Nanoreactors For Nanostructured Materials

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

2 International Journal of Chemical Reactor Engineering Vol. 6 [2008], Article A62
this direction. A number of advanced materials with cost competitiveness and

enhanced performance in sectors such as automotive and transportation, energy,
electronics and optoelectronics, separations, packaging, coating, biomedical
applications, hybrid composites for building-construction, enhanced oil recovery,
space modules etc. are poised to bring about economic transformation of the
chemical industry. 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. 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, magnetic or photo-
assisted transformation or self-assembled systems as nanoreactors for
nanostructured products are becoming important. 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.
Scientific curiosity about the behavior of matter at smaller length scales,
besides generating a significant fundamental understanding, has led to
development of a number of new advanced materials with well defined size,
structure and form that contribute and decide their unique properties. The
materials normally range from nano to micro scale and have greatly impacted
various sectors with very many applications in diversified areas. Many different
types of nanomaterials synthesized in different types of nanoreactors are
summarized in Figure 1.
http://www.bepress.com/ijcre/vol6/A62
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, 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. Classification of nanomaterials and nanoreactors in different areas.
Conducting chemical reactions in confined spaces creates an opportunity

to synthesize new materials with unexpected properties. Nature uses relatively
simple systems such as enzymes or complex assemblies such as cells to produce
different materials of desired properties. 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. Coupling of reactions in time and space with intrinsic control on the
kinetics of reactions, mass and transport of species, convection and mixing, all
together optimizes the performance to obtain final structure with minimum cost,
time and waste produced. Construction of an artificial cell while is the ultimate
target, 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.
In the past few years, research on nanosystems has developed significantly
due to their potential applications in biology, electronics, advanced materials and
information technology. The nanostructured materials exhibit novel electrical,

optical, magnetic and mechanical properties due to altered electronic structures

(Nayak et al., 2005). Synthesis of such materials in self-assembled surfactant
templates can provide a means of exercising some control on their shapes,
crystallinity and sizes which are so crucial to their properties. Surfactants with
hydrophilic polar head and hydrophobic hydrocarbon chain, when dissolved in
water can form various aggregates such as micelles, reverse micelles,
interconnected cylinders, vesicles, planer or onion like lamellar phases, spherical
or cylindrical nanocrystal etc. 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, hydrocarbon type and
chain length, operating conditions of temperature, concentration of surfactants,
extent of dilution, presence of additives, electrolytes etc. on the shape, size,
crystallinity, nature and type of self-assembly have been studied. A number of
different types of nanoparticles ranging from metals, semiconductors, polymers,
inorganic oxides etc. have been prepared in micelles (Samuelson et al., 2001),
reverse micelles (Ingert et al., 2001), liquid crystals (Delinger et al., 2001),
microemulsion (Hingorani et al., 1995; Manziek et al. 1998), microgels
(Antonietti et al., 1997), block copolymers ( Bronstein et al., 1999; Forster et al.,
2003), etc. In the rest of the paper, we shall summarily discuss these nanoreacors
along with their characteristics, methods of formation, applications to different
systems and the rationale for engineering design and analysis.
2. ORGANIZED MEDIA: SOME IMPORTANT FACTS
2.1. Normal Micelle
The literature on normal micelles is extensive and for reasons of brevity we shall
only summarize some important facts. Typical normal micelles are depicted in
Figure 2.
Figure 2. Normal micelle
• Lyophilic assemblies of colloid size; several hundreds of amphiphilic

molecules or ions of surfactants form dispersed phase that is
distributed in the bulk of the solvent phase.
• Interphase or stern layer separates the microphase of direct micelles
from the dispersion medium. The layer contains polar head groups of
surfactant and a shell of retained water molecules. The rigidity,
flexibility, water permeability, local ionic strength, electrostatic
potential, pH, etc. can be altered and depend on extent and type of
electrolyte, nature of organic solvent, cosurfactant, etc.
• The entropic factor in the Gibbs potential (ΔG=ΔH-TΔS, <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 hydrophobic
interactions drive the process and eliminates the nonpolar hydrocarbon
radicals from water and their association in the nucleus of the micellar
systems. Eliminating water contact and restructuring of water depends
on concentration of surfactant which decreases with the length of
hydrocarbon radicals.
• Micellar systems continuously undergo the formation and breakdown
processes. The half life of surfactant micelles range from a millisecond

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), where a is the surface area of head
group and ν and ι are the volume and length of alkyl chains, defines
various aggregation geometries possible. For instance 0<P<1/2, the
micelle formation is expected whereas for 1/2<P<1, vesicles may form
and for P>1 inverted structures are expected. All these geometries
have nanometer dimensions and can be used as nanoreactors. The
packing size and shape can change from spherical, rod-like to
hexagonal type as concentration of surfactant, electrolyte etc. changes.
• Solvation thermodynamics is decisive in the favorable overlap of
hydration shells of hydrophobic parts of molecules. A variety of self
assembled morphologies can result as a consequence of aggregation in
aqueous solution. 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, hydration, steric effects etc. The typical
aggregation number varies between 40 to 150.
• The presence of hydrophilic surface and hydrophilic core, 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, (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, microviscosity, charge, etc.
A number of examples illustrating synthesis of different nano particles are
included in the Table 1.
Table 1. Some experimental studies on microemulsion for nanoparticles

Sr. System Special features and applications References
No
1 An aqueous solution of Normal and reverse micelle microemulsion were used Vestal et al.,
SDS and reactant cation to synthesis single-phase CoCrFeO4 nanoparticles with 2002
mixture + methylamine a controlled size range of 6-16 nm. 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.
2 Tween 20/clove oil/water Basic acid, an unsatd. triterpene acid isolated from Lala et al., 2006
Mimusops elangii, was tested for its antileishmanial
properties both in vitro and in vivo. The in vitro
antileishmanial activity of basic acid being
encouraging, its activity in vivo was evaluated in
hamster models of visceral leishmaniasis, both in free
form, as well as incorporated in two different delivery
systems, viz microemulsions and polylactide
nanoparticles.
3 O/W microemulsion & sub-micron A process for the prepn. of an oil in water (O/W) Larm et al., 2006
emulsion process & compositions microemulsion or sub-micron emulsion compn. for
(patent) dermal delivery of at least one pharmaceutically active
ingredient.
4 An aqueous solution of SDS and Magnesium aluminate, MgAl2O4, spinel nanoparticles Vestal et al.,
reactant cation Mixture + NH4OH were synthesized using normal micelle microemulsion 2003
methods.
5 SDS/hexane/n-butanol/water Studied the presence in the environment of the Segura et al.,

SDS/hexane/n-pentanol/water polycyclic arom. hydrocarbon benzo[a]pyrene (BaP) in 2002

SDS/hexane/n-hexanol/water the city of Granada using room-temp. phosphorescence
SDS/hexane/3-pentanol/water (RTP) applied to microemulsions.
6 Microemulsion and micelle systems A microemulsion delivery system for water insol. or Dennis et al.,
containing long polymer chain sparingly water-sol. drugs comprise a long polymer 2002
surfactants and short fatty acid chain surfactant component and a short fatty acid
surfactant components for surfactant component, with the amt. of each being
solubilizing drugs selected to provide stable microemulsion or micellar
systems.
7 SDS/heptane/1-butanol/phosphate The electrophoretic behavior of five bases and Furumoto et al.,
buffer corresponding nucleosides in the oil in water (o/w) 2001
SDS/toluene/1-butanol/carbonate microemulsion capillary electrophoresis,
buffer microemulsion electrokinetic chromatog. (MEEKC),
were examd. in comparison with those in normal
capillary zone electrophoresis (CZE).
8 Phase behavior of sodium In a ternary phase diagram of sodium naphthenates Horvath-Szabo et
naphthenates, toluene, and water (SN), toluene, and water the following phases can be al., 2001
formed at 25o: normal micellar soln.; inverse micellar
soln.; lamellar liq. crystal; microemulsion; and turbid
birefringent gel phase.
9 Tween 80/pentanol/ethyl oleate Microemulsions are phys. stable oil/water systems that Al-Adham et al.,
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, toxicity, or inability to access
the site of action.
10 SDS/aromatic Water-SDS-arom.hydrocarbon-propanol Santhanalakshmi
hydrocarbon/propanol microemulsions are constructed and used as media for et al., 1995
I- oxidn. by S2O2-8 ions.
2.2. Reverse Micelle
Figure 3. 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, 1993; Pillai et
al., 1995; Kon-no et al., 1997; Adair et al., 1998; Osseo-Asare, 1999; John et al.,
2002; Capek, 2004). The biomineralization process in nature uses organized
aggregates of bio macromolecules to synthesize nanoparticles with dimensional,
morphological and architechtural specificity and excersizing full control over
nucleation, 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.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). The water to surfactant molar ratio has a
decisive influence on the diameter of the reverse micelles. The aggregation
number is typically in the range of 20 to 30, lower than in direct-micelles. The
shape can be spherical, rod-like or lamellar and depends on the concentration of
surfactant, electrolyte, other additives, etc. The droplets undergo continuous
collisions and exchange their contents.
The anionic sodium bis (2-ethylhexyl) sulfosuccinate (AOT) and nonionic
poly oxyethylated surfactants are most commonly used to generate reverse

micelles and have the advantage that no cosurfactant need be used. Also, 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. The use of nonionic surfactants also eliminates the ill-effects of
counterions. Other ionic or nonionic surfactants can also be used but must be
chosen with care to ensure their inertness in the system, interference of the
counter ions etc.
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. 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. 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, 1998). Only a small percentage
of droplet collisions therefore result in actual dimer formation and hence the
interchange mechanism is often rate controlling step. Also the reaction rate, once
the transfer occurs, is usually faster. This has the implications that the bulk
nucleation and growth models may not adequately explain the nanoparticles
formation. In fact, 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. The size of the channel containing the two
microdroplets and the surfactant film flexibility plays a significant role in the
growth process. The surfactant molecule can get adsorbed on the particle surface
and stabilize it preventing further growth. The entire surfactant film can
participate in the process especially when it is rigid. For flexible surfactant films,
the adsorption of surfactant on particles and their transfer across droplets creates
an inversion of film curvature which depends on film flexibility and elasticity.
The nanoparticles size and size distribution depends on a number of
parameters (Pileni, 1997; Lopez-Quitela et al., 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. General model that
accounts for all such parameters with Monte Carlo simulations give some generic
trends for particle size and size distribution; thus it is established that:
• Particle size and polydispersity increases with the increase of reactant
concentration
• Particle size increases with the surfactant film flexibility
• 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- controlled systems. In the other case of surfactant-controlled
systems, none of the microemulsion based parameters are involved in deciding
particle size. In such systems the adsorption behaviour of surfactants or capping
agents dictates; in fact the use of microemulsion is irrelevant and similar results
can be obtained in direct bulk solutions. Preparation of catalytic particles, where
adsorption is strong belong to this type. The presence of cosurfactant can affect
the flexibility of surfactant film and the adsorption behavior. 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 enthalpy changes on
the other hand are nearly constant. A minimum stable critical radius νc (ΔG=0) is
therefore predicted. For radius smaller than νc, the particle size is governed by
microemulsion controlled behaviour while for the radius greater than νc, the
surfactant control behaviour is followed.
The shape of nanoparticles synthesized in reverse- micelles would
normally be spherical unless some system specific special care is exercised. A
number of examples illustrating synthesis of metals, metal oxides and other
inorganic particles are included in the Table 2 (see Tables 2.1 to 2.18). Synthesis
of non spherical assemblies of nanostructures has also been the focus of attention.
Of special interest are the 1-d nanostructures (nano wires, nanotubes, nanorods,
etc.) 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. The primary mechanism responsible for the
formation of such structures involves either a template-directed growth or the
oriented aggregation. In the former, the elongated water droplet generates
elongated nuclei that grows into nanostructure with one dimension considerably
larger than the template. The nuclei formation can also occur in the
interconnecting channels. In the other mechanism, the surfactant encapsulates the
primary particles which linearly attach each other due to specific interactions
between particles, surfactants and other additives present. The intrinsic
crystallographic structure of the solid may also contribute to this mechanism.
Numerous examples that subscribe to either one of these mechanisms are reported
in the literature. A few assorted examples of nanorods, nanowires and nanotubes
are provided in the table 2. The integration of one-dimensional building blocks
into ordered superstructures produce hierarchical assembles with complex
functional architectures and hence attributes. A few of such examples (nanorods,
tubes, cubes, etc.) are also included in Table 2.

Table 2. Some experimental studies on Reverse microemulsion

Table 2.1. Some experimental studies on reverse microemulsion for nanoparticles
No
1 Cetyltrimethylammonium chloride Authors have synthesized and and studied magnetic Xu et al.,
(CTAC), n-hexanol, and cyclohexane properties of BaFe12O19 hexaferrite nanoparticles. 2007
They report the variation of elec. cond. during the
formation and reaction of microemulsion droplets
suggesting nonpercolating microemulsion conducting
systems.
2 Water/AOT/isooctane Monodispersed palladium nanoparticles have been Semagina et
synthesized to study structure sensitivity of solvent- al., 2007
free selective hydrogenation of 2-methyl-3-butyn-2-
ol .The method for isolation of monodispersed Pd
nanoparticles from a reverse microemulsion was
developed using hydrocarbon evapn. and methanol-
assisted particle purifn. from a surfactant.
3 sodiumdodecylsulfate/toluene-pentanol The influence of polyampholytes on the phase Note et al.,
(1:1)/water behavior of microemulsion used as template for the 2007
nanoparticle formation has been studied. A series of
hydrophobically modified polyampholytes by the
copolymn. of the cationic monomer (N,N'-diallyl-
N,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.
4 Nonionic surfactants, heptane and aq. salt Reverse microemulsions is used, to synthesize BiOX Henle et al.,
solns Nanosized BiOX (X = Cl, Br, I) (X = Cl, Br, I) nanoparticles. The reverse micelles act 2007
Particles as nanoscale templates for the ionic pptn. process.
5 CTAB/hexanol/water Synthesized the nanosized precursors of yttria- Tai et al.,
stabilized zirconia (YSZ) via a reverse 2007
microemulsion.
6 TX-100 + CTAB / n-butanol + n-hexanol The study demonstrates preparation of single-crystal Sun et al.,
cyclohexane /water hydroxyapatite (HAP) nanorods by the reverse 2006
microemulsion method with diam. 8-15 nm and
length 25-50 nm.
7 OP/hexanol/cyclohexane/aqueous solution Methylene blue (MB)-doped silica nanoparticles Xian et al.,
(NPs) were prepared in a reverse microemulsion and 2006
used as a novel matrix for biochem. application.
8 Triton X-100/ n-hexane/ n-hexanol/water W/O microemulsion was used to prepare nanoscaled Zhou et al.,
nickel by direct electrodeposition, Ni nano-particles 2006
were modified onto the Ni substrate. Further they
studied the cathodic process of Ni2+ in the W/O
microemulsion .
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. et al., 2006
phase contains only metal ions (Fe2+ and Fe3+).
Further, the microstructure and size control of iron
oxide nanoparticles was studied.
10 OP (polyethylene glycol p-octylphenyl Nanometer-sized Bi4Ti3O12 particles by chem. Xie et al.,
ether, t)/ cyclohexane /n-butanol/water reaction of Bi(NO3)3.5H2O, Ti(SO4)2, and NH3 soln. 2006
in a reverse microemulsion system has been reported.
11 (Igepal CO 520, AOT, TOPO)/ A method for synthesiszing polyaniline nanoparticles Jae-Hyun et
(Cyclohexane/cyclopentane/ using reverse microemulsion process has been al., 2006
cycloheptane)/ Water reported.

12 Brij-30/n-heptane Ultrafine tungsten and tungsten oxide powders with Xiong et al.,
Triton X-100/n-hexanol /cyclohexane. controllable particle size and structure was prepared 2006
by a reverse microemulsion-mediated synthesis
method.
13 Triton X-100/cyclohexane /n- A synthesis method for nanocryst. lithium silicate by Khomane et
hexanol/water coupling of sol-gel method in reverse microemulsion al., 2006
is reported. The nanoparticle prepd. in the
microemulsion shows enhanced CO2 sorption
capacity and shorter retention times at higher temp.
14 DBSA/iso-Pr alc./isooctane/water The study fabricates the pyrrole-oligomer Han et al.,
nanoparticles doped dodecylbenzenesulfonic acid 2006
(DBSA) in reverse microemulsion, DBSA plays the
roles of both surfactant and dopant.
15 Mixt. of Span80 and Tween80/ Authors have successfully prepd.Nano-sized Guo et al.,
theolin/butanol/water monoclinic sulfur particles via the chem. reaction 2006
between sodium polysulfide and hydrochloric acid in
a reverse microemulsions system.
16 Coated water soluble nanoparticles Core-shell nanoparticles and methods of making Ying et al.,
comprising an inorganic shell and these nanoparticles are provided. The nanoparticles 2006
semiconductor core and their preparation may include semiconductor nanocrystals. A shell
may encapsulate a nanoparticle core, and may
include a non-org. material, esp. silica.
17 Polyoxyethelyne(5)nonyphenyl ether/ Using reverse microemulsion techniques combined Yi et al.,
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.
Table 2.2. Reverse microemulsion as nanoreactor

No
1 Cetyltrimethylammonium bromide/ n- 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.,
sulfosuccinate)/isooctane/water indium-tin oxide (ITO) particles in reverse 1999
microemulsions is reported. The study further shows
that tin mols. are doped into the indium oxide
homogeneously rather than forming a discrete tin
oxide domain in indium-tin oxide particles formed in
microemulsions.
Table 2.3. Reverse microemulsion for nanorods
No
1 Triton X-100/cyclohexane /n-hexanol Ba0.7Sr0.3TiO3 nanorods in reverse microemulsion at Chen et al.,
/water room temp. The tuning of the size of nanorods by 2007
changing w value (molar ratio of water to surfactant),
aging time and reactant concn is reported .
2 TX-100 + CTAB/ n-butanol + n-hexanol / A simple system for the synthesis of single-crystal Sun et al.,
cyclohexane/water hydroxyapatite (HAP) nanorods by the reverse 2006
microemulsion.
3 SDS/cyclohexane/ n-Amylalcohol Pure γ-phase CuI nanorods. by reverse Li et al.,
microemulsions using low temperature. 2006
4 CTAB/cyclohexane/H2O Authors have explained the methods to synthesize Li et al.,
and NP10/cyclohexane/H2O the BaCO3 nanorods and nanobelts in reverse 2006
microemulsion. From various comparison expts.

Authors have shown that several exptl. parameters,

such as the concn. of surfactant and reactant, and
solvent hydrothermal treatment play important roles
in the morphol. control of BaCO3 nanostructures.
Table 2.4. Reverse microemulsion for nanotubes
No
1 AOT /hexane/water Authors have shown the fabrication method for Yoon et al.,
polypyrrole (PPy) nanotubes with different diams. 2006
using cylindrical micelle templates in reverse
microemulsions. They further studied electronic
response PPy nanotubes with various diameters
2 AOT /hexane/water Authors have described a convenient one-step Zhang et al.,
method to chem. prep. bulk quantities of microns 2006
long poly(3,4-ethylenedioxythiophene) (PEDOT)
nanotubes using reverse microemulsion polymn., the
use of potential-time profiling to uncover factors that
favor tubular polymer growth, the prepn. of PEDOT-
metal and PEDOT-metal oxide composites having
tubular morphol., and transport properties and
potential device applications of individual PEDOT
tubes.
3 TOA/H3PO4 Titanium phosphate nanotubes with alternating Yin et al.,
interlayer spacings have been synthesized in a 2004
reverse microemulsion formed in an amine extn.
system.
4 AOT /hexane/water Polypyrrole (PPy) nanotubes by reverse Jang et al.,
microemulsion polymn. in an apolar solvent in the 2003
presence of FeCl3 and sodium bis(2-

ethylhexyl)sulfosuccinate have been reported, and
factors affecting the formation of PPy nanotubes
have also been investigated.
Table 2.5. Reverse microemulsion for nanowires
No
1 SDS/water/heptane/n-hexane The study reports the synthesis of ZnO nanowires Sun et al.,
with high-aspect-ratio of up to ca. 600 in a 2006
quaternary reverse microemulsion contg. via a
hydrothermal method. The role of SDS in the
formation of morphologies has been ellucided.
2 CTAB/BuOH/n-heptane/HAuCl4(aq.) The hydrophobic Au nanostructures with different Shen et al.,
shapes have been prepared by using BuOH situ redn. 2005
in W/O microemulsion through microwave dielec.
heating.
Table 2.6. Reverse microemulsion as a template
No
1 Marlophen NP5 (RO(CH2CH2O)xH, x =5, To synthesize BiOX (X = Cl, Br, I) nanoparticles Henle et al.,
R = nonylphenyl, M= 440 g/mol, SASOL ) Authors have used Reverse microemulsion. The 2007
/ n-heptane /water reverse micelles act as nanoscale templates for the
ionic pptn. process.
2 SDS/toluene-pentanol (1:1)/water Present work focuse on the use of branched Note et al.,
poly(ethyleneimine) (PEI) as reducing as well as 2006
stabilizing agent for the formation of gold
nanoparticles in different media. The reverse
microemulsion droplets of the quaternary system

were successfully used for the prepn. of gold

nanoparticles
3 SDBS/ dimethylbenzene/ water Solvothermal synthesis of hollow nanostructure, Lu et al.,
hollow spindle-like hematite with uniform size and 2006
morphol. The formation mechanism as a
coordination-assisted dissoln. process occurred in a
reverse microemulsion system.
4 Polyoxyethelyne(5)nonyphenyl ether/ Using reverse microemulsion techniques combined Yi et al.,
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.
5 AN/ PPO19–PEO33PPO19 /NMP Mesoporous polymer materials can be fabricated Jang et 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.
Microemulsion Methods
Table 2.7. Reverse microemulsion co-precipitation
No
1 Triton X-100 /n-heptane/ hexanol and an Ce-Cu mixed oxide precursors with varing Ce:Cu at. Fuerte et al.,
aqueous solution of cerium and copper ratio have been prepd. by freeze-drying and 2007
nitrates. microemulsion copptn.
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., 2007
by two different methods (impregnation of ceria and
copptn. of the two components within reverse
microemulsions) have been examd. with respect to

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

was subsequently calcined under various conditions

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

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

inorg. bases. A strong base, NaOH, and a

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

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

CTAB/n-hexane/water
CTAB/n-octane/water
CTAB/n-decane/water
24 Triton N- 10 1/ cyclohexane / hexanol / aq. water-in-oil microemulsions in which monodisperse Chang et
NH40H. silica colloids are produced by the controlled al., 1994
hydrolysis of tetra-Et orthosilicate (TEOS) in water
Igepal CO-520 /cyclohexane / aq. NH40H. nanodroplets. The resulting pure silica spheres can
be grown to 40-80 nm diam. and can be used as seed
particles for prodn. of larger silica colloids upon
further reactions with TEOS in the microemulsion.
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.,
successfully been used to synthesize lanthanum and 1994
nickel oxalate particles, which could readily be
processed to form a fine LaNiO3 powder.
26 CTAB/ n-butanol/ octane/ Water Nanoparticles of barium ferrite (BaFe12O19) were Pillai et al.,
synthesized using a novel method called 1993
microemulsion processing. In this process, the aq.
cores (typically 5-25nm in size) of water-
cetyltrimethylammonium bromide-n-butanol-octane
microemulsions were used as constrained
microreactors for the co-pptn. of precursor
carbonates (typically 5-15nm in size).
27 Igepal CO-430/ cyclohexane / aqueous A method is presented for prepn. of ultra- Kumar et
solution of metal salts Y:Ba:Cu=1:2:3 homogeneous nanoparticles of precursor oxalate al., 1993
powders by copptn. in the aq. cores of water-in-oil
Igepal CO-430 / cyclohexane / aqueous microemulsions for the prepn. of YBa2Cu3O7-x (123-
solution of oxalic acid phase) superconductors.
28 water-in-oil microemulsion The authors describe a new technique for the Kumar et
synthesis of ultrahomogeneous nanoparticles of al., 1993
precursor oxalate powder by copptn. in the aq. core
of a water-in-oil microemulsion for the prepn. of Bi-
Pb-Sr-Ca-Cu-O (2223) oxide superconductor
Table 2.8. Reverse microemulsion and hydrothermal

No
1 Triton X-100 /cyclohexane / 1-hexanol Nitrogen-doped TiO2 nanocatalysts with a Cong et al.,
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. compds. such as
triethylamine, urea, thiourea, and hydrazine hydrate.
2 SDS/cyclohexane/n-hexanol/water The zircon-type tetragonal (t-) LaVO4 nanowires were Fan et al.,
controlled synthesized by a new approach, a 2007
microemulsion-mediated hydrothermal method, in
which the aq. 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.
3 CTAB/n-octane/n-butanol/water The single crystal octahedra of tetragonal CdMoO4 Gong et al.,
were synthesized on large scale via a microemulsion- 2006
mediated hydrothermal route at 120ofor 10 h.

4 CTAB/ water/cyclohexane/n-pentanol Indium hydroxide, In(OH)3, nano-microstructures Yang et al.,

with two kinds of morphol., nanorod bundles and 2006
caddice spherelike agglomerates, were successfully
prepd. by the cetyltrimethylammonium bromide
(CTAB)/ water/cyclohexane/n-pentanol
microemulsion-mediated hydrothermal process.
5 CTAB/ water/cyclohexane/n-pentanol CaWO4 nanocrystals with av. diams. of 20-30 nm and Sun et al.,
nanorods with mean lengths of 600-1000 nm were 2006
controllably synthesized through a facile
microemulsion-mediated hydrothermal procedure.
6 CTAB/ water/cyclohexane/n-pentanol Octahedral BaWO4 microparticles were prepd. via a Liu et al.,
simple microemulsion-mediated hydrothermal 2005
procedure.
7 Triton X-100 /cyclohexane / n-hexanol / Nanocryst. TiO2 catalysts with different anatase/rutile Yan et al.,
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. at low temp. by the microemulsion-
aqueous phase. mediated hydrothermal method.
8 CTAB/ toluene/butanol/water The crystal morphol. of silicalite-1 was adjusted Lin et al.,
through a microemulsion-based hydrothermal 2005
synthesis. The surfactant cetyltrimethylammonium
bromide (CTAB) with cosurfactant butanol was used
to form water-in-oil microemulsions contg. the
silicalite-1 synthesis gel. The crystal morphol. of
silicalite-1 was adjusted from coffin-shaped to novel
rod-shaped and to irregular-shaped nanoparticles by
varying the microemulsion compn.
9 CTAB/ n-hexane/ n-pentanol /water Well-dispersed cryst. SnO2 nanoparticles were prepd. Chen et al.,
by a novel and simple water-in-oil (w/o) 2004
microemulsion-assisted hydrothermal process, using

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

silicalite-1 synthesis gel.

Table 2.9. Reverse microemulsion precipitation
No
1 Non-ionic emulsifier based on The prepn. of titania nanosized spherical powders DeBenedetti
polyethylene glycol hexadecyl ether/light through a microemulsion pptn. method was et al., 2006
mineral oil/water investigated. The process is based on the pptn. of
particles from a soln. contg. low-cost precursor,
previously emulsified in an immiscible liq. The ppts.
were obtained dropping an aq. soln. of TiCl4 into a
stable microemulsion contg. a light mineral oil and a
surfactant.
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., 2006
droplets by a detailed exptl. and theor. anal. of the
pptn. of calcium carbonate (CaCO3) and barium
sulfate (BaSO4).
3 CTAB/1-hexanol/water Nanostructured NiZn ferrites were synthesized using Uskokovic
two different techniques: first, a pptn. procedure in et al., 2005
the reverse micelles of a CTAB/1-hexanol/H2O
microemulsion, and second, pptn. in a bulk aq. soln.
Table 2.10. Reverse microemulsion sol-gel
No
1 TX 100/cyclohexane/n-hexanol/water report on the synthesis of nanocryst. lithium silicate Khomane et
by coupling of sol-gel method in reverse al., 2006
microemulsion.
2 CTAB/resorcinol/formaldehyde/water Carbon aerogels were successfully fabricated by a Wu et al.,
microemulsion-templated sol-gel polymn. method. 2006

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

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., 1994
isopropoxide. Three types of fine water dispersions
have been used as the base sol: reverse Triton X-100
micelles in cyclohexane; quaternary water-in-oil
microemulsions contg. cyclohexane, 1-pentanol,
sodium dodecyl sulfate, and water; and dispersions of
water in pentanol in the presence of sodium dodecyl
sulfate.
MICROEMULSION STRUCTURE
Table 2.11. Nanotubes as nanoreactors
No
1 Thermal reaction process using CNTs as Fabrication of high-quality, large-yield, single- Hu et al.,
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.e. Gd-acetate clusters inside SWNHs et al., 2006
were transformd into ultrafine Gd2O3 nanoparticles
3 Carbon nano tubes Nanofluids were obtained by filling carbon nanotubes Wang et al.,
with toluene using supercritical carbon dioxide. The 2005
method claims as a novel route to developing
nanoscale chemical reactions using CNTs as
nanoreactors.
4 Nanowires of FexB prepared by boriding Carbon nanotubes as nanoreactors for building iron Han et al.,
Fe nanowires which were encapsulated in nanowires. 2000

carbon nanotubes (CNTs)
Table 2.12. Core Shell Structures

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. Microstructures are hydrolyzed to give
polymeric nanotubes with potential applications in
drug delivery and as nanoreactors.
Table 2.13. Drug Delivery systems
No
1 poly(2-methyloxazoline)-block- The research is mainly focused on triblock Ranquin et
poly(dimethylsiloxane)-block-(2- copolymeric nanoreactors as alternative for al., 2005
methyloxazoline) triblock copolymers. liposomes as encapsulating carrier for prodrug
activating enzymes. The study demonstrated efficient
cleavage of three natural substrates and one prodrug,
2-fluoroadenosine, by the nanoreactors.
2 Polymer nanocontainers for drug delivery This review focuses on applications of triblock Sauer et al.,
copolymers in the drug delivery system such as 2004
enzyme encapsulation and gene transfection
isdiscussed and illustrated using model systems.
Table 2.14. Hydrogels
No
1 Hydrogel networks based on N- Authors have prepared hydrogel and synthesized Mohan et

isopropylacrylamide (NIPAM) and sodium highly stable and uniformly distributed silver al., 2007
acrylate (SA) nanoparticles which can be effectively employed as
antibacterial material
Table 2.15. Mesoporous Silicates
No
1 Mesoporous molecular sieve silicate SBA- A highly efficient enrichment and subsequent tryptic Zuo et al.,
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. The procedure allows
for rapid protein enrichment and digestion inside
SBA-15, and has great potential for protein anal.
2 Mesoporous high-aluminum The study synthesized Ag/AlxSi1-xO2-0.5x Kolesnik et
aluminosilicate matrices nanocomposite materials by using mesoporous high- al., 2004
aluminum aluminosilicate matrices as nanoreactors.
3 Cationic Surfactant-Templated The work reviews the phys. chem. of soln. silicate Lin et al.,
Mesoporous Silica species and surfactants in the synthesis of 2002
mesoporous silicas.
4 Mesoporous MCM-41 materials in The channels of the mol. sieve are employed as Lee et al.,
aqueous solution nanoreactors to study free radical attacks on C60 in 2002
aq. media and further reveal the proximity effect of
free radical reactions in a nano-restricted
environment.
5 Mesoporous silica SBA-15 A method for prep. of highly conductive Lim et al.,
polypyrrole/poly(Me methacrylate) nanocomposite. 2001
Compression-molded nanocompostie exhibited elec.
cond. of 1.7 S/cm and very highly oriented and uni-

directional structures.
Table 2.16. Micro reaction Cages
No
1 Micro Reaction Cages with Tailored Hollow polyelectrolyte capsules were prepared in Daehne et
Properties micro- and submicrometer size from melamine resin al., 2001
capsules coated by several layers of poly (Na
styrenesulfonate) and poly(allylamine-HCl). The
modified walls behaved like ion exchange
membranes and showed selectivity toward adsorption
and permeation of org. ions. The study shows that
modified capsules offer many possibilities for novel
applications as containers for controlled pptn., as
nanoreactors for catalyzed reactions, or as sensors.
Table 2.17. Self Assembly

No
1 Self-Assembled Nanoreactors A review of work on mol. nanoreactors (capsules and Vriezema et
boxes, micelles, vesicles), macromol. nanoreactors al., 2005
(polymersomes, polymer micelles), and
biomacromol. nanoreactors (protein cages, viruses)
2 Surfactant templated silica mesophases Authors have prepared surfactant templated silica Gibaud et
mesophases belong to the class of self-assembled al., 2003
materials that exhibit long range ordered two-
dimensional (2D) hexagonal, three-dimensional (3D)
hexagonal, or 3D cubic mesostructures when the

compn. of the initial deposited soln. and its aging

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

nanoparticles self-organized into sea urchin-like
shape
Table 2.18. Soft colloidal templates
No
1 Soft colloidal templates (reverse micelles) Colloidal solns. were assumed to be very efficient Pileni et al.,
templates for controlling particle size and shape. It is 2003
also shown that large no. of groups used reverse
micelles to control the size of spherical nanoparticles.
This makes it possible to determine the various
parameters involved in such processes, and
demonstrates that nanoparticles can be considered to
be efficient nanoreactors.

2.3. Vesicles
Figure 4. Vesicles
Surfactants self-assemble in aqueous solution due to presence of dual

functionality viz. the hydrophilic and the hydrophobic parts and can acquire a
variety of morphologically different structures. The urge to minimize contact with
water for the hydrophobic groups is responsible for the aggregation process. A
number of different structures are possible ranging from spherical to rod-like to
bi-layers. The packing factor, as explained earlier, broadly decides the actual
shape and for P >1/2 vesicle formation is predicted. In bi-layers, 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. The opposite open ends of the
planar structure can join together creating a closed environment within. These
structures as depicted in Figure 4 are called vesicles. 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), also called as small unilamellar
vesicles (SUV) or R= 50nm to 10µm, also called as large unilamellar vesicles
(LUV). The radius of curvature decides the small or large vesicles. The
unilamellar vesicles form the uniform homogeneous solution also called as L4
phase. As the surfactant concentration increase, multilamellar vesicles- containing
concentric shells such as in onions are formed. On further increase in
concentration the structure transforms into planar bilayers. The various structures
may also co-exist in equilibrium in what appears to be a homogeneous solution on
macroscopic scale.
Surfactants that can form bilayers in solution are thus essential for vesicle
formation. Small head groups with bulky hydrophobic parts can meet the packing
requirements of the surfactant in solution and are therefore the possible
candidates. Typically double chain hydrocarbon surfactants such as normal

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

present have been reported (Kamenka et al., 1992; Kaler et al. 1989). The
classical catanionic systems containing admixture of cationic and anionic
surfactants forms vesicles over a wider range. 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. The vesicles formation occur through the formation of precipitate
which turns to vesicles on heating. Alternatively for excess of anionic or cationic
surfactants a unilamellar vesicle can be formed. The nature of surfactant head
groups, their chain lengths, counter ion presents etc. will have a decisive influence
on the process. 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.
Spontaneous formation of vesicles has also been observed for some
nonionic single chain surfactants. The vesicles can be stabilized by addition of
cosurfactant, stiff rod-like amphiphiles, surfactants with polymeric hydrophilic
head groups, ionic surfactants etc. In addition to the aqueous phase, vesicle
formation in organic solvents and their organometallic complexes has also been
known. Table 3 illustrates a few assorted examples. The spontaneous formation of
vesicles and their transformation to structurally different forms under the
influence of change in surfactant type and concentration, counterions present, pH,
temperature, shear, ionic strength etc. are system specific as described by its
phase behavior. The dynamics of structural formation and transformation are
inadequately understood. The experimental evidence suggests that the micellar to
vesicle transformation proceeds through the rod-like and/or disc-like aggregates
as intermediate structures. The vesicle may gel by a slow ordering process to form
glassy structures. Such transformation process can occur at time scales slower or
faster and different probing techniques such as conductivity measurements, light
scattering, various spectroscopies etc. can reveal their kinetics. The issues of
transitions to different structural forms are also related to their thermodynamic
stability. At least in some situations and especially for unilamellar vesicles
thermodynamic stability seems to be well established. The control of size, size
distribution, structure and properties of vesicle is possible through control over
their preparation process.
Table 3. Some experimental studies on vesicles

No
1 Phase behavior and structural studies of The SDBS/CTAT mixture has many features that Kaler et al.,
one such mixture, sodium appear to be common to aqueous mixtures of 1992
dodccylbenzenesulfonate (SDBS) and asymmetric cationic and anionic surfactants. Vesicle
cetyl trimethylammonium tosylate formation apparently results from the production of
(CTAT) in H2O. an anion-cation surfactant pair which then acts as a
double-tailed zwitterionic surfactant. Although
unilamellar vesicles have been created by numerous
physical and chemical techniques from multilamellar
dispersions, all such vesicle systems revert to the
equilibrium, multilamellar phase over time.
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. These rodlike al., 1993
symmetric tail groups: sodium dodecyl micelles are transformed abruptly into vesicles over
sulfate and dodecyltrimethylammonium a very narrow composition range. For this symmetric
bromide. system, formation of hydrated crystals of 1: 1
anion/cation surfactant dominates the phase
behavior. 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.
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., 1996

charged surfactants microstructures (e.g., liquid crystalline and

cetyltrimethylammonium bromide precipitate phases), 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. Bilayer properties of the
vesicles depend on the ratio of CTAB to SOS, with
CTAB-rich bilayers stiffer than SOS-rich ones.
4 Amphiphilic ion pairs, derived from a Ion-pair amphiphiles represent a new and unique Fukuda et al.,
series of trimethyl-n-alkylammonium class of vesicle-forming surfactants that warrant a 1990
bromides and saturated fatty acids, form detailed examination from both a theoretical and
vesicles upon sonic dispersal in water. practical standpoint. Unlike conventional double-
chain surfactants, however, 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.
5 Versatile self-vesiculating amphiphile Vesicle formation from catanionic micellar mixtures Ambühl et
system based on amino acid surfactanta was confirmed by freeze fracture electron al., 1993
microscopy and quasi-elastic light scattering
measurements. Molecular reorganization of the N-
methylated amino acid headgroups upon vesiculation
(E- end 2-configuration equilibrium) was revealed
by using sodium N-lauroylsarcosinate as anionic
component.
6 Vesicle Formation from Aqueous Spontaneous vesicle formation in the aqueous Kondo et al.,
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, transmission electron microscopy,
glucose trapping experiments, 5 potential
measurements, and surface tension measurements.

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

their fusion once deposited on the multilayer surface.

11 Enzymes inside lipid vesicles This study focuses on preparation, reactivity and Walde, et al.,
applications of enzymes in lipid vesicles and reports 2001
no. of methods that can be used for the prepn. of
enzyme-contg. lipid vesicles (liposomes) which are
lipid dispersions that contain water-sol. enzymes in
the trapped aq. space. This has been shown by many
investigations carried out with a variety of enzymes.
12 Self-assembly of regular hollow Salt-free mixts. of anionic and cationic surfactants, Dubois et al.,
icosahedra in salt-free catanionic solutions such bilayers can self-assemble into hollow 2001
aggregates with a regular icosahedral shape. These
aggregates are stabilized by the presence of pores
located at the vertices of the icosahedra. The
resulting structure have a size of about one
micrometer and mass of about 1010 daltons, making
them larger than any known icosahedral protein
assembly or virus capsid.
13 Nanostructured Hollow Polymer Spheres Hollow polymer spheres synthesized from a vesicle- McKelve et
directed polymerization can be dried and redispersed al., 2002
in water using a variety of nonionic ethoxylated
alcohol surfactants as stabilizers. The final
dispersions consist of both polymer shells and
surfactant micelles, which remain together in
colloidal suspension for at least several months.
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
micelles.
14 Statistical mechanics of closed fluid The work discusses the statistical mechanics of Morse et al.,
membranes systems, such as vesicle phases, that consist of many 1995
closed, disconnected fluid membranes. It is shown
that the internal undulation free energy of a single
such membrane always contains a logarithmically
scale-dependent ‘‘finite-size’’ contribution, with a
universal coefficient, that arises essentially from the
absence of undulation modes of wavelength longer
than the size of the surface. The study briefly
discusses the conceptually related problem of a
polydisperse ensemble of fluctuating one-
dimensional aggregates, such as rodlike micelles, for
which they obtain the experimentally observed
scaling of micelle size with concentration. It is
concluded by discussing the application of the
results to the interpretation of recent experiments on
equilibrium vesicle phases.
15 Thermodynamics of Unilamellar Vesicles The influence of mixing on the curvature free energy Bergström.,
of a thermodynamically open, 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, average
composition in the bilayers, etc).
16 Stability of spontaneous vesicles Equilibrium unilamellar vesicles are stabilized by Jung et al.,
one of two distinct mechanisms depending on the 2001

value of the bending constant. Helfrich undulations

ensure that the interbilayer potential is always
repulsive when the bending constant, K, is of order
kBT. When K 〉〉 kBT, unilamellar vesicles are
stabilized by the spontaneous curvature that picks
out a particular vesicle radius; other radii are
disfavored energetically. Adding electrolyte to the
sodium perfluorooctanoate/CTAB vesicles leads to
vesicles with two bilayers; 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.
17 Effect of Surfactant Tail-Length The recently developed molecular-thermodynamic Yuet et al.,
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. The theory accounts for the
essential free-energy contributions to the free energy
of vesiculation, gves, with particular emphasis on
their relative importance and interplay in the process
of vesicle formation. It is shown that mixed
surfactant vesicles can be stabilized energetically in
highly asymmetric surfactant mixtures, such as those
consisting of CTAB and sodium pentyl sulfate
(SPS).
The complex-vesicular based structures are one amongst the principal

structures formed when lipids, proteins and polymers self-assemble in solution.
Such closed bilayers are prototype examples and a model system for
understanding cell membranes. The possibility to encapsulate active molecules
within it makes them interesting for drug delivery and bilayer medicine, gene
therapy and variety of other pharmaceutical and cosmetic applications.
The surface of a vesicle is more organized than that of a micelle and can
be used as a seat for chemical transformation. Likewise interior of a vesicle can
be used as nanoreactor for some reactions. The molecular properties of a vesicle
interface with water is sensitive to additives, impurities, hydrodynamics and other
such factors and can change its activity for chemical transformation. 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. The changed
microenvironment at the substrate binding site is expected to contribute to such
measures. The counterions, besides charge compensation, can also act as a
catalyst for some systems. Metal complexes attached to vesicular surfaces provide
examples illustrating the role of substrate binding sites and counterions effect. A
number of examples such as Cu(II) vesicles for Diels-Alder reaction (Rispens et
al., 2001), Cytochrome 450 (Groves et al., 1995) - an enzyme containing Iron (III)
protoporphyrin complex (Mansuy, 1994; Feiters, et al., 2000) and active for
oxidation, dehydrogenation, oxidative formylation, dehydration reactions, the
manganese (III) tetra hexadecyl phenyl porphyrin chloride complex for regio
selective epoxidations of steroids, the rhodium (III) formate system for reducing
molecular oxygen, Hemocynin system (Klein et al., 2001) for oxidative
degradation of ligand, amphiphilic diphosphene ligands along with their rhodium
complexes for hydroformylations etc are known.
The other set of reactions use the interior of vesicles as a nanoreactors for
conducting enzymatic reactions. The catalysts (enzyme) are embedded within the
inner compartment while the substrate moves from the bulk solution crossing the
membrane barrier. It is imperative that the enzyme and the membrane wall should
be sufficiently stable and not degrade, at least over the period of transformation.
Also, external factors such as pH, temperature, ionic strength etc. should not
destabilize the system. A number of different techniques for preparing the
nanoreactor assembly, ranging from simple mixing of various ingradients, 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 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. The characteristic properties of the substrate,
product and the surfactant material forming the bilayers also plays important role.

Synthesis of a number of bimolecules ranging in complexity from simple

glycogen to complete protein synthesis has been reported in vesicles. The
technique of encapsulating necessary enzymes along with other required
components holds the key to successive synthesis of complex biomolecules. A
few assorted examples are included in table 3.
A number of different methods to improve the stability of vesicles are also
developed. They include the use of vesicle membrane as a template to organize
monomers and then polymerize them improving the stability to mechanical,
chemical and attack from digestive enzymes. Other techniques include use of
fluorinated lipids, non-ionic sugar lipids and mechanical and thermal treatments.
2.4. Polyelectrolyte Multilayer Capsule (PEMC)
The technique of layer-by-layer (LbL) self assembling of charged polyelectrolytes

(PE) on to planer or colloidal structures, allow to create nanovessels with a direct
control on their thickness and 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, morphologies etc. The
outside shell can also be used to anchor different materials such as dyes, metal
alkoxides, nanoparticles etc. Small molecules can be easily incorporated into the
polyelectrolye film (~Mw 4000) and transformed. The oppositely charged PEs
interweave to create void spaces that act as a reactor. A number of nanostructures
of metals, metal oxides/hydroxides, semiconductors etc. are prepared using planer
polyelectrolyte films. Likewise coated colloids can be used to fabricate hollow
spheres and 2-d and 3-d microporous material. The fabrication of polyelectrolyte
multilayers involves the simple principle of electrostatic interactions between
oppositely charged PEs as the driving force; 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 layer-by-layer
deposition can be continued in a controlled manner to achieve desired thickness,
composition, permeability etc. The thin films so produced have potential
applications as bioactive films, electrochromic membranes, LED, pattering etc.
Likewise the colloids can be subjected to LbL deposition to generate hollow
capsules of varied thickness and morphologies. It is possible to replace one
charged PE component with charged preformed inorganic nanoparticle layer.
Areas such as catalysis, drug delivery, separation materials, chromatography,
coating, biosensing etc. can immensely benefit from this approach.
Nanoparticles are usually embedded in a solid matrix or polymer thin
films for them to be usuable in practice. The simple procedure involves mixing of
polymers and nanoparticles; however the structures so created can often be
inhomogeneous. The other method requires the preparation of the nanoparticles
with appropriate charges and surface modifications in stabilized media and then
uses the LbL approach to create orderely and homogeneous films containing
nanoparticles. The LbL technique allows control on the film thickness by
adjusting deposition cycles; however the control on size of the particle during and
after film formation is difficult. The technique of in-situ synthetic approach on the
preformed film can become advantageous and a number of particles of metals,
metal oxide/hydroxides semiconductors etc. are prepared using this technique. A
few assorted examples are listed in Table 4.
The LbL colloidal templating approach can be employed on the preformed
polyelectrolyte layers onto colloids to produce uniform core-shell particles and
hollow spheres. 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,
hydrolysis, sol-gel reactions, polymerizations or thermal oxidation etc. Again a
few assorted examples are included in the table 6. 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, pore diameter are available in
the literature.

Table 4. Some experimental studies on Polyelectrolyte Multilayers

No
1 Polyelectrolyte Capsule The study demonstrates result of the synthesis of two types of Choi et al., 2005
Nanoreactors nanoparticles, these specially designed PEMCs contg. both (131)
silver and goethite nanocrystals can be used as antimicrobial
capsules, which can move by an external magnetic field. Such
a technology has the potential for use in sterilization at the
desirable sites.
2 Silver nanocomposite Multilayer thin films, prepared through the sequential Liu et al., 2005
multilayer films electrostatic deposition of a pos. charged third-generation (132)
poly(amidoamine) dendrimer (PAMAM) and neg. charged
poly(styrenesulfonate) (PSS) and poly(acrylic acid) (PAA),
were utilized as nanoreactors for the formation of silver
nanoparticles.
3 Polyelectrolyte multilayer The recent advances in the synthesis and characterization of a Shi et al., 2004
variety of nanostructured materials generated by using (133)
polyelectrolyte multilayers assembled onto both planar and
colloidal substrates as nanoreactors have been discussed.
4 Poly(acrylic acid) & poly Polyelectrolyte multilayer nanoreactors for preparing silver Wang et al., 2002
(allylamine hydro chloride) nanoparticle composites. (134)
multilayer films
5 Hollow Polyelectrolyte Hollow polyelectrolyte capsules were fabricated by means of Sukhorukov et al.,
Shells stepwise adsorption of polyelectrolytes followed by 1999
dissolution of the templating core. The capsule wall thickness
was approximately 20 nm. The diameter of the capsules is
given by the size of the templates (3.3 μm). These capsules
exclude poly(styrenesulfonate) (PSS) from a molecular weight
of 4200 upward but are permeable for small ions and 6-

carboxyfluorescein (6-CF). By means of adding PSS in acidic
form to the bulk solution, a Donnan equilibrium between the
bulk and internal solution encapsulated within the capsules
was created.
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. However, 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.
7 Hollow Polymer Shells by The study describes a method for constructing hollow Donath et al.,
Colloid-Templated polyelectrolyte shells by colloid-templated consecutive 1998
Assembly of polyelectrolyte adsorption followed by decomposition of the
Polyelectrolytes templating core. Micron-size polyelectrolyte shells of
poly(sodium styrenesulfonate) (PSS) and poly(allylamine
hydrochloride) (PAH), with thicknesses ranging from a few to
tens of nanometers, have been produced.
8 Hollow Capsule Processing Hollow polymer, inorganic and inorganic - organic composite Caruso., 2000
through Colloidal capsules of submicrometer to micrometer size have been
Templating and Self- 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. The figure shows a TEM image of a cross-section
of hollow inorganic capsules. The geometry, size, wall

thickness and composition of the hollow capsules can be

readily controlled.
9 Nanoengineering of The creation of core-shell particles is attracting a great deal of Caruso., 2001
Particle Surfaces interest because of the diverse applicability of these colloidal
particles; e.g., as building blocks for photonic crystals, in
multi-enzyme biocatalysis, and in drug delivery. This review
presents the state-of-the-art in strategies for engineering
particle surfaces, such as the layer-by-layer deposition process,
which allows fine control over shell thickness and
composition.
10 Inorganic and hybrid Hollow silica and silica-polymer spheres with diameters Caruso., 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. The hollow spheres produced are envisioned to have
applications in areas ranging from medicine to pharmaceutics
to materials science.
11 Physicochemical properties Certain topics in the field of research on very small Henglein., 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. 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., 1991
nonlinear optics crystallites, with principal emphasis on the electro-optic Stark
effect and all optical third order nonlinearity. There are also
introductory discussions on physical size regimes, crystallite
synthesis, quantum confinement theory, and linear optical

properties. The experiments describe CdSe crystallites,
exhibiting strong confinement of electrons and holes, and
CuCl crystallites, exhibiting weak confinement of the exciton
center of mass. In the CdSe system, neither the Stark effect nor
the third order nonlinearity is well understood.
13 Semiconductor clusters, Current research into semiconductor clusters is focused on the Alivisatos., 1996
Nanocrystals, and quantum properties of quantum dots - fragments of semiconductor
dots consisting of hundreds to many thousands of atoms - with the
bulk bonding geometry and with surface states eliminated by
enclosure in a material that has a larger band gap. Quantum
dots exhibit strongly size-dependent optical and electrical
properties. The ability to join the dots into complex assemblies
creates many opportunities for scientific discovery.
14 Light-emitting diodes made Electroluminescent devices have been developed recently that Colvin et al.,
from cadmium selenide are based on new materials such as porous silicon and 1994
nanocrystals and a semiconducting polymers. By taking advantage of
semiconducting polymer developments in the preparation and characterization of direct-
gap semiconductor nanocrystals, and of electroluminescent
polymers, we have now constructed a hybrid organic/inorganic
electroluminescent device. 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.
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.,2003
assembly of silica-coated gold (Au@SiO2) or silica-coated
silver (Ag@SiO2) nanoparticles with different shell

thicknesses and an electrostatically bridging polyelectrolyte,

poly(diallyldimethylammonium chloride) (PDADMAC). The
spectral position of the surface plasmon band of the composite
colloid spheres is tailored through (i) the type of silica-coated
nanoparticles used, (ii) the thickness of the silica shell, and
(iii) the number of nanoparticle layers deposited.
16 Electroluminescence from Spectrally clean and fairly narrow electroluminescence (EL) Dabbousi et al.,
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. The EL is tunable in the visible by changing the dot
diameter. There was apparent size dependence to the
efficiency with smaller dots having higher threshold voltages
than larger dots. 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,
efficiency, and stability of dot EL devices.
17 Gold Nanoparticle-Based A simple colorimetric technique for the detection of small Kim et al., 2001
Sensing of concentrations of aqueous heavy metal ions, including toxic
"Spectroscopically Silent" metals such as lead, cadmium, and mercury, is described.
Heavy Metal Ions Functionalized gold nanoparticles are aggregated in solution in
the presence of divalent metal ions by an ion-templated
chelation process; this causes an easily measurable change in
the absorption spectrum of the particles.
18 Sensing strategy for lithium The detection of Li+ is currently in demand for both Obare et al., 2002
ion based on gold biomedical and industrial applications. The study reports the
nanoparticles functionalization of 4 nm Au particles with a 1,10-
phenanthroline ligand that binds selectively to Li+. The ligand
binds to Li+ by forming a 2:1 ligand-metal complex, causing

Au nanoparticles to aggregate. Au nanoparticle aggregation
causes a shift in the extinction spectrum with a concomitant
color change, providing a useful optical method of detecting
Li+ in aqueous solution.
19 multilayered nanostructural Sequential adsorption of a cationic polyelectrolyte and Kleinfeld et al.,
films from macromolecular individual sheets of the silicate mineral hectorite has allowed 1994
precursors controlled, stepwise formation of multilayered films on silicon
wafers. Each component adsorbs rapidly by an ion-exchange
mechanism, and x-ray diffractometry indicates structural order
even in films with thicknesses greater than 0.2 micrometer.
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, thus preserving structural order in the
growing film.
20 Alternate assembly of Alternate layer-by-layer assembly of colloidal SiO2 particles Lvov et al., 1997
ordered multilayers of SiO2 with polycations has been investigated by quartz crystal
and other nanoparticles and microbalance (QCM), scanning electron microscopy, and
polyions atomic force microscopy (AFM). QCM measurement
confirmed the high regularity and reproducibility of the
assembling process that depends on particle concentration,
particle size, and ionic strength. The individual adsorption step
was completed within 15 s. The thickness of adsorbed layers
increased with increasing SiO2 concentrations at the three
particle sizes used (45, 25, and 78 nm in diameter), unlike the
case for other polyion assemblies. It also increased with
increasing ionic strength of aqueous SiO2 dispersions.
21 Molecular self-assembly of Multilayer ultrathin films composed of titanium dioxide Liu et.al.,1997

TiO2/polymer nanosized particles and ionic polystyrene molecules have been

nanocomposite films fabricated on single-crystal silicon, quartz, and glass substrates
by a novel molecular self-assembly process. X-ray
photoelectron spectroscopy (XPS) indicates that the formed
cationic TiO2 particles adsorb only on negatively charged and
not on positively charged surfaces. Contact angle
measurements demonstrate that the water contact angle
oscillates regularly in accordance with which molecules form
the outermost layer of the films.
22 Layer-by-Layer Self- The morphology and gas permeation properties of Kotov et al., 1998
Assembly of montmorillonite-polyelectrolyte self-assembled multilayer
Alumosilicate- systems have been investigated. Without any special
Polyelectrolyte Composites pretreatment, a stable film of montmorillonite-polymer
composite was assembled on a hydrophobic
poly(ethyleneterephthalate) support by means of layer-by-
layer deposition. All individual alumosilicate platelets were
found to be oriented in parallel to the substrate, while their
surface density strongly depended on the nature of the
polyelectrolyte (charge and molecular weight). The organic-
inorganic films were found to be very flexible and crack-
resistant even under a considerable mechanical stress.
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. Postdeposition reduction of
the metal ions by heating or exposure to NaBH4 then yields
composite films containing metal nanoparticles.
24 Dendrimer-Silver Silver complexes of poly(amidoamine) (PAMAM) dendrimers Balogh et al.,
Complexes and as well as different {silver-PAMAM} dendrimer 2001
Nanocomposites as nanocomposite solutions have been tested in vitro against

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

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. These
groups were then used to bind various inorganic ions that were
subsequently converted into nanoparticles.
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, solution pH, temperature etc. and availability and possibility
to use different molecular precursors have given rise to preparation of number of
different nanomaterials with different morphologies and structures. The
methodology is intrinsically slow and suffers on account of step-by-step
procedure of fabrication. The limitation to remain confined to use of liquid,
mostly aqueous phase and charged polymers poses another limitation.
2.5. Liquid Crystals
Figure 5. Liquid crystals
Lyotropic liquid crystals are obtained when molecules with interlinked

hydrophobic and hydrophilic blocks are mixed with water. The hydrophobic parts
cluster together to minimize water contact whereas the hydrophilic parts dissolve
in water. The covalent linkage does not allow microphase separation and
appropriate to packing parameters of the two parts and the water to surfactant
ratio, liquid crystal with a well defined phase is obtained (see Figure 5). The
variation in the amphiphile to water ratio can change the phase from hexagonal to
lamellar. Addition of non-polar solvent can increase the hydrophobic contents and
eventually leads to obtain an inverse hexagonal liquid-crystalline phase. 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. The size, shape, connectivity and

dimensionality of these reactors is controlled by the nature of the liquid crystalline

phase. 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. The templating effect of the
shape of the nano container can decide the shape of the product and
correspondingly 3-d spheres, 2-d sheets or 1-d rods can be synthesized (Dellinger
et al., 2004).
In a typical experiment the liquid crystals containing the substrate to be
reduced is shear mixed with another liquid crystal containing the reducing agent.
The two interconnect forming the nanomaterial. The transport or diffusion of
species from one to another control the rate of formation and is dictated by the
geometry. Thus very small particles are formed for a 1-d geometry as compared to
2-d sheet like geometry or 3-d volumetric space. 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. The amphiphile to
water ratio also controls the lamellar spacing in the lamellar phase. 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. The effect is, however, usually not very pronounced to effect
particle size. In other words, particle size shows weak dependency on lamellar
spacing. 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.
Table 5. Some experimental studies on Swollen Liquid Crystals

No
1 SDS,water, NaCl, The study reports the prepn. of direct hexagonal liq. crystals, Dos et al.,
pentanol, and containing oil-swollen cylinders arranged on a triangular lattice in 2005
cyclohexane, SLCs water. SLCs are made by using SDS and CTAB surfactants and their
containing CTAB . properties have been studied.
2 Highly Swollen Liquid Synthesis and self-assembly of nanomaterials can be controlled by Surendran et
Crystals using cationic, the properties of soft matter. On one hand, dedicated nanoreactors al., 2005
anionic, and nonionic such as reverse microemulsions or miniemulsions can be designed.
surfactants On the other hand, direct shape control can be provided by the topol.
of liq. crystals that confine the reacting medium within a specific
geometry.
3 PbS Nanocrystallites The study reports the synthesis and characterization of Yang et al.,
Synthesized in the monodispersed lead sulfide (PbS) particles with diameters in the 1996
Bicontinuous Cubic Phase range 4-14 nm, using bicontinuous cubic phase as a matrix. It was
of a Lipid found, through polarized optical microscopy and small-angle X-ray
scattering studies, 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 0.5 M. The
exposure of this ternary mixture to aqueous 0.40 M lead nitrate
(Pb(NO3)2) solution led to the formation of PbS nanocrystallites
within the mesophase.
4 Organic Lyotropic Liquid Various nanoscale semiconducting superlattices have been generated Braun et al.,
Crystals by direct templating in a lyotropic organic liquid crystal. These 1999
include superlattices of CdS, CdSe, and ZnS, templated in a liquid
crystal formed by oligoethylene oxide oleyl ether amphiphiles and

water. The semiconductor growth process copied the symmetry and

characteristic dimensions of the original mesophase by avoiding
growth of mineral within regularly spaced hydrophobic regions.
5 Semiconducting Organic-inorganic nanostructured composites provide a rich source Braun et al.,
superlattices templated by of new materials for a host of technological applications. For 1996
molecular assemblies example, the incorporation of organic molecules in an inorganic
lattice can toughen an otherwise brittle material, or be used to tailor
its electronic properties, and cooperative interactions between
organic and inorganic molecules are being used to generate a range
of porous materials for separation and catalytic technologies. The
study describes the growth of stable semiconductor–organic
superlattices based on cadmium sulphide and cadmium selenide.
6 Liquid-crystal templates Lyotropic liquidcrystalline phases are versatile media for Attard et al;
for nanostructured metals nanostructure design of metals. 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. Hexachloroplatinic acid and ammonium
tetrachloroplatinate were used as the Pt sources. the lyotropic liquid-
crystalline phases were prepared from octaethyleneglycol
monohexadecyl ether, Pt salt and water.
7 Mesoporous platinum The lyotropic liquid crystalline phases of surfactants exhibit a rich Attard et al;
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. The
electrochem. 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. surface areas. These results suggest that the use of liquid
crystalline plating solns. could be a versatile way to create
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.

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.
Table 6. Some experimental studies on Block Copolymers

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

nanoreactor for prepn. of metal nanoparticles inside their micelle

core, and then as templates where the micelles are used as
porogens.
7 Poly(tert-Bu acrylate- star-like amphiphilic block copolymers with 6 and 12-arms with Heise et al.,
block-Me methacrylate) remarkably low polydispersity were prepd and the polymers show 1999
a unique response of the mol. geometry to the polarity of the
solvent.
8 Review of metal A brief non-comprehensive survey of some recent work on the situ Ciebien et al.,
nanoclusters in block prodn. of metal nanoclusters in polymer films. 1998
copolymer films
Besides vesicles, the normal spherical micelles, micellar rods or hexagonal

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

• Ionenes (cationic + anionic polyelectrolytes): effective for bind both

hydrophilic and phobic compounds. Foaming phenomenon absent on
mixing, shaking, etc.
Also, on solubilization of reactant, a number of changes occur in the
various physico-chemical, spectrochemical, electrochemical and adsorption
properties. Typically they include:
• Physical properties: Aggregation, rigidity, adsorption, solubility, etc.
• Chemical properties: hydrophobic, hydration, molecular complexation,
conformation protolytic, redox, etc.
• Electro-properties: electronic spectrs, electrochemical parameters,
electronic excitation energy transfer, charge transfer.
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. Such sharp gradients can be seen in other
properties such as microviscosity, polarity and acidity. Use of different types of
surfactants can further change these properties. For instance the microviscosity
changes by a factor of three for surfactant changing from DDS to TX-100 (Singh
et al. 1982). Also change from micelles to vesicular form using
dimylristoylphosphatidyl choline changes the aqueous phase viscosity (0.89 cp) to
more than 100 cp (Neal et al., 1995). Increase in viscosity lowers the associated
vibration energy losses. The fluorescence intensities also likewise undergo order
of magnitude variations (Hinze et al., 1984) as compared to aqueous system.
The distribution of species upon solubilization into different microphases
as also the variations in solubility, rate and dynamics, equilibrium rates etc.
change the extent of reaction. The characteristics of inter and intra-molecular
excitation-energy transfer, electron transfer, charge distribution on a molecule
bring about changes in spectroscopic, electrochemical, electrophoretic conditions
affecting the sensitivity and selectivity (Shtykov, 2002; Pramauro et al. 1996).
Thus, for instance, we can use
• Charge on the reactant to control its binding efficiency or formation of
inclusion-complex.
• Functional groups on surfactant molecules to control catalytic or
regioselective ability of self-assembled structure.
• The presence of aromatic rings, unsaturated bonds or presence of chiral
atoms in surfactants to control binding.
• A control on aggregation number, microviscosity, charge density, surface
potential, hydration etc. can aid in improving the sensitivity and selectivity
of reaction and separation processes.
Addition of electrolytes, solvents, co-surfactants helps in establishing and
manipulating the control.
The properties of nanoreactors are unique to their nanosize dimensions.

Controlling the size of the nanocrystals / nanoparticles in these reactors, which are
self assembled structures, is generally a relatively easier task, despite a few
discrepancies which may always exist due to peculiar nature of the specific
system. Controlling the shape of nanocrystals is however a more intricate and
challenging job. 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, 2003). The presence of impurities,
additives, electrolytes, pH of the medium, nature and type of ions etc. can modify
the growth of some crystal faces. The shape is therefore not uniquely decided by
the shape of the template. Notwithstanding these complications, once optimized
the regularity in the functioning of the nanoreactor can be ascertained. Scale-up
of nanoreactors for large scale manufacturing therefore means increasing their
number multifold ensuring same properties. 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. The small size of the reactor allows for a faster reaction rate
and transport rate across the boundaries, leading to savings in time and cost. The
yields are quantitative with minimal waste.
In order to understand the supramolecular self assemblies with cavities
that can be used as nanoreactors, it is necessary to put them in proper perspective.
As we know, even simple atomic/molecular systems self-assemble on length scale
measuring in Angstroms. The molecular assemblies can be simulated using ab-
initio quantum mechanical and molecular dynamics methods. The large number
of structures that are possible can be experimentally probed using instrumental
tools such as optical scattering, nmr spectroscopy, neutron scattering etc. The
theoretical studies require to properly define the potential interactions and the
force field. The simple system involves long range interactions, Vander der Walls
dispersion forces and repulsive excluded volume (Leonard-Jone potentials). Such
isotropic and centro symmetric potentials can generate a few simple structures.
The presence of directional interactions (dipole, hydrogen or covalent-bonding,
ligand binding etc.) anisotropic shapes of molecules can generate variety of
diverse structures (Glotzer, et al., 2004).
The potential interactions and their types vary considerably as we move
from molecules to colloids. They include
• Long range attractive Van der wall’s interaction for particle pairs.
• Excluded volume interactions due to adsorbed steric layers.
• Repulsive forces between two colloidal particles due to charge distribution
on the surface (especially when electrolyte is present).
• Depletion potential (small non adsorbing molecules create attractive forces
between colloids due to entropic, free volume effect). This is especially

important since its range and strength can be independently varied to

create assembly.
• Short-range adhesive forces due to changes in steric layer and induced
dipole forces.
Like in atomistic/molecular systems only a few limited structures of
assembly can be generated using above potential interactions. The presence of
noncentro symmetric and anisotropic shape and strength of interactions are
needed for a wide choice of assembly structures. The type, strength and range of
pair potential interactions indicate thermodynamic limitations on formation of
some assembly processes. The nano and colloidal assemblies also suffer kinetic
limitations. The crystal grows more slowly with tendencies for defects such as
vacancies, wrong stacking, grain boundaries etc. 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, φ the reduced amorphous liquid volume fraction and D(ϕ ) the reduced
short time self diffusivity generalization of Stokes-Einstein diffusivity. 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. The characteristic time in the nucleation rate (a 2 D) scales as a3

indicating strong kinetic retardation with the particle radius.
For the ranges, type and strength of the interaction potentials considered
both molecular and colloidal systems can exhibit glass transition as well as
gelation phenomenon. 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 short range attractive interaction can
also slow down the dynamics and hold the system in a nonordered metastable
state. Nonequilibrium aggregation and gelation may also occur hampering the
assembly process.
Simulation methods for self assembly of nanoparticles and colloidal
systems use Monte Carlo (MC) simulations (Ethayaraja, et al., 2007) to generate
equilibrium phase diagrams by assuming hard sphere, soft sphere, DVLO and
other such pair potentials. 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. The molecular dynamics (MD) and
Brownian dynamics (BD) methods (Dudowicz et al., 2004) also use similar pair
potentials to deterministically generate the particle configurations. They solve the
Newton`s second law equation for force balance where the force on each particle
is obtained from the gradient of potential. MD simulations generate constant
energy ensemble particle configurations/trajectories, usually under isothermal and

isobaric conditions. The solvent dynamics has to be modeled explicitely that
make simulations prohibitive. 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.
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, excluded volume, coulumbic interactions, screening effects etc. The
effects of particle specifics such as composition, surface modification interactions
etc. enter through this term (ii) the drag force, FD, conventionally expressed as FD
= 6лaηυ where a is particle radius, η the solvent viscosity and υ the velocity of
particle. 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.
Theorem < FR (t ), FR (t ' ) >= (σk B T )(σπaηδ (t − t ' )) with zero mean FR . The
dependence of FD and FR on particle size clearly indicates its importance for the
assembly process. The characteristic time for a sphere to travel its own radius
scales as cube of the radius. For smaller particles, this implies that the dispersion
delocalization time is realy short. This has implications for nucleation kinetics,
gel and glassy and other phenomenon that mediate the assembly process.
In addition to MC, MD and BD simulations, other methods such as
discrete particle dynamics (DPD) (Frenkel et al., 2001) use soft particles to
represent fluid elements and hard particles to capture packing effects of colloids
due to excluded volume. Notwithstanding the method used for simulations, it is
important to correctly describe the interactions in these complex systems, which
in a broad way, can be assigned as attractive (-philic) or repulsive (-phobic)
character. The interaction potential to be used for surfactants, block copolymer,
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). The self assembly of particles into 1-d, 2-d
and 3-d arrays is thus a sensitive issue requiring detail understanding of the
effects of particle shape, size on potential interactions, Brownian motion, type of
solvent, impurities, additives etc. Simulation methods help us build this
understanding of the fundamentals which is very useful for new technological
applications.
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, 2-d and 3-d assemblies remain as a
challenge. 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

(Glotzer et al., 2004). Similarly development of practical methodologies to

commercial and technologically important self assembly processes should be
addressed. Self assembly as a manufacturing method and its large scale practical
implementation also requires the attention. 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. 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, directionality, tunability of
interaction strengths, addressability and programmability of self assembling
characters. Nucleic acids have the characteristic ability to store and transcribe
genetic information. 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. Tirrell (2005) cite a number of recent
studies on self assemblies using nucleic acid bas pairings, templating the synthesis
of other materials and conjugating and coupling to peptides, lipids etc.
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, spheres, tubes, open vessels etc.), mixes, splitters, transport lines (channels,
tubes etc.). Many of these and such functionalities are present in biological
systems such as cells. Additionally components producing using and dissipating
the energy are also present. The cell system is indeed very sophisticated with
presence of control elements such as signal carriers and actuators. It is noteworthy
to realize that a biological system unit with all its sophistication and complexities
is still chemical at its molecular level. The energy devices as well as control
elements are thus essentially molecular in nature and can be synthesized as
molecular electrical wires, switches, gears, valves, motors, pumps, shuttles etc.
We have already seen that by a judicious choice of the hydrophobic interactions,
it is possible to direct the self assembly as micelle, lipid bilayers, vesicles etc.
Other forms of interactions such as hydrogen bonding, π stacking, metal
coordination and electrostatic interactions can also direct the self assembly.
Catenanes and Rotaxcenes are good examples of self-assembling of molecular
complexes under the influence of electrostatic interactions and orbital overlap
forces. The electrostatic forces, under certain conditions can also localize
components to create interlocked molecules that can be used as valves, circuits,
elevators etc. The idea of integrating all such components into a comprehensive
system mimicking the behavior of a cell is very interesting and vigorously
pursued. The network of vesicles-nanotubes developed by Shimizu et al (2005) is
one such step in this direction. The perspective article by Stephanopolous et al.
(2005) vividly describes the process system engineering issues of nanosystems
and their integration and should be referred to for details.
4. CONCLUDING REMARKS
Organized assemblies, such as the ones described herein, formed through a self-
assembling process represent nanoreactors that can be used for preparing
nanostructured materials of desired functionalities and attributes. The types and
characteristics of these nanoreactors and control of their efficiencies for
conducting chemical transformations have been extensively investigated. A
number of illustrative examples of formation of nanoparticles and their assemblies
in the form of films, spheres, hollow structures, rods, tubes and other two and
three-dimensional structures, vividly demonstrate the engineering ability to create
the desirable structures and attributes. 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. Thus, our ability to dissolve dissimilar substances, bring them together
and concentrate them in microphases, create multi-center multifunctional
interactions between components, play with the nature, geometric compatibility,
orientations and extent of components, and alterations in the microphase
properties such as viscosity, polarity, etc. with large gradients over nanometer
distance can all be utilized in a judicious way to create the desired nano
architecture.
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. Hierarchical porous interconnected structures affords the possibility
to introduce transport channels for moving the molecules in and out. High internal
surface area with a possibility of local deposition, doping or insertion of active
component prove useful for multi step reactions where yield to desired product
can be maximized. Computer simulations can provide a very useful lead in
elucidating the efforts of various parameters on performance.
Self-organized systems are the crude man-made mimics of the natural cell
systems. The simple surfactant used for construction of the enclosed confined
environments already show a number of features such as compartmentalization,
self-assembling etc. of the cell system. Number of studies reporting effects of
variation in surfactant type, 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. The self-assembly of lipids and detergents into bilayer
membrane vesicles with a range of bilayer thicknesses (3-5nm) and vesicular
length scales of (100-10,000nm) diameter provided the mimics for cell membrane
and brought us a little more close to natural system. 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.
Thus for instance macromolecular ampiphiles for vesicular drug delivery systems

has advanced very rapidly approaching commercial realities. More complex but
closer to natural cells, enzyme based ampiphiles , proteins, virus bodies are
finding new applications to create sophisticated nanovescles. These organized
media and nanoreactors have clearly proved to be very useful for preparation of
nanostructured materials. Of course much more needs to be done to advance them
to a stage of full potential.
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Nanoreactors For Nanostructured Materials

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I NTERNATIONAL J OURNAL OF C HEMICAL

Nanoreactors for Nanostructured Materials

KEYWORDS: nanoreactors, nanostructured materials, organized self-assemblies

Chemical reaction engineering is the science of chemical transformation of input

Published by The Berkeley Electronic Press, 2008

this direction. A number of advanced materials with cost competitiveness and

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, hollow Vesicles

3-d mesoporous structures Lipid membranes

Biomaterials Liquid crystals

Protein & virus cages

Other self-assemble system

Figure 1. Classification of nanomaterials and nanoreactors in different areas.

Conducting chemical reactions in confined spaces creates an opportunity

Published by The Berkeley Electronic Press, 2008

optical, magnetic and mechanical properties due to altered electronic structures

2. ORGANIZED MEDIA: SOME IMPORTANT FACTS

2.1. Normal Micelle

Figure 2. Normal micelle

• Lyophilic assemblies of colloid size; several hundreds of amphiphilic

Published by The Berkeley Electronic Press, 2008

to second whereas the surfactant molecule in a micelle has half life of

Table 1. Some experimental studies on microemulsion for nanoparticles

Published by The Berkeley Electronic Press, 2008

SDS/hexane/n-pentanol/water polycyclic arom. hydrocarbon benzo[a]pyrene (BaP) in 2002

2.2. Reverse Micelle

Figure 3. Reverse micelle

Reverse micelles provide another example of organized self assemblies of

Published by The Berkeley Electronic Press, 2008

• Particle size increases with the increase in droplet size

Published by The Berkeley Electronic Press, 2008

Table 2. Some experimental studies on Reverse microemulsion

Published by The Berkeley Electronic Press, 2008

Sr. System Special features and applications References

Published by The Berkeley Electronic Press, 2008

Authors have shown that several exptl. parameters,

presence of FeCl3 and sodium bis(2-

Published by The Berkeley Electronic Press, 2008

were successfully used for the prepn. of gold

microemulsions) have been examd. with respect to

Published by The Berkeley Electronic Press, 2008

was subsequently calcined under various conditions

nm. The procedure was carried out using sodium

Published by The Berkeley Electronic Press, 2008

inorg. bases. A strong base, NaOH, and a

microemulsion method. The ultrafine particles,

Published by The Berkeley Electronic Press, 2008

Table 2.8. Reverse microemulsion and hydrothermal

Published by The Berkeley Electronic Press, 2008

4 CTAB/ water/cyclohexane/n-pentanol Indium hydroxide, In(OH)3, nano-microstructures Yang et al.,

microemulsion-assisted hydrothermal process, using

Published by The Berkeley Electronic Press, 2008

silicalite-1 synthesis gel.

microemulsion-templated sol-gel polymn. method. 2006

Published by The Berkeley Electronic Press, 2008

7 SDS/cyclohexane/1-pentanol/water Microemulsion gels and coatings have been obtained Papoutsi et

Fe nanowires which were encapsulated in nanowires. 2000