"In the past decade nanomaterials have attracted the interest of scientists and engineers all over the world due to their unique properties. Through their devoted experimental efforts, limited advances have been made on the synthesis of nanomaterials, the integration of nanomaterials into the structures of larger scales, and the property study of nanomaterials to explore possible applications. Despite the huge amount of money, resources, and effort invested in nanomaterials, several challenges still remain as obstacles on the way towards the successful large scale use of nanomaterials to benefit human life and society. For example, the need for low-cost, robust, and highly productive manufacturing methods and the demand for efficient integration of nanomaterials with materials and devices of larger length scales are still left unmet. The objective of this work was to utilize cost-efficient nanofabrication methods such as template-assisted fabrication, electrodeposition, and chemical vapor deposition to fabricate nanomaterials, integrate nanomaterials with larger structures to form a hierarchical composite, and explore the application of unique nanostructured electrode in lithium-ion batteries. Thus the thesis consists of three main parts: (1) fabrication of one-dimensional inorganic nanomaterials such as metal nanowires, metal nanorods, and carbon nanotubes with good control over shape and dimension; (2) synthesis of hierarchical carbon nanofibers on carbon microfibers and/or glass microfibers; and (3) development of nanostructured anodes to improve high-rate capability of lithium-ion batteries by adapting nanorod arrays as miniature current collectors. "

The thesis is divided into two parts. The first part deals with the research work carried out on the synthesis and chemical modification of nanomaterials whereas the second part describes the preparation and characterisation of polymer films and their use as separation membranes. Part I of the thesis describing the synthetic strategies and chemical manipulation schemes employed on various types of nanomaterials is divided into six chapters. Chapter 1 describes a chemist’s approach towards synthesizing and tuning the properties of different classes of nanomaterials along with a brief account of their potential applications. Chapter 2 of the thesis describes the synthesis and characterization of various metal nanostructures (viz. nanoparticles, nanorods, nanosheets etc.) of nickel, ruthenium, rhodium and iridium using a solvothermal procedure. Chapter 3 deals with the nanoparticles of the novel oxide metal ReO3. ReO3@Au, ReO3@Ag, ReO3@SiO2 and ReO3@TiO2 core-shell nanostructures with ReO3 as the core nanoparticle have been synthesized through a two-step process and characterized. Dependence of the plasmon band of the ReO3 nanoparticles on the interparticle separation has been examined by incorporating the nanoparticles in various polymer matrices and the results compared with those obtained with gold nanoparticles. Chapter 4 presents the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity (water, DMF and toluene) in the presence of several surfactants. In Chapter 5 of the thesis, fluorous chemical method of separation of metallic and semiconducting single-walled carbon nanotubes is described. This method involves the selective reaction of the diazonium salt of a fluorous aniline with the metallic nanotubes in an aqueous medium and subsequent extraction of the same in a fluorous solvent leaving the semiconducting nanotubes in the aqueous layer. Chapter 6 presents the studies on the interaction of single walled nanotubes and graphene with various halogen molecules (I2, IBr, ICl and Br2) of varying electron affinity probed by employing Raman spectroscopy and electronic absorption spectroscopy. Part II of the thesis describes a general method of fabricating ultrathin free-standing cross-linked polymer films and their subsequent use as separation membranes. A particular class of 1-D nanomaterials namely cadmium hydroxide nanostrands were used in this method throughout, to generate a sacrificial layer upon which the polymer films were generated.

The thesis consists of eight chapters of which the first chapter presents a brief overview of inorganic nanostructures. Synthesis and magnetic properties of MnO and NiO nanocrystals are described in Chapter 2, with emphasis on the low-temperature ferromagnetic interactions in these antiferromagnetic oxides. Chapter 3 deals with the synthesis and characterizations of nanocrystals of ReO3, RuO2 and IrO2 which are oxides with metallic properties. Pressure-induced phase transitions of ReO3 nanocrystals and the use of the nanocrystals for carrying out surface-enhanced Raman spectroscopy of the molecules form Chapter 4. Use of ionic liquids to synthesize different nanostructures of semiconducting metal sulfides and selenides is described in Chapter 5. Synthesis of Mn-doped GaN nanocrystals and their magnetic properties are described in Chapter 6. A detailed investigation has been carried out on the growth kinetics of nanostructures of a few inorganic materials by using small-angle X-ray scattering and other techniques (Chapter 7). The study includes the growth kinetics of nanocrystals of Au, CdS and CdSe as well as of nanorods of ZnO. Results of a synchrotron X-ray study of the formation of nanocrystalline gold films at the organic-aqueous interface are also included in this chapter. Chapter 8 discuses the use of the organic-aqueous interface to generate Janus nanocrystalline films of inorganic materials where one side of the film is hydrophobic and other side is hydrophilic. This chapter also includes the formation of nanostructured peptide fibrils at the organic-aqueous interface and their use as templates to prepare inorganic nanotubes.

Chapter 1. Supramolecular Gels and their Applications Supramolecular gels are viscoelastic materials composed of a solid like three dimensional fibrillary network that is embedded in a liquid. Supramolecular gels are derived from low molecular weight compounds (typically MW < 3000). In the 1990s, the investigations on gels were mainly focused on designing new gelator molecules. However, during the last decade, research focus shifted towards designing functional gels and their applications. As a result of extensive work in this area, gels have been found to have varied applications in the templated synthesis of inorganic nanomaterials, hybrid materials, light harvesting systems, as responsive system and sensors, and also in drug delivery, tissue engineering etc. This chapter gives an introduction to supramolecular hydrogels/organogels and relevant bile acid chemistry touching upon the gelation properties of the bile acid derivatives. Diverse applications of the supramolecular gels are also illustrated with several examples. Scheme 1. Various applications of functional supramolecular gels Chapter 2. Bile Acid derived novel Hydrogelators Part 1. Hydrogelation of Bile acid protected Amino acids and Hybrid Materials Hydrogels from low molecular weight molecules have significant importance in biomedical applications. In this chapter, we report injectable hydrogel formation from bile acid conjugates of various amino acids. Hydrogel formation was found to be dependent on multiple factors such as bile acid backbone structure, linkage between the bile acid and the amino acid, pH etc. Single crystal structures of lithocholyl phenylalanine, lithocholyl-glycine, lithocholyl-L valine and lithocholyl-L alanine were also determined. Finally, the hydrogel frameworks were utilized to produce hybrid materials with Gold and ZnO nanoparticles. Scheme 2. (a) Crystal structure of LC-LF-OH gelator molecule, (b) photograph of gel, (c) SEM and (d) AFM image of LC-LF-OH xerogel Part 2. Hydrogelation of bile acid-dipeptide conjugates and in situ synthesis of silver and gold nanoparticles in the hydrogel matrix Fabricating supramolecular hydrogels with embedded metal nanostructures are important for the design of novel hybrid nanocomposite materials for diverse applications such as bio sensing and chemo sensing platforms, catalytic and antibacterial functional materials etc. Supramolecular self-assembly of bile acid-dipeptide conjugates have led to the formation of new supramolecular hydrogels. Gelation of these molecules depends strongly on the hydrophobic character of the bile acids. Ag+ and Au3+ salts were incorporated in the hydrogels, and photo reduction and chemical reduction led to the in situ generation of Ag and Au NPs in these supramolecular hydrogels without the addition of any external stabilizing agent. The color, size and shape of silver nanoparticles formed by photo reduction depended on the amino acid residue on the side chain. Furthermore, the hydrogel-Ag nanocomposite was tested for its antimicrobial activity. Scheme 3. Bile acid based dipeptide hydrogelators and soft hybrid materials Chapter 3. Sonogels of bile salts of In(III): use in the formation of self-templated indium sulfide nanostructures In this chapter, facile hydrogel formation by Indium(III) cholate and deoxy cholate are reported. When In(III) solution was added to aqueous solutions of sodium cholate and sodium deoxy cholate and sonicated, the mixtures formed gels. The gels thus obtained were translucent/turbid and thermos irreversible. Rheological measurements showed that all of them could be classified as viscoelastic soft solids. Scanning electron microscopy and atomic force microscopy showed typical entangled three dimensional fibrous networks. The In-Ch hydrogel were further used to prepare nanostructured In2S3 in which the cholate units possibly acted as a surfactant to confine the growth of the Nano flakes. Scheme 4. In-Ch hydrogel (Photograph and SEM image of In-Ch gel) Chapter 4. Palladium-Hydrogel Nanocomposite for C-C Coupling Reactions Supported metallic nanoparticles are important composite materials owing to their enormous potential for applications in various fields. This chapter describes the in situ formation of palladium nanoparticles in a calcium-cholate (Ca-Ch) hydrogel by reduction with sodium cyan borohydride. The hydrogel matrix appeared to assist the controlled growth as well as stabilization of palladium nanoparticles. The palladium nanoparticle/Ca-Ch hydrogel hybrid was characterized by scanning and transmission electron microscopy, atomic force microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. Furthermore, PdNP/Ca-Ch hybrid xerogel was shown to act as an active catalyst for Suzuki reaction under aqueous aerobic conditions, up to 4 cycles. This PdNP/Ca-Ch xerogel retained its catalytic activities on storage for several months. Scheme 5. Palladium-hydrogel nanocomposite for C-C coupling reactions in water Chapter 5. Sensitization of Terbium/Europium in self-assembled cholate hydrogel: An approach towards the detection of amine vapours "Luminescent" lanthanides have intrinsic low molar absorptivity, although this problem can be addressed by complexing the lanthanide ion with suitable chelating ligands which improve the luminescence properties drastically. However the design of such systems often involves careful planning and laborious synthetic steps. It is therefore desirable to have a simpler way to sensitize lanthanides with high efficiency. It was observed in our group that trivalent lanthanides formed hydrogels on the addition of sodium cholate. This chapter describes the discovery of the several biphenyl derivatives (such as 4-biphenylcarbaxaldehyde, 4-acetylbiphenyl) for sensitization of Tb(III) and Eu(III) in lanthanide hydrogels. Sensitization of Tb(III) and Eu(III) were observed by doping was characterized by scanning and transmission electron microscopy, atomic force microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. Furthermore, PdNP/Ca-Ch hybrid xerogel was shown to act as an active catalyst for Suzuki reaction under aqueous aerobic conditions, up to 4 cycles. This PdNP/Ca-Ch xerogel retained its catalytic activities on storage for several months. Scheme 6. Schematic representation of the sensitization process (the arrangement of themolecules in the gel fiber is arbitrary)(For figures pl refer the abstract pdf file)