Les WNTs sont une famille de glycoprotéines qui, secrétées dans le milieu extracellulaire, jouent un rôle important dans l’embryogenèse. Chez l’adulte, leur dérégulation va entrainer diverses affections incluant des troubles du développement accompagnés ou non de malformations mais aussi des cancers. Au niveau de l’ovaire, le rôle des WNTs demeure peu défini même si des études chez l’humain et la souris prouvent l’implication de certains membres de cette famille dans le développement ovarien ainsi que dans les processus de maturation folliculaire et d’ovulation. Dans ce contexte, nous avons voulu évaluer l’expression de quelques membres de la famille des WNTs (-2, -2b, -4, -5a et -5b) durant l’expansion des cellules du cumulus et évaluer l’effet de certains d’entre eux sur le COC ainsi que la maturation de l’ovocyte chez la vache. Les COCs bovins étaient placés dans une solution de maturation in vitro pendant 0, 6, 12 et 22h et les niveaux d’ARNm mesurés par PCR en temps réel. L’abondance de l’ARNm pour WNT-2b était significativement plus élevée après 6h de maturation comparée aux COCs immatures (à 0h), alors que l’ARNm codant pour WNT-2, -4, -5a et -5b n’augmentait qu’en fin de culture. L’addition d’EGF provoquait l’expansion du COC et la progression de l’ovocyte vers la métaphase II (MII) comme nous l’espérions mais, à notre grande surprise, l’ajout de WNT-2b au milieu de maturation provoquait également l’expansion du COC (82% et 69% pour EGF et WNT-2b respectivement) et la progression de l’ovocyte vers le stade MII (62% et 56% EGF et WNT-2b respectivement). La combinaison d’EGF et WNT-2b n’a pas produit de meilleurs résultats. Notre étude met en lumière l’implication des WNTs dans la maturation du COC chez la vache. Leurs voies d’activation restent toutefois à déterminer. / The Wnts comprise a large family of secreted glycoproteins which, when secreted in the extracellular space, play a key role in embryonic development. In adults, Wnts play a role in homeostasis and their deregulation likely causes several problems including developmental abnormalities with or without deformities, and cancer. The role of Wnts in the ovaries is not clearly defined although studies in humans and mice show the involvement of some Wnts in ovarian development, follicular maturation and in the process of ovulation. In this study, we tested the hypothesis that members of the Wnt family are involved in oocyte maturation in cattle. The specific objectives were to measure the expression of key Wnts (Wnt-2, -2b, -4, -5a and -5b) in cumulus cells during expansion, and to assess the effect of select Wnt proteins on expansion of the cumulus oocyte complex (COC) and oocyte maturation. Bovine COCs were placed into IVM medium for 0, 6, 12 and 22 h and mRNA levels measured by real-time PCR. The abundance of Wnt-2b mRNA in the cumulus cells was significantly higher at 6 h of maturation compared to immature (time 0) COCs, whereas mRNAs encoding Wnt-2, -4, -5a and -5b did not increase until the end of culture. The addition of EGF induced COC expansion and progression of the oocyte to meiosis II (MII) as expected but, unexpectedly, addition of Wnt-2b also induced expansion and (82% and 69%, EGF and Wnt2b, respectively) and progression to MII (62% and 56%, EGF and Wnt2b, respectively); a combination of WNT-2b and EGF did not improve the rates over either alone. Our study provides new evidence for a role for Wnts in the maturation of the COC in cattle. The Wnt signalling pathways are still unknown and more studies are needed.

Ce manuscrit est consacré à l'élaboration de phases stationnaires monolithiques organiques pour lesmicrosystèmes électrochromatographiques plastiques. La partie bibliographique situe d'abord l'intérêt destechniques électrocinétiques en microsystème. Ensuite, l'état de l'art sur l'utilisation des monolithes dans cestechniques séparatives est présenté en portant une attention particulière à la description du processus dephotopolymérisation. La fonctionnalisation de surface du copolymère d'oléfine cyclique (COC) est ensuitedétaillée afin d'envisager l'ancrage du monolithe aux parois du canal.La partie expérimentale a porté tout d'abord sur le développement et la caractérisation de deux monolithesacrylates dédiés à la chromatographie à polarités des phases inversées. Le travail expérimental s'est ensuiteorienté vers le développement d’un nouveau procédé permettant la synthèse et l’ancrage du monolithe dansles microcanaux en COC, ceci en une seule étape et à partir des photoinitiateurs de type I. Ce protocolepermet l'obtention d'efficacités intéressantes qui restent cependant inférieures à celles obtenues en capillaire.Des adaptations des conditions d'irradiation ont alors été apportées pour la synthèse de ces monolithes àl’intérieur des microsystèmes afin d'obtenir des efficacités de l’ordre de 250 000 plateaux/m. Pour terminer,les domaines d'applications et la longévité du dispositif ont été illustrés par la séparation de différentesfamilles de solutés (PAH, mycotoxines, catécholamines, acides aminés, amines biogènes) et l'analysed'échantillons réels tels que les vins (pour déterminer la teneur en certaines amines biogènes : histamine ettyramine). / This manuscript is dedicated to the synthesis of organic monolithic stationary phases in plasticelectrochromatographic microchips. The bibliography part shows the benefit of electrokinetic techniques formicrosystems. After an overview on the use of monoliths in separation techniques, the manuscript is focusedon the description of photopolymerization process. Finally, a detailed review of the different protocols offunctionnalization of cyclic olefin copolymer (COC) surface to allow anchoring of the monolith to thechannel walls is produced.The experimental study firstly deals with the development and characterization of two acrylate monolithsdedicated to the reversed phase mode in chromatography. Then, the experimental part focus on a new onestepmethod for the simultaneous synthesis and anchoring of organic monolith inside COC microchipchannel, thanks to the use of type I photoinitiators. This protocol improves efficiencies which neverthelessstay below those obtained in capillary. Further, the adjustment of the irradiation conditions allows to reachup to 250 000 plates/m. Finally, the field of applications and the durability of microsystem have beenillustrated by the separation of different kinds of solutes (HAP, mycotoxins, catecholamines, biogenicamines) and the analysis of real matrices such as wine samples (for the quantitative determination of twobiogenic amines : histamine and tyramine).

In this thesis Graphit-iC™, an amorphous carbon coating developed by Teer Coatings Ltd. was modified and deposited onto CoCr and WHMWPE substrates in order to improve the wear properties. It was identified that depositing a hard coating onto soft substrate would cause high stresses and lead to coating delamination. Consequently the polyethylene substrates were ion implanted with nitrogen to reduce the hardness differential at the substrate-coating boundary. The coating was characterised using a pin on disc method in order to determine wear and friction. Hardness and fatigue was characterised using nano-indentation and the coating adhesion was measured using scratch testing. Application of the coatings resulted in a significant reduction in wear. Wear factors as low as 3.65x10¯18m³/Nm were achieved for coated CoCr substrates compared to 3.53x10¯15m³/Nm reported in the literature for uncoated CoCr. The coating resulted in friction coefficients between 0.12 and 0.19 with hardness ranging from 6.65 and 15.63GPa. Similarly coating UHMWPE resulted in a reduction in the wear factor to less than 9.6x10¯17m³/Nm. It was concluded that the deposition of amorphous carbon coatings can improve wear of hip joint prostheses, although consideration must be made for the adhesion of the coating to the substrate so that it does not contribute to an early failure of the device. Improved adhesion can be achieved by reducing the hardness differential between the coating and adhesion, either through softening the coating or by using interlayers.

Ce manuscrit est consacré à l'élaboration de phases stationnaires monolithiques organiques pour lesmicrosystèmes électrochromatographiques plastiques. La partie bibliographique situe d'abord l'intérêt destechniques électrocinétiques en microsystème. Ensuite, l'état de l'art sur l'utilisation des monolithes dans cestechniques séparatives est présenté en portant une attention particulière à la description du processus dephotopolymérisation. La fonctionnalisation de surface du copolymère d'oléfine cyclique (COC) est ensuitedétaillée afin d'envisager l'ancrage du monolithe aux parois du canal.La partie expérimentale a porté tout d'abord sur le développement et la caractérisation de deux monolithesacrylates dédiés à la chromatographie à polarités des phases inversées. Le travail expérimental s'est ensuiteorienté vers le développement d'un nouveau procédé permettant la synthèse et l'ancrage du monolithe dansles microcanaux en COC, ceci en une seule étape et à partir des photoinitiateurs de type I. Ce protocolepermet l'obtention d'efficacités intéressantes qui restent cependant inférieures à celles obtenues en capillaire.Des adaptations des conditions d'irradiation ont alors été apportées pour la synthèse de ces monolithes àl'intérieur des microsystèmes afin d'obtenir des efficacités de l'ordre de 250 000 plateaux/m. Pour terminer,les domaines d'applications et la longévité du dispositif ont été illustrés par la séparation de différentesfamilles de solutés (PAH, mycotoxines, catécholamines, acides aminés, amines biogènes) et l'analysed'échantillons réels tels que les vins (pour déterminer la teneur en certaines amines biogènes : histamine ettyramine).

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-02-02T15:21:11Z No. of bitstreams: 1 RodrigoAlbertBarachoRuegg_DISSERT.pdf: 974954 bytes, checksum: 9e856f1f06a920e1fa423c790937ebd9 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-02-09T20:46:59Z (GMT) No. of bitstreams: 1 RodrigoAlbertBarachoRuegg_DISSERT.pdf: 974954 bytes, checksum: 9e856f1f06a920e1fa423c790937ebd9 (MD5) / Made available in DSpace on 2017-02-09T20:46:59Z (GMT). No. of bitstreams: 1 RodrigoAlbertBarachoRuegg_DISSERT.pdf: 974954 bytes, checksum: 9e856f1f06a920e1fa423c790937ebd9 (MD5) Previous issue date: 2016-09-05 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / In Brazil, the production and consumption of giblets are under development, in particular the liver, which is the source of nutrients considered to be a rich source of vitamin A. This vitamin is a micronutrient that plays an essential role in vision, growth, development and maintenance of the epithelial tissue, and in immunological processes in reproduction. Being a food easy acquisition and low commercial value, the chicken liver is a bet to combat vitamin A deficiency (VAD), which affects mainly children and pregnant women in developing countries. This study aimed to analyze the concentration of retinol by high performance liquid chromatography (HPLC) in livers of farms of chickens, organic and hillbillies in different conditions of thawing and cooking, marketed in the city of Natal/RN. In addition, this study aimed to validate an adaptation of the methodology proposed by Hosotani & Kitawaga (2003) for retinol analysis in this food so that the method of analysis become simple, fast and cheap. The mean values of retinol in farm chicken liver for the three brands analyzed were: 9152,9 ? 719; 4673,1 ? 389; 5943,6 ? 614 mg/100 g (p < 0,05). The average retinol organic chicken liver was 3401,33 ? 597,12 g / 100 g. The average retinol in hillbilly chicken liver was 30094.79 ? 4628,75 g/100 g. It was observed that the baking oven for 35 minutes at 200 ? C and thawing process in microwave for one minute caused a significant loss of 39,9 % (p < 0,05) and 26,2 % (p < 0,01), respectively, the retinol concentration in farm chicken liver. The method validation technique resulted in a rapid extraction and determination and quantification need retinol in chicken liver samples, with an average retention time of 5,2 minutes at 23 ? C, with excellent results linearity (R = 0,9999 ) standard stock stability and freeze-thaw process accurately coefficient of variation below 15% and recovery with values of 93 % to 101,2 %. Despite significant losses in thermal processes, consumption of an average serving of roasted liver (88 g) supplies the daily requirement of vitamin A for a man over 14 years up to 6 times and 20 times the daily needs of children 1 to 3 years. The study showed a significant difference between farm livers brands as well as free-range and organic chicken livers, and a significant loss in the retinol content in chicken livers when subjected to thermal processing. The validated method is suitable and safe for retinol analysis in this type of food. / In Brazil, the production and consumption of giblets are under development, in particular the liver, which is the source of nutrients considered to be a rich source of vitamin A. This vitamin is a micronutrient that plays an essential role in vision, growth, development and maintenance of the epithelial tissue, and in immunological processes in reproduction. Being a food easy acquisition and low commercial value, the chicken liver is a bet to combat vitamin A deficiency (VAD), which affects mainly children and pregnant women in developing countries. This study aimed to analyze the concentration of retinol by high performance liquid chromatography (HPLC) in livers of farms of chickens, organic and hillbillies in different conditions of thawing and cooking, marketed in the city of Natal/RN. In addition, this study aimed to validate an adaptation of the methodology proposed by Hosotani & Kitawaga (2003) for retinol analysis in this food so that the method of analysis become simple, fast and cheap. The mean values of retinol in farm chicken liver for the three brands analyzed were: 9152,9 ? 719; 4673,1 ? 389; 5943,6 ? 614 mg/100 g (p < 0,05). The average retinol organic chicken liver was 3401,33 ? 597,12 g / 100 g. The average retinol in hillbilly chicken liver was 30094.79 ? 4628,75 g/100 g. It was observed that the baking oven for 35 minutes at 200 ? C and thawing process in microwave for one minute caused a significant loss of 39,9 % (p < 0,05) and 26,2 % (p < 0,01), respectively, the retinol concentration in farm chicken liver. The method validation technique resulted in a rapid extraction and determination and quantification need retinol in chicken liver samples, with an average retention time of 5,2 minutes at 23 ? C, with excellent results linearity (R = 0,9999 ) standard stock stability and freeze-thaw process accurately coefficient of variation below 15% and recovery with values of 93 % to 101,2 %. Despite significant losses in thermal processes, consumption of an average serving of roasted liver (88 g) supplies the daily requirement of vitamin A for a man over 14 years up to 6 times and 20 times the daily needs of children 1 to 3 years. The study showed a significant difference between farm livers brands as well as free-range and organic chicken livers, and a significant loss in the retinol content in chicken livers when subjected to thermal processing. The validated method is suitable and safe for retinol analysis in this type of food.

Nous avons développé un module de detection de bactérie base sur le suivi électrochimique d’une PCR. Le système a été realisé en Copolymère d’Oléfin Cyclique (COC). Il s’agit ici de présenter une nouvelle approche pour concevoir des systèmes de despistage d’infection nosocomiale en quelques heures. INTRODUCTION Avec le développement des flux migratoires de population et l’apparition de résistance aux antibiotiques, les infections nosocomiales sont devenues un enjeu de santé majeur. Les besoins en systèmes de diagnostique accessibles financièrement augmentent considérablement. L’approche qui consiste à intégrer entièrement une chaîne d’analyse commence à avoir les faveurs des systèmes de santé et en particulier de l’Organisation Mondiale de la Santé (OMS). Une compagnie nord américaine Cepheid a par ailleurs déjà développé un système automatisé de détection de germes basé sur l’identification de l’ADN par PCR. Cependant le coût élevé des technologies ralentit sa démocratisation malgré un apport considérable pour les tests cliniques de routine. Ici nous nous proposons une stratégie d’analyse qui permet de maîtriser les drastiquement les coûts de consommable. Tout d’abord tout le système est réalisé en COC, un thermoplastique qui peut être façonné à très grande échelle pour quelques dizines de centimes l’unité. [1]. Ensuite le système de détection, implique un suivi électrochimique qui remplace avantageusement les plateformes optiques traditionnellement coûteuses. Si la première cible de ce système est le dépistage de maladie nosocomiale, il apparaît aussi qu’il est transposable à d’autres domaines où la détection basée sur une PCR peut apporter des solutions. THEORIE L’échantillon, un écouvillon nasal est prélevé sur le patient. Ensuite les bactéries sont lysées grâce à l’utilisation de détergent. Une fois les parois bactériennes détruites, l’ADN est extrait sur phase solide par l’intermédiaire de billes magnétiques de type « charge switch » assemblées en colonnes [2]. Après lavage l’ADN est élué, puis amplifié par PCR en temps réel. Durant cette phase l’amplification de l’ADN est suivie grâce à l’utilisation d’un intercalant redox. Ce principe de détection fait l’objet d’un brevet [3] et nous présentons ici sa première implémentation dans un système de type laboratoire sur puce. Le complexe redox qui sert d’intercalant est détecté par voltammétrie à onde carrée (en anglais : Square Wave Voltammetry SQWV). Ce complexe interagit avec l’ADN double brin par intercalation pendant la phase d’élongation, ainsi il n’est plus disponible pour l’échange d’électrons avec les électrodes de détection. En conséquence, on observe une chute du niveau de courant mesuré pendant la SQWV qui correspond à l’augmentation de la quantité d’ADN. PRATIQUE De noveaux protocoles de fabrication de systèmes en thermoplastique ont été développés permettant de réaliser des système en COC robustes et étanches. L’intégration des électrodes sérigraphiées a été réalisée avec succès. Le desgin de la puce a été choisi afin de permettre la parallélisation d’expérience en vue des tests de sensibilité de détection. Afin de réaliser les cycles de chauffage nécessaire à l’amplification par PCR un système dédié, comprenant un bloc thermique, un système de régulation et une partie logicielle à été développé. La preuve de concept de l’efficacité du système a été démontré sur de l’ADN modèle : le Litmus. Il est possible de distinguer différentes concentration en ADN de départ. / With the development of human mobility and antibiotics resistance, nosocomial infections have become a major health problem. The need for fast and efficient diagnosis systems, ,while affordable by the health care systems, is increasing. The “sample to result” integration allowed by microfludics is a strong asset in such developments. Cepheid developed an integrated system for germ genotyping based on real-time PCR, but due to expensive laser-induced fluorescence detection its cost still reduces its range of applications in routine clinics. Here, we propose a new strategy allowing further cost reduction. First, the whole analysis streamline is integrated in a single chip made of Cyclo Olefin Copolymer (COC) [1]. This material can be mass-processed by CD technology, to yield chips at a few cents a piece. Second, the detection involves an electrochemical method that alleviates need for optics. Methicillin Resistant Staphylococcus Aureus (MRSA) was chosen as the initial primary target for validation. The technologies developed will further be applied to other strains of Bacteria or other fields such as agriculture, food testing, GMOs or security. The sample, a nasal swab, undergoes a chemical lysis, and DNA is extracted by selective capture on magnetic beads self-assembled into dense microcolumns arrays, as presented at MicroTAS 2009 [2]. DNA is then eluted, amplified by PCR in real time in the chip, while detected in situ by a high sensitivity electrochemical detection catalyzed by an intercalating redox compound. This proprietary technology [3] is being implemented here for the first time in a lab on chip. New protocols were developed to make a robust and leakage-free COC microfluidic chip with integrated electrodes. COC is a biocompatible and solvent resistant thermoplastic material. The COC microfluidic chip consists of a substrate with a hot-embossed microchannel and screen printed carbon and silver electrodes. The chip is sealed by solvent bonding [4]. This provides simple and cost effective fabrication, directly upscalable to mass production PCR Thermal control is done externally with a customized thermocycler. A redox compound is introduced together with DNA sample enabling electrochemical detection through Square Wave Voltammetry (SQWV). This compound intercalates in double-stranded DNA during the extension step, reducing its mobility and redox activity, so the peak current decreases during amplification of the target DNA. A sensitivity below 1ng/µL suitable for MRSA detection was achieved. The data were obtained by SQWV measurements. There is a clear correlation between the increase of DNA concentration and the decrease of the peak current for the redox compound: PCR amplification was also performed inside the chip, demonstrating the compatibility of this platform with thermal cycling and biomolecular reactions. Real-time electrochemical measurement during cycling was not possible yet due to experimental setup geometrical constraints, but work is in progress and results will be presented at the conference. Future experiments will focus on the integration of the bacteria lysis and DNA extraction steps on the same chip.

Endothelial cells, EC, are the cell type closest to the blood stream in vessel walls. These cells can affect the origin of atherosclerosis, plaques clogging the vessels. The behaviour of EC is affected by neighbouring smooth muscle cells and shear stress from the blood flow. The aim with this thesis was to fabricate a structure for an aorta-on-a-chip that can be used to study these two parameters and their influence on EC and vascular diseases. Previous research using a two-channel system resulted in leakage and low viability of the muscle cells. A three-channel system has therefore been made to include a middle channel with the muscle cells incorporated in a gel. Cell medium is flowed in the outer channels to provide the cells with nutrition. The flow in the channel with EC has been calculated to correspond to the shear stress in an aorta. Membranes of polyethylene terephthalate and polycarbonate were used to divide the channels and both were shown to be compatible with EC. Different bonding procedures were investigated to manufacture leakage-free chips. In the study, adhesive bonding clogged the channels and the parameters for thermal bonding of COC, cyclic olefin copolymer, were not fully optimised. This made chemical bonding with layers of PDMS, polydimethylsiloxane, the best alternative. APTES, (3-Aminopropyl)triethoxysilane, treatment in addition to plasma treatment on the surfaces improved the bonding strength. Polycarbonate membranes got better results in the bonding tests than polyethylene terephthalate. The resulting aorta-on-a-chip was therefore successfully fabricated in PDMS and polycarbonate membranes using plasma and APTES treatment for bonding.

This dissertation describes the development of a high-power, plastic-based, thick-film lithium-ion microbattery for use in a hybrid micropower system for autonomous microsensors. A composite porous electrode structure and a liquid state electrolyte were implemented in the microbatteries to achieve the high power capability and energy density. The use of single-walled carbon nanotubes (SWNTs) was found to significantly reduce the measured resistance of the cathodes that use LiAl0.14Mn1.86O4 as active materials, increase active material accessibility, and improve the cycling and power performance without the need of compression. Optimized uncompressed macro cathodes were capable of delivering power densities greater than 50 mW/cm2, adequate to meet the peak power needs of the targeted microsystems. The anodes used mesocarbon microbeads (MCMB) with multi-walled carbon nanotubes (MWNTs) and had significantly better power performance than the cathodes. The thick-film microbattery was successfully fabricated using techniques compatible with microelectronic fabrication processes. A Cyclic Olefin Copolymer (COC)-film was used as both the substrate and primary sealing materials, and patterned metal foils were used as the current collectors. A liquid-state electrolyte and Celgard separator films were used in the microbatteries. These microbatteries had electrode areas of c.a. 2 mm x 2 mm, and nominal capacities of 0.025-0.04 mAh/cell (0.63-1.0 mAh/cm2, corresponding to an energy density of ~6.3-10.1 J/cm2). These COC-based batteries were able to deliver constant currents up to 20 mA/cm2 (100% depth of discharge, corresponding to a power density of 56 mW/cm2 at 2.8 V) and pulse currents up to 40 mA/cm2 (corresponding to a power density of 110 mW/cm2). The high power capability, small size, and high energy density of these batteries should make them suitable for the hybrid micropower systems; and the flexible plastic substrate is also likely to afford some unique integration possibilities for autonomous microsystems. The mechanism by which the SWNTs improved the rate performance of composite cathodes was studied both experimentally and theoretically. It was concluded that the use of SWNT improved cathode performance by improving the electronic contacts to active material particles, which consequently improved the accessibility of these particles and improved the rate capability of the composite cathodes.

L'analyse chimique est indispensable à de nombreuses étapes de la mise au point et dusuivi des procédés de retraitement des combustibles nucléaires usés, de la gestion des déchetsnucléaires, ou encore de l’optimisation des combustibles du futur. Le cycle global d’analysecomprend généralement plusieurs étapes de séparations chimiques longues, manuelles etdifficiles à mettre en oeuvre en raison de leur confinement en boite à gants. Il apparaîtaujourd’hui nécessaire de proposer des solutions innovantes et viables dans le butd’automatiser ces étapes mais aussi de réduire le volume de déchets radioactifs en fin de cycleanalytique. Une solution est alors la conception de plateformes analytiques miniaturiséesautomatisées et jetables.L’objectif de cette thèse est de concevoir un système miniaturisé alternatif à lapremière étape actuelle d’analyse des combustibles usés séparant, par chromatographied’échange d’ions, l’Uranium et le Plutonium des autres éléments constituant l’échantillon. Cesystème doit permettre à la fois de conserver les performances analytiques du processusactuel, de réduire drastiquement l’exposition des expérimentateurs par l’automatisation, ainsique le volume de déchets produits en fin de cycle analytique. Ainsi, la séparation a étéimplantée sur un microsystème jetable en plastique (COC), au design spécialement adapté àl’automatisation : un lab-on-CD.Le prototype développé intègre une micro-colonne séparative d’échange d’anionsremplie d’un polymère monolithique dont la synthèse in-situ ainsi que la fonctionnalisation desurface ont été optimisées spécifiquement pour la séparation voulue. Le développement duprotocole de séparation adapté à ces micro-colonnes a été réalisé à l’aide d’un outil desimulation de l’élution des différents éléments d’intérêts. Cet outil permet de prévoir lagéométrie de la colonne (section et longueur) afin d’obtenir, en fonction de l’échantillon, desfractions de collecte de l’Uranium et du Plutonium pures.Finalement, le prototype actuel est capable de conduire simultanément 4 séparationsde façon automatisée et permet de réduire à la fois le nombre de manipulations, le tempsd’analyse mais aussi de diviser approximativement par 1000 le volume des déchets liquidesgénérés. / The chemical analysis of spent nuclear fuels is essential to design future nuclear fuelscycle and reprocessing methods but also for waste management. The analysis cycle consistsof several chemical separation steps which are time consuming and difficult to implement dueto confinement in glove boxes. It is required that the separation steps be automated and thatthe volume of radioactive waste generated be reduced. The design of automated, miniaturizedand disposable analytical platforms should fulfill these requirements.This project aims to provide an alternative to the first analytical step of the spent fuelsanalysis: the chromatographic separation of Uranium and Plutonium from the minor actinidesand fission products.The goal is to design a miniaturized platform showing analytical performancesequivalent to the current process, and to reduce both the exposure of workers throughautomation, and the volume of waste produced at the end of the analysis cycle. Thus, theseparation has been implemented on a disposable plastic microsystem (COC), specificallydesigned for automation: a lab on a Compact Disk or lab-on-CD.The developed prototype incorporates an anion-exchange monolithic micro-columnwhose in-situ synthesis as well as surface functionalization have been optimized specificallyfor the desired separation. The development of an adapted separation protocol was carried outusing a simulation tool modeling the elution of the various elements of interest. This tool isable to predict the column geometry (length and cross section) suited to obtain pure fractionsof Uranium and Plutonium as a function of the sample composition.Finally, the prototype is able to automatically carry out four separationssimultaneously reducing the number of manipulations, the analysis time and reducing thevolume of liquid waste by a factor of 1000.

The advancement in smart technologies for organic conducting polymers as flexible substrates in LEDs, PVs and solid state lighting necessitates the development of ultra-high barrier films to protect the devices from moisture and oxygen. The current encapsulation methodology of using layers of plastics and inorganic oxides has several deficiencies. Alternatively, the use of single layer of polymer nanocomposites is a promising substitute for these inorganic based encapsulation layers. The use of polymer materials have the advantage of flexibility, active electrodes printability and easy to make the devices for large area applications. The nano-fillers with high aspect ratio as nanocomposites ingredient in polymers reinforces its mechanical strength and also acts as a scavenging material for moisture and increases the residence time and/or for the penetrating moisture in the film. Chapter 1 gives the basic overview in the field of barrier technology films and coatings from polymers and inorganic oxide as either mono/multi layer hermetic encapsulation methods. The understanding of both chemistry and physics behind the moisture permeation and its interaction with the film material was discussed. The inclusion of functional nano-fillers as moisture trapping agents in the film provide better device protection achieved. The methods and instruments to measure such ultra-low permeation within the films are discussed. Finally, the advantage of polymer based nanocomposites for low-permeable films with existing materials are briefly discussed in this chapter. In this thesis, we employed both thermoplastic and thermoset polymer nanocomposites as encapsulation layer for device sealing. The use of ion-containing polymers (ionomers) as a sealant layer was also studied. Chapter 2 presents the detailed experimental procedures with materials and methods used in this thesis along with the synthesis methodologies to make films from the polymer. In chapter 3, we used cyclic olefin copolymer COC (copolymer of ethylene and norbornene) as an encapsulation layer with silica and layered silicate nano-fillers. The compatibility between hydrophilic silica and hydrophobic COC was achieved by maleic anhydride grafted PE with anchoring on COC as a compatibilizer and then silica filler was added to make the nanocomposite films. FTIR spectroscopy confirms the bond formation of silica with COC/MA-g-PE. The mechanical (tensile and DMA) and thermal studies (DSC) suggested that there is an improvement observed when adding silica/silicate layers in the polymer matrix with increased tensile strength, storage modulus and Tg. The calcium degradation test show enhanced performance towards moisture impermeation in the film. Chapter 4 deals with the synthesis of PVB based nanocomposite film with silica/layered silicate as nanofillers in the base matrix with varying degree of acetalization in the film. The FTIR and NMR spectroscopy show the evidence for acetal link formation in the in-situ synthesized PVB with silica/silicate nanofillers with three different acetyl contents. The tensile and DMA studies show the observed improvement in mechanical strength (increased tensile strength, storage modulus) were due to the intercalation of clay galleries during PVB formation and the interaction of silica particles interactive bond formation with –OH groups of PVA in PVB. The higher clay/silica particles show agglomerated nature and reduction in film strength. Thermal studies (DSC) show that there is an improvement observed in Tg when adding silica/silicate layers in the polymer matrix with moderate to low acetal content. The calcium degradation test show enhanced performance towards moisture impermeation in the film. Chapter 5 describes the inclusion of ionic groups (ionomers) in PVB and its effects on moisture permeation and mechanical properties. PVB ionomer was synthesized using formyl benzene 2-sulfonic acid sodium salt and 2-carboxy benzaldehyde (both sulfonic and carboxylic acid sources) as co-aldehyde with butyraldehyde and PVA. These acid groups were neutralized with potassium, magnesium and zinc ions. The level of acid content in the films was maintained between 6 to 28 mol percent. The sulfonic acid films with zinc and magnesium ions of 14 mol% exhibit good mechanical strength and low moisture permeation. Chapter 6 deals with the epoxy terminated silicone polymer nanocomposites as moisture barrier coatings for device encapsulation. Both silica and clay silicate layers were used to reinforce the silicone matrix. The silica nanoparticles were grafted with amino-silane groups, this would help in better mixing of silica particles in the silicone matrix due to the amine groups interaction in curing with epoxy groups. The calcium degradation test was used to determine the WVTR of the nanocomposites and device encapsulation was employed to estimate the degradation after exposure to ambient environment. Chapter 7 presents the concluding remarks of the results presented. The benefits as well as limitations of the polymer nanocomposite film and the future developmental work to be carried out are discussed in this chapter.