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I NTERNATIONAL J OURNAL OF C HEMICAL

R EACTOR E NGINEERING
Volume 6 2008 Article A62

Nanoreactors for Nanostructured Materials
Ramdas B. Khomane∗ Bhaskar D. Kulkarni†


National Chemical Laboratory, rb.khomane@ncl.res.in

National Chemical Laboratory, bd.kulkarni@ncl.res.in
ISSN 1542-6580
Copyright 2008
c The Berkeley Electronic Press. All rights reserved.

Nanoreactors for Nanostructured Materials
Ramdas B. Khomane and Bhaskar D. Kulkarni

Abstract
Organized systems such as micelles, reverse micelles, vesicles, polyelectrolyte
capsules, liquid crystals, etc., formed through a self-assembling process represent
nanoreactors that can be used for preparing nanostructured materials. Besides a
fascinating academic subject, these nanoreactors provide a unique way to develop
a special type of advanced material for a wide variety of applications in electron-
ics, photonics, biomedical and other areas. The article examines the formation,
functioning, properties and special attributes of these nanoreactors with a view to-
wards their engineering analysis, design and possible integration in manufacturing
technology.

KEYWORDS: nanoreactors, nanostructured materials, organized self-assemblies

Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 1

1. INTRODUCTION:

Chemical reaction engineering is the science of chemical transformation of input
raw-materials into desired products in reaction vessel-called chemical reactor. For
a rational design of a reactor due considerations need to be given to understand (i)
the effects of concentration, temperature and flow fields etc. on the reactor
performance (ii) measure the rate of transformation (as a function of space and
time, as the case may be) (iii) to monitor conversion of raw materials, and (iv)
formation of desired and other side products, Extensive studies on the type of
reactions (series, parallel or a combination thereof), the inter and intra phase heat
and mass transport limitations, the presence of exotherms, the mechanism of
cooling, the type of flow field- extent and mixing, micromixing, degree of
segregated ness etc. on product and product distribution have been reported in the
past (Doraiswamy et al., 1984; Carberry et al., 1987; Froment et al., 1990; Fogler,
1981). Enabling technologies such as experimental tools and measuring
instruments including on-line sensors help in generating data at required locations
and frequency in time which can be analyzed using fundamental models to
determine kinetic and transport parameters and along with thermodynamic data
provides a rigorous basis to formulate and use such fundamental models for
rational reactor design, optimization, control, monitoring, etc. The experimental
data and its analysis further drives the search for newer type of contacting
devices, generate better catalysts for the transformation process, unravel
fundamental transformation mechanisms, and provide for the in-sight for scale-
up. The process also yields optimized performance with better quality of product
at higher utilization efficiency of material, energy, utilities, lesser load on
environment and cost and time for scale-up (Kulkarni, 2003).
Chemical reaction engineering has evolved to be a matured area and
chemical industries and manufactures have immensely benefited by its
applications across the various categories of chemical products ranging from basic
chemicals, specialty chemicals, pharmaceuticals, food and biotechnology
products, polymers on one hand to new advanced materials with structures and
architectures that are responsible for the performance attributes of the products on
the other. The research needs to acquire physico-chemical, kinetic and
thermodynamic data and to build first principles models to obtain and predict
process performance, facilitate reactor design for improved performance, predict
and link process conditions to product quality and properties at various length and
time scales continue (Klipstein, 2001).
The new challenges to reaction engineering emerge from advanced
material synthesis and manufacture. Reports of the appearance of new materials
replacing the conventionally used materials (wood, glass, metal, fibers etc.) with
an improved performance and extended range of applications are clear pointers in

Published by The Berkeley Electronic Press, 2008

The materials normally range from nano to micro scale and have greatly impacted various sectors with very many applications in diversified areas.com/ijcre/vol6/A62 . http://www. packaging.bepress. A number of advanced materials with cost competitiveness and enhanced performance in sectors such as automotive and transportation. separations. Scientific curiosity about the behavior of matter at smaller length scales. space modules etc. A clear understanding of the fundamental science and especially the chemistry (and biology in some instances) at interfaces together with our ability to model structure-activity-performance relationship and the connected issue of controlling molecular structure during processing conserving its desirable properties is thus the emerging need. are poised to bring about economic transformation of the chemical industry. 6 [2008]. magnetic or photo- assisted transformation or self-assembled systems as nanoreactors for nanostructured products are becoming important.2 International Journal of Chemical Reactor Engineering Vol. has led to development of a number of new advanced materials with well defined size. Many different types of nanomaterials synthesized in different types of nanoreactors are summarized in Figure 1. Article A62 this direction. In the present work we will take stock of nanoreactors for preparation of such structured materials and examine them from the view point of chemical reaction engineering parameters. biomedical applications. electronics and optoelectronics. energy. Development of non conventional reactors that will allow structured contacting with ease of rapid heating or cooling or use of alternative fields such as electric. enhanced oil recovery. besides generating a significant fundamental understanding. hybrid composites for building-construction. structure and form that contribute and decide their unique properties. coating.

advanced materials and information technology. convection and mixing. Conducting chemical reactions in confined spaces creates an opportunity to synthesize new materials with unexpected properties. hollow Vesicles materials spheres 2-d surface arrays LB Films 3-d mesoporous structures Lipid membranes Polymer Bilayers Biomaterials Liquid crystals Membranes Microgels Liposomes Dendrimers Polyelectrolytes Multilayer capsules Protein & virus cages Other self-assemble system Figure 1.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 3 Nanomaterials and nanoreactors Sector Area Materials Nanovescles Transportation Catalysis Metals Micelles Energy Separations Metal oxide / hydroxide Reverse micelles Health care Electronics Semiconductor Rod-like micelles Building/construction Optics Porous inorganic structures Microemulsions Advanced composite Medicine biosensing Coated colloids. The nanostructured materials exhibit novel electrical. Nature uses relatively simple systems such as enzymes or complex assemblies such as cells to produce different materials of desired properties. Classification of nanomaterials and nanoreactors in different areas. In the past few years. The transformation processes are multi- step in nature where multiple components and multi-catalytic species are present or generated at the right location at the right time leading to high yield and selectivity. Published by The Berkeley Electronic Press. electronics. Construction of an artificial cell while is the ultimate target. 2008 . mass and transport of species. Coupling of reactions in time and space with intrinsic control on the kinetics of reactions. time and waste produced. all together optimizes the performance to obtain final structure with minimum cost. research on nanosystems has developed significantly due to their potential applications in biology. the initial attempts to construct covalent or noncovalent reactors and self assemblies of small molecular components have generated results that are sufficiently exciting and continue to fan inspiration in this direction.

http://www. methods of formation. presence of additives. 2001). electrolytes etc. concentration of surfactants.bepress. ORGANIZED MEDIA: SOME IMPORTANT FACTS 2.. 6 [2008].. nature and type of self-assembly have been studied. 2001).. when dissolved in water can form various aggregates such as micelles. have been prepared in micelles (Samuelson et al. 2003). 1997). 2. reverse micelles (Ingert et al. 2005). In the rest of the paper. applications to different systems and the rationale for engineering design and analysis. 1999. A number of different types of nanoparticles ranging from metals. Extensive studies on the formation and characterization of such self-assembled structures and effects of number of parameters such as nature and type of polar head group. block copolymers ( Bronstein et al.. we shall summarily discuss these nanoreacors along with their characteristics.4 International Journal of Chemical Reactor Engineering Vol. Article A62 optical. 1998). extent of dilution. hydrocarbon type and chain length. magnetic and mechanical properties due to altered electronic structures (Nayak et al. operating conditions of temperature. Surfactants with hydrophilic polar head and hydrophobic hydrocarbon chain. size. spherical or cylindrical nanocrystal etc. microemulsion (Hingorani et al. etc.. interconnected cylinders. semiconductors. crystallinity and sizes which are so crucial to their properties. Normal Micelle The literature on normal micelles is extensive and for reasons of brevity we shall only summarize some important facts. polymers. vesicles. Forster et al. Manziek et al. Typical normal micelles are depicted in Figure 2.. Synthesis of such materials in self-assembled surfactant templates can provide a means of exercising some control on their shapes.. 2001).1. microgels (Antonietti et al. 1995. liquid crystals (Delinger et al. on the shape. inorganic oxides etc. planer or onion like lamellar phases.. reverse micelles.com/ijcre/vol6/A62 . crystallinity.

several hundreds of amphiphilic molecules or ions of surfactants form dispersed phase that is distributed in the bulk of the solvent phase. The layer contains polar head groups of surfactant and a shell of retained water molecules. The hydrophobic interactions drive the process and eliminates the nonpolar hydrocarbon radicals from water and their association in the nucleus of the micellar systems. 2008 . Eliminating water contact and restructuring of water depends on concentration of surfactant which decreases with the length of hydrocarbon radicals. The half life of surfactant micelles range from a millisecond Published by The Berkeley Electronic Press. • Micellar systems continuously undergo the formation and breakdown processes. etc. water permeability. pH. cosurfactant. The rigidity.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 5 Figure 2. electrostatic potential. • Interphase or stern layer separates the microphase of direct micelles from the dispersion medium. <0) describing the spontaneous micellization contributes more to micelle formation than the enthalpy. This is due to change in the states of the surfactant and water molecules on micellization. • The entropic factor in the Gibbs potential (ΔG=ΔH-TΔS. nature of organic solvent. Normal micelle • Lyophilic assemblies of colloid size. local ionic strength. can be altered and depend on extent and type of electrolyte. etc. flexibility.

A number of examples illustrating synthesis of different nano particles are included in the Table 1. hydration. charge. The typical aggregation number varies between 40 to 150. Article A62 to second whereas the surfactant molecule in a micelle has half life of 10-5 to 10-7 seconds. • The packing parameters Ρ( ν/ιа). electrolyte etc. http://www. vesicles may form and for P>1 inverted structures are expected. The packing size and shape can change from spherical.bepress. (b) stabilization of transient state of reaction due to favorable interaction with surfactant and (c) the medium effect as reflected in properties such as polarity.6 International Journal of Chemical Reactor Engineering Vol. rod-like to hexagonal type as concentration of surfactant. A variety of self assembled morphologies can result as a consequence of aggregation in aqueous solution. • The presence of hydrophilic surface and hydrophilic core. etc. microviscosity. the micelle formation is expected whereas for 1/2<P<1. where a is the surface area of head group and ν and ι are the volume and length of alkyl chains. • Solvation thermodynamics is decisive in the favorable overlap of hydration shells of hydrophobic parts of molecules. All these geometries have nanometer dimensions and can be used as nanoreactors. allows the micelles to dissolve both polar and nonpolar substances and can alter (enhance) the reaction rate due to (a) concentration of reactant at the interface or in the interior. changes. The aggregation morphologies are decided by the free energy term comprising of contributions from (a) favorable clustering of hydrophobic parts of molecules (b) a tendency to closely pack so as to minimize unfavorable hydrocarbon-water interaction (c) a counter tendency to spread due to electrostatic repulsion between charged head groups. For instance 0<P<1/2.com/ijcre/vol6/A62 . 6 [2008]. defines various aggregation geometries possible. steric effects etc.

. 2006 emulsion process & compositions microemulsion or sub-micron emulsion compn. 2006 Mimusops elangii. SDS and reactant cation to synthesis single-phase CoCrFeO4 nanoparticles with 2002 mixture + methylamine a controlled size range of 6-16 nm. 4 An aqueous solution of SDS and Magnesium aluminate. MgAl2O4. triterpene acid isolated from Lala et al. its activity in vivo was evaluated in hamster models of visceral leishmaniasis. reactant cation Mixture + NH4OH were synthesized using normal micelle microemulsion 2003 methods. Published by The Berkeley Electronic Press.. both in free form. viz microemulsions and polylactide nanoparticles. 2 Tween 20/clove oil/water Basic acid. for (patent) dermal delivery of at least one pharmaceutically active ingredient. Using CoCrFeO4 nanoparticles as precursors for the formation of a bulk sample resulted in a material that displayed an unusual susceptibility behavior but not the anomalous temperature-dependent hysteresis trend usually observed in conventional CoCrFeO4 bulk materials. Some experimental studies on microemulsion for nanoparticles Sr. of an oil in water (O/W) Larm et al. spinel nanoparticles Vestal et al.. an unsatd. 3 O/W microemulsion & sub-micron A process for the prepn. The in vitro antileishmanial activity of basic acid being encouraging. System Special features and applications References No 1 An aqueous solution of Normal and reverse micelle microemulsion were used Vestal et al. as well as incorporated in two different delivery systems. was tested for its antileishmanial properties both in vitro and in vivo.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 7 Table 1. 2008 .. 5 SDS/hexane/n-butanol/water Studied the presence in the environment of the Segura et al..

and turbid birefringent gel phase.. 9 Tween 80/pentanol/ethyl oleate Microemulsions are phys.. 10 SDS/aromatic Water-SDS-arom. 2001 formed at 25o: normal micellar soln. or inability to access the site of action. buffer corresponding nucleosides in the oil in water (o/w) 2001 SDS/toluene/1-butanol/carbonate microemulsion capillary electrophoresis. by S2O2-8 ions. buffer microemulsion electrokinetic chromatog. microemulsion. 6 Microemulsion and micelle systems A microemulsion delivery system for water insol. crystal. or Dennis et al.oxidn. with the amt.8 International Journal of Chemical Reactor Engineering Vol. were examd.. containing long polymer chain sparingly water-sol. stable oil/water systems that Al-Adham et al. and water (SN).bepress. inverse micellar soln. toxicity. Article A62 SDS/hexane/n-pentanol/water polycyclic arom. lamellar liq. toluene. toluene. drugs comprise a long polymer 2002 surfactants and short fatty acid chain surfactant component and a short fatty acid surfactant components for surfactant component. in comparison with those in normal capillary zone electrophoresis (CZE). hydrocarbon benzo[a]pyrene (BaP) in 2002 SDS/hexane/n-hexanol/water the city of Granada using room-temp. 6 [2008]. of each being solubilizing drugs selected to provide stable microemulsion or micellar systems.com/ijcre/vol6/A62 . 8 Phase behavior of sodium In a ternary phase diagram of sodium naphthenates Horvath-Szabo et naphthenates... Tween 80/cyclohexanol/ethyl oleate have potential use as delivery systems for many 2000 pharmaceuticals which are normally of limited use due to their hydrophobicity. http://www. phosphorescence SDS/hexane/3-pentanol/water (RTP) applied to microemulsions. 1995 I. and water the following phases can be al...hydrocarbon-propanol Santhanalakshmi hydrocarbon/propanol microemulsions are constructed and used as media for et al. (MEEKC). 7 SDS/heptane/1-butanol/phosphate The electrophoretic behavior of five bases and Furumoto et al.

3). Reverse Micelle Figure 3. Water can be solubilized in the core forming water-in-oil droplets (5 nm) which eventually become the w/o microemulsion as the water content increases (5 to 100nm).2. John et al. 2004). other additives. 1995. lower than in direct-micelles. 1999. Pillai et al. 2008 . The shape can be spherical.. Osseo-Asare. Adair et al. The biomineralization process in nature uses organized aggregates of bio macromolecules to synthesize nanoparticles with dimensional. Reverse micelle Reverse micelles provide another example of organized self assemblies of surfactants in solution and are most widely used as reaction media or templates for biomimetic synthesis of various inorganic nanoparticles (Pileni.. The water to surfactant molar ratio has a decisive influence on the diameter of the reverse micelles.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 9 2. 1993. morphological and architechtural specificity and excersizing full control over nucleation.. 2002. Capek. electrolyte. Kon-no et al.. 1997. rod-like or lamellar and depends on the concentration of surfactant. etc. The anionic sodium bis (2-ethylhexyl) sulfosuccinate (AOT) and nonionic poly oxyethylated surfactants are most commonly used to generate reverse Published by The Berkeley Electronic Press. 1998. growth and the patterns formed. The hydrophilic head and hydrophobic tail of surfactants in apolar solvent self assemble to give reverse micelles where the polar core contains the hydrophilic heads and the apolar shell the hydrophobic chains (see Fig. The aggregation number is typically in the range of 20 to 30. The droplets undergo continuous collisions and exchange their contents.

Also the reaction rate. The entire surfactant film can participate in the process especially when it is rigid. Also. The nanoparticles size and size distribution depends on a number of parameters (Pileni. The use of nonionic surfactants also eliminates the ill-effects of counterions. One of the easiest method of preparing nanoparticles in reverse micelles involves preparing two reverse microemulsions containing reactant A and B and mix them together to produce the product. is usually faster. interference of the counter ions etc. The surfactant molecule can get adsorbed on the particle surface and stabilize it preventing further growth. The size of the channel containing the two microdroplets and the surfactant film flexibility plays a significant role in the growth process. thus it is established that: • Particle size and polydispersity increases with the increase of reactant concentration • Particle size increases with the surfactant film flexibility http://www. once the transfer occurs. the adsorption of surfactant on particles and their transfer across droplets creates an inversion of film curvature which depends on film flexibility and elasticity. General model that accounts for all such parameters with Monte Carlo simulations give some generic trends for particle size and size distribution. 1998).10 International Journal of Chemical Reactor Engineering Vol.com/ijcre/vol6/A62 . the micelles formed are nerealy spherical and monodispersed irrespective of the nature of the apolar solvent and the droplet size is independent of the CMC of surfactant.bepress. In fact. The collision rate dynamics is usually very fast (1010 dm3/mol/s) at ambient conditions as compared to the rate of interchange of droplet contents (106 to 108 dm3 /mol/s) for AOT (Sagar. The possible mechanism of particle formation involves (i) colloiding of two droplets (ii) coalescing to form dimer (iii) exchange the contents (iv) chemical reaction and particle formation and (v) disintegrate into droplets.. Only a small percentage of droplet collisions therefore result in actual dimer formation and hence the interchange mechanism is often rate controlling step. 2003) which include (1) the droplet size (2) inter droplet exchange (30 reactant concentration (4) the drolet volume fraction (5) critical nucleus (6) the reactant excess ratio (7) film flexibility (8) the growth mechanisms arising out of autocatalysis and ripening. For flexible surfactant films. 6 [2008]. Other ionic or nonionic surfactants can also be used but must be chosen with care to ensure their inertness in the system. Article A62 micelles and have the advantage that no cosurfactant need be used. This has the implications that the bulk nucleation and growth models may not adequately explain the nanoparticles formation. the nucleation and growth is determined by the intermicellar exchange of reactants (autocatalytic reaction) and/or product (the ripening process). In the former the exchanged reactants undergo reaction at the surface of the particles inside the droplets and deposit and grow on them while in the later the smaller particles from one droplet gets transferred to the other containing larger particle that grows further. Lopez-Quitela et al. 1997.

Published by The Berkeley Electronic Press.1 to 2. The positive entropy change (TΔS) in the Gibbs free energy equation due to adsorption of surfactant decreases with the increase in radius R of the particle. the particle size is governed by microemulsion controlled behaviour while for the radius greater than νc. The integration of one-dimensional building blocks into ordered superstructures produce hierarchical assembles with complex functional architectures and hence attributes.) are also included in Table 2. In the other mechanism. nanorods. A number of examples illustrating synthesis of metals. in fact the use of microemulsion is irrelevant and similar results can be obtained in direct bulk solutions. etc. Preparation of catalytic particles.controlled systems. A few assorted examples of nanorods. where adsorption is strong belong to this type. nanowires and nanotubes are provided in the table 2. the surfactant control behaviour is followed. For radius smaller than νc. none of the microemulsion based parameters are involved in deciding particle size. Of special interest are the 1-d nanostructures (nano wires. A minimum stable critical radius νc (ΔG=0) is therefore predicted. A few of such examples (nanorods.micelles would normally be spherical unless some system specific special care is exercised. the surfactant encapsulates the primary particles which linearly attach each other due to specific interactions between particles. The nuclei formation can also occur in the interconnecting channels. nanotubes. In the former. The presence of cosurfactant can affect the flexibility of surfactant film and the adsorption behavior. The intrinsic crystallographic structure of the solid may also contribute to this mechanism.) and the self organization of colloidal nanoparticles into 2-d to 3-d assemblies as superlattices exhibiting the combined properties of individual as well as collective particle behaviour. Synthesis of non spherical assemblies of nanostructures has also been the focus of attention. cubes. surfactants and other additives present. tubes. In such systems the adsorption behaviour of surfactants or capping agents dictates. etc.18). metal oxides and other inorganic particles are included in the Table 2 (see Tables 2. In the other case of surfactant-controlled systems. 2008 . The primary mechanism responsible for the formation of such structures involves either a template-directed growth or the oriented aggregation.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 11 • Particle size increases with the increase in droplet size • Particle size decreases with the increase in the excess of the reactants The above generic trends are exhibited by systems that are microemulsuion. the elongated water droplet generates elongated nuclei that grows into nanostructure with one dimension considerably larger than the template. The enthalpy changes on the other hand are nearly constant. The shape of nanoparticles synthesized in reverse. Numerous examples that subscribe to either one of these mechanisms are reported in the literature.

bepress. and methanol- assisted particle purifn.N'-dimethylammonium chloride) and the anionic monomers maleamic acid or butylmaleamic acid has been synthesized and the influence on the inverse micellar region of the quaternary system has been investigated. 3 sodiumdodecylsulfate/toluene-pentanol The influence of polyampholytes on the phase Note et al. al.N'-diallyl- N. 2007 They report the variation of elec.The method for isolation of monodispersed Pd nanoparticles from a reverse microemulsion was developed using hydrocarbon evapn.. A series of hydrophobically modified polyampholytes by the copolymn. and cyclohexane properties of BaFe12O19 hexaferrite nanoparticles. of the cationic monomer (N. http://www. to synthesize BiOX Henle et al. heptane and aq. cond. 6 [2008]. 2007 free selective hydrogenation of 2-methyl-3-butyn-2- ol . Some experimental studies on reverse microemulsion for nanoparticles Sr. n-hexanol. 2 Water/AOT/isooctane Monodispersed palladium nanoparticles have been Semagina et synthesized to study structure sensitivity of solvent. (1:1)/water behavior of microemulsion used as template for the 2007 nanoparticle formation has been studied. 4 Nonionic surfactants. Article A62 Table 2.12 International Journal of Chemical Reactor Engineering Vol. Some experimental studies on Reverse microemulsion Table 2. during the formation and reaction of microemulsion droplets suggesting nonpercolating microemulsion conducting systems. System Special features and applications References No 1 Cetyltrimethylammonium chloride Authors have synthesized and and studied magnetic Xu et al. from a surfactant.com/ijcre/vol6/A62 .1.. salt Reverse microemulsions is used... (CTAC).

The reverse micelles act 2007 Particles as nanoscale templates for the ionic pptn.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 13 solns Nanosized BiOX (X = Cl.. (NPs) were prepared in a reverse microemulsion and 2006 used as a novel matrix for biochem. 9 n-hexadecil trimethylammonium bromide The magnetite nanopowders were synthesized by a Koutzarova (CTAB)/ n-butanol/ n-hexanol/water single microemulsion technique in which the aq. Further. Br. process. 5 CTAB/hexanol/water Synthesized the nanosized precursors of yttria... t)/ cyclohexane /n-butanol/water reaction of Bi(NO3)3. I) (X = Cl.5H2O. cyclohexane /water hydroxyapatite (HAP) nanorods by the reverse 2006 microemulsion method with diam. 8-15 nm and length 25-50 nm. the microstructure and size control of iron oxide nanoparticles was studied.. I) nanoparticles. 11 (Igepal CO 520. Further they studied the cathodic process of Ni2+ in the W/O microemulsion . Xie et al. 2006 cycloheptane)/ Water reported. et al. nickel by direct electrodeposition. 10 OP (polyethylene glycol p-octylphenyl Nanometer-sized Bi4Ti3O12 particles by chem. and NH3 soln. 2006 in a reverse microemulsion system has been reported.. TOPO)/ A method for synthesiszing polyaniline nanoparticles Jae-Hyun et (Cyclohexane/cyclopentane/ using reverse microemulsion process has been al. 2008 . Published by The Berkeley Electronic Press. Ti(SO4)2.. Ni nano-particles 2006 were modified onto the Ni substrate. 2006 phase contains only metal ions (Fe2+ and Fe3+).. Tai et al. 8 Triton X-100/ n-hexane/ n-hexanol/water W/O microemulsion was used to prepare nanoscaled Zhou et al. AOT. application. Br. ether. 7 OP/hexanol/cyclohexane/aqueous solution Methylene blue (MB)-doped silica nanoparticles Xian et al. 6 TX-100 + CTAB / n-butanol + n-hexanol The study demonstrates preparation of single-crystal Sun et al. stabilized zirconia (YSZ) via a reverse 2007 microemulsion.

DBSA plays the roles of both surfactant and dopant. in the microemulsion shows enhanced CO2 sorption capacity and shorter retention times at higher temp. 15 Mixt. reaction 2006 between sodium polysulfide and hydrochloric acid in a reverse microemulsions system.bepress./isooctane/water The study fabricates the pyrrole-oligomer Han et al. 16 Coated water soluble nanoparticles Core-shell nanoparticles and methods of making Ying et al.14 International Journal of Chemical Reactor Engineering Vol.. Triton X-100/n-hexanol /cyclohexane. Reverse microemulsion as nanoreactor http://www.A synthesis method for nanocryst. esp. The nanoparticles 2006 semiconductor core and their preparation may include semiconductor nanocrystals. 14 DBSA/iso-Pr alc.Nano-sized Guo et al. comprising an inorganic shell and these nanoparticles are provided. Table 2. The nanoparticle prepd. of Span80 and Tween80/ Authors have successfully prepd.. theolin/butanol/water monoclinic sulfur particles via the chem.. A shell may encapsulate a nanoparticle core.com/ijcre/vol6/A62 . 13 Triton X-100/cyclohexane /n. silica. 6 [2008]. material... controllable particle size and structure was prepared 2006 by a reverse microemulsion-mediated synthesis method. Article A62 12 Brij-30/n-heptane Ultrafine tungsten and tungsten oxide powders with Xiong et al.. 17 Polyoxyethelyne(5)nonyphenyl ether/ Using reverse microemulsion techniques combined Yi et al. nanoparticles doped dodecylbenzenesulfonic acid 2006 (DBSA) in reverse microemulsion. Cyclohexane/ ammonium hydroxide with templating strategies authors have synthesized 2006 four types of nanoparticles and studied the formation of different nanoparticle architectures with tailored silica shell thickness and porosity. and may include a non-org. lithium silicate by Khomane et hexanol/water coupling of sol-gel method in reverse microemulsion al. 2006 is reported.2.

sulfosuccinate)/isooctane/water indium-tin oxide (ITO) particles in reverse 1999 microemulsions is reported. /water room temp. Reverse microemulsion for nanorods Sr.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 15 Sr. The study further shows that tin mols. cyclohexane/water hydroxyapatite (HAP) nanorods by the reverse 2006 microemulsion. From various comparison expts. by reverse Li et al. are doped into the indium oxide homogeneously rather than forming a discrete tin oxide domain in indium-tin oxide particles formed in microemulsions.. The tuning of the size of nanorods by 2007 changing w value (molar ratio of water to surfactant).3TiO3 nanorods in reverse microemulsion at Chen et al. 2008 .7Sr0. System Special features and applications References No 1 Cetyltrimethylammonium bromide/ n. and NP10/cyclohexane/H2O the BaCO3 nanorods and nanobelts in reverse 2006 microemulsion. Table 2. 2006 4 CTAB/cyclohexane/H2O Authors have explained the methods to synthesize Li et al.An effective strategy to produce zeolite nanocrystals Chen et al. butanol / by using microwave heating in reverse 2005 cyclohexane microemulsion... 2 AOT (2-ethylhexyl The preparation method for monodispersed ultrafine Kim et al. System Special features and applications References No 1 Triton X-100/cyclohexane /n-hexanol Ba0. 2 TX-100 + CTAB/ n-butanol + n-hexanol / A simple system for the synthesis of single-crystal Sun et al.. 3 SDS/cyclohexane/ n-Amylalcohol Pure γ-phase CuI nanorods. aging time and reactant concn is reported .3.. Published by The Berkeley Electronic Press.. microemulsions using low temperature.

They further studied electronic response PPy nanotubes with various diameters 2 AOT /hexane/water Authors have described a convenient one-step Zhang et al.4-ethylenedioxythiophene) (PEDOT) nanotubes using reverse microemulsion polymn.4. in an apolar solvent in the 2003 http://www. 3 TOA/H3PO4 Titanium phosphate nanotubes with alternating Yin et al.bepress. and solvent hydrothermal treatment play important roles in the morphol. interlayer spacings have been synthesized in a 2004 reverse microemulsion formed in an amine extn. the prepn.... and transport properties and potential device applications of individual PEDOT tubes. system. polypyrrole (PPy) nanotubes with different diams. Article A62 Authors have shown that several exptl.. bulk quantities of microns 2006 long poly(3. 2006 using cylindrical micelle templates in reverse microemulsions.com/ijcre/vol6/A62 . System Special features and applications References No 1 AOT /hexane/water Authors have shown the fabrication method for Yoon et al. 6 [2008]. the use of potential-time profiling to uncover factors that favor tubular polymer growth. Table 2. control of BaCO3 nanostructures. of surfactant and reactant.16 International Journal of Chemical Reactor Engineering Vol. 4 AOT /hexane/water Polypyrrole (PPy) nanotubes by reverse Jang et al.. microemulsion polymn. method to chem. Reverse microemulsion for nanotubes Sr. such as the concn. prep. of PEDOT- metal and PEDOT-metal oxide composites having tubular morphol. parameters..

. System Special features and applications References No 1 Marlophen NP5 (RO(CH2CH2O)xH. Reverse microemulsion for nanowires Sr. R = nonylphenyl. 2005 in W/O microemulsion through microwave dielec. 600 in a 2006 quaternary reverse microemulsion contg. System Special features and applications References No 1 SDS/water/heptane/n-hexane The study reports the synthesis of ZnO nanowires Sun et al. 2 SDS/toluene-pentanol (1:1)/water Present work focuse on the use of branched Note et al. Br.. SASOL ) Authors have used Reverse microemulsion. poly(ethyleneimine) (PEI) as reducing as well as 2006 stabilizing agent for the formation of gold nanoparticles in different media. with high-aspect-ratio of up to ca.. shapes have been prepared by using BuOH situ redn. Table 2. heating.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 17 presence of FeCl3 and sodium bis(2- ethylhexyl)sulfosuccinate have been reported. I) nanoparticles Henle et al.6. x =5. process. Table 2. M= 440 g/mol. The role of SDS in the formation of morphologies has been ellucided. Reverse microemulsion as a template Sr.. via a hydrothermal method. The reverse microemulsion droplets of the quaternary system Published by The Berkeley Electronic Press. The 2007 / n-heptane /water reverse micelles act as nanoscale templates for the ionic pptn.) The hydrophobic Au nanostructures with different Shen et al. 2 CTAB/BuOH/n-heptane/HAuCl4(aq.5. To synthesize BiOX (X = Cl. and factors affecting the formation of PPy nanotubes have also been investigated. 2008 .

of gold nanoparticles 3 SDBS/ dimethylbenzene/ water Solvothermal synthesis of hollow nanostructure. 2007 by two different methods (impregnation of ceria and copptn. The formation mechanism as a coordination-assisted dissoln. of the two components within reverse http://www.bepress. 4 Polyoxyethelyne(5)nonyphenyl ether/ Using reverse microemulsion techniques combined Yi et al. Lu et al. Microemulsion Methods Table 2. microemulsion copptn. System Special features and applications References No 1 Triton X-100 /n-heptane/ hexanol and an Ce-Cu mixed oxide precursors with varing Ce:Cu at. 6 [2008].com/ijcre/vol6/A62 .7. by freeze-drying and 2007 nitrates.. hollow spindle-like hematite with uniform size and 2006 morphol. 2 Triton X-100/n-heptane/hexanol / aq Nanostructured catalysts based on combinations Gamarra et solution solutions of CuO and CeO2 between oxidised copper and cerium entities prepd. al. from micelle/polymer precursors prepared by the 2005 micelle template method in reverse microemulsion systems and the pore size could be tuned by varying the type and concentration of surfactant... Reverse microemulsion co-precipitation Sr. Article A62 were successfully used for the prepn. process occurred in a reverse microemulsion system.18 International Journal of Chemical Reactor Engineering Vol... Cyclohexane/ ammonium hydroxide with templating strategies the work synthesizes four 2006 types of nanoparticles and studies the formation of different nanoparticle architectures with tailored silica shell thickness and porosity. aqueous solution of cerium and copper ratio have been prepd. 5 AN/ PPO19–PEO33PPO19 /NMP Mesoporous polymer materials can be fabricated Jang et al. Fuerte et al.

4 CTAB/1-butanol/n-heptane/H2O Nanopowder of Y Al garnet (YAG. Either oxalic acid. of iron salts in alk.. Y3Al5O12) doped Caponetti et with Nd ions (Nd:YAG) was prepd.. in the al. of CO in a H2-rich stream (CO-PROX). Al. cyclohexane /aq solutions of ferrous and superparamagnetic particles in order to protect them 2007 ferric salts from gastric dissoln. Afterwards. Coppt.Dy3+ phosphors with good Sun et al. Lanthanum-strontium manganites were synthesized Uskokovic La(NO3)3 and Sr(NO3)2 using co-pptn. agent. monodispersity and narrow size distribution were 2006 synthesized by the coupling of water-in-oil (W/O) microemulsion with copptn. method. with respect to their catalytic performance for preferential oxidn. 6 CTAB/ 1 hexanol/ aq solution MnCl2. Y. 3 Sorbitan triesterate/Xylan/ chloroform / This work evaluates an exptl.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 19 microemulsions) have been examd. set-up to coat Silva et al. hydroxide precursors where thermally treated at 900oC to achieve the garnet phase. size of the phosphor particles. 2007 CTAB/ 1-hexanol/ 1-butanol/ aq solution microemulsion. La(NO3)3 and Sr(NO3)2 hydroxide or tetramethylammonium hydroxide was used for the pptn. method with a reverse micellar et al. of precursor cations in a form that Published by The Berkeley Electronic Press. medium.. magnetic particles were produced by copptn. First. of surfactant that was used had an important effect on the shape and av. 2008 . 5 W/O microemulsion Nanosized SrAl2O4:Eu2+. sodium MnCl2. and NH3 was used as a pptg.. an emulsification/crosslinking reaction was carried out in order to produce magnetic polymeric particles. and Nd nitrates were used as starting materials. 2007 H2O/cetyltrimethylammonium bromide/1-butanol/n- heptane system. The amt.

Fe3O4) coated with oleic acid used in the prepn. into a water-in-oil microemulsion. reaction of ferrous and ferric salts with two org. w/o-microemulsions were employed to Lopez- solutions (salts.. The et al. 2006 microemulsion. cyclohexylamine and oleylamine.com/ijcre/vol6/A62 .bepress. of the microspheres was synthesized in a classical co-pptn.e.. procedure. In both cases. and the other in reverse micelles of CTAB/1-hexanol/water microemulsion. and 500 nm. by the microemulsion polymn. copptn. 2006 http://www. 9 CTAB/1-hexanol/water Nanostructured lanthanum-strontium manganites Uskokovic were synthesized using two different co-pptn. Liu et al. 7 Reverse microemulsion mediated co. ammonia and hydroxide) produce nanoparticles of the perovskite Trosell et Ca0. 6 [2008].20 International Journal of Chemical Reactor Engineering Vol. 8 Brij-97/cyclohexane/ aq. bases. resp. which have a size of approx. 11 Marlipal O13/70/ cyclohexane/ aqueous In this paper. et al. one in bulk soln. by using oxalic acid. Article A62 was subsequently calcined under various conditions in order to obtain perovskite manganite phase.. 180. Nedkov et precipitation sizes of 80. acryamide (AM) in the presence of emulsifiers with the size of 1-5 µm.Typical hexagonal plate-like particles with approx. were obtained by al.5MnO3. 2006 methacrylic acid (MAA). 2006 nanoparticles are formed by the copptn.5Sr0. 10 SDS /styrene / cetyl alcohol / Water Magnetic polymer-coated microspheres were prepd. of styrene (St). 20-50 al.. precursor cations were pptd. ferrous and ferric A 1-pot microemulsion method to produce Vidal-Vidal salts solutions monodisperse and coated small nanoparticles.. 2006 approaches.. The magnetic material (i.. and solid-state reaction techniques.

. The procedure was carried out using sodium hydroxide or ammonia as co-pptn.. 2001 Igepal CO-520/ n-heptane / aq solutions of of microemulsions. 15 Brij-97/cyclohexane/ aq solutions of Three different nonionic surfactants (Triton X-100. conventional copptn. reaction of ferrous and ferric salts with Published by The Berkeley Electronic Press. 12 NP5+NP9 /cyclohexane/ aqueous solution Microemulsion method has been applied and Garcia et of Pb2+. Does.. via 2002 two processing routes. (MCP). phases in NaOH copptd. cobalt pentacyanonitrosylferrate. agent. 2002 Co(AOT)2 / isooctane / water materials. and chromium hexacyanochromate.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 21 nm. Vaucher et nanoparticles of three different mol. copptn. the microemulsion-refined copptn.. and ceramic route al. Zr4+. 2003 with the purpose of encapsulating hematite into zircon crystals used as ceramic pigment. 14 NaAOT/ isooctane / aqueous K3Fe(CN)6 Here the authors describe the synthesis of cryst. or emulsioned samples avoids the zircon crystn. and Brij-97) were used for the prepn. the copptn. by copptn. 13 NP5+NP9/ cyclohexane/ aqueous solution Ultrafine lead titanate (PbTiO3) powders in Fang et al. The stabilization of sodium silicozirconate cryst.-based magnetic al. of water-in-oil microemulsions. and the magnetic properties were Triton X-100 /cyclohexane / n-hexanol / aq studied. cobalt hexacyanoferrate. crystallinity. 2008 . (CPC) and microemulsion-refined copptn. reactions involving mixts. and their effects on the particle ferrous and ferric salts size. namely. Pb(NO3)2–TiO(NO3)2 tetragonal form have been successfully prepd. and then the hematite encapsulation. ferrous and ferric salts Igepal CO-520. Ti4+ compared with sol-gel. Santra et al. is the technique that results in the formation of the finer powder of lead titanate than the conventional copptn. The iron oxide nanoparticles are formed by solutions of ferrous and ferric salts.

using either oxalic acid or ammonia soln. mixed 1998 cyclohexane/ water poly(oxyethylene)5 nonyl phenol ether and poly(oxyethylene)9 nonyl phenol ether as the nonionic surfactants. been prepd. using oxalic acid as the precipitant. were used in each surfactant to observe whether the basicity has some influence on the crystn. soln. poly(oxyethylene)9 nonyl phenol ether/ cyclohexane as the oil phase. Article A62 inorg.bepress. contg.. Wang et al. NaOH. OP-10 using a reaction within reversed micelles. 16 NP5+NP9/cyclohexane/water Three processing routes have been used to prep. NH4OH. conventional copptns. of the hydroxide precursors was effected through addn. into the microemulsions. ammonia soln. Copptn. via three types of processing routes: 1998 conventional solid reaction. as the precipitant. 19 Cyclohexane / n-hexyl alcohol /water Cerium(IV) oxide ultrafine particles were prepd. namely conventional 1999 copptn. and a comparatively mild base..22 International Journal of Chemical Reactor Engineering Vol. and titanium as the water phase. using di-Et oxalate as the precipitant. process during particle formation. barium titanate powders. A strong base. bases.com/ijcre/vol6/A62 . 18 Poly(oxyethylene)5 nonyl phenol ether + The microemulsion system used consists of Ee et al. Masui et al. zirconium. 6 [2008]. and an aq. and microemulsion-refined copptns. as the precipitant. known as a 1997 http://www.. cations of lead. of an aq. and double-microemulsion copptn.. 17 NP5+NP9/cyclohexane/water Ultrafine perovskite lead zirconate powders have Fang et al.. using either oxalic acid or ammonia soln. single-microemulsion copptn. solution.

. 20 Igipal CA520/n-heptane/water The authors describe a new technique using Vaqueiro et microemulsions to produce ultrafine precursors of Y al.) al. The ultrafine particles. AOT/n-hexane/water to control the copptn. 23 AOT/n-heptane/water A microemulsion was studied as a reaction medium Wang et al. 2008 . A copptn.-in-oil (nonaq. which were obtained by mixing the water-in-oil microemulsions contg. with those of ammonium hydroxide. were characterized by high-resoln. themselves.. fine-gained ppt. electron microscope (HREM) observations.. nanoparticles of precursor powder by copptn. 1997 Fe garnet. environment promoted stoichiometric copptn. of hydroxide or carbonate precursors was made in a W/O microemulsion medium. (Ba-Fe oxalate) was ensured by the steric barrier provided by the surfactant monolayer. while the nonaq. AOT/n-decane/water CTAB/n-heptane/water Published by The Berkeley Electronic Press.. of oxalate precursors of the 1995 AOT/n-octane/water superconducting YBa2Cu3O7-δ ceramics.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 23 microemulsion method. cerium nitrate soln. 1995 microemulsion system where the metal ions were supplied by the surfactant (metal di-2- ethylhexylsulfosuccinate) mols. in a 1996 H2O and oil microemulsion is disclosed. A monodisperse. 21 Microemulsion A method for synthesizing ultrahomogeneous Shah et al. 22 Alcohol-in-oil microemulsion Ultrafine BaFe12O19 with uniform particle size was Chhabra et synthesized from an alc.

NH40H. successfully been used to synthesize lanthanum and 1994 nickel oxalate particles.com/ijcre/vol6/A62 . of larger silica colloids upon further reactions with TEOS in the microemulsion. which could readily be processed to form a fine LaNiO3 powder. cores (typically 5-25nm in size) of water- cetyltrimethylammonium bromide-n-butanol-octane microemulsions were used as constrained microreactors for the co-pptn.bepress. 1993 powders by copptn. in the aq.. of ultra. the aq. of precursor carbonates (typically 5-15nm in size). The resulting pure silica spheres can be grown to 40-80 nm diam. Kumar et solution of metal salts Y:Ba:Cu=1:2:3 homogeneous nanoparticles of precursor oxalate al. silica colloids are produced by the controlled al. 6 [2008]. 27 Igepal CO-430/ cyclohexane / aqueous A method is presented for prepn. synthesized using a novel method called 1993 microemulsion processing. cores of water-in-oil http://www.. 26 CTAB/ n-butanol/ octane/ Water Nanoparticles of barium ferrite (BaFe12O19) were Pillai et al. 1994 hydrolysis of tetra-Et orthosilicate (TEOS) in water Igepal CO-520 /cyclohexane / aq.. nanodroplets. Article A62 CTAB/n-hexane/water CTAB/n-octane/water CTAB/n-decane/water 24 Triton N.10 1/ cyclohexane / hexanol / aq..24 International Journal of Chemical Reactor Engineering Vol. water-in-oil microemulsions in which monodisperse Chang et NH40H. In this process. and can be used as seed particles for prodn. CdS quantum dots were incorporated into the silica colloids during the silica sphere synthesis by the simultaneous copptn 25 NP-5/petroleum ether/water The inverse microemulsion technique has Gan et al.

. compds. 3 CTAB/n-octane/n-butanol/water The single crystal octahedra of tetragonal CdMoO4 Gong et al. and hydrazine hydrate. 2008 . such as triethylamine. in the aq. 28 water-in-oil microemulsion The authors describe a new technique for the Kumar et synthesis of ultrahomogeneous nanoparticles of al. a 2007 microemulsion-mediated hydrothermal method. Published by The Berkeley Electronic Press. tetrabutyl titanate dissolved in nitric acid homogeneous anatase structure were successfully 2007 (5 mol/L) as the aqueous phase synthesized through a microemulsion-hydrothermal method by using some org. in which the aq.. controlled synthesized by a new approach.8. urea.. thiourea. 2006 mediated hydrothermal route at 120ofor 10 h. of Bi- Pb-Sr-Ca-Cu-O (2223) oxide superconductor Table 2. 1993 precursor oxalate powder by copptn. 2 SDS/cyclohexane/n-hexanol/water The zircon-type tetragonal (t-) LaVO4 nanowires were Fan et al. of YBa2Cu3O7-x (123- solution of oxalic acid phase) superconductors.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 25 Igepal CO-430 / cyclohexane / aqueous microemulsions for the prepn. were synthesized on large scale via a microemulsion. System Special features and applications References No 1 Triton X-100 /cyclohexane / 1-hexanol Nitrogen-doped TiO2 nanocatalysts with a Cong et al. Reverse microemulsion and hydrothermal Sr.. core of a water-in-oil microemulsion for the prepn. cores of sodium dodecyl sulfate (SDS)/cyclohexane/n-hexanol/water microemulsion were used as constrained microreactors for a controlled growth of t-LaVO4 nanocrystals under hydrothermal conditions.

TiO2 catalysts with different anatase/rutile Yan et al. The surfactant cetyltrimethylammonium bromide (CTAB) with cosurfactant butanol was used to form water-in-oil microemulsions contg. Chen et al. nano-microstructures Yang et al. 9 CTAB/ n-hexane/ n-pentanol /water Well-dispersed cryst.. were successfully prepd. nanorods with mean lengths of 600-1000 nm were 2006 controllably synthesized through a facile microemulsion-mediated hydrothermal procedure. nanorod bundles and 2006 caddice spherelike agglomerates.. by a novel and simple water-in-oil (w/o) 2004 http://www.. 8 CTAB/ toluene/butanol/water The crystal morphol.bepress. via a Liu et al. 7 Triton X-100 /cyclohexane / n-hexanol / Nanocryst. In(OH)3. 6 [2008]. the silicalite-1 synthesis gel. The crystal morphol. simple microemulsion-mediated hydrothermal 2005 procedure.. SnO2 nanoparticles were prepd. with two kinds of morphol. Tetrabutyl titanate and (NH4)2SO4 were ratios and high surface area (113-169 m2/g) have 2005 dissolved in the hydrochloric acid as the been prepd. of silicalite-1 was adjusted from coffin-shaped to novel rod-shaped and to irregular-shaped nanoparticles by varying the microemulsion compn.. of silicalite-1 was adjusted Lin et al. of 20-30 nm and Sun et al..26 International Journal of Chemical Reactor Engineering Vol. by the cetyltrimethylammonium bromide (CTAB)/ water/cyclohexane/n-pentanol microemulsion-mediated hydrothermal process.com/ijcre/vol6/A62 . mediated hydrothermal method. at low temp. through a microemulsion-based hydrothermal 2005 synthesis. 5 CTAB/ water/cyclohexane/n-pentanol CaWO4 nanocrystals with av. diams.. Article A62 4 CTAB/ water/cyclohexane/n-pentanol Indium hydroxide. 6 CTAB/ water/cyclohexane/n-pentanol Octahedral BaWO4 microparticles were prepd. by the microemulsion- aqueous phase.

using low-cost tin chloride as the starting material. the prepn. 14 CTAB/toluene/1-butanol/water The crystal morphology of silicalite-1 was adjusted Lin et al. were synthesized on large scale via a microemulsion. and recuperation of oxide nanoparticles by rotoevapn. to the microemulsion. 10 CTAB/n-pentanol/n-hexane/H2O Ni sulfide nanocrystals with novel morphologies of Chen et al. The surfactant cetyltrimethylammonium bromide (CTAB) with cosurfactant butanol was used to form water-in-oil microemulsions containing the Published by The Berkeley Electronic Press.. through a microemulsion-based hydrothermal 2005 synthesis. 11 CTAB/cyclohexane/n-pentanol/water A convenient microemulsion-mediated hydrothermal Cao et al. of Al and Ba precursors (isopropoxides) in the oil phase followed by addn. 12 PEG 200/isooctane/propanol/water The main steps of the exptl.. dissoln.. hydrothermal treatment in an autoclave. aging. procedure consisted of Balint et al. 13 CTAB/n-octane/n-butanol/water The single crystal octahedra of tetragonal CdMoO4 Gong et al. each of which is a single crystal with a growth direction of. 2006 mediated hydrothermal route at 120 degrees C for 10 h.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 27 microemulsion-assisted hydrothermal process.. of a stable reverse water-in-oil 2002 microemulsion. two-dimensional nanosheets and 1-dimensional (1D) 2004 nanoneedles or nanotubes were successfully achieved in the CTAB/n-pentanol/n-hexane/H2O microemulsion under hydrothermal condition at 130o.. 2008 . process was employed for the 1st synthesis of BaF2 2003 whiskers with lengths up to 50 µm and aspects ratios ≤1000.

bepress. soln. 6 [2008]. 2005 the reverse micelles of a CTAB/1-hexanol/H2O microemulsion. 2 Marlipal/cyclohexane/water This study provides the basis for the scale-up of the Niemann et synthesis route in water-in-oil (w/o)-microemulsion al. of titania nanosized spherical powders DeBenedetti polyethylene glycol hexadecyl ether/light through a microemulsion pptn.. 2006 mineral oil/water investigated. were obtained dropping an aq. of TiCl4 into a stable microemulsion contg. of the pptn. soln. and theor.28 International Journal of Chemical Reactor Engineering Vol. Article A62 silicalite-1 synthesis gel. Reverse microemulsion precipitation Sr. http://www. System Special features and applications References No 1 TX 100/cyclohexane/n-hexanol/water report on the synthesis of nanocryst. pptn. Reverse microemulsion sol-gel Sr.com/ijcre/vol6/A62 . a light mineral oil and a surfactant. 2006 droplets by a detailed exptl... low-cost precursor.. in a bulk aq.9. method was et al. Table 2. lithium silicate Khomane et by coupling of sol-gel method in reverse al. of calcium carbonate (CaCO3) and barium sulfate (BaSO4).10. contg. of particles from a soln. 2 CTAB/resorcinol/formaldehyde/water Carbon aerogels were successfully fabricated by a Wu et al. and second. anal. procedure in et al. 2006 microemulsion. System Special features and applications References No 1 Non-ionic emulsifier based on The prepn. a pptn. previously emulsified in an immiscible liq.. The ppts. The process is based on the pptn. Table 2. 3 CTAB/1-hexanol/water Nanostructured NiZn ferrites were synthesized using Uskokovic two different techniques: first.

and very homogeneous distributions of highly active Pt nanoparticles in a hexaaluminate matrix are obtained. Through the addn. 2004 assembly sol-gel method.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 29 microemulsion-templated sol-gel polymn. method. via a sol gel Espiard et technique carried out in an inverse microemulsion of al. of tetraethoxysilane (TEOS). Schicks et in i-octane/water direct oxidn. 2006 When a suitable molar ratio of surfactant to resorcinol (S/R) and an appropriate resorcinol- formaldehyde concn. catalysts with large surface areas. approach consisting of a combination gel thin films of inverse microemulsion and sol-gel techniques at low temp. using a chem. 3 AOT/hexane or heptane or isooctane/water Size-tunable silica nanotubes were prepd. using a Jang et al. Sodium bis(2-ethylhexyl) sulfosuccinate (AOT) was used as surfactant for the reverse microemulsion system. reverse microemulsion-mediated self. were selected. stabilized by either an anionic surfactant AOT or isopropanol. room-temp. the org. 1995 water in a toluene soln. Published by The Berkeley Electronic Press.. 5 Photoluminescence characteristics of Nd (III) oxide nanocrystal/TiO2/organically-modified Que et al. neodymium oxide silane (ormosil) composite thin films were prepd. gels thus obtained could be dried with little shrinkage by heating at ambient pressure. a well-controlled morphol. 6 AOT/toluene/water Colloidal silica particles are prepd. of methane to synthesis gas have been al. of Pt salts. 2001 nanocrystal/titania/ormosil composite sol. 4 Nonionic surfactants/Al.. 2003 synthesized via a microemulsion-mediated sol-gel route.& Ba-i-propylate Novel nano-engineered catalysts for the high-temp. 2008 ...

The 2005 method claims as a novel route to developing nanoscale chemical reactions using CNTs as nanoreactors. sodium dodecyl sulfate. Hu et al. 4 Nanowires of FexB prepared by boriding Carbon nanotubes as nanoreactors for building iron Han et al. with toluene using supercritical carbon dioxide. 1-pentanol.. single. 2006 were transformd into ultrafine Gd2O3 nanoparticles 3 Carbon nano tubes Nanofluids were obtained by filling carbon nanotubes Wang et al. 6 [2008]. 1994 isopropoxide..e.30 International Journal of Chemical Reactor Engineering Vol. and water. cyclohexane. System Special features and applications References No 1 Thermal reaction process using CNTs as Fabrication of high-quality.11..com/ijcre/vol6/A62 . Nanotubes as nanoreactors Sr. http://www. Three types of fine water dispersions have been used as the base sol: reverse Triton X-100 micelles in cyclohexane. Gd-acetate clusters inside SWNHs et al.. quaternary water-in-oil microemulsions contg. nanoreactors for Mg3N2 nanowires crystalline Mg3N2 nanowires 2006 2 Single-Wall Carbon Nnaohorns (SWNHs) Hollow nanospaces of SWNHs works as a chemical Miyawaki for Gd2O3 nanoparticles reaction field i. Article A62 7 SDS/cyclohexane/1-pentanol/water Microemulsion gels and coatings have been obtained Papoutsi et TX 100/cyclohexane/1-pentanol/water by the sol-gel method using titanium(IV) al.. and dispersions of water in pentanol in the presence of sodium dodecyl sulfate. large-yield.bepress. MICROEMULSION STRUCTURE Table 2.

System Special features and applications References No 1 Hydrogel networks based on N.. The study demonstrated efficient cleavage of three natural substrates and one prodrug. copolymers in the drug delivery system such as 2004 enzyme encapsulation and gene transfection isdiscussed and illustrated using model systems. Microstructures are hydrolyzed to give polymeric nanotubes with potential applications in drug delivery and as nanoreactors.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 31 Fe nanowires which were encapsulated in nanowires. Hydrogels Sr. Table 2. copolymeric nanoreactors as alternative for al. Table 2.12. 2 Polymer nanocontainers for drug delivery This review focuses on applications of triblock Sauer et al.13. System Special features and applications References No 1 poly(2-methyloxazoline)-block. 2000 carbon nanotubes (CNTs) Table 2. The research is mainly focused on triblock Ranquin et poly(dimethylsiloxane)-block-(2. Core Shell Structures Sr.14.. 2005 methyloxazoline) triblock copolymers. System Special features and applications References No 1 polystyrene-b-poly(L-lactide) (PS-PLLA) Authors have invewtigated degradable core-shell Ho et al.. with PLLA-rich fractions cylinder microstructures in chiral diblock 2006 copolymers. 2008 . by the nanoreactors. Drug Delivery systems Sr.Authors have prepared hydrogel and synthesized Mohan et Published by The Berkeley Electronic Press. 2-fluoroadenosine. liposomes as encapsulating carrier for prodrug activating enzymes.

15 digestion of proteins in SBA-15 for matrix-assisted 2006 laser desorption/ionization mass spectrometry with time-of-flight/time-of-flight analyzer (MALDI- TOF/TOF) peptide mapping.bepress. polypyrrole/poly(Me methacrylate) nanocomposite. 2001 Compression-molded nanocompostie exhibited elec. media and further reveal the proximity effect of free radical reactions in a nano-restricted environment.32 International Journal of Chemical Reactor Engineering Vol. chem. silicate Lin et al. 2004 aluminum aluminosilicate matrices as nanoreactors. 5 Mesoporous silica SBA-15 A method for prep.. of highly conductive Lim et al. The procedure allows for rapid protein enrichment and digestion inside SBA-15.com/ijcre/vol6/A62 .. Article A62 isopropylacrylamide (NIPAM) and sodium highly stable and uniformly distributed silver al. aqueous solution nanoreactors to study free radical attacks on C60 in 2002 aq. Mesoporous Silica species and surfactants in the synthesis of 2002 mesoporous silicas.. 2007 acrylate (SA) nanoparticles which can be effectively employed as antibacterial material Table 2. sieve are employed as Lee et al. http://www. 4 Mesoporous MCM-41 materials in The channels of the mol.5x Kolesnik et aluminosilicate matrices nanocomposite materials by using mesoporous high. 3 Cationic Surfactant-Templated The work reviews the phys. of soln. 2 Mesoporous high-aluminum The study synthesized Ag/AlxSi1-xO2-0.. 6 [2008].15. and has great potential for protein anal.. Mesoporous Silicates Sr..al. System Special features and applications References No 1 Mesoporous molecular sieve silicate SBA.A highly efficient enrichment and subsequent tryptic Zuo et al.

polymer micelles). or as sensors. Table 2.. of 1.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 33 cond. or 3D cubic mesostructures when the Published by The Berkeley Electronic Press.. System Special features and applications References No 1 Self-Assembled Nanoreactors A review of work on mol. 2001 capsules coated by several layers of poly (Na styrenesulfonate) and poly(allylamine-HCl). 2005 (polymersomes. macromol. nanoreactors (protein cages. The study shows that modified capsules offer many possibilities for novel applications as containers for controlled pptn.and submicrometer size from melamine resin al. The modified walls behaved like ion exchange membranes and showed selectivity toward adsorption and permeation of org. 2003 materials that exhibit long range ordered two- dimensional (2D) hexagonal. and biomacromol. Micro reaction Cages Sr. ions. micelles. Table 2. nanoreactors (capsules and Vriezema et boxes.17.. vesicles).. System Special features and applications References No 1 Micro Reaction Cages with Tailored Hollow polyelectrolyte capsules were prepared in Daehne et Properties micro. as nanoreactors for catalyzed reactions. Self Assembly Sr.7 S/cm and very highly oriented and uni- directional structures. three-dimensional (3D) hexagonal. 2008 . nanoreactors al. viruses) 2 Surfactant templated silica mesophases Authors have prepared surfactant templated silica Gibaud et mesophases belong to the class of self-assembled al.16.

by the layer- by-layer self-assembly of (1) polyelectrolyte- semiconductor nanoparticle. of nanostructured materials in the labs.. of the initial deposited soln. promote the formation of the cubic mesophase. Fendler et construction of nanosized or nanostructured materials al. of the nanocomposites during oxidative polymn. With 46 references Author have explained the "wet" colloid chem. crystals and/or amorphous particles in biol. rate of the solvent is one of the key parameters that control the final mesostructure and can. 4 PANI/TiO2 nanocomposites in reverse Spherical polyaniline (PANI)/TiO2 nanoparticles Sui et al. and (3) polyelectrolyte-graphite oxide (and reduced graphite oxide) ultrathin films.. Article A62 compn. After 60 http://www. systems) and on hierarchically organized self-assembly (spontaneous stepwise assembly of functional units).bepress. Author have further shown that the evapn. (2) polyelectrolyte-clay platelets-semiconductor nanoparticle. 1996 as inspired by biomineralization (the in vivo formation of inorg. prepn. of aniline with ammonium peroxydisulfate in the presence of TiO2 colloidal dispersion. 3 Self-Assembled Nanostructured Materials The work reviews on the "wet" colloid chem.34 International Journal of Chemical Reactor Engineering Vol. under certain conditions. and its aging time have been optimized. micelles were synthesized in Triton-x100 2004 (OP)/hexamethylene/water reverse micelle nanoreactor.com/ijcre/vol6/A62 . 6 [2008]. The study shows that reverse micelles provide a template for control of the unique structure and morphol.

and demonstrates that nanoparticles can be considered to be efficient nanoreactors. of groups used reverse micelles to control the size of spherical nanoparticles. the spherical nanoparticles self-organized into sea urchin-like shape Table 2.. It is 2003 also shown that large no. Published by The Berkeley Electronic Press. Soft colloidal templates Sr. This makes it possible to determine the various parameters involved in such processes. templates for controlling particle size and shape. System Special features and applications References No 1 Soft colloidal templates (reverse micelles) Colloidal solns. were assumed to be very efficient Pileni et al.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 35 days setting time in the reverse micelle.18. 2008 .

also called as large unilamellar vesicles (LUV). A number of different structures are possible ranging from spherical to rod-like to bi-layers. the hydrophilic and the hydrophobic parts and can acquire a variety of morphologically different structures.bepress.com/ijcre/vol6/A62 . In the simplest form they can be spherical and comprised of a single bilayer (unilamellar vesicles) with dimension in the range of radius (R= 4-20nm). The radius of curvature decides the small or large vesicles. The unilamellar vesicles form the uniform homogeneous solution also called as L4 phase. the hydrophilic parts of the surfactant face the aqueous pool while the hydrophobic parts rearrange themselves in the form of a comb-in-comb locking their teeth to constitute the interior forming planar structures.36 International Journal of Chemical Reactor Engineering Vol. Vesicles Figure 4. The packing factor.containing concentric shells such as in onions are formed. Vesicles Surfactants self-assemble in aqueous solution due to presence of dual functionality viz. broadly decides the actual shape and for P >1/2 vesicle formation is predicted. On further increase in concentration the structure transforms into planar bilayers. These structures as depicted in Figure 4 are called vesicles. Article A62 2. The urge to minimize contact with water for the hydrophobic groups is responsible for the aggregation process. The opposite open ends of the planar structure can join together creating a closed environment within. As the surfactant concentration increase. also called as small unilamellar vesicles (SUV) or R= 50nm to 10µm. In bi-layers. multilamellar vesicles. as explained earlier. Small head groups with bulky hydrophobic parts can meet the packing requirements of the surfactant in solution and are therefore the possible http://www. Surfactants that can form bilayers in solution are thus essential for vesicle formation. 6 [2008].3. The various structures may also co-exist in equilibrium in what appears to be a homogeneous solution on macroscopic scale.

Ionic surfactants mixed with cosurfactants can also meet the packing requirements. Alternative methods such as high pressure extrusion of lamellar phases. The sponge phase (also called as L3 phase) and the plane lamellar phases are stable for positive and negative values of the Gaussian modules. 1983. In general. where the shear tears apart and fragments the sheet have been used. 1984). The transformation process to MLV produces a shear thickening effect as the resistance to flow increases. For a small field the shear orients the bilayer first and then transformation to MLV occurs as shear increases. the use of large molecular weight amphiphiles such as block copolymers. For large enough negative values a transition from planer lamellar to vesicles is expected.. the oppositely charged blockes forms the inner part of the vesicle and the two polymers form inner and the outer part of the vesicle. viz. In some other situations more intense form of external force such as sonication may become necessary. Table 3 shows a few of these assorted examples. Of course the studies involve the use of small shear that may initiate the spontaneous formation. The simple methods of shaking. vortex formation are oftentimes enough to form vesicles.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 37 candidates. A number of systems illustrating the use of such aphiphile has now been reported in the literature. an inverse – square root of the shear rate dependency and the size of the MLV is observed. concentration etc. Preparation of vesicles. stirring. involves dispersion of lamellar bilayers in the solvent using external energy input. this is followed by shear thinning behavior for further increase in the shear rate and strain. Evaporation of the surfactant solution in volatile solvents leads to thin films which when brought in contact with water can form vesicles. 2008 . the mean bending modulus. in general.. The size change is continuous for small change of shear rate while discontinuous changes occur for sudden and large changes of shear rate. The structural transitions are system specific depending on molecular composition. In addition to the use of low molecular weight surfactants. Contrary to the general belief that some external force is needed to form the vesicles. The deformation of bilayer structure when subjected to shear depends on the extent of shear field and rate of shear. The free energy of bending of a bi-layer system is governed by bending elasticity described by the elastic modulus. Also. a number of reports on spontaneous formation of vesicles are now available (Ninham et al. Typically double chain hydrocarbon surfactants such as normal phospholipids. and the Gaussian modulus. graft copolymers or polymerizable amphiphile can also be used to prepare vesicles. the vesicles can be formed in aqueous as well as the oil continuous reverse systems. perfluro surfactants or nonionic single chain compounds with small hydrophilic groups have been used. The size and size distribution of vesicles is controlled by the molecular weight of the copolymer. Brady et al. In general. Anionic surfactants showing strong dependence of vesicle formation on the counterion Published by The Berkeley Electronic Press.

temperature. counterions present. their chain lengths. ionic surfactants etc. various spectroscopies etc. pH.38 International Journal of Chemical Reactor Engineering Vol. Spontaneous formation of vesicles has also been observed for some nonionic single chain surfactants.com/ijcre/vol6/A62 . will have a decisive influence on the process. size distribution. The vesicle may gel by a slow ordering process to form glassy structures. ionic strength etc. In addition to the aqueous phase. light scattering. are system specific as described by its phase behavior. Such transformation process can occur at time scales slower or faster and different probing techniques such as conductivity measurements. surfactants with polymeric hydrophilic head groups. The issues of transitions to different structural forms are also related to their thermodynamic stability. 1992. The vesicles formation occur through the formation of precipitate which turns to vesicles on heating. Article A62 present have been reported (Kamenka et al. 6 [2008]. The vesicles can be stabilized by addition of cosurfactant. The simple single chain surfactants have been studied in details to dense phase diagrams showing the occurrence of vesicles in some region and their borders or transition to other forms such as micelles etc. counter ion presents etc. The control of size. structure and properties of vesicle is possible through control over their preparation process.bepress. The experimental evidence suggests that the micellar to vesicle transformation proceeds through the rod-like and/or disc-like aggregates as intermediate structures. Kaler et al. shear. At least in some situations and especially for unilamellar vesicles thermodynamic stability seems to be well established. The dominating interactions in cationic surfactants are electrostatic in nature and the solution has high ionic strength and the counterions pair to form salt that effectively shield the interactions. The nature of surfactant head groups.. Table 3 illustrates a few assorted examples. 1989). The classical catanionic systems containing admixture of cationic and anionic surfactants forms vesicles over a wider range. vesicle formation in organic solvents and their organometallic complexes has also been known. stiff rod-like amphiphiles. http://www. The dynamics of structural formation and transformation are inadequately understood. Alternatively for excess of anionic or cationic surfactants a unilamellar vesicle can be formed. can reveal their kinetics. The spontaneous formation of vesicles and their transformation to structurally different forms under the influence of change in surfactant type and concentration.

These rodlike al. Some experimental studies on vesicles Sr. system. Vesicle cetyl trimethylammonium tosylate formation apparently results from the production of (CTAT) in H2O.. 2008 . all such vesicle systems revert to the equilibrium. The study develops a theoretical thermodynamic cell model to predict important properties of the mixed micellar solutions such as monomer and micellar composition and counterion binding as well as the equilibria between the crystalline and micellar phases. System Special features and applications References No 1 Phase behavior and structural studies of The SDBS/CTAT mixture has many features that Kaler et al.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 39 Table 3. formation of hydrated crystals of 1: 1 anion/cation surfactant dominates the phase behavior. sodium appear to be common to aqueous mixtures of 1992 dodccylbenzenesulfonate (SDBS) and asymmetric cationic and anionic surfactants... For this symmetric bromide. Although unilamellar vesicles have been created by numerous physical and chemical techniques from multilamellar dispersions. 2 Phase behavior and microstructural It is known that micelles of anionic surfactants grow Herrington et evolution in mixtures of surfactants with upon addition of cationic surfactant. an anion-cation surfactant pair which then acts as a double-tailed zwitterionic surfactant. multilamellar phase over time. 3 The phase behavior and aggregate Differences in the lengths of the two hydrophobic Yatcilla et morphology of mixtures of the oppositely chains stabilize vesicles relative to other al. 1993 symmetric tail groups: sodium dodecyl micelles are transformed abruptly into vesicles over sulfate and dodecyltrimethylammonium a very narrow composition range. 1996 Published by The Berkeley Electronic Press. one such mixture.

4 Amphiphilic ion pairs.. Molecular reorganization of the N- methylated amino acid headgroups upon vesiculation (E. Solutions of mixture of didodecyldimethylammonium bromide 1995 Didodecyldimethylammonium Bromide (DDAB) and sodium dodecyl sulfate (SDS) has been and Sodium investigated with differential interference Dodecyl Sulfate Mixtures microscopy. form detailed examination from both a theoretical and vesicles upon sonic dispersal in water. 5 potential http://www..com/ijcre/vol6/A62 .bepress.. transmission electron microscopy. 1993 microscopy and quasi-elastic light scattering measurements.end 2-configuration equilibrium) was revealed by using sodium N-lauroylsarcosinate as anionic component. series of trimethyl-n-alkylammonium class of vesicle-forming surfactants that warrant a 1990 bromides and saturated fatty acids. and vesicles form spontaneously (CTAB) and sodium octyl sulfate (SOS) over a wide range of compositions in both CTAB- are explored rich and SOSrich solutions. however.g. glucose trapping experiments. practical standpoint.40 International Journal of Chemical Reactor Engineering Vol. special attention will have to be paid to the nature and concentration of all ionic species present in solution and to the appropriate ion-exchange equilibria. derived from a Ion-pair amphiphiles represent a new and unique Fukuda et al. with CTAB-rich bilayers stiffer than SOS-rich ones. Unlike conventional double- chain surfactants. Article A62 charged surfactants microstructures (e. Bilayer properties of the vesicles depend on the ratio of CTAB to SOS.. 6 Vesicle Formation from Aqueous Spontaneous vesicle formation in the aqueous Kondo et al. liquid crystalline and cetyltrimethylammonium bromide precipitate phases). 5 Versatile self-vesiculating amphiphile Vesicle formation from catanionic micellar mixtures Amb¨uhl et system based on amino acid surfactanta was confirmed by freeze fracture electron al. 6 [2008].

of solns. 9 9:1 mixture of DPPC and DPPG This work presents a method that allows the on. part of which release their cargo in the interior of the others during a thermotropic phase transition. et al. et al. 2004 vols.. In this study before deposition. cadmium sulfide (CdS) particles in the gaps between the layers of the multilamellar vesicles leading to a new pathway in the prepn. 2008 . of nanometer-scale particles. The reactors comprise a nested system of lipid vesicles. 2005 copolymer materials. the vesicles are rigidified by polycation adsorption onto their surface to avoid Published by The Berkeley Electronic Press. 10 Phospholipid Vesicles A method to embed phospholipid vesicles into Michel. polyelectrolyte multilayers built up by the alternate 2004 deposition of polyanions and polycations. nanoreactors and further describes the formation of 2007. owing to the increasing Tokarczyk et interest in self-assembled structures from block al. in the interior of vesicular nanoreactors..to femtoliter al. The micrographs of the DDAB-SDS mixtures confirm the spontaneous formation of polydispersed vesicles including "giant vesicle" with a diameter less 40 pm. Bolinger et demand release and mixing of zepto.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 41 measurements. and surface tension measurements.. 7 Multilamellar vesicles This study considers the biological systems as Bota.. 8 Block copolymer A review of recent literature concerning amphiphilic Kita- block copolymer vesicles.

which remain together in colloidal suspension for at least several months. 2002 in water using a variety of nonionic ethoxylated alcohol surfactants as stabilizers. icosahedra in salt-free catanionic solutions such bilayers can self-assemble into hollow 2001 aggregates with a regular icosahedral shape. Article A62 their fusion once deposited on the multilayer surface..com/ijcre/vol6/A62 .bepress. Dubois et al. 6 [2008]. of enzyme-contg.42 International Journal of Chemical Reactor Engineering Vol. These aggregates are stabilized by the presence of pores located at the vertices of the icosahedra. 11 Enzymes inside lipid vesicles This study focuses on preparation.. The final dispersions consist of both polymer shells and surfactant micelles. making them larger than any known icosahedral protein assembly or virus capsid. lipid vesicles (liposomes) which are lipid dispersions that contain water-sol. 13 Nanostructured Hollow Polymer Spheres Hollow polymer spheres synthesized from a vesicle. applications of enzymes in lipid vesicles and reports 2001 no.. of anionic and cationic surfactants. Small-angle neutron scattering (SANS) is used to measure the polymer shell thickness (63 Å) and core radius (560 Å) of the surfactant-stabilized hollow polymer spheres in the presence of surfactant http://www. The resulting structure have a size of about one micrometer and mass of about 1010 daltons. enzymes in the trapped aq. This has been shown by many investigations carried out with a variety of enzymes. space.McKelve et directed polymerization can be dried and redispersed al. et al. 12 Self-assembly of regular hollow Salt-free mixts. reactivity and Walde. of methods that can be used for the prepn.

. with a universal coefficient. membranes systems. one of two distinct mechanisms depending on the 2001 Published by The Berkeley Electronic Press. average composition in the bilayers. for which they obtain the experimentally observed scaling of micelle size with concentration. 2008 . The study briefly discusses the conceptually related problem of a polydisperse ensemble of fluctuating one- dimensional aggregates. that arises essentially from the absence of undulation modes of wavelength longer than the size of the surface. such as vesicle phases. It is shown that the internal undulation free energy of a single such membrane always contains a logarithmically scale-dependent ‘‘finite-size’’ contribution. that consist of many 1995 closed. It is concluded by discussing the application of the results to the interpretation of recent experiments on equilibrium vesicle phases. of a thermodynamically open... 15 Thermodynamics of Unilamellar Vesicles The influence of mixing on the curvature free energy Bergstr¨om. reversibly formed 2001 vesicle bilayer is investigated by deriving expressions for the various contributions to the bilayer bending constant kbi as functions of the structure of aggregated surfactants as well as the solution state (electrolyte concentration. such as rodlike micelles. 16 Stability of spontaneous vesicles Equilibrium unilamellar vesicles are stabilized by Jung et al. 14 Statistical mechanics of closed fluid The work discusses the statistical mechanics of Morse et al. disconnected fluid membranes. etc).Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 43 micelles.

the attractive interactions between the bilayers can overcome the cost of small deviations from the spontaneous curvature to form two-layer vesicles. but larger deviations to form three and more layer vesicles are prohibited. 6 [2008]. The theory accounts for the essential free-energy contributions to the free energy of vesiculation. K. gves. such as those consisting of CTAB and sodium pentyl sulfate (SPS).bepress. other radii are disfavored energetically. unilamellar vesicles are stabilized by the spontaneous curvature that picks out a particular vesicle radius.. 17 Effect of Surfactant Tail-Length The recently developed molecular-thermodynamic Yuet et al. Helfrich undulations ensure that the interbilayer potential is always repulsive when the bending constant. with particular emphasis on their relative importance and interplay in the process of vesicle formation. http://www. Asymmetry on the Formation of Mixed theory was used to study the formation of vesicles in 1996 Surfactant Vesicles mixtures containing cetyltrimethylammonium bromide (CTAB) and sodium alkyl sulfates of various tail lengths. It is shown that mixed surfactant vesicles can be stabilized energetically in highly asymmetric surfactant mixtures. Adding electrolyte to the sodium perfluorooctanoate/CTAB vesicles leads to vesicles with two bilayers. When K 〉〉 kBT.44 International Journal of Chemical Reactor Engineering Vol. Article A62 value of the bending constant.com/ijcre/vol6/A62 . is of order kBT.

dehydration reactions. Published by The Berkeley Electronic Press. the manganese (III) tetra hexadecyl phenyl porphyrin chloride complex for regio selective epoxidations of steroids.. should not destabilize the system. A number of different techniques for preparing the nanoreactor assembly. et al. Feiters. impurities. 2001). The vesicular catalysis rates are often order of magnitude higher than in micelles and several orders of magnitude higher in comparison to reaction in pure water. Hemocynin system (Klein et al. The counterions.. can also act as a catalyst for some systems. Likewise interior of a vesicle can be used as nanoreactor for some reactions. The other set of reactions use the interior of vesicles as a nanoreactors for conducting enzymatic reactions. Metal complexes attached to vesicular surfaces provide examples illustrating the role of substrate binding sites and counterions effect. The possibility to encapsulate active molecules within it makes them interesting for drug delivery and bilayer medicine. ionic strength etc. temperature. It is imperative that the enzyme and the membrane wall should be sufficiently stable and not degrade. 2001) for oxidative degradation of ligand. The characteristic properties of the substrate. Cytochrome 450 (Groves et al.. hydrodynamics and other such factors and can change its activity for chemical transformation. The surface of a vesicle is more organized than that of a micelle and can be used as a seat for chemical transformation. to more sophisticated extrusion and dehydration / rehydration methods are in use to create an optimum configuration for reaction environment and better and faster conversion rates and product selectivity and yield. The changed microenvironment at the substrate binding site is expected to contribute to such measures. the rhodium (III) formate system for reducing molecular oxygen. amphiphilic diphosphene ligands along with their rhodium complexes for hydroformylations etc are known. besides charge compensation.. A number of examples such as Cu(II) vesicles for Diels-Alder reaction (Rispens et al.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 45 The complex-vesicular based structures are one amongst the principal structures formed when lipids. proteins and polymers self-assemble in solution. gene therapy and variety of other pharmaceutical and cosmetic applications. 1994. product and the surfactant material forming the bilayers also plays important role. external factors such as pH. The method of preparation has a decisive influence on the performance since the catalyzed reaction in the reactor critically depends on the diffusion of the reactants and counterdiffusion of products through the lipid bilayer. oxidative formylation. ranging from simple mixing of various ingradients. at least over the period of transformation. Also. dehydrogenation. 2008 . The molecular properties of a vesicle interface with water is sensitive to additives. 2000) and active for oxidation. 1995) .an enzyme containing Iron (III) protoporphyrin complex (Mansuy. Such closed bilayers are prototype examples and a model system for understanding cell membranes. The catalysts (enzyme) are embedded within the inner compartment while the substrate moves from the bulk solution crossing the membrane barrier.

They include the use of vesicle membrane as a template to organize monomers and then polymerize them improving the stability to mechanical. pattering etc. The layer-by-layer deposition can be continued in a controlled manner to achieve desired thickness. Areas such as catalysis. Likewise coated colloids can be used to fabricate hollow spheres and 2-d and 3-d microporous material. chromatography. non-ionic sugar lipids and mechanical and thermal treatments.bepress. semiconductors etc. It is possible to replace one charged PE component with charged preformed inorganic nanoparticle layer. electrochromic membranes. A number of different methods to improve the stability of vesicles are also developed. Likewise the colloids can be subjected to LbL deposition to generate hollow capsules of varied thickness and morphologies. The simple procedure involves mixing of polymers and nanoparticles. A few assorted examples are included in table 3. permeability etc. allow to create nanovessels with a direct control on their thickness and composition. The other method requires the preparation of the nanoparticles http://www. thus for instance the positive charge on the substrate is reversed to negative charge upon adsorption of polyanions and subsequently becomes vulnerable to attack from polycations. The oppositely charged PEs interweave to create void spaces that act as a reactor.46 International Journal of Chemical Reactor Engineering Vol. composition. The interior of polyelectrolyte multilayer capsules (PEMC) so created can be loaded with desired reactants and used for their transformation to products of desired shape. 6 [2008]. biosensing etc. metal oxides/hydroxides. nanoparticles etc.4. however the structures so created can often be inhomogeneous. Small molecules can be easily incorporated into the polyelectrolye film (~Mw 4000) and transformed. Article A62 Synthesis of a number of bimolecules ranging in complexity from simple glycogen to complete protein synthesis has been reported in vesicles. 2. Nanoparticles are usually embedded in a solid matrix or polymer thin films for them to be usuable in practice.com/ijcre/vol6/A62 . morphologies etc. coating. metal alkoxides. A number of nanostructures of metals. The outside shell can also be used to anchor different materials such as dyes. separation materials. The technique of encapsulating necessary enzymes along with other required components holds the key to successive synthesis of complex biomolecules. are prepared using planer polyelectrolyte films. Polyelectrolyte Multilayer Capsule (PEMC) The technique of layer-by-layer (LbL) self assembling of charged polyelectrolytes (PE) on to planer or colloidal structures. LED. The fabrication of polyelectrolyte multilayers involves the simple principle of electrostatic interactions between oppositely charged PEs as the driving force. chemical and attack from digestive enzymes. Other techniques include use of fluorinated lipids. can immensely benefit from this approach. drug delivery. The thin films so produced have potential applications as bioactive films.

Again a few assorted examples are included in the table 6. are prepared using this technique. sol-gel reactions. The LbL technique allows control on the film thickness by adjusting deposition cycles. One can also use the inorganic molecular precursors/PE multilayeres onto colloids or in filtration of preformed nanoparticles into film- coated colloids to conduct suitable nanoreactor chemistry such as reduction. 2008 . hydrolysis. Published by The Berkeley Electronic Press. polymerizations or thermal oxidation etc. The LbL colloidal templating approach can be employed on the preformed polyelectrolyte layers onto colloids to produce uniform core-shell particles and hollow spheres. The generic technique can also be used to obtain tunable morphologies with desired properties and functionalities for 2-d ordered surface arrays and 3-d macroporous materials with controlled pore sizes and periodic structures. Examples illustrating the formation of open or closed pores with controllable pore wall thickness. The technique of in-situ synthetic approach on the preformed film can become advantageous and a number of particles of metals. however the control on size of the particle during and after film formation is difficult. A few assorted examples are listed in Table 4.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 47 with appropriate charges and surface modifications in stabilized media and then uses the LbL approach to create orderely and homogeneous films containing nanoparticles. pore diameter are available in the literature. metal oxide/hydroxides semiconductors etc.

charged poly(styrenesulfonate) (PSS) and poly(acrylic acid) (PAA). 6 [2008]. 2005 Nanoreactors nanoparticles. The capsule wall thickness was approximately 20 nm. These capsules exclude poly(styrenesulfonate) (PSS) from a molecular weight http://www...com/ijcre/vol6/A62 . (134) multilayer films 5 Hollow Polyelectrolyte Hollow polyelectrolyte capsules were fabricated by means of Sukhorukov et al. 2002 (allylamine hydro chloride) nanoparticle composites.. System Special features and applications References No 1 Polyelectrolyte Capsule The study demonstrates result of the synthesis of two types of Choi et al. charged third-generation (132) poly(amidoamine) dendrimer (PAMAM) and neg.bepress. The diameter of the capsules is given by the size of the templates (3. 2004 variety of nanostructured materials generated by using (133) polyelectrolyte multilayers assembled onto both planar and colloidal substrates as nanoreactors have been discussed. Article A62 Table 4. 4 Poly(acrylic acid) & poly Polyelectrolyte multilayer nanoreactors for preparing silver Wang et al. these specially designed PEMCs contg.48 International Journal of Chemical Reactor Engineering Vol...3 μm). both (131) silver and goethite nanocrystals can be used as antimicrobial capsules. Such a technology has the potential for use in sterilization at the desirable sites. were utilized as nanoreactors for the formation of silver nanoparticles. prepared through the sequential Liu et al. 3 Polyelectrolyte multilayer The recent advances in the synthesis and characterization of a Shi et al. 2005 multilayer films electrostatic deposition of a pos. Some experimental studies on Polyelectrolyte Multilayers Sr. 2 Silver nanocomposite Multilayer thin films. which can move by an external magnetic field. Shells stepwise adsorption of polyelectrolytes followed by 1999 dissolution of the templating core.

a Donnan equilibrium between the bulk and internal solution encapsulated within the capsules was created. wall Published by The Berkeley Electronic Press. both the Langmuir-Blodgett technique and chemisorption from solution can be used only with certain classes of molecules. An alternative approach-fabrication of multilayers by consecutive adsorption of polyanions and polycations-is far more general and has been extended to other materials such as proteins or colloids. The geometry. with thicknesses ranging from a few to tens of nanometers. Micron-size polyelectrolyte shells of poly(sodium styrenesulfonate) (PSS) and poly(allylamine hydrochloride) (PAH). Colloid-Templated polyelectrolyte shells by colloid-templated consecutive 1998 Assembly of polyelectrolyte adsorption followed by decomposition of the Polyelectrolytes templating core. 7 Hollow Polymer Shells by The study describes a method for constructing hollow Donath et al. have been produced. size. 2000 through Colloidal capsules of submicrometer to micrometer size have been Templating and Self.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 49 of 4200 upward but are permeable for small ions and 6- carboxyfluorescein (6-CF).organic composite Caruso. 8 Hollow Capsule Processing Hollow polymer. inorganic and inorganic . 2008 .. fabricated by using a variety of colloidal particles as templates Assembly for the build-up of nanostructured multilayers and subsequently removing the core by chemical or thermal pathways. However. By means of adding PSS in acidic form to the bulk solution. 6 Layered Polymeric Multilayer films of organic compounds on solid surfaces have Decher. 1997 Multicomposites been studied for more than 60 years because they allow fabrication of multicomposite molecular assemblies of tailored architecture. The figure shows a TEM image of a cross-section of hollow inorganic capsules..

9 Nanoengineering of The creation of core-shell particles is attracting a great deal of Caruso. e. This review presents the state-of-the-art in strategies for engineering particle surfaces.bepress. 1998 hollow spheres by colloidal between 720 and 1000 nanometers were fabricated by templating consecutively assembling silica nanoparticles and polymer onto colloids and subsequently removing the templated colloid either by calcination or decomposition upon exposure to solvents. which allows fine control over shell thickness and composition. 1989 of extremely small colloidal semiconductor particles have been selected in the present metal and semiconductor article to show that many effects occur in this neglected size particles dimension which was not anticipated even a few years ago. Article A62 thickness and composition of the hollow capsules can be readily controlled. 11 Physicochemical properties Certain topics in the field of research on very small Henglein. 2001 Particle Surfaces interest because of the diverse applicability of these colloidal particles. 6 [2008]. An increasing number of laboratories are now working in this field. 12 Quantum crystallites and A review and analysis of the optical properties of quantum Brus.. such as the layer-by-layer deposition process.50 International Journal of Chemical Reactor Engineering Vol.. with principal emphasis on the electro-optic Stark effect and all optical third order nonlinearity. as building blocks for photonic crystals..g.com/ijcre/vol6/A62 . There are also introductory discussions on physical size regimes. in multi-enzyme biocatalysis. 10 Inorganic and hybrid Hollow silica and silica-polymer spheres with diameters Caruso. 1991 nonlinear optics crystallites.. The hollow spheres produced are envisioned to have applications in areas ranging from medicine to pharmaceutics to materials science. crystallite http://www. and in drug delivery..

we have now constructed a hybrid organic/inorganic electroluminescent device. By taking advantage of semiconducting polymer developments in the preparation and characterization of direct- gap semiconductor nanocrystals. The ability to join the dots into complex assemblies creates many opportunities for scientific discovery. and CuCl crystallites..fragments of semiconductor dots consisting of hundreds to many thousands of atoms . 14 Light-emitting diodes made Electroluminescent devices have been developed recently that Colvin et al. exhibiting strong confinement of electrons and holes. from cadmium selenide are based on new materials such as porous silicon and 1994 nanocrystals and a semiconducting polymers. In the CdSe system.2003 assembly of silica-coated gold (Au@SiO2) or silica-coated silver (Ag@SiO2) nanoparticles with different shell Published by The Berkeley Electronic Press. Current research into semiconductor clusters is focused on the Alivisatos. Quantum dots exhibit strongly size-dependent optical and electrical properties. Light emission arises from the recombination of holes injected into a layer of semiconducting p-paraphenylene vinylene (PPV) with electrons injected into a multilayer film of cadmium selenide nanocrystals. exhibiting weak confinement of the exciton center of mass. 13 Semiconductor clusters.. 2008 .. neither the Stark effect nor the third order nonlinearity is well understood. The experiments describe CdSe crystallites. and quantum properties of quantum dots .Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 51 synthesis. 1996 Nanocrystals. 15 Coated colloids with Tailored optical properties have been imparted to polystyrene tailored optical properties (PS) colloids of various sizes by the layer-by-layer (LbL) Salgueirino. quantum confinement theory. and of electroluminescent polymers. and linear optical properties.with the bulk bonding geometry and with surface states eliminated by enclosure in a material that has a larger band gap.

The EL is tunable in the visible by changing the dot diameter. efficiency. 17 Gold Nanoparticle-Based A simple colorimetric technique for the detection of small Kim et al. and mercury. 16 Electroluminescence from Spectrally clean and fairly narrow electroluminescence (EL) Dabbousi et al. including toxic "Spectroscopically Silent" metals such as lead.. The study reports the nanoparticles functionalization of 4 nm Au particles with a 1. Article A62 thicknesses and an electrostatically bridging polyelectrolyte. and stability of dot EL devices. Heavy Metal Ions Functionalized gold nanoparticles are aggregated in solution in the presence of divalent metal ions by an ion-templated chelation process. 2001 Sensing of concentrations of aqueous heavy metal ions. and (iii) the number of nanoparticle layers deposited. There was apparent size dependence to the efficiency with smaller dots having higher threshold voltages than larger dots. (ii) the thickness of the silica shell.com/ijcre/vol6/A62 ..10- phenanthroline ligand that binds selectively to Li+. CdSe quantum-dot/polymer from CdSe quantum dots in thin films containing 1995 composites homogeneous mixture of a stable hole transport polymer (PVK) and an electron transport molecular species (PBD) were obtained. cadmium.52 International Journal of Chemical Reactor Engineering Vol. The ligand http://www. 18 Sensing strategy for lithium The detection of Li+ is currently in demand for both Obare et al.bepress. 2002 ion based on gold biomedical and industrial applications.. 6 [2008]. this causes an easily measurable change in the absorption spectrum of the particles. is described. poly(diallyldimethylammonium chloride) (PDADMAC). Selecting a lower work function cathode and separating the hole transport and electron transport layers from the emitter layer should improve the turn-on voltage. The spectral position of the surface plasmon band of the composite colloid spheres is tailored through (i) the type of silica-coated nanoparticles used.

. 19 multilayered nanostructural Sequential adsorption of a cationic polyelectrolyte and Kleinfeld et al.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 53 binds to Li+ by forming a 2:1 ligand-metal complex. causing Au nanoparticles to aggregate. stepwise formation of multilayered films on silicon wafers.. 21 Molecular self-assembly of Multilayer ultrathin films composed of titanium dioxide Liu et. unlike the case for other polyion assemblies. QCM measurement confirmed the high regularity and reproducibility of the assembling process that depends on particle concentration. The individual adsorption step was completed within 15 s. 2008 . 20 Alternate assembly of Alternate layer-by-layer assembly of colloidal SiO2 particles Lvov et al. thus preserving structural order in the growing film. scanning electron microscopy. Au nanoparticle aggregation causes a shift in the extinction spectrum with a concomitant color change. 1997 ordered multilayers of SiO2 with polycations has been investigated by quartz crystal and other nanoparticles and microbalance (QCM).. and polyions atomic force microscopy (AFM). films from macromolecular individual sheets of the silicate mineral hectorite has allowed 1994 precursors controlled.1997 Published by The Berkeley Electronic Press. and 78 nm in diameter).al. 25.2 micrometer. It also increased with increasing ionic strength of aqueous SiO2 dispersions. Each component adsorbs rapidly by an ion-exchange mechanism. particle size. The large lateral extent of the silicate sheets (about 25 to 35 nanometers) allows each layer to cover any packing defects in the underlying layer. providing a useful optical method of detecting Li+ in aqueous solution. and x-ray diffractometry indicates structural order even in films with thicknesses greater than 0. and ionic strength. The thickness of adsorbed layers increased with increasing SiO2 concentrations at the three particle sizes used (45.

6 [2008]... The organic- inorganic films were found to be very flexible and crack- resistant even under a considerable mechanical stress. Without any special Polyelectrolyte Composites pretreatment.com/ijcre/vol6/A62 . a stable film of montmorillonite-polymer composite was assembled on a hydrophobic poly(ethyleneterephthalate) support by means of layer-by- layer deposition. Article A62 TiO2/polymer nanosized particles and ionic polystyrene molecules have been nanocomposite films fabricated on single-crystal silicon. The morphology and gas permeation properties of Kotov et al. 23 Multilayered Alternating adsorption of polyethyleneimine-metal ion Dai et al. 2002 Polyelectrolyte Films complexes and polyanions results in the formation of multilayered polyelectrolyte films. X-ray photoelectron spectroscopy (XPS) indicates that the formed cationic TiO2 particles adsorb only on negatively charged and not on positively charged surfaces. 1998 Assembly of montmorillonite-polyelectrolyte self-assembled multilayer Alumosilicate. All individual alumosilicate platelets were found to be oriented in parallel to the substrate.54 International Journal of Chemical Reactor Engineering Vol. systems have been investigated. Contact angle measurements demonstrate that the water contact angle oscillates regularly in accordance with which molecules form the outermost layer of the films.. Postdeposition reduction of the metal ions by heating or exposure to NaBH4 then yields composite films containing metal nanoparticles. Complexes and as well as different {silver-PAMAM} dendrimer 2001 http://www. quartz. 22 Layer-by-Layer Self.bepress. 24 Dendrimer-Silver Silver complexes of poly(amidoamine) (PAMAM) dendrimers Balogh et al. and glass substrates by a novel molecular self-assembly process. while their surface density strongly depended on the nature of the polyelectrolyte (charge and molecular weight).

27 Multilayer Films A simple route for the preparation of Pt nanoparticles is Shen et al.sandwiched between polymers. the three-dimensional Pd nanoparticle multilayer films are directly formed on electrode surfaces via electrochemical reduction of PdCl42. PtCl62. and Escherichia coli bacteria. 2001 Containing Pd Pd nanoparticles is described. Pseudomonas aeruginosa. 2000 Published by The Berkeley Electronic Press.anions were assembled on a glassy carbon electrode Shen et al. on 4- aminobenzoic acid-modified glassy carbon electrodes.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 55 Nanocomposites as nanocomposite solutions have been tested in vitro against Antimicrobial Agents Staphylococcus aureus. QPVP-Os (a quaternized poly(4-vinylpyridine) complexed with [Os(bpy)2Cl]2+/+). 26 Pt nanoparticles assembled PtCl62. then electrochemically reduced to yield zero valent Pt nanoparticles. 28 Multilayer Nanoreactors for Multilayer thin films of sequentially adsorbed polyelectrolytes Joly et al. The three- dimensional Pt nanoparticle films are directly formed on an electrode surface by electrochemical reduction of PtCl62- sandwiched between CoTMPyP layers. even in the presence of sulfate or chloride ions.and polycation. 25 Multilayer Polymer Films A simple route to the fabrication of multilayer films containing Liu et al... Following layer-by-layer Nanoparticles assembly of PdCl42.. and [tetrakis(N- Nanoparticles on a Glassy methylpyridyl)porphyrinato]cobalt (CoTMPyP) were Carbon Electrode assembled on a 4-aminobenzoic acid modified glassy carbon electrode through the layer-by-layer method. 2008 . 2002 in multilayer films with [tetrakis(N-methylpyridyl)porphyrinato]cobalt cations through layer-by-layer method. 2003 Containing Pt described. using the standard agar overlay method.. Both PAMAM silver salts and nanocomposites displayed considerable antimicrobial activity without the loss of solubility and activity.

http://www. 6 [2008].56 International Journal of Chemical Reactor Engineering Vol. Article A62 Metallic and were utilized as nanoreactors for both metallic (Ag) and Semiconducting Particles semiconductor nanoparticles (PbS). Polyelectrolyte multilayers with a controlled content of free carboxylic acid binding groups were fabricated with weak polyelectrolytes via suitable pH adjustments of the processing solutions.bepress.com/ijcre/vol6/A62 . These groups were then used to bind various inorganic ions that were subsequently converted into nanoparticles.

The covalent linkage does not allow microphase separation and appropriate to packing parameters of the two parts and the water to surfactant ratio. Addition of non-polar solvent can increase the hydrophobic contents and eventually leads to obtain an inverse hexagonal liquid-crystalline phase. Liquid Crystals Figure 5. 2. Liquid crystals Lyotropic liquid crystals are obtained when molecules with interlinked hydrophobic and hydrophilic blocks are mixed with water. solution pH. The size. temperature etc. The methodology is intrinsically slow and suffers on account of step-by-step procedure of fabrication. The hydrophobic parts cluster together to minimize water contact whereas the hydrophilic parts dissolve in water.5. 2008 . The variation in the amphiphile to water ratio can change the phase from hexagonal to lamellar. The liquid crystals have characteristic dimensions in the nanometer range and the confined space in the hydrophobic and/or hydrophilic portions can be used to conduct specific chemical transformation. connectivity and Published by The Berkeley Electronic Press. mostly aqueous phase and charged polymers poses another limitation. liquid crystal with a well defined phase is obtained (see Figure 5). The limitation to remain confined to use of liquid. and availability and possibility to use different molecular precursors have given rise to preparation of number of different nanomaterials with different morphologies and structures.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 57 The versatility and simplicity of the LbL approach to build PE multilayers on chosen substrates (planer or colloidal) with tunability afforded through choice of PE composition. shape.

Article A62 dimensionality of these reactors is controlled by the nature of the liquid crystalline phase. usually not very pronounced to effect particle size. The 3-d geometry of the aqueous domain for a hexagonal phase becomes 2-d for lamellar phase and 1-d for the inverse phase. 6 [2008]. The effect is. 2004). The two interconnect forming the nanomaterial. however. http://www. The hydrophilic part of the liquid crystal retains the same dimension while the hydrophilic aqueous domain changes the thickness and hence the size of the nanoreactor. particle size shows weak dependency on lamellar spacing.. Thus very small particles are formed for a 1-d geometry as compared to 2-d sheet like geometry or 3-d volumetric space. 2-d sheets or 1-d rods can be synthesized (Dellinger et al. The templating effect of the shape of the nano container can decide the shape of the product and correspondingly 3-d spheres. The amphiphile to water ratio also controls the lamellar spacing in the lamellar phase. The transport or diffusion of species from one to another control the rate of formation and is dictated by the geometry.bepress. The particle size also depends on the concentration of precursor (substrate) in the liquid crystal and decreases with decrease in concentration due to enhanced liquid crystal order. In a typical experiment the liquid crystals containing the substrate to be reduced is shear mixed with another liquid crystal containing the reducing agent.com/ijcre/vol6/A62 .58 International Journal of Chemical Reactor Engineering Vol. Similarly the particle size may show no dependency on the concentration of reducing agent (since it is usually high and any further increase has no effect) or may sometimes increase as the increase in concentration of reducing agent may reduce liquid-crystalline order. In other words.

The study reports the prepn. The exposure of this ternary mixture to aqueous 0. 2008 .. SLCs are made by using SDS and CTAB surfactants and their containing CTAB . CdSe. using bicontinuous cubic phase as a matrix. and nonionic such as reverse microemulsions or miniemulsions can be designed. On one hand. of direct hexagonal liq. that the viscous isotropic bicontinuous cubic phase continued to exist in the ternary sodium dioctyl sulfosuccinate (AOT)/water/sodium sulfide (Na2S) system as long as the concentration of aqueous Na2S solution was below 0. and ZnS. crystals that confine the reacting medium within a specific geometry. Dos et al. 4 Organic Lyotropic Liquid Various nanoscale semiconducting superlattices have been generated Braun et al.. through polarized optical microscopy and small-angle X-ray scattering studies. dedicated nanoreactors al..40 M lead nitrate (Pb(NO3)2) solution led to the formation of PbS nanocrystallites within the mesophase. the properties of soft matter. It was of a Lipid found. properties have been studied. and containing oil-swollen cylinders arranged on a triangular lattice in 2005 cyclohexane.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 59 Table 5. direct shape control can be provided by the topol. Some experimental studies on Swollen Liquid Crystals Sr. Synthesized in the monodispersed lead sulfide (PbS) particles with diameters in the 1996 Bicontinuous Cubic Phase range 4-14 nm. 2005 anionic. System Special features and applications References No 1 SDS. surfactants On the other hand. These 1999 include superlattices of CdS. NaCl. Crystals by direct templating in a lyotropic organic liquid crystal..5 M. 3 PbS Nanocrystallites The study reports the synthesis and characterization of Yang et al. pentanol. crystals. of liq. SLCs water. 2 Highly Swollen Liquid Synthesis and self-assembly of nanomaterials can be controlled by Surendran et Crystals using cationic. templated in a liquid crystal formed by oligoethylene oxide oleyl ether amphiphiles and Published by The Berkeley Electronic Press.water.

for nanostructured metals nanostructure design of metals.com/ijcre/vol6/A62 . For 1996 molecular assemblies example. 5 Semiconducting Organic-inorganic nanostructured composites provide a rich source Braun et al.bepress. Hexachloroplatinic acid and ammonium tetrachloroplatinate were used as the Pt sources. reduction of platinum salts confined to the aqueous environments of these phases leads to the deposition of platinum films that have a well-defined long-ranged porous nanostructure and high sp. the lyotropic liquid- crystalline phases were prepared from octaethyleneglycol monohexadecyl ether. The electrochem. The semiconductor growth process copied the symmetry and characteristic dimensions of the original mesophase by avoiding growth of mineral within regularly spaced hydrophobic regions. or be used to tailor its electronic properties. the incorporation of organic molecules in an inorganic lattice can toughen an otherwise brittle material. The reduction of platinum salts 1997 dissolved within the aqueous domains of a hexagonal mesophase leads to Pt whose nanostructure is a cast of the liquid-crystalline phase architecture.60 International Journal of Chemical Reactor Engineering Vol. could be a versatile way to create http://www. 6 Liquid-crystal templates Lyotropic liquidcrystalline phases are versatile media for Attard et al. Pt salt and water. Article A62 water.. and cooperative interactions between organic and inorganic molecules are being used to generate a range of porous materials for separation and catalytic technologies. 6 [2008]. superlattices templated by of new materials for a host of technological applications. The study describes the growth of stable semiconductor–organic superlattices based on cadmium sulphide and cadmium selenide. films from lyotropic polymorphism of structures that have long-range periodicities and 1997 liquid crystalline phases whose characteristic repeat distances range from 2 to 15 nm. 7 Mesoporous platinum The lyotropic liquid crystalline phases of surfactants exhibit a rich Attard et al. These results suggest that the use of liquid crystalline plating solns. surface areas.

Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 61

mesoporous electrodes for batteries, fuel cells, electrochem.
capacitors, and sensors.
8 Nanostructured cobalt Lyotropic liquid crystalline phases formed at high concns. of Bartlett et al;
films from lyotropic nonionic surfactants provide a versatile templating medium that can 2001
liquid crystalline media be used to produce nanostructured materials with regular arrays of
pores of nanometer dimension and extended periodicity. The authors
used this technique to prepare nanostructured cobalt films on gold
substrates by electrochem. deposition of cobalt from cobalt acetate
dissolved in the aqueous domains of the hexagonal lyotropic liquid
crystalline phase of Brij 56 (C16EO10). Low angle x-ray and
transmission electron microscope studies show that the resulting
cobalt films have a regular nanostructure consisting of a hexagonal
array of cylindrical pores.

Published by The Berkeley Electronic Press, 2008

62 International Journal of Chemical Reactor Engineering Vol. 6 [2008], Article A62

2.6. Polymer Micelles

Figure 6. Polymer micelles

The surfactant molecules when dispersed in water is able to create a large variety
of self-assembled forms, primarily because it contain two pairs with different and
opposite properties. The hydrophobic and hydrophilic parts can be altered
(different head groups, hydrocarbon chain, chain length etc.) giving rise to
different morphologies. It is easier to visualize replacing the surfactant with other
moieties that have such opposite properties. Thus far instance, polymer containing
at least two blocks with different properties can aggregate in solvent to create
self-assembled structure (see Figure 6). The idea seems interesting especially
since polymers can be prepared using different monomers in different
compositions, molecular weight and its distribution, functionalities, shape etc.
offering a possibility to construct diblocks of desired properties and hence the
self-assembled morphologies when dispersed in solvent. The driving force for
structures to form is dictated by the microphase separation of the insoluble blocks
in the copolymers.
Micelles, micellar rods, vesicles, lamellae, branched worm-like micelles,
oriented helices etc. are some of the more common structures formed using
diblock copolymers. (Coil-coil) and (rod-coil) diblock copolymers and multi-
block copolymers with and without cross-linkable groups have been used. The
ratio of the two blocks allow to control the size, polarity, stability of structures
such as vesicles. The stability of vesicles formed using block polymers is better as
compared to those formed using amphiphiles due to increased stability, thickness
and rigidity of the membranes. This, however, also means lower permeability and
less fluidic characteristics of the membranes. A number of different
polymerosomes giving special functions such as stimuli-responsive vesicles for
drug delivery, or incorporating the channel protein in the membrane to allow
passive diffusion of small solutes or incorporating ion-carrying ionophores to
fascilitate transport of ions, or electron conducting vesicle membranes or
catalytically active polymerosomes have been demonstrated. A few assorted
examples are included in Table 6.

http://www.bepress.com/ijcre/vol6/A62

Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 63

Table 6. Some experimental studies on Block Copolymers
Sr. System Special features and applications References
No
1 Polystyrene-block- The study investigated changes in the domain period by gold Sohn et al., 2002
poly(4-vinylpyridine) nanoparticles, employing thin films of sym. diblock copolymers.
(PS-PVP) diblock The study reports dependence of the lamellar period on the vol.
copolymers fraction of nanoparticles by an intermediate case of homogeneous
distribution and local segregation of nanoparticles within the PVP
lamellae.
2 Styrene (PS)-acrylic The study reports the formation of novel self-assembled ultrathin Boontongkong
acid (PAA) diblock (ca. 20 nm) films comprising in-plane arrays of nanoscale surface et al., 2002
copolymer cavities. The use of cavitated, metal-loaded PAA domains as arrays
of open nanoreactors for inorg. nanocluster synthesis is reported.
3 Poly(styrene)-co- The synthesis of gold nanoparticles from Star-block copolymers Advincula et al.,
poly(2-vinylpyridine) and also by using polyelectrolyte complex (PEC) with water-sol. 2002
(PS-co-P2VP) terthiophene deriv. for the redn. of HAuCl4 to gold nanoparticles.
copolymer
4 Amphiphilic block Issues related to mediation between incompatible materials, Goltner, 2001
copolymers amphiphilic block copolymers vs. surfactants, micelles and
nanoreactors, design of porous ceramics, biomimetic
mineralization are discussed.
5 Poly(2-vinylpyridine)- Interaction of diblock copolymers with noble metal compds. in aq. Bronstein et al.,
block-poly(ethylene media and metal nanoparticle formation were studied. The P2VP- 1999
oxide) b-PEO micelles contg. metal compds. work as "nanoreactors" for
metal nanoparticle formation.
6 Polybutadiene-b- The use of amphiphilic block copolymers (ABCs) as synthetic Bronstein et.al.,
poly(ethylene oxide) templates for prepn. of porous silica with metal nanoparticles is 1999
(PB-b-PEO) reported. The block copolymer is used in a first step as a

Published by The Berkeley Electronic Press, 2008

block-Me methacrylate) remarkably low polydispersity were prepd and the polymers show 1999 a unique response of the mol. 6 [2008]. 7 Poly(tert-Bu acrylate.64 International Journal of Chemical Reactor Engineering Vol.bepress. and then as templates where the micelles are used as porogens. geometry to the polarity of the solvent. of metal nanoclusters in polymer films.com/ijcre/vol6/A62 . Article A62 nanoreactor for prepn. 8 Review of metal A brief non-comprehensive survey of some recent work on the situ Ciebien et al. star-like amphiphilic block copolymers with 6 and 12-arms with Heise et al.. 1998 copolymer films http://www. nanoclusters in block prodn.. of metal nanoparticles inside their micelle core.

The block polymers also aids in stabilizing the particles. the normal spherical micelles. The homopolymers-metal particle hydrides behave as micellar systems and number of different methods to form them exists. The metal colloids form interior core and reactants diffuse from outside through the membrane shell to react inside. Similar to polymer micelles. star polymers and hyperbranched polymers) can stabilize nanoparticles. other structures such as covalent systems (dendrimers. have shown immense benefits. Description of the various nanoreactors in the earlier section gives out some important hints for the rational choice and engineering analysis and design of such systems. 2008 . A dendrimer is a single molecule with regular branches emanating from the central core in radial directions that adapt to form globular shape. 3. They provide a unique example of heterogenising homogeneous catalyst. Unlike micelles. metal colloids catalyst for oxidation. The available compartments in these structures can indeed be used as nanoreactors and numerous examples of synthesis of metal nanoparticles are reported in literature. A number of metal colloids. Reactions such as catalytic hydrogenation of olefins. • Bile salts: effective for binding aromatic compounds Published by The Berkeley Electronic Press. micellar rods or hexagonal phase are some of the more common morphologies when block copolymers are dispersed in solvent. Thus for instance. The polymer micelles can also be used to encapsulate enzymes for biotransformation that have been shown to remain active. metal oxides and sulfides have been synthesized in polymer micelles. A number of examples of their use in catalysis are reported in Table 6. • Reverse micelles or w/o microemulsion: effective for binding of hydrophilic molecules or ions. the choice of type of nanoreactor can be summarized as follow: • Direct micelles or o/w microemulsion: effective for binding of hydrophobic molecules. Homopolymers such as PVP (polyvinyl pyrrolidone) can also stabilize metal colloids. The compartment in these systems can be used as nanoreactors. DISCUSSIONS The type and form of the organized assembly and hence the nanoreactor decides the efficacy of the processes occurring in it. they are not self-assembled structures and hence dynamic in nature. The hyperbranched and star polymers are suitably synthesized structures. The polymer-metal hydride itself can be used for reactants transformations.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 65 Besides vesicles. The polymer shell is soluble in solvent affording catalyst recovery. C-C coupling reactions etc. The interaction and the correspondence between the nature of the nanoreactor and the reactants needs to be clearly understood.

Pramauro et al. a number of changes occur in the various physico-chemical. change the extent of reaction. conformation protolytic. 1984) as compared to aqueous system. rigidity. hydration etc. Article A62 • Ionenes (cationic + anionic polyelectrolytes): effective for bind both hydrophilic and phobic compounds. etc. molecular complexation. The effective properties such as dielectric constant of the medium can vary over an order of magnitude (80-5) as we move from aqueous to micellar phase over a distance of 1 to 2 nm. redox. unsaturated bonds or presence of chiral atoms in surfactants to control binding. microviscosity. The distribution of species upon solubilization into different microphases as also the variations in solubility. The characteristics of inter and intra-molecular excitation-energy transfer. hydration. electrochemical parameters. For instance the microviscosity changes by a factor of three for surfactant changing from DDS to TX-100 (Singh et al. electrophoretic conditions affecting the sensitivity and selectivity (Shtykov. electrochemical. 2002. polarity and acidity. solvents. Also. for instance. can aid in improving the sensitivity and selectivity of reaction and separation processes. 1995).89 cp) to more than 100 cp (Neal et al. Also change from micelles to vesicular form using dimylristoylphosphatidyl choline changes the aqueous phase viscosity (0. http://www. etc. Typically they include: • Physical properties: Aggregation. Foaming phenomenon absent on mixing. spectrochemical. etc. electronic excitation energy transfer. charge transfer. 1996). 6 [2008]. equilibrium rates etc. on solubilization of reactant. 1982). • The presence of aromatic rings. electrochemical and adsorption properties.com/ijcre/vol6/A62 . co-surfactants helps in establishing and manipulating the control. • Functional groups on surfactant molecules to control catalytic or regioselective ability of self-assembled structure. solubility. Such sharp gradients can be seen in other properties such as microviscosity. Use of different types of surfactants can further change these properties. Addition of electrolytes. charge distribution on a molecule bring about changes in spectroscopic. • Electro-properties: electronic spectrs. electron transfer... charge density. • A control on aggregation number. rate and dynamics. surface potential. we can use • Charge on the reactant to control its binding efficiency or formation of inclusion-complex. Thus. The fluorescence intensities also likewise undergo order of magnitude variations (Hinze et al.bepress. adsorption. shaking. • Chemical properties: hydrophobic.66 International Journal of Chemical Reactor Engineering Vol. Increase in viscosity lowers the associated vibration energy losses.

which are self assembled structures. Notwithstanding these complications. pH of the medium.) anisotropic shapes of molecules can generate variety of diverse structures (Glotzer. additives. Controlling the size of the nanocrystals / nanoparticles in these reactors. • Repulsive forces between two colloidal particles due to charge distribution on the surface (especially when electrolyte is present). This is especially Published by The Berkeley Electronic Press. 2008 . Scale-up of nanoreactors for large scale manufacturing therefore means increasing their number multifold ensuring same properties. 2003). The potential interactions and their types vary considerably as we move from molecules to colloids. et al. The theoretical studies require to properly define the potential interactions and the force field. is generally a relatively easier task. it is necessary to put them in proper perspective. nature and type of ions etc. electrolytes. Controlling the shape of nanocrystals is however a more intricate and challenging job.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 67 The properties of nanoreactors are unique to their nanosize dimensions. The changes in the shape occur due to variations and differences in the growth rates of various crystallographic faces that are influenced in a complex way by a number of factors (Pileni. The molecular assemblies can be simulated using ab- initio quantum mechanical and molecular dynamics methods. The presence of impurities. Such isotropic and centro symmetric potentials can generate a few simple structures. The shape is therefore not uniquely decided by the shape of the template. hydrogen or covalent-bonding. even simple atomic/molecular systems self-assemble on length scale measuring in Angstroms. In order to understand the supramolecular self assemblies with cavities that can be used as nanoreactors. The large number of structures that are possible can be experimentally probed using instrumental tools such as optical scattering. nmr spectroscopy. • Excluded volume interactions due to adsorbed steric layers. The presence of directional interactions (dipole. The consistency in the quality of material produced thus remains unaffected and no additional parameter optimization is necessary when the scale of production moves from grams to kilograms and more. despite a few discrepancies which may always exist due to peculiar nature of the specific system.. • Depletion potential (small non adsorbing molecules create attractive forces between colloids due to entropic. The simple system involves long range interactions. once optimized the regularity in the functioning of the nanoreactor can be ascertained. can modify the growth of some crystal faces. As we know. They include • Long range attractive Van der wall’s interaction for particle pairs. free volume effect). leading to savings in time and cost. Vander der Walls dispersion forces and repulsive excluded volume (Leonard-Jone potentials). ligand binding etc. neutron scattering etc. The yields are quantitative with minimal waste. The small size of the reactor allows for a faster reaction rate and transport rate across the boundaries. 2004).

et al. DVLO and other such pair potentials. The molecular dynamics (MD) and Brownian dynamics (BD) methods (Dudowicz et al. The later can be obtained from Brownian dynamics as mean square displacement of colloidal sphere [ lim < Δξ 2 (t ) > σDO T = kTt πμa ] where a is the sphere t →∞ radius.. type and strength of the interaction potentials considered both molecular and colloidal systems can exhibit glass transition as well as gelation phenomenon. MD simulations generate constant http://www. The slowing down of dynamics and crystallization rates near glass transition due to caging effect of repulsive excluded volume of surrounding particles can become severe to a level where thermodynamically feasible assemblies can also be blocked. The crystal grows more slowly with tendencies for defects such as vacancies. Article A62 important since its range and strength can be independently varied to create assembly. 2004) also use similar pair potentials to deterministically generate the particle configurations.68 International Journal of Chemical Reactor Engineering Vol. Simulation methods for self assembly of nanoparticles and colloidal systems use Monte Carlo (MC) simulations (Ethayaraja. φ the reduced amorphous liquid volume fraction and D(ϕ ) the reduced short time self diffusivity generalization of Stokes-Einstein diffusivity. The kinetic pre-exponential factor ( K 0 ) in the nucleation rate per unit volume [Ι = K 0 exp(− ΔG KT )] can be obtained in dimensionless reduced units as K 0 = Αϕ 5 / 3 D(ϕ ) where A is a constant. For the ranges. The short range attractive interaction can also slow down the dynamics and hold the system in a nonordered metastable state. Like in atomistic/molecular systems only a few limited structures of assembly can be generated using above potential interactions. The MC method operates probabilistically to generate particle configurations with a view to obtain ordered structures in the form of a number of thermodynamic ensembles. 2007) to generate equilibrium phase diagrams by assuming hard sphere.com/ijcre/vol6/A62 . Nonequilibrium aggregation and gelation may also occur hampering the assembly process. strength and range of pair potential interactions indicate thermodynamic limitations on formation of some assembly processes. 6 [2008]. • Short-range adhesive forces due to changes in steric layer and induced dipole forces. The presence of noncentro symmetric and anisotropic shape and strength of interactions are needed for a wide choice of assembly structures. The type. They solve the Newton`s second law equation for force balance where the force on each particle is obtained from the gradient of potential. soft sphere.bepress.. The nano and colloidal assemblies also suffer kinetic limitations. grain boundaries etc. The characteristic time in the nucleation rate (a 2 D) scales as a3 indicating strong kinetic retardation with the particle radius. wrong stacking.

2008 . Simulation methods help us build this understanding of the fundamentals which is very useful for new technological applications. This has implications for nucleation kinetics. Synthesis of nanoparticles and structures in different shapes and form has by now been a standard procedure. however arranging these building blocks into desirable organized structures such as 1-d. it is important to correctly describe the interactions in these complex systems.. In addition to MC. The effects of particle specifics such as composition. FR (t ' ) >= (σk B T )(σπaηδ (t − t ' )) with zero mean FR . The characteristic time for a sphere to travel its own radius scales as cube of the radius. The self assembly of particles into 1-d. The interaction potential to be used for surfactants. 2-d and 3-d assemblies remain as a challenge. gel and glassy and other phenomenon that mediate the assembly process. 2-d and 3-d arrays is thus a sensitive issue requiring detail understanding of the effects of particle shape. The hydrodynamic interactions are considered to be absent and (iii) the resultant force FR generated due to Brownian bombardment of solvent molecule as described by the fluctuation-dissipation. liquid crystals and other forms must be chosen appropriately and may require additional support from ab-initio quantum mechanical (surface morphology) or density functional theories (force). FD. conventionally expressed as FD = 6лaηυ where a is particle radius. η the solvent viscosity and υ the velocity of particle. coulumbic interactions. block copolymer. Brownian motion. The dependence of FD and FR on particle size clearly indicates its importance for the assembly process. usually under isothermal and isobaric conditions. Notwithstanding the method used for simulations. other methods such as discrete particle dynamics (DPD) (Frenkel et al.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 69 energy ensemble particle configurations/trajectories. enter through this term (ii) the drag force. The equation of motion describing the force balance comprises of three terms viz (i) the conservative force Fc acting on each particle and includes the van der walls. impurities. surface modification interactions etc. Methods such as BD include the effect implicitely where the potential of mean force as mediated by the presence of other particles and solvent is used. For smaller particles. MD and BD simulations. The solvent dynamics has to be modeled explicitely that make simulations prohibitive. can be assigned as attractive (-philic) or repulsive (-phobic) character. which in a broad way. additives etc. screening effects etc. this implies that the dispersion delocalization time is realy short. Theorem < FR (t ). type of solvent. excluded volume. size on potential interactions. 2001) use soft particles to represent fluid elements and hard particles to capture packing effects of colloids due to excluded volume. A number of question such as what kind of structures should we assemble and for what purpose and how-have been raised in recent years and partial solutions and direction for further research and work are spelled out Published by The Berkeley Electronic Press.

70 International Journal of Chemical Reactor Engineering Vol. templating the synthesis of other materials and conjugating and coupling to peptides. http://www. Article A62 (Glotzer et al. open vessels etc. The energy devices as well as control elements are thus essentially molecular in nature and can be synthesized as molecular electrical wires. lipid bilayers.bepress. The variety of synthesis methods described in the earlier part allow us to create structures that can be used as molecular reactors (in various forms such as rings.). lipids etc. metal coordination and electrostatic interactions can also direct the self assembly. π stacking. The issue discussed in more details by Tirrell (2005) requires careful considerations to precision synthesis of precursors and building internal guidance into the process of evolution whereby the desired self assembly results. addressability and programmability of self assembling characters. Nucleic acids have the characteristic ability to store and transcribe genetic information. motors. vesicles etc. The idea of integrating all such components into a comprehensive system mimicking the behavior of a cell is very interesting and vigorously pursued. shuttles etc. Incorporating them or their equivalent synthetic analogues into the system can enhance the possibility of specific assembly (base pairing) and eventually the self assembly processing. tubes. (2005) vividly describes the process system engineering issues of nanosystems and their integration and should be referred to for details. The network of vesicles-nanotubes developed by Shimizu et al (2005) is one such step in this direction. The biological systems posses such in-built mechanisms whereas their artificial analogue have to be provided with sufficient information content that relates to molecular recognition. it is possible to direct the self assembly as micelle. We have already seen that by a judicious choice of the hydrophobic interactions. Other forms of interactions such as hydrogen bonding. The electrostatic forces. Self assembly as a manufacturing method and its large scale practical implementation also requires the attention.). It is noteworthy to realize that a biological system unit with all its sophistication and complexities is still chemical at its molecular level. tubes etc.com/ijcre/vol6/A62 . under certain conditions can also localize components to create interlocked molecules that can be used as valves. splitters. Similarly development of practical methodologies to commercial and technologically important self assembly processes should be addressed. mixes. tunability of interaction strengths. The perspective article by Stephanopolous et al. transport lines (channels. pumps. elevators etc.. Catenanes and Rotaxcenes are good examples of self-assembling of molecular complexes under the influence of electrostatic interactions and orbital overlap forces. 2004). circuits. spheres. 6 [2008]. The cell system is indeed very sophisticated with presence of control elements such as signal carriers and actuators. Additionally components producing using and dissipating the energy are also present. switches. Many of these and such functionalities are present in biological systems such as cells. gears. Tirrell (2005) cite a number of recent studies on self assemblies using nucleic acid bas pairings. directionality. valves.

and alterations in the microphase properties such as viscosity. doping or insertion of active component prove useful for multi step reactions where yield to desired product can be maximized. The simple surfactant used for construction of the enclosed confined environments already show a number of features such as compartmentalization. Hierarchical porous interconnected structures affords the possibility to introduce transport channels for moving the molecules in and out. hollow structures. orientations and extent of components. Thus for instance macromolecular ampiphiles for vesicular drug delivery systems Published by The Berkeley Electronic Press. tubes and other two and three-dimensional structures. nature and other attributes improve upon the ability of such systems to some extent and yet are no where near the sophistication seen in natural cell systems. High internal surface area with a possibility of local deposition. create multi-center multifunctional interactions between components. spheres. with large gradients over nanometer distance can all be utilized in a judicious way to create the desired nano architecture. self-assembling etc. Thus. polarity. rods. The self-assembly of lipids and detergents into bilayer membrane vesicles with a range of bilayer thicknesses (3-5nm) and vesicular length scales of (100-10.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 71 4. bring them together and concentrate them in microphases. geometric compatibility. play with the nature. Computer simulations can provide a very useful lead in elucidating the efforts of various parameters on performance. 2008 . of the cell system. our ability to dissolve dissimilar substances. At the functional level. we understand the fundamental difference between a homogeneous system and a micro- heterogeneous organized media and that local effects can bring about a dramatic change. The types and characteristics of these nanoreactors and control of their efficiencies for conducting chemical transformations have been extensively investigated. The maneuverability and control at operational level allow us to develop open cellular structure with possibility to tune the material structure at different length scales. such as the ones described herein. etc.000nm) diameter provided the mimics for cell membrane and brought us a little more close to natural system. formed through a self- assembling process represent nanoreactors that can be used for preparing nanostructured materials of desired functionalities and attributes. The development and use of macro molecules with a ability to impart intelligence for self-assembling in desired architectures kept the march forward with numerous interesting results. CONCLUDING REMARKS Organized assemblies. vividly demonstrate the engineering ability to create the desirable structures and attributes. A number of illustrative examples of formation of nanoparticles and their assemblies in the form of films. Number of studies reporting effects of variation in surfactant type. Self-organized systems are the crude man-made mimics of the natural cell systems.

REFERENCES: Adair. 32-39. These organized media and nanoreactors have clearly proved to be very useful for preparation of nanostructured materials. Attard. Skrabal. “Microemulsions are membrane-active. Vol. 1998. Mater. Vol. 9. Of course much more needs to be done to advance them to a stage of full potential. J. R. 36-38. 2080–3. Vol. “Configurational changes accompanying vesiculation of mixed single-chain amphiphiles” Langmuir.. 838-840. Luisi. S.. P. et al. enzyme based ampiphiles . P. H. Al-Adham.. C. Wang. 933–937. Alivisatos. et al. Bartlett.. 223rd ACS National Meeting. P.. Int.. Vol. Abstracts of Papers. I. R. 2002..P. virus bodies are finding new applications to create sophisticated nanovescles. 1997.72 International Journal of Chemical Reactor Engineering Vol.. 278. 36. antimicrobial. Corker... Vol. “Liquid- crystal templates for nanostructured metals” Angew. Bronstein L. H. 2501-2503. Eng. J. Goltner.. S. S. I. “Nonclassical shapes of noble- metal colloids by synthesis in microgel nanoreactors.. G. Journal of Applied Microbiology. Elliott. “Morphology and oxide phase control in the microemulsion mediated synthesis of barium stabilized alumina nanoparticles”. and Watzke. Templer. Advincula. Owen. Bangerter. Chem. April 7-11. Article A62 has advanced very rapidly approaching commercial realities. B. Vol. 4.bepress. I. proteins.. “Mesoporous platinum films from lyotropic liquid crystalline phases” Science. Vol.. F. M.. Balint. Physical Chemistry Chemical Physics. “Controlled preparation of Gold nanoparticles using well- defined Star-Block copolymers and polylectrolyte complexes”. Henke. N. 89. Grohn F. 1996. 2000. et al. 139-242... 271. “Recent developments in the preparation and properties of nanometer-size spherical and platelet-shaped particlea and composite particles”. 1997. Coleman. 2002. Antonietti M.. R. 6 [2008].. J. Vol.. S.H. H. M. 1993.. Amb¨uhl.. J. R. self-preserving systems”. et al.com/ijcre/vol6/A62 . A. G. J. “Semiconductor clusters. Science. More complex but closer to natural cells. Ed. and quantum dots”.” Angew Chem Int Ed. Sci. J. 1315-1317. Hartmann J. R. http://www. L. G. N. Engl. Attard. nanocrystals. M. 23. 36. 1997.

1999. S. “Integrated Nanoreactor Systems: Triggering the Release and Mixing of Compounds Inside Single Vesicles”. Chemistry of Materials.. Journal of Physical Chemistry B. P. 2004. Published by The Berkeley Electronic Press. “Cavitated Block Copolymer Micellar Thin Films: Lateral Arrays of Open Nanoreactors”.. Evans. “Semiconducting superlattices templated by molecular assemblies” Nature. V. Soc. 2002. L. P. 111.” Biological Systems as Nanoreactors: Anomalous Small-Angle Scattering Study of the CdS Nanoparticle Formation in Multilamellar Vesicles”. A. E. Macromolecules. Chem. and Ninham. and Cohen. Soc. Sawicki. Bota. 6259–62. M. Vol. J. Osenar. 11. Osenar. 2001. 2001.. C119-C123.. 35. Braun. Bartlett. 3647-3652. 1. R. Vol.. Am. S. Chem.. 126. I. Vol. et al. Colfen H.. N. B. “Dendrimer silver complexes and nanocomposites as antimicrobial agents”. Valetsky PM...Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 73 Balogh.. Nano Lett. W. 4279. M. Bergstr¨om.. Vol. E. V. “Induced micellization by interaction of poly(2-vinylpyridine)-block- poly(ethylene oxide) with metal compounds.15.” Langmuir. 121. Colloid Interface Sci. 1999. P.. Sidorov SN. Groot.. 1911-1915. d. B.. N. Ghanem.148. Brady. 1402-1405. 1999.. Braun. et al. Vol. Vol.. Vol. Birkin..4280. “The electrochemical deposition of nanostructured cobalt films from lyotropic liquid crystalline media” J.. Kennedy. Bolinger et al. “Nanostructure Templating in Inorganic Solids with Organic Lyotropic Liquid Crystals” J. Vol.. P. 294-306. I. Tohver.380. 1996. A. Y. 1984. B. Bronstein LH. Soc. Kachar.. Vol. Am. 18-21. “Spontaneous vesicles” J. P. Journal of the American Chemical Society... 2007. Vol. 2001. Hartmann J. Antonietti M. Boontongkong. 106. Stupp. 325-328. L. 8594-8595. V. P. D.. Vol. S. Micelle characteristics and metal nanoparticle formation. “Successive Use of Amphiphilic Block Copolymers as Nanoreactors and Templates: Preparation of Porous Silica with Metal Nanoparticles”. Bronstein. 240... P. F. Stupp. Electrochem. et al. 7302-7309. “Thermodynamics of unilamellar vesicles: Influence of mixing on the curvature free energy of a vesicle bilayer” J.. M. 2008 .

Vol. Liu. Brus. Journal of the American Chemical Society.com/ijcre/vol6/A62 . 554-560. and Gao. 1991. “Novel morphologies of nickel sulfides: nanotubes and nanoneedles derived from rolled nanosheets in a w/o microemulsion”. I. Chang. 1987.bepress. Caruso. 23. 1111–1114. E. Langmuir. D. 2000. Adv Mater. L.116. Carberry J. L. Asher. F. 1994.74 International Journal of Chemical Reactor Engineering Vol. 11– 22. Journal of Colloid and Interface Science. Vol. 6739-44. 1196-11197. A. Vol. Chen. 2004... 125. “Quantum crystallites and nonlinear optics”. F. Journal of Crystal Growth. “Induced Micellization by Interaction of Poly(2- vinylpyridine)-block-poly(ethylene oxide) with Metal Compounds. Science. 2001. 413–419. Chem Eur J. 6. Micelle Characteristics and Metal Nanoparticle Formation”. S. “Preparation of Nd:YAG Nanopowder in a Confined Environment”. D. Chen. et al. F. 2004. L. 2003. 49-74. 3947-3952. et al. “Preparation and Properties of Tailored Morphology. 1999. Caponetti. and Gao.. A.. 262. L. Journal of the American Chemical Society. Langmuir. 13. “Nanoengineering of particle surfaces”. Vol. 465–474. M. 2007. “Novel synthesis of well-dispersed crystalline SnO2 nanoparticles by water-in-oil microemulsion-assisted hydrothermal process”. “The First Fluoride One-Dimensional Nanostructures: Microemulsion-Mediated Hydrothermal Synthesis of BaF2 Whiskers”... Vol. Vol. Vol.. 15. L. “Chemical reaction and reactor engineering” Marcel Dekker Inc. et al... H. 6 [2008]. 1069p. Monodisperse Colloidal Silica-Cadmium Sulfide Nanocomposites”. 279. Cao. “Preparation of metal nanoparticles in water-in-oil (w/o) microemulsions” Adv. 53. Vol. Heinemann... http://www. et al.. 6256-6262. New York. 110.. Capek. Caruso. S-Y. and Varma. Colloid Interface Sci. Vol. Article A62 Bronstein. Vol. 137-142. J. 1998. “Hollow capsule processing through colloidal templating and self- assembly”. “Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating”. 282. 2004. M. Appl Phys A. Vol.. Caruso.

. 10. et al.O. Vol. Decher G.. “Light-emitting-diodes made from cadmium selenide nanocrystals and a semiconducting polymer”.. J. “Synthesis and Characterization of Nitrogen-Doped TiO2 Nanophotocatalyst with High Visible Light Activity”. S. W. “Multilayer thin films: sequential assembly of nanocomposite materials”. Materials Letters. 1995. 543p. 123. B. 2007. 2005. Nature. et al. 2003. Vol..V. et al.. “Nanophase BaFe12O19 synthesized from a nonaqueous microemulsion with Ba. 6976-6982. and Schlenoff.B. “Electroluminescence from CdSe quantum-dot polymer composites”. 497–501. Weinheim. 111. DeBenedetti. et al.17. 5431- 5436. Yushan. 2002. New Journal of Chemistry. Vol. 685-691. B. “Synthesis of Two Types of Nanoparticles in Polyelectrolyte Capsule Nanoreactors and Their Dual Functionality”. 3378-3380. et al. Chemistry of Materials. and Bruening M. Journal of Electroceramics.L. 2262-2266. Vol... 127.. Journal of Physical Chemistry C.. 1316–1318. Journal of Materials Research. F. Li. 1995. “Synthesis of barium strontium titanate nanorods in reverse microemulsion”. 2001. 370. Vol. 37-40. Chen.. 16136-16142. pp. Zhu. 61. 2. Vol.. 1998. Published by The Berkeley Electronic Press.et al. 354– 357. 17. 2008 . 22. Colvin.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 75 Chen. 2007. Cong. Vol.. Choi. 2005.L. Appl Phys Lett. et al. J. Vol. Ciebien.. Qi'an. “Brief review of metal nanoclusters in block copolymer films”. Shuang. Vol. 66. Journal of the American Chemical Society. Zhongwei. Journal of the American Chemical Society. Yan. V. Vol. “Catalytic nanoparticles formed by reduction of metal ions in multilayered polyelectrolyte films”. Chhabra. 1994. Dabbousi.. Y. Wiley/VCH. “Fabrication of Micro Reaction Cages with Tailored Properties”. Dai J. Nano Lett.and Fe-containing surfactants”.. et al.. 2006. Wanping. “Synthesis of TiO2 nanospheres through microemulsion reactive precipitation”. Daehne. Vol. L. 2689-92. “Synthesis of Template-Free Zeolite Nanocrystals by Reverse Microemulsion-Microwave Method”.

.. Ee. 3418-3423.. Lett.. G.. “Microemulsion and micelle systems for solubilizing drugs”. J. B.V. C. L. 2004. 528p. Dos S. “BiOCl nanoparticles synthesized in lyotropic liquid crystal nanoreactors. 1998. 2005. D´esert S. Ethayaraja.” Scripta Mater. 1995. “Self-assembly of regular hollow icosahedra in salt-free catanionic solutions” Nature. 92. 4362-4369. E.M. Doraiswamy L. 391-407. 277. 6 [2008]. 1232–1237. 2001. 23.. Vol. Braun P. Vol. 1893–7... et al. “Fuzzy nanoassemblies: toward layered polymeric multicomposites”. A. et al.. Gulik-Krzywicki. Dellinger T. Dennis. Vol. Dubois.. M. Vautrin C. Vol... 2001. Dem´e. 1998. Dudowicz. et al... Langmuir.. 672-675. 1997. Mater. M. and Monto Carlo simultion”. 1045-1055. Science. 5. 21. Dedieu. Application: US 2001-924290 20010808(2002). Delinger. Vol. “Novel hollow polymer shells by colloid-templated assembly of polyelectrolytes”. et al. Perez E and Zemb T. et al. J. 2007. 1-4. P. Vol.bepress. Guyot. “Lyotropic liquid crystals as nanoreactors for nanoparticle synthesis” Chem. http://www. J.. T. 16. Article A62 Decher. 1. 33. Donath. P. “Flory-Huggins model of equilibrium polymerization and phase separation in the stockmayer fluid” Phys. “Low temperature synthesis of PZT powders via microemulsion processing”. S. Examples and Reactor Design” John Wiley and Sons Inc. Braun. Espiard... Materials Research Bulletin. “Heterogeneous reactions: Analysis. Vol. Mark. “Existence and Stability of New Nanoreactors: Highly Swollen Hexagonal Liquid Crystals”. 1984.V. Vol. 2201-2207. Angew Chem Int Ed.411..com/ijcre/vol6/A62 . mechanism.M. Vol. Journal of Inorganic and Organometallic Polymers..M. and Sharma.76 International Journal of Chemical Reactor Engineering Vol. “Nanoparticle formation in water-in-oil microemulaions: experiments.et al. Rev.K. 37. 2004. Langmuir. M. D. E. “Surface functionalized colloidal silica particles from an inverse microemulsion sol gel process”. T. Vol. 2201–2205. 44. M... Vol.

” John Wiley and Sons Inc.. “Chemical reactor analysis and design. 1998. Bischoff. 112. J.. “Comparative study on phase development of lead titanate powders”. Vol. 2001. Vol. Vol.” J Mater Chem. New York. Fuerte. et al. Feiters.” Washington DC..13. Computational Science Series. Frenkel. 169. “Synthesis and characterization of ultrafine lead zirconate powders”. Am. Vol. 2002.. “From simple to supramolecular cytochrome P450 mimics” Chem. edition 2. H. K. T.. Furumoto. 284-290. 180. X. London: Academic Press. M.. Froment. 1981. B. H. Journal of Power Sources. 2003. 2001.. Rev. edition 1 and 1990. 29. et al. Vol. 304-312.. 2008 . Fogler. 1616-1624. 1990. K. 3438-3443. R. Chem. 1996.. Forster S.. 22. “Self-Assembled Nanostructured Materials”. et al. D. 1979. J. 2007. Fang. 2000. Electrophoresis.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 77 Fan. A.1637. and Okuda.. 24. “Bilayer-forming ion-pair amphiphiles from single-chain surfactants”. “Understanding molecular simulation: From algorithms to applications”. Chemistry of Materials. 47-52. Vol. H.. 396p. Soc. Fukuda. Sumit. Kawata.F.. “From self-organizing polymers to nanoand biomaterials. Fendler. “Microemulsion-mediated hydrothermal synthesis and characterization of zircon-type LaVO4 nanowires”. 52. “Migration mechanism of bases and nucleosides in oil-in- water microemulsion capillary electrophoresis”. Vol. Daza. Vol. W.B. Valenzuela. G. Published by The Berkeley Electronic Press. Cet al. et al. American Chemical Society. Vol. 507-513. Ceramics International.S. 375-384. Vol. 2007. 1635. 1.. Journal of Solid State Chemistry.. J. 8. “Chemical reactors. 2671–88. Konrad M.. J. “Preparation and characterisation of SOFC anodic materials based on Ce-Cu”.. L.. Soc. H. Materials Letters.. Fang.

408-12.com/ijcre/vol6/A62 ..78 International Journal of Chemical Reactor Engineering Vol. 37. “Preparation and characterization of monoclinic sulfur nanoparticles by water-in-oil microemulsions technique”. “Fabrication and characterizations of oligopyrrole doped with dodecylbenzenesulfonic acid in reverse microemulsion”. 1356-1359. 1995. et al. “Synthesis of single crystal CdMoO4 octahedral microparticles via microemulsion-mediated route”. P. 304. 83-86.50. et al. W.. mechanism and biochemistry”. Y. 797-818. 2001. Journal of Physical Chemistry B. Materials Chemistry and Physics. New York.. Vol. D. 296. 2004. Journal of Colloid and Interface Science.et al. Vol. M. et al. 100(Reactions and Synthesis in Surfactant Systems). 2006. M. http://www. et al. Vol. “Encapsulation of hematite in zircon by microemulsion and sol- gel methods”. 110-117. 162. In “Cytochrome P450: Structure. 6114-6118. Vol. Vol. S. Vol. “Catalytic processes during preferential oxidation of CO in H2- rich streams over catalysts based on copper-ceria”. 12.. 2978-2985. 2003. Ed. 2003.et al. et al. 2007. Glotzer. “Self-assembly: From nanoscale to microscale colloids” AIChE Journal. Vol. 263-8. 6 [2008]. et al.. 27. Advanced Materials. “Evaporation-Controlled Self-Assembly of Silica Surfactant Mesophases”. Goltner. Plenum Press. C. Journal of Sol-Gel Science and Technology. “Inorganic nanostructure design with amphiphilic block copolymers”. Garcia. 267- 275.. 1994.C.. Gibaud. Journal of colloid and interface science. J. Article A62 Gamarra. Vol. Vol. 169.T. Han. L. Gong Q.. 2006. et al.R. Han. Powder Technology. “Carbon nanotubes as nanoreactors for boriding iron nanowires”. 2000. 110-116. Ortiz de Montellano. “Preparation of fine LaNiO3 powder from oxalate precursors via reactions in inverse microemulsions”. Surfactant Science Series Vol. 107.bepress. 2006. Gan. Journal of Power Sources.. A. Groves. et al. Guo. A.

Zasadzinski. 2355-2358. Chem. E. 89.. “Tubular nanostructures from degradable core-shell cylinder microstructures in chiral diblock copolymers”. et al. Vol. Henglein. 461–467.. Vol.. 251-254.18... Chemistry of Materials.” J Mater Res.27. Vol... J. A. Published by The Berkeley Electronic Press.. 2006. “Effect of process variables on the grain growth and microstructure of ZnO– Bi2O3 varistors and their nanosize ZnO recursors. 2001. 2008 .O. 13792-13802. “Phase behavior of sodium naphthenates. 1861–1873. Vol. Pileni M.S. 2006. Jae-Hyun. L.10. 2007. et al. 247-254. 452-453. Phys. Kaler. 1984. Vol. A. “Nanosized BiOX (X = Cl. Horvath-Szabo. 136–9. 366-373.. et al. W. 1999. Herrington. Henle. Hinze. Vol. Nano Letters. et al.models for unimolecular micelles and nanoreactors”. 6. K. 40. “SANS studies on the formation of PANI nanoparticles in the reverse micelles”. Chem... 1993. Trends Anal. “Carbon Nanotubes as Nanoreactors for Fabrication of Single- Crystalline Mg3N2 Nanowires”. and Chiruvolu. R-M. G. 2001. Shah D. Ingert. 3. Vol. D. “Star-like amphiphilic block copolymers . et al.. J. Chem Rev. D.L. Multani M. Vol. Miller. and water”.. 19.” Adv Funct Mater. toluene. 11. 97. Division of Polymer Chemistry). et al.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 79 Heise. 1989. 193-199. 1995. Hu. Polymer Preprints (American Chemical Society. 242. 2006. Kim. Ho. A. Vol. J.. S. “Phase behavior of aqueous mixtures of dodecyltrimethylammonium bromide (DTAB) and Sodium Dodecyl Sulfate (SDS)” J. “Micellar enhanced analytical fluorimetry”. Vol. Hingorani S. Advanced Materials. “Limitations in producing nanocrystals using reverse micelles as nanoreactors. D. Vol.et al.. 1136-1140.P. W. N.. Br. “Small-particle research—physicochemical properties of extremely small colloidal metal and semiconductor particles”. Journal of Colloid and Interface Science. I) Particles Synthesized in Reverse Microemulsions”. Bulletin of the Korean Chemical Society.

. 1989. J. A. et al. 67. 7. Colloid Interface Sci. B.. N. M.. K. 6. E. Jang. W. Kaler. Murthy. 2001. J. et al. E.. Khomane.. E.. John. “Reverse microemulsion mediated sol-gel synthesis of lithium silicate nanoparticles under ambient conditions: Scope for CO2 sequestration”. et al.98.J. 1354–1359. Y.. Langmuir. “Multilayer nanoreactors for metallic and semiconducting particles”.1374. Chemical communications. Herrington. Vol. R. Chem. Vol.. Joly... B. K. et al. S.W. 1994. Opin.T. Yoon. W. “The origins of stability of spontaneous vesicles” Proceedings of the National Academy of Sciences of the United States of America. 6 [2008].. Vol.. A. 2005. J. D.com/ijcre/vol6/A62 . 1992. V. Vol. Coldren. A. Bose.222. Keller. 2004. Vol.. Article A62 Jang J. Zasadzinski. and Zana. N. H.. Vol. McPherson. Lampietro. S. 2002. 799-802. R.T. “Recent developments in materials synthesis in surfactant systems” Curr. 213.9. N. and Zasadzinski. G... 6698-6707.. and Zasadzinski.. Murthy.. 720- 721. Kaler. L. H. Talmon. Vol. Jung.. Kaler. Jang. 1353-1357. J. 61. H.. A. 2003. 1371. “Study of mixed aggregates in aqueous solutions of sodium dodecyl sulfate and dodecyltrimethylammonium bromide” Colloids Surf.bepress. 288-295. Vol. “Fabrication of mesoporous polymer using soft template method”.W. B.. 16. 245. “Phase behavior and structures of mixtures of anionic and cationic surfactants” J. A. “Layer-by-layer assembly of intercalation compounds and heterostructures on surfaces: toward molecular ‘beaker’ epitaxy”. Phys. 2000. and Yoon. “Spontaneous vesicle formation in aqueous mixtures of single-tailed surfactants” Science. Chorro. 2006. Vol. 96. “Facile fabrication of polypyrrole nanotubes using reverse microemulsion polymerization”.. 3415-3418. J. Chemical Engineering Science.L. http://www. 8817–8818.. Chemical Communications. “Novel fabrication of size-tunable silica nanotubes using a reverse-microemulsion-mediated sol-gel method”.80 International Journal of Chemical Reactor Engineering Vol. 1200-1202.116. Simmons. K.A... Vol.. E. Vol. B..16. Rodriguez. J Am Chem Soc. 1992. Kamenka. Advanced Materials.

Science.. “Gold nanoparticle-based sensing of ‘spectroscopically silent’ heavy metal ions”. Chem. Vol. 2496-2498. 2001 (http://www. V.. Kim. 3540-3563.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 81 Kim... crack resistance. H. Oh. K. Klipstein. Uchiyama.. 1999. D. 46. Esumi. Nishiyama.R. 2008 . 1599-1603. 1998. Published by The Berkeley Electronic Press. et al.. “Vision 2020: Reaction engineering roadmap” published by the Centre for Waste Reduction Technologies of the AIChE.chemicalvision2020. 2004. “Layer-by-layer self-assembly of alumosilicate-polyelectrolyte composites: mechanism of deposition. Jong-Dae. Dalton Trans. N. 1994. 2001. 11. Y. 1997. “Synthesis and chareacterization of microparticles in reverse micelles. Dae-Wook.... Ueno. and Abe. Kleinfeld. Lee. “Aggregation of a crown ether-based copper amphiphile as a mimic for the superstructure of hemocyanin” J. 886–895. “Preparation of Ultrafine Monodispersed Indium-Tin Oxide Particles in AOT-Based Reverse Microemulsions as Nanoreactors”. 15.org/pdfs/reaction_roadmap..A. Eds. 3056-3064. and Ferguson G.S. “Stepwise formation of multilayered nanostructural films from macromolecular precursors”. Kolesnik. Kondo. M. “Synthesis of silver nanoparticles in mesoporous high- aluminum aluminosilicate matrices”. Chem Mater. E. Soc. Vol. 550-583.. 2380-2384. Vol. 370–373. vol. 10. “Spontaneous vesicle formation from aqueous solutions of didodecyldimethylammonium bromide and Sodium Dodecyl Sulfate mixtures” Langmuir.pdf). 53. Polymer. Kita-Tokarczyk et al. Seong-Geun. 265. 1995. I. H. M. Vol.. K. Kon-no. 165–167. K. Vol. Marcel Dekker: New York. In structure-performance relationship in surfactants”.. Klein G.. Kotov N.. 2005.et al. Yoshino. Langmuir.1. et al. Russian Chemical Bulletin. 2001.. Nano Lett. Vol. and perspectives for novel membrane materials”.... “Block copolymer vesicles-using concepts from polymer chemistry to mimic biomembranes”. et al..Y.

2002. Physical Chemistry Chemical Physics. Vol. 526-529.. G.D. et al.16.. B. 62. P. Lim. et al.bepress. 60. Kumar. “EPR studies of free radical reactions of C60 embedded in mesoporous MCM-41 materials in aqueous solution”. 2001. Kumar.. 2006.. P. et al. “Microemulsion & sub-micron emulsion process & compositions”. 68-74.L-lactide nanoparticles against experimental leishmaniasis”.. X.. 1993.. http://www. L. Abstracts of Papers. December 19. C-H. Li.com/ijcre/vol6/A62 .. Vol. “Microstructural study and size control of iron oxide nanoparticles produced by microemulsion technique” Current Topics in Solid State Physics. Vol. Journal of Drug Targeting. 1302-1307. “Preparation of bismuth lead strontium calcium copper oxide superconductors by coprecipitation of nanosize oxalate precursor powders in the aqueous core of water-in-oil microemulsions”. et al. Materials Letters. 171-179. and Harding. Lee. Vol. 3106-3111. April 1-5. Li. “Preparation of (YBa2Cu3O7-x) superconductor by coprecipitation of nanosize oxalate precursor powder in microemulsions”. 2006. “Critical evaluation of the therapeutic potential of bassic acid incorporated in oil-in-water microemulsions and poly-D. 3. Applied Physics Letters. Vol. Kulkarni. Application: WO 2005-AU1321 20050831. B. “Fabrication of a novel polypyrrole/poly(methyl methacrylate) coaxial nanocable using mesoporous silica as a nanoreactor”. Vol.82 International Journal of Chemical Reactor Engineering Vol. et al. 14. 2006. Article A62 Koutzarova. 2006. R. 6 [2008]. “Microemulsion-based synthesis of BaCO3 nanobelts and nanorods”. Solid State Communications.. Vol. 4. 221st ACS National Meeting. et al. et al. Materials Letters. S. Larm. 1993. at IIChE annual congress in Bhubaneswar. Lala. et al. 2006. M. 138. “Preparation and characterization of CuI nanorods using Cu(dmg)2 as precursor via water-in-oil (w/o) microemulsions”. 765-7. “Chemical engineering education and research: new challenges” HL Ray Memorial lecture. 2138-2142. T. 2003..

Z. Z. Y. J. Liu. Z.. Langmuir.. “Molecular self-assembly of TiO2/polymer nanocomposite films”. 2117-2120. et al. 101. Vol.. Langmuir.A. Liu.V. and Yates M. “Surfactant-assisted synthesis of single crystal BaWO4 octahedral microparticles”. Kluwer Academic Publishers. J Phys Chem B.5MnO3 nanoparticles in w/o-microemulsion”. 287. Lopez-Quitela.17. Langmuir : the ACS journal of surfaces and colloids. Vol. Opin. 2006.M. Lopez-Quitela. 2001. Vol. 2006. 302. 135-155. 6747–6750. Journal of Magnetism and Magnetic Materials. 2005.. 1385–1388. L. Vol.. 927-935. 21. Vol. 1997. and Yates. “Synthesis of manganite perovskite Ca0. Schomaecker.J. M. Lopez-Trosell. 2003. 2005. Materials Research Bulletin. Liu. Vol.8. “Synthesis of nanomaterials in microemulsions: formation mechanism and growth control” Curr. “Simple preparation method of multilayer polymer films containing Pd nanoparticles”. Accounts of Chemical Research.5Sr0. Z. Kamat. J... 333-339. 35.. Lin. Journal of Colloid and Interface Science.A. Y. P.. H-P. Liz-Marzan.. In Nanoscale Materials. et al. 2117-20.. et al. Liu. Liu. Vol. 21. M. Published by The Berkeley Electronic Press. “Silver nanocomposite layer-by-layer films based on assembled polyelectrolyte/dendrimer”. Boston. “Structural and Morphological Control of Cationic Surfactant- Templated Mesoporous Silica”.. Vol. A. 2005. Lin. 41. 2003.al. “Altering the Crystal Morphology of Silicalite-1 through Microemulsion-Based Synthesis”. and Chu. L.-C. 2002. Colloid Interface Sci.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 83 Lin J-C. Materials Chemistry and Physics. et. “Altering the crystal morphology of silicalite-1 through microemulsion-based synthesis”. 92. ‘Synthesis of nanoparticles in microemulsions. M. R. 529-535. 137-144. et al. “Preparation and characterization of magnetic P(St-co-MAA-co- AM) microspheres”.. 604-611. 2005. Vol. Vol. Eds. 2008 . 59- 63.. Y.

84 International Journal of Chemical Reactor Engineering Vol. 6 [2008], Article A62

Lu, J. et al., “Fabrication, characterization, and formation mechanism of hollow
spindle-like hematite via a solvothermal process”, Journal of Colloid and
Interface Science, 2006, Vol. 303, 437-443.

Lvov, Y. et al., “Alternate assembly of ordered multilayers of SiO2 and other
nanoparticles and polyions”, Langmuir, 1997, Vol. 13, 6195–6203.

Mansuy, D. “Cytochromes P-450 and model systems: great diversity of catalyzed
reactions” Pure and Applied Chemistry, 1994, Vol. 66, 737-744.

Manziek L, Langenmayr E, Lamola A, Gallagher M, Brese N, Annan N.
“Functionalized emulsion and suspension polymer particles—nanoreactors for the
synthesis of inorganic materials.” Chem Mater., 1998, Vol.10, 3101–8.

Masui, T. et al., “Characterization of Cerium(IV) Oxide Ultrafine Particles
Prepared Using Reversed Micelles”, Chemistry of Materials, 1997, Vol. 9, 2197-
2204.

McKelvey, C. A. and Kaler, E. W., “Characterization of Nanostructured Hollow
Polymer Spheres with Small-Angle Neutron Scattering (SANS)” Langmuir, 2002,
Vol. 245, 68-74.

Michel, M. et al., “Layer by Layer Self-Assembled Polyelectrolyte Multilayers
with Embedded Phospholipid Vesicles”, Langmuir, 2004, vol. 20, 4835-4839.

Miyawaki, J. et al., “Synthesis of Ultrafine Gd2O3 Nanoparticles Inside Single-
Wall Carbon Nanohorns”, Journal of Physical Chemistry B, 2006, Vol. 110,
5179-5181.

Mohan, Y. M. et al., “Hydrogel networks as nanoreactors: A novel approach to
silver nanoparticles for antibacterial applications”, Polymer, 2007, Vol. 48, 158-
164.

Morse, D. C. and Milner, S. T., “Statistical mechanics of closed fluid membranes”
Phys. Rev. E, 1995, Vol. 52, 5918-5945.

Nayak, S. and Lyon, L.A., Angew. Chem.International Edition, 2005, Vol. 44,
7686-7708.

Neal, S.L. et al., “Comparing organized media types using fluorescence probe
characterization methods” Anal. Chim. Acta, 1995, Vol. 307, 419-430.

http://www.bepress.com/ijcre/vol6/A62

Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 85

Nedkov, I.et al., “Influence of microstructure and preparation methods on the
magneto-crystalline structure and magnetic properties of submicron barium
hexaferrite powders”, Journal of Materials Research, 2006, Vol. 21, 2606-2610.

Niemann, B. et al., “Microemulsion-assisted precipitation of particles:
Experimental and model-based process analysis”, Chemical Engineering and
Processing, 2006, Vol. 45, 917-935.

Ninham, B. W., Evans, D. F. and Wei, G. J., “The curious world of hydroxide
surfactants. Spontaneous vesicles and anomalous micelles”J. Phys. Chem., 1983,
Vol. 87, 5020- 5025.

Note, C. et al., “Poly(ethyleneimine) as reducing and stabilizing agent for the
formation of gold nanoparticles in w/o microemulsions”, Colloids and Surfaces,
A: Physicochemical and Engineering Aspects, 2006, Vol. 290, 150-156.

Note, C. et al., “The influence of polyampholytes on the phase behavior of
microemulsion used as template for the nanoparticle formation’, Journal of
Dispersion Science and Technology, 2007, Vol. 28, 155-164.

Obare, S.O. et al., “Sensing strategy for lithium ion based on gold nanoparticles”,
Langmuir, 2002, Vol. 18, 10407–10410.

Osseo-Asare, K., “Microemulsion-mediated synthesis of nanosize oxide
materials. In handbook of microemulsion science and technology, 1999, Kumar,
P., Mittal K.L., Eds.; Marcel Dekker: New York, 549-603.

Papoutsi, D. et al., “Sol-Gel Derived TiO2 Microemulsion Gels and Coatings”,
Langmuir, 1994, Vol. 10, 1684-9.

Pileni, M.P., “Nanosized particles made in colloidal assemblies” Langmuir, 1997,
Vol. 13, 3266-3276.

Pileni, M.P., “Reverse micelles as nanoreactors”, J. Phys.Chem., 1993, Vol. 97,
6961-6973.

Pileni, Marie-Paule., “The role of soft colloidal templates in controlling the size
and shape of inorganic nanocrystals”, Nature Materials, 2003, Vol. 2, 145-150.

Published by The Berkeley Electronic Press, 2008

86 International Journal of Chemical Reactor Engineering Vol. 6 [2008], Article A62

Pillai, V. et al. “Preparation of nanoparticles of silver halides, superconductors
and magnetic materials using water-in-oil microemulsions as nano-reactors”, Adv.
Colloid Interface Sci., 1995, Vol. 55, 241-269.

Pillai, V. et al., “Structure and magnetic properties of nanoparticles of barium
ferrite synthesized using microemulsion processing”, Colloids and Surfaces, A:
Physicochemical and Engineering Aspects, 1993, Vol. 80, 69-75.

Pramaurao, E. et al., “Surfactants in analytical chemistry. Application of
organized amphiphilic media” , 1996, Elsevier.

Que, W. X.et al., “Photoluminescence characteristics of neodymium oxide
nanocrystal/titania/ormosil composite sol-gel thin films”, Applied Physics A:
Materials Science & Processing, 2001, Vol. 73, 485-488.

Ranquin, A. et al., “Therapeutic Nanoreactors: Combining Chemistry and Biology
in a Novel Triblock Copolymer Drug Delivery System”, Nano Letters, 2005, Vol.
5, 2220-2224.

Rispens et al. “Efficient Catalysis of a Diels-Alder Reaction by Metallo-Vesicles
in Aqueous Solution” Chemical Reviews, 2001, Vol. 105, 1445-1489.

Sagar, W.F.C., Controlled formation of nanoparticles from microemulsion, 1998,
Vol. 276-283.

Salgueirino-Maceira, V., “Coated colloids with tailored optical properties”, J Phys
Chem B, 2003, Vol. 107, 10990–10994.

Samuelson L, Liu W, Nagarajan R, Kumar J, Bruno FF, Cholli A, Tripathy S.
“Nanoreactors for the enzymatic synthesis of conducting polyaniline.” Synth
Met., 2001, Vol. 119, 271–2.

Santhanalakshmi, J. and Kalaivani, R., “Effect of micellar and microemulsion
media on the oxidation of iodide by peroxodisulfate reactions”, Current Science,
1995, Vol. 69, 918-924.

Santra, S. et al., “Synthesis and Characterization of Silica-Coated Iron Oxide
Nanoparticles in Microemulsion: The Effect of Nonionic Surfactants”, Langmuir,
2001, Vol. 17, 2900-2906.

http://www.bepress.com/ijcre/vol6/A62

859-868. 19. 1996. “Preparation of bismuth lead strontium calcium copper oxide (2223) superconductors”. “Chemicla analysis in nanoreactor: main concepts and applications” Journal of Analytical Chemistry. 5397–5401.. Vol. Shen. Shtykov. Langmuir. T. Y. “Study of different normal-microemulsion compositions by room-temperature phosphorescence to determine benzo[a]pyrene in environmental samples”. “Metal nanoparticle/polymer superlattice films—fabrication and control of layer structure”. Vol. Vol. 2008 .Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 87 Sauer. “Supramolecular nanotube architectures based on amphiphilic molecules. 2002. D. et al. Shimizu. Shen. 91-98. “Nano-engineered catalysts for high-temperature methane partial oxidation”. Analytica Chimica Acta. Vol. 81.. 29. 66. 987-1019. 2007. et al. 246. and Meier. 2005. 105. et al. Catalysis Today. S.et al.. “Preparation of multilayer films containing Pt nanoparticles on a glassy carbon electrode and application as an electrocatalyst for dioxygen reduction”. Published by The Berkeley Electronic Press. Vol.. Journal of Catalysis.Y. et al. 2005... M. “Polyelectrolyte multilayer nanoreactors toward the synthesis of diverse nanostructured materials”. Segura C. Shah. 1628-1634. 2003. 57. O. Adv Mater.. et al. 2004. W. 879(Carrier-Based Drug Delivery). “Preparation of Pt nanoparticles assembled in multilayer films”. Schmitt. Shen. et al. Vol. M.. X. “Morphology control of the fabricated hydrophobic gold nanostructures in W/O microemulsion under microwave irradiation”. Journal of Physics and Chemistry of Solids. et al. 1997. J.. A. 1401-1444. 474. Semagina. Vol. US patent Application: US 94-195584 19940214. 224-237. 287-296. ACS Symposium Series. N. et al. 550–551. 2002.” Chem Reviews. Vol. Progress in Polymer Science. Vol. “Synthesis of monodispersed palladium nanoparticles to study structure sensitivity of solvent-free selective hydrogenation of 2-methyl-3- butyn-2-ol”.. “Polymer nanocontainers for drug delivery”. et al.N. Schicks. 61–65. 2002. 308-314. Shi. 2003. J. Vol. 9. 2004. Chem Lett.

334. Materials Letters. K. 2004.bepress. Sun. Journal of Crystal Growth. 2006. 103. 103-107. 2007. 2005.“Anionic surfactant-assisted hydrothermal synthesis of high-aspect- ratio ZnO nanowires and their photoluminescence property”. “Synthesis of single-crystal HAP nanorods”.. L. Et al. 107. synthetic cells. Sukhorukov. Singh. Sun. Vol. 2006. Vol. Vol. 2002. Bulletin of the Korean Chemical Society. 1999. 2006. 2006.. Article A62 Silva. A: Physicochemical and Engineering Aspects. Ceramics International. Sui. Colloids and Surfaces. Vol. 2777-2782. “The synthesis and photoluminescent properties of calcium tungstate nanocrystals”.N.. “Synthesis of single-crystal HAP nanorods”. 951-954.. 1073-1080. Sim. Jae-Hyun. http://www. 1982.. 6434-6440. et al. 231-235. 32.88 International Journal of Chemical Reactor Engineering Vol. 32. Vol. 251. Vol. “Changes of the lamellar period by nanoparticles in the nanoreactor scheme of thin films of symmetric diblock copolymers”. et al. X et al. “SANS studies on the formation of PANI nanoparticles in the reverse micelles”. Y. 42-47.. et al. 27. “Synthesis and characterization of xylan-coated magnetite microparticles”. Vol.com/ijcre/vol6/A62 . et al.. “Nanoscale process systems engineering: Toward molecular factories. 1858-1869. 51. A. “Self-organization of spherical PANI/TiO2 nanocomposites in reverse micelles”. 6 [2008]. International Journal of Pharmaceutics. 12. Sun. et al. G.. H. Sohn.. 2006. and adaptive devices” AIChE Journal.. et al. et al.B.. et al. 251-254. B-H. Vol. J Phys Chem B.. 289. N. Journal of Materials Chemistry. Vol. Vol. 951-954. G. Sun. 1730-1734. “Micellar enhanced fluorimetric determination of 1-NN- dimethylaminonaphthalene-5-sulphonyl chloride and o-phthalaldehyde-2- mercaptoethanol derivatives of amino acids” Analyst (London). Y. “Hollow polyelectrolyte shells: exclusion of polymers and donnan equilibrium”. Stephanopoulos. 60. Ceramics International. et al. Vol.

Uskokovic. 28. et al.. M. Vol. Uskokovic. 2. 59-62. “Molecule-Based Magnetic Nanoparticles: Synthesis of Cobalt Hexacyanoferrate. 2007. et al. 168-174. Tirrel. Materials & Design. Tai. “Synthesis of lanthanum-strontium manganites by oxalate- precursor co-precipitation methods in solution and in reverse micellar microemulsion”. Vestal. et al.. Vaucher. G. 834-836. Vol. Vol. 501-504. Vaqueiro. “Highly Swollen Liquid Crystals as New Reactors for the Synthesis of Nanomaterials”. 2006. 266. 2008 . Uskokovic. “Synthesis of yttrium iron garnet nanoparticles via coprecipitation in microemulsion”. Vol. 615- 619. “Modular materials by self-assembly” AIChE Journal. M. Chemistry of Materials. et al. Journal of Magnetism and Magnetic Materials. et al. et al. 2005. 225-229. Published by The Berkeley Electronic Press. 2386-2390.. Y. P. Vol. Journal of Solid State Chemistry. Rare Metals. R.. Vol. 2003. “Synthesis of SrAl2O4:Eu2+. 667-672. A: Physicochemical and Engineering Aspects. “A mechanism for the formation of nanostructured NiZn ferrites via a microemulsion-assisted precipitation method”. 2006. 2007. Vol. “Normal micelle synthesis and characterization of MgAl2O4 spinel nanoparticles”. Vol. Vol.. Materials Letters.Dy3+ phosphors by the coupling route of microemulsion with coprecipitation method”. S. 25.. and Chromium Hexacyanochromate Coordination Polymers in Water-in-Oil Microemulsions”. et al “Four novel co-precipitation procedures for the synthesis of lanthanum-strontium manganites”. 1997. C. 214-220. et al. V.. 7. et al. S. 17. 2005..Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 89 Sun. Journal of Materials Chemistry. C. 303. 51. V. Vaucher. V. Vol. “Preparation of silazane grafted yttria-stabilized zirconia nanocrystals via water/CTAB/hexanol reverse microemulsion”. Nano Letters. 1505-1514. 61. Cobalt Pentacyanonitrosylferrate. and Drofenik.. Surendran. Colloids and Surfaces. 2002. 2005.. 175.

http://www. et al.. 309-14. Vidal-Vidal.. et al. D. Langmuir. Vol. Vol. 3370-3375.. 51. 280. Vol. Biomolecular Engineering. “Enzymes inside lipid vesicles: preparation. T. Chemical Reviews. 1445-1489. Electrochimica Acta. J. D. Walde. Vriezema. 82.. 143-177.90 International Journal of Chemical Reactor Engineering Vol. Wang. 675-681.et al. A: Physicochemical and Engineering Aspects. Vol. “Self-Assembled Nanoreactors”. 6527-6532. Article A62 Vestal. “Synthesis of CoCrFeO4 Nanoparticles Using Microemulsion Methods and Size-Dependent Studies of Their Magnetic Properties”. C. Wang. Chemistry of Materials. Y. B. X. 2005. Applied Physics A: Materials Science & Processing. 18.com/ijcre/vol6/A62 . et al. “Synthesis of monodisperse maghemite nanoparticles by the microemulsion method”. Xie. et al. P. “Polyelectrolyte Multilayer Nanoreactors for Preparing Silver Nanoparticle Composites: Controlling Metal Concentration and Nanoparticle Size”. A: Physicochemical and Engineering Aspects. 1995. 2002. Wang. 2001. 2006. “Nanofluids in carbon nanotubes using supercritical CO2: a first step towards a nanochemical reaction”. 2006. L. Vol. et al.. Colloids and Surfaces. 1999. Vol. 5. Journal of the American Ceramic Society. “Synthesis of nanophase oxalate precursors of YBaCuO superconductor by coprecipitation in microemulsions”. et al. 873-881. Wu. et al. 44. Vol. “Ultrafine barium titanate powders via microemulsion processing routes”. L. Xian. 637-639. Vol. 232-236. et al. et al. et al. Journal of Materials Chemistry.. Vol. 44-51. Wang. “A novel method for the preparation of Bi4Ti3O12 nanoparticles in w/o microemulsion”. “Preparation of methylene blue-doped silica nanoparticle and its application to electroanalysis heme proteins”. C. J.. Carbon.. 2006. 2006. 2002. 3817-3822.105. 288.bepress. Vol. R. 6 [2008]. reactivity and applications”. Colloids and Surfaces. “Fabrication and nano-structure control of carbon aerogels via a microemulsion-templated sol-gel polymerization method”. Vol... 80. 2005.. 14. 18.

. W... 1996. 5866-5870. 126. B... Ting. P.. 614-619. 2006. 1996. Chem. E. . S.S. N. Han. Yin. et al. Ying.. Vol. K. 5874-5879. Xu. D.. et al. “Synthesis and Magnetic Properties of BaFe12O19 Hexaferrite Nanoparticles by a Reverse Microemulsion Technique”. Vol.. 111.. Liufeng.. “Coated water soluble nanoparticles comprising an inorganic shell and semiconductor core and their preparation”. J. “Nanoparticle Architectures Templated by SiO2/Fe2O3 Nanocomposites”. Ping. Chemistry of Materials. Z. Vol. Appl. S. et al. Brasher. J. Pat. Herrington. 2004. Ratna. B. Vol. Application: US 2004-911402 20040804. 2006... M. Yoon. Journal of Physical Chemistry B. “Synthesis and Characterization of Ultrafine Tungsten and Tungsten Oxide Nanoparticles by a Reverse Microemulsion-Mediated Method”. Kaler. J. Phys.100. and Zasadzinski. L.. Yang. T. Phys.. 17255-17259.. et al. 45.. 2006.18. J. 8882-8883. Chiruvolu. Vol. 2008 . Vol. Publ.. 2005. “Sensing Behaviors of Polypyrrole Nanotubes Prepared in Reverse Microemulsions: Effects of Transducer Size and Transduction Mechanism”. 8973-8979. A. 23 pp. “Microemulsion-Based Synthesis of Titanium Phosphate Nanotubes via Amine Extraction System”. Yang. L. Vol. Journal of Physical Chemistry C.18. Vol. 2006. Yan. 14074-14077. R. Chem.. He. Qaqri. “Phase behavior of aqueous mixtures of dodecyltrimethylammonium bromide (DTAB) and Sodium Dodecyl Sulfate (SDS)” J. Wang. M. 109. Yi. H. Chemistry of Materials. “Preparation of Controllable Crystalline Titania and Study on the Photocatalytic Properties”. 100. Xijiang. K. Maoju. Journal of Physical Chemistry B. Yatcilla. et al.. “Structural and Morphological Characterization of PbS Nanocrystallites Synthesized in the Bicontinuous Cubic Phase of a Lipid” J. 110. 8673-8678. et al. 2006.Khomane and Kulkarni: Nanoreactors for Nanostructured Materials 91 Xiong. Published by The Berkeley Electronic Press. U. “In(OH)3 and In2O3 Nanorod Bundles and Spheres: Microemulsion-Mediated Hydrothermal Synthesis and Luminescence Properties”. Journal of the American Chemical Society. Inorganic Chemistry. 2007. Vol. 2211-2218. L.

“Electrodeposition of nanoscaled nickel in a reverse microemulsion”. Vol. P.39. X. Macromolecules. Vol... 142-1146. Vol. 12. 2006. Vol. Rapid Communications in Mass Spectrometry.bepress. Zhang. 3802. et al. Zuo. et al. 20. Electrochemistry Communications. 6 [2008]. 470-472. and Blankschtein. 1996. “Molecular-thermodynamic modeling of mixed cationic/anionic vesicles” Langmuir. 8.3818. C. “Chemical Synthesis of PEDOT Nanotubes”. “Highly efficient enrichment and subsequent digestion of proteins in the mesoporous molecular sieve silicate SBA-15 for matrix-assisted laser desorption/ionization mass spectrometry with time-of-flight/time-of-flight analyzer peptide mapping”. 2006. http://www. 2006. et al. K. Article A62 Yuet. H..92 International Journal of Chemical Reactor Engineering Vol.com/ijcre/vol6/A62 . D.. Zhou. 3139-3144.