
a puncture and we had to change a tire,” said Mrs. Bunker.
“That’s too bad,” remarked her husband.
“Did you have any adventures?” asked Mrs. Bunker.
“Oh, I should say we did!” cried Violet “There was——”
“The cutest little colt!” broke in Rose, “and he——”
“Was in the straw,” continued Russ, “and when Rose saw him she
——”
“Thought he was a bear,” said Laddie.
Thus several of the little Bunkers had a turn in telling what had
happened.
“That was quite an adventure!” laughed Mrs. Bunker, when she
had been told all that had taken place at the Armstrong farm.
“I’m trying to make up a riddle about the colt, but I haven’t got very
far yet,” said Laddie. “It’s something about straw and a horseshoe
and—oh, well, maybe I’ll think of it after a while,” he said hopefully.
They had a delightful time, lunching in the restaurant, and nothing
much happened except that Mun Bun spilled a glass of water in his
lap and got wet. But as it was a warm day it didn’t matter.
Margy discovered a little kitten wandering about the eating place,
and she insisted on giving pussy some of her milk. The result was,
Margy’s hands not being very steady, that she upset a glass of milk
on the floor.
But, as the restaurant keeper said, it didn’t matter, for the floor
needed mopping anyhow.
Once more the little party started off in the two automobiles, Mrs.
Bunker and Norah in the touring car taking the lead. In about an hour
more they were at Cedarhurst. Then very soon, turning down a quiet
country road, the six little Bunkers saw in the distance a white
farmhouse in the middle of broad fields—a farmhouse with barns
and other buildings around it.
“That’s a dandy place!” exclaimed Russ.
“Lovely,” murmured Rose.
“Is that where we’re going to stay?” asked Violet.
“Yes, that is Farmer Joel’s,” her father answered.
A little later the little Bunkers were fairly tumbling out of the auto
truck in their eagerness to see all the sights. Mrs. Bunker and Norah
were already at the place.
“My, but I’m glad to see you all!” cried Farmer Joel, and the six
little Bunkers needed but one look at him to make sure they would
love him, for Mr. Todd was a kindly man. And his sister, Miss Lavina,
was just as loving and kind.
“Well, I’m glad you’re here,” said Miss Todd. “Now that I see so
many lovely children it makes me want to stay and play with you. But
brother Joel says I need a vacation, so I’m going off on a visit.”
The big farm was the most delightful place in the world at which to
spend a vacation. As Adam North had said, there were broad fields
—some green pastures, and others where hay and grain were
growing. There were two orchards, one of apple trees and another of
peach trees.
“And don’t eat apples yet, for they aren’t ripe,” warned Farmer Joel
as the children, putting on their old clothes, started out to explore
things.
“I want to see some horses!” cried Laddie.
“I want to go where the sheep are,” Mun Bun said.
“So do I,” chimed in Margy.
“I’ll go to the kitchen to help mother,” offered Rose, but her mother
said:
“No, you run out and play now. Norah and I can manage the work
all right. Later on if you want to help you may.”
So Rose went out with Russ and the others.
“There’s a brook, Russ!” called Violet, as she caught sight of the
sparkle of a little stream.
“That’s good. Then I’ll make a water wheel and a mill,” said Russ.
He and Laddie were looking at the brook, poking in sticks to find
out how deep it was and making ready to build the dam for the water
wheel, when suddenly they heard the voice of Rose crying:
“Oh, drive him away! Make him go away! Oh! Oh! Oh!”
“What’s that?” asked Russ, looking up.
“It was Rose,” answered Laddie. “I guess——”
The loud barking of a dog interrupted him, and Rose cried again:
“Oh, Russ, come and drive him away!”
CHAPTER VIII
IN THE HAY
Russ looked up from the dam he was making for the water wheel.
He could not see Rose. Nor could Laddie, who was helping his
brother make the little mill pond. But Rose kept on yelling and the
dog kept on barking.
“Oh, somebody please come!” cried Rose.
“I’m coming!” shouted Russ.
He leaped up, followed by Laddie, and, as they turned around a
clump of bushes and looked down the brook they saw Rose standing
with her back against a big tree while in front of her, leaping about
and barking loudly, was a large brown dog.
“Oh, Russ! Russ!” begged his sister, as she caught sight of him
and Laddie. “Come and drive this dog away! He wants to bite me!”
“I’ll drive him away!” declared Russ.
“And I’ll help,” added Laddie. “He’s a bad dog!”
Before the two brothers could reach their sister there came
running toward Rose another boy. This boy had a freckled face and
red hair.
“Don’t hit my dog!” cried this red-haired boy. “He won’t hurt you.
Hi, Jimsie!” called this new boy, “behave yourself! Down! Quiet! Quit
your barking!”
The dog looked around at the voice, wagged his tail to show that
he was friendly, and stopped barking. Just then up rushed Russ and
Laddie with sticks in their hands. Rose also had a stick which she
had raised toward the dog, but she had not hit him.
“Don’t beat my dog Jimsie!” begged the strange boy. “He didn’t
mean any harm.”
“What did he try to bite my sister for?” demanded Russ, who was
angry.
“Oh, he didn’t exactly try to bite me,” said Rose. “He just barked a
lot and he wouldn’t let me get away, and I was afraid he’d bite me.”
“Jimsie wouldn’t bite anybody,” said the boy, whose name was
Ralph Watson. He lived on the farm next to that of Mr. Todd.
“Well, then, what made him bark at my sister?” asked Russ.
“’Cause she had a stick,” answered Ralph.
“Does he bark at everybody who has a stick?” asked Laddie. “If he
does why doesn’t he bark at Russ and me—we have sticks?”
“I guess he will bark at you as soon as he sees you have sticks,”
Ralph answered. “I’ll try him.” He moved around until he stood
beside Russ and Laddie, and as the dog’s eyes followed his young
master Jimsie caught sight of the two Bunker boys and the sticks
they held. At once Jimsie began to bark, greatly excited.
“There! I told you!” cried Ralph.
“What makes him bark so just because he sees a stick?” asked
Russ. “Does he think we’re going to hit him with ’em? I wouldn’t hit
any dog, unless he was going to bite somebody.”
“No, Jimsie doesn’t think he’s going to be hit,” explained Ralph.
“He just wants you to throw the sticks in the brook so he can jump in
and bring ’em out. Always when he sees any one with a stick he
thinks they’re going to play with him and throw the stick into the
water. I guess he thought you were going to play with him,” said
Ralph to Rose, “and when you didn’t—why, he just barked.”
“Oh, I see!” exclaimed Rose, with a laugh, for she was over her
fright now. “That was his way of asking me to throw the stick in the
water.”
“Yes,” answered Ralph with a smile that lighted up his jolly,
freckled face. “Sometimes he barks like anything when I take a stick
and don’t throw it in for him to bring out.”
And, indeed, Jimsie seemed very much excited now because
Russ and Laddie would not toss their sticks into the brook. And at
last, to please the dog, Russ tossed his stick in.
Instantly Jimsie plunged in after it, swimming out and bringing the
stick back to shore, dropping it at the feet of Russ as if asking that it
be thrown in again.
“Oh, isn’t he cute!” exclaimed Rose.
“He’s a good dog!” declared Russ.
“Will he bring out a stick for me?” asked Laddie.
“He’ll do it for anybody,” answered Ralph.
“I’ll try it,” said Laddie.
In he tossed his stick, and in plunged Jimsie after it, bringing it
back to shore, which made Laddie laugh. Then Jimsie gave himself
a shake, sending a shower of drops all over Rose, who was near
him.
“Oh!” cried the little Bunker girl in surprise.
“Jimsie, don’t you know any better than that?” cried Ralph, in a
scolding voice. “Shame on you!”
“Oh, I don’t mind,” said Rose quickly. “This is an old dress and
water won’t spot it. There, go in and get my stick!” she ordered, as
she tossed hers into the brook. “You wanted me to throw it before,
but I didn’t know what you meant by your barking. Now get the stick.”
Jimsie quickly brought the stick to shore for Rose. Then Ralph
tossed one in and his dog got that. Russ and Laddie wanted to try
their sticks over again, but Rose said:
“Oh, the poor dog will get tired! Don’t make him do so much.”
“He likes it,” Ralph said. “He’d chase sticks all day, I guess, if
you’d throw ’em for him. But maybe it’s time he quit. I have to go
after the cows, anyhow.”
“Where are they? Could we go with you?” asked Laddie eagerly.
“Do you live around here?” Russ wanted to know.
Ralph Watson told his name and where he lived, but he said it was
a long distance to the cow pasture where he had to go, and he
added that the mother of the Bunker children might not let them go.
“I’ll take you to-morrow if you want to come, though,” Ralph
promised.
“Then we’ll go,” said Rose.
Then, in answer to a question, she told the others that she had
been walking along the brook looking for watercress, of which Daddy
Bunker was very fond. Rose was using the stick to poke aside the
bushes on the edge of the brook when suddenly Jimsie had sprung
out at her, driving her back against the tree, where she had stood,
afraid to move while the dog barked so furiously.
“If I had only known he wanted to play I’d have played with him,”
finished Rose, with a laugh. “But I thought he was a savage dog.”
“Oh, Jimsie is never ugly,” said Ralph. “He barks a lot, but I guess
that’s because he has to do it when he helps me drive the cows.
Well, I’ll see you again,” he added, as he started away with his dog.
“He’s a nice boy,” said Rose, when he was out of sight.
“I’d like to have that dog,” remarked Russ.
“I think—now maybe—I guess I have a riddle about a dog,” began
Laddie, but before he could ask it, or even before he could think
what it was, yells and screams came from another part of the brook.
“That’s Mun Bun!” exclaimed Rose.
“Sounded like Margy, too,” said Russ.
“Maybe they’ve fallen into the water,” suggested Laddie.
Just then Violet was heard asking:
“Oh, what did you want to go and do that for? Now you have gone
and done it! Are your feet wet? Did you get hurt, Mun Bun?”

Download textbook Nanocomposites Nanophotonics Nanobiotechnology And Applications Selected Proceedings Of The Second Fp7 Conference And International Summer School Nanotechnology From Fundamental Research To Innovation ebook all chapter pdf

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Download textbook Nanocomposites Nanophotonics Nanobiotechnology And Applications Selected Proceedings Of The Second Fp7 Conference And International Summer School Nanotechnology From Fundamental Research To Innovation ebook all chapter pdf

Uploaded by

Copyright:

Available Formats

Nanocomposites Nanophotonics

Nanobiotechnology and Applications

For further volumes:

ISSN 0930-8989 ISSN 1867-4941 (electronic)

Library of Congress Control Number: 2014945121

© Springer International Publishing Switzerland 2015

Printed on acid-free paper

Springer is part of Springer Science+Business Media (www.springer.com)

This book presents a selection of the latest developments in nanotechnology and

Part I: Nanocomposites and Nanostructures

Part II: Nanophotonics

Chapter 11 (Donets) presents technological aspects of corrosion resistant steels sur-

Part III: Nanobiotechnology

Chapter 16 (Martseniuk) is devoted to the analysis of properties of water, diffused in

Part IV: Applications

Chapter 22 (Kucherenko) describes urease-based conductometric biosensors that

Part I Nanocomposites and Nanostructures

2 Physical and Mechanical Properties of Surface Nanocrystalline

3 Energy Spectra of the Fibonacci Superlattice Based

4 Carbon-Based Piezoresistive Polymer Composites . . . . . . . . . . . . . . . . 51

5 Structure and Physical and Mechanical Properties of Nanocomposite

6 New Nanosized Systems Based Lanthanide Diketonate Complexes

7 Poly(Methacrylamidoaryl Methacrylate)’s Surface Morphology . . . . 95

8 Investigation of Nonlinear Magnetic Properties Magneto-Mechano-

9 Electrochemical Elaboration of Nano Powders Based

10 Heat-Resistant SiO2 –Al2 O3 –TiO2 Ceramics with Nanostructured

11 Technological Aspects of Corrosion-Resistant Steels Surfacing by

12 An Ellipsometric Model for Establishing Thickness of Thin Water

13 The Effect of Sintering Temperature on Linear and Nonlinear

14 Impact of Carbon Nanotube on Homocysteine Clusters:

15 Heat Capacity of 1D Chains of Atom/Molecule Adsorbates in the

Part III Nanobiotechnology

16 About Some Physical Properties of Water in Nanosystems and the

17 Effect of Gold Nanoparticles on Proliferative Properties

18 Nanobiotechnologies in the System of Farm Animals’

19 Proteins as Nanomachines: Hysteretic Enzymes Revisited . . . . . . . . . . 223

20 Application of Carbon Nanotubes for Plant Genetic Transformation 233

21 Platinum Nanoparticles with Adsorptive Layer of Chlorella vulgaris

22 Biosensors Based on Urease Adsorbed on Nickel, Platinum,

23 Magnetic Properties of Nanoparticle RMnO3 (R = Pr, Nd, and Tb)

24 Technological Approaches for Growth of Silicon Nanowire Arrays . . 301

25 Influence of Physical Parameters on the Transconductance gm of

26 Structural, Optical, and Photocatalytic Properties of Quasi-One-

27 Two-Dimensional Spin-FET Transistor . . . . . . . . . . . . . . . . . . . . . . . . . . 337

28 Future Strain Properties of Multilayer

29 Kinetics of Nonequilibrium Transition in Spin-Crossover Compounds 375

M. I. Bagatskii B.Verkin Institute for Low Temperature Physics and Engineering

Volodymyr Dyakonov A. A. Galkin Donetsk Physico-Technical Institute, National

Berna Ozansoy Kasap Central Laboratory, Middle East Technical University,

L. V. Ovseenko Institute of General and Inorganic Chemistry of NAS of Belarus,

O. V. Shcherbak Biotechnology laboratory, Institute of Animal Breeding and

V. T. Uvarov National Science Center Kharkov, Institute of Physics and Technology,

O. Fesenko, L. Yatsenko (eds.), Nanocomposites, Nanophotonics, 3

Fig. 1.1 Formulae 1–12

Fig. 1.2 IPR isomers of C60 , C70 , C76 and C80

1.2 Nontrivial Fullerene Discovery

Science is often presented to students as a fully logical structure, impersonal, and

1.3 Types of Endohedral Fullerene Complexes

1.3.1 Fullerenes with Noble Gas Atoms and Molecules as Guests

1.3.2 Endohedral Metallofullerenes

You might also like