Studies on Catalysis by Ordered Mesoporous SBA-15 Materials Modified with Transition Metals

To meet the challenges related to the chemical industry,development of efficient catalysts is necessary.The mesoporous materials like SBA-15 are considered as good catalyst candidates of 21st century.SBA-15 mesoporous materials are catalytically inactive,but allow the dispersion of catalytically active phases into the framework.So these materials can be considered as an interesting alternative for preparing catalytically active metal nanoparticles in-situ into it.In the present work various transition metals are incorporated to improve the catalytic activity of SBA-15 material.The fundamental aspects of the preparation,characterization and the activity studies are briefly viewed in this thesis. Systematic investigation of the physico-chemical properties and catalytic activity studies of the prepared materials were carried out and presented in this Study.

Oligo(p-Phenylenevinylene) Derived Organogels: A Novel Class of Functional Supramolecular Materials

The main objective of the present study is to have a detailed investigation on the gelation properties, morphology and optical properties of small π-conjugated oligomers. For this purpose we have chosen oligo(p-phenylenevinylene)s (OPVs), a class of molecules which have received considerable attention due to their unique optical and electronic properties. Though a large number of reports are available in the literature on the self-assembly properties of tailor made OPVs, none of them pertain to the design of nanostructures based on organogels. In view of this, we aimed at the creation of functional chromophoric assemblies of π-conjugated OPVs through the formation of organogels, with the objective of crafting nanoscopic assemblies of different size and shape thereby modulating their optical and electronic properties.In order to fulfill the above objectives, the design and synthesis of a variety of OPVs with appropriate structural variations were planned. The design principle involves the derivatization of OPVs with weak H-bonding hydroxymethyl end groups and with long aliphatic hydrocarbon side chains. The noncovalent interactions in these molecules were expected to lead the formation of supramolecular assembly and gels in hydrocarbon solvents. In such an event, detailed study of gelation and extensive analysis of the morphology of the gel structures were planned using advanced microscopic techniques. Since OPVs are strongly fluorescent molecules, gelation is expected to perturb the optical properties. Therefore, detailed study on the gelation induced optical properties as a way to probe the nature and stability of the selfassembly was planned. Apart from this, the potential use of the modulation of the optical properties for the purpose of light harvesting was aimed. The approach to this problem was to entrap an appropriate energy trap to the OPV gel matrix which may lead to the efficient energy transfer from the OPV gel based donor to the entrapped acceptor. The final question that we wanted to address in this investigation was the creation of helical nanostructures through proper modification of the OPV backbone With chiral handles.The present thesis is a detailed and systematic approach to the realization of the above objectives which are presented in different chapters of the thesis.

Investigations of Optical Interaction Processes in Certain Photonic Materials Using Z-scan and Thermal Lens Techniques

International School of Photonics, Cochin University of Science and Technology

Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Innovative Human Resource Practices and Selected HR Outcomes in Software Firms in Kerala

In this study the relationship between Innovative HR practices and selected HR outcomes is investigated.The current study represents a unique attempt to study the effects of innovative HR practices,with job satisfaction,organisational commitment and organisational citizenship bahaviour considered as the consequent variables.Results have affirmed the role of intervening variables such as job satisfaction and organisational commitment in establishing the link between IHRP and OCB obliterating any direct relation between IHRP and organisational citizenship behaviour.This finding may enable researchers in the human resource management to develop more robust understandings of the positive effects of innnovative HR practices on HR outcomes.Thus the present study provides the obvious contribution of weaving up yet another linkage between the two complimentary disciplines of Human Resource Management and Organisational Behaviour.The present study also contributes to the understanding of OCB by exploring its antecedents and extending the intervening role of job satisfaction and organisational commitment.The findings indicate that a higher level of introduction/initiation and satisfaction of innovative HR practices produces high job satisfaction and organisational commitment which lead to OCB.The researcher drew upon the perception-attitude-behaviour model to further realise the expected relationship among innovative HR practices,job satisfaction,organisational commitment and organisational citizenship behaviour.Consequently,this study makes a contribution to the broader organisational citizenship behaviour literature by manifesting the extended relationship path from innovative HR practices to organisational citizenship behaviour,and demonstrating that innovative Hr practices at the organisational level has an effect on employee attitudes and behaviours as well.

Functionalized Silicon Polymers: Novel Materials for Catalysis

Dept.of Applied Chemistry,Cochin University of Science and Technolgy

Dielectric properties of certain biological materials at microwave frequencies.

In the medical field, microwaves play a larger role for treatment than diagnosis. For the detection of diseases by microwave methods, it is essential to know the dielectric properties of biological materials. For the present study, a cavity perturbation technique was employed to determine the dielectric properties of these materials. Rectangular cavity resonators were used to measure the complex permittivity of human bile, bile stones, gastric juice and saliva. The measurements were carried out in the S and J bands. It is observed that normal and infected bile have different dielectric constant and loss tangent. Dielectric constant of infected bile and gastric juice varies from patient to patient. Detection and extraction of bile stone with possible method of treatment is also discussed.

Nonlinear Optical Properties of Organic and Polymer Systems

Present thesis has discussed the design and synthesis of polymers suitable for nonlinear optics. Most of the molecules that were studied have shown good nonlinear optical activity. The second order nonlinear optical activity of the polymers was measured experimentally by Kurtz and Perry powder technique. The thesis comprises of eight chapters.The theory of NLO phenomenon and a review about the various nonlinear optical polymers has been discussed in chapter 1. The review has provided a survey of NLO active polymeric materials with a general introduction, which included the principles and the origin of nonlinear optics, and has given emphasis to polymeric materials for nonlinear optics, including guest-host systems, side chain polymers, main chain polymers, crosslinked polymers, chiral polymers etc.Chapter 2 has discussed the stability of the metal incorporated tetrapyrrole molecules, porphyrin, chlorin and bacteriochlorin.Chapter 3 has provided the NLO properties of certain organic molecules by computational tools. The chapter is divided into four parts. The first part has described the nonlinear optical properties of chromophore (D-n-A) and bichromophore (D-n-A-A-n-D) systems, which were separated by methylene spacer, by making use of DPT and semiempirical calculations.Chapter 4: A series of polyurethanes was prepared from cardanol, a renewable resource and a waste of the cashew industry by previously designed bifunctional and multifunctional polymers using quantum theoretical approach.Chapter 5: A series of chiral polyurethanes with main chain bis azo diol groups in the polymer backbone was designed and NLO activity was predicted by ZlNDO/ CV methods.In Chapter 7, polyurethanes were first designed by computational methods and the NLO properties were predicted by correction vector method. The designed bifunctional and multifunctional polyurethanes were synthesized by varying the chiral-achiral diol compositions

Resource abundance and Survival of indigenous ornamental fishes of central Kerala with emphasis on handling and packing stress in Puntius filamentosus(VALENCIENNES)

This thesis Entitled Resource abundance and survival of indigenous ornamental fishes of central kerala with emphasis on handling and packing stress in puntius filamentosus (valenciennes).Kerala state is endowed with 41 west flowing and three east flowing rivers originating in the Western Ghats. These rivers and their vast network of tributaries and distributaries harbour rich and diversified fish fauna. Most of the freshwater fishes available in Kerala are highly appreciated as ornamental fishes in the national and international markets.Today the ornamental fish industry is one of the largest industries all over the world. The demand for ornamental fishes has been increasing steadily with the enlargement of the industry, such that the current demand for indigenous ornamental fishes have exceeded the supply. This has led to serious concern about the resources available in the country that can be utilised judiciously for the economic benefit of the state. With an aim to fill up the lacuna, a database of freshwater ornamental fishes of Kerala was created as part of the present study. Ornamental fishes destined for export marketing should thrive well in the aquarium conditions.The study reiterates fishes caught from different environmental conditions and feeding habits have a greater ability to adapt and acclimatise to an entirely new environment and food habits. Marketing studies based on the statistics available with Marine Products Export Development Authority show that these species are not being exported at the required level over the past 6 years, when compared to the availability in the water bodies of Kerala. Sustainable utilisation of these resources from the wild using modern management principles and code of conduct for responsible fishing are advisable until captive breeding technology is popularised.

Studies on certain exploted marine finfish resource of India

This thesis Entitled Studies on certain exploited marine Finfish Resources of india.Marine fish catch forecasting is short term or long term basis for purposes of explation and management. Among the short term forecasts, two approaches need serious consideration in India: 1. to improve the methods of understanding the influence of environmental characteristics on the abundance or availability of fish in different areas in different periods and to make the forecasts of the same, 2. to make analysis of time series catch data (ARIMA models) to make forecasts of catch in the next year or in a particular period during next year. There is some evidence of suitability of these approaches to Indian marine fisheries but attempts aiming at comprehensive studies should be made. In the area of long term forecasts, considerable work is done in India on single species assessments but in the context of multi species, multigear nature of Indian marine fisheries, assessments of all species together in a mixed fishery are urgently required for effective managements of fisheries.

Analysis of resource use efficiency of the spinning mills in Kerala

This thesis discusses the factors which influence the productive and financial performance of the spinning mills in Kerala. The study will also help to assess the effect of ongoing reforms in the industrial sector in India. The main objective of the study is to identify and analyse the factors affecting the efficiency of the spinning mills. The unique feature of the study is that it compares the performance of private sector in relation to its public counterparts and also performance of small sector in relation to medium sector. The study is carried out with reference to the relative performance of differmills in Kerala and to identify the sources of differences in performance. The study covers twenty one spinning mills in Kerala, of which ten are in the private sector, four under NTC, three under co—operat;ive sector and four under KSTC.Measured in terms of firm-size fifteen belong to small size with a spindleage of less than 26,000 and six are in the medium size with a spindleage of 26,000 to 50,0OO.1 The period of study is 1982-83 to 1991-92. Hence, only those companies, of which data of 10 years upto 1991-92 wereavailable, are taken for study.

Packaging materials for shrimp, fish and fish products, their properties, selection and effect of different packaging materials on their shelf life

Packaging is important not only in extending the shellife of fish and fishery products but also improving their marketability. In the recent years, significant development have taken place in the packaging industry. During the past decade in India, there is almost a packaging revolution with the availability of variety packaging materials, thus generating better packaging consciousness in other producer/manufacturing industries. But unfortunately, such realisation is not forthcoming in the fisheries sector and packaging techniques for local and export trade continues to be on traditional lines with their inherent drawbacks and limitations. Better packaging ensures improved quality and presentation of the products and ensures higher returns to the producer. Among several packaging materials used in fishery industry, ISI specifications had been formulated only for corrugated fibre board boxes for export of seafoods and froglegs. This standard was formulated before containersiation came into existance in the export of marine products. Before containerisation, the standards were stringent in view of the rough handling, transportation and storage. Two of the common defects reported in the master cartons exported from India are low mechanical strength and tendency to get wet. They are weakened by the deposits of moisture caused by temperature fluctuations during loading, unloading and other handling stages. It is necessary to rectify the above defects in packaging aquatic products and hence in the present study extensive investigations are carried out to find out the reasons for the damage of master cartons, to evolve code of practice for the packaging oi frozen shrimp for exports, development of alternative style of packaging for the shipping container, development of suitable consumer packaging materials for fish soup powder, cured dried mackeral, fish pickles in oil and frozen shrimp. For the development of suitable packaging materials, it is absolutely essential to know the properties of packaging materials, effect of different packaging materials on theirshelf life and their suitability for food contact applications.