Les liquides ioniques sont des fluides non volatiles, constitués de cations et d’anions, qui sont conducteurs ioniques, isolants électriques, et peuvent avoir des valeurs de capacité très élevées. Ces liquides sont susceptibles non seulement de remplacer les électrolytes solides, mais également de susciter des champs électriques intenses (>SI{10}{megavoltpercentimetre}) au sein d’une couche dite double couche électronique (electric double layer, EDL) à l’interface entre le liquide et le matériau sur lequel il est déposé. Ceci conduit à une injection de porteurs de charge bidimensionelle avec des densités allant jusqu’à SI{e15}{cm^{-2}}. Cet effet de grille remarquablement fort des liquides ioniques est réduit en présence d’états piégés ou de rugosité de surface. À cet égard, les dicalchogénures de métaux de transitions, de très haute qualité cristalline et atomiquement plats, font partis des semi-conducteurs les plus adaptés aux grilles EDL.Nous avons réalisé des transistors à effet de champ avec des EDL dans des nanotubes multi-couches de ce{WS2}, avec des performances comparables à celles de transistors EDL sur des ilots de ce{WS2}, et meilleurs que celles de nanotubes de ce{WS2} avec une grille solide. Nous avons obtenu des mobilités allant jusqu’à SI{80}{squarecentimetrepervoltpersecond} pour les porteurs n et p, et des ratios de courants on/off dépassant SI{e5}{} pour les deux polarités. Pour de forts dopages de type électron, les nanotubes ont un comportement métallique jusqu’à basse température. De plus, utiliser un liquide ionique permet de créer une jonction pn de manière purement électrostatique. En prenant avantage de cet effet, nous avons pu réaliser un transistor photoluminescent dans un nanotube.La possibilité de susciter de très forte densités de charges donne la possibilité d’induire des phases métalliques ou supraconductrices dans des semi-conducteurs a large bande interdite. Nous avons ainsi réussi à induire par effet de champ une phase métallique à basse température dans du diamant intrinsèque avec une surface hydrogénée, et nous avons obtenu un effet de champ dans du silicone dopé métallique.Les liquides ioniques offrent beaucoup d’avantages, mais leur champ d’application est encore réduit par l’instabilité du liquide, ainsi que par les courants de fuites et l’absorption graduelle d’impuretés. Un moyen efficace de s’affranchir de ces inconvénients, tout en conservant la possibilité d’induire de très fortes densités de porteurs, est de gélifier le liquide ionique. Nous sommes allés plus loin en fabriquant des gels ioniques modifiés, avec les cations fixés sur une seule surface et les anions libres de se mouvoir au sein du gel. Cet outil nous a permis de réaliser une nouvelle diode à effet de champ de faible puissance. / Ionic liquids are non-volatile fluids, consisting of cations and anions, which are ionically conducting and electrically insulating and hold very high capacitances. These liquids have the ability to not only to replace solid electrolytes, but to create strongly increased electric fields (>SI{10}{megavoltpercentimetre}) in the so-called electric double layer (EDL) on the electrolyte/channel interface, which leads to the injection of 2D charge carrier densities up to SI{e15}{cm^{-2}}. The remarkably strong gate effect of ionic liquids is diminished in the presence of trapped states and roughness-induced surface disorder, which points out that atomically flat transition metal dichalcogenides of high crystal quality are some of the semiconductors best suited for EDL-gating.We realised EDL-gated field-effect transistors based on multi-walled ce{WS2} nanotubes with operation performance comparable to that of EDL-gated thin flakes of the same material and superior to the performance of backgated ce{WS2} nanotubes. For instance, we observed mobilities of up to SI{80}{squarecentimetrepervoltpersecond} for both p- and n-type charge carriers and our current on-off ratios exceed SI{e5}{} for both polarities. At high electron doping levels, the nanotubes show metallic behaviour down to low temperatures. The use of an electrolyte as topgate dielectric allows the purely electrostatic formation of a pn-junction. We successfully fabricated a light-emitting transistor taking advantage of this utility.The ability of high charge carrier doping suggests an electrostatically induced metal phase or superconductivity in large gap semiconductors. We successfully induced low temperature metallic conduction into intrinsic diamond with hydrogen-terminated surface via field-effect and we observed a gate effect in doped, metallic silicon.Ionic liquids have many advantageous properties, but their applicability suffers from the instability of their liquid body, gate leakage currents and absorption of impurities. An effective way to bypass most of these problems, while keeping the ability of ultra-high charge carrier injection, is the gelation of ionic liquids. We even went one step further and fabricated modified ion gel films with the cations fixed on one surface and the anions able to move freely through the film. With this tool, we realised a novel low-power field-effect diode.

Esta tese tem como objetivo estudar a derivatização da celulose sob condições homogêneas, utilizando líquidos iônicos (LIs), em micro-ondas, através de um método simples e reprodutível. Foram estudadas três etapas: i) Síntese dos LIs, buscando otimizar seu preparo; ii) Efeitos da estrutura dos LIs sobre a dissolução de celulose; iii) Otimização da derivatização da celulose em LIs. Foi realizado um planejamento experimental para a otimização da síntese dos LIs, mostrando-se que o uso de solvente molecular como diluente não traz vantagens. Na dissolução de celuloses fibrosas em LIs, observou-se a importância das estruturas dos cátions e ânions destes. Estudou-se a influência de um solvente molecular, DMSO, na reação de derivatização de celulose em LIs e percebeu-se que o uso do mesmo não é vantajoso. Por fim, realizou-se um planejamento experimental da acetilação da celulose, mostrando-se quais fatores mais afetam esse processo: tempo de reação, razão molar de anidrido acético/celulose e temperatura / The work reported has the target of studying the acylation of cellulose under homogeneous reaction conditions. Imidazolium-based ionic Liquids (ILs) were employed as solvents, and the reaction was assisted by a microwave. These following processes have been studied: Optimization of the synthesis of ILs; ii) Effects of the structure of ILs on the dissolution of cellulose; iii) Optimization of cellulose acylation. Experimental design has been applied in order to optimize the synthesis of ILs. The use of DMSO as a diluent decreased the efficiency of the synthesis. Dissolution of cellulose (eucalyptus, mercerized eucalyptus and mercerized cotton) in several ILs has shown the importance of the counter-ion and the structure of the cation side-chain. The addition of DMSO decreased the amount of dissolved cellulose. Experimental design has been applied in order to optimize the acetylation of cellulose. Reaction time, molar ratio acetic anhydride/anhydroglucose unit, and cellulose concentration influenced the reaction outcome.

O dióxido de enxofre (SO2) é um dos principais poluentes atmosféricos e a busca por sistemas capazes de absorver, detectar e/ou quantificar este gás tem sido de grande interesse. Neste contexto, os líquidos iônicos (LI) têm demonstrado potencial aplicação em metodologias de captura e armazenamento de gases. Neste estudo, nosso maior interesse consiste em entender os principais fatores que governam as interações entre o SO2 e diferentes íons formadores de líquidos iônicos. Em particular, foi explorada a interação específica de transferência de carga entre ânions (base de Lewis) e o SO2 (ácido de Lewis). A abordagem deste trabalho foi baseada em uma investigação sistemática de LI formados pelo cátion 1-butil,3-metilimidazólio (BMI) e diferentes ânions, utilizando da espectroscopia vibracional (Raman e IR), sobretudo a espectroscopia Raman ressonante, aliada a cálculos teóricos baseados na teoria do funcional da densidade (DFT). Os resultados de espectroscopia vibracional Raman e IR, mostraram mudanças na posição e formato da banda referente ao modo de estiramento simétrico vs(SO2) dependendo do ânion e da concentração de SO2 em LI. Verificou-se deslocamentos significativos para menor número de onda em relação ao SO2 líquido puro (1145 cm-1) em menores concentrações de SO2 em LI. Na série dos haletos, Cl-, Br- e I-, quanto maior o ânion, maior o deslocamento (1138, 1133 e 1123 cm-1, respectivamente para a fração molar 0,5). No caso do tiocianato, considerado como um pseudo-haleto, a banda do modo vs(SO2) aparece em cerca de 1130 cm-1 na mesma fração molar, ou seja, em um valor intermediário entre o Br- e o I-. Esses deslocamentos observados podem ser interpretados de acordo com a interação específica de transferência de carga do ânion para o SO2. Um resultado observado que merece destaque consiste na dependência da banda Raman do modo vs(SO2) com a energia da radiação excitante, o que é denominado de dispersão Raman. Tal fenômeno pôde ser explicado utilizando o modelo de \"excitação seletiva do estado de solvatação\" em que foi possível caracterizar os diferentes estados de solvatação do SO2 em líquidos iônicos. / Sulfur dioxide (SO2) is one of the main atmospheric pollutants and the search for systems capable of absorbing detect and/or quantify such gas has been of great interest. In this context, ionic liquids (IL) have shown potential application in capture methodologies and gas storage. In this study, our interest consists in the understanding of the main factors that govern the interactions between SO2 and diferents ions of ionic liquids. In particular, the charge transfer specific interaction was explored between anions (Lewis base) and SO2 (Lewis acid). The approach of this study was based on a systematic investigation of LI formed by 1-butyl cation, 3-methylimidazolium (BMI) and different anions, using vibrational spectroscopy (Raman and IR), especially resonance Raman spectroscopy, allied with theoretical calculations based on density functional theory (DFT). The vibrational spectroscopic results (Raman and IR) showed changes in the position and shape of the band assigned to the symmetric stretching mode vs(SO2) depending on the anion and SO2 concentration in LI. There were significant shifts to lower wavenumbers with respect to pure liquid SO2 (1145 cm-1) at lower SO2 concentrations in IL. In the series of halides, Cl-, Br- and I-, the bigger the anion, the larger the displacement (1138, 1133 and 1123 cm-1, respectively at 0.5 mole fraction). In the case of thiocyanate, regarded as a pseudo-halide, the band vs(SO2) appears at about 1130 cm-1 at the same molar fraction, i.e. at an intermediate value between the Br- and I-. The observed displacement can be interpreted accordingly to the specific interaction of charge transfer from the anion to SO2. A result that is worth mentioning is the dependence of the wavenumber of the Raman band vs(SO2) with the energy of the exciting radiation, which is called Raman scattering. This phenomenon could be explained using the model of \"solvation state selective excitation\" in which was possible to characterize the diferente solvation states of the SO2 in ionic liquids

Cette thèse porte sur l’éco-extraction et l’encapsulation de pigments naturels pour une exploitation et application dans les industries alimentaire, cosmétique et pharmaceutique. Dans ce but, l'extraction assistée par micro-ondes (MAE) ou par ultrasons (UAE) et celle par liquides ioniques (LI) ont été évaluées pour l'extraction de caroténoïdes et d'anthocyanes de plantes vietnamiennes. Les résultats obtenus montrent que le MAE a été un système permettant d'accélérer et d'améliorer tous les types d'extraction testés alors que les ultrasons se sont montrés particulièrement efficaces lorsque les pigments étaient présents à la surface des tissus végétaux. Cependant, l’UAE améliore également les résultats par rapport à des extractions sans assistance. Les LI classiques ne sont pas adaptés pour l’extraction des pigments caroténoïdes et anthocyaniques qui sont généralement non volatils et thermosensibles car il n'a pas été possible de séparer les pigments extraits des LI dans des conditions douces. Pour remédier à ce problème, des LI réversibles ont été évalués. Le DBU/ 1-hexanol était efficace pour extraire les caroténoïdes relativement accessibles, mais, en raison d'une viscosité élevée, il perdait son efficacité pour d'autres tissus. La deuxième partie de cette thèse concerne l’encapsulation d’anthocyanes d’hibiscus dans des levures. Nous avons d’abord travaillé avec des levures entières. Les résultats ont montré que les cellules de levure étaient un bon matériau pour l'encapsulation des anthocyanes. Cependant, pour les levures non désactivées, les enzymes ont provoqué une perte indésirable de couleur des anthocyanines pendant le stockage. Les microparticules de levures traitées thermiquement ont montré un effet protecteur élevé pendant le stockage. Puis, comme les anthocyanes étaient majoritairement encapsulées dans le réseau pariétal des levures, nous avons utilisé les écorces de levures séparées du reste des cellules. Les microparticules des écorces de levure ont apporté une bonne protection pour les anthocyanes contre l'humidité, la chaleur et la lumière. En comparant avec les microparticules de maltodextrine, celles des écorces de levure étaient plus stables dans des conditions d'humidité élevée. En général, les microparticules de levure ont montré une capacité à protéger les anthocyanes et à garder la couleur rouge de la poudre d’anthocyanes encapsulées. Ces résultats montrent que la poudre d’anthocyanes encapsulées dans des levures ou écorces de levure a un avenir prometteur pour être appliquée dans les industries alimentaire, cosmétique et pharmaceutique. / This thesis deals with extraction processes using assistance technologies or green solvents and encapsulation systems of natural pigments in order to exploit and apply them in the food, cosmetic and pharmaceutical industries. In this goal, microwave-assisted extraction (MAE), ultrasonic-assisted extraction (UAE) and Ionic liquids (IL) were evaluated for the extraction of carotenoids and anthocyanins from Vietnamese plants. The results obtained show that the MAE was always a rapid and helpful system for all types of extraction tested whereas ultrasounds were particularly efficient when pigments are present on the surface of plant tissues. However, UAE was also improving results compared to conditions without assistance. Traditional IL are not suitable for the extraction of carotenoid and anthocyanin pigments that are generally non-volatile and heat-sensitive because it has not been possible to separate pigments extracted from IL under mild conditions. Therefore switchable IL were evaluated. DBU/ 1-hexanol was efficient to extract carotenoids that were relatively accessible, but, due to its high viscosity, it lost efficacy for other tissues. The second part of this thesis concerns the encapsulation of Hibiscus anthocyanins in yeasts. We have first worked with whole yeast cells. The results showed that yeast cells were a good material for the encapsulation of anthocyanins. However, yeast enzymes caused undesirable colour loss of anthocyanin during storage. Microparticles of heat-treated yeasts showed a high protective effect during storage. Then, as it was interesting to keep the pigments in the cell wall and deactivate the yeast enzymes, we used yeast hulls. Yeast hull particles brought a good protection to anthocyanins against moisture, heat and light. In comparison with maltodextrin microparticles, yeast hull ones were more stable in high humidity. In general, yeast microparticles have shown an ability to protect anthocyanins and to keep the red color of encapsulated anthocyanin powder. These results show that yeast encapsulated anthocyanins powder has a promising future to be applied in the food, cosmetic and pharmaceutical industries.

Made available in DSpace on 2017-07-24T19:37:54Z (GMT). No. of bitstreams: 1 Alvaro Fontana.pdf: 7055530 bytes, checksum: 4a9069c1fa7120a7895a1587f1fe173e (MD5) Previous issue date: 2015-09-18 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / In this work were performed organic synthesis of the monomer derivatives of poly (p-phenylenevinylene) whose main interest was to obtain a monomer with an aromatic ring having attached two bromine atoms (this step not being performed), a cyano group, a side chain of six carbon atoms and a sulfonic group linked to the end of side chain. The syntheses were performed starting from the compound 2,5-dimethylphenol and adding the aromatic ring an iodine atom, made subsequently replacing the iodine atom by a cyano group, and the sequences of reactions by adding a side chain with six carbon atoms attached at its one end a sulfonic group. The characterization of the obtained compounds was performed by spectroscopy techniques, Infrared, nuclear magnetic resonance 1H and 13C and GC-MS. These analyzes showed that the structures of the proposed monomers were achieved almost entirely. Part of this doctoral work was performed in the laboratory of the Emeritus Professor Dr. Alan Maxwell Bond at Monash University, Melbourne - Australia, such as sandwich doctorate program. The study in Australia comprised learning and application of cyclic voltammetry technique ac coupled to Fourier transform in chemical reactions studying the kinetics of 1 and 2 electron transfer, in this case, taking as an example the molecule N,N,N',N'-Tetramethyl-p-phenylenediamine, TMPD. The molecular solvents used for the study of electron transfer in the molecule TMPD were acetone and acetonitrile, and the following ionic liquids: [BMPIPTFSI], [BMIM] [TFSI], [BMIm][BF4] and [BDMIM] [TF2N]. In all the results obtained it was found the process known as internal reference, where the first electron transfer reaction in the molecule, because it is faster, can be used to compare the values of the thermodynamic and kinetic parameters obtained in the first process with the parameter values obtained in the second electron transfer process in the same molecule. / Neste trabalho foram realizadas sínteses orgânicas de monômeros derivados de poli(p-fenilenovinileno) cujo principal interesse foi a obtenção de um monômero com um anel aromático tendo ligado a ele, dois átomos de bromo (não sendo realizada essa etapa), um grupamento ciano, uma cadeia lateral com seis átomos de carbono, e um grupamento sulfônico ligado a extremidade da cadeia lateral. As sínteses foram realizadas partindo-se do composto 2,5-dimetilfenol e adicionando-se ao anel aromático um átomo de iodo, posteriormente feita a troca do átomo de iodo por um grupo ciano e nas sequências das reações adicionando-se uma cadeia lateral com seis átomos de carbono oposta ao grupo ciano e ligado na extremidade da cadeia lateral um grupo sulfônico. A caracterização dos compostos foi realizada através das técnicas, infravermelho, ressonância magnética nuclear 1H, 13C e CG-MS. Essas análises evidenciaram que as estruturas dos monômeros propostos foram alcançadas em quase sua totalidade. Parte deste trabalho de doutoramento foi realizada no laboratório do professor Emeritus Dr. Alan Maxwell Bond na Monash University em Melbourne – Austrália, como doutorado sanduíche. O estudo feito na Austrália compreendeu a aprendizagem e aplicação da técnica de voltametria cíclica ac acoplada à transformada de Fourier, estudando-se a cinética de transferência de 1 e 2 elétrons, neste caso, utilizando-se como exemplo, a molécula N,N,N′,N′-Tetramethyl-p-phenylenediamine, TMPD. Os solventes moleculares utilizados para o estudo da transferência de elétrons nesta molécula foram acetona e acetonitrila e também os seguintes líquidos iônicos: [BMPIPTFSI], [BMIM][TFSI], [BMIm][BF4] e [BDMIM][TF2N]. Em todos os resultados obtidos constatou-se o processo chamado de referência interna, onde, a primeira reação de transferência de elétrons nesta molécula, por ser mais rápida, pode ser utilizada para comparar os valores dos parâmetros termodinâmicos e cinéticos obtidos no primeiro processo de transferência de elétrons com os valores dos parâmetros obtidos no segundo processo na mesma molécula.

Líquidos iônicos imidazólios (LIIs) associados a ânions com caráter básico foram sintetizados, caracterizados e seu comportamento estudado em solução. Inicialmente a troca isotópica H/D preferencial no grupo C2-CH3 de sais de 1-nbutil-2,3-dimetilimidazólio (BMMI) foi avaliada. Ficou evidente que o contato entre os pares de íons e a atuação do ânion como uma base neutra influenciaram fortemente a deuteração. Após a análise dos resultados de RMN, cálculos de DFT (Teoria do Funcional de Densidade) e Difração de Raios X, um complexo entre uma molécula de água e alguns LI foi sugerido, modificando fortemente a estrutura organizacional e afetando também a troca isotópica nestes sais. Através do mecanismo reacional proposto, surgiu a possibilidade de deuteração de novos substratos contendo H ácidos, usando os LIIs como catalisadores. A reação de troca isotópica em alcinos e cetonas foi estudada e bons resultados foram obtidos. O efeito da variação de cátions e ânions na atividade catalítica foi analisado, assim como a variação dos substituintes dos substratos. Além disso, um estudo cinético foi realizado através de análises de RMN de 1H e o mecanismo reacional foi proposto. Por fim, a capacidade de formação de pares iônicos em soluções aquosas de LIIs foi avaliada na captura de CO2. Ótimos resultados foram obtidos e atribuídos à ocorrência de sorção física e química devido à ativação da água pelo LII. / Imidazolium based ionic liquids (ImIL) associated with basic anions were synthesized, characterized and studied. Initially the preferred H/D isotopic exchange to C2-CH3 group of 1-nbutyl-2,3-dimethylimidazolium salts (BMMI) was studied. In this context, it became evident that the ion-pairing formation and the anion action as a neutral base strongly influence the deuteration reaction. NMR analysis, theoretical calculation (Density Functional Theory) and X-ray Diffraction have been performed and a complex between a water molecule and the IL have been suggested, strongly modifying the IL structure and characteristics. The isotope exchange reaction in alkynes and ketones was studied using imidazolium based ionic liquids as catalysts and good results obtained. The effect of cation and anion variation on the catalyst activity were analyzed, also a variation of the substrate substituent’s. Also, a kinetic study was performed by 1H NMR analyzes and the reaction mechanism were proposed. Finally, the ability to form ion pair contact of ILs in aqueous solutions was evaluated for CO2 capture. Great results were obtained and this success can be attributed to the occurrence of physical and chemical sorption due to water activation by the IL.

Esta tese tem como objetivo estudar a derivatização da celulose sob condições homogêneas, utilizando líquidos iônicos (LIs), em micro-ondas, através de um método simples e reprodutível. Foram estudadas três etapas: i) Síntese dos LIs, buscando otimizar seu preparo; ii) Efeitos da estrutura dos LIs sobre a dissolução de celulose; iii) Otimização da derivatização da celulose em LIs. Foi realizado um planejamento experimental para a otimização da síntese dos LIs, mostrando-se que o uso de solvente molecular como diluente não traz vantagens. Na dissolução de celuloses fibrosas em LIs, observou-se a importância das estruturas dos cátions e ânions destes. Estudou-se a influência de um solvente molecular, DMSO, na reação de derivatização de celulose em LIs e percebeu-se que o uso do mesmo não é vantajoso. Por fim, realizou-se um planejamento experimental da acetilação da celulose, mostrando-se quais fatores mais afetam esse processo: tempo de reação, razão molar de anidrido acético/celulose e temperatura / The work reported has the target of studying the acylation of cellulose under homogeneous reaction conditions. Imidazolium-based ionic Liquids (ILs) were employed as solvents, and the reaction was assisted by a microwave. These following processes have been studied: Optimization of the synthesis of ILs; ii) Effects of the structure of ILs on the dissolution of cellulose; iii) Optimization of cellulose acylation. Experimental design has been applied in order to optimize the synthesis of ILs. The use of DMSO as a diluent decreased the efficiency of the synthesis. Dissolution of cellulose (eucalyptus, mercerized eucalyptus and mercerized cotton) in several ILs has shown the importance of the counter-ion and the structure of the cation side-chain. The addition of DMSO decreased the amount of dissolved cellulose. Experimental design has been applied in order to optimize the acetylation of cellulose. Reaction time, molar ratio acetic anhydride/anhydroglucose unit, and cellulose concentration influenced the reaction outcome.

La réaction de cyclisation de type Wacker, de composés polyols et aminopolyols insaturés constitue un outil puissant et efficace pour la synthèse d’hétérocycles oxygénés ou azotés.Dans ce travail de thèse, nous proposons l’étude d’une réaction catalysée par un complexe de palladium(II) de type domino-cyclisation, mettant en jeu une réaction de couplage. Cette séquence catalytique revient à une fonctionnalisation d’un hétérocycle par une chaîne latérale, tout en créant deux centres stéréogènes en une seule étape. L’influence de la nature des réactifs mis en jeu, ainsi que des conditions expérimentales sur l’activité et la diastéréosélectivité de la réaction sont discutées. Les applications vers la synthèse de produits naturels (anisomycine) ou d’analogues (varitriol) sont présentées.La réaction d’oxycarbonylation catalysée par un complexes de palladium(II) est une transformation intéressante de polyols insaturés en lactones bicycliques, présentant un motif de type tétrahydrofurane avec une excellente stéréosélectivité-cis. Le premier exemple de réaction d’oxycarbonylation catalysée par des complexes de palladium chiraux dans les liquides ioniques est décrit. Une étude approfondie de la nature des ligands démontre que les bis(oxazolines) chirales constituent les meilleurs ligands du palladium pour la cyclisation du pent-4-ène-1,3-diol racémique 69a. Le dédoublement cinétique du composé 69a sous atmosphère de monoxyde de carbone, en présence d’un complexe chiral de palladium(II) et de p-benzoquinone employant l’acide acétique ou le liquide ionique [bmim]NTf2 comme solvant, a permis d’isoler le 2,6-dioxabicyclo-[3.3.0]octane-3-ones avec jusqu’à 57% d’excès énantiomérique pour l’énantiomèrede configuration (R,R)-70a, et jusqu’à 80% d’excès énantiomérique pour l’énantiomèrede configuration (S,S)-70a. / Intramolecular Wacker-type cyclization of unsaturated polyols and aminopolyols represents a powerful method in the synthesis of oxygen- or nitrogen-containing heterocycles. The thesis offers an insight into the systematic study of domino intramolecular palladium(II)-catalyzed cyclization and coupling reaction allowing the implementation of side chains into heterocyclic skeletons along with the formation of two stereocenters in a single step. Different types of coupling partners and reaction conditions were examined, the influence of substrate substituents on diastereoselectivity is discussed. The applications in the synthesis of naturally occuring compounds or their analogs are outlined (anisomycin, varitriol). Palladium(II)-catalyzed oxycarbonylation represents an interesting transformation of unsaturated polyols into bicyclic lactones with tetrahydrofuran structural motif with excellent cis-stereoselectivity. The first example of the use of ionic liquids as reaction media in the asymmetric Pd(II)-catalyzed oxycarbonylation is described. Based on a ligand screening, the chiral bis(oxazoline)-type ligands were successfully used in the Pd(II)-promoted bicyclisationof racemic pent-4-ene-1,3-diol (±)-69a. The kinetic resolution of (±)-69a in the presenceof chiral catalyst and p-benzoquinone under carbon monoxide atmosphere using acetic acid and/or ionic liquid as solvent afforded enantioenriched 2,6-dioxabicyclo[3.3.0]octane-3-ones(R,R)-70a (57% ee) and (S,S)-70a (80% ee), respectively.

Cette thèse s’inscrit dans le cadre d’un Programme d’Étude Amont (PEA) dirigé par la DGA et piloté par l’entreprise Nexter-System, consistant à élaborer des "Systèmes de camouflage adaptatifs Vis et IR". Ce projet concerne l’élaboration de macropixels adaptatifs à réflexion modulable. Le projet de recherche avait pour objectif de réaliser des couches minces de polymères électrochromes de couleur magenta, cyan et jaune pouvant commuter dans un état achromatique, afin de les intégrer dans des dispositifs complets tout organique (collaboration LPPI, Université de Cergy-Pontoise) ou hybrides (collaboration CEA Le Ripault). De plus, ces matériaux doivent être stables électrochimiquement et optiquement, et présenter des temps de commutation relativement courts (inférieurs à 10 secondes dans l’idéal). / This thesis is incorporated in a project which involves developing electro-adjustable reflection macro-pixels for armored vehicle's adaptative camouflage. The purpose of the research project was creating thin layers of magenta, cyan and yellow electrochromic polymers switchable to an achromatic state, in order to incorporate them in organic or hybrid complete devices. Moreover, these materials had to be electrochemically and optially stable, and had to present a short response time. In order to meet the materials color coordinates of the technical specification, the handgap of the organic semi-conductors has been realized by a particular design of the monomers, either by adding electron-rich or electron-poor groups, or by copolymerization between several co-monomers. According to sought properties and the possibilities offered by the monomers, the pi-conjugated polymers had been synthetized by chemical way (by oxydation or Suzuki or Stille reaction) then deposited by spray-casting, or electrodeposited at the surface of a transparent conductor substrate. The electrochromic thin layers had been electrochemically and spectroelectrochemically studied so as to test their cyclic stability and to determine their color coordinates, their opticl contrast and their response time. The use of ionic liquid EMITFSI for synthesis and electrochemical characterization had been explored, and pointed out a significant improvement of the cyclability of the created magenta, cyan and yellow polymers. The preparation of complete electrochromic devices (with organic or inorganic counterelectrode) has been started and has permitted to realize macro-pixels (2x2cm 2) and then demonstrative plates constituted of 16 macro-pixels (4x4cm 2 for each macropixel, with, in particular, yellow pixels including optimized poly(diphenyldithieno[3,2-b;2'3']thiophene)) with electro-control of the color commutation, constituting the fundamental component of an active surface tor the military vehicle's camouflage.

Les travaux presentés dans ce manuscrit ont été consacrés à l’étude de composés organo-soufrés comme composants d’électrolyte pour systèmes électrochimiques de stockage d’énergie, en particulier dans les batteries lithium-soufre. Des liquides ioniques originaux, basés sur des cations sulfonium fonctionnalisés par des chaînes de type glyme ont été synthétisés et caractérisés, puis testés en tant qu’électrolytes dans des supercondensateurs symétriques avec électrodes en carbone activé. Il est apparu que l’adaptation de la structure des liquides ioniques à la porosité du carbone activé est d’importance fondamentale pour le développement de systèmes plus performants. L’ étude menée sur les batteries lithium-soufre a permis une meilleure compréhension des mécanismes de fonctionnement d’un système redox soufre/diphenyl disulfure dans des solvants glymes. L’influence des solvants sur les équilibres chimiques entre polysulfures organiques et minéraux et sur le fonctionnement du système a été étudiée. D’après les premiers résultats obtenus, cette stratégie semble particulièrement prometteuse pour améliorer les performances des batteries lithium-soufre. / The work presented in this manuscript concentrates on investigating the use of organosulfur compounds as potential electrolyte components for electrochemical energy storage systems, in particular in lithium-sulfur batteries. Novel glyme-functionalised sulfonium-based ionic liquids were synthesised and characterised before being tested as pure electrolytes for symmetrical supercapacitors based on activated carbon electrodes. The adaptation of the structure of the ionic liquids to the porosity of activated carbon was found to be of fundamental importance for the design of more efficient systems. For lithium-sulfur batteries, the study has enabled a better understanding of the mechanisms involved during the operation of the sulfur/diphenyl disulfide redox couple in a range of glyme-based solvents. Similarly, the influence of the glyme-based solvents on the chemical equilibria between organic and mineral polysulfides and on the system operation has been investigated. The initial results demonstrated that this is a particularly promising strategy in order to significantly improve the performances of lithium-sulfur batteries.