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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Engineered delivery tools for gene therapy and optogenetics

Schiller, Lara Timantra 18 April 2018 (has links)
No description available.
2

Model Studies Towards the Total Synthesis of Lyconadin A via An Acyl Radical Cascade Reaction

Zhu, Koudi 30 June 2006 (has links) (PDF)
Lyconadin A is an alkaloid possessing a unique structure and antitumor activity. The total synthesis of Lyconadin A was proposed via an acyl radical cascade reaction. To investigate the possibility and stereoselectivity of the cascade cyclization, phenyl selenoester 16 was chosen as a model substrate to study the 7-exo-5-exo radical cyclization. A synthetic route to phenyl selenoester 16 was developed. The 7-exo-5-exo radical cyclization was found to occur with a high yield and excellent stereoselectivty. Attempts were also tried to synthesize another radical precursor 14 albeit with less success. A synthetic pathway to the synthesis of 14 as well as its potential use in the context of the synthesis of Lyconadin A was proposed.
3

Synthèse et fonctionnalisation d'exo-glycals : application à la préparation d'anti-tumoraux / Synthesis and functionnalization of exo-glycals : toward potential anti-cancer compounds

Novoa, Alexandre 12 February 2010 (has links)
Ce travail est une contribution à la synthèse et à la fonctionnalisation d'exo-glycals en vue d'accéder à des composés à activité anti-tumorale potentielle. Les objectifs de ce travail ont été doubles. Dans un premier temps, la transformation d'exo-glycals d'accès aisé en exoglycals plus fonctionnalisés par réaction de couplage pallado-catalysé a été réalisée ouvrant ainsi une nouvelle voie d'accès à des exo-glycals disubstitués. L'hydrogénation des composés issus de ces réactions de couplage a permis l'obtention de nouveaux types de C-glycosides. Dans un second temps, le développement de nouvelles applications des exo-glycals fonctionnels pour accéder à des molécules biologiquement actives a été entrepris. De nouveaux analogues de la phenstatine, molécule présentant une forte activité sur l'antiprolifération cellulaire, ont été synthétisés et leurs propriétés biologiques ont été évaluées. Parallèlement, un C-glycoside a été utilisé en tant que répartiteur de fonction pour la synthèse de peptidomimétiques inhibiteurs potentiels de la liaison VEGF165/NRP-1 impliquée dans le processus de l'angiogénèse tumorale. / The objective of this work consists in the synthesis and functionnalization of exo-glycals toward potential anti-cancer compounds. On the one hand, the transformation of easily accessible exo-glycals to more elaborated ones using palladium cross-coupling reaction has been performed and offered a new route to disubstituted exo-glycals. The hydrogenation of these compounds gave original C-glycosides. On the other hand, the new functionnal exo-glycals have been developped to prepare biologically active compounds. Analogs of phenstatin have been obtained and tested for their cellular growth inhibition. Furthermore, a C-glycoside has been used as a scaffold for peptidomimetics synthesis against the tumor angiogenesis process.
4

Caractérisation de composants de filtrage modal pour l'observation d'exoplanète par interférométrie annulante.

Romain, Grille 18 December 2009 (has links) (PDF)
L'interférométrie annulante permet l'étude d'exoplanètes dans l'IR (6-20 um) et la mesure de leur émission atmosphérique, reflet d'une possible activité biologique. Pour atteindre le contraste interférométrique nécessaire pour dissocier le signal planétaire du signal stellaire, les fronts d'onde issus des différents télescopes doivent se superposer parfaitement. La meilleure solution consiste à utiliser un guide d'onde monomode récupérant le flux planétaire indépendamment des aberrations optiques. Mon travail a consisté à caractériser de tels composants d'optique intégrée. J'ai mis en oeuvre pour cette étude trois méthodes : la distinction modale monochromatique par imagerie, la mesure de la plage de monomodicité par FTS et la mesure des performances de filtrage par interférométrie. Pour mener à bien ce travail, il a été nécessaire d'effectuer une analyse système de l'ensemble du banc optique, en particulier pour l'étude par interférométrie, dont les contraintes sur les vibrations, les flux lumineux ainsi que sur le positionnement des éléments optiques sont très fortes. L'étude porte sur des guides creux métalliques (HMW) et des guides diélectriques en halogénure d'argent (SH). Mon travail sur les HMW vient clore leur étude entreprise avant ma thèse. Les trois méthodes ont été utilisées pour caractériser des composants SH (guides plans et fibres optiques). Les HMW sont de bons filtres modaux mais nécessitent une fabrication très rigoureuse pour limiter les pertes en propagation. Les fibres SH nécessitent des longueurs plus conséquentes (avec des pertes linéiques plus faibles), pouvant être réduite par l'ajout de couche absorbante sur la gaine.
5

Characterization and silencing of differentially abundant proteins from Pyrenophora tritici-repentis

Fu, Heting Unknown Date
No description available.
6

Directing a SmI2 radical cyclisation using a C-Si bond : a second generation approach to pestalotiopsin A, 6-epitaedolidol and punctaporonin C

Harb, Hassan Youssef January 2011 (has links)
An improved second generation approach to pestalotiopsin A and 6-epitaedolidol has been developed. A silicon group bonded directly to carbon has been used as a stereocontrol element in cyclisation substrates for a SmI2 – mediated 4-exo-trig radical cyclisation. The silicon groups acts as a steric block to set up three new stereocentres in high to complete diastereocontrol. Several approaches to the cyclisation substrates are outlined, including a silyl transfer/aldol cascade and a novel C2-symmetric N-heterocyclic carbene – copper catalyst to asymmetrically install a C-Si bond. The silicon group is a versatile handle for further manipulation and has been oxidised using Fleming oxidation conditions to install the hydroxyl functionality required in the target compounds. The silicon group also simplifies the alcohol protecting group strategy in the approach to pestalotiopsin A and 6‐epitaedolidol. The first application of N-heterocyclic carbene – copper catalysed silyl transfer in natural product synthesis and the first use of a SmI2 – mediated cyclisation directed by a C-Si stereocontrol element are described.
7

Self-assembly of tubular supramolecular architectures via a combination of endo- and exo-recognition processes

Heck, James Arthur January 1995 (has links)
No description available.
8

Expressão heteróloga, análise bioquímica e avaliação da produção fermentativa de uma enzima exo-arabinanase da família GH93 / Heterologous expression, biochemical analysis and evaluation of the fermentative production of an exo-arabinanase enzyme of the GH93 family

Josman Andrey Velasco Mendoza 31 July 2018 (has links)
Segundo a classificação CAZy (Carbohydrate Active enZymes), as glicosil hidrolases (GH) da família 93 são exo-?-1,5-arabinanases que atuam nas ligações ?-1,5 que unem os resíduos de L-arabinofuranosideo que conformam a cadeia principal de arabinana desramificada, liberando arabinose ou arabinobiose. Esta recém descrita família de enzimas, além de ter o potencial de participar junto com outras proteínas na sacarificação de resíduos industriais como a polpa de beterraba, oferece a possibilidade de sintetizar novas moléculas, pois alguns membros desta família podem catalisar reações de transarabinosilação utilizando glicerol, xilitol e sorbitol como aceptores. Embora as GH93 apresentem caraterísticas atrativas para aplicações industriais, até o momento apenas cinco enzimas desta família foram caraterizadas bioquimicamente, sendo que a maioria delas apresentou maior atividade em pHs ácidos e nenhuma com caraterísticas termofílicas. Neste trabalho uma exo-?-1,5-arabinanase abnt do fungo termofílico Thielavia terrestris foi expressa heterólogamente pela primeira vez em fungo filamentoso, utilizando Aspergillus nidulans linhagem A773 transformado com o vetor pEXPYR como sistema de expressão. A enzima foi caraterizada bioquimicamente e sua produção fermentativa avaliada, utilizando dois tipos de indutores em diferentes concentrações e condições de cultivo, escolhendo a melhor condição para o escalonamento. A proteína recombinante de 39,8 KDa mostrou ser uma glicoproteína com uma atividade especifica de 248 U.mg-1 em arabinana desramificada 0,28 mM, pH 5 e temperatura de 70 ?C (valores ótimos para enzima), um Km 0,29 mM, Vmax 0,45 ?mol.min-1, Kcat 115,4 s-1, e eficiência catalítica de 3,9 *105 s-1 M-1, mostrando também um aumento de 34% na liberação de produto quando incubada na presença de CoCl2 1mM. Esta é a primeira exo-arabinanase reportada na literatura com comportamento termofílico e prolongada estabilidade em pHs ácidos. No processo fermentativo a melhor produção de abnt foi atingida usando 3% (m/v) do indutor em condições de cultivo submerso, o escalonamento do processo não afetou a produção enzimática. O sistema de expressão A. nidulans+pEXPYR foi capaz de produzir a mesma quantidade de proteína recombinante utilizando como indutor, um composto cinquenta vezes mais barato que o normalmente utilizado. / According to CAZy (Carbohydrate Active enZymes) classification, glycosyl hydrolases (GH) from family 93 are exo-?-1,5-arabinanases acting on ?-1,5 bonds that bind L-arabinofuranose residues in the main chain of arabinan releasing arabinose or arabinobiose. This new family of enzymes was described recently and, besides having the potential to participate along with other proteins in the saccharification of agro industrial wastes such as sugar beet pulp, offers the possibility of synthesize new molecules, since some members of this family can catalyze reactions of transarabinosylation using glycerol, xylitol and sorbitol as acceptors. Although, GH93 presents attractive characteristics for industrial applications, only five enzymes have been characterized biochemically so far, most of them presenting higher activity in acidic pHs and none with thermophilic characteristics. In this work an exo-?-1,5-arabinanase abnt of the thermophilic fungus Thielavia terrestris was heterologously expressed for the first time in a filamentous fungus using Aspergillus nidulans strain A773 transformed with the pEXPYR vector as expression system. The enzyme was characterized biochemically and its fermentative production was evaluated using two types of inducers in different concentrations and conditions of cultivation, setting the best condition for scale up. The recombinant protein of 39.8 KDa showed be a glycoprotein with a specific activity of 248 U.mg-1 in 0.28 mM debranched arabinana at pH 5 and temperature of 70 °C (optimum values for enzyme), a Km 0,29 mM, Vmax 0.45 ?mol.min-1, Kcat 115.4 s-1, and catalytic efficiency of 3.9 * 105 s-1 M-1, also showed an increase of 34% in product release when incubated in the presence of 1 mM CoCl2. This, is the first exo-arabinanase reported in the literature with thermophilic behavior and prolonged stability at acidic pHs. In the fermentation process the best abnt production was achieved using 3% (m/v) of the inducer under submerged culture conditions, and the scaling process did not affect the enzymatic production. The A. nidulans+pEXPYR expression system was able to produce the same amount of recombinant protein using as an inducer, a compound fifty fold less expensive then the normally used.
9

Estudos estruturais de glicosidases de fungos / Structural studies of fungal glycoside hydrolases

Cardona, Adriana Lucely Rojas 08 June 2005 (has links)
As glicosidases são enzimas que apresentam uma grande variedade de enovelamentos, assim como uma alta especificidade frente a diferentes substratos. Estas enzimas têm em comum a presença de dois resíduos catalíticos, responsáveis pela clivagem das ligações glicosídicas. O uso de glicosidases nas indústrias têxtil e alimentícia, no processamento de polpa de papel e na síntese de oligossacarídeos tem incentivado a engenharia destas proteínas no sentido de melhorar suas propriedades catalíticas e estabilidade. Estudos estruturais das glicosidases têm aumentado nosso entendimento de seus mecanismos de ação catalitica, assim como dos processos de interação proteína-carboidrato. Neste trabalho apresentamos os estudos cristalográficos de duas glicosidases de fungos, sendo elas a beta-galactosidase de Penicillium sp. e a Exo-inulinase de Aspergillis awamori, assim como estudos por espalhamento de raios-X a baixos ângulos (SAXS) da beta-xylosidase de Trichoderma reesei. As estruturas cristalográficas da beta-galactosidase e de seu complexo com galactose foram determinadas pela técnica de substituição isomórfa simples com espalhamento anômalo (SIRAS) até 1.9 A angstron de resolução para a estrutura sem substrato e 2.0 angstron de resolução para o complexo. A estrutura do complexo com galactose foi usada para identificar os resíduos catalíticos, sendo o resíduo Glu 200 identificado como doador de próton e o resíduo Glu 299 como o nucleófílo. As estruturas cristalográficas da Exo-inulinase de Aspergillus awamori e de seu complexo com frutose foram também determinadas pela técnica de substituição isomórfa simples com espalhamento anômalo (SIRAS) até 1.55 angstron e 1.8 angstron de resolução, respectivamente. A partir da estrutura do complexo foi possível identificar os resíduos Asp41 e Glu241 como o nucleófilo e o doador de próton, respectivamente. Além disto, foi possível verificar que o Asp189, o qual faz parte do motivo conservado Arg-Asp-Pro (RDP), é importante no reconhecimento do substrato através de duas pontes de hidrogênio. Com o intuito de obter informações estruturais sobre a P-xylosidase seu envelope foi determinado a partir dos dados do espalhamento de raios-X a baixos ângulos. O envelope da p-xylosidase em solução foi calculado a 20 A de resolução, sendo o raio de giro e a dimensão máxima 36.9 angstron e 90 angstron, respectivamente. Usando algoritmos de reconhecimento de possíveis domínios foi determinado que esta proteína apresenta, além dos dois domínios característicos da família GHF3, um barril TIM e um domínio alfa/beta, um terceiro domínio. A predição da estrutura secundária e os dados de dicroísmo circular indicam que este terceiro domínio apresentaria um enovelamento tipo beta. / Glycosidases belong to a group of enzymes displaying a great variety of protein folds and substrate specificities. Two critically located acidic residues make up the catalytic machinery of these enzymes, responsible for the cleavage of glycosidic bonds. The applications of glycosidases in textile, food, and pulp processing, as well as in catalysts and oligosaccharide synthesis have encouraged the engineering of these proteins in order to obtain improved catalytic properties and stability. Furthermore, structural studies extend our understanding of the catalytic mechanism and the role of glycosidases in the recognition processes of their different substrates. In this work, we describe crystallographic studies of two fungi glycosidases, beta-galactosidase from Penicillium sp and Exo-inulinase from Aspergillis awamori, and the small-angle x-ray scattering (SAXS) studies of another glycosidase, beta-xylosidase (from Trichoderma reesei). The crystallographic structures of j3-galactosidase its complex with galactose were solved by single isomorphous replacement with anomalous scattering (SIRAS) using the quick cryo-soaking technique, at 1.90 angstron and 2.10 angstron resolution, respectively . The X-ray structure of the enzyme-galactose complex was useful in identifying the residue Glu 200 as the proton donor and residue Glu 299 as the nucleophile involved in catalysis. The x-ray structure of exo-inulinase and its complex with fructose were also solved by SIRAS using the quick cryo-soaking technique at 1.55 angstron and 1.8 angstron resolutions, respectively. The solved structure of the enzyme-fructose complex revealed two catalytically important residues, Asp41 and Glu241, as nucleophile and proton donor, respectively. It was also possible to see that residue Asp189, which belongs to the Arg-Asp-Pro motif, provides hydrogen bonds important for substrate recognition. In order to gain structurai insights about the beta-Xylosidase from Trichoderma reesei, we calculated their SAXS envelope. The low resolution shape of this enzyme in solution was obtained fiom synchrotron x-ray scattering data at 20 angstron resolution. The radii of gyration and the maximum dimension of the beta-Xylosidase were calculated to be 36.9 angstron and 90 angstron, respectively. In contrast to the fold of the only structurally characterized member of GHF-3, the beta-D-glucan exohydrolase, which has two distinct domains, the shape of the beta-xylosidase indicates the presence of three domains located in the same plane. Domain recognition algorithms were used to show that the C-terminal part of the mino acid sequence of the protein forms the third domain. Circular dichroism spectroscopy and secondary structure prediction programs show that this additional domain adopts predominantly the B-conformation.
10

Expressão heteróloga, análise bioquímica e avaliação da produção fermentativa de uma enzima exo-arabinanase da família GH93 / Heterologous expression, biochemical analysis and evaluation of the fermentative production of an exo-arabinanase enzyme of the GH93 family

Mendoza, Josman Andrey Velasco 31 July 2018 (has links)
Segundo a classificação CAZy (Carbohydrate Active enZymes), as glicosil hidrolases (GH) da família 93 são exo-?-1,5-arabinanases que atuam nas ligações ?-1,5 que unem os resíduos de L-arabinofuranosideo que conformam a cadeia principal de arabinana desramificada, liberando arabinose ou arabinobiose. Esta recém descrita família de enzimas, além de ter o potencial de participar junto com outras proteínas na sacarificação de resíduos industriais como a polpa de beterraba, oferece a possibilidade de sintetizar novas moléculas, pois alguns membros desta família podem catalisar reações de transarabinosilação utilizando glicerol, xilitol e sorbitol como aceptores. Embora as GH93 apresentem caraterísticas atrativas para aplicações industriais, até o momento apenas cinco enzimas desta família foram caraterizadas bioquimicamente, sendo que a maioria delas apresentou maior atividade em pHs ácidos e nenhuma com caraterísticas termofílicas. Neste trabalho uma exo-?-1,5-arabinanase abnt do fungo termofílico Thielavia terrestris foi expressa heterólogamente pela primeira vez em fungo filamentoso, utilizando Aspergillus nidulans linhagem A773 transformado com o vetor pEXPYR como sistema de expressão. A enzima foi caraterizada bioquimicamente e sua produção fermentativa avaliada, utilizando dois tipos de indutores em diferentes concentrações e condições de cultivo, escolhendo a melhor condição para o escalonamento. A proteína recombinante de 39,8 KDa mostrou ser uma glicoproteína com uma atividade especifica de 248 U.mg-1 em arabinana desramificada 0,28 mM, pH 5 e temperatura de 70 ?C (valores ótimos para enzima), um Km 0,29 mM, Vmax 0,45 ?mol.min-1, Kcat 115,4 s-1, e eficiência catalítica de 3,9 *105 s-1 M-1, mostrando também um aumento de 34% na liberação de produto quando incubada na presença de CoCl2 1mM. Esta é a primeira exo-arabinanase reportada na literatura com comportamento termofílico e prolongada estabilidade em pHs ácidos. No processo fermentativo a melhor produção de abnt foi atingida usando 3% (m/v) do indutor em condições de cultivo submerso, o escalonamento do processo não afetou a produção enzimática. O sistema de expressão A. nidulans+pEXPYR foi capaz de produzir a mesma quantidade de proteína recombinante utilizando como indutor, um composto cinquenta vezes mais barato que o normalmente utilizado. / According to CAZy (Carbohydrate Active enZymes) classification, glycosyl hydrolases (GH) from family 93 are exo-?-1,5-arabinanases acting on ?-1,5 bonds that bind L-arabinofuranose residues in the main chain of arabinan releasing arabinose or arabinobiose. This new family of enzymes was described recently and, besides having the potential to participate along with other proteins in the saccharification of agro industrial wastes such as sugar beet pulp, offers the possibility of synthesize new molecules, since some members of this family can catalyze reactions of transarabinosylation using glycerol, xylitol and sorbitol as acceptors. Although, GH93 presents attractive characteristics for industrial applications, only five enzymes have been characterized biochemically so far, most of them presenting higher activity in acidic pHs and none with thermophilic characteristics. In this work an exo-?-1,5-arabinanase abnt of the thermophilic fungus Thielavia terrestris was heterologously expressed for the first time in a filamentous fungus using Aspergillus nidulans strain A773 transformed with the pEXPYR vector as expression system. The enzyme was characterized biochemically and its fermentative production was evaluated using two types of inducers in different concentrations and conditions of cultivation, setting the best condition for scale up. The recombinant protein of 39.8 KDa showed be a glycoprotein with a specific activity of 248 U.mg-1 in 0.28 mM debranched arabinana at pH 5 and temperature of 70 °C (optimum values for enzyme), a Km 0,29 mM, Vmax 0.45 ?mol.min-1, Kcat 115.4 s-1, and catalytic efficiency of 3.9 * 105 s-1 M-1, also showed an increase of 34% in product release when incubated in the presence of 1 mM CoCl2. This, is the first exo-arabinanase reported in the literature with thermophilic behavior and prolonged stability at acidic pHs. In the fermentation process the best abnt production was achieved using 3% (m/v) of the inducer under submerged culture conditions, and the scaling process did not affect the enzymatic production. The A. nidulans+pEXPYR expression system was able to produce the same amount of recombinant protein using as an inducer, a compound fifty fold less expensive then the normally used.

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