18 resultados para Self-organisation, Nature-inspired coordination, Bio pattern, Biochemical tuple spaces

em Cochin University of Science


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Chemistry occupies a unique middle position in the scientific arena, between physics and mathematics on the one side and biology, ecology, sociology and economics on the other [1]. Chemistry is the science of matter and of its transformations, and life is its highest expression [2]. According to reductionist thinking biology is reducible into chemistry, chemistry into physics, and ultimately physics into mathematics. Reductionism implies the ease of understanding one level in terms of another.The work presented this thesis comprises synthesis and characterization of suitably substituted thiocarbohydrazone and carbohydrazone ligand building blocks, self-assembled metallosupramolecular square grid complexes as well as some di/multinuclear complexes. The primary aim was the deliberate syntheses of some novel transition metal framework complexes, mainly metallosupramolecular coordination square grids by self-assembly and their physico-chemical characterization. The work presented, however, also include synthesis and characterization of four mononuclear Ni(II) complexes of two thiosemicarbazones, which we carried out as a preliminary and supporting study. Based on the present work we would like to conclude that the carbohydrazones, thiocarbohydrazones and their coordination framework complexes of transition metals are promising systems for wide application in science and technology varied from physics to biotechnology. Novel classes of materials and biologically important potential compounds open up further scope of researches and we hopefully welcome any sort of related research to make this work more valuable.

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This thesis deals with the studies on the synthesis and characterisation of the complexes of embelin with manganese (II), cobalt(II), nickel (II), copper (II), zinc (II), cadmium (II), chromium (III), iron (III) lanthanum(III), praseodymium (III) neodymium (III) Samarium (III), gadolinium (III) dysprosium (III), yttrium (III) thorium (IV) and uranium (VI). Elemental analysis as well as spectral, thermal and magnetic data were used to ascertain the composition of the complexes and to establish the structures of the metal complexes. Wherever possible, the electronic spectra and magnetic data were used to predict the stereochemistry of the complexes.The thesis is divided into four chapters.

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Man uses a variety of synthetic material for his comfortable materialistic life. Thus human interactions may become harmful for various terrestrial and aquatic lives. This is by contaminating their habitat and by becoming a threat to organisms itself. Thus the application and dispersal of several organic pollutants can lead to the development of several mutated forms of the species when exposed to sublethal concentrations of the pollutants. Otherwise, a decrease in number or extinction of these exposed species from earth's face may happen. Pesticides, we use for the benefit of crop yield, but its persistence may become havoc to non-target organism. Pesticides reaching a reservoir can subsequently enter the higher trophic levels. Organophosphorus compounds have replaced all other pesticides, due to its acute toxicity and non-persistent nature.Hence the present study has concentrated on the toxicity of the largest market-selling and multipurpose pesticide, chlorpyrifos on the commonly edible aquatic organism, fish. The euryhaline cichlid Oreochromis mossambicus was selected as animal model. The study has concentrated on investigating biochemical parameters like tissue-specific enzymes, antioxidant and lipid-peroxidation parameters, haematological and histological observations and pesticide residue analysis.Major findings of this work have indicated the possibility of aquatic toxicity to the fish on exposure to the insecticide chlorpyrifos. The insecticide was found as effective to induce structural alteration, depletion in protein content, decrease in different metabolic enzyme levels and to progress lipid peroxidation on a prolonged exposure of 21 days. The ion-transport mechanism was found to be adversely affected. Electrophoretic analysis revealed the disappearance of several protein bands after 21days of exposure to chlorpyrifos. Residue, analysis by gas chromatography explored the levels of chlorpyrifos retaining on the edible tissue portions during exposure period of 21days and also on a recovery period of 10 days.

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The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

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In fish processing plants, there is huge amount of skin that is left as the waste. When this skin is taken and processed into fish collagen, it will save large amount of money that is used for extraction of collagen from other animal s.Fish collagen can be used as an alternative to replace mammalian collagen, especially collagen extracted from bovine, when we consider the outbreak of bovine spongiform encephalopathy (BSE), transmissible spongiform encephalopathy (TSE) and the foot - and-mouth disease (FMD) issues. BSE and TSE are progressive neurological disorders affecting cattles caused by proteinacious infectious particles called prions.The study aims in producing collagen that has been extracted from fish skin to replace other animal collagen so as to overcome the problem of other animal collagen issues. Also the study utilized the abandoned fish waste produced by fish processing industry since bone, skin, fin and scales of fish can be a useful source of collagen.

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The basic objective of the present study has been to observe the process and pattern of employment diversification among the rural women workers in Ernakulam district. The evidences are that the women workers in the rural areas of the state are being increasingly diversified into the tertiary sector. The clear cut evidence for the fact that in Kerala non-agricultural employment of rural women is increasing with more and more of them getting diversified into the tertiary sector. The women get more self esteem and recognition in terms of the work being done by them. In the urban areas of the state as a poverty eradicating measure the Kerala government has already introduced a new scheme under the banner of Kudumbasree. Another fact noticed in the study that the sectoral shift of women workers has posed a grave problem to the agricultural sector. The reluctance of workers to do manual jobs on land and the prevalence of high wages among the agricultural labours has left many a cultivable area fallow or has induced farmers to shift to less labour –intensive crops. The situation is expected to worsen in future as even the high wages fail to attract the young generation to this sector. To conclude the study has fulfilled all its objectives, viz; highlighting the rural employment structure in Kerala, examining the process, pattern, determinants and consequences of diversification among rural women workers in the sample villages. Being the first of its kind at the micro level in the state it contributes to the available literature in the area enriching the database that is crucially lacking for devising projects at the village and block-level. There exists ample scope for future research of similar nature in an urban background where the secondary data-sources are hinding towards a reversal of trends from non-agriculture to agriculture.

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The present study is an attempt to address issues related to sediment properties like texture, mineralogy and geochemistry as well as water quality of two important rivers of central Kerala-the Periyar and the Chalakudy rivers. The main objectives of the study are to investigate the textural and mineralogical characteristics as well as transportation and depositional mechanisms of the sediments of Periyar and Chalakudy rivers, to find out the geochemical variability of organic carbon, phosphorus and certain major (Na,K,Ca and Mg) and minor/trace(Mn,Pb,Ni,Cr, and Zn) elements in the bulk sediments and mud fraction of these rivers, to evaluate the status of heavy metal pollution registered in the sediments of these rivers, to assess the physico-chemical characteristics and water quality of Periyar and Chalakudy rivers and to estimate the dissolved nutrient flux through the Periyar and Chalakudy rivers into the receiving coastal waters. The granulometric characteristics as well as statistical parameters of the sediments of Periyar and Chalakudy rivers depend on the flow pattern controlled by the gradient of the terrain. Compared to Periyar, fluctuations in the dispersal of particles are more in Chalakudy river. In Periyar river, the P and Fe in bulk sediments show a positive correlation with C-org, while in Chalakudy river, both the elements are related to THM concentration. In general, C-org, Fe and P Shows an increasing trend downstream. In Periyar river, the P and Fe in bulk sediments show a positive correlation with C-org, while in Chalakudy river, both the elements are related to THM concentration. Among these two rivers, the pollution of water is several fold higher in Periyar river due to influx due to influx of considerable quantity of liquid and solid wastes of industrial/domestic/urban origin. Nutrient analysis reveals 2-3 times increase in N and P during monsoon season whereas SiO2-Si shows a decreasing trend.

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The problem investigated is on the haematological aspects of two freshwater pulmonate snails, Indoplanorbis exustus (Deshayes),and Lymnaea acuminata f.rufescens (Gray). An important aspect of the present investigation is to emphasize the utilization of freshwater organisms as models for research directed at understanding the basic biomedical problems that remain unresolved. Another aspect is to demonstrate how haemolymph can be treated as a tissue because of late, it has been shown that several parameters of blood can be taken as reliable indicators for diagnostic purposes, and also to monitor environmental pollution. The various haematological parameters studied are total haemocyte number,packed cell volume, haemoglobin, and inorganic as well organic constituents in three size groups of both the snail species. The effect of copper toxicity was measured in terms of total haemocyte count, and the activity pattern of selected phosphatases and transaminases.The study concluded that enzyme activity levels can be taken as reliable indicators to monitor pollution. Age is a factor that determines several of the physiological, biochemical and metabolic activities. This study also indicates that haemolymph can be taken as an organ system to study the various changes taking place at organ systems levels.

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A novel N4O coordination mode offers carbohydrazone ligands as a building block for interesting frameworks through self-assembly. Bridging mode of oxygen of bis(2-benzoylpyridine ketone) carbohydrazone (H2L) with metal centers facilitates the formation of the macrocyclic molecular square [Zn(HL)]4(BF4)4 · 10H2O, offers wide range of applications for carbohydrazones.

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In the present study on natural antioxidants, the focus has been kept mainly on oil seeds, especially sesame and its by-products. Sesame, which has been under cultivation in India for centuries is called the 'Queen of oil seed crops' because of the high yield of oil obtained and the nutritional qualities of the seed, oil, and meal. Though India is the largest producer of sesame in the world, research on the various health benefits of sesame has been carried out by Japanese Sesame has an important place in the foods and tradit..ional medicine of India from time immemorial. Foreseeing the potential of sesame and its byproducts as an important antioxidant source and its availability in bulk, the present study was focussed on Sesamum species. There are not many reports on the wild species of Sesamum in India, especially of the Kerala region. Hence, in the present study we also included antioxidants of Sesamurnrnalabaricumdistributed throughout the coastal region.The important characteristics of sesame are attributed to the presence of the umquc compounds lignans. Lignans arc a group of natural products of phenyl propanoid ongm, whieh are widely distributed in nature. They display important physiological functions in plants, in human nutrition and medicine, given their extensive health promotive and curative properties. Much interest has been focussed on their effectiveness as antineoplastic agents and research in this area has revealed several modes of action by which they can regulate the growth of mammalian cells. Sesame is an important source of furofuran lignans, of which sesamin and the rare oxygenated derivative sesamoIin are the most abundant. Others include sesamol and glucosides of lignans. Sesarnin and episesamin are reported to have hypocholesterolemic effect, suppressive effect on chemically induced cancer, alleviation of allergy symptoms etc. Sesamol, sesamolin and the lignan glycosides are reported to inhibit lipid peroxidation. Present investigation on sesame and its byproducts have been carried out to explore the possibility of developing a natural antioxidant extract from available resources to be used as a substitute to synthetic ones in vegetable oils and foods. Preliminary analysis showed that sesame cake, a byproduct could still be utilized as a major source of lignans. Sesame cake, which is now used only as a cattlefeed, can be better utilized in the form of a valuable antioxidant source. The present study explains the development of a feasible process for the extraction of antioxidant compounds from sesame cake. The antioxidant extract so prepared from sesame cake has been tested for vegetable oil protection and is found to be effective at low concentration. In addition, studies also include the antioxidant, radical scavenging, anticancer, mosquitocidal and pesticidal activities of extract and individual compounds.

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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.

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The study has wider policy implications as it identifies the possible variables which influence the sustainability of participatory productive sector projects. The method which is developed to study the sustainability of projects under People’s Planning in Chempu Panchayat could be used for studying the same in other panchayats also. Unlike the case of the standard features of sustainability identified, the independent variables vary according to the nature of the project. Hence, this needs to be modified accordingly while applying the method in a dissimilar domain. Selection of a single panchayat for the present study is relevant on the basis of a common package of inputs for decentralised planning which is forwarded by the State Planning Board respectively for the three-tier panchayat system in Kerala. The dynamic filed realities could be brought out in view of a comprehensive planning approach through an in depth study of specific cases.The assessment of the nature and pattern of productive sector projects in the selected Village Panchayat puts the projects under close scrutiny. The analysis has depended largely on secondary sources of information, especially from panchayat level plan documents, and also on the primary information obtained using direct observation and on-site inspection of project sites. An analysis of the nature and pattem of productive sector projects is important as it gives all necessary information regarding follow-up, monitoring/evaluation and even termination of a particular project. It has also revealed the tendencies of including infrastructure and service sector projects under ‘productive’ category, especially for maintaining the stipulated ratio (40:30:30) of grant-in-aid distribution. The study regarding the allocation and expenditure pattern of plan funds is vital in policy level as it reveals the under-noticed allocation and expenditure pattern of plan funds other than grant-in-aid. One major limitation of the study has been the limited availability of secondary data, especially regarding project-wise expenditure and monitoring/evaluation reports of various project committees.

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Biotechnology is currently considered as a useful altemative to conventional process technology in industrial and catalytic fields. The increasing awareness of the need to create green and sustainable production processes in all fields of chemistry has stimulated materials scientists to search for innovative catalysts supports. lmmobilization of enzymes in inorganic matrices is very useful in practical applications due to the preserved stability and catalytic activity of the immobilized enzymes under extreme conditions. Nanostructured inorganic, organic or hybrid organic-inorganic nanocomposites present paramount advantages to facilitate integration and miniaturization of the devices (nanotechnologies), thus affording a direct connection between the inorganic, organic and biological worlds. These properties, combined with good chemical stability, make them competent candidates for designed biocatalysts, protein-separation devices, drug delivery systems, and biosensors Aluininosilicate clays and layered double hydroxides, displaying, respectively, cation and anion exchange properties, were found to be attractive materials for immobilization because of their hydrophilic, swelling and porosity properties, as well as their mechanical and thermal stability.The aim of this study is the replacement of inorganic catalysts by immobilized lipases to obtain purer and healthier products.Mesocellular silica foams were synthesized by oil-in-water microemulsion templating route and were functionalized with silane and glutaraldehyde. " The experimental results from IR spectroscopy and elemental analysis demonstrated the presence of immobilized lipase and also functionalisation with silane and glutaraldehyde on the supports.The present work is a comprehensive study on enzymatic synthesis of butyl isobutyrate through esterification reaction using lipase immobilized onto mesocellular siliceous foams and montmorillonite K-10 via adsorption and covalent binding. Moreover, the irnrnobil-ization does not modify the nature of the kinetic mechanism proposed which is of the Bi-Bi Ping—Pong type with inhibition by n-butanol. The immobilized biocatalyst can be commercially exploited for the synthesis of other short chain flavor esters. Mesocellular silica foams (MCF) were synthesized by microemusion templating method via two different routes (hydrothermal and room temperature). and were functionalized with silane and glutaraldehyde. Candida rugosa lipase was adsorbed onto MCF silica and clay using heptane as the coupling medium for reactions in non-aqueous media. I From XRD results, a slight broadening and lowering of d spacing values after immobilization and modification was observed in the case of MCF 160 and MCF35 but there was no change in the d-spacing in the case of K-10 which showed that the enzymes are adsorbed only on the external surface. This was further confirmed from the nitrogen adsorption measurements

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In the present thesis , observations on the ecology of seaweed flora of Kerala, their distribution and zonation pattern, monthly/seasonal density of seaweeds at each station, frequency of occurrence, standing crop, monthly/seasonal/place-wise data on physico—chemical characters of ambient waters at the stations and their influence on seaweed density have been made. This data will help us in the farming of economically important seaweeds, by providing information on the ideal conditions of seaweed biomass production. Biochemical observations on protein, carbohydrate and lipid contents of different species of nutritive value. Seaweeds with high content of proteins, carbohydrates and lipids can be recommended for food and feed formulations after subjecting them to toxicological studies. The study on monthly/seasonal/placewise variation in biochemical composition of seaweeds will provide necessary information on the appropriate time and place of harvesting the algal species for exploiting its constituents .

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The study is undertaken by the researcher with the object of examining the remuneration pattern of executive personnel in the manufacturing public enterprises in Kerala so as to find out whether there is any rationale or criteria involved in remunerating executives. It is also envisaged to find out the pattern of executive remuneration in the various categories of industries and inter—industry disparities among the public sector enterprises. This is considered to be a very fruitful area for investigation, particularly in view of the generally prevailing notion that public sector executives in Kerala are not remunerated properly and glaring inequalities and disparities are existing among the various categories of industries and within the same industry. Therefore the study is to explore the criteria used for the determination of executive remuneration and the relative weightage of various factors such as size of the firm, rate of return sales volume etc of the organisation and various other factors such as qualification, experience, level of job and functions of executives. Further the study is extended to find out the role of 'pay' towards motivation and efficiency of the executive personnel