Synthesis of constrained tricyclic nucleosides and the core of nagilactone B

Cette thèse décrit deux thèmes principaux: 1) la conception, la synthèse, et l'évaluation biophysique des nucléosides tricycliques, et 2) la synthèse de nagilactone B, un produit naturel norditerpenoïde dilactone de la famille de produits naturels “podolactone”. Le premier chapitre décrit la stratégie de design rationnel des nucléosides nommé “restriction conformationnelle double” basée sur les études de modélisation structurales des duplex ADN–ARN modifiés. Cette stratégie implique un blocage du cycle furanose dans une configuration de type N- ou S, et une restriction de la rotation torsionelle autour de l’angle γ. La première contrainte a été incorporée avec un pont méthylène entre l’oxygène en position 2′ et le carbone 4′ du nucléoside. Cette stratégie a été inspirée par les acides nucléiques bloqués (ou “locked nucleic acid”, LNA). La deuxième contrainte a été réalisée en ajoutant un carbocycle supplémentaire dans l'échafaud de l’acide nucléique bloqué. Les défis synthétiques de la formation des nucléotides modifiés à partir des carbohydrates sont décrits ainsi que les améliorations aux stabilités thermiques qu’ils apportent aux duplex oligonucléïques dont ils font partie. Chapitres deux et trois décrivent le développement de deux voies synthétiques complémentaires pour la formation du noyau de nagilactone B. Ce produit naturel a des implications pour le syndrome de Hutchinson–Gilford, à cause de son habilité de jouer le rôle de modulateur de l’épissage d’ARN pré-messager de lamine A. Ce produit naturel contient sept stereocentres différents, dont deux quaternaires et deux comprenant un syn-1,2-diol, ainsi que des lactones à cinq ou six membres, où le cycle à six ressemble à un groupement α-pyrone. La synthèse a débuté avec la cétone de Wieland-Miescher qui a permis d’adresser les défis structurels ainsi qu’explorer les fonctionnalisations des cycles A, B et D du noyau de nagilactone B.

Cadmium Selenide Based Core-Shell Quantum Dots for Biosensing and Imaging Applications

The overall focus of the thesis involves the synthesis and characterization of CdSe QDs overcoated with shell materials for various biological and chemical sensing applications. Second chapter deals with the synthesis and characterization of CdSe and CdSe/ZnS core shell QDs. The primary attention of this work is to develop a simple method based on photoinduced charge transfer to optimize the shell thickness. Synthesis of water soluble CdSe QDs, their cytotoxicity analysis and investigation of nonlinear optical properties form the subject of third chapter. Final chapter deals with development of QD based sensor systems for the selective detection of biologically and environmentally important analytes from aqueous media.

Microscopic origin of exchange bias in core/shell nanoparticles

We report the results of Monte Carlo simulations with the aim to clarify the microscopic origin of exchange bias in the magnetization hysteresis loops of a model of individual core/shell nanoparticles. Increase of the exchange coupling across the core/shell interface leads to an enhancement of exchange bias and to an increasing asymmetry between the two branches of the loops which is due to different reversal mechanisms. A detailed study of the magnetic order of the interfacial spins shows compelling evidence that the existence of a net magnetization due to uncompensated spins at the shell interface is responsible for both phenomena and allows to quantify the loop shifts directly in terms of microscopic parameters with striking agreement with the macroscopic observed values.

Large enhanced dielectric permittivity in polyaniline passivated core-shell nano magnetic iron oxide by plasma polymerization

Commercial samples of Magnetite with size ranging from 25–30nm were coated with polyaniline by using radio frequency plasma polymerization to achieve a core shell structure of magnetic nanoparticle (core)–Polyaniline (shell). High resolution transmission electron microscopy images confirm the core shell architecture of polyaniline coated iron oxide. The dielectric properties of the material were studied before and after plasma treatment. The polymer coated magnetite particles exhibited a large dielectric permittivity with respect to uncoated samples. The dielectric behavior was modeled using a Maxwell–Wagner capacitor model. A plausible mechanism for the enhancement of dielectric permittivity is proposed

Toxic Metal Distribution in the Core Sediment of Cochin Estuarine System (CES)

This article present the result from a study of two sediment cores collected from the environmentally distinct zones of CES. Accumulation status of five toxic metals: Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu) and Lead (Pb) were analyzed. Besides texture and CHNS were determined to understand the composition of the sediment. Enrichment Factor (EF) and Anthropogenic Factor (AF) were used to differentiate the typical metal sources. Metal enrichment in the cores revealed heavy load at the northern (NS1 ) region compared with the southern zone (SS1). Elevation of metal content in core NS1 showed the industrial input. Statistical analyses were employed to understand the origin of metals in the sediment samples. Principal Component Analysis (PCA) distinguishes the two zones with different metal accumulation capacity: highest at NS1 and lowest at SS1. Correlation analysis revealed positive significant relation only in core NS1, adhering to the exposition of the intensified industrial pollution

Geochemistry of core sediment from antarctic region

Southern Ocean (SO) is the fourth largest Ocean comprising the southern portions of the Atlantic Ocean, Indian Ocean and Pacific Ocean. Sediment core sample (660 34’S and 580 40’E)was collected onboard O.R.V Sagar Nidhi from January to March 2010 in the Fourth Southern Ocean expedition cruise launched by the National Centre for Antarctic and Ocean Research, Goa . Sedimentary records from this area reveal the sensitivity and climatic variability’s of the region over a large time scale. Organic matter (OM) and textural behaviour of the samples were analyzed and processed concurrently. Distribution of OM, Total Organic Carbon (TOC), Protein, Lipid and Carbohydrate along with the trace metal was highlighted. Textural variation was in the array of Sand >Clay >Silt. Sand content ranges from 30.29% to 80.11%. The order of relative distribution of OM was Lipid >Protein > TOC > Carbohydrate. The average concentrations of TOC, Protein, Lipid and Carbohydrate were 2.2 mg/g, 1.2 mg/g, 3.3 mg/g and 1.1mg/g respectively. Protein to carbohydrate ratio and lipid to carbohydrate ratio were also encountered to understand the respective freshness and nutritional quality of the sediments. Trace metal distribution showed the average concentration was maximum for Mn and minimum for Co.

Environmental Geochemistry of Core Sediment in the Cochin Estuary (CE), India

Distribution of toxic metal in the sediment core is an important area of research for environmental impact studies. Sediment cores were collected from two prominent region(C1 and C2) of CE and subjected to geochemical analysis to determine distribution of toxic metals (Cd, Co, Cr, Cu and Pb ), texture characteristics, total organic carbon (TOC) and CHNS. Statistical analysis was done to understand the interrelationship between the components. In the studied cores, metal contamination level was identified for Pb, Cu; Cr, in C1 and C2 respectively. The metal distribution depends on the granulometric factor, geogenic mineral components and anthropogenic input. Correlation analysis (CA) and Principal component(PCA) analysis also support these results

Core sediment biogeochemistry in specific zones of Cochin Estuarine System (CES)

Geochemical composition is a set of data for predicting the climatic condition existing in an ecosystem. Both the surficial and core sediment geochemistry are helpful in monitoring, assessing and evaluating the marine environment. The aim of the research work is to assess the relationship between the biogeochemical constituents in the Cochin Estuarine System (CES), their modifications after a long period of anoxia and also to identify the various processes which control the sediment composition in this region, through a multivariate statistical approach. Therefore the study of present core sediment geochemistry has a critical role in unraveling the benchmark of their characterization. Sediment cores from four prominent zones of CES were examined for various biogeochemical aspects. The results have served as rejuvenating records for the prediction of core sediment status prevailing in the CES

Geochemical metal fractionation profile of the core sediment in the Cochin estuarine system

Geochemical composition is a set of data for predicting the climatic condition existing in an ecosystem. Both the surficial and core sediment geochemistry are helpful in monitoring, assessing and evaluating the marine environment. The aim of the research work is to assess the relationship between the biogeochemical constituents in the Cochin Estuarine System (CES), their modifications after a long period of anoxia and also to identify the various processes which control the sediment composition in this region, through a multivariate statistical approach. Therefore the study of present core sediment geochemistry has a critical role in unraveling the benchmark of their characterization. Sediment cores from four prominent zones of CES were examined for various biogeochemical aspects. The results have served as rejuvenating records for the prediction of core sediment status prevailing in the CES

AN APPRAISAL OF CORE SEDIMENT ARCHIVES ON ORGANOCHLORINE INSECTICIDES IN A TROPICAL ESTUARY, INDIA

Cochin University of Science And Technology

Sedimentology and Geochemistry of core sediments from the Ashtamudi estuary and the adjoining coastal plain,central Kerala,India

The evolution of coast through geological time scale is dependent on the transgression-regression event subsequent to the rise or fall of sea level. This event is accounted by investigation of the vertical sediment deposition patterns and their interrelationship for paleo-enviornmental reconstruction. Different methods like sedimentological (grain size and micro-morphological) and geochemical (elemental relationship) analyses as well as radiocarbon dating are generally used to decipher the sea level changes and paleoclimatic conditions of the Quaternary sediment sequence. For the Indian coast with a coastline length of about 7500 km, studies on geological and geomorphological signatures of sea level changes during the Quaternary were reported in general by researchers during the last two decades. However, for the southwest coast of India particularily Kerala which is famous for its coastal landforms comprising of estuaries, lagoons, backwaters, coastal plains, cliffs and barrier beaches, studies pertaining to the marine transgression-regression events in the southern region are limited. The Neendakara-Kayamkulam coastal stretch in central Kerala where the coast is manifested with shore parallel Kayamkulam Lagoon on one side and shore perpendicular Ashtamudi Estuary on the other side indicating existence of an uplifted prograded coastal margin followed by barrier beaches, backwater channels, ridge and runnel topography is an ideal site for studying such events. Hence the present study has been taken up in this context to address the gap area. The location for collection of core samples representing coastal plain, estuarylagoon and offshore regions have been identified based on published literature and available sedimentary records. The objectives of the research work are:  To study the lithological variations and depositional environments of sediment cores along the coastal plain, estuary-lagoon and offshore regions between Kollam and Kayamkulam in the central Kerala coast  To study the transportation and diagenetic history of sediments in the area  To investigate the geochemical characterization of sediments and to elucidate the source-sink relationship  To understand the marine transgression-regression events and to propose a conceptual model for the region The thesis comprises of 8 chapters. The first chapter embodies the preamble for the selection and significance of this research work. The study area is introduced with details on its physiographical, geological, geomorphological, rainfall and climate information. A review of literature, compiling the research on different aspects such as physico-chemical, geomorphological, tectonics, transgression-regression events are presented in the second chapter and they are broadly classified into three viz:- International, National and Kerala. The field data collection and laboratory analyses adopted in the research work are discussed in the third chapter. For collection of sediment core samples from the coastal plains, rotary drilling method was employed whereas for the estuary-lagoon and offshore locations the gravity/piston corer method was adopted. The collected subsurficial samples were analysed for texture, surface micro-texture, elemental analysis, XRD and radiocarbon dating techniques for age determination. The fourth chapter deals with the textural analysis of the core samples collected from various predefined locations of the study area. The result reveals that the Ashtamudi Estuary is composed of silty clay to clayey type of sediments whereas offshore cores are carpeted with silty clay to relict sand. Investigation of the source of sediments deposited in the coastal plain located on either side of the estuary indicates the dominance of terrigenous to marine origin in the southern region whereas it is predominantly of marine origin towards the north. Further the hydrodynamic conditions as well as the depositional enviornment of the sediment cores are elucidated based on statistical parameters that decipher the deposition pattern at various locations viz., coastal plain (open to closed basin), Ashtamudi Estuary (partially open to restricted estuary to closed basin) and offshore (open channel). The intensity of clay minerals is also discussed. From the results of radiocarbon dating the sediment depositional environments were deciphered.The results of the microtextural study of sediment samples (quartz grains) using Scanning Electron Microscope (SEM) are presented in the fifth chapter. These results throw light on the processes of transport and diagenetic history of the detrital sediments. Based on the lithological variations, selected quartz grains of different environments were also analysed. The study indicates that the southern coastal plain sediments were transported and deposited mechanically under fluvial environment followed by diagenesis under prolonged marine incursion. But in the case of the northern coastal plain, the sediments were transported and deposited under littoral environment indicating the dominance of marine incursion through mechanical as well as chemical processes. The quartz grains of the Ashtamudi Estuary indicate fluvial origin. The surface texture features of the offshore sediments suggest that the quartz grains are of littoral origin and represent the relict beach deposits. The geochemical characterisation of sediment cores based on geochemical classification, sediment maturity, palaeo-weathering and provenance in different environments are discussed in the sixth chapter. In the seventh chapter the integration of multiproxies data along with radiocarbon dates are presented and finally evolution and depositional history based on transgression–regression events is deciphered. The eighth chapter summarizes the major findings and conclusions of the study with recommendation for future work.

Core Labor Rights

The working paper’s main objective is to explore the extent to which non-compliance to international labor rights is caused by global competition. From the perspective of institutional economics, compliance with core labor rights is beneficial for sustainable development. Nonetheless, violations of these rights occur on a massive scale. The violators usually blame competitive pressures. A number of studies have come to the conclusion that non-compliance does not provide for a competitive edge, thereby denying any economic rationale for non-compliance. While we sympathize with this conclusion, we find that these studies suffer from faulty assumptions in the design of their regression analyses. The assumption of perfect markets devoid of power relations is particularly unrealistic. While workers' rights promise long-term benefits, they may incur short-term production cost increases. On the supply side, the production sites with the highest amount of labor rights violations are characterized by a near perfect competitive situation. The demand side, however, is dominated by an oligopoly of brand name companies and large retailers. Facing a large pool of suppliers, these companies enjoy more bargaining power. Developing countries, the hosts to most of these suppliers, are therefore limited in their ability to raise labor standards on their own. This competitive situation, however, is the very reason why labor rights have to be negotiated internationally. Our exploration starts with an outline of the institutionalist argument of the benefits of core labor rights. Second, we briefly examine some cross-country empirical studies on the impact of trade liberalization (as a proxy for competitive pressures). Third, we develop our own argument which differentiates the impact of trade liberalization along the axes of labor- and capital-intensive production as well as low and medium skill production. Finally, we present evidence from a study on the impact of trade liberalization in Indonesia on the garment industry as an example of a low skill, laborintensive industry on the one hand, and the automobile as an example for a medium skill, capital-intensive industry on the other hand. Because the garment industry’s workforce consists mainly of women, we also discuss the gender dimension of trade liberalization.