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Restoration of mangrove forests: resilience of pedogenetic processes and soil quality / Restauração de manguezais: resiliência de processos pedogenéticos e qualidade do soloJimenez, Laís Coutinho Zayas 04 July 2019 (has links)
Mangroves are coastal ecosystems that provide many ecosystem services, for example: (i) carbon sequestration; (ii) mitigation of greenhouse gas emissions; (iii) retention and immobilization of contaminants; (iv) nursery for several marine species; so it is necessary to develop mangrove protection and recovery initiatives, which are among the most impacted and degraded ecosystems in the world. In addition, many ecosystem services are related to pedogenetic soil processes, however, few studies have carried out this approach. Therefore, this study aimed to analyze two mangrove recovery initiatives in different soil contexts, aiming at identifying the restoration of pedogenetic processes and soil quality. Therefore, two mangroves with reforestation areas were analyzed in two compartments of the Brazilian coast: a) one in the state of Ceará (CE) located in the northeast region marked by a source material rich in quartz and semiarid climate; b) another located in the state of Rio de Janeiro (RJ), in the Southeast region, which presents material rich in iron and a humid tropical climate. In both sites, it was possible to observe the reestablishment of pedogenetic processes such as paludization, gleization and sulfidization, which are related to ecosystem services such as carbon sequestration and retention and immobilization of contaminants. Our study also identified the soil quality improvement using the Soil Management Assessment Framework (SMAF) tool, it is emphasized that this approach has never been used in studies involving mangroves. In fact, mangrove revegetation initiatives were able to increase soil quality of parameters such as: bulk density, carbon content, phosphorus content and pH, and the increase in soil quality positively affected the restoration of ecosystem functions such as sequestering carbon. In addition, the SMAF tool proved to be a useful tool for studies of soil quality, however, adjustments should be considered, as well as the number of variables inserted. In general we also identify that the reestablishment of pedogenetic processes may occur in a short period of time and that this approach is fundamental to infer about the capacity of impacted mangroves to develop their ecosystem functions. / Manguezais são ecossistemas costeiros que provisionam múltiplos serviços ecossistêmicos, por exemplo: (i) sequestro de carbono; (ii) mitigação das emissões de gases de efeito estufa; (iii) retenção e imobilização de contaminante; (iv) berçário para diversas espécies marinhas. Assim é necessário desenvolver iniciativas de proteção e recuperação de manguezais, uma vez que estão entre os ecossistemas mais impactados e degradados em todo o mundo. Neste sentido, muitos serviços ecossistêmicos estão relacionados a processos pedogenéticos do solo, no entanto, poucos estudos realizaram essa abordagem. Diante disso, este estudo teve como objetivo analisar duas iniciativas de recuperação de manguezais, em diferentes contextos edáficos, visando identificar o restabelecimento de processos pedogenéticos e a restauração da qualidade do solo. Portanto, foram analisados dois manguezais com áreas de replantio em dois compartimentos da costa brasileira: a) um no estado do Ceará (CE) localizado na região nordeste marcada por um material de origem rico em quartzo e clima semiárido; b) outro localizado no estado do Rio de Janeiro (RJ), região Sudeste, que apresenta material de origem rico em ferro e clima tropical úmido. Em ambos os locais estudados foi possível observar em resposta ao desenvolvimento da vegetação, o restabelecimento de processos pedogenéticos como paludização, gleização e sulfidização que estão relacionados à serviços ecossistêmicos como sequestro de carbono e retenção e imobilização de contaminantes. Nosso estudo também identificou o aumento qualidade do solo utilizando a ferramenta Soil Management Assessment Framework (SMAF), ressalta-se que essa é uma abordagem que nunca foi utilizada em estudos envolvendo manguezais. De fato, as iniciativas de revegetação de manguezais foram capazes aumentar a qualidade do solo a partir de parâmetros como: densidade, conteúdo de carbono, conteúdo de fósforo e pH e o aumento da qualidade do solo afetou positivamente o restabelecimento de funções ecossistêmicas como sequestro de carbono. Além disso, a ferramenta SMAF mostrou-se ser uma ferramenta útil para estudos de qualidade do solo, no entanto ajustes devem ser considerados, assim como o número de variáveis inseridas. Em geral também identificamos que o restabelecimento de processos de pedogenéticos pode ocorrer em curto período de tempo e que essa abordagem é fundamental para inferir sobre a capacidade de manguezais impactados de desenvolver suas funções ecossistêmicas.
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Etude des propriétés de nanoparticules de LiCoO2 en suspension pour une application redox-flow microfluidique / Study of LiCoO2 nanoparticles suspensions for a microfluidic redox-flow applicationRano, Simon 25 September 2017 (has links)
Ce travail de thèse porte sur la réalisation d’une batterie redox-flow fonctionnant grâce à la circulation de suspensions de matériaux d’insertion du lithium afin d’accroitre leur densité d’énergie. Le recours à des cellules microfluidiques permet de s’affranchir des limitations causées par les membranes échangeuses d’ions. Il s’articule dans un premier temps sur la synthèse contrôlée par voie hydrothermale de nanoparticules de LiCoO2 et leur caractérisation en suspension aqueuses. Cette étape permet de déterminer à la fois les propriétés électrochimiques des suspensions, leur état d’agrégation ainsi que leur comportement rhéologique en vue d’une utilisation redox-flow. Le transfert électronique entre une particule en suspension et les électrodes de la cellule est un aspect fondamental de ce type de batteries. Ce transfert est étudié grâce la technique de collision électrochimique dans laquelle la réponse de chaque agrégat est détecté individuellement par une ultramicroélectrode ce qui permet d’établir de nombreuses propriétés physique-chimiques de ces suspensions. Ce travail propose ensuite de s’affranchir de l’utilisation des membranes et de leurs limitations par le recours aux techniques de la microfluidique. La formation d’un écoulement co-laminaire en microcanal permet d’obtenir une cellule redox-flow opérationnelle. La conception et le fonctionnement de ces cellules est étudié en vue de la mise en circulation de suspensions de nanoparticules dans ce type de systèmes. / The aim of this work is to make a redox-flow battery that runs on lithium insertion material suspensions in order to increase the energy density of such systems. The use of microfluidic technics allows to solve the issues and limitations of ion exchange membrane by removing them. In the first part controlled size LiCoO2 nanoparticles are synthesized by hydrothermal route and dispersed into suspensions. The aggregation state of these suspensions are investigated using diffusion light scattering and transmission electronic cryoscopy. Rheological properties were also characterized for redox-flow use. The electronic transfer between a particle in suspension and the flow cell electrodes is crucial for their performances. This transfer is studied in the second part using the single event collision technic which consist of isolating individual aggregate electrochemical response at the surface of an ultramicroelectrode. This approach allows an extensive investigation of suspensions aggregates size, mobility and insertion reaction kinetic. Finally this works propose to replace the conventional ion exchange membrane by the mean of microfluidic technics. In co-laminar condition the fluid interface acts as a separation membrane to create a membrane-less redox-flow battery. The last part focuses on the fabrication of microfluidic cells and the behavior of suspensions in micro-channels.
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A multicomponent membrane model for the vanadium redox flow batteryMichael, Philip Henry 06 November 2012 (has links)
With its long cycle life and scalable design, the vanadium redox flow battery (VRB) is a promising technology for grid energy storage. However, high materials costs have impeded its commercialization. An essential but costly component of the VRB is the ion-exchange membrane. The ideal VRB membrane provides a highly conductive path for protons, prevents crossover of reactive species, and is tolerant of the acidic and oxidizing chemical environment of the cell. In order to study membrane performance and optimize cell design, mathematical models of the separator membrane have been developed. Where previous VRB membrane models considered minimal details of membrane transport, generally focusing on conductivity or self-discharge at zero current, the model presented here considers coupled interactions between each of the major species by way of rigorous material balances and concentrated solution theory. The model describes uptake and transport of sulfuric acid, water, and vanadium ions in Nafion membranes, focusing on operation at high current density. Governing equations for membrane transport are solved in finite difference form using the Newton-Raphson method. Model capabilities were explored, leading to predictions of Ohmic losses, vanadium crossover, and electro-osmotic drag. Experimental methods were presented for validating the model and for further improving estimates of uptake parameters and transport coefficients. / text
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Distribution et mobilité de l'arsenic dans les sols : effets de cycles redox successifsParsons, Christopher 19 October 2011 (has links) (PDF)
L'arsenic est un metalloïde toxique et cancérigène. Ubiquiste dans la pedosphere, il est très sensibleaux fluctuations des conditions redox du sol, ce qui influe significativement sa toxicité et mobilité. Nousétudions le cycle biogéochimique global de l'arsenic, en tenant compte de l'usage croissant des ressources, etpassons en revue l'importance respective de l'arsenic geogénique et anthropogénique dans l'environnement.La contamination à l'arsenic est souvent diffuse dans les bassins sédimentaires de l'Europe. Cependant, desconcentrations dans l'eau interstitielle du sol peuvent être élevées lors de périodes de saturation du solcausées par la monté des eaux souterraines ou les inondations, prévues d'augmenter dû aux changementsclimatiques. La spectrométrie de fluorescence X quantitative et sans standard a été utilisée pour analyserl'arsenic dans des sols relativement contaminés de la plaine alluviale de la Saône au moyen de protocoles depréparation d'échantillons conçus pour optimiser la précision d'analyse et l'exactitude in situ aux bassesconcentrations d'arsenic. L'arsenic dans ces sols est associe aux (hydr)oxydes du fer et de manganèse de lataille d'argile colloïdale. Ceux-ci subissent une dissolution réductrice par les microorganismes lors desinondations, libérant une importante concentration d'arsenic dans la phase aqueuse. Si, par la suite, l'arsenicdégagé n'est pas éliminé avec l'eau de crue évacuée, il est ré-immobilisé pendant l'oxydation du sol et lareprécipitation des oxydes métalliques. Grâce à une combinaison novatrice d'analyses chimiques par voiehumide, d'écologie microbienne, de spectroscopie ainsi que de modélisation thermodynamique et cinétique,nous démontrons que les cycles d'oxydo-réduction séquentiels entraînent une atténuation d'arsenic aqueuxdans des conditions réductrices dû à la coprécipitation croissante, et a une diminution de l'activitémicrobienne causée par l'appauvrissement en matière organique labile. Des processus d'atténuationsimilaires sont observés en l'absence d'activité microbienne pour Cr et As dans des argiles pyriteuses lorsquecelles-ci sont exposés aux oscillations redox provoquées par l'ajout de substances humiques réduites. Ainsi,nous montrons que les effets cumulatifs de cycles redox successifs sont extrêmement importants pour lamobilité de divers contaminants dans l'environnement.
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THE STRATIGRAPHY AND GEOCHEMISTRY OF THE RAPITAN IRON FORMATION, NORTHWEST TERRITORIES AND YUKON, CANADABaldwin, Geoffrey James 16 May 2014 (has links)
The Neoproterozoic was a time of major change in Earth’s surficial history, including a major rise in atmospheric oxygen, the first appearance of complex metazoan life, and a series of worldwide glaciations. A particular interesting element of these so called “snowball Earth” glacial deposits is the presence of iron formation, a distinctive Precambrian rock type that is largely absent from the post-Paleoproterozoic record. Despite being relatively poorly studied with respect to their geochemistry and sedimentology, Neoproterozoic iron formations are used to support many models for the record of oxygen concentrations of the Earth. The classical example of Neoproterozoic iron formation is the Rapitan iron formation of northwestern Canada. This hematite-jasper iron formation is associated with glaciogenic turbidites and diamictites. Despite being the archetype, the Rapitan iron formation has not been studied in the context of recent ideas about the Neoproterozoic. In this thesis, the stratigraphy, geochemistry, and basin architecture of the Rapitan iron formation are reassessed. Using the REE+Y and the redox-sensitive elements Mo and U, it is shown that the Rapitan iron formation was deposited in a partially restricted basin from biogenically reduced iron under variable redox conditions. Elemental Re and Mo isotopes further show that although oxic and ferruginous conditions predominated during deposition of the iron formation, a transition towards a sulfidic water column locally terminated deposition. Finally, regional stratigraphy and geochemistry show that the iron formation was preferentially deposited in deep, newly formed basins that were protected from significant siliciclastic sedimentation. These basins were delimited by inferred crustal-scale faults trending roughly perpendicular to the axis of the rift basin, and allowed significant changes in thickness and sedimentological character over short distances along strike. These factors help build an overall geotectonic regime under which Neoproterozoic iron formations were deposited: young, deep rift basins that had undergone marine incursion, and were intermittently sealed by an ice shelf, allowing for the generation of an anoxic, iron-rich water column. The absence of the Eu anomaly and the heavy Mo isotopic signature indicate that the open ocean was fully oxygenated at the time of Rapitan iron formation deposition, as opposed to ferruginous as previously suggested.
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Extramitochondriale und mitochondriale Produktion reaktiver Sauerstoffspezies im Hippokampus MeCP2-defizienter Mäuse / Extramitochondrial and mitochondrial ROS production in the hippocampus of MeCP2-deficient miceHirt, Ursula 28 January 2014 (has links)
Das Rett-Syndrom ist eine postnatal progressiv verlaufende neurologische Entwicklungsstörung, die x-chromosomal vererbt. Das klassische Rett-Syndrom entsteht durch eine spontane Mutation des MECP2-Gens, welches für die Kodierung des Transkriptionsfaktors MeCP2 (methyl CpG binding protein 2) verantwortlich ist. Das Krankheitsbild verläuft in vier Stadien und ist vor allem von geistiger Retadierung, motorischer Dysfunktion und Unregelmäßigkeiten der Atmung geprägt. In verschiedenen Untersuchungen wurden bereits verschiedene zelluläre Dysfunktionen und Beeinträchtigungen der Mitochondrien bestätigt, weshalb wir weitere Untersuchungen anstrebten.
Ziel dieser Dissertation war es, mögliche Einflüsse verschiedener Enzyme auf die ROS-Produktion zu untersuchen und somit die Erkenntnisse aus vorangegangenen Arbeiten zu erweitern. Im Fokus dieser Untersuchungen lagen zum einen die mitochondriale ROS-Produktion sowie die extramitochondriale ROS-Produktion. Durch unterschiedliche pharmakologische Modulationen wurden beide Systeme beeinflusst, um den jeweiligen Beitrag zur gesamten ROS-Produktion abzuschätzen.
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Efeito da competição sobre biomarcadores salivares de estresse físico e oxidativo em jogadores de futebolGaldino, Leandro Cezar Domingos 29 July 2014 (has links)
Conselho Nacional de Desenvolvimento Científico e Tecnológico / Chapter II: Football is a sport with intermittent characteristics, high intensity and emphasis on components of strength, speed and endurance. This sport competition offers a unique setting for assessing stress responses and changes in redox balance. The collection and analysis of less-invasive samples such as saliva, offer the opportunity to collect in the field of training or competition. So, the aim of this study was to evaluate the effect of competition on salivary biomarkers of stress and redox balance in soccer players. The sample consisted of 14 male subjects (24.05 ± 3.1 years, 173 ± 0.05 cm, 71.84 kg ± 8:50). The volunteers were monitored during the college national championship (four games) with an interval of 24 hours between games. Saliva samples were collected before and after the games and put up until the time of analysis. Our findings show that in 4 games SAA and the rate of secretion of total protein post-games showed significant increases over the pre-game moments. Game 1.2 and 3 cortisol levels showed significant increases in post-game moments in relation to pre-game moments. With regard to changes in redox balance, was not observed changes in rates of oxidative damage to lipids before and after 4 games, which were quantified by the concentration of the products of lipid peroxidation (TBARS). On the other hand, total antioxidant response in Game 3 was significantly increased in the post-game compared to the pre-game, shown by the total antioxidant capacity (FRAP). Catalase activity did not change significantly in any of the time points. These results suggest that 3 markers of stress (autonomous activity) showed changes due to athletic competition. The secretion rate of total protein can be an attractive marker of stress, ease and low cost of the method. The games even with little recovery range were not enough to promote oxidative damage to lipids, probably because of the induced training adaptations. / CAPITULO II: O futebol é um esporte com características intermitentes, de intensidade extenuante com ênfase nos componentes de força, velocidade e resistência. Nesse sentido, a competição esportiva oferece um cenário único para avaliar as respostas ao estresse e alterações no balanço redox. A análise e coleta de amostras menos-invasivas, como a coleta de saliva, têm se destacado por oferecer oportunidade de coletas no próprio campo de treinamento ou competição. O objetivo desse estudo foi avaliar o efeito da competição sobre biomarcadores salivares de estresse e balanço redox em atletas de futebol. A amostra foi composta por 14 indivíduos homens (24,05± 3.1 anos, 173 ± 0,05 cm, 71.84 ± 8.50 kg). Os voluntários foram monitorados durante o campeonato brasileiro universitário e realizaram quatro jogos de futebol com intervalo de 24h de descanso entre os jogos. Amostras de saliva foram coletadas antes e após o término dos jogos e acondicionadas até o momento da análise. Nossos achados mostram que nos 4 jogos a sAA e a taxa de secreção de Proteínas totais pós-jogos apresentaram aumentos significativos em relação aos momentos pré-jogos. No jogo 1, 2 e 3 a concentração de cortisol foi maior nos momentos pós-jogos em relação aos momentos pré-jogos. No que diz respeito às alterações do balanço redox, não foi verificado alterações nas taxas de danos oxidativos a lipídeos antes e após os 4 jogos, que foram quantificados através da concentração dos produtos de peroxidação lipídica (TBARS). Por outro lado, a resposta antioxidante total no jogo 3 apresentou aumento significativo no momento pós-jogo em relação ao pré-jogo, mostrado pela capacidade antioxidante total (FRAP). A atividade da catalase não sofreu alteração significativa em nenhum dos momentos avaliados. Esses resultados sugerem que os 3 marcadores de estresse (atividade autônoma) apresentaram alterações frente a competição esportiva. A taxa de secreção de Proteínas Totais pode ser um marcador atraente de estresse, pela facilidade e baixo custo do método. Os jogos mesmo com pouco intervalo de recuperação não foram suficiente para promover danos oxidativos a lipídeos, fato esse ocorreu provavelmente pelas adaptações induzidas pelo treinamento da equipe. / Mestre em Genética e Bioquímica
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Vers des batteries lithium organiques innovantes mettant en jeu des polymères à base de Nméthylphénothiazines modifiées / Towards innovative organic lithium batteries involving modified nmethylphenothiazine-based polymersGuilmin, Romain 04 February 2016 (has links)
La N-méthylphénothiazine (MPT) est une cible de choix pour développer des matériaux organiques redox performants pour électrodes positives de batterie lithium-ion. Ces matériaux dits organiques sont aujourd’hui une alternative crédible aux matériaux inorganiques, actuellement utilisés dans les accumulateurs, de par leurs coûts et toxicité moindres.C’est dans cette optique que des polymères redox contenant l’unité N-méthylphénothiazine ont été synthétisés et caractérisés. Leurs propriétés électrochimiques ont été étudiées en solution via l’utilisation de molécules modèles puis en cellule électrochimique à négative de lithium.Mais pourquoi la N-méthylphénothiazine ? Cette cible redox présente deux systèmes réversibles mais en l’état, seul le premier est exploitable. L’objectif de cette thèse a donc été de modifier chimiquement la molécule afin de moduler les valeurs de potentiels de ses deux systèmes et ainsi les rendre électrochimiquement actifs dans la fenêtre de stabilité des électrolytes de la technologie lithium, permettant de presque doubler la capacité théorique.Ces dérivés ont ensuite pu être polymérisés et testés électrochimiquement, des performances intéressantes ont été obtenues pour certains d’entre eux. Mais malgré l’utilisation de matériaux insolubles à l’état neutre, les cyclages galvanostatiques ont mis en évidence une dissolution des matériaux à l’état oxydé, du moins pour les polymères de plus faibles masses, induisant une diminution de la capacité. / The N-methylphenothiazine (MPT) is a prime target with the aim of developing innovative redox organic materials useful as positive electrode of lithium-ion battery. These organic materials are today a credible alternative to inorganic materials by their lower cost and toxicity.It is in this context that MPT-based redox polymers have been synthesized and characterized. Their electrochemical properties have been investigated in lithium cells to estimate their potential.But why the N-methylphenothiazine ? This redox target has two reversible systems but only the first is exploited. The project was therefore the chemical modification of the MPT molecule to modulate potential values of two systems. These chemical developments thus allow improving notably the MPT derivative theoretical capacities accessible in the electrochemical stability range of lithium-ion technology electrolyte.These derivatives were synthesized and tested in lithium cell. Some of them present interesting performances. But despite the use of insoluble materials at the neutral state, cell tests showed material dissolution in the oxidized state, which decreases significantly the obtained capacities.
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Comportement de l’uranium et de ses simulants dans les verres d’aluminosilicates en contact avec des métaux fondus / Behavior of uranium and its surrogates in molten aluminosilicate glasses in contact with liquid metalsChevreux, Pierrick 02 December 2016 (has links)
Ce travail s’inscrit dans le cadre du développement d’un procédé innovant de conditionnement de déchets nucléaires contenant des métaux contaminés en actinides. Le principe de ce procédé consiste à incorporer des concentrations élevées en actinides dans un bain de verre au contact de métaux fondus. Parmi eux, l’aluminium et/ou l’acier inoxydable imposent un environnement très réducteur et induisent des phénomènes d’oxydoréduction au sein du verre. Ces phénomènes provoquent un changement du degré d’oxydation des actinides qui modifie leur solubilité dans le verre et peut potentiellement entraîner leur réduction à l’état métallique. Afin de mieux comprendre les processus mis en jeu, cette étude va s’intéresser au comportement de l’uranium et de ses simulants à savoir l’hafnium et le néodyme, dans des verres aluminosilicatés du système Na2O-CaO-SiO2-Al2O3 et élaborés en conditions très réductrices. La première partie de ce manuscrit est consacrée à l’étude comparative des solubilités de l’uranium et de l’hafnium dans le verre en fonction des conditions redox et de la composition du verre. Pour cela, une méthodologie a été mise en place et un montage spécifique a été utilisé afin d’imposer la fugacité en oxygène et de contrôler la teneur en alcalins du verre. Les résultats indiquent que la solubilité de l’uranium dans le verre est très inférieure à celle de l’hafnium (HfIV) dans des conditions réductrices. Pour des fugacités en oxygène inférieures à 10-14 atm, la solubilité de l’uranium est comprise entre 4 et 7 % massiques d’UO2 dans la gamme de températures de 1250°C-1400°C. L’étude de la spéciation de l’uranium par spectroscopie d’absorption des rayons X (XANES) montre que l’uranium est majoritairement présent sous la forme UIV dans le verre pour de telles fugacités en oxygène imposées. Dans la seconde partie de ce travail, les mécanismes d’interactions verre-métal ont été identifiés afin de localiser l’uranium ainsi que ses simulants (néodyme et hafnium) dans le système verre-métal. Ces mécanismes sont principalement gouvernés par la présence d’aluminium métal et sont similaires pour l’uranium et ses simulants. Dans des conditions particulières, le suivi cinétique des expériences met en évidence la présence transitoire de l’uranium et de ses simulants à l’état métallique dans des alliages ou des composés définis. Au cours du temps, une ré-oxydation de ces éléments métalliques a lieu en accord avec les données thermodynamiques. Dans le cas de l’uranium, le processus de ré-oxydation reste à confirmer. Enfin, une approche thermodynamique à l’aide des diagrammes de phases a permis d’expliquer la formation et la dissolution des différentes phases cristallines présentes au sein du verre lors des interactions verre-métal / This study concerns an innovative process used for conditioning nuclear waste that contain metallic parts contaminated with actinides. High actinides concentrations are expected to be incorporated in the glass melt in contact with the molten metals. Among these metals, aluminum and/or stainless steel impose a strongly reducing environment to the glass melt involving redox reactions. These reactions modify actinides oxidation states and therefore change their solubilities in the glass and could also reduce them into the metallic form. In this work, we focus on the behavior of uranium and its surrogates, namely hafnium and neodymium, in aluminosilicate glasses from the Na2O-CaO-SiO2-Al2O3 system melted in highly reducing conditions. The first step consists in comparing the hafnium and uranium solubilities in the glass as functions of redox conditions and glass composition. A methodology has been set up and a specific device has been used to control the oxygen fugacity and the alkali content of the glass. The results show that uranium is far less soluble in the glass than hafnium (HfIV) in reducing conditions. The uranium solubility ranges from 4 to 7 wt% UO2 for an oxygen fugacity below 10-14 atm at 1250°C-1400°C. Uranium oxidation states have been investigated by X-ray absorption spectroscopy (XANES). It has been pointed out that UIV is the main form in the glass for such imposed oxygen fugacities. The second step of this work is to identify the glass-metal interaction mechanisms in order to determine the localization of uranium and its surrogates (Nd, Hf) in the glass-metal system. Mechanisms are mostly ruled by the presence of metallic aluminum and are similar for uranium, neodymium and hafnium. Glass-metal interaction kinetics demonstrate that uranium and its surrogates can temporarily be reduced into the metallic form for particular conditions. A re-oxidation occurs with time which is in good agreement with thermodynamics. Regarding uranium, the re-oxidation process must be corroborated. Finally, the formation and dissolution processes of the different crystalline phases observed during these glass-metal interactions have been studied using a thermodynamic approach based on phase diagrams
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Characterization of the ferredoxin/thioredoxin system and its targets in Physcomitrella patens / Caractérisation de mutants du système ferrédoxine-thiorédoxine chez Physcomitrella patensGütle, Desirée 29 March 2017 (has links)
La régulation redox est un mécanisme ancien présent chez les organismes biologiques et impliquée dans diverses voies métaboliques. En particulier chez les organismes photosynthétiques elle est responsable des mécanismes d‘adaptation rapide dans un environnement constamment modifié. Dans les chloroplastes le système ferrédoxine/thiorédoxine est la cascade redox principale qui relie l‘activité de plusieurs enzymes plastidiales à la source lumineuse. Le rôle central dans ce système est joué par la ferrédoxine-thiorédoxine réductase (FTR), une protéine hétérodimérique qui récupère des électrons à partir de la ferrédoxine photoréduite et les transfère pour réduire des thiorédoxines plastidiales. Ces protéines peuvent alors réduire des enzymes cibles, requérant l‘accessibilité de paires de cystéines dans un disulfure dont la réduction résulte en une activation/ inactivation de la cible. Jusqu‘à présent des plantes viables n‘ont pu être obtenues en l‘absence de ce système de régulation. Dans cette thèse des secteurs du système redox ont été explorés chez la plante modèle Physcomitrella patens (une mousse). Par manipulation de gènes l‘influence de l‘enzyme FTR sur la croissance et le développement de la plante a été analysée suivant différents paramètres. De manière à impacter la fonction de la réductase des changements nucléotidiques simples ont été introduits au niveau des codons programmant les cystéines catalytiques et dans un deuxième temps le gène complet a été supprimé. De façon inattendue nous n‘avons observé aucun effet significatif sur la viabilité et le développement des plantes mutantes. De plus, nous avons détecté dans P. patens des thiorédoxines additionnelles absentes chez les plantes à graine qui sont fonctionnelles vis à vis des enzymes cibles mais non-réduites par la FTR. Ceci rend possible un scénario de compensation chez les mutants via un système de réduction FTR-indépendant qui reste à caractériser. Deux des cibles photorégulées, la fructose-1,6-bisphosphatase (FBPase) et la sédoheptulose-1,7-bisphosphatase (SBPase), fonctionnent dans la phase de régénération du cycle de Calvin-Benson cycle et elles possèdent plusieurs caractéristiques de catalyse et de régulation similaires. En combinant des approches biochimiques et structurales, une comparaison fonctionnelle et structurale des deux phosphatases de P. patens a été conduite. De plus l‘analyse phylogénétique a révélé une origine procaryotique indépendante des deux séquences en dépit de leurs similitudes structurales et catalytiques. De plus trois articles de revue résument la plasticité et la représentativité du modèle P. patens pour la recherche forestière, les principes généraux de la régulation redox relativement aux aspects évolutifs et fonctionnels chez les plantes ainsi que l‘ état de l‘art de la régulation redox chez les espèces ligneuses en utilisant principalement le peuplier comme modèle / Redox regulation is an ancient mechanism present in biological organisms and is involved in diverse cellular pathways. In particular in photosynthetic organisms it is responsible for fast adaption mechanisms to a constantly changing environment. In chloroplasts the ferredoxin/thioredoxin system represents the main redox regulatory cascade which links the activity of several plastid enzymes to the energy source, light. A central role in this system is played by the heterodimeric ferredoxin-thioredoxin reductase (FTR), which gains electrons from the photo-reduced ferredoxin and transfers those further on via reduction to plastidal thioredoxins. Those proteins in turn reduce their target enzymes and require therefore the availability of redox sensitive cysteine pairs whose reduction results in an inactivation/activation switch of the targets. So far no viable plants could be obtained in complete absence of this redox regulation system. In this thesis single sections of the system were explored in the model plant Physcomitrella patens. Through gene manipulation the influence of the FTR enzyme on plant growth and development was analysed. In order to impact on the function of the reductase, firstly single nucleotide exchange of the catalytic cysteines was performed and later on the gene was completely deleted. Surprisingly, no significant effect could be observed on the viability and development of mutant lines compared to WT plants. Furthermore we found that P. patens possesses in contrast to seed plants additional thioredoxins which are functional for reduction of FTR target enzymes but are most likely not supplied with electrons by this reductase. Thus a possible rescue scenario independent of FTR could be assumed for P. patens and also by other redox regulation systems present in chloroplasts. Two of the FTR target enzymes, fructose-1,6-bisphosphatase and sedoheptulose-1,7-bisphosphatase, are functional in the regeneration phase of the Calvin-Benson cycle and share similar characteristics in regulation and catalysis. By combining biochemical and structural approaches, a functional comparison of both phosphatases was conducted using cDNAs from P. patens. A stricter TRX-dependent regulation and catalytic cleavage ability for both substrates, FBP and SBP, could be observed for PpSBPase, whereas PpFBPase is only capable of cleaving FBP. By obtaining the oxidized X-ray structure of both enzymes these observations can be associated with the distinct positions of regulatory sites and the various sizes of the substrate binding pocket. In addition, the phylogenetic analysis revealed an independent prokaryotic origin for both phosphatases. Furthermore we summarized in three review articles the amenability of P. patens as model plant for forest research, the general principles of redox regulation in respect of evolution and functional mechanisms in plants, and the current state of the art in forest redox regulation using poplar as exemplary model
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