Les propriétés des liquides ioniques telles que leur bas point de fusion, leur non-volatilité, leur stabilité thermique, et surtout leur faculté à solubiliser des composés organiques et inorganiques, en ont fait des composés d'intérêt en électrophorèse capillaire dans la recherche de nouveaux milieux de séparation. Au cours de ces travaux, deux principaux axes de recherche ont été suivis. Dans le but de pallier le manque de données sur ces nouveaux milieux, la détermination des paramètres physico-chimiques (absorbance, viscosité, conductivité) et thermodynamiques (constantes apparentes d'inclusion, seuil d'agrégation) a été réalisée en mettant en oeuvre l'instrumentation de l'électrophorèse capillaire et deux techniques électrophorétiques (électrophorèse capillaire d'affinité, analyse frontale), montrant bien l'intérêt de l'électrophorèse capillaire pour caractériser les liquides ioniques. La deuxième partie de ce travail a été dédiée à l'étude d'une application des liquides ioniques en électrophorèse capillaire, qui a porté sur l'évaluation de deux nouveaux liquides ioniques chiraux à base de cation dérivé de choline, en tant que sélecteurs chiraux pour des séparations énantiomériques.

Organofluorine compounds constitute a large part of all the drugs, crop protection agents and advanced materials produced nowadays. Therefore, there is a great interest in developing the new methods of synthesis of organofluorine compounds. In this thesis we report a novel method of synthesis of monofluorinated cyclopropanes based on the Michael-initiating ring closure (MIRC) reaction. Our method allows obtaining polysubstituted monofluorinated cyclopropanes from ethyl dibromofluoroacetate and various Michael acceptors. We have also implemented the asymetric version of cyclopropanation using a novel oxazolodinone-derived chiral fluorinated reagent. In the final part of this thesis we report the synthesis of a fluorinated analog of L-FAP4, a potent agonist of group II metabotropic glutamate receptors (mGluR II). Incorporation of a fluorine atom is expected to increase the biological activity and bioavailabiblity of this compound.

Organosulfur compounds have been used by humans for centuries and played a pivotal role in shaping our history. The chemistry presented herein deals primarily with three distinct organic transformations involving organosulfur species. The three transformations are used in tandem to complete the synthesis of natural products. The first chapter examines a new diastereoselective alkylation reaction of sulfenate anions with stereoinduction provided by chiral amino iodides. A series of β-amino sulfoxides are accessed in good yields and selectivities from alkylations with the corresponding lithium arene- and E-1-alkenesulfenate anions. The relative reactivity of different electrophiles towards a selection of lithium sulfenate anions was also evaluated by performing competition experiments. In the second chapter 1,2-dibromotetrachloroethane (C2Br2Cl4) was evaluated as a more economical halogenating agent for the in-situ Ramberg-Bäcklund rearrangement (RBR). A series of trans-stilbenoids were successfully synthesized using this protocol in excellent yields. The new RBR system also worked well for dialkyl and cyclic substrates, but the reaction was plagued by polyhalogenation for hexyl benzyl sulfone. The methodology was extended to the formal total synthesis of natural polyphenol E-resveratrol. Chapter three investigates asymmetric aza-Michael reactions of chiral β-amino sulfoxides/sulfones to synthesize thiomorpholine S-oxides and S,S-dioxides, respectively. Remarkably, cyclizations of the β-amino sulfoxides provide the trans- 3,5-substituted heterocycles, while the β-amino sulfones provide the complementary cis-3,5-substituted heterocycles. The aza-Michael chemistry was exploited along with the sulfenate and RBR protocols to access two ant venom alkaloids. / NSERC

There is currently a great interest in the field of porous organosilica materials because of the high surface areas (> 1000 m²/g) and narrow pore size distributions which are beneficial for applications such as chromatography, chiral catalysis, sensing or selective adsorption. Periodic mesoporous organosilicas (PMOs) represent an interesting class of hybrid silica materials because of the wide variety of bridging organic groups which can be incorporated within the precursors [(OR)3Si-R-Si(OR)3] giving rise to materials with exceptional properties. We have synthesized and characterized various aromatic PMOs composed of supporting structural monomers (phenylene- or biphenylenebridged) and functional stilbene monomers (cis and trans) (1, 2). The effect of the different synthetic procedures and varying amounts of functional stilbene monomer on the properties of the materials was examined. The functional transstilbene component was determined to be well distributed in a phenylene-bridged PMO using P123 as a pore template from TEM techniques with Os staining. The trans-stilbene linkers were completely transformed to aryl aldehydes through ozonolysis with dimethylsulfide workup. Further transformation of the carbonyl functionality to an aryl imine showed a moderate level of success. Enantiomeric forms of a novel, chiral PMO precursor (CM) were synthesized and incorporated into biphenylene-bridged PMOs. Under basic pH conditions templated with C18TMACl, although very low levels of CM are incorporated, enantiomeric forms of chiral, porous materials are obtained as was verified by distinct mirror-image circular dichroism spectra. Powder XRD patterns suggest that a tightly packed asymmetric biphenylene arrangement may be necessary for the optical activity. Preliminary results using these materials as a chiral chromatographic phase are promising. Finally, a thin film morphology of an ethane-bridged PMO incorporating a thiol ligand, (3-mercaptopropyl)trimethoxysilane, was prepared on a fibre optic cable and used as a component in a heavy-metal sensing application. / Thesis (Ph.D, Chemistry) -- Queen's University, 2011-03-11 17:24:48.997

No description available.

Le but de cette thèse est de construire un modèle décrivant la matière nucléaire symétrique et asymétrique dans une approche relativiste incluant des effets de la chromodynamique quantique, en particulier la symétrie chirale et le confinement. Le système considéré est une assemblée de nucléons en interaction {\it via} l'échange de mésons. L'attraction est assurée par la présence d'un champ scalaire invariant chiral lié aux fluctuations du condensat de quarks. La saturation est obtenue après ajout de la réponse scalaire nucléo- nique liée à la sous-structure en quarks du nucléon. Les paramètres liés au secteur scalaire de l'interaction et au confinement des quarks dans le nucléon sont estimés à partir de données sur réseau. Le reste des paramètres est contraint autant que possible par la phénoménologie hadronique. Le modèle n'est ainsi quasiment pas ajustable, le fait qu'il donne de si bons résultats constitue l'originalité de ce travail de thèse. Dans un premier temps, nous avons choisi de travailler à l'approximation de champ moyen dans le schéma Hartree--Fock. La propagation du champ scalaire dans les termes de Fock conduit à des effets de réarrangement qui permettent de satisfaire le théorème de Hugenhotz--Van Hove. Nous soulignons également le rôle du terme tenseur du $\rho$ dans l'énergie d'asymétrie ainsi que dans la dépendance en isospin de la masse effective de Landau. Enfin, nous donnons l'équation d'état des étoiles à neutrons prédite par ce modèle. Dans un deuxième temps, nous avons décidé d'inclure des effets au-delà du champ moyen en incluant l'énergie de corrélation due aux boucles de pions. Un ingrédient important est l'introduction d'un paramètre de Landau--Migdal contrôlant les interactions à courte portée. L'énergie de corrélation améliore la description des propriétés de la matière nucléaire au niveau du point de saturation.

An enantioselective heart-cut two-dimensional liquid chromatography-atmospheric pressure photoionization-tandem mass spectrometry method was developed for the analysis of 25 methylsulfonyl polychlorinated biphenyl metabolites in tissue extracts. Enantioseparation was achieved for 9 out of the 10 chiral analytes in less than 91 minutes, improving upon previous gas chromatography-based methods. Use of a pyrenyl-ethyl silica column in the first dimension enabled separation of all but two pairs of isobaric analytes. Limits of detection of 0.01 to 1.73 ng on-column were achieved. The precision and accuracy were within acceptable limits, but poor sensitivity was achieved for several meta-methylsulfonyl-substituted congeners. Despite this limitation, the method was successfully applied to the analysis of Greenland sledge dog (Canis familiaris) plasma and adipose tissue extracts. Concentration and enantiomer fraction data are presented. None of the target analytes were detected in Norwegian glaucous gull (Larus hyperboreus) plasma extracts.

La notion de valence est très répandue à l’échelle de l’atome et est à l’origine de la diversité et des propriétés des composés covalents (molécules, macromolécules, cristaux). L’un des grands challenges à l’heure actuelle est de décliner cette notion de valence à l’échelle des particules, qui pourraient devenir des briques élémentaires programmées, c’est-à-dire la matière première de nouveaux matériaux qui seraient obtenus par assemblage spontané. Dans ce contexte, nous avons développé des particules à patchs possédant à leur surface des discontinuités chimiques et topologiques permettant de limiter le nombre de particules voisines et d’engendrer des interactions directionnelles avec ces dernières. L’objectif de nos travaux consiste dans un premier temps à imiter les hybridations simples de l’atome de carbone divalent (sp), trivalent (sp2) et tétravalent (sp3). Des particules de silice contenant un nombre spécifique de cavités dans lesquelles se trouvent des chaines de polystyrène ont été synthétisées et fonctionnalisées sélectivement. Des molécules colloïdales constituées d’une particule à patchs, au centre, entourée de nanoparticules satellites en nombre contrôlé ont été obtenues par assemblages covalents ou supramoléculaires. Ces premiers clusters miment la géométrie de molécules simples telles que CF4, BF3, CO2 ou H2O. En différenciant des lots de satellites soit par leur taille, soit par leur composition chimique, nous avons montré qu’il est possible d’étendre la formation de molécules colloïdales vers de structures plus complexes du type AXnYm (n+m = 4) ou encore des molécules colloïdales chirales. Enfin, nous avons développé une autre voie permettant d’obtenir de nouveaux atomes colloïdaux contenant un nombre défini de patchs surfaciques de taille contrôlée. / The concept of valence is well-known at the atomic level and is at the origin of the diversity and properties of covalent compounds (molecules, macromolecules, crystals). Nowadays, one of the major challenges is to decline this notion of valence at the scale of colloidal particles, which could become programmed elementary bricks, that is to say the raw material of new materials that would be obtained by spontaneous assembly. In this context, we have developed patchy particles with chemical and topological discontinuities at their surface that limit the number of neighboring particles and induce directional interactions with them. The objective of our work consists first in imitating simple hybridizations of the divalent (sp), trivalent (sp2) and tetravalent (sp3) carbon atoms. The silica particles containing a specific number of cavities in which residues of polystyrene chains are chemically and selectively functionalized. Colloidal molecules consisting of a patchy particle, in the center, surrounded by satellite nanoparticles in controlled number were obtained by covalent or supramolecular routes. These first clusters mimic the geometry of simple molecules such as CF4, BF3, CO2 or H2O. By differentiating batches of satellites either by their size or by their chemical composition, we have shown that it is possible to extend the formation of colloidal molecules to more complex AXnYm (n + m = 4) structures or chiral colloidal molecules. Finally, we have developed another way to obtain new colloidal atoms containing a precise number of surface patches with a controlled area.

Orientador: Prof. Dr. Anderson Orzari Ribeiro / Tese (doutorado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2016. / Considerando o histórico de fármacos enantiomericamente puros e suas interações específicas com células alvos, nesse trabalho foram sintetizadas e caracterizadas quinze ftalocianinas com substituintes opticamente ativos e analisada suas propriedades fotoquímicas para possível aplicação como fármaco fotossensibilizador. Todas as ftalocianinas foram caracterizadas por RMN 1H, espectroscopia de massas, absorção na região do UV-vis, rendimentos quânticos de fluorescência e geração de espécies reativas de oxigênio sob irradiação. Resultados evidenciam que os diferentes grupos inseridos na periferia do anel ftalocianínico influenciam na solubilidade e na agregação do macrociclo, porém não influenciam significativamente nos rendimentos quânticos de geração de espécies reativas nas condições empregadas. Em relação a atividade óptica dos grupos e seus pares enantioméricos, pode-se concluir que não há relação direta entre configuração espacial e características fotoquímicas e fotofísicas, visto que não houve nenhuma relação que possa ser estabelecida como "regra" para esses compostos. Posteriores testes biológicos devem ser realizados par determinar interação entre células e as diferentes ftalocianinas sintetizadas. / Considering the history of enantiomerically pure drugs and their specific interaction with target cells, in this study were synthesized and characterized fifteen phthalocyanines with optically active substituents to be applied as photosensitizers in photodynamic therapy.. All phthalocyanines were characterized by 1H NMR, mass spectrometry, absorption and fluorescence emission, quantum yields of fluorescence and the quantum yield of generation of oxygen reactive species under irradiation. Results show that the different groups inserted on the phthalocyanine peripheral ring have influence on the solubility and the aggregation of the macrocycle in solution. With respect to optical characteristics, analyzing the groups and their enantiomeric pairs, it can be concluded that there is no direct link between configuration and photochemical and photophysical characteristics, as no relationship could be established as "rule" for these compounds. Further analyses should be taken to understand the influence of chiral ligands in the interaction of these phthalocyanines with target cells.

Les amphidinols sont une nouvelle classe de molécules naturelles de type polycétide dont l’amphidinol-3 est la seule molécule possédant sa structure entièrement établie. L’amphidinol-3 exhibe les meilleures activités biologiques de cette famille, principalement antifongique ethémolytique. La synthèse du fragment C17-C30 a été le premier objectif de ces travaux de thèse. Cette synthèse est basée sur l’utilisation du para-tolylsulfoxyde comme auxiliaire de chiralité et d’un bromoallylsilane comme corps central. Tous les centres asymétriques sont contrôlés avec de très hauts rapports diastéréomériques à l’exception de la configuration du méthyle en C23. La non-maîtrise de ce centre, ainsi que des difficultés probables de couplage nous ont obligés à repenser notre stratégie. Suite au changement rétrosynthétique, la synthèse du fragment C13-C29 a été réalisée. L’étape clef de cette voie synthétique est alors le couplage entre l’anion lithié d’un dérivé de 1,3-dithiane avec un aldéhyde α-branché. Après de nombreux ajustements de groupements protecteurs, le fragment C13-C29 est obtenu avec tous ses centres asymétriques maîtrisés. / Amphidinols are a new class of polyketide extracted from dinoflagellates and exhib promising biological activities, such as antifungal and hemolytic. The amphidinol-3 is the only amphidinol possessing its fully elucidated structure and is the most biologically potent.The C17-C30 fragment is the first goal of our research. The synthesis is based on sulfoxide as chiral auxiliary and on a bromoallylsilane as bifunctionnal central core. All stereogenic centers are fully controlled with high diastereomeric ratios except the one bearing a methyl in C23 position. The lack of selectivity during the hydrogenation affording the C23 stereogenic center and plausible failures of fragment couplings force us to explore a new retrosynthesis. Our second goal is the synthesis of C13-C29 fragment. The new strategy is based on a coupling between a 1,3-dithiane derivative and an α-branched aldehyde. After protecting group optimization, the C13-C29 fragment is synthetized with all its stereogenic centers fully controlled.