L’impact de l’unité centrale sur les propriétés optoélectroniques d’imino-thiophènes électrochromes : s ynthèse et caractérisation

De nouvelles molécules électrochromes à base de thiophène et comportant des liaisons azométhine ont été synthétisées et caractérisées afin d’étudier les relations entre leur structure et leurs propriétés. Le but premier de cette étude a été d’obtenir plus d’information pouvant guider le développement de nouvelles molécules électrochromes performantes à l’aide d’une meilleure compréhension de ce qui influence leurs caractéristiques. La synthèse a été réalisée en évitant l’emploi de conditions réactionnelles difficiles et les quantités d’éléments de transition ont été minimisées. Les nouvelles structures ont permis de vérifier l’effet de la variation de l’unité centrale sur les propriétés finales. Les modifications ont principalement porté sur la longueur effective de conjugaison par l’ajout d’unités de thiophène, ainsi que l’incorporation d’une liaison vinylique. L’effet de la présence de chaînes alkyles sur les positions C3 et C4 des thiophènes du coeur de chaque molécule a également été étudié. Les propriétés telles le potentiel d’oxydation, le nombre d’électrons échangés, la réversibilité des phénomènes d’oxydoréduction, l’absorbance, ainsi que l’électrochromisme chimique et électrochimique ont été étudiées, principalement par voltampérométrie cyclique et spectrométrie UV-visible en solution. De plus, des calculs théoriques ont été effectués afin d’appuyer les résultats obtenus expérimentalement. La modification du coeur de la molécule par ajout de thiophènes voisins n’a pas entraîné de grand déplacement bathochrome du λAbs, et dans le cas des thiophènes dialkylés, un déplacement hypsochrome d’au moins 66 nm a eu lieu causé par la torsion du squelette. L’étude des structures à l’état solide a même révélé l’obtention d’un nouveau composé possédant des propriétés vapochromiques prononcées. Les nouveaux composés électrochromes possèdent des valeurs de λAbs allant de 431 à 513 nm, et des potentiels d’oxydation de 0,8 à 1,2 V.

Comparaison des réponses physiologiques lors d’un exercice incrémental maximal sur vélo immergé et sur terrain sec : aspects biomécaniques, cardiopulmonaires et hémodynamiques.

L’exercice en immersion dans l'eau peut générer des réponses hémodynamiques et cardiorespiratoires différentes à celles de l’exercice sur terraine sec. Cependant, aucune étude n’a comparé ces réponses sur vélo aquatique (VA) à celles sur vélo sur terrain sec (VS) à une même puissance mécanique externe (Pext). À cet égard, le premier travail de cette thèse visait, d’abord, à trouver les équivalences de Pext lors du pédalage sur VA en immersion à la poitrine par rapport au VS au laboratoire, en considérant que cela restait non déterminé à ce jour. Une équation de mécanique des fluides fut utilisée pour calculer la force déployée pour le système de pédalage (pales, leviers, pédales) et des jambes à chaque tour de pédale. Ensuite, cette force totale a été multipliée par la vitesse de pédalage pour estimer la Pext sur VA. Ayant trouvé les équivalences de Pext sur VA et VS, nous nous sommes fixés comme objectif dans la deuxième étude de comparer les réponses hémodynamiques et cardiorespiratoires lors d'un exercice maximal progressif sur VS par rapport au VA à une même Pext. Les résultats ont montré que le VO2 (p<0.0001) et la différence artério-veineuse (C(a-v)O2) (p<0.0001) étaient diminués lors de l’exercice sur VA comparativement à celui sur VS. Parmi les variables hémodynamiques, le volume d’éjection systolique (VES) (p˂0.05) et le débit cardiaque (Qc) (p˂0.05) étaient plus élevés sur VA. En plus, on nota une diminution significative de la fréquence cardiaque (FC) (p˂0.05). Étant donné qu’à une même Pext les réponses physiologiques sont différentes sur VA par rapport à celles sur VS, nous avons effectué une troisième étude pour établir la relation entre les différentes expressions de l'intensité relative de l'exercice (% du VO2max,% de la FCmax,% du VO2 de réserve (% de VO2R) et % de la FC réserve (% FCR)). Les résultats ont démontré que la relation % FCR vs % VO2R était la plus corrélée (régression linéaire) et la plus proche de la ligne d’identité. Ces résultats pourraient aider à mieux prescrire et contrôler l’intensité de l'exercice sur VA pour des sujets sains. Finalement, une dernière étude comparant la réactivation parasympathique après un exercice maximal incrémental effectué sur VA et VS en immersion au niveau de la poitrine a montré que la réactivation parasympathique à court terme était plus prédominante sur VA (i,e. t, delta 10 à delta 60 et T30, p<0.05). Cela suggérait, qu’après un exercice maximal sur VA, la réactivation parasympathique à court terme était accélérée par rapport à celle après l'effort maximal sur VS chez de jeunes sujets sains. En conclusion, nous proposons une méthode de calcul de la puissance mécanique externe sur VA en fonction de la cadence de pédalage. Nous avons démontré que pendant l’exercice sur VA les réponses hémodynamiques et cardiorespiratoires sont différentes de celles sur VS à une même Pext et nous proposons des équations pour le calcul du VO2 dans l’eau ainsi qu’une méthode pour la prescription et le contrôle de l’exercice sur VA. Finalement, la réactivation parasympathique à court terme s’est trouvée accélérée après un effort maximal incrémental sur VA comparativement à celle sur VS.

Sustainability of Medicinal Plants in Kerala Economic Considerations in Domestication and Conservation of Forest Resources

The present study on the sustainability of medicinal plants in Kerala economic considerations in domestication and conservation of forest resources. There is worldwide consensus on the fact that medicinal plants are important not only in the local health support systems but in rural income and foreign exchange earnings. Sustainability of medicinal plants is important for the survival of forest dwellers, the forest ecosystem, conserving a heritage of human knowledge and overall development through linkages. More equitable sharing of the benefits from commercial utilization of the medicinal plants was found essential for the sustainability of the plants. Cultivation is very crucial for the sustainability of the sector. Through a direct tie-up with the industry, the societies can earn more income and repatriate better collection charges to its members. Cultivation should be carried out in wastelands, tiger reserves and in plantation forests. In short, the various players in the in the sector could find solution to their specific problems through co-operation and networking among them. They should rely on self-help rather than urging the government to take care of their needs. As far as the government is concerned, the forest department through checking over- exploitation of wild plants and the Agriculture Dept. through encouraging cultivation could contribute to the sustainable development of the medicinal plant sector.

Industrial Growth in Madhya Pradesh: Structure and Economic Backwardness

It examine the aspects of Madhya Pradesh’s industrial structure which throw light on the development, viability and the efficiency of not only the over all industrial sector but also some of the selected industries of the state. The major objectives of are to examine the nature and characteristics of economic backwardness in Madhya Pradesh in an inter-state comparative framework and to analyse the pace and pattern of industrial growth in Madhya Pradesh against the backdrop of liberalization. To explore the industrial structure of Madhya Pradesh using the major structural ratios and industry mix. This study has underlined some structural as well as region specific constraints to the accelerated growth of the manufacturing industry in Madhya Pradesh. The industrial structure of Madhya Pradesh is concentrated and lop-sided. This is evidenced by the dominancy of single industry, basic metal and alloys. A diversified industrial structure is essential for promoting interdependent growth of the manufacturing industry based on the inter-industry linkages and agglomeration. The thesis gives a broad spectrum of regional disparities in development and evidence for Madhya Pradesh’s backwardness also portrayed and reflects the changing industrial structure of the state.

International Initiatives for Regulating Access to Genetic Resources

In light of the various international instruments and international agencies that are actively engaged in resolving the issue of ABS, the present work tries to find an answer to the larger question how far the above agencies have succeeded in regulating access and make sure of benefit sharing. In this process, the work comprehensively analyses the work of different agencies involved in the process. It tries to find out the major obstacles that stand in the way of fulfilment of the benefit sharing objective and proposes the ways and means to tackle them. The study first traces the legal foundations of the concept of property in GRs and associated TK.For this, it starts with analysis of the nature of property and the questions related to ownership in GRs as contained in the CBD as well as in various State legislations. It further examines the notion of property before and after the enactment of the CBD and establishes that the CBD contains strong private property jurisprudence.Based on the theoretical foundation of private property right,Chapter 3 analyses the benefit sharing mechanism of the CBD, i.e. the Nagoya Protocol. It searches for a theoretical convergence of the notion of property as reflected in the two instruments and successfully establishes the same. It makes an appraisal of the Nagoya regime to find out how far it has gone beyond the CBD in ensuring the task of benefit sharing and the impediments in its way.Realizing that the ITPGRFA forms part of the CBD system, Chapter 4 analyses the benefit sharing structure of ITPGRFA as revealed through its multilateral system. This gives the work the benefit of comparing two different benefit sharing models operating on the same philosophy of property. This chapter tries to find out whether there is conceptual coherence in the notion of property when the benefit sharing model changes. It alsocompares the merits and demerits of both the systems and tries to locate the hurdles in achieving benefit sharing. Aware of the legal impediments caused by IPRs in the process of ABS, Chapter 5 tries to explore the linkages between IPRs and GRs and associated TK and assesses why contract-based CBD system fails before the monopoly rights under TRIPS. Chapter 6 analyses the different solutions suggested by the international community at the TRIPS Council as well as the WIPO (World Intellectual property Organisation) and examines their effectiveness. Chapter 7 concludes that considering the inability of the present IP system to understand the grass root realities of the indigenous communities as well as the varying situations of the country of origin, the best possible way to recognise the CBD goals in the TRIPS could be better achieved through linking the two instruments by means of the triple disclosure requirement in Article 29 as suggested by the Disclosure Group during the TRIPS Council deliberations. It also recommends that considering the nature of property in GR, a new section/chapter in the TRIPS dealing with GRs would be another workable solution.

Studies on exopolysaccharide production by probiotic Lactic acid bacteria

The thesis mainly discussed the isolation and identification of a probiotic Lactobacillus plantarum, fermentative production of exopolysaccharide by the strain, its purification, structural characterisation and possible applications in food industry and therapeutics. The studies on the probiotic characterization explored the tolerance of the isolated LAB cultures to acid, bile, phenol, salt and mucin binding. These are some of the key factors that could satisfy the criteria for probiotic strains . The important factors required for a high EPS production in submerged fermentation was investigated with a collection of statistical and mathematical approach. Chapter 5 of the thesis explains the structural elucidation of EPS employing spectroscopic and chromatographic techniques. The studies helped in the exploration of the hetero-polysaccharide sequence from L. plantarum MTCC 9510. The thesis also explored the bioactivities of EPS from L. plantarum. As majority of chemical compounds identified as anti-cancerous are toxic to normal cells, the discovery and identification of new safe drugs has become an important goal of research in the biomedical sciences. The thesis has explored the anti-oxidant, anti-tumour and immunomodulating properties of EPS purified from Lactobacillus plantarum. The presence of (1, 3) linkages and its molecular weight presented the EPS with anti-oxidant, anti-tumour and immunomodulating properties under in vitro conditions.

The Impact of Integrated Marine Fisheries ‘Development Project Among the Artisanal Fishermen in Kerala

Despite various intervensions, artisanal fishermen remain one of the weaker sections in Kerala's society. Host of the welfare and developmental programmes introduced for them had produced very little impact on their living conditions. Further, they are unable to compete with mechanised sector for fishing. Host of the technological development which had taken place after Indo-Norvegean Project favoured the growth of mechanised sector. As a consequence of this, fishing become unviable for artisanal fishermen who propagate the idea of ” sustainable development” in the fishing industry. It is commonly believed that an integrated approach may help them to improve their living conditions substantially. In the light of the above background the scholar has made an attempt to study the impact of Integrated Marine Fisheries Development Project among artisanal fishermen in Kerala It is realised from the findings of the study that the most important needs of artisanal fishermen arecredit facilities and marketing support. Without marketing linkages effective credit management is not possible. Marketing activities and credit management are interdependent

The economics of chemical industry in kerala

The main purpose of the present study is to examine the growth and development problems of a new industry ,the chemical industry in the state of kerala. Problems of productivity and efficiency are studied with respect to the different branches of the industry such as fertilizers and insecticides basic inorganic and organic chemicals drugs and pharmaceuticals and miscellaneous chemicals. A study of partial input output linkages between the different chemical units is also attempted. The chemical industry is generally characterized by high linkage effects .These linkages could be used to generate subsidiary industries and thereby help in the growth and diversification of the industry. The efficiency of the working of individual units is also studied to understand the problems involved and to suggest remedial measures.

“Studies on short polyester fiber - polyurethane elastomer composite with different interfacial bonding agents”

The work presented in this thesis is regarding the development and evaluation of new bonding agents for short polyester fiber - polyurethane elastomer composites. The conventional bonding system based on hexamethylenetetramine, resorcinol and hydrated silica was not effective as a bonding agent for the composite, as the water eliminated during the formation of the RF resin hydrolysed the urethane linkages. Four bonding agents based on MDI/'I‘DI and polypropyleneglycol, propyleneglycol and glycerol were prepared and the composite recipe was optimised with respect to the cure characteristics and mechanical properties. The flow properties, stress relaxation pattern and the thermal degradation characteristics of the composites containing different bonding agents were then studied in detail to evaluate the new bonding systems. The optimum loading of resin was 5 phr and the ratio of the -01 to isocyanate was 1:1. The cure characteristics showed that the optimum combination of cure rate and processability was given by the composite with the resin based on polypropyleneglycol/ glycerol/ 4,4’diphenylmethanediisocynate (PPG/GL/MDI). From the rheological studies of the composites with and without bonding agents it was observed that all the composites showed pseudoplastic nature and the activation energy of flow of the composite was not altered by the presence of bonding agents. Mechanical properties such as tensile strength, modulus, tear resistance and abrasion resistance were improved in the presence of bonding agents and the effect was more pronounced in the case of abrasion resistance. The composites based on MDI/GL showed better initial properties while composites with resins based on MDI/PPG showed better aging resistance. Stress relaxation showed a multistage relaxation behaviour for the composite. Within the-strain levels studied, the initial rate of relaxation was higher and the cross over time was lesser for the composite containing bonding agents. The bonding agent based on MDI/PPG/GL was found to be a better choice for improving stress relaxation characteristics with better interfacial bonding. Thennogravimetirc analysis showed that the presence of fiber and bonding agents improved the thennal stability of the polyurethane elastomer marginally and it was maximum in the case of MDI / GL based bonding agents. The kinetics of degradation was not altered by the presence of bonding agents

Optical and Thermal Properties of Diethyl-(2R, 3R) (1)-tartrate Based Chiral Polyurethanes with Main Chain Amido Chromophores

The toluene diisocyanate based optically active chiral polyurethanes were synthesized according to the symmetry conditions. The noncentrosymmetric (both charge asymmetry and spatial asymmetry) environment were attained by the incorporation of the chiral units (diethyl-(2R,3R)(þ)-tartrate) and donor-acceptor building blocks in the main chain which induce a helical conformation in the macromolecular chain. A series of optically active polyurethanes containing chiral linkages in the polymer back bone have been synthesized by using DBTDL catalyst by incorporating the amido diols which were obtained by the aminolysis of e-caprolactone by using the diamines, diaminoethane, diaminobutane, and diaminohexane respectively. The effect of incorporation of the chiral molecule diethyl-(2R,3R)(þ)-tartrate on the properties of polyurethanes was studied by changing the chromophores and also by varying the chiral-chromophore composition. Various properties of polyurethanes were investigated by UV, Fluorescence, TG/DTA, XRD, polarimetric techniques, Kurtz-Perry powder techniques, etc.

Isosorbide based chiral polyurethanes: optical and thermal studies

A new class of chiral polyurethanes containing amido linkages in the polymer backbone have been synthesized by reacting toluene diisocyanate with isosorbide (IS) chiral moiety and the chromophores [N,N0-ethane- 1,2-diyl bis(6-hydroxy hexanamide), N,N0-butane-1,4-diyl bis(6-hydroxy hexanamide) and N,N0-hexane-1,6-diyl bis (6-hydroxy hexanamide)]. The corresponding chromophores were obtained by the aminolysis of e-caprolactone by using the diamines, diaminoethane, diaminobutane and diaminohexane, respectively. All the polymers were synthesized according to the symmetry conditions so as to obtain the non-centrosymmetric environment. A series of polyurethanes were synthesized by varying the chiral– chromophore composition. The polyurethanes developed were characterized by optical and thermal methods.

Linking sustainability indicators of Indian wild caught ornamental fish industry

The Indian ornamental fish industry is divided into two- the domestic market and the export market. 90% of the freshwater ornamental fish exported from India are wild caught indigenous species. The study formed the criteria and indicators assessing the sustainability of wild caught ornamental fish exported from India. These indicators were then analyzed for their interactions, connections, linkages and relationships using cognitive mapping. The work is first of its kind in the ornamental fisheries

Sustainability and Consumer Preference of Wild Caught Ornamental Fishes from Kerala: Scope of Certification

The Indian ornamental fish industry is divided into two-the domestic market and the export market. 90% of the freshwater ornamental fish exported from India are wild caught indigenous species. The study formed the criteria and indicators assessing the sustainability of wild caught ornamental fish exported from India. These indicators were then analyzed for their interactions, connections, linkages and relationships using cognitive mapping. The work is first of its kind in the ornamental fisheries

Migration and Spatial Development

This is an empirical study with theoretical interpretation and elaboration simultaneously on the migration process and the related spatial development in contemporary China. In so doing, there is always a combination of series of studies of the modernization of the migrants themselves with accumulation of forms of capital and changes of lebenswelt (life world) as well as the regions of their origins by the effective use of the gained resources from outgoing migration and remigration. With great efforts made to put the issues together for analysis, the author has taken three approaches to the study based on the political and economic institutional arrangements, the field work data and the elaboration of respective findings. First, as the analytical parts of the institutional changes, which have gone through the whole research, many of the policies from state level to townships involved in the migration, remigration and spatial development have been interpreted with Chinese political and cultural insight. The making of these, as the means of understanding the contexts of macro level and micro level cases is served as key linkages between scholarly imagination and social reality. Indeed most of the discussions made to explain the phenomena such as the sudden upsurge of migration flows, the emergence of three generations, the strong and weak trends of remigration as well as the related spatial development planning, etc are mainly due to the domination, at least the impact of governments decision-making in spite of growing market functioning in often operative manners. Secondly, case studies of the effects of migration and remigration are carried out between the years of 1995 and 2005 in the costal urban regions as designations and the interior rural regions as origins. Conducted mainly by the author, the cases drawn in the research focus on the process of migration with an accumulation of forms of capital away from home and the effective use of the resources flowing back to home areas. As a result, ways of accumulation and utilization of the economic, social and cultural capital are described and interpreted in terms of the development and modernization of both the migrants themselves and the regions where they come out from or move to in the future. Thirdly, in accordance with the findings generated from the cases, the author proposes in the final chapter an important argumentation as conclusion that the duel social-economic structure will inevitably be broken up and reformulated with flows of migrants and forms of capital they possess as types of future spatial development that will be put into practice. With scenarios and all the other conclusions worked out in the end, the research concludes that the pluralistic spatial development in the condition of constant space flows between regions can be a decisive line of thinking in the process of urbanization, industrialization and modernization in the long run in the future. Since this is an exploratory study of the past and present, the author has left some space open for academic debates and put forward suggestions on the inclusion of future research before implementing policies necessary for migration associated spatial practice and development.

Design, implementation and application of a generic framework for integrated regional land-use modeling

Land use is a crucial link between human activities and the natural environment and one of the main driving forces of global environmental change. Large parts of the terrestrial land surface are used for agriculture, forestry, settlements and infrastructure. Given the importance of land use, it is essential to understand the multitude of influential factors and resulting land use patterns. An essential methodology to study and quantify such interactions is provided by the adoption of land-use models. By the application of land-use models, it is possible to analyze the complex structure of linkages and feedbacks and to also determine the relevance of driving forces. Modeling land use and land use changes has a long-term tradition. In particular on the regional scale, a variety of models for different regions and research questions has been created. Modeling capabilities grow with steady advances in computer technology, which on the one hand are driven by increasing computing power on the other hand by new methods in software development, e.g. object- and component-oriented architectures. In this thesis, SITE (Simulation of Terrestrial Environments), a novel framework for integrated regional sland-use modeling, will be introduced and discussed. Particular features of SITE are the notably extended capability to integrate models and the strict separation of application and implementation. These features enable efficient development, test and usage of integrated land-use models. On its system side, SITE provides generic data structures (grid, grid cells, attributes etc.) and takes over the responsibility for their administration. By means of a scripting language (Python) that has been extended by language features specific for land-use modeling, these data structures can be utilized and manipulated by modeling applications. The scripting language interpreter is embedded in SITE. The integration of sub models can be achieved via the scripting language or by usage of a generic interface provided by SITE. Furthermore, functionalities important for land-use modeling like model calibration, model tests and analysis support of simulation results have been integrated into the generic framework. During the implementation of SITE, specific emphasis was laid on expandability, maintainability and usability. Along with the modeling framework a land use model for the analysis of the stability of tropical rainforest margins was developed in the context of the collaborative research project STORMA (SFB 552). In a research area in Central Sulawesi, Indonesia, socio-environmental impacts of land-use changes were examined. SITE was used to simulate land-use dynamics in the historical period of 1981 to 2002. Analogous to that, a scenario that did not consider migration in the population dynamics, was analyzed. For the calculation of crop yields and trace gas emissions, the DAYCENT agro-ecosystem model was integrated. In this case study, it could be shown that land-use changes in the Indonesian research area could mainly be characterized by the expansion of agricultural areas at the expense of natural forest. For this reason, the situation had to be interpreted as unsustainable even though increased agricultural use implied economic improvements and higher farmers' incomes. Due to the importance of model calibration, it was explicitly addressed in the SITE architecture through the introduction of a specific component. The calibration functionality can be used by all SITE applications and enables largely automated model calibration. Calibration in SITE is understood as a process that finds an optimal or at least adequate solution for a set of arbitrarily selectable model parameters with respect to an objective function. In SITE, an objective function typically is a map comparison algorithm capable of comparing a simulation result to a reference map. Several map optimization and map comparison methodologies are available and can be combined. The STORMA land-use model was calibrated using a genetic algorithm for optimization and the figure of merit map comparison measure as objective function. The time period for the calibration ranged from 1981 to 2002. For this period, respective reference land-use maps were compiled. It could be shown, that an efficient automated model calibration with SITE is possible. Nevertheless, the selection of the calibration parameters required detailed knowledge about the underlying land-use model and cannot be automated. In another case study decreases in crop yields and resulting losses in income from coffee cultivation were analyzed and quantified under the assumption of four different deforestation scenarios. For this task, an empirical model, describing the dependence of bee pollination and resulting coffee fruit set from the distance to the closest natural forest, was integrated. Land-use simulations showed, that depending on the magnitude and location of ongoing forest conversion, pollination services are expected to decline continuously. This results in a reduction of coffee yields of up to 18% and a loss of net revenues per hectare of up to 14%. However, the study also showed that ecological and economic values can be preserved if patches of natural vegetation are conservated in the agricultural landscape. -----------------------------------------------------------------------