O objetivo central desta tese é o de compreender, a partir dos usos do território do estado de São Paulo pelo sistema penal, como são ampliadas as desigualdades socioespaciais, em diferentes escalas de análise do município ao território do estado federativo. Foi demonstrado como a prisão, um objeto do sistema penal, promove desigualdades espaciais pelo consumo acelerado de recursos econômicos do orçamento do Estado, mas também pela criação de locais e sujeitos estigmatizados. No entanto, malgrado o aumento exponencial dos recursos para expansão do sistema prisional paulista nos últimos anos, a prisão continua sendo ineficaz no combate à criminalidade. Mas consome, cada vez mais, somas maiores de recursos públicos em detrimento de outras áreas e demandas sociais. As desigualdades ampliadas por este processo podem responder por parte dos sentimentos de insegurança da população em tempos de globalização neoliberal. O sistema prisional o conjunto de todas as unidades prisionais que se articulam para cumprir diferentes regimes de privação de liberdade funciona de modo seletivo, atendendo interesses político-econômicos hegemônicos, em detrimento da garantia de igualdade de direitos entre todos os distintos sujeitos sociais que compõem a totalidade da sociedade brasileira. Deste modo, a seletividade penal envolve não apenas combate aos crimes, mas principalmente a repressão dos sujeitos sociais não hegemônicos, os mais reprimidos pelo braço penal do Estado. O aprisionamento, em conjunto com dois outros processos sociais contemporâneos - a seletividade da ação policial e a discriminação entre classes sociais nos tribunais - somado à escolha também seletiva dos territórios utilizados para implantação das novas unidades prisionais, expressa a reprodução das desigualdades espaciais no Estado de São Paulo neste início de Século XXI. Como alternativas à prisão, foram demonstradas possibilidades teóricas de se reverter este processo de ampliação das desigualdades espaciais, e de encontrar outras soluções para a conflitividade social. Elas passam tanto pelo redirecionamento dos usos do capital excedente pelo Estado, quanto pela conscientização social acerca dos principais mecanismos de sustentação dos sistemas penal e prisional na sociedade contemporânea. O que poderia promover mudanças culturais e, a partir delas, mudanças estruturais como, por exemplo, o fim da prisão. As novas possibilidades de uso dos recursos sociais e econômicos do Estado poderiam diminuir desigualdades espaciais, convergindo com outras formas de lida com as contradições da atual sociedade contemporânea capitalista. Um debate teórico e político bastante complexo, mas fundamental para constituição de um novo projeto civilizatório para São Paulo e para o Brasil, realizado a partir de contribuição inédita da ciência geográfica. / The main objective of this thesis was to understand as socio-spatial inequalities are magnified at different scales of analysis, from municipality to state, considering the territory use of the state of São Paulo by penal system. It was demonstrated how prison, an object of the penal system, promotes spatial inequalities not only by inflated consumption of economic resources from the state budget, but also by creating stigmatized individuals and locations. However, despite the exponential increase in resources to expand São Paulo prison system in recent years, the prison remains ineffective in combating crime. Moreover, it consumes increasingly larger sums of public funds at the expense of other areas and social demands. The inequalities enlarged by this process may account for part of the populations feelings of insecurity in times of neoliberal globalization. The prison system _ the set of all prisons that are organized to meet different regimes of detention _ works selectively, serving hegemonic political-economic interests in detriment of ensuring equal rights for all different social individuals that comprise the whole of Brazilian society. Thus, the criminal selectivity involves not only combating crimes, but also reprehending non-hegemonic social individuals, the most repressed by the state penal system. The imprisonment, together with two other contemporary social processes _ selectivity of police action and discrimination between social classes in the courts _, as well as the selective choice of territories used for deployment of new prisons, expressed the reproduction of spatial inequalities in the State of São Paulo at the beginning of the 21st Century. As alternatives to prison, theoretical possibilities have been demonstrated to reverse this process of expansion of spatial inequalities, and to find other solutions to social conflicts. Those alternatives involve redirecting the use of the surplus capital by the State, as well as creating social awareness about the key mechanisms that support criminal and prison systems in contemporary society; which could promote cultural and structural changes leading to the end of prisons. The new possibilities of social and economic resources of the state could reduce spatial inequalities, converging with other ways of dealing with contradictions of the current contemporary capitalist society. A rather complex theoretical and political debate would be essential for constituting a new civilization project for São Paulo and for Brazil, held from a unprecedented contribution from geographical science.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-01-09T16:42:49Z No. of bitstreams: 1 diogosoaresresende.pdf: 5068811 bytes, checksum: e6f520585ffef78e123573bd1e41ff4d (MD5) / Approved for entry into archive by Diamantino Mayra (mayra.diamantino@ufjf.edu.br) on 2017-01-31T11:22:04Z (GMT) No. of bitstreams: 1 diogosoaresresende.pdf: 5068811 bytes, checksum: e6f520585ffef78e123573bd1e41ff4d (MD5) / Made available in DSpace on 2017-01-31T11:22:04Z (GMT). No. of bitstreams: 1 diogosoaresresende.pdf: 5068811 bytes, checksum: e6f520585ffef78e123573bd1e41ff4d (MD5) Previous issue date: 2016-09-01 / FAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais / Esta dissertação propõe uma ferramenta computacional para síntese e análise da proteção em sistemas de subtransmissão e de distribuição de energia elétrica na presença de desequilíbrios. Tais sistemas, em especial os de distribuição, são geralmente desequilibrados e podem conter trechos mono, bi ou trifásicos, além de operarem com carregamento distribuído de maneira assimétrica, o que torna as grandezas elétricas observadas diferentes para cada fase analisada. Neste trabalho foram desenvolvidos dois métodos, que foram implementados na ferramenta proposta: (i) procedimentos automáticos para ajustes ótimo de dispositivos de proteção em sistemas de distribuição desequilibrados; (ii) método para a análise gráfica do desempenho da proteção aplicada a sistemas desequilibrados. A ferramenta proposta foi desenvolvida em ambiente MatLab e permite também a síntese dos ajustes de proteções de sobrecorrente (mediante a utilização de um Algoritmo Genético) e de distância, além de calcular as relações de transformação para TCs e TPs. A ferramenta foi calibrada através da comparação dos resultados obtidos pela mesma com os obtidos por equipamentos reais de proteção, tendo também sido realizados testes com diferentes sistemas da literatura. / This thesis proposes a computacional tool for synthesis and analysis of protection in electricity subtransmission and distribution systems in presence of imbalances. Such systems, in particular distribution, are generally unbalanced, and can contain mono-, bi- or triphasic sections, and operate with asymmetrically distributed loads, which makes electrical quantities observed different for each phase analyzed. In this work were developed two methods, which have been implemented in the proposed tool: (i) automatic procedures for optimal settings of protection devices in unbalanced distribution systems; (ii) method for graphical analysis of protection’s performance applied to unbalanced systems. The proposed tool was developed in MatLab and also allows the synthesis of overcurrent (using a Genetic Algorithm) and distance settings and calculates the transformation ratios to PTs and CTs. The tool is calibrated by comparing the results obtained by the same with those obtained by actual equipment protection, has also been made tests with different systems in the literature.

Made available in DSpace on 2014-08-20T14:07:33Z (GMT). No. of bitstreams: 1 tese_paulo_ricardo_ebert_siqueira.pdf: 745146 bytes, checksum: e9aa866b96f415063e476a4469145bbb (MD5) Previous issue date: 2010-07-19 / The presence of Calepitrimerus vitis (Nalepa, 1905) in vineyards in the countryside of Rio Grande do Sul was verified from the 2004/2005 harvest associated with symptoms of tanning on the leaves. In Brazil there are no recommendations for monitoring of this mite, just as there is no acaricide recommended for management of the species in vineyards. To detect differences in infestation of C. vitis among cultivars was conducted the monitoring of population fluctuations of C. vitis vinifera cultivars Chardonnay and Merlot, in a commercial vineyard in Dom Pedrito, RS, during the years 2005/2006 and 2006/2007, in order to identify differences in infestation between cultivars of a crop year to another. It was observed that the cultivars Chardonnay and Merlot, the population peaks of C. vitis occurred between late February and early March and there is a high correlation between the number of C. vitis found on the underside of the leaves and the percentage of leaves with the species. In the greenhouse, during the years 2006/2007 and 2007/2008 was evaluated the efficiency of sticky traps to monitor C. vitis in cuttings for propagation, comparing catches in cuttings derived from nurseries and vineyards with different histories of infestation. We observed that the sticky traps to detect the presence in the cuttings of C. vitis. During the crop years 2007/2008 and 2008/2009 was conducted the monitoring of population dynamics of C. vitis in Cabernet Sauvignon, in a commercial vineyard located in the town of Candiota-RS, through the use of sticky traps and direct observation on the abaxial surface of leaves. As observed in the Dom Pedrito-RS, Candiota-RS was observed a significant and high correlation (r ² ≥ 0.95) between the number of C. vitis on the abaxial surface of leaves and percentage of leaves with the mites. The sticky traps used for monitoring were more efficient in detecting C. vitis during periods of high and low population levels. Was evaluated in a commercial vineyard, insecticides and acaricides in order to reduce the population of C. vitis in autumn and in spring 2008 and autumn 2009. The acaricides spirodiclofen and cyhexatin were the most promising in reducing the infestation during the autumn. The use of sulfur in a single autumn spray or two sprays, one in autumn and another in the spring, effectively controlled C. vitis in the spring. The use of acaricides abamectin and spirodiclofen a single spring spray or two sprays, one in autumn and another in the fall and spring, effectively controlled the population of C. vitis in the spring. The acaricides abamectin, azadirachtin, cyhexatin, sulfur and spirodiclofen evaluated for control of C. vitis were tested for selectivity to predatory mite Neoseiulus californicus (McGregor, 1954). It was found that 24 hours after application in vineyard acaricide cyhexatin was slightly harmful, and all other products tested as harmless. From the third day of application in the vineyards all products were harmless to N. californicus, to cause mortality under 30% / A presença de Calepitrimerus vitis (Nalepa, 1905) em vinhedos na Região da Campanha do Rio Grande do Sul foi verificada a partir da safra 2004/2005 associada a sintomas de bronzeamento nas folhas. No Brasil não existem recomendações para o monitoramento deste ácaro, assim como não se encontra nenhum acaricida recomendado para o manejo da espécie na cultura da videira. Visando detectar diferenças de infestação de C. vitis entre cultivares foi realizado o monitoramento da flutuação populacional de C. vitis nas cultivares viníferas Chardonnay e Merlot, em vinhedo comercial no município de Dom Pedrito-RS, durante os anos agrícolas 2005/2006 e 2006/2007, permitindo identificar diferenças de infestação entre as cultivares de uma safra agrícola para a outra. Foi observado que nas cultivares Chardonnay e Merlot, os picos populacionais de C. vitis ocorrem entre o final de fevereiro e o início de março e que há uma alta correlação entre o número de C. vitis presentes na face abaxial das folhas e o percentual de folhas com incidência da espécie. Em casa de vegetação, durante os anos agrícolas 2006/2007 e 2007/2008 foi avaliada a eficiência de armadilhas adesivas para monitorar C. vitis em estacas destinadas a propagação, comparando as capturas em estacas oriundas de viveiros e vinhedos com diferentes históricos de infestação. Foi observado que as armadilhas adesivas detectam a presença nas estacas de C. vitis. Durante os anos agrícolas 2007/2008 e 2008/2009 foi realizado o acompanhamento da dinâmica populacional de C. vitis na cultivar Cabernet Sauvignon, em vinhedo comercial localizado no município de Candiota-RS, através do emprego de armadilhas adesivas e da observação direta na face abaxial das folhas. Assim como verificado em Dom Pedrito-RS, em Candiota-RS foi observada uma correlação significativa e alta (r² ≥ 0,95) entre o número de C. vitis na face abaxial das folhas e o percentual de folhas com incidência do ácaro. As armadilhas adesivas utilizadas para o monitoramento foram mais eficientes na detecção de C. vitis tanto em períodos de alta como de baixos níveis populacionais. Avaliou-se em vinhedo comercial, inseticidas e acaricidas visando a redução populacional de C. vitis no outono e na primavera de 2008 e no outono de 2009. Os acaricidas espirodiclofeno e cihexatina foram os mais promissores na redução da infestação durante o outono. O emprego de enxofre em uma única pulverização no outono ou em duas pulverizações, sendo uma no outono e outra na primavera, controlou eficientemente C. vitis na primavera. O emprego dos acaricidas abamectina e espirodiclofeno uma única pulverização na primavera ou em duas pulverizações, sendo uma no outono e outra na primavera, controlou eficientemente a população de C. vitis na primavera. Os acaricidas abamectina, azadiractina, cihexatina, enxofre e espirodiclofeno, avaliados para o controle de C. vitis, foram submetidos a testes de seletividade ao ácaro predador Neoseiulus californicus (McGregor, 1954). Foi verificado que 24 horas após a aplicação no vinhedo o acaricida cihexatina foi levemente nocivo, sendo todos os demais produtos testados considerados inócuos. A partir do terceiro dia de aplicação no vinhedo todos os produtos foram inócuos a N. californicus, por causarem mortalidade inferior a 30%.

L'intérêt pour la synthèse de Fischer-Tropsch (FTS) est d'actualité. Elle permet la conversion de matière première (biomasse) en combustible liquide. Comparés aux catalyseurs à base de cobalt, ceux à base de fer présentent une désactivation rapide, une activité et une sélectivité faibles en produisant une quantité non désirable de CO2. Après plusieurs décennies d'études, l'origine de ces défauts reste méconnue. Les catalyseurs classiques sont généralement fortement chargés en fer (>70 wt.%) et composés de nombreuses phases empêchant l'établissement d'une relation structure-activité. Il est nécessaire de développer des catalyseurs contenant du fer plus actifs, plus sélectifs et plus stables par une approche rationnelle. La synthèse de nanoparticules de taille contrôlée (3.5 nm) encapsulées dans les murs d'une silicalite-1 creuse (Fe@hollow-silicalite-1) est présentée. L'encapsulation empêche le frittage pendant la synthèse de Fischer-Tropsch, permettant de garder une bonne dispersion du fer. Contrairement aux autres catalyseurs, le catalyseur Fe@hollow-silicalite-1actif ne produit pas de CO2. L'hydrophobicité de la silicalite-1 est très certainement à l'origine de la non-production de CO2 par inhibition de la réaction directe du gaz à l'eau. On démontre que le catalyseur Fe@hollow-silicalite-1convertit le CO2 en CO par réaction du gaz à l'eau inversée (R-WGS). Afin d'établir une relation structure-activité, des catalyseurs à base de fer de taille bien contrôlée sont synthétisés et caractérisés (MET, in-situ XANES, in-situ Mössbauer). Deux catégories de TOF suivant la taille des particules, ~10-2 s-1 pour les plus larges (>20 nm) et ~10-3 s-1 pour les plus petites, sont observées / Fischer-Tropsch synthesis (FTS) is gaining renewed interests as it allows converting alternative feedstocks (biomass) into liquid fuels. Compared to Co-based catalysts, state of the art Fe catalysts show lower activity, faster deactivation and lower selectivity as it produces an undesirable amount of CO2. Despite decades of studies, the origins of low activity and selectivity and fast deactivation are still unclear. Typical Fe based catalysts are highly metal loaded (>70 wt.%) and composed of many different phases, which strongly impedes the establishment of structure-activity relationships. There is a need to develop more active, more selective and more stable iron FTS catalysts by rational approaches.The synthesis of well-controlled 3.5 nm iron nanoparticles encapsulated in the walls of a hollow-silicalite-1 zeolite (Fe@hollow-silicalite-1) is presented. The encapsulation prevents particle sintering under FTS conditions leading to a high and stable Fe dispersion. The catalyst Fe@hollow-silicalite-1 is active and highly selective in FTS. Most importantly, Fe@hollow-silicalite-1 does not produce CO2 in contrast to all other Fe-based catalysts. The strong hydrophobicity of the silicalite-1 is likely the origin of the lack of CO2 production by inhibition of the forward WGS reaction. We demonstrated that Fe@hollow-silicalite-1converts CO2 into CO by the reverse WGS reaction. In order to establish a structure-activity relationship, a series of Fe-based catalysts with well-controlled particle sizes were synthesized and characterized (TEM, in-situ XANES, in-situ Mössbauer, XRD). We observed two distinct categories of TOFs depending on the particle size, ~10-2 s-1 for larger (>20 nm) and ~10-3 s-1 for smaller ones

Cette étude a fait l'objet de deux parties. L'une porte sur l'effet de différents types d'activation (chimique, thermique, mécanique) de kaolins (géo-matériaux riches en kaolinite) sur leurs propriétés de décoloration vis-à-vis de l'huile de riz. L'autre traite de l'effet de la taille et de la morphologie de kaolinites de synthèse sur leurs propriétés d'adsorption.Cette étude a montré que lorsque le kaolin était chauffé à plus de 100°C avant de subir une activation acide en milieu sulfurique, citrique ou oxalique, la capacité de décoloration vis-à-vis de l'huile de riz était fortement réduite. Cet effet a été directement mis en relation avec la destruction partielle ou totale de la structure de la kaolinite, associée à une forte lixiviation de l'aluminium de l'échantillon et à la précipitation de silice amorphe. Il s'est donc avéré que la préservation des sites aluminols présents sur les surfaces externes des particules de kaolinites semblait être un critère primordial à conserver en vue d'obtenir de bonne capacité de décoloration. Dans ce contexte, les meilleures capacités de décoloration (82% environ) ont été obtenues en utilisant conjointement un traitement thermique modéré (<100°C), un broyage mécanique de l'échantillon avant l'étape d'activation acide, une concentration en acide de l'ordre de 0.3 à 0.5 mol/L et un rapport (argile)/(solution acide) de l'ordre de 1/50. Notons que les plus fortes valeurs de surfaces spécifiques n'ont pas forcément été associées aux échantillons présentant les meilleures capacités de décoloration en raison de la présence de silice amorphe et de la non-préservation des sites aluminols de la kaolinite ; sites responsables de l'adsorption des pigments de molécules de chlorophylle-a.Par ailleurs, aucune étude à notre connaissance ne reliait directement les morphologies de particules de phyllosilicates à leurs propriétés d'adsorption vis-à-vis de deux cations inorganiques. Dans le cas des kaolinites naturelles, une charge permanente souvent significative et attribuable à des impuretés minéralogiques empêche toute tentative de relier directement la forme des particules à un coefficient de sélectivité entre deux cations pour des sites latéraux donnés. Des kaolinites ont donc été synthétisées par voie hydrothermale en considérant différentes conditions physico-chimiques, afin d'obtenir des morphologies variées (hexagones plus ou moins anisotropes). Pour ces échantillons synthétiques pour lesquels aucune impureté minéralogique et charge permanente n'a été détectée, des isothermes expérimentales d'adsorption entre Na+ et H+ ont été mesurées. Ces cations ont été choisis étant donné leur présence ubiquiste dans les eaux naturelles et leur fort pouvoir compétiteur par rapport aux cations traces métalliques. Grâce aux surfaces spécifiques des sites latéraux et des densités de site issues de la cristallographie des différentes faces présentes dans nos échantillons ((010), (110), (1-10)), un coefficient de sélectivité entre Na+ et H+ sur l'ensemble des sites latéraux d'une morphologie donnée a pu être estimé à l'aide d'un modèle de complexation de surface. Les résultats ont montré que le coefficient de sélectivité Na+/H+ dépendait très fortement de la morphologie de la particule, et que par conséquent les propriétés d'adsorption des kaolinites ne pouvaient pas être obtenues avec précision sans une connaissance fine de la morphologie des particules. / The dissertation consists of two main parts; the first part is devoted to the effect of physical/thermal and chemical activation of kaolin on bleaching of rice bran oil. In this study, samples were prepared from natural Ranong kaolin. This study focused on the effects of both thermal treatment (from 100 to 900°C) and chemical activation (sulfuric acid, hydrochloric acid, citric acid and oxalic acid using different acid concentrations or different clay/acid ratio) on the capacity of kaolins to bleach rice bran oil. When kaolin was treated with high temperature (>100°C) prior to reflux and with a high acid concentration during reflux, the kaolinite structure was partially or completely destroyed associated to a dramatic leaching of alumina, and amorphous silica dominated the samples. The measured maximum bleaching capacity obtained was not consistent with the highest specific surface area and pore volume; rather, it depended on the alumina contents in the samples. Thus, the partial preservation of the kaolinite structure is crucial to obtain an appropriate bleaching capacity of kaolin. This is directly related to the preservation of the aluminol sites present at the kaolinite surface. XRF analysis showed that the alumina contents of 28-34% were values to reach in order to obtain optimum bleaching capacities of kaolin, independently of the different acid used. Finally, optimum bleaching of ~83%, ~82% and ~81% were achieved by grinding the kaolin prior to reflux with low acid concentration of hydrochloric acid (0.5 M), sulfuric acid (0.3 M) and citric acid (0.5 M), respectively with clay/acid ratio of 1:50.The second part of the thesis aims to elucidate the influence of morphology of kaolinites on their sorption properties. For that, Na+/H+ sorption isotherms in water saturated conditions of synthetic kaolinites and natural well crystallized kaolinite, called KGa--1b commercialized by the Clay Mineral Society, were performed and interpreted. Kaolinites used in this study were hydrothermally synthesized from partially crystallized kaolinite as a function of different final pH (pHF) ranging from 0.8 to 8.3. Results obtained for KGa--1b were compared with data obtained in literature for this mineral, in order to fully validate this approach. This study found that cation exchange capacity, due to both isomorphic substitutions in the crystals (permanent charge), and silanol and aluminol edge sites were highly variable. Typically, CEC at pH=9 varied from ~0.8 cmolc/kg for well crystallized kaolinite (pHF 0.8) to ~33 cmolc/kg for disordered lath-shaped kaolinite (pHF 8.3). Na+/H+ sorption isotherms were obtained for all synthetic kaolinites as a function of pH ranging from pH 3 to 11. Results showed that sorption of Na+ increases dramatically with pH. Typically for all kaolinite samples except for the one synthesized at pHF=8.3, Na+ sorption is rigorously equal to zero when pH<7, indicating no permanent charge in the samples (in contrast to natural KGa--1b kaolinite), and increases when pH>7 due to sorption on edge sites. The amount of dissolved silica measured during Na+/H+ isotherm is higher for experiments performed with kaolinites synthesized in basic conditions (for pHF 7.4 and pHF 8.3) than for kaolinites synthesized in acid conditions (for pHF 0.8 and pHF 3.3). These latter results lead to conclude that sorption site density can be considered constant when pH is between 4 and 10, independently of the morphologies of particles. In this context, a thermodynamic modeling procedure using a complexation model was applied to interpret the data obtained with hexagonal- and lath-shaped particles. During this procedure, selectivity coefficient between Na+ and H+ cations were obtained considering the total edge site densities calculated from lateral specific surfaces estimated for synthetic kaolinites and crystallography data.

L'estuaire de l'Escaut est un estuaire en voie de restauration. L'étude s'intéresse à l'écologie de la communauté zooplanctonique dans le tronçon d'eau douce de l'Escaut, ou, suite à l'amélioration de la qualité de l'eau le copépode calanoide Eurytemora affinis est devenu dominant depuis 2007 et les copépodes cyclopoïdes ont diminués en abondance. Nous avons cherché à trouver quels facteurs environnementaux expliquent ce changement de la composition de la communauté zooplanctonique. Les résultats d'analyses RDA et GLM entre les abondances des taxons zooplanctoniques et les facteurs environnementaux montrent un lien étroit entre l'augmentation de l'abondance d'E. affinis et l'augmentation des concentrations en oxygène ainsi que la diminution des concentrations en N-NH4. En fait, le tronçon amont de l'estuaire est devenu 'permissive' pour le développement d'E. affinis à partir ou la concentration en O2 a dépassé le seuil de 4 mg L-1 et la concentration en N- NH4 est restée en dessous de 2 mg L-1. La cause du déclin en abondance des cyclopoids reste à trouver. Dans l'Escaut, le phytoplancton est fortement dominé par les diatomées, mais la concentration en Si dissoute s'avère parfois limitant. La question se pose sur quelles composantes de la communauté phytoplanctonique le zooplancton dominant se nourrit. La sélectivité de broutage d'E. affinis a été quantifiée à l'aide d'expériences d'incubation et des quantification de contenu pigmentaire à l'aide d'HPLC. E. affinis sélectionne des diatomées au sein de la communauté phytoplanctonique et en moindre mesure des cryptomonades. L'impact de la population d'E. affinis sur le stock de phytoplancton - et sur les diatomées dominantes- est < 4.5 % jour-1, ce qui implique que dans le tronçon d'eau douce de l'Escaut le zooplancton n'est pas limité par la nourriture et ne présente pas de limitation pour le développement les niveaux trophiques supérieurs. Certains taxons phytoplanctoniques (chlorophycées, par exemple) sont apparemment stimulés en croissance par la présence d'E. affinis dans les bouteilles expérimentales et l'impact précis d'E. affinis sur le phytoplancton non-diatomées est moins clair. L'activité de broutage du microzooplancton a également été testée avec des expériences d'incubation. Son impact sur la communauté phytoplanctonique est variable en intensité et en sélectivité, nécessitant plus d'expérimentation. / The Scheldt is an estuary on way of recovery. The study concerns the ecology of the zooplankton community in the freshwater reach of the estuary. In parallel to water quality improvement, the copepod Eurytemora affinis has become dominant since 2007 and abundance of cyclopoid copepods has decreased. We tried to find out which environmental factors had caused these changes in the zooplankton community composition. The results of RDA and GLM analysis between the abundance of zooplankton taxa and the environmental factors showed a strong link between E. affinis abundance and the increasing O2 concentration, but also the decreasing NH4-N concentration. The upstream Scheldt became permissive for E. affinis development as soon as oxygen concentration was above the threshold level of 4 mg L-1 and the NH4-N concentration remained below 2 mg L-1. The cause of the decrease in cyclopoid abundance remains unclear. The phytoplankton community of freshwater Scheldt is strongly dominated by diatoms, but the dissolved silica concentration could become limiting for their development. The question arises on which phytoplankton taxa the dominant zooplankton feeds. Grazing selectivity of E. affinis adults and CV was measured by incubation experiments using natural Scheldt water and by gut pigment content quantification. Phytoplankton taxa concentration was quantified by HPLC. E. affinis selects diatoms and sometimes cryptophytes. The impact of the E. affinis population on the phytoplankton standing stock is < 4.5% d-1, which means that the zooplankton community is not food limited and hence does not present a limitation to the development of higher trophic levels. The grazing activity of the microzooplankton community has also been measured by incubation experiments. Its impact on the freshwater Scheldt phytoplankton community is variable in intensity and in selectivity, and clearly needs further investigation.

Les hydrates de gaz sont des cristaux composés de molécules d’eau formant des cages, piégeant des molécules de gaz. A l’état naturel, ces hydrates se forment en présence de mélanges gazeux dans les fonds océaniques et seraient impliqués dans la formation des comètes et des planètes. Comprendre la sélectivité moléculaire et la stabilité des hydrates mixtes (co-incluant plusieurs espèces gazeuses) est primordiale et constitue le coeur de ce travail de doctorat. En s’appuyant sur la spectroscopie Raman et la diffraction des neutrons, complétés de calculs de chimie quantique, les hydrates formés à partir de mélanges de CO, N2 et de CO2 ont été étudiés.Outre leur intérêt astrophysique, ces systèmes permettent d’appréhender l’impact de propriétés physico-chimiques (moment dipolaire,solubilité, adsorption sur la glace) sur la sélectivité.La cinétique de formation et les signatures vibrationnelles des molécules encapsulées dans différents types de cages ontété analysées pour la première fois dans les hydrates purs de CO et de N2. En variant pression et température, une capacité exceptionnelle de diffusion des molécules gazeuses à travers les cages est révélée. La sélectivité moléculaire, la stabilité structurale et l’occupation des cages ont été étudiées dans les hydrates mixtes CO-N2, CO-CO2 et CO2-N2.L’affinité aqueuse et le moment dipolaire des molécules gazeuses pilotent la sélectivité des gaz piégés (encapsulation préférentielle du CO et du CO2). De plus, l’azote joue un rôle de promoteur cinétique des structures formées. Ces résultats fondamentaux ouvrent de nouvelles perspectives tant appliquées (séparation des gaz) que fondamentales (hydrates en milieu naturel). / Gas hydrates are crystalline compounds consisting of water molecules forming cages within which gas molecules are encapsulated. In natural environments, gas hydrates are formed in the presence of gaseous mixtures in the ocean floor and would be involved in the formation of comets and planets. Understanding the molecular selectivity and the stability of mixed hydrates (co-including several gaseous species) is crucial and constitutes the core of this research work. With the help of Raman spectroscopy and neutron diffraction,supplemented by quantum chemistry calculations, hydrates formed from mixtures of CO, N2 and CO2 have been investigated. In addition to their astrophysical interest, these systems offer the opportunity to better understand the impact of physical-chemistry properties (dipolar moment, water solubility,adsorption on ice) on the selectivity.The formation kinetics and the vibrational signatures of the encapsulated molecules in various types of cage have been analyzed in pure CO and N2 hydrates for the first time. By varying pressure and temperature, the gaseous molecules exhibit an exceptional ability for diffusing through the cages. Molecular selectivity, structural stability and cage occupancy have been studied in the mixed hydrates CO-N2, CO-CO2 and CO2-N2. The aqueous affinity and the dipolar moment of the gas molecules trigger the selectivity of the trapped gases (preferential encapsulation of COand CO2). In addition, the nitrogen molecule acts as a kinetic promoter of the formed structure. These fundamental results open new opportunities on both applied (gas separation)and fundamental (hydrates in natural environment) aspects.

La conception de matériaux capables de piéger sélectivement le CO2 revêt un enjeu majeur dans le développement de procédé de capture post-combustion pour de nombreux secteurs industriels. Nos travaux visent l'élaboration de nouveaux polymères de coordination de type MOF (“Metal-Organic Framework”) préparés par auto-assemblage de briques moléculaires polycarboxyliques avec des métaux de transition qui constituent les noeuds du réseau tridimensionnel. Ces matériaux hybrides microporeux présentent des propriétés d’adsorption du CO2 importantes. Notre approche a consisté à synthétiser des polymères de coordination dans le but d'accroître la capacité et la sélectivité d'adsorption du CO2 vis-à-vis d'autres gaz comme CO, CH4, N2 et O2 grâce à des interactions physiques impliquant le moment quadripolaire élevé du CO2 et le potentiel électrostatique existant dans les pores du matériau. Dans ce mémoire sont décrites les synthèses des différentes briques moléculaires organiques constituées de polyamines et de polyazamacrocycles Nfonctionnalisées par des terminaisons benzocarboxylate. Des matériaux homo- et hétéro- bimétalliques présentant des structures cristallines originales ont été obtenus à partir de briques moléculaires triazamacrocycliques N-fonctionnalisées par des terminaisons acides carboxyliques et différents cations métalliques (Zn2+, Co2+, Cd2+ et Ni2+). Les études de ces polymères de coordination poreux ont révélé leur capacité d’adsorption importante du CO2 avec une sélectivité remarquable dans les conditions normales de température et de pression. / The design of material able for CO2 capture is a major issue to achieve post-combustion capture process for many industries. Our work aims to develop new coordination polymer MOF (“Metal-Organic Framework”) prepared by self-assembling polycarboxylic linkers and transition metals. These microporous hybrids materials show important CO2 adsorption properties and are promising in the field of gas separation. The main topic of our work is to synthesise MOFs with high adsorption capacity and selectivity for CO2 over other gases (CO, CH4, N2 and O2). The gas-solid interactions are due to physical phenomena involving the high quadrupolar moment of CO2 and the electrostatic potential lying in the pore of the material. In this manuscript, the synthesis of various organic linkers incorporating N-functionalised polyamines and polyazamacrocycles with benzocarboxylate functions is described. Homo- and hetero- bimetallic materials with original tridimensional structure were obtained from a N-functionalised triazamacrocyclic linker and different metal cations (Zn2+, Co2+, Cd2+ and Ni2+). Studies of porous coordination polymers have shown high CO2 adsorption capacity with a remarkable selectivity in the ambient temperature and pressure conditions.

L’intégrase (IN) du VIH-1 est une enzyme clé du cycle viral catalysant l’insertion stable de l’ADN viral dans le génome de la cellule infectée. L’IN participe également à de nombreuses étapes du cycle viral telles que la transcription inverse ou la maturation virale. Ainsi, la compréhension des mécanismes régulant l’intégration du VIH-1 représente un enjeu majeur dans le cadre notamment d’approches thérapeutiques. En effet, les études montrent que ces mécanismes sont finement régulés dans la cellule par des facteurs viraux et cellulaires agissant à différentes étapes du cycle viral. C’est donc dans ce contexte que nous avons étudié les facteurs à la fois viraux et cellulaires régulant ce processus. Dans un premier temps, les déterminants viraux modulant l’intégration dans la chromatine ont été analysés dans le cas de plusieurs modèles rétroviraux. Puis, dans un second temps, nous avons étudié l’impact de facteurs cellulaires, identifiés au laboratoire, sur les mécanismes d’insertion de l’ADN viral dans le génome cellulaire. Mon travail de thèse s’est ainsi articulé en trois axes majeurs aboutissant à : ● La démonstration de la régulation de l’intégration rétrovirale par la structure chromatinienne de l’hôte ● L’identification de nouveaux cofacteurs cellulaires participant à la régulation de l’intégration dans la chromatine dont le complexe de remodelage FACT « Facilitates Chromatin Transcription » ● L’identification d’une nouvelle interaction fonctionnelle entre l’IN du VIH-1 et la queue amino-terminale de l’histone humaine H4 et de son rôle dans la sélectivité de l’intégration / HIV-1 integrase (IN) is a key enzyme of the viral cycle that catalyzes the stable insertion of viral DNA into the genome of the infected cell. IN also participates in many stages of the viral cycle such as reverse transcription or viral maturation. Thus, an understanding of the mechanisms regulating the integration of HIV-1 is a major challenge, particularly in the context of therapeutic approaches. Indeed, studies show that these mechanisms are finely regulated in the cell by viral and cellular factors acting at different stages of the viral cycle. It is in this context that we studied both viral and cellular factors regulating this process. Initially, the viral determinants modulating the integration in chromatin were analyzed in the case of several retroviral models. Then, we studied the impact of cellular factors, identified in the laboratory, on the mechanisms of insertion of the viral DNA in the cellular genome. My thesis work has thus been articulated in three major axes leading to: • The demonstration of the regulation of retroviral integration by the chromatin structure of the host • The identification of new cellular cofactors participating in the regulation of chromatin integration, including the FACT remodeling complex "Facilitates Chromatin Transcription" • The identification of a new functional interaction between the HIV-1 IN and the amino-terminal tail of human H4 histone and its role in the selectivity of integration.

L'objectif de ce projet de thèse a été d’étudier l’activité catalytique de catalyseurs commerciaux contenant de nanoparticules métalliques pour l'hydrogénation du limonène. La réaction a été réalisée en l'absence de solvants et dans des conditions douces c’est à dire à basse température (30°C) et sous faible pression d'hydrogène (3 bar), conduisant à une production stable du (+)-p-1-menthene. Dans notre étude, les nanoparticules métalliques actives (Pt, Pd et Ru) et les supports (carbone, silice et alumine) ont été systématiquement modifiés et testés dans des conditions de réaction modérées (température ambiante, 3 bar H2). Notre étude a révélé une activité et sélectivité importante du catalyseur hétérogène Pt/C pour la réduction du R-(+)-limonène en (+)-p-1-menthène qui est le produit partiellement hydrogéné. Le Pt/C ainsi que Pt/Al2O3 est l’un des systèmes les plus actifs parmi les catalyseurs actuellement disponibles dans le commerce. De plus, l'activité catalytique et la stabilité de Pt/C ont été maintenues au cours des essais de recyclage en réacteur fermé. Ce catalyseur a également été utilisé en réacteur à flux continu, donnant des résultats prometteurs. L'hydrogénation sélective de la liaison C=C terminale du limonène par rapport de la liaison interne a été rationalisée par des études cinétiques détaillées qui révèlent une vitesse 8 fois plus importante par la double liaison terminale. Cette première étude nous a permis de développer la synthèse de nouveaux catalyseurs hétérogènes contenant diverses nanoparticules métalliques (Pt, Ru, Pt3Sn et Ni). Ils ont été préparés à partir d'une approche colloïdale et ont été testés dans l'hydrogénation de limonène. Ces catalyseurs contiennent la même charge métallique et des tailles de particules similaires (environ 2 nm) dispersées de façon homogène sur des oxydes non structurés (silice et d'alumine), du carbone, ou incorporés à l'intérieur des murs ou à la surface des pores de matériaux mésostructurés siliciques (SBA-15). L’ensemble des catalyseurs de la série du Pt ont révélés une activité accrue lors de l'hydrogénation sélective du limonène en p-menthène puis en p-menthane avec une vitesse de réaction très élevé. Parmi tous ces catalyseurs, celui contenant des nanoparticules de Pt dans les murs de la silice a montré au bout de deux heures de réaction un TOF d'environ 2200 h-1 et un rendement maximal pour le p-menthène d'environ 85% après 10 heures de réaction. Ce même catalyseur a été testé dans un réacteur en flux continu et affiche après 6 heures un rendement en p-menthene stable de 80%. Aucun produit d'isomérisation n’a été détecté dans le mélange brut au cours de la réaction. En conclusion, nous pouvons dire que l'utilisation d'un catalyseur hétérogène commercial comme le Pt/C ou l’utilisation d’un catalyseur hétérogène métallique développé à partir d'une approche colloïdale, Pt@SBA-15{murs}, permet d'obtenir une conversion sélective du limonène en p-menthène en réacteur fermé ainsi également en réacteur à flux continu. Des informations sur la cinétique de cette réaction ont également pu être obtenues / The goal of this PhD project was in an early stage to study the activities of several commercial metal nanoparticles based catalysts for the mild hydrogenation of limonene. The hydrogenation of limonene has been performed in neat limonene and under mild conditions, e.g. low temperature (30°C) and low molecular hydrogen pressure (3 bar), aiming at a sustainable production route for (+)-p-1-menthene. In our study, the active metal nanoparticles (Pt, Pd and Ru) and supports (carbon, silica and alumina) were systematically varied and tested. It was found that the heterogeneous catalyst Pt/C alongside Pt/Al2O3 under mild reaction conditions (room temperature and 3 bar H2) was highly active and selective in the reduction of R-(+)-limonene to the partial hydrogenation product (+)-p-1-menthene. Moreover, the catalytic activity and stability of Pt/C were maintained during recycling tests under batch conditions and thus allowed the implementation of this catalytic system into continuous flow operation. The selective hydrogenation of terminal C=C bond over the internal one in limonene was rationalized by detailed kinetic studies which revealed an 8-fold difference in reaction rate between the two reactions. This previous study with commercial catalysts gave the possibility to tune the synthesis of heterogeneous metal-based catalysts for the next step of the study, where different heterogeneous metal based catalysts (Pt, Ru, Pt3Sn, and Ni), developed from a colloidal-based approach were tested in the hydrogenation of limonene. Those catalysts contain the same metal loading and similar particle sizes (ca. 2 nm) homogeneously dispersed onto non structured oxides (silica and alumina), carbon, or embedded into the walls or at the pore surface of a mesostructured silica materials (SBA-15). All the catalysts from the Pt series were particularly active in the selective hydrogenation of limonene towards p-menthene with further conversion into p-menthane, showing a very high reaction rate. Among of all those catalysts, the one containing Pt nanoparticles embedded in the walls of the silica showed the highest TOF, of ca. 2200 h-1 after two hours of reaction and a maximum yield in p-menthene of ca. 85 % was obtained after 10 hours of reaction. The same catalyst was tested in a continuous flow system and a stable yield of ca. 80% during 6 hours of reaction was reached. No products of isomerization were detected in the crude mixture during the reaction. We could therefore conclude that, using either a heterogeneous commercial catalyst like Pt/C or using a heterogeneous metal based catalyst developed from a colloidal-based approach like SBA-15{walls}, it was possible to achieve a selective conversion of limonene into p-menthene in batch and in continuous flow conditions