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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.
151

Élaboration et caractérisation de matériaux hybrides "nanoparticules Zn0 - cristaux liquides" pour applications aux cellules photovoltaïques / Elaboration and characterization of hybrid materials "nanoparticles ZnO - Liquid crystals" for photovoltaic cells applications

Halaby Macary, Mikhael 09 January 2019 (has links)
Ce travail de thèse s'inscrit dans l'essor important que connaît actuellement le domaine des énergies renouvelables en terme de recherche et de nouvelles technologies de l'énergie. Il est consacré à l'étude de nouveaux matériaux hybrides "nanoparticules ZnO - cristaux liquides" en vue d'applications aux cellules solaires de type hétérojonctions en volume. La motivation est d'utiliser les propriétés d'auto-organisation et de transport de charges des cristaux liquides et d'augmenter les interfaces donneur-accepteur afin d'améliorer leurs performances. Pour la mesures des mobilités des porteurs de charge, un banc de mesure "temps de vol" entièrement automatisé a été développé. Deux cristaux liquides calamitiques ont été caractérisés (DSC, microscopie optique polarisée, UV et "temps de vol"). Deux types de transports de charge, l'un ionique, l'autre électronique sont mis en évidence pour des charges positives et négatives avec des mobilités indépendantes du champ électrique et des comportements différents en fonction de la température. Un procédé d'élaboration des matériaux hybrides a été mis au point. Les caractérisations de ces matériaux montrent l'influence de la concentration en nanoparticules (0,05 à 38% en volume). La taille des domaines dans les phases cristal liquide augmente avec la concentration alors que la température de transition isotrope-SmA diminue fortement. Un résultat important est que les phénomènes de transport sont conservés pour des concentrations importantes (jusque 12% en volume). Le transport électronique est même amélioré. Les propriétés des matériaux élaborés apparaissent intéressantes pour des applications aux cellules photovoltaïques. / This thesis work is a part of the significant growth that is currently taking place in the field of the renewable energy in terms of research and new energy technologies. It is dedicated to the study of new hybrid material "zno particles - liquid crystals" for the applications in "bulk heterojunction" solar cells. The motivation is to increase the donor-acceptor interfaces in hybrid material and to combine the self-organizing and charge transport properties of liquid crystals, in order to improve their performance. A completely automated "time of flight" measuring set-up is developed, for the measurement of the charge carriers mobility in the aforementioned hybrid material. Using the dsc, polarized optical microscopy, uv-visible spectroscopy and "time of flight", we have characterized two calamitic liquid crystals. Two types of charge transport, one ionic, and the other electronic, are highlighted for positive and negative charges with electric field independent mobility and different behaviors with temperature. A process for the elaboration of hybrid materials is developed. The characterization of these materials show the influence of nanoparticles concentrations (0,05 to 38% by volume). The size of the domains in the liquid crystal phases increases with the concentration whereas the isotropic-sma phase transition temperature decreases monotically. Under controlled dispersion of zno nanoparticles in host liquid crystal up to 12% by volume, we have conserved the transport phenomena in hybrid material and study has shown that electronic transport is improved. The characterized hybrid materials have shown their potential application in organic photovoltaic.
152

Modellering och analys av avståndsmätare baserad på Time-to-Digital Converter / Modeling and analysis of rangefinder based on Time-to-Digital Converter

Sundelin, Johan January 2019 (has links)
This bachelor thesis has been performed at Saab Dynamics AB in Karlskoga, with the purpose to design simulation models and analyze the technology study for distance measurement based on Time Of Flight (TOF) -principle. The distance measurement is implemented by short laser pulses and Time-to-Digital Converter (TDC). This method uses the time difference between when the laser pulse is transmitted to the time when its reflection from an object returns to the detector. With this technology as a starting point for this thesis, an analysis has been made by looking at the subsystems when it gets affected by different parameters. The simulation will give an expected result which has been compared with the measurement results. On this basis a ranking of the parameters according by the influence of the functionality has been delivered. / Det här examensarbetet har utförts vid Saab Dynamics AB i Karlskoga med syftet att modellera och analysera en teknikstudie för avståndsmätning baserad på Time-Of-Flight-principen (TOF-principen). Avståndsmätningen genomförs med korta laserpulser och Time-to-Digital Converter (TDC). Det är en metod för avståndsmätning som baseras på tidsskillnaden från den tidpunkt då laserpulsen skickas från laserdioden till den tidpunkt då fotodioden har detekterat den reflekterade laserpulsen. Med den nya teknikstudien som utgångspunkt för arbetet har en analys på hur avståndsmätarens delsystem påverkats av olika parametrar genomförts där förväntat resultat har jämförts med mätresultat. Med detta som grund har en rangordning av parametrarna efter hur stor inverkan de har på funktionaliteten levererats.
153

Estudos sobre fotogeração, efeitos de interfaces e de transporte de portadores em células solares orgânicas / Studies about photogeneration, interface effects, and charge carrier transport in organic solar cells

Coutinho, Douglas José 18 June 2015 (has links)
Esta tese teve por objetivo, desde seu início, investigar as propriedades elétricas de um dispositivo ITO/PEDOT:PSS/P3HT:PCBM/Ca/Al, o qual é uma estrutura bem conhecida de célula solar orgânica do tipo de heterojunção de volume (bulk-heterojunction – BHJ), e com isso dar uma contribuição à melhora de seu desempenho. Porém, o primeiro passo foi introduzir no Grupo de Polímeros Bernhard Gross, um método eficaz de produzir células solares do tipo BHJ com boa eficiência e reprodutibilidade. Esse primeiro desafio foi alcançado com sucesso. A eficiência (η) de um dispositivo fotovoltaico de multicamadas depende de muitos fatores. Dentre eles, uma boa superposição entre o espectro solar e a curva de absorção da camada absorvedora, uma excelente conversão da energia luminosa em portadores de carga, um eficiente processo de condução e uma perda mínima por recombinação e armadilhamento de portadores. Além disso, a compatibilidade eletrônica entre as interfaces tem um papel fundamental na definição na tensão de circuito aberto (VOC), no valor da corrente de curto-circuito (JSC), e no fator de preenchimento (FF). Baseado nesses efeitos, realizamos uma série de medidas experimentais, que auxiliado por um modelo teórico proporcionaram um estudo detalhado da evolução em função da temperatura da mobilidade dos portadores (μ) e de seu tempo de vida (τ). Os principais experimentos nessa tese foram realizados em diferentes temperaturas (entre 100 e 340 K). Foram eles: medidas de fotocorrente - Jph(V), a técnica de foto-CELIV, e medidas de transiente de fotovoltagem (TPV). Em paralelo, desenvolvemos o modelo teórico para a descrição analítica de Jph(V) que assumiu contatos não-injetores e que o livre caminho médio (w = μτF) de elétrons e buracos eram iguais (F é o campo elétrico). Nos ajustes teórico/experimental usamos a probabilidade de dissociação dos estados de transferência de carga (P) e o produto μτ como parâmetros de ajuste. A condição na qual o livre caminho médio é maior que a espessura da amostra (w >> L) reproduz a corrente de saturação reversa, Jsat = qGPLG é a taxa de geração dos éxcitons. Para w << L, a fotocorrente varia linearmente com o livre caminho médio, ou seja, J(F) = qGPμτF. A comparação entre os resultados experimentais e os teóricos permitiram, além da obtenção da evolução das grandezas μ e τ com a temperatura, estabelecer uma relação efetiva entre os parâmetros da célula (η, JSC, e FF) e as propriedades elétricas da camada ativa P3HT:PCBM. As medidas termo-mecânicas (DMA) forneceram informações adicionais sobre mudanças estruturais da camada ativa, as quais foram correlacionadas com variações dos parâmetros da célula e com fatores de perda. Finalmente, medidas de tempo-de-voo (TOF) e de CELIV foram realizadas para estudos mais detalhados sobre mecanismos de transporte ao longo da camada ativa, a efeitos de injeção pelos eletrodos, e para o entendimento de efeitos de degradação pela ação do oxigênio. / This thesis aims to investigate electrical characteristics of an ITO/PEDOT:PSS/P3HT:PCBM/Ca/Al device, which is a well-known structure of a bulk-heterojunction (BHJ) organic solar cell, and to contribute to improve its performance. However, the first step was to introduce in the Group of Polymer Bernhard Gross an effective method for producing BHJ solar cells, manufacturing thus devices exhibiting excellent performance and reproducibility. This thesis aims to investigate electrical characteristics of an ITO/PEDOT:PSS/P3HT:PCBM/Ca/Al device, which is a well-known structure of a bulk-heterojunction (BHJ) organic solar cell, and to contribute to improve its performance. However, the first step was to introduce in the Group of Polymer Bernhard Gross an effective method for producing BHJ solar cells, manufacturing thus devices exhibiting excellent performance and reproducibility. This goal was successfully achieved. The good efficiency (η) of a multilayer photovoltaic cell depends on many factors, including good overlap between the solar spectrum and the light absorbing layer, an excellent conversion of the absorbed light energy in pairs of electronic carriers, efficient charge transport and the minimum losses by recombination or by the action of deep traps for the carriers. Furthermore, the compatibility between electronic interfaces plays a crucial role in defining the open-circuit voltage (VOC) and the value of short-circuit current (JSC), and on the fill factor (FF). Anchored on these effects, we carried out a series of experiments, aided by a theoretical modeling, which provided a detailed study of the temperature evolution of fundamental electric quantities such as carrier mobility (μ) and its lifetime (τ). These studies were performed with the help of different experiments: photocurrent in function of the applied voltage  Jph(V), Photo-CELIV technique, and Transient Photovoltage (TPV) measurements, which were carried out at several temperatures in the 100 to 340 K range. In parallel, we developed an analytical model for Jph(V) that assumed non-injecting contacts and equal mean-free-paths for electrons and holes. The theoretical/experimental entities used as fitting parameters were the charge-transfer-state dissociation probability (P) and the μτ product. The condition in which the mean-free-path (w = μτF) is higher the sample thickness (L), the model reproduces the experimental reverse saturation current, Jsat = qGPL, which is coincident with the experimental value. F is the internal electric field and G is the generation rate of excitons by the absorbed light. When w << L, J(F) = qGPμτF, which is also coincident with experimental behavior. The confrontation between the experimental results and the theoretical model provided, in addition to the study of the evolution of μ and τ with temperature, to establish a more effective relationship between the parameters (η, JSC, e FF) of the cell and the electrical properties of the P3HT:PCBM active layer. Thermomechanical analysis (DMA) provided additional information of structural changes of active layer, which can be correlated with change in the loss factor and in the cell parameters. Finally, Time-of-Flight (TOF) and CELIV techniques were used in the more accurate study of charge transport along the active layers, effects of injection by the electrodes, and the degradation effect caused by oxygen.
154

Molecular cluster cations of carbon monoxide and carbon dioxide

Bulat, Muhammer 27 December 2010 (has links)
Diese Dissertation handelt vom metastabilen Zerfall und von der Oberflächenwechselwirkung im hyperthermalen Energiebereich relativ schwach gebundener molekularer Kohlenmonoxid und Kohlendioxid Clusterkationen mit einer Edelstahloberfläche und einer Siliziumoberfläche. Im Rahmen dieser Arbeit wurde ein hierfür geeignetes spezielles Flugzeitmassenspektrometer entwickelt und aufgebaut. Entwurf, numerische Optimierung der Auflösung, ionenoptische Simulationen und Aufbau der jeweiligen Komponenten wie Elektronenquellen, Beschleuniger, Ablenkplatten, Massenfilter und Reflektron werden detailliert beschrieben. Das entwickelte Flugzeitmassenspektrometer besitzt mit einer kompakten Gesamtfluglänge von ~1.5m eine hohe Massenauflösung von m/Delta m = 3000. Es bietet die Möglichkeit, eine Massentrennung von Clusterionen mit einer Größe von bis zu n = 190 vorzunehmen. Diese massenselektierten Clusterionen können daraufhin auf metastabilen Zerfall und auf ihre Wechselwirkung mit einer Oberfläche untersucht werden. Dazu wurden Kohlendioxid-Clusterionen mit n / This thesis deals with the metastable decay and the surface scattering in the hyperthermal energy range of relatively weakly bound molecular cluster cations. With carbon monoxide and carbon dioxide two related model systems were chosen for a systematic size dependent study. Surface impact experiments were carried out with stainless steel and silicon surfaces. Results were obtained by a new, reflectron time-of-flight mass spectrometer (Re-TOFMS). Additional to the experimental data we present in this work a detailed description of the instrumental design considerations, numerical optimization, ion optical simulations. Hence each ion optical component like electron guns, accelerator, deflector, mass gate and reflectron are described. Despite the compact dimensions with a total flight length of ~1.5m the developed instrument possesses a high mass resolution above m/Delta m = 3000. Additionally it offers the possibility to perform mass separation of big cluster ions with sizes n
155

[en] STUDY OF THE STABLE AND METASTABLE (LIF)NLI+ ION EMISSION INDUCED BY 252CF FISSION FRAGMENTS / [pt] ESTUDO DA EMISSÃO DE ÍONS ESTÁVEIS E METAESTÁVEIS (LIF)NLI+ INDUZIDA POR FRAGMENTOS DE FISSÃO DO 252CF

RAFAEL MARTINEZ RODRIGUEZ 14 January 2004 (has links)
[pt] Um espectrômetro de massa por tempo-de-vôo 252Cf-PDMS foi empregado para a realização de três atividades: a) o aperfeiçoamento do espectrômetro com a instalação de novos dispositivos; b) a análise da emissão secundária de agregados iônicos por um alvo de LiF; c) a análise da fragmentação em vôo de íons positivos (LiF)nLi+ metaestáveis. O aperfeiçoamento do espectrômetro consistiu: i) na blindagem elétrica do detector start para aumentar a sua estabilidade; ii) na caracterização de dois pares de placas defletoras já existentes; iii) na instalação de um novo tipo de detector sensível à posição com anodo multi-fios, e iv) no projeto e na instalação de uma lente Einzel para aumentar a transmissão de íons secundários entre a amostra e o detector. A emissão secundária de agregados iônicos por um filme de LiF policristalino, bombardeado por fragmentos de fissão de ~ 60 MeV foi analisada através da técnica tempo-de-vôo (TOF). O detector sensível à posição recém instalado permite o emprego da técnica XY-TOF para analisar distribuições angulares de íons Li e dos agregados (LiF)nLi+. Determinaram-se as distribuições angulares dos agregados com n = 0 a 3, através de medidas simultâneas de suas velocidades axiais e radiais, evento por evento. A vida media de íons metaestáveis (LiF)nLi+* é determinada fazendo uso da configuração do espectrômetro e especialmente do comprimento do tubo de vôo livre. Após serem emitidas, as espécies iônicas metaestáveis monocarregadas são aceleradas por um campo elétrico da ordem de 2 kV/mm, e conduzidas a uma região de campo externo nulo, onde podem se dissociar espontaneamente em um fragmento iônico e outro neutro. Para facilitar a analise dos dados, impede-se a detecção do fragmento iônico através de um filtro eletrostático. Foram analisados os agregados iônicos com n = 1 a 5. Encontrouse que os valores das vidas medias estão na faixa de 30 a 100 ns. Discute-se também a detecção de espécies neutras produzidas por colisão de agregados (LiF)nLi+ com moléculas de gás residual. / [en] A 252Cf-PDMS time-of-flight mass spectrometer was used for the accomplishment of three activities: a) improvement of the spectrometer by introducing new devices; b) analysis of the LiF cluster ion secondary emission; c) analysis of the (LiF)nLi+ metastable íon fragmentation, in flight. The spectrometer improvement consists of: i) the shielding of the start detector to increase its stability, ii) the characterization of two existing deflecting- plate pairs, iii) the installation of a new type of position-sensitive delay line detector for secundary ions, and iv) the project and manufacture of a Einzel lens to increase the transmission of the secondary íons between the sample and the detector. The secondary cluster ion emission of policrystalline LiF, induced by the impact of fission fragments (60 MeV), is analyzed by the time-of-flight technique (TOF). The new position sensitive delay-line detector allows the use of the XY-TOF technique to analyze angular distributions of Li ions and (LiF)nLi+ clusters. Event by event, their axial and radial velocities are measured simultaneously, allowing the angular distributions measurement of clusters with n = 0 to 3. Mean lives of metastable clusters are determined through the measurement of the detection rate dependence on the target bias. After been emitted, the monocharged metatable ions are acelerated by a 2 kV/mm electric field towards a field-free region, where they can spontaneously dissociateinto two fragments, one ion and another neutral. To facilitate the data analysis, it is avoided the detection of ionic fragments by placing an electrostatic filter in front of the detector. Mean lives values of 30 to 100 ns are determined for ionic clusters with n = 1 to 5. The production of neutral species by collision of the (LiF)nLi+ clusters with the gas molecules is also discussed.
156

Liquid chromatography coupled with electrospray-ionization mass spectrometry and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry method development and applications for the analysis of food and medicinal herbs

Lee, Kim Chung 01 January 2009 (has links)
No description available.
157

Isolamento e caracterização da delta toxina do veneno de Crotalus durissus terrificus / Isolation and characterization of delta toxin from the venom of Crotalus durissus terrificus

Lucélia de Almeida Campos 25 August 2006 (has links)
O veneno de C. d. terrificus tem sido descrito como sendo de pouca complexidade, tendo 4 frações caracterizadas, convulxina, giroxina. crotoxina e crotamina. O presente trabalho visou o isolamento e caracterização da Delta toxina cuja existência havia sido aventada em trabalhos anteriores. Após a realização de uma varredura de tampões em uma coluna de exclusão molecular Superdex-75 acoplada a um sistema FPLC, na presença de três diferentes tampões, chegou-se a uma condição ideal de fracionamento do veneno crotálico. Em seqüência realizou-se a segunda etapa de purificação em sistema HPLC em uma coluna C4, onde foi possível identificar o pico de interesse. O pico puro passou por análises em MALDI-ToF sendo sua massa estimada em 14.074,92 Da, Quando analisado por eletroforese em gel de poiiacrilamida, a delta toxina apresentou massa molecular de cerca de 14 kDa e uma migração anômala, Por eletroforese 2D, a proteína apresentou caráter ácido, com pl entre 4 e 5 e massa molecular de aproximadamente 42 kDa, revelando \"spots\" muito semelhantes podendo ser isoformas com características de uma proteína glicosiiada. Após digestão dos spots com tripsina, os fragmentos foram confrontados com o banco de dados do \"swissprot\", mostrando alto grau de homologia \"até 43% de cobertura\" com a troca ri na, um ativador de protrombina do veneno de Tropidechis carinatus, esses dados foram confirmados com a análise de aminoácidos. De posse desses resultados, optou-se por testar a capacidade da fração purificada de ativar fator X e II, usando substratos sintéticos. Os resultados apontaram para uma ativação direta do fator X, uma vez que não houve ativação do fator II, atividade que também não foi detectada no veneno total. A mesma se mostrou um potente ativador da agregação de forma direta, uma vez que os ensaios de agregação plaquetária foram realizados com plaquetas lavadas, logo na ausência de fatores séricos. Quando os ensaios de agregação foram realizados na presença de alguns inibidores observou-se que nem a atividade metalo proteinase, nem a serino proteinase, tampouco um domínio lectina estavam envolvidos no processo, uma vez que EDTA, benzamidina e D-galactose não inibiram a atividade da proteína. No presente trabalho isolamos a Delta toxina do veneno de C. d. terrificus. A mesma se comportou como previsto por Vital Brazil em 1980, eluindo na posição por ele aventada, sendo uma proteína ativadora de Fator X que ativa agregação plaquetária mesmo em concentrações muito baixas e de massa molecular de 40 kDa levando nos a crer se tratar de um homotrímero cujos componentes são unidos por ligações fracas. / The Crotalus durissus terrificus venom has been so far described as being of low complexity, with four major components described: convulxin, gyroxin, crotoxin and crotamine. In recent studies, other components of this venom were characterized as, for example, an analgesic factor. In 1980, Vital Brazil predicted the existence of a toxin which could be involved in platelet aggregation, and named it delta toxin. However, this toxin has never been isolated or characterized. The aim of the present work was to purify and characterize this toxin. After FPLC size exclusion chromatography followed by reverse phase HPLC, an homogeneous fraction was obtained, with a molecular weight of 14,074.92 Da. When analyzed by SOS-PAGE, this toxin presented an anomalous behavior, with a molecular weight of 14 kDa, while in 2D gels, spots around 40 kDa and with an isoelectrical point between 4 and 5 were observed suggesting isoforms with glicosilation microheterogeneity. After trypsin digestion, the fragments were submitted to the swissprot databank showing high homology (43% coverage, 15 matching peptides) with trocarin, a prothrombin activator from Tropidechis carinatus. These data were further confirmed by aminoacid analysis. The toxin was tested for its ability to activate factor II and X using synthetic substrates. Our data indicate a direct activation of factor X. The same toxin also behaved as a potent direct platelet aggregation activator on washed platelets. Assays with specific inhibitors indicate that neither metalloproteinase, nor serinoproteinase or t lectin domains are involved in the aggregating activity, since EDTA, benzamidin and D-galactose did not inhibit the toxin. In the present work, we were able to identify, purify and characterize a new toxin from the brazilian rattlesnake. It behaved as predicted by Vital-Brazil and displayed direct factor X activating properties, also inducing platelet aggregation, even at low concentrations. Our data also indicate that it is probably a homotrimer with the subunities linked by hydrophobic and/or electrostatic interactions.
158

Isolamento e caracterização da delta toxina do veneno de Crotalus durissus terrificus / Isolation and characterization of delta toxin from the venom of Crotalus durissus terrificus

Campos, Lucélia de Almeida 25 August 2006 (has links)
O veneno de C. d. terrificus tem sido descrito como sendo de pouca complexidade, tendo 4 frações caracterizadas, convulxina, giroxina. crotoxina e crotamina. O presente trabalho visou o isolamento e caracterização da Delta toxina cuja existência havia sido aventada em trabalhos anteriores. Após a realização de uma varredura de tampões em uma coluna de exclusão molecular Superdex-75 acoplada a um sistema FPLC, na presença de três diferentes tampões, chegou-se a uma condição ideal de fracionamento do veneno crotálico. Em seqüência realizou-se a segunda etapa de purificação em sistema HPLC em uma coluna C4, onde foi possível identificar o pico de interesse. O pico puro passou por análises em MALDI-ToF sendo sua massa estimada em 14.074,92 Da, Quando analisado por eletroforese em gel de poiiacrilamida, a delta toxina apresentou massa molecular de cerca de 14 kDa e uma migração anômala, Por eletroforese 2D, a proteína apresentou caráter ácido, com pl entre 4 e 5 e massa molecular de aproximadamente 42 kDa, revelando \"spots\" muito semelhantes podendo ser isoformas com características de uma proteína glicosiiada. Após digestão dos spots com tripsina, os fragmentos foram confrontados com o banco de dados do \"swissprot\", mostrando alto grau de homologia \"até 43% de cobertura\" com a troca ri na, um ativador de protrombina do veneno de Tropidechis carinatus, esses dados foram confirmados com a análise de aminoácidos. De posse desses resultados, optou-se por testar a capacidade da fração purificada de ativar fator X e II, usando substratos sintéticos. Os resultados apontaram para uma ativação direta do fator X, uma vez que não houve ativação do fator II, atividade que também não foi detectada no veneno total. A mesma se mostrou um potente ativador da agregação de forma direta, uma vez que os ensaios de agregação plaquetária foram realizados com plaquetas lavadas, logo na ausência de fatores séricos. Quando os ensaios de agregação foram realizados na presença de alguns inibidores observou-se que nem a atividade metalo proteinase, nem a serino proteinase, tampouco um domínio lectina estavam envolvidos no processo, uma vez que EDTA, benzamidina e D-galactose não inibiram a atividade da proteína. No presente trabalho isolamos a Delta toxina do veneno de C. d. terrificus. A mesma se comportou como previsto por Vital Brazil em 1980, eluindo na posição por ele aventada, sendo uma proteína ativadora de Fator X que ativa agregação plaquetária mesmo em concentrações muito baixas e de massa molecular de 40 kDa levando nos a crer se tratar de um homotrímero cujos componentes são unidos por ligações fracas. / The Crotalus durissus terrificus venom has been so far described as being of low complexity, with four major components described: convulxin, gyroxin, crotoxin and crotamine. In recent studies, other components of this venom were characterized as, for example, an analgesic factor. In 1980, Vital Brazil predicted the existence of a toxin which could be involved in platelet aggregation, and named it delta toxin. However, this toxin has never been isolated or characterized. The aim of the present work was to purify and characterize this toxin. After FPLC size exclusion chromatography followed by reverse phase HPLC, an homogeneous fraction was obtained, with a molecular weight of 14,074.92 Da. When analyzed by SOS-PAGE, this toxin presented an anomalous behavior, with a molecular weight of 14 kDa, while in 2D gels, spots around 40 kDa and with an isoelectrical point between 4 and 5 were observed suggesting isoforms with glicosilation microheterogeneity. After trypsin digestion, the fragments were submitted to the swissprot databank showing high homology (43% coverage, 15 matching peptides) with trocarin, a prothrombin activator from Tropidechis carinatus. These data were further confirmed by aminoacid analysis. The toxin was tested for its ability to activate factor II and X using synthetic substrates. Our data indicate a direct activation of factor X. The same toxin also behaved as a potent direct platelet aggregation activator on washed platelets. Assays with specific inhibitors indicate that neither metalloproteinase, nor serinoproteinase or t lectin domains are involved in the aggregating activity, since EDTA, benzamidin and D-galactose did not inhibit the toxin. In the present work, we were able to identify, purify and characterize a new toxin from the brazilian rattlesnake. It behaved as predicted by Vital-Brazil and displayed direct factor X activating properties, also inducing platelet aggregation, even at low concentrations. Our data also indicate that it is probably a homotrimer with the subunities linked by hydrophobic and/or electrostatic interactions.
159

Transport de charges dans des couches minces hybrides à base de polymère conjugué et de nanocristaux de semi-conducteurs / Charge transport in hybrid thin films based on conjugated polymers and semiconductor nanocrystals

Couderc, Elsa 01 December 2011 (has links)
Cette thèse a pour but d'étudier le transport de charges pho- togénérées dans des matériaux hybrides composés de polymères π-conjugués et de nanocristaux de semi- conducteurs, conçus pour des applications en opto-électronique. La synthèse chimique permet d'obtenir des nanocristaux de CdSe à l'échelle du gramme ayant une faible polydispersité et des formes contrôlées (sphériques, branchées). Les ligands de surface des nanocristaux de CdSe sont échangés par de petites molécules (pyridine, éthanedithiol, phénylènediamine, butylamine, benzènedithiol) afin d'augmenter leur conductivité. L'échange de ligands modifie les niveaux énergétiques des nanocristaux, comme le montrent des études optiques et électrochimiques. Le poly(3-hexylthiophène) déposé sous forme de couches minces présente différents degrés de couplage intermoléculaire et de désordre énergétique selon la méthode de dépôt et le solvant utilisé. Dans les films hybrides, des mesures de diffraction de rayons X en incidence rasante montrent que la structuration cristalline de la matrice organique est modifiée par la présence des nanocristaux. Les mesures de Temps-de-Vol dans les couches hybrides montrent que les mobilités des trous et des électrons varient avec le contenu en nanocristaux, ainsi qu'avec leur forme et leurs ligands. De faibles fractions de nanocristaux provoquent une amélioration de la mobilité des trous, tandis que de plus grandes fractions la détériorent. Les mobilités électroniques sont soumises à une fraction-seuil, as- similable à un seuil de percolation. La fraction optimale de nanocristaux, du point de vue des mobilités des trous et des électrons, est de 36% en volume pour les nanocristaux sphériques avec les ligands de synthèse. Enfin, les simulations Monte-Carlo des courants transitoires photo-générés, dans un échantillon de poly(3-hexylthiophène) et dans un hybride, montrent d'une part que la distribution énergétique du poly(3-hexylthiophène) domine l'allure des courants simulés et d'autre part que les nanocristaux peuvent être assimilés à des sites difficilement accessibles du réseau cubique. / The aim of this work is the study of photogenerated charge transport in hybrid films composed of π-conjugated polymers and of semiconductor nanocrystals, designed for applications in optoelectronics. Chemical synthesis provides gram-scale samples of CdSe nanocrystals, of low polydispersity and con- trolled shapes (spherical, branched). In order to enhance their conductivity, the surface ligands of CdSe nanocrystals (stearic acid, oleylamine) are exchanged by smaller molecules, namely pyridine, ethanedithiol, phenylenediamine, butylamine and benzenedithiol. Optical and electrochemical studies show that the lig- and exchange modifies the nanocrystals' energy levels. Poly(3-hexylthiophene) thin films exhibit varying degrees of energetical disorder and of intermolecular coupling, depending on the processing method and on the solvent used. In hybrid films, the crystallinity of P3HT, probed by grazing incidence X-ray diffraction, is modified by the presence of nanocrystals. Time-of-Flight measurements of hybrid films show that elec- tron and hole mobilities vary with the content of nanocrystals, with their shape, and with their ligands. Small volume fractions of nanocrystals enhance the hole mobility, and large fractions degrade it. Electron mobilities are percolation-limited: they reach a stable value for a threshold fraction of nanocrystals. The optimal fraction of nanocrystals for electron and hole mobilities is 36 vol% in hybrids made of spherical nanocrystals with their synthesis synthesis ligands. Finally, Monte Carlo simulations of photogenerated current transients in pristine poly(3-hexylthiophene) and in a hybrid sample show on one hand that the energy distribution of poly(3-hexylthiophene) rules the shape of the simulated transients, and on the other hand that nanocrystals can be described as little accessible sites of the hopping lattice.
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Développement d'un système de mesure de temps de vol picoseconde dans l'expérience ATLAS / Development of a picosecond time-of-flight system in the ATLAS experiment

Grabas, Hervé 03 December 2013 (has links)
Cette thèse présente une étude de la sensibilité à la physique au delà du modèle standard et en particulier aux couplages anormaux entre les photons et les bosons W. Ceci est réalisé en détectant dans ATLAS les protons intacts après interaction et en mesurant leur temps de vol avec une précision de quelques pico-secondes de part et d’autre du détecteur central.Je décrirai également les photo-détecteurs de grande superficie avec une précision de quelques pico-secondes et les algorithmes de reconstruction de temps basés sur l’échantillonnage rapide du signal. Le circuit intégré spécifique SamPic pour une mesure de temps de très haute précision sera enfin présenté ainsi que les premiers résultats de mesure avec ce circuit. Ils montrent en particulier une précision exceptionnelle, meilleure que 5 ps, sur la mesure de temps entre deux impulsions. / In this thesis, we present a study of the sensitivity to Beyond Standard Model physics brought by the design and installation of picosecond time-of-flight detectors in the forward region of the ATLAS experiment at the LHC. The first part of the thesis present a study of the sensitivity to the quartic gauge anomalous coupling between the photon and the W boson, using exclusive WW pair production in ATLAS. The event selection is built considering the semi-leptonic decay of WW pair and the presence of the AFP detector in ATLAS. The second part gives a description of large area picosecond photo-detectors design and time reconstruction algorithms with a special care given to signal sampling and processing for precision timing.The third part presents the design of SamPic: a custom picosecond readout integrated circuit. At the end, its first results are reported, and in particular a world-class 5ps timing precision in measuring the delay between two fast pulses.

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