O estresse tem se mostrado como um agravante de diversas patologias e transtornos psiquiátricos, como o transtorno depressivo maior (TDM). Estudos apontam que o hipocampo, bem como as vias serotonérgicas presentes neste, estão envolvidas com as respostas de estresse bem como nos efeitos deletérios causados por este. O antagonismo do receptor 5-HT 7, presente nestas vias, tem apresentado um efeito antidepressivo e ansiolítico em alguns trabalhos, porém poucos são os estudos que investigam o papel do receptor 5-HT 7 nas estruturas encefálicas em relação às repostas de estresse. Diante desse dado, o presente trabalho utilizou o modelo Labirinto em Cruz Elevado (LCE) 24 horas após a restrição para investigar o papel do receptor 5-HT 7 do hipocampo na consolidação da memória aversiva. A metodologia utilizada consistiu na injeção bilateral de SB-258741, um antagonista do receptor 5-HT7, no hipocampo dorsal de ratos Wistar machos, feita logo após o estresse de restrição de movimento com exposição ao LCE 24 horas depois. Como resultado desta metodologia, foi observado um aumento na porcentagem de entradas dos animais nos braços abertos, mas não na porcentagem de tempo em que o animal permaneceu nestes braços. Este dado mostra que a injeção de um antagonista de 5-HT 7 no hipocampo leva a uma atenuação dos efeitos comportamentais da consolidação de memória aversiva, corroborando com efeito ansiolítico consequente ao antagonismo deste receptor, observado na literatura. Nesse sentido, a investigação sobre o papel desse receptor, nas respostas de estresse, pode ser útil para o desenvolvimento de novos fármacos para os tratamentos dos efeitos prejudiciais do estresse. / Stress has been shown to be an aggravating factor for various diseases and psychiatric disorders, such as major depressive disorder (MDD). Studies suggest that the hippocampus, as well as serotonergic pathways present in this structure, are involved in stress responses as well as in the deleterious effects caused by this factor. The receptor antagonism of 5-HT 7 receptor, present in these pathways, has shown an antidepressant and anxiolytic effect in some studies, but few studies are investigating the role of 5-HT 7 receptor in brain structures related to stress responses. Given this data, this study used the Elevated Plus Maze (EPM) 24 hours after the restrain stress to investigate the role of 5-HT 7 receptor in the hippocampus consolidation of aversive memory. The methodology in this study consisted of bilateral injection of SB-258741, an antagonist of the 5-HT7 receptor, into the dorsal hippocampus of male Wistar rats, made 5 minutes after the restrain stress with exposure to EPM after 24 hours. As a result of this method, an increase in the percentage of animals entries into the open arms, but not at the percentage of time the animal remained in these arms, was observed. This data shows that the injection of a 5-HT 7 antagonist in the hippocampus leads to an attenuation of the aversive memory consolidation behavioral effects, corroborating with the consequent anxiolytic effect to the antagonism of this receptor, presented in the literature. In this sense, research on the role of this receptor in stress responses may be useful for the development of new drugs for the treatment of the harmful effects of stress.

O estresse tem se mostrado como um agravante de diversas patologias e transtornos psiquiátricos, como o transtorno depressivo maior (TDM). Estudos apontam que o hipocampo, bem como as vias serotonérgicas presentes neste, estão envolvidas com as respostas de estresse bem como nos efeitos deletérios causados por este. O antagonismo do receptor 5-HT 7, presente nestas vias, tem apresentado um efeito antidepressivo e ansiolítico em alguns trabalhos, porém poucos são os estudos que investigam o papel do receptor 5-HT 7 nas estruturas encefálicas em relação às repostas de estresse. Diante desse dado, o presente trabalho utilizou o modelo Labirinto em Cruz Elevado (LCE) 24 horas após a restrição para investigar o papel do receptor 5-HT 7 do hipocampo na consolidação da memória aversiva. A metodologia utilizada consistiu na injeção bilateral de SB-258741, um antagonista do receptor 5-HT7, no hipocampo dorsal de ratos Wistar machos, feita logo após o estresse de restrição de movimento com exposição ao LCE 24 horas depois. Como resultado desta metodologia, foi observado um aumento na porcentagem de entradas dos animais nos braços abertos, mas não na porcentagem de tempo em que o animal permaneceu nestes braços. Este dado mostra que a injeção de um antagonista de 5-HT 7 no hipocampo leva a uma atenuação dos efeitos comportamentais da consolidação de memória aversiva, corroborando com efeito ansiolítico consequente ao antagonismo deste receptor, observado na literatura. Nesse sentido, a investigação sobre o papel desse receptor, nas respostas de estresse, pode ser útil para o desenvolvimento de novos fármacos para os tratamentos dos efeitos prejudiciais do estresse. / Stress has been shown to be an aggravating factor for various diseases and psychiatric disorders, such as major depressive disorder (MDD). Studies suggest that the hippocampus, as well as serotonergic pathways present in this structure, are involved in stress responses as well as in the deleterious effects caused by this factor. The receptor antagonism of 5-HT 7 receptor, present in these pathways, has shown an antidepressant and anxiolytic effect in some studies, but few studies are investigating the role of 5-HT 7 receptor in brain structures related to stress responses. Given this data, this study used the Elevated Plus Maze (EPM) 24 hours after the restrain stress to investigate the role of 5-HT 7 receptor in the hippocampus consolidation of aversive memory. The methodology in this study consisted of bilateral injection of SB-258741, an antagonist of the 5-HT7 receptor, into the dorsal hippocampus of male Wistar rats, made 5 minutes after the restrain stress with exposure to EPM after 24 hours. As a result of this method, an increase in the percentage of animals entries into the open arms, but not at the percentage of time the animal remained in these arms, was observed. This data shows that the injection of a 5-HT 7 antagonist in the hippocampus leads to an attenuation of the aversive memory consolidation behavioral effects, corroborating with the consequent anxiolytic effect to the antagonism of this receptor, presented in the literature. In this sense, research on the role of this receptor in stress responses may be useful for the development of new drugs for the treatment of the harmful effects of stress.

The origin and evolution of granites has been widely studied because granitoid rocks constitute a major portion of the Earth ́s crust. The formation of granitic magma is, besides temperature mainly triggered by the water content of these rocks. The presence of water in magmas plays an important role due to the ability of aqueous fluids to change the chemical composition of the magma. The exsolution of aqueous fluids from melts is closely linked to a fractionation of elements between the two phases. Then, aqueous fluids migrate to shallower parts of the Earth ́s crust because of it ́s lower density compared to that of melts and adjacent rocks. This process separates fluids and melts, and furthermore, during the ascent, aqueous fluids can react with the adjacent rocks and alter their chemical signature. This is particularly impor- tant during the formation of magmatic-hydrothermal ore deposits or in the late stages of the evolution of magmatic complexes. For a deeper insight to these processes, it is essential to improve our knowledge on element behavior in such systems. In particular, trace elements are used for these studies and petrogenetic interpretations because, unlike major elements, they are not essential for the stability of the phases involved and often reflect magmatic processes with less ambiguity. However, for the majority of important trace elements, the dependence of the geochemical behavior on temperature, pressure, and in particular on the composition of the system are only incompletely or not at all experimentally studied. Former studies often fo- cus on the determination of fluid−melt partition coefficients (Df/m=cfluid/cmelt) of economically interesting elements, e.g., Mo, Sn, Cu, and there are some partitioning data available for ele- ments that are also commonly used for petrological interpretations. At present, no systematic experimental data on trace element behavior in fluid−melt systems as function of pressure, temperature, and chemical composition are available. Additionally, almost all existing data are based on the analysis of quenched phases. This results in substantial uncertainties, particularly for the quenched aqueous fluid because trace element concentrations may change upon cooling. The objective of this PhD thesis consisted in the study of fluid−melt partition coefficients between aqueous solutions and granitic melts for different trace elements (Rb, Sr, Ba, La, Y, and Yb) as a function of temperature, pressure, salinity of the fluid, composition of the melt, and experimental and analytical approach. The latter included the refinement of an existing method to measure trace element concentrations in fluids equilibrated with silicate melts di- rectly at elevated pressures and temperatures using a hydrothermal diamond-anvil cell and synchrotron radiation X-ray fluorescence microanalysis. The application of this in-situ method enables to avoid the main source of error in data from quench experiments, i.e., trace element concentration in the fluid. A comparison of the in-situ results to data of conventional quench experiments allows a critical evaluation of quench data from this study and literature data. In detail, starting materials consisted of a suite of trace element doped haplogranitic glasses with ASI varying between 0.8 and 1.4 and H2O or a chloridic solution with m NaCl/KCl=1 and different salinities (1.16 to 3.56 m (NaCl+KCl)). Experiments were performed at 750 to 950◦C and 0.2 or 0.5 GPa using conventional quench devices (externally and internally heated pressure vessels) with different quench rates, and at 750◦C and 0.2 to 1.4 GPa with in-situ analysis of the trace element concentration in the fluids. The fluid−melt partitioning data of all studied trace elements show 1. a preference for the melt (Df/m < 1) at all studied conditions, 2. one to two orders of magnitude higher Df/m using chloridic solutions compared to experiments with H2O, 3. a clear dependence on the melt composition for fluid−melt partitioning of Sr, Ba, La, Y, and Yb in experiments using chloridic solutions, 4. quench rate−related differences of fluid−melt partition coefficients of Rb and Sr, and 5. distinctly higher fluid−melt partitioning data obtained from in-situ experiments than from comparable quench runs, particularly in the case of H2O as starting solution. The data point to a preference of all studied trace elements for the melt even at fairly high salinities, which contrasts with other experimental studies, but is supported by data from studies of natural co-genetically trapped fluid and melt inclusions. The in-situ measurements of trace element concentrations in the fluid verify that aqueous fluids will change their composition upon cooling, which is in particular important for Cl free systems. The distinct differences of the in-situ results to quench data of this study as well as to data from the literature signify the im- portance of a careful fluid sampling and analysis. Therefore, the direct measurement of trace element contents in fluids equilibrated with silicate melts at elevated PT conditions represents an important development to obtain more reliable fluid−melt partition coefficients. For further improvement, both the aqueous fluid and the silicate melt need to be analyzed in-situ because partitioning data that are based on the direct measurement of the trace element content in the fluid and analysis of a quenched melt are still not completely free of quench effects. At present, all available data on element complexation in aqueous fluids in equilibrium with silicate melts at high PT are indirectly derived from partitioning data, which involves in these experiments assumptions on the species present in the fluid. However, the activities of chemical components in these partitioning experiments are not well constrained, which is required for the definition of exchange equilibria between melt and fluid species. For example, the melt-dependent variation of partition coefficient observed for Sr imply that this element can not only be complexed by Cl− as suggested previously. The data indicate a more complicated complexation of Sr in the aqueous fluid. To verify this hypothesis, the in-situ setup was also used to determine strontium complexation in fluids equilibrated with silicate melts at desired PT conditions by the application of X-ray absorption near edge structure (XANES) spectroscopy. First results show a strong effect of both fluid and melt composition on the resulting XANES spectra, which indicates different complexation environments for Sr. / Die Entstehung und Entwicklung von Graniten steht seit Jahrzehnten im Fokus vieler geologischer Studien, da sich die Erdkruste zu großen Teilen aus granitoiden Gesteinen zusammensetzt. Von besonderer Bedeutung für die Bildung von granitischen Schmelzen ist neben der Temperatur, der Wassergehalt der Schmelze, da dieser Parameter die chemische Zusammensetzung der Schmelze entscheidend verändern kann. Die Entmischung wässriger Fluide aus Schmelzen führt zur Neuverteilung von Elementen zwischen diesen Phasen. Bedingt durch die geringere Dichte des wässrigen Fluids im Vergleich zur Schmelze und dem Nebengestein, beginnt dieses aus tieferen Erdschichten aufzusteigen. Damit verknüpft ist nicht nur eine räumliche Trennung von Schmelze und Fluid, sondern auch die Alterierung des Nebengestein. Dieser Prozess ist insbesondere bei der Bildung von magmatisch-hydrothermalen Lagerstätten und in späten Entwicklungsstadien magmatischer Komplexe wichtig. Für ein detailliertes Verständnis dieser Prozesse ist es notwendig, das Elementverhalten in solchen Systemen in Abhängigkeit von Parametern wie Temperatur, Druck und chemischer Zusammensetzung des Systems experimentell zu untersuchen, und Elementverteilungskoeffizienten als Funktion dieser Variablen zu bestimmen. Für die Untersuchungen sind insbesondere Spurenelemente geeignet, da diese im Gegensatz zu Hauptelementen nicht essentiell für die Stabilität weiterer auftretender Phasen sind, aber sehr sensibel auf Änderungen intensiver Variablen reagieren können. Zudem werden bei geochemischen Mineral- und Gesteinsanalysen viele Spurenelemente, Spurenelementverhältnisse, und Spurenelementisotope als petrogenetische Indikatoren verwendet, d.h. diese Daten liefern Informationen darüber, wann und in welcher Tiefe und bei welchen chemischen Bedingungen ein Gestein gebildet worden ist, und welche weiteren Prozesse es auf dem Weg zur Erdoberfläche durchlaufen hat. Allerdings sind für vie- le Spurenelemente die Abhängigkeiten der Verteilung zwischen Fluiden und Schmelzen von intensiven Variablen nicht, oder nur unzureichend experimentell untersucht worden. Zusätzlich dazu basiert die Mehrheit der experimentell gewonnenen Verteilungskoeffizienten und deren Interpretation, insbesondere hinsichtlich der Elementkomplexierung im Fluid, auf der Analyse von schnell abgekühlten Phasen. Bisher ist nicht geklärt, ob solche Analysen repräsentativ sind für die Zusammensetzungen der Phasen bei hohen Drücken und Temperaturen. Das Ziel dieser Studie war die Erarbeitung eines experimentellen Datensatzes zur Spu- renelementverteilung zwischen granitischen Schmelzen und wässrigen Fluiden in Abhängigkeit von der Schmelzzusammensetzung, der Salinität des Fluids, des Drucks und der Temperatur. Ein Hauptanliegen der Arbeit bestand in der Weiterentwicklung einer experimentellen Methode bei welcher der Spurenelementgehalt im Fluid in-situ, d.h. unter hohen Drücken und Temperaturen, und im Gleichgewicht mit einer silikatischen Schmelze bestimmt wird. Die so gewonnenen Daten können anschließend mit den Resultaten von Abkühlexperimenten vergli- chen werden, um diese und auch Literaturdaten kritisch zu bewerten. Die Daten aller unter- suchten Spurenelemente dieser Arbeit (Rb, Sr, Ba, La, Y und Yb) zeigen: 1. unter den untersuchten Bedingungen eine Präferenz für die Schmelze unabhängig von der chemischen Zusammensetzung von Schmelze und Fluid, Druck oder Temperatur, 2. die Verwendung von chloridhaltigen Fluiden kann die Verteilungskoeffizienten um 1 bis 2 Größenordnungen anheben und 3. für die Verteilungskoeffizienten von Sr, Ba, La, Y und Yb eine starke Abhängigkeit von der Schmelzzusammensetzung im chloridischen System. Der Vergleich der Daten der verschiedenen Methoden zeigt, dass insbesondere für chloridfreie Fluide große Diskrepanzen zwischen den in-situ Daten und Analysen von abgeschreckten Proben bestehen. Dieses Ergebnis beweist eindeutig, dass beim Abschrecken der Proben Rückreaktionen stattfinden, und dass Daten, welche auf Analysen abgeschreckter Fluide basieren, nur eingeschränkt verwendet werden sollten. Die Variation der Verteilungskoeffizienten von Sr, Ba, La, Yb, und Y als Funktion der Schmelzzusammensetzung ist entweder auf eine Änderung der Komplexierung im Fluid und/oder einen anderen veränderten Einbau dieser Elemente in die Schmelze zurückzuführen. Daher wurde im Rahmen dieser Arbeit erstmals versucht, die Elementkomplexierung in silikatischen Fluiden direkt bei hohen Temperaturen und Drücken zu bestimmen. Die Daten für Sr zeigen, dass abhängig von der Schmelzzusammensetzung unterschiedliche Komplexe stabil sein müssen.

Le stockage géologique du CO2 dans les aquifères salins représente une stratégie prometteuse pour la réduction des émissions de CO2 anthropiques. Ce type de stockage requiert des connaissances fondamentales afin d'évaluer les scénarios d'injection, d'estimer la capacité des réservoirs et les risques de fuite. C'est dans ce contexte que des outils microfluidiques haute pression/haute température ont été développés afin d'étudier différents mécanismes liés aux technologies de stockage de CO2. Les laboratoires géologiques sur puce (GLoCs) permettent de mener des expériences à des conditions de pression et de température typiques des réservoirs (25 < T < 50°C, 50 < p < 10 MPa) et d'en mimer des propriétés géologiques.Ce manuscrit présente dans un premier temps les stratégies de fabrication des GLoCs et l'accès à leurs caractéristiques (porosité et perméabilité). La détection du CO2 directement au sein de GLoCs grâce à l'implémentation de fibres optiques par spectroscopie infrarouge est ensuite présentée, ainsi que la mise en œuvre de la technique de laminographie X menées à l'ESRF pour le suivi de dissolution de carbonates dans des microcanaux. Le manuscrit explicite ensuite les investigations, menées avec des GLoCs concernant les différents mécanismes de piégeage du CO2 à l'échelle du pore. La visualisation directe et le traitement d'image ont permis de suivre l'évolution des phases de CO2 et des phases aqueuses au sein du GLoC et les mécanismes de déplacement et de saturation. Enfin, les travaux en cours sont exposés, comme les expériences de drainage avec des saumures réactives ou la formation d'hydrates au sein de milieux poreux. / CO2 geological storage in deep saline aquifers represents a mediation solution for reducing the anthropogenic CO2 emissions. Consequently, this kind of storage requires adequate scientific knowledge to evaluate injection scenarios, estimate reservoir capacity and assess leakage risks. In this context, we have developed and used high pressure/high temperature microfluidic tools to investigate the different mechanisms associated with CO2 geological storage in deep saline aquifers. The silicon-Pyrex 2D porous networks (Geological Labs On Chips) can replicate the reservoir p,T conditions (25 < T < 50°C, 50 < p < 10 MPa), geological and topological properties. This thesis manuscript first highlights the strategies developed during this work to fabricate the GLoCs and to access to global characteristics of our porous media such as porosity and permeability, which are later compared to numerical modelling results. The carbon dioxide detection in GLoCs mimicking p,T conditions of geological reservoirs by using the direct integration of optical fiber for IR spectroscopy is presented. I then detail the strategies for following the dissolution of carbonates in GLoCs with X-rays laminography experiments.Then, the manuscript focuses on the use of GLoCs to investigate each CO2 trapping mechanism at the pore scale. The direct optical visualization and image processing allow us to follow the evolution of the injected CO2/aqueous phase within the reservoir, including displacement mechanisms and pore saturation levels.Eventually, I present the ongoing works such as experiments with reactive brines and hydrates formations in porous media.

Depuis au moins 540 Ma deux grands systèmes de subduction coexistent sur Terre : d'une part, les systèmes de subduction-collision (chaînes Hercynienne, Himalayenne ou Alpine) et d'autre part, les systèmes de subduction de type péri-pacifique. Pour ces derniers, l'avant-arc constitue une zone clef pour retracer l'évolution de la subduction au cours du temps. En effet ces zones au contact avec le slab peuvent enregistrer des événements tectoniques et/ou des conditions métamorphiques variées (e.g. formation de « paired metamorphic belts »), qui sont autant d'indicateurs du contexte géodynamique. Le massif métamorphique de El Oro en Equateur est un exemple exeptionnel où une section complète et basculée de l'avant-arc Triasique est préservée. L'ensemble est constitué d'une série métasédimentaire de bas à haut grade métamorphique intrudée par des granitoïdes de type S, juxtaposé avec un laccolithe gabbroïque et des schistes bleus. Ce travail de thèse s'est concentré sur l'étude du métamorphisme de haute-température basse-pression et ses relations les schistes bleu. Afin de contraindre l'événement tectono-métamorphique affectant l'avant-arc Equatorien au Trias et la formation d'une "paired metamorphic belt", nous avons utilisé des outils structuraux, métamorphiques, géochimiques, géochronologiques et de modélisation thermique. Nos résultats montrent que durant cette période l'avant-arc Equatorien connait un intense épisode de fusion partielle en régime extensif. La base de la croûte est migmatisée sur une épaisseur de 10km. Les estimations Pression-Température indiquent que les conditions de fusion partielle varient de 4.5 kbar et 650°C pour la partie supérieure métaxitique et jusqu'à 7.5 kbar et 720°C pour la partie inférieure diatexitique. La gradient géothermique inféré est divisé en deux segments : un segment supérieur caractérisé par un gradient de 40°C/km et un segment inférieur caractérisé par un gradient quasi-isothermique. L'absence de paragénèse de ultra-haute température est attribuée à la grande fertilité du protolithe métasédimentaire. Les résultats géochimiques montrent que les plutons granodioritiques sont issus d'un mélange entre : (1) les liquides de fusion partielle produit par la réaction de deshydration de la muscovite des métasédiments et (2) un magma basique. Les âges U-Pb sur zircons et monazites révèlent que l'événement anatectique fût bref entre 229 et 225 Ma. La source de chaleur à l'origine de l'événement thermique est attribuée à la mise en place d'un pluton gabbroïque à ~ 230 Ma en base de croûte. Successivement, se sous-plaque les schistes-bleu refroidissant rapidement l'avant-arc. L'événement anatectique observé dans le massif de El Oro au Trias s'insrit à plus grande échelle au sein d'une large anomalie thermique affectant l'ensemble du continent sud Américain entre 260 et 220 Ma. Durant cette période la marge est un soumise à un régime extensif accompagné d'un important magmatisme d'origine crustal, principalement en position d'arc et d'avant-arc. Nous attribuons cette anomalie thermique d'ampleur continental à une "avalanche mantellique". A la lumière du contexte géodynamique globale nous inteprétons la formation de la paired metamorphic belt de El Oro à la rupture du slab. / Since about 540 Ma, two subductions systems co-exist on Earth: the subduction-collision systems (Hercynian, Himalayan or Alpin belts) and the circum-pacific subduction system. For the last the forearc region constitutes a key zone to understand the dynamic of the subduction. Indeed the forearc region in contact with the slab may records various tectonics events and/or metamorphic conditions (e.g. formation of paired metamorphic belt). Theses geological records are direct evidences of the linked geodynamical context. The El Oro metamorphic complex in Ecuador is a unique example where a whole Triassic forearc section is tilted and well preserved. The complex is made of low to high grade metasedimentary rocks intruded by S-type granitoids, juxtaposed with gabbroic rocks and blueschists. This study is focused on the high-temperature metamorphism and its retionaships with the high-pressure metamorphism. In order to constrain the tectono-metamorphic affecting the forearc region and the formation of a paired metamorphic belt we used strutural, metamorphic, geochemical, geochronological and themal modeling studies. Our results show that during Triassic times the Ecuadorian forearc underwent a strong episode of partial melting in extentional context. The migmatized part of crust is 10 km thick. Pressure-Temperature estimates indicate that partial melting started at 4.5 kbar and 650°C for the upper metatexitic part until 7.5 kbar and 720 °C for the lower diatexitic part. The resulting geothermal gradient exhibits two parts: an upper part caracteristed by a thermal gradient of 40°C/km and a lower part caractérized by a near-adiabatic gradient. The absence of ultra-high tempetature paragenesis is attributed to the high fertility of the metasedimentary protolith. Geochemical results show that granodiorite made of a miwing between: (1) the melt extacted under muscovite dehydration melting and (2) a basic magma. U-Pb ages on zircon and monazite reveal that the anatectic event was short, between 229 and 225 Ma. The origin of the thermal anomaly is attributed to the emplacement of the gabbroic plutonic unit at ~230 at root level. Successively, the blueschites are underplating triggering a strong coolng of the forearc region. The anatectic recorded in the El Oro metamorphic complex at Triassic times is part of a larger thermal anomaly affecting the whole south american margin between 260 and 220 Ma. During this period the margin is under extentional conditions and exhibit a strong S-type magmatic activity. This magmatism is mainly located in arc and forearc position. We attribute this large-scale thermal anomaly to slab fall in the lower mantle. In the light of the geodynamical context, we suggest that the formation of the El Oro paired metamorphic belt is related to slab breakoff.

Made available in DSpace on 2014-12-17T14:03:37Z (GMT). No. of bitstreams: 1 MariliaSNS_TESE.pdf: 2303324 bytes, checksum: d055f1a32ee94b3ffe5f389dbf9dffe0 (MD5) Previous issue date: 2014-04-08 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Compounds derived from fungi has been the subject of many studies in order to broaden the knowledge of their bioactive potential. Polysaccharides from Caripia montagnei have been described to possess anti-inflammatory and antioxidant properties. In this study, glucans extracted from Caripia montagnei mushroom were chemically characterized and their effects evaluated at different doses and intervals of treatment. It was also described their action on colonic injury in the model of colitis induced by 2,4,6-trinitrobenzene sulfonic acid (TNBS), and its action on cells of the human colon carcinoma (HT-29). Compounds extracted of C. montagnei contain high level of carbohydrates (96%), low content of phenolic compounds (1.5%) and low contamination with proteins (2.5%). The (FT-IR) and (NMR) analysis showed that polysaccharides from this species of mushroom are composed of &#945;- and &#946;-glucans. The colonic damage was evaluated by macroscopic, histological, biochemical and immunologic analyses. The results showed a reduction of colonic lesions in all groups treated with the glucans of Caripia montagnei (GCM). GCM significantly reduced the levels of IL-6 (50 and 75 mg/kg, p < 0.05), a major inflammatory cytokine. Biochemical analyses showed that such glucans acted on reducing levels of alkaline phosphatase (75 mg/kg, p < 0.01), nitric oxide (p < 0.001), and myeloperoxidase (p < 0.001). These results were confirmed microscopically by the reduction of cellular infiltration. The increase of catalase activity suggest a protective effect of GCM on colonic tissue, confirming their anti-inflammatory potential. GCM displayed cytostatic activity against HT-29 cells, causing accumulation of cells in G1 phase, blocking the cycle cell progression. Those glucans also showed ability to modulate the adhesion of HT-29 cells to Matrigel? and reduced the oxidative stress. The antiproliferative activity against HT-29 cells displayed by GCM (p <0.001) can be attributed to its cytostatic activity and induction of apoptosis by GCM / Compostos derivados de fungos tem sido alvo de muitos estudos a fim de desenvolver o conhecimento acerca de seu potencial bioativo. Polissacar?deos de Caripia montagnei j? foram descritos por possu?rem propriedades anti-inflamat?ria e antioxidante. Neste estudo, os polissacar?deos extra?dos do fungo Caripia montagnei foram caracterizados quimicamente e seus efeitos sobre as les?es intestinais foram avaliados em diferentes intervalos de tratamento no modelo de colite induzida por ?cido 2,4,6 - trinitrobenzenossulf?nico (TNBS), verificou-se ainda sua a??o sobre c?lulas do carcinoma de c?lon humano, HT-29. Na an?lise realizada no extrato obtido de C. montagnei foi verificado que este ? formado principalmente, por carboidratos (96%) apresentando um baixo teor de compostos fen?licos (1,5%) e baixa contamina??o prot?ica (2,5%). As an?lises por espectroscopia de infra vermelho (FT-IR) e resson?ncia magn?tica nuclear (RMN) mostraram que os polissacar?deos desta esp?cie de fungo s?o &#945; e &#946; -glucanas. O dano col?nico foi avaliado por an?lises macrosc?picas, histol?gicas, bioqu?micas e imunol?gicas. Os resultados mostraram a redu??o das les?es no c?lon em todos os grupos tratados com as glucanas (GCM). GCM reduziram significativamente os n?veis de IL-6 (50 e 75 mg/Kg, p < 0,05), uma importante citocina inflamat?ria. As an?lises bioqu?micas mostraram que essas glucanas atuaram na redu??o dos n?veis de fosfatase alcalina (75 mg/Kg, p < 0,01), ?xido n?trico (p < 0,001) e mieloperoxidase (p < 0,001). Estes resultados foram confirmados pela redu??o da infiltra??o celular observado microscopicamente. O aumento da atividade da catalase, sugere um efeito protetor de GCM no tecido do c?lon, o que confirma o seu potencial anti-inflamat?rio. GCM mostraram atividade citost?tica sobre as c?lulas HT-29, causando ac?mulo de c?lulas na fase G1 e impedindo, assim, a progress?o do ciclo celular. As glucanas deste estudo tamb?m mostraram habilidade em modular a ades?o de c?lulas HT-29 ao Matrigel? e reduzir o estresse oxidativo nessas c?lulas. A atividade antiproliferativa contra c?lulas HT-29 exibida por GCM pode ser atribu?da ? sua a??o citost?tica ou indu??o da apoptose por essas glucanas

Les mécanismes extensifs, matérialisés physiquement sous la forme de rifts ou de marges passives, impliquent des interactions entre les processus tectoniques, sédimentaires et métamorphiques, particulièrement quand ils sont associés à un métamorphisme de haute température. L'étude de ces mécanismes ne peut donc se faire correctement que par une approche triple afin de cerner ces différents aspects et de contraindre les interactions qui les relient. Une telle étude est difficile du fait de la profondeur à laquelle ont lieu ces mécanismes et donc de l'absence d'observation directe des objets géologiques qu'ils produisent. L'alternative consiste à étudier une paléo marge passive portée à l'affleurement. Dans le cadre de cette thèse, notre choix s'est porté sur la Zone Nord Pyrénéenne qui correspond à une paléo-marge passive mésozoïque qui a été mise à l'affleurement lors de la compression pyrénéenne à l'Éocène/Oligocène (40-20 Ma). Cette marge a subi une métamorphise HT/BP et constitue donc un bon analogue pour notre étude. Nous nous sommes concentrés en particulier sur la partie Est de la ZNP, dans la région du massif de l'Agly qui rassemble les bassins de Saint Paul-de-Fenouillet, du Bas-Agly et de Boucheville qui ont enregistré différentes intensités du métamorphisme. Le bassin de Boucheville étant le moins bien documenté mais ayant enregistré le métamorphisme le plus important, nous nous sommes attachés à le caractériser en détail. Nous avons effectué une étude structurale, stratigraphique et sédimentaire de ces trois bassins afin de bien contraindre leur géométrie et leur histoire. Nous avons couplé cette étude avec des analyses du métamorphisme, principalement par des mesures par spectrométrie Raman des températures maximum enregistrées lors de l'extension crétacée. Enfin, nous avons combiné ces résultats afin de produire des coupes restaurées de l'ensemble de notre zone d'étude. Ces coupes restaurées nous ont permis de proposer un modèle de la mise en place des bassins sédimentaires mésozoïques dans la partie orientale de la ZNP. Il apparaît au premier ordre que la zone est constituée, sur une coupe N-S, par un haut fond topographique constitué du futur massif de l'Agly, limité au nord par un détachement à vergence nord et au sud par un détachement à vergence sud. De part et d'autre de ce haut fond se mettent en place des bassins sédimentaires présentant une augmentation de l'épaisseur des dépôts au droit de ces détachements. Au seconde ordre, il faut considérer que le système n'est pas cylindrique et que le massif de l'Agly se comporte comme une zone de transfert entre une subsidence forte au nord-est dans le bassin du Bas-Agly et une subsidence forte au sud-ouest dans le bassin de Boucheville. / Extensive mechanisms induce interactions between tectonic, sedimentary and metamorphic processes, especially when they are associated with a high temperature metamorphism. Therefore, the study of these mechanisms requires a threefold approach in order to identify these processes and understand the interactions between them. Such study is hardened because of the depth of these mechanisms and the lack of direct observation. To overcome such difficulties we chose to study a paleo passive margin now visible thanks to many outcrops. For this thesis, we focused on the North Pyrenean Zone (NPZ) which happens to be a Mesozoic passive margin which outcroped during Eocene / Oligocene (40-20 Ma) Pyrenean compression. This margin recorded HT / LP metamorphism which makes it a good analogue for our study. We focused on the eastern part of the NPZ, in the Agly Massif area where are located the Saint Paul-de-Fenouillet basin, the bas-Agly basin and the Boucheville basin all of which recorded different intensity of metamorphism. The Boucheville basin is the worst documented but recorded the most metamorphism which is why we decided to study it in detail. We undergone a structural, stratigraphic and sedimentary analysis of these three basins in order to better understand their geometry and geological history. We combined this study with metamorphism analyzes mainly provided by Raman spectrometry on maximum temperatures recorded during Cretaceous extension. Finally, we synthetised these results to produce restored cross sections of our study area. Those cross sections allowed us to suggest a model for Mesozoic sedimentary basin formation in the eastern part of the NPZ. Considering first order analysis, on a N-S cross section, the area made of a shoal,the future Agly Massif. It is bordered on its northern side by a north verging detachment fault and on its southern by a south verging detachment fault. On both sides of this shoal are sedimentary basins much thicker towards these detachment faults. However, we must consider the system is not cylindrical. The Agly Massif acts as a transfer zone between two highly subsident basins, the Bas-Agly basin at its north-east and the Boucheville basin at its south-west.

Democracy purports to accurately reflect the choices of the general public. It is justly credited with the creation and expansion of modern mechanisms of redistribution. Yet, in recent decades it appears to have become more of an inhibitor than a catalyst in the pursuit of an equitable society. Those treated most unequally were not bystanders. Both in Britain and Israel, roughly two fifths of them did not support the expansion of the welfare state. This thesis shows their engagement with politics was often different than others. It observes the dynamics in a three-force triangle consisting of poor people, democracy and the welfare state. Even though historically this Triangle fuelled the movement towards progressive redistribution, the findings suggest it is no longer the pivotal engine to mitigate market inequalities. The principal beneficiaries of welfare appear to be incapable of mobilising democracy to expand it. The research indicates that poor people were alarmingly uncommitted to democracy and/or the welfare state. Although these institutions underpinned their social and political rights, many barely recognised how they serve their interests. In addition, the poor could not identify themselves as a collective, were more vulnerable to fallacies, emotions and traditions, and tended to prioritise other policy domains. This thesis challenges the operational definitions of political exclusion and illuminates the need to scrutinise and theorise the political behaviour of the underprivileged electorate. Policy-wise, a new strategy is required to revive relationships between poor people, democracies and welfare states. We should be looking at active and inclusive institutional mechanisms rather than technical solutions of postal or compulsory voting.

The number of police recorded incidents in England and Wales involving cannabis more than doubled between 2004 and 2009 even though use of the drug was in decline and official policy was geared towards tackling drugs ‘that cause most harm’(Home Office 2008). Drawing on ethnographic fieldwork carried out in a single London borough during the 12 months leading up to the 2011 riots, this research examines the place of drugs within everyday policing, focusing on the working lives of street-level police officers who are not attached to specialist drug squads. The concept of bifurcation (Garland 1996, 2001) is used to make sense of, ”a series of policies that appear deeply conflicted, even schizoid, in their relation to one another” (Garland 2001, pg. 110). Analysis of the ethnographic data shows how the ‘structured ambivalence’ of state responses is evident in relation to front-line policing, including the policing of drugs. We find that the backbone of modern policing, Response Teams, are being pulled towards a ‘classic’ style of policing where officers ‘act out’ and impose order through the visible exercise of their powers, reasserting the authority of the state. This is a far cry from officers in Safer Neighbourhood Teams who work predominantly on Community Policing efforts, adapting their working styles, engaging with community partners, and focusing on ‘damage limitation’ efforts. The thesis charts these different orientations in relation to officers’ general activities, before going onto show how they are visible in the way each team approaches drugs policing. From here it will be argued that the increase in recorded incidents involving drugs reflects the influence of New Public Managerialism and the focus on output-based targets. These performance targets were easily fulfilled by targeting low-level drugs offences, and once met, officers were free to police as they saw fit. Instead of officers evolving their practices as the organisation evolved, NPM allowed officers to stand firm and maintain their culture, policing practice, and sense of mission. The author accompanied both Response Teams and Safer Neighbourhood Teams of the Metropolitan Police Service during their shifts, and also conducted 23 interviews with officers. This research also developed new digital ethnography methods that might be utilised by ethnographers in other disciplines.

This thesis is about an organised group or ‘squad’ of young men in Port Vila, the capital of the Pacific Islands nation-state of Vanuatu, and their practices of place making in the rapidly developing context of ‘town’. The young men studied are second-generation migrants and thus first-generation born and raised ‘urbanites'. Based on twenty months of fieldwork, this thesis examines how these young men are transforming Freswota Community - the residential area in which they live - from a place with no shared and relevant social meaning into a place imbued with greater collective significance. First, I demonstrate how these young men experience themselves as ‘unplaced’, a condition which entails two aspects. They are displaced from the social structure and kinship systems within which their parents previously ordered their lives and from which they have drawn their social identity. Additionally, the young men experience themselves as marginalised from the formal education and employment structures of town. Following this, I show that it is through practices of place making, which they refer to as ‘planting roots’, that these young men are emplacing themselves in the Freswota area. ‘Planting roots’ includes such processes as developing their own shared history, naming roads, building topogeny and developing their own community social structure and social order. I argue that these processes are leading to the emergence of a new phenomenon: primary town emplacement. By coming into relationship with Freswota land, these young men are not only transforming it from virtual no-place into some place, they are also transforming themselves from ‘unplaced’ persons into emplaced ‘Freswota men’. I conclude that this is generating a new locative identity: it is now the Freswota community rather than their parents’ home island places that is emerging as their primary location of belonging and the source both of their sense of self and their social identification. A central aim of this thesis is to draw attention to the positive and creative ways in which unemployed young men, usually criticised and stigmatised as delinquents in newly and rapidly urbanising contexts, are actively engaged in developing their community and their relationships in order to live more viable and socially productive lives.