Nano Particle- A particle of matter is normally referred to as an NP if its extension in all three dimensions is less than 100nm.

( It is about one thousandth of the width of human hair).Nanocrystallite- A Nanocrystallite is generally understood to possess crystalline order in addition to nanoscale size, although not necessarily the crystal structure characteristic of the corresponding bulk material. Clusters- Clusters are particles containing a very small number of atoms such that it is no longer possible to clearly distinguish bulk atoms from those at the surface. There is no universally accepted definition but a general rule is a few hundred atoms or smaller. Nano composites- A composite is a material that is made up of various components. Nano gold deposited in the pores of porous alumina membranes is a composite material. Colloids-Colloids is a dispersed phase of one substance that exist as discrete entities within a continuous phase, usually water. For example, a colloid made from the bottom up begins with the nucleation of appropriate atoms or molecules in a supersaturated solution. When enough colloids are formed, condensation occurs to form three dimensional structures. The physical conformation of the structure is dependent upon the size of the colloids and the chemical nature of their surface. Monodisperse- NPs with a relative standard deviation of the size of distribution of less than 5% are said to be monodisperse. For example, monodisperse iron nanocrystals with a mean diameter of 4nm should contain between 2400 and 3300 iron atoms.Reduction-is defined as loss of oxygen, gain of hydrogen or gain of electrons, the gain of electrons enables to calculate an oxidation state.(One part of a redox process which involves the exchange of electrons the side which gets reduced receives the electrons and thus reduces its oxidation state.) Oxidation state-the formal charge on the atom due to its acquisition or donation of electrons to form bonds. Emulsifier- A surface-active agent that promotes the formation of an emulsion. Radical- 1.two or more atoms bound together as a single unit and forming part of a molecule. 2. An atom or group of atoms with at least one unpaired electron; in the body it is usually an oxygen molecule that has lost an electron and will stabilize itself by stealing an electron from a nearby molecule

Surfactant- Surfactants (soaps and detergents) are surface active chemical agents. Surfactants are compounds or polymers having both hydrophilic and hydrophobic parts (they are amphiphilic) that reduce interfacial free energy, such as the surface tension at an air-water interface. Surfactants can be anionic, cationic, or non-ionic depending on the structure of the polar end.

Passivation- to reduce the chemical reactivity of a surface by applying a coating. Emulsion- a colloid in which both phases are liquids. Sols- Colloids are what make sols. A sol is a colloidal suspension of solid particles within a liquid.Gel- A gel is a solid that contains liquid within its pore structure.Sol-gel chemistry- chemistry based on the hydrolysis and condensation of suitable organo-metallic precursors to produce metal oxide networks.Ostwald ripening- In Ostwald ripening larger particles that are energetically favored due to curvature phenomena grow at the expense of smaller, less stable particles.Template- A template is a material that acts as a gauge, pattern, or mold that is used to guide the manufacture of another piece. Micelles-Micelles are made of molecules called amphiphiles, that is single molecules that have both a polar and a non polar chemical group. Ligand- A substance (an atom or molecule or radical or ion) that forms a complex around a central atom.Calcine-Heat a substance so that it oxidizes or reduces.Precursor- A substance from which another substance is formed. Zeoliterepresent a large family of micro porous tectosilicates having pore sizes smaller than 1.4 nm. Zeolite materials are constructed of negatively charged aluminosilicates host frameworks that are sufficiently porous to accommodate a variety of different countercations (as charge compensating ions) and in many cases guest molecules that can be reversibly adsorbed and desorbed. Zeolites exhibit 3D framework structures with uniform sized pores of molecular dimensions, typically ranging from 0.3 to 1nm in diameter, and pore volume ranging from 0.1 to 0.35cc /g. Self-assembly- apparently spontaneous self organization of objects; it arises as a system strives to find minimal free energy. Self-assembly- means that components, constituents, molecules, etc. all come together spontaneously without the input of energy or design. Some input energy is usually required, of course, but it is expressed at new levels of subtlety. The driving energy may be sequestered in the surface of a nanoparticle, in the from of a molecular recognition couple or within an excited state of a molecule.

The making of relatively weak intermolecular bonds are controlled by entropic trade offs and small H, thus giving the appearance of self assembly. Hydrolysis- Is the process of breaking bonds by the action of H2O. Condensation- is the formation of a bond with the simultaneous release of a water molecule. Pyrolysis -Transformation of a substance produced by the action of heat. Annealing- Hardening something by heat treatment. Sintering- Cause (ores or powdery metals) to become a coherent mass by heating without melting. Aerogel- An aerogel is an extremely low-density (porosity>90%) and high internal surface area (>1000m2g-1) micro porous structure derived from a sol-gel process in which the liquid component is replaced by gas. Super critical extraction of the liquid and the subsequent baking form compounds called aerogels. Xerogel-Xerogel generally have porosity that is much lower and hence higher density. Extraction of the liquid at non supercritical conditions forms compound called xerogels.
Dendrimers- Since 1985 a new class of polymers called dendrimers has been developed. Dendrimer molecules are highly branched and lower

in molecular weight than most linear polymers. Whereas most polymers are

synthesized by chain reactions or by many repetitions of one type of reaction in one pot, dendrimers are synthesized one step at a time. Because the branching confers dendrimers with a more compact shape than other polymers, they are valuable for construction of organic or hybrid inorganic-organic int erface. Dispersion medium Gas Dispersed phase Liquid Name of system Aerosol Examples Fog, mist, clouds

Gas

Solid

Aerosol

Smoke

Liquid

Gas

Foam

Whipped cream

Liquid

Liquid

Emulsion

Milk, mayonnaise

Liquid Solid

Solid Liquid

Sol Gel

Gold in water Ruby glass, gold in glass Pumice, Styrofoam

Solid

GAs

Solid foam

Nano particles (NPs) form a new class of materials possessing unique properties that are characteristics of neither the molecular nor the bulk solid state limits. They have become the focus of considerable fundamental and applied research leading to important technological applications in areas such as heterogeneous catalysis, optical communications, gas sensing, nano electronics, and medicine. NPs come in wide range of sizes and shapes, with varied electronic, optical and chemical properties. However, the properties of NPs are intimately connected to their nanoscale size and atomic scale structure.Almost every element in the periodic table, together with various alloys and compound can form NPs.NPs are also ubiquitous in nature, for example, as soot particles in the atmosphere and soot in interstellar space, and they are even produced by certain types of bacteria.One often distinguishes between two types of Nano particle structures: those of low potential energy, which are close to thermodynamic equilibrium, and those of higher potential energy, which are formed by kinetically limited processes. It is often possible to transform the latter into the former by suitable thermal annealing; however, kinetically controlled structures can be preferable for application if they exhibit structure features with desirable properties.

The distinguishing feature of NPs, irrespective of their detailed structure, is that they possess a large surface area relative to their volume and a large fraction of atoms that are under-coordinated compared to the bulk. These surface atoms are responsible for many of the unique properties of NPs and some insights into their structure can be gained by considering macroscopic surfaces. The techniques for the creation of nanostructures can be divided into two broad categories. Top down approaches use lithographic patterning to structure macroscopic materials at the nanoscale, such as electron beam lithography, atomic beam holography, scanning probe lithography. Bottom up approaches utilize growth and self assembly to build nanostructures from atomic or molecular precursors. Some non-lithography techniques are natural self organized epitaxial growth, chemical synthesis of colloidal nanostructures, synthesis of nanostructures in glass and polymer materials, and template based chemical and electro chemical synthesis of nano structures. It is typically difficult to create structures smaller than 50nm with top-down technique, while it is often difficult to create structures larger than 50 nm by bottom up technique.No single fabrication/synthesis method is universally applicable for the production of nano meter scale semiconductor devices.Probably the most useful methods of synthesis in terms of their potential to be scaled up are chemical methods. Bottom up fabrication approaches selectively combine atoms or molecules to form nanomaterials. Bottom up fabrication methods, therefore , are considered to be additive. Bottom up fabrication methods reside within the realm of chemistry and biology. Nature, of course, has perfected bottom up fabrication of nanomaterials. Advantages of bottom up methods are numerous. Self-assembly processes, for example, occur under thermodynamic control conditions. Because such processes exploit much weaker intermolecular interactions, as opposed to strong covalent bonds, nanomaterials are fabricated under milder conditions of temperature, pressure, and pH. The upscale potential of bottom up methods is enormous. As with any other chemical process, it is relatively straightforward to scale up a process that takes place in a beaker of on a lab bench (e.g., the domain of the chemist) to a batch production process in a manufacturing line (e.g., the domain of the chemical engineer). However, there exist significant challenges

facing bottom up methods. Overall robustness, long range order (related to complicated patterns), and directed growth all leave something to be desired. In order for bottom up fabrication of nanomaterials to become the dominant fabrication mode of industry, all of these concerns need to be overcome. We divide bottom up methods according to the phase within which the process occurs e.g., Gaseous-Phase method, Liquid-phase methods, and solid phase bottom up fabrication.

METAL NANOCRYSTALS BY REDUCTION Reduction of metals, particularly gold salts like hydrogenated tetrachloroaurate by organic bases such as sodium citrate is a very old procedure. As the solution becomes saturated, Au nanoparticles nucleate and start to precipitate. Control of solution parameters such as pH, concentration of reducing agent, and potential stabilizing ligands lead to control over particle size. Reaction scheme of formation of Au55 ligand-stabilized cluster. At the top left, a solution containing dissolved metal cations is shown. The cations are converted into gold atoms after addition of reducing agent like citrate. Once formed, the atoms nucleate and grow into aggregates that eventually stop at the cluster phase (depending upon the reaction conditions). Ligands attach to the Au55 vertices of the cluster; there are 12 vertices in this structure. Not shown are the counter anions, the chloride atoms of Au55[P(Ph)3]12Cl6.

Au clusters One of the most popular methods to form metal clusters and colloids is through the reduction of metal cations. Common reducing agents include the base complements of organic acids such as sodium citrate, reducing alcohols, Na2S, borohydrides [B2H6], sodium borohydride [NaBH4], and even hydrogen gas. The small clusters wish to agglomerate to form larger clusters via Ostwald ripening. In order to fabricate metal nano clusters of predetermined size, special steps need to be taken. First , addition of a potential ligand species to the reaction mixture is required. The ligand serves to bind reduced metals and thereby modulate the growth of the embryonic clusters. Depending on relative concentrations of reactants (the metal salt, reducing agent and ligand), growth of clusters that are mono disperse with desired dimensions is possible. The generic process for synthesis of nano clusters is summarized as Reduction of metal cation agglomeration prevention ligand stabilization or ligand exchange extraction from solvent further surface modification. Gold colloid synthesis is straight forward. Of all the procedures available today, a method called the Turkevitch route is very popular

HAuCl4+(C6H5O7)Na3 Au + Oxidized products Approximately 5X10-6 mol of HAuCl4 is dissolved in 19mL of deionized water and heated to boiling; 1mL of 0.5% sodium citrate is added with constant stirring for 30 min. The solution undergoes color changes from yellow to clear gray, purple, deep purple, and finally to ruby-red. Water is added to maintain the level of solution to 20 mL.The Brust route is similar but employs sodium borohydride as the reducing agent: HAuCl4+[CH3(CH2)7]4NBr(TOAB)+toluene+NaBH4 Au This technique utilizes an emulsion layer made of water and toluene; 4.0X10-3 mol of tetraoctylammonium bromide (TOAB, surfactant, the phase transfer catalyst and the stabilizing ligand) is added to 80mL of water and then 9.0X10-4 mol of HAuCl4 in 30 mL water is added to the TOAB solution and stirred vigorously of 10 min. The aqueous phase is clear and the organic phase is orange. Sodium borohydride is added drop wise to the mixture and the color changes for orange to white to purple to dark red. To make sure that the product clusters are monodisperse with regard to size, the solution is stirred for an additional 24hr. The organic phase is washed with sulfuric acid to neutralize the solution. TOAB is not considered to be a strong ligand and will readily undergo ligand exchange with stronger ligands like thiols that bind covalently to the gold clusters. Nano particles of Molybdenum (Mo) can be reduced in toluene solution with NaBEt3H at room temperature, providing a high yield of Mo nano particles having dimensions of 1-5 nm. The equation for the reaction is MoCl3+3NaBEt3HMo+3NaCl+3BET3+(3/2)H2 where Et denotes the ethyl radical (C2H5).* Nano particles of aluminum have been made by decomposing Me2EtNAIH3 in toluene and heating the solution to 105C for 2hr (Me is methyl,CH3). Titanium isopropoxide is added to the solution. The titanium acts as a catalyst for the reaction. The choice of catalyst determines the size of the particles produced. For instance 80 nm particles have been made using titanium. A surfactant such as oleic acid can be added to the solution to coat particles and prevent aggregation. The solvothermal and hydrothermal syntheses involve heating the reactants in water or a solvent at high temperatures and pressures. The role of solvent or water is that of pressure-transmitting medium and the solubility of the reactants is pressure and temperature dependent. A sealable Teflon-lined container, called a bomb, is used to keep the solvent and the reactants inside. After sealing, the container is kept

at high temperatures inside an oven (temperatures vary from 100 C to 500 C). The pressure of the container depends on the level of filling of the solvent or water. Solvothermal (hydrothermal) conditions provide unique supercritical conditions that can lead to unique or unexpected morphologies of the products. The method is simple, economical, robust, and most of the time the conversion efficiency is close to 100%. Various experimental parameters such as concentration of reagents, pH, and introduction to additives can be varied to tune the morphologies of the products. The effect of various experimental parameters on the reaction equilibria seems to be the key. Solvothermal and hydrothermal syntheses have been used to synthesize a variety of nanorods which are summarized in Table 7.2. Solvothermal synthesis During solvothermal synthesis, sometimes layered precursors are used as the starting materials and template molecules such as amines are used. The layered precursors with template amine molecules in the interlamellar space on solvothermal treatment lead to the transformation of a two dimensional structure into a one-dimensional structure. Simple conditions such as using different acidic solvents (e.g. H2SO4, HCl, salicylic acid) can lead to nanorods of different aspect ratio. The major drawback of these methods is that the mechanism of synthesis is sometimes not clearly established and reproducibility may be an issue.Nickel nanorods (diameter 12 to 15 nm; length, 50 to 100nm) have been synthesized by a solvothermal decomposition of nickel acetate in the presence of n-octylamine (nickel acetate to n-octylamine molar ratio is 1:300) at 250C (104). The formation of Ni nanorods id favored by the presence of n-octyl amine; it reduces , under solvothermal conditions, the Ni2+ ions to Ni and also acts as a shapecontrolling agent to produce metallic nickel nanorods. In the absence of linear alkyl amines, only NiO nanoparticles are produced. Using a similar approach, in the presence of n-octylamine, nanorods of ruthenium and rhodium metals have been produced stating from corresponding acetyl acetonate precursors, Ru(acac) 3 . The metallic nanorods are stable in air because of amine coating and can be redispersed in hydrocarbon solvents. Photochemical synthesis may be considered as one pot synthesis. It is mild, efficient, and an environmentally friendly method. Gold nanorods with control over aspect ratio can be synthesized using photochemistry in the presence of Ag+ ions. An aqueous solution containing CTAB [Cetyl trimethyl ammonium bromide] and tetradodecyl ammonium bromide has been used as the growth solution

along with HAuCl4.3H2O as the source of gold. A small amount of acetone and cyclohexane is used to loosen the micellar structure. Different amounts of 0.01M AgNO3 aqueous solution is added to the above solution and it is irradiated with UV light (~254nm). The resulting precipitate after dispersion in water yields Au nanorods. The formation of gold nanorods is indicated by the appearance of a longitudinal band in the UV-Vis spectrum around 600 to 800nm. Depending on the amount of Ag+ ions (15.8 to32l), Au nanorods with aspect ratio 2.8 t0 4.8 can be synthesized. Silver ions plays a crucial role in the formation of nanorods and a sample prepared without silver nitrate consists of only spherical particles Increase in Ag+ content in the solution leads to a decrease in the diameter of the rods. A combination of crystal aggregation and stabilization of a particular crystal face has been suggested to be the mechanism. Silver ions are reduced to silver Nanocrystals when irradiated and they are oxidized back into Ag+ in the presence of HAuCl- 4:Au3+ gets reduce in the process. This leads to fresh surfaces of Au nanocrystals followed by growth along a particular direction. A photochemical reaction of ketone to synthesize gold nanorods in a micellar solution of CTAB consisting pf HAuCl4, AgNO3, acetone, And ascorbic acid is possible. The presence of ketone is crucial for the formation of the rods in this case. The UV irradiation leads to the formation of ketyl radials and the radicals reduce the Au+ ions to Au. The Au act as the nuclei for the anisotropic growth of Au nanocrystals in the presence of ascorbic acid and the growth solution , consisting of AuBr2-, AgBr clusters, and CTAB. The proposed mechanism is given below;
Ascorbic Acid Au3 Au

(CH 3 ) 2 CO h (CH 3 ) 2 CO * (CH 3 ) 2 CO * RH (CH 3 )* COH *R 2 Au (CH 3 )* COH Au0 (CH 3 ) 2 CO H 2 nAu0 Aun ( Nanorods)
CTAB is denoted by RH and R*is the radical generated from CTAB by hydrogen abstraction by (CH3)2*COH which reduces Au+ to Au. The energy and intensity of the UV light used during the growth of gold nanorods has been studied. Under similar experimental conditions (aqueous solution consisting of CTAB, tetraoctyl ammonium bromide, H AuCl4.3H2O, AgNO3, acetone, cyclohexane is used) 300 nm UV light

produces longer nanorods with narrower size distribution as compared to irradiation with 254nm light. Also, high intensity accelerates the growth of Au nanorods. Longer irradiation time reduces the concentration of rods, with a concordant increase in the number of spherical particles. The advantage of the photochemical method compared to the electrochemical method is that spherical particles are not present.
Electrochemical synthesis

Electrochemical methods have been mainly used to deposit metals or semiconductors into the templates. One does not need expensive instrumentation, and the synthesis can be carried out under ordinary temperature and pressures. A general scheme for the synthesis of nanorods by electrochemical method is given in scheme below. First a thin film of metal is deposited on the template, which will serve as the working electrode for the deposition. This is followed by the deposition of the sacrificial metal. Then the deposition of the materials of interest is carried out electrochemically. Finally, the templates are removed by chemical treatment to get nanorods.

Martin and coworkers pioneered the electrochemical deposition of nanorods of metals such as Ag, Au, Co, Cu, Ni, Pt, Pd, and Zn using hard templates such as anodic aluminium oxide (AAO). The metal ions in the solutions are reduced by applying a negative potential and the morphology of the rods is controlled by two parameters, the pore size of the template, and the amount of the charge passed, since the length of the nanorods will be decided by this. It is possible to deposit multi elements (e.g. grow multi segmented rods) within pores of the template. One can adopt a pulsed electrochemical deposition with a bath containing multiple ions with well-separated redox potentials. It is also possible to deposit semiconductors into the pores of the template; for example ZnO nanorods or nano wires can be prepared by applying a cathodic current to an aqueous solution containing zinc nitrate.

The major drawback of the electrochemical methods are (1) modification of the template electrochemically, for example, plating to make it a working electrode is inconvenient, and (2) to make nanorods, the metal ions in the solution should be easily reducible.; if we cannot reduce a metal electrode chemically, this approach cannot be used.

Thermolysis Nano particle can be made by decomposing solids at high temperature having metal cations, and molecular anions or metal organic compounds. The process is called thermolysis. For example, small lithium particles can be made by decomposing lithium azide, LiN3. The material is placed in an evacuated quartz tube and heated to 400C in the apparatus as shown in Fig. At about 370C the LiN3 decomposes, releasing N2 gas, which is observed by an increase in the pressure on the vacuum gauge. In a few minutes the pressure drops back to its original low value, indicating small colloidal metal particles. Particles is less than 5nm can be made by this method. Passivation can be achieved by introducing an appropriate gas. The presence of these nanoparticles can be detected by electron paramagnetic resonance (EPR) of the conduction electrons of the metal particles. EPR measures the energy absorbed when em radiation such as microwaves induces a transition between the spin states ms split by a DC magnetic field. Generally the experiment measures the derivative of the absorption as a function of an increasing DC magnetic field. Normally because of the low penetration depth of

the microwaves into a metal , it is not possible observe the EPR of the conduction electrons. However, in a collection of nano particles there is a large increase in surface area, and the size is of the order of penetration depth, so it is possible to detect the EPR of the conduction electrons. Generally EPR derivative signals are quite symmetric, but for the case of conduction electrons, relaxation effects make the lines very asymmetric, and the extent of asymmetry is related to the small dimensions of the particles

Hybrid method A nano scale hybrid inorganicorganic material is defined as a material having properties that depend on the size of at least one component. The organic part of most hybrid materials is not crystalline but amorphous, usually a surfactant or polymer. Often a surfactant or polymer coating is necessary to prevent nanoscale inorganic materials from coagulating into bulk materials. Polymer composites, in which dispersed inorganic particles or fibers improve the mechanical properties of a plastic or an elastomer, have been commercial since the first carbon black

filled rubber tires.Inorganic-organic materials are ubiquitous on the nano-scale, sometimes by design in order to combine the separate properties of the inorganic and organic components into one material, and sometimes by necessity because an organic surface is the only way an inorganic material can be dispersed in a solvent for processing.Organic materials serve as templates for the synthesis of nanoparticles, such as TOPO- stabilized II-IV semiconductor nanoparticles, for the ordering of inorganic nanoparticles in dendrimers and block copolymers, and for the synthesis of nano-porous zeolites. The organic templates often is removed to obtain a final inorganic product such as a zeolite, or an ordered array of nanoparticles on a surface, and an inverse opal photonic band gap material. Because the inorganic-organic interface must be stabilized to maintain nano structures, surfactants and polymers will continue to be essential components of many new hybrid materials. Semiconductor nanoparticles The most nearly monodisperse, stable, and highest quantum efficiency of nanoparticles of II-Vi semiconductors, such as CdSe, are produced in non-polar organic media at temperatures of 250C to 300C with surface coatings of trioctylphosphine oxide [TOPO]. Often a protective inert shell of a large band gap material (silicon dioxide, zinc oxide, or zinc sulfide) is grown on the surface to retard reactions of the smaller band gap nanoparticle with the environment. Aqueous dispersions are produced either by replacing the TOPO with a hydrophilic stabilizer, or by carrying out the synthesis under aqueous conditions in the first place using stabilizers such as 2-mercaptoglycolic acid (HSCH2CO2H) or 2-mercaptoethanol (HSCH2CH2OH). Colloidal stability in water often requires a large excess of the water-soluble stabilizer in solution, which equilibrates with a much smaller amount of stabilizer on the surface of the particles. In contrast to low molecular weight stabilizers, a large excess of the water-soluble stabilizer is not required because the many bonding sites on the polymer add up to much stronger binding of a polymer than of a monodentate ligand. Aqueous dispersions of nanoparticles stabilized initially by 2mercaptoglycolic acid and 2-mercaptoethanol have poorer optical properties than the TOPO-stabilized nanoparticles due to broader particle size distribution, which result in broader emission bands and surface trapped states that reduce

the quantum yield of fluorescence. In toluene-water mixtures, 4.6 nm diameter TOPO-coated CdSe particles form a disordered monolayer at a water toluene interface, but not at a toluene-air interface. Template synthesis is the fabrication of nanomaterials within porous materials and interstitial spaces. We focus primarily on porous materials formed by inorganic and organic inorganic hybrid materials. According to the IUPAC definition, there exists three classifications of porous materials: macro porous (d>50nm), mesoporous (2<d<50nm), and micro porous (d<2nm). Ordered mesoporous materials typically result from process of inorganic polymerization during which supramolecular templating is simultaneously proceeding. Most often, however, a so called cooperative self assembly takes place between the templating species and the mineral network formation, yielding highly organized mesoscopic architectures. Thus the surfactantinorganic hybrid mesophase forms cooperatively from the species present in solution, which are not in a liquid crystalline state prior to mixing of the precursors. The key feature of the synthesis of the mesostructured materials is to achieve a well defined segregation of organic and inorganic domains at the nanometer scale. Here, the nature of the hybrid interface plays a fundamental role. The free energy of the meso-structure formation (G) is composed of four main terms, which represent, respectively, the contribution of the inorganicorganic (Ginter), the inorganic framework (Ginorg), the self assembly of the molecules (Gorg), and the contribution of the solution (Gsol). In the cooperative assembly route , template concentration may be well below those necessary for obtaining liquid crystalline assemblies or even micelles. Thus, the creation of a compatible hybrid interface between the inorganic walls and the organic templates (Ginter) is essential for the generation of a well ordered hybrid structure with appropriate curvature. From the kinetics point of view, the formation of the organized hybrid meso structure is viewed as resulting from the balance between organic-inorganic phase separation, organization of the SDA, and inorganic polymerization. Hence, two aspects are fundamental for finetuning mesophase formation: the reactivity of the inorganic precursors (e.g. rate of polymerization, pH, and isoelectric point) and the interactions involved to generate the hybrid interface.

A generalized cooperative mechanism of formation was proposed based on the specific electrostatic interactions between an inorganic precursor I and a surfactant head group S. The hybrid inorganic-surfactant mesophases obtained are strongly dependent on the interactions between the surfactants and the inorganic precursors (i.e., the hybrid interface).

In the case of ionic surfactants, the formation of the mesostructured material is mainly governed by electrostatic interactions. In the simplest case, the charges of the surfactant (S) and the inorganic species (I) are opposite under the synthesis conditions. Along with the S+I- interaction, cooperative interaction between inorganic and organic species can also be achieved by using the reverse charge matching, interactions S-I+. With these two direct synthesis routes identified, and , two other synthesis paths, considered to be indirect, also yield hybrid mesophases from the self assembly of inorganic and surfactant species. Synthesis routes involving interactions between surfactants and inorganic ions with similar charges are possible through the mediation of ions with the opposite charge (S+ X-I+ or S- M+I-). The S+ X-I+ path takes place under acidic conditions, in the presence of halide anions (X- = Cl-, Br-) and the S- M+I- route is characteristic of basic media, in the presence of alkali metal ions (M+ =Na+, K+ ). Besides the syntheses based on ionic interactions, the assembly approach has been extended to pathways using neutral (S 0) (87) or non ionic surfactants (N0) (88). In the approaches denoted by (S0I0) and (N0I0), hydrogen is to be considered to be main driving force for the formation of the mesophase. Sol gel method

Sol-gel synthesis is one of the oldest forms of nanotechnology that has incredible potential for nano manufacturing. Colloid chemist have developed this technology dating back numerous decades, developing one of the simplest, inexpensive, low temperature, and most effective bottom up wet chemical synthesis of nano materials that are highly pure and monodisperse in size. Inorganic metal oxides as well as inorganic-organic hybrid materials are synthesized routinely by sol-gel methods. The sol is the homogeneous solution of molecular reactant precursor that are concerted into an infinite molecular weight three-dimensional polymer: the gel that forms an elastic-solid fill material with the same volume as the liquid. Mixtures of precursors (different metals,

oxides, and even organics) lead to binary, ternary, and higher order systems. Colloid size, structure and morphology are dependent on the solution pH, temperature, composition, concentrations and the solvent. Transformation from the sol into the gel, for example, is stimulated by a change in the pH of the solution. Sol-gel synthesis proceeds by hydrolysis and condensation of silicate precursors like triethlorthosilicate (TEOS). Hydrolysis of a silicon precursor proceed where R is an ethyl group in TEOS. Subsequent condensation is illustrated by: Using sol-gel synthesis zero , one, two dimensional and higher order structures and morphologies can be synthesized.. Different metal groups and combinations of metals like aluminium, potassium, titanium, and others result in colloidal ( and eventually ceramic ) materials of great diversity, properties and function.Metal nanoparticles are often synthesized on inorganic supports. Sol-gel processes in this way; contribute to the synthesis of metal zero-dimensional materials. The inorganic support serves to isolate metal precursors before Si(OR ) 4 thereby prevent y (OH ) y yROH reduction and yH 2O Si(OR ) 4agglomeration of the metal. The sol-gel product also serves in the capacity of template.
2Si(OR ) 4 y (OH ) y [( RO ) 4 y (OH ) y 1 ] Si O _ Si [(OR ) 4 y (OH ) y 1 ] H 2O Starting from the absolute bottom with molecules and via the process of

nucleation and Ostwald ripening, larger and larger particles are grown until the reaction is terminated. Following a sintering process, an array of close-packed spherical particles can be used to form aero gels or xerogels or act as template to form other nanoparticles. Through sol-gel method mono disperse particles can be generated in large quantities. Most sol-gel systems are based on silicate chemistry but others exist as well, such as the formation of mono disperse hematite nanoparticles as drug delivery vehicles. Sol-Gel method is a good method for obtaining fine nanoparticle with narrow size distribution and controlled chemical composition at relatively low temperature. In this process, dispersion of the particles of the metal compound (sol) usually in an aqueous phase is first prepared and then converted into gel. from ferric hydroxides/ferric oxy hydroxides. Sol-gel chemistry is exploited to form silica

The polymer gel so formed is three dimensional skeleton surrounding the inter connected pores. Gelation is achieved by means of chemical dehydrating agent with surfactant. 2-ethylhexanol (dehyrating agent) and SPM-80 (surfactant) are commonly used in the process. Typically this involves a hydrolysis reaction followed by condensation or polymerization. In principle, particle size achieved at the precipitation state is maintained during sol and gel formation. Si(OC2H5)4+C2H5OH(SiO2)n (gel)+Other products The sol gel process is summarized in fig. below. Steps 1 to 3 indicate the process up to gelation. While the gelled spheres or collapsed gels (xerogels) can be collected, a better means of exploiting their surface area is to capture the gel on the surface. This way a greater surface to bulk area is obtained. Another possibility is aero gels. Aerogels are composed of three dimensional, continuous networks of particles with air (or any other gas) trapped at their intersection. Aerogels are porous and extremely light, yet they can withstand 100 times their weight. Another very clever way of maximizing the surface area is colloidal crystallization on surfaces. In this process, water is very carefully removed so that the sol gel structure is not lost in the precipitate. Nanostructured silica with controlled pore size, shape and ordering can be obtained this way. When surfactants are mixed with water, long range spatially periodic architectures are created in a nano foam, with lattice parameters in the range of 2nm to 15nm. To obtain nanoparticles in a bulk form the nanoparticles must be consolidated while maintaining the nano size. The usual goal is to form a high density solid that is free of voids. Sintering is a common technique for consolidating metallic and ceramic materials. The material is first compacted into a low density solid which may contain binders. Next, higher temperatures and sometimes pressures are used to increase the density by the diffusion of vacancies out of the pores. Compacted nano crystalline metals can have densities which are 96-98% of the bulk. In sol-gel synthesis, a sol is prepared first from the suitable precursors. The sol becomes a gel on aging. The gel after drying and calcination leads to nanorods. The sol-gel process has been used mainly for the synthesis of metal oxide nanorods, with a few exceptions. The advantage of sol-gel process compared to other methods are (1) better composition control, (2) good homogeneity, (3) low processing temperature, (4) and adaptability for easier

fabrication. Typical examples of nanorods synthesized by the sol-gel process along with the chemicals used are summarized in table below. We illustrate two examples of sol-gel synthesis; Nanorods of K2Ti4O9 and K2 Ti6O13 have been synthesized by mixing CH3OK and Ti(OC2H5)$ in ethanol. The molar ratio of CH3OK to Ti(OC2H5)4 is varied. A required volume of HCL is added to control the hydrolysis and condensation reactions. The sol after keeping for about 4 to 5 days is dried to get a xerogel. The xerogel on calcination leads to K2Ti4O9 nanorods if the ratio of CH3OK to Ti(OC2H5)4 is 1:1. If the CH3OK to Ti(OC2H5)4 ratio is 1:2, the final product is K2Ti6O13 nanorods. The second example is the synthesis of -alumina nanorods from boehmite nanofibers using a modified sol-gel process. First, a solution of aluminium isopropoxide in anhydrous ethanol is prepared. To this, ethanol with 4% water is added leading to a viscous liquid after 15h. The viscous liquid heated at 600 C leads to alumina nanorods (diameter <10nm; length 50 to 200nm). Since in the synthesis less water is taken, only partial hydrolysis takes place. The removal of one water molecule from two AlO(OH) octahedra leads to the formation of Al2O3 nanorods, (CH3CH2CH2O3)3Al+2H2OAlO(OH)+3CH3CH2CH2OH

Miscelles and micro emulsions Surfactants (soaps and detergents) are surface active chemical agents. Surfactants are compounds or polymers having both hydrophilic and hydrophobic parts (they are amphiphilic) that reduce interfacial free energy, such as the surface tension at an air-water interface. Surfactants can be anionic, cationic, or non-ionic depending on the structure of the polar end. The hydrophobic end dissolves oil or grease, and the hydrophilic end dissolves in water. Surfactants dissolve molecularly in water at low concentrations. As the concentration increases critical micelle concentration (CMC) is reached at which further added surfactant forms aggregates called micelles. The simplest amphiphilic structure is the micelle. Although micelles are homogeneous in the sense that they consist of the V cpp same molecule, but are considered as supra-molecular structures because the Acap Lcap molecular components of micelles are held together by the intermolecular forces. Assuming that all amphiphiles in a solution are identical, predictions about their

structure are made by application of the critical packing parameter. The cpp is given by Where V is the volume of the amphiphile, Acap is the area of the head group, and Lcap is the length of the head group. Packing shapes vary from cone like to cylinder like to wedge like. For single tail surfactants that have relatively large head groups (e.g., sodium dodecyl sulfate, SDS), cpp is equal to 1/3 and the packing shape is conical with the tails petering out into a point. Spherical micelles conform to these criteria as well. Single tailed amphiphiles with small head groups (e.g., hexadecltrimethylammonium bromide, CTAB) pack into a truncated cone with cpp between 1/3 and and show incipient cylindrical tendencies. Double tailed amphiphiles with large heads (e.g., phosphatidic acid) form truncated cones (cpp=1/2-1) that in turn form flexible bilayers. Double tailed amphiphiles with small heads (e.g., phosphatidyl serine) form cylinders (cpp=1) that settle eventually into planer bilayers (like membranes) or into inverted truncated cones (wedges). In the cases where cpp>1, inverted micelles (reverse micelles) are formed under the proper solution conditions (e.g., phosphatidyl ethanol amine). An emulsion is a cloudy colloidal system of micron size droplets of one immiscible (i.e., non mixing) liquid dispersed in another, such as oil in water. It is formed by rigorous stirring, and is thermodynamically unstable because the sizes of the droplets tend to grow with time. If surfactants are present, then nano sized particles, ~100nm, can spontaneously form as a thermodynamically stable, transparent micro emulsion that persists for a long time. Surfactant molecules can organize in various ways, depending on their concentration. For low concentrations they can adsorb at an air-water interface. Bacteria and nanoparticles synthesis Among the microorganisms, prokaryotic bacteria have received the most attention in the area of biosynthesis of nanoparticles. Early studies reveal that Bacillus subtilis 168 is able to reduce Au3+ ions to produce octahedral gold particles of nanoscale dimensions (5-25nm) within bacterial cells by incubation of the cells with gold chloride, under ambient temperature and pressure conditions. Organic phosphate compounds play a role in the in vitro development of octahedral Au, possibly as bacteria-Au-complexing agents. Fe(III)- reducing bacteria Shewanella algae can reduce Au(III) ions in anaerobic environments. In

the presence of S. algae and hydrogen gas, the Au ions are completely reduced, which results in the formation of 10 to 20 nm gold particles. It is already established that silver is highly toxic to most microbial cells. Nonetheless several bacterial strains are reported as silver resistant and may even accumulate silver at the cell wall to as much as 25% of the dry weight biomass, thus suggesting the use for the industrial recovery of silver form ore material. The silver resistant bacterial strain Pseudomonas stutzeri AG259 accumulates silver nanoparticles, along with some silver sulfide, in the cell where particle size ranges from 35 to 46nm. Larger particles are formed when P. stuteri AG259, isolated from a silver mine, is placed in a concentrated aqueous solution of silver nitrate. Nanoparticles of well defined size, ranging from a few to 200nm or more, and distinct morphology are deposited within the periplasmic space of the bacteria. Cell growth and metal incubation conditions may be the reasons for the formation of different particle sizes. The exact reaction mechanisms leading to the formation of silver nanoparticles by this species of silver resistant bacteria is yet to be elucidated. The ability of microorganisms to grow in the presence of high metal concentrations might result from specific mechanisms of resistance. Such mechanism include the following; efflux systems, alteration of solubility and toxicity by changes in the redox state of the metal ions, extracellular complexation or precipitation of metals, and the lack of specific metal transport systems. Bacteria not normally exposed to large concentrations of metal ions may also be used to grow nanoparticles. The exposure of Lactobacillus strains, which are present in buttermilk, to silver and gold ions resulted to the large-scale production of metal nanoparticles within the bacteria cells. Moreover, the exposure of lactic acid bacteria present in the whey of buttermilk to mixtures of gold and silver ions can be used to grow alloy nanoparticles of gold and silver.In addition to gold and silver nanoparticles, there is much attention in the development of protocol for the synthesis of semiconductors (the so called quantum dots) such as CdS, ZnS, and PbS. These luminescent quantum dots are emerging as a new class of materials for biological detection and cell imaging, based on the conjugation of semiconducting quantum dots and biorecognition molecules. Clostridium thermoaceticum precipitates CdS at the cell surface as well as in the medium from CdCl2 in the presence of cysteine hydrochloride in the growth medium. Most probably, cysteine acts as the source of sulfide. When

Klebsiella aerogenes is exposed to Cd2+ ions in the growth medium, 20 t0 200nm CdS formed on the cell surface. The formation of CdS is confirmed by quantitative energy dispersive x-ray analysis. The buffer composition of the growth mechanism plays an important role in forming the cadmium sulfide crystallite. Intracellular CdS nanocrystals, composed of wurtzite crystal phase of the cells and increases about 20 fold in E coli grown in the stationary phase as compared with that grown in the late logarithmic phase. Spherical aggregates of 2 to 5 nm diameter sphalerite (ZnS) particles are formed within natural biofilms dominated by sulfate reducing bacteria of the family Desulfobacteriaceae. A combination of geochemical and microbial processes leads to ZnS biomineralization in a complex natural system. It is appropriate to mention that the concentration of Zn can be significantly reduced to below acceptable levels for drinking water with the use of this method. Magnetotactic bacteria are a heterogeneous group of prokaryotes. They orient and migrate along geomagnetic field lines. All magnetotactic bacteria contain magnetosomes, which are intracellular structures comprising magnetic iron mineral crystals enveloped by a membrane vesicle. Magnetic Fe sulfide nanoparticles are synthesized by using sulfate-reducing bacteria where particles having a size of a few nanometers are formed on the surface, and the magnetic mineral is separated from the solution by a high-gradient magnetic field of 1T. Bacterially produced iron sulfide is an adsorbent for a wide range of heavy metals and some anions. Magnetite is a common product of bacterial iron reduction and could be a potential physical indicator of biological activity in geological settings. Single domain tiny magnetic particles (<12nm), which exhibit octahedral shapes, are formed exclusively outside of the bacterial cells by a thermophilic fermentive bacterial strain TOR39. Transition metals such as Co, Cr, and Ni may be substituted for magnetic crystals biosynthesized in the thermophilic iron-reducing bacteria Thermoanerobacter ethanolicus (TOR-39) by way of electrochemical process. The mineralization process are highly controlled by the magnetotactic bacteria, leading to the formation of uniform, species-specific magnetic nanoparticles. Sometimes, the particles are assembled into single or multiple chains and anchored inside the cell, enabling the bacteria to passively orient themselves along geomagnetic field lines. Interestingly, the magnetotactic bacteria Magnetospirillium magnetotacticum produce single-domain magnetic crystal

(Fe3O4) that are subsequently assembled into folded chain and flux closure ring morphologies. The magnetic crystals with large magnetic moments, when constrained to lie on a two dimensional surface, are responsible for the head-totail assembly. Based on the magnetization measurements and the magnitude of the magnetization field, it is established that biogenic magnetite nanoparticles are not superparamagnetic. Magnetic nanoparticles are also assembled into ordered structures when the motion of the magnetic bacteria M. magnetotacticum (MS-1) is controlled by applying a magnetic field. After assembling the bacteria with microelectromagnets, the cellular membranes of the bacteria are removed by cell lysis to leave the biogenic magnetic nanoparticles at desired locations. Different patterns of magnetic structures are observed after removing the cellular membrane of tapped MS-1 bacteria. These types of ordered magnetic structures could serve as a system for studying the interactions between closely spaced magnetic nanoparticles. Thus, a different approach, the combination of biomineralization and micromanipulation, can be anew procedure for growing and assembling nanoparticles into customised structures. All magnetotactic bacteria contain magnetosomes, which are intracellular structures comprising magnetic iron mineral crystals enveloped by a membrane vesicle. The magnetosome membrane (MM) is most likely a structural entity that anchors the crystal at particular locations in the cell, as well as the locus of biological control over the nucleation and growth of the magnetosome crystals. Knowledge of biochemical and genetic control on magnetic production is essential to understanding how the magnetotactic bacteria produce magnetosomes and organize them in chains. The biomineralization of magnetosome particles is achieved by a complex mechanism that involves the uptake and accumulation of iron and the deposition of the mineral particle with a specific size and morphology within a specific section provided by the MM. Since the MM is thought to be of paramount importance in magnetosome formation, researchers have focused on the role of MM proteins, which occur in the MM but not in the soluble (periplasmic or cytoplasmic) fraction or in the cytoplasmic or outer membranes, in magnetosome synthesis. The mam (MM) genes appear to be conserved in a large gene cluster within several magnetotactic bacteria (Magnetospirillum species and strain MC-1) and may be involved in magnetic biomineralization.

The mono dispersity of the silver/gold nanoparticles produced either intra- or extracellularly by the above mentioned methodology in not very high and far inferior to that obtained through conventional chemical methods. More by chance than by design, it is observed that alkalothermophilic (extremophilic) actinomycete, Thermomonospora sp., when exposed to gold ions, reduce metal ions extracellularly, yielding gold nanoparticles with much polydispersity. A complete reduction of the 10-3 M aqueous HAuCl4 solution at pH 9.0 and 50C results to spherical and reasonably monodisperse nanoparticles. In contrast, intracellular synthesis of gold nanoparticles occurs in alkalotolerant actinomycete Rhodococcus sp, where particles are more concentrated on the cytoplasmic membrane that on the cell wall.

Y east and nanoparticles synthesis Among the eukaryotes, yeasts are explored mostly in the biosynthesis of the semiconductor nanoparticles. Exposure of Candida glabrata to Cd2+ ions leads to the intracellular formation of CdS quantum dots. The synthesis of Phytochelation (PC) is activated in the presence of Cd. The strucutre of PC involves a repeating sequence of -glutamyl-cysteine pairs to give polypeptides the general formula ( Glu-Cys)n Gly, with n values commonly ranging from 2 to 6. They bind Cd ions immediately, forming Cd-Pc complexes that are transported into the vacuole. Then, the complex is degraded and the nanoparticles are formed. Torulopsis sp., which was found in an extensive screening program, is capable of synthesizing PbS nanocrystals intracellularly when challenged with Pb2+. Crystallites, which are extracted from the biomass by freeze thawing, exhibit a sharp absorption maximum ~330nm and are 2-5nm in size. CdS quantum dots synthesized intracellularly in Schizosaccharomyces pombe yeast cells exhibit ideal diode characteristics. Biogenic CdS nanoparticles in the size range 1-1.5 nm have been used in the fabrication of a heterojunction with poly(p-phenylenevinylene). Such a diode exhibits an approximately 75-mA/cm2 current in the forward bias mode at 10V, while breakdown occurred at 16V in the reverse direction. Fungi and nanoparticle synthesis

The use of fungi in nanoparticle synthesis is potentially exciting since they secrete large amounts of enzymes and are simpler to deal with in the laboratory. However, the genetic manipulation of eukaryotic organisms as a means of overexpressing specific enzymes identified in nanomaterial synthesis would be much more difficult that that in prokaryotes.An extensive screening process resulted to two genera, which when challenged with aqueous metal ions such as AuCl4- and Ag+, yielded large quantities of metal nanoparticles either extracellularly or intracellularly. The appearance of a distinctive purple color in the biomass of Verticillium after exposure to the 10-4 M HAuCl4 solution indicates the formation of gold nanoparticles intracellularly and can be clearly seen in the UV-Visible absorption spectrum recorded from the gold loaded biomass as a resonance at ~550nm. This resonance is clearly missing in the biomass before exposure to gold ions and in the filtrate after reaction. Further evidence of the intracellullar formation is provided by a transmission electron micrograph analysis of the thin sections of the cells after the formation of gold nanoparticles.The exposure of Verticillium sp. To silver ions resulted to a similar intracellular growth of silver nanoparticles. The exact mechanism leading to the intra cellular formation of gold and silver nanoparticles by Verticillium is not fully understood. Since the nanoparticles are formed on the surface of the mycelia and not in the solution, it is thought that the first step involves the trapping of metal ions on the surface of the fungal cells possibly via electrostatic interaction between the ions and the negatively charged carboxylate groups in the enzymes present in the cell wall of the mycelia.

Electrochemical synthesis