Le Bassin de Franceville situé au SE du Gabon présente une série de black shales (Formation FB) d'âge Paléoprotérozoïque (2.1 Ga) surmontant les grès de la Formation FA. Ce bassin peu déformé et non métamorphique représente une archive exceptionnelle des processus de dépôt de cette période de l’histoire de la Terre où la vie commence à se développer. En particulier, la Formation FB contient le protore d'un gisement mondial d'oxydes de manganèse exploité par la société Eramet-Comilog. L’objectif de ce travail est de préciser les conditions de formation de ce protore et de le replacer dans l’histoire du remplissage du bassin. Ce protore d'une épaisseur moyenne de 75 m est constitué de carbonates de manganèse ; il a fait l'objet d'une récente campagne de 24 forages carottés d'une profondeur moyenne de 125 m sur le plateau de Bangombé (Pl. Bangombé).A travers une approche pluridisciplinaire comprenant l'étude de ces forages et des affleurements clefs du bassin, ce travail porte sur la caractérisation i) de l'environnement de dépôt du protore et des séries qui l'encadrent (du toit du FA au toit du FB) ; ii) du mode de formation des carbonates de Mn à 2.1 Ga et iii) de l'architecture et de la répartition des hautes teneurs en Mn du protore représentant un gisement potentiel du futur.L’étude pétro-sédimentaire détaillée a permis de distinguer neuf unités (U1 à U9) au sein de la Formation FB organisées suivant un cycle rétrogradant jusqu’à U5 puis progradant jusqu’à U9. Ce découpage montre une évolution du milieu de dépôt depuis un domaine de shoreface contrôlé par des courants deltaïques (U1) évoluant vers des dépôts d’offshore restreint (U2). Ce bassin enregistre ensuite un système de chenaux-levées turbiditiques (U3) qui alimentent un réseau d'injectites reconnu sur l’ensemble du Pl. de Bangombé et qui traverse 150 m de série (U4 à U7) en affectant le protore et ainsi les teneurs en Mn. L'environnement de dépôt du protore (U5 et U6) marque l’isolement du bassin qui devient affamé et contrôlé par une sédimentation biochimique à l’origine du dépôt des carbonates de Mn. L'Unité 7 correspond à la réouverture des apports détritiques en domaine d'offshore supérieur puis en domaine de shoreface dominé par des dépôts de tempêtes et de chenaux sous-aquatiques deltaïques (U8), et enfin lagunaire (U9) dans lequel apparaissent les premiers métazoaires de l’histoire de la planète, suivant une séquence régressive.Une étude géochimique a permis de préciser les conditions de dépôt du protore qui se forme en milieu alcalin anoxique à sub-oxique. Dans ce milieu, nous montrons pour la première fois une précipitation directe des carbonates de Mn sous forme bactériomorphe induite par l'activité photosynthétique des cyanobactéries qui consomment le CO2/HCO3 et conduisant à une augmentation du pH favorable à la formation des carbonates de Mn. L'activité cyanobactérienne est conditionnée par l’absence de courants de fond qui augmentent la turbidité du milieu et stoppent cette dernière.Les corrélations diagraphiques et séquentielles permettent de préciser la répartition spatiale et temporelle du FB permettant ainsi de replacer le protore dans l’histoire tectono-sédimentaire du bassin. Une première phase syn-tectonique (U1 à U3) contrôle l’épaisseur et la mise en place de dépôts turbiditiques dans les parties subsidentes, de dépôts argileux sur les pentes et de dépôt de carbonates sur les hauts-fonds. La seconde phase post tectonique (U4 à U7) permet la mise en place de dépôts relativement isopaques, bien que le protore enregistre une subsidence plus importante au nord du Pl. de Bangombé. On observe ainsi, sur le Pl. de Bangombé, des teneurs en Mn qui augmentent vers le sud alors que l’épaisseur du protore augmente vers le NNE. Postérieurement au dépôt du FB, le protore est structuré par des failles qui le compartimentent en touches de piano limitant ainsi sa continuité sur le Pl. de Bangombé. / The Franceville Basin (2.1 Ga) in southeastern Gabon, hosts a black shale series well preserved (FB Formation) which represents an exceptional example of unmetamorphised Paleoproterozoic sediment strata. This basin includes the protore of one of the largest Mn-oxide laterite ore worldwide, mined by Eramet-Comilog. The aim of this this work is to determine formation conditions of this protore and to characterize the global sedimentary evolution of the FB Formation which include the protore. This 75 m thick protore is constituted of Mn carbonate-rich black shales which represent a potential ore deposit for the future. It was drilled, on the Bangombé plateau, during a recent campaign of 24 boreholes with an average depth of 125 m.Through multidisciplinary study on these cores and key outcrops of the basin, this work focuses on : i) the depositional environment of the Mn-protore and FB Formation ; ii) the processes of formation of the Mn-carbonates at 2.1 Ga and iii) the architecture and distribution of Mn-rich levels of the protore on the Bangombé Plateau.A detailed sedimentological and petrological study allowed us to redefine the division of the FB into nine units, named U1 to U9 from the base to the top. These units show a fine upward cycle up to U5 and a reverse coarse loop until U9. This division leads to a new interpretation to propose an evolution from a shoreface depositional environment controlled by deltaic currents (U1) to an offshore depositional environment with anoxic conditions (U2). In this basin, a system of submarine fan is developed, feeding a network of sand injections (injectites) covering the Bangombé plateau (70 km²) and with a thickness of 150 m affecting U4 to U7, including the Mn-protore. The protore depositional environment formed below the wave base limit (U4, U5 and U6) in a starved basin, controlled by biochemical sedimentation allowed the formation of Mn-carbonates. The end of starved basin, would allow the re-opening of the detrital input into the offshore basin (U7). This basin is then filled by storm bar deposits intersected by deltaic sub-aquatic channels (U8). The U9 unit corresponds to a quiet lagoon environment, allowing the multicellular organism development for the first time on the planet.A geochemical study allowed the characterization of the depositional environment of Mn-carbonates as an anoxic to sub-oxic and alkaline environment. For the first time, we showed that the manganese carbonates, present as bacteriomorph forms, are precipitated from the seawater by the mediated photosynthetic cyanobacterial activity, which allows CO2 / HCO3 depression of the environment and a local increase of pH. The cyanobacterial activity is controlled by the absence of bottom currents, which increase the detrital input. This would stop the activity of the cyanobacteria and thus would lead to the decrease of the Mn-concentration along the protore.Finally, well-log and a sequential correlation analyses allowed us to detail spatial and timing repartition of FB Formation deposit, controlled by a tectono-sedimentary model. We propose two- tectono-sedimentary phases. A first syn-tectonic phase (U1 to U3) controls the depocentres and sedimentation gaps. Turbidite coarse deposits are located in the most subsident part, clay deposits rather on the slope and carbonates on shoals. A second post-tectonic phase (U4 to U7) allows isopach deposits. The Mn-protore formed during the post-tectonic phase. However, it shows a variable thickness due to subsidence to the north of the Bangombé plateau. So, on the Bangombé plateau, Mn-contents increase towards the south, whereas the protore thickness increases towards the NNE. Moreover sand injectites decrease Mn-content in the eastern part of the Bangombé plateau and impact on the economic evaluation of the Mn-carbonates. Currently, the protore is structured by post-sedimentary faults, which lead to a non-continuity of the high Mn levels on the Bangombé plateau.

Remote sensing has transformed coral reef science in the last decades. It is now possible to audit reef health and geomorphology at global scale and very high spatial resolution. This work utilizes the vast and no-cost archive of imagery housed within Google Earth (GE). GE was used to interrogate the morphometric properties (size, shape, complexity, etc) of the components that combine to yield a reef environment (reef structures, sediment sheets, and so forth). The data populated a morphometric database for reefs globally that are partitioned by their architecture. The database has been investigated using information theory. The aim of the work is to identify whether motifs of carbonate platforms within these reef types are predictable on the basis of environmental parameters. The results are relevant to assess depositional patterns to develop rules for predicting how facies are distributed in modern systems and ancient reservoirs.

Dans ce travail, nous développons deux grands axes de recherche liés aux carbonates fondus. Le premier est l'optimisation des piles à combustible à base de carbonates fondus, avec deux approches : (i) l'amélioration de la durée de vie de la cathode grâce à des couches ultra-minces d'oxydes métalliques élaborés par la technique de dépôt de couches atomiques; (ii) la modification des électrolytes Li-K et Li-Na par addition de Cs ou de Rb. Le second est consacré à la valorisation du CO2 par sa réduction électrochimique dans les électrolytes à carbonates fondus, où nous analysons la réduction du CO2 par chronopotentiométrie et chronoamperométrie. Finalement, afin de tester les modifications subies par certains des composants analysés dans les deux premières parties, nous avons installé et adapté une configuration de cellule complète couplée à la chromatographie en phase gazeuse. Nous avons obtenu quelques résultats significatifs dans l’ensemble des approches abordées ; en ce qui concerne le point (i), nous avons constaté que TiO2 et CeO2 sont appropriés pour protéger la cathode contre la corrosion sans affecter ses propriétés électrochimiques en réduisant presque de moitié la dissolution du Ni. Les résultats obtenus pour le point (ii) sont également fructueux, car nous avons établi une méthode pour comparer deux électrolytes différents en déterminant les coefficients de diffusion des ions superoxyde et du dioxyde de carbone. Nous avons également comparé les performances de la cathode de NiO dans les électrolytes modifiés avec Cs et Rb. De ces études, nous avons constaté que l'addition de Cs améliore significativement le coefficient de diffusion de CO2 en réduisant la résistance de transfert de charge et la résistance totale à l'électrode, étant l'additif le plus prometteur testé ici. En ce qui concerne la réduction du CO2, nous avons constaté que la réaction implique des espèces adsorbées et instables et se produit en deux étapes à un électron ou une étape à deux électrons ; ainsi, il s’agit très probablement d’un mécanisme de réduction simultanée d’espèces adsorbées et dissoutes. Finalement, nous avons effectué les premiers tests sur cellule complète MCFC dans notre laboratoire, obtenant une performance et une puissance acceptables. Cependant, de petites améliorations sont encore nécessaires pour pouvoir tester les composants modifiés de cellule MCFC. / In this work, we develop two major research routes related to molten carbonates. The first one is the molten carbonate fuel cell optimization, with two approaches: (i) cathode lifetime improvement through ultra-thin layers of metal oxides deposited by atomic layer deposition; (ii) Li-K and Li-Na electrolyte modification by Cs or Rb additions. The second one is dedicated to CO2 valorization through its electrochemical reduction in molten carbonate electrolytes, where we analyze CO2 reduction by means of chronopotentiometry and chronoamperometry. Finally, in order to test some of the component modifications described in the two first parts, we installed and adapted a single-cell setup coupled to gas chromatography. We obtained some significant results in all the approaches; concerning point (i), we found that TiO2 and CeO2 are suitable for cathode corrosion protection without affecting the electrochemical properties of the electrode and reducing almost by half the dissolution of Ni. The results obtained from point (ii) are also fruitful, since we established a method for comparing two different electrolytes and obtained the diffusion coefficients of the superoxides and carbon dioxide. We also compared the performance of the state-of-the-art NiO cathode in Cs and Rb modified electrolytes. From these studies, we found that Cs addition improves significantly the CO2 diffusion coefficient and reduces the charge transfer and total resistance at the electrode, being a promising additive. Regarding CO2 reduction, after all the tests performed, we found that the reaction involves adsorbed and instable species and occurs in two one-electron steps or in two-electron unique step; thus, it follows most probably a mechanism of simultaneous reduction of the adsorbed and dissolved species. Finally, we performed the first MCFC single-cell tests in our laboratory obtaining an acceptable cell performance and output power. However, small improvements are still necessary to be able to test MCFC modified components.

Spur and groove (SaG) morphology is a common ornamentation of reef-armored Holocene carbonate platform margins. Composed of margin-normal promontories constructed of coral framestone, termed “spurs”, interleaved with similarly orientated gullies, “grooves”, this morphology varies based on a host of physical controls. Primarily, the surrounding oceanographic conditions as well as the size and shape of the platform the SaG is encompassing, directly influence the development and organization of SaG. Since grooves act as conduits for carbonate sediment transport, this study seeks to examine the relationship between SaG organization dictated by platform size and shape and how that in turn influences platform-top sedimentation. The analysis reveals trends that suggest platform shape plays a larger role than platform size in allowing highly organized SaG to develop on multiple margins around the platform. In turn, those trends would suggest these sites to have more stable platform top sediment deposits. However, many variables go in to the creation and maintenance of platform top cays. While this study enhanced the current understanding of how oceanographic conditions influence SaG development and organization, expanding on the concepts and results found in this study coupled with coring data of SaG and platform-top cays, could further link the connection between SaG and sediment transport.

A Formação Teresina, Neopermiano da Bacia do Paraná, é uma unidade estratigráfica principalmente terrígena, com algumas ocorrências de fácies carbonáticas, sendo depositada durante a última fase regressiva do mar epicontinental da bacia. O ambiente deposicional da Formação Teresina, especialmente no que se refere às suas fácies carbonáticas, ainda é alvo de debate. As fácies carbonáticas da Formação Teresina e fácies evaporíticas associadas ocorrem em toda a formação, mas são mais frequentes no norte do Estado do Paraná e no sul do Estado de São Paulo, na porção superior da unidade. Esta região constitui a área de estudo desta dissertação, que visou interpretar os processos sedimentares básicos, assim como fatores tectônicos e climáticos que influenciaram a formação destes depósitos carbonáticos e evaporíticos. Para isto, foram utilizadas informações de poços e realizados levantamentos detalhados de seções colunares, com coleta de amostras para análises petrográfìcas por microscopia óptica e microscopia eletrônica de varredura (MEV). Foram identificadas e descritas oito fácies carbonáticas e/ou evaporíticas: mudstone com conchas de ostracodes, mudstone peloidal, packstone bioclástico, wackstone bioclástico, boundstone tabular, packstone-grainstone oolítico, brecha de mudstone-chert e chert enterolítico-nodular. O sistema deposicional foi interpretado como uma rampa carbonática com zona interna alta protegida por barreiras arenosas influenciadas por ondas e correntes associadas. Nas partes mais rasas, os períodos áridos e de intensa evaporação e baixo aporte terrígeno provocariam aumento da salinidade e induziria a deposição das fácies evaporíticas de chert enterolítico-nodular e brecha de mudstone-chert. A porção intermediária corresponderia à zona protegida da ação das ondas, com águas rasas e baixa energia. Isto permitiria a deposição de sedimentos finos por decantação, que constituem as fácies mudstone com conchas de ostracodes e wackstone bioclástico. Nesta mesma porção, as condições geoquímicas da água teriam incentivado atividade microbiana, gerando as fácies mudstone peloidal e boundstone tabular. Bandas ricas em dolomita identificadas em fácies de boundstone tabular no norte do Estado do Paraná estariam relacionadas com precipitação mineral induzida por atividade microbiana. Filamentos e nanoestruturas orgânicas observadas podem corresponder a remanescentes fossilizados de extracellular polymeric substance (EPS), usados por bactérias redutoras de sulfato nos processos de precipitação da dolomita-calcita. A ação das ondas causava agitação constante da água, o que originaria a sedimentação das fácies packstone-grainstone oolítico em baixios e das fácies heterolíticas terrígenas em zona distal entre o nível de base das ondas de tempo bom e o nível de base das ondas de tempestade. Mapas de isópacas e de frequência de ocorrência de calcários elaborados a partir da integração dos dados de poços e seções colunares demonstraram aumento da concentração de calcários no flanco norte do Arco de Ponta Grossa (APG). A espessura da formação aumenta em direção ao APG. Em algumas regiões próximas ao APG, as isópacas tornam-se paralelas ao eixo desta estrutura tectônica. Os resultados obtidos sugerem que o Arco de Ponta Grossa atuou como barreira geográfica que restringiu a entrada de águas do oceano vindas do sul e influenciou a deposição das fácies carbonáticas e evaporíticas. A restrição da circulação das águas promoveu o aumento da salinidade na área imediatamente ao norte do arco. Além disso, uma provável zona de convergência de ventos paralela ao Arco de Ponta Grossa e situada ao sul da área de estudo teria dificultado a entrada de massas de ar úmido provenientes do Oceano Panthalassa vindas de sul. Isto favoreceu a instalação de condições áridas na área de estudo. O significado tectônico e climático das fácies carbonáticas e evaporíticas da Formação Teresina podem auxiliar as correlações entre a Bacia do Paraná e bacias na África, tais como as bacias do Huab e Karoo, além de contribuir para reconstruções paleogeográficas do Gondwana no final do Permiano. / The Teresina Formation, Late Permian of the Paraná Basin, is mainly composed of terrigenous sediments, with some occurrences of carbonate and evaporite facies. It corresponds to the upper portion of the last regressive phase of the Paraná Basin epicontinental sea. The depositional system responsible for the carbonate and evaporite facies of the Teresina Formation is still target of discussion. These facies occur in a huge area of the basin, but they have a greater thickness and are more frequent in the north of the Paraná State and in the southern of the São Paulo State, in the upper portion of the formation. This region constitutes the study area of this dissertation in order to interpret the depositional processes as well as the tectonic and climatic factors acting during the formation of these deposits. The study included the interpretation of data from wells, detailed description of columnar sections, with sampling for petrographical analysis under the optical and scanning electron microscopes (SEM). Eight carbonate and/or evaporite facies were identified: mudstone with ostracod shells, peloidal mudstone, bioclastic wackstone, bioclastic packestone, tabular boundstone, oolitic packstone-grainstone, nodular and enterolithic chert and mudstone-chert breccia. The depositional system was interpreted as a carbonate ramp with a protected zone by growth of oolitic sand bars and sediment transport dominated by wave action and associated currents. In the inner regions, arid periods of intense evaporation and low terrigenous input would increase the salinity, causing the deposition of enterolithic and nodular chert and mudstone-chert breccia facies. The intermediate portion corresponds to a lagoon with shallow and low energy waters, allowing the deposition of fine grained sediments recorded in the mudstone with ostracod shells and bioclastic wackstone facies. In the same portion, the hypersaline conditions of the water would have stimulated microbial activity, promoting the deposition of peloidal mudstone and tabular boundstone facies. Dolomite bands identified in the tabular boundstone facies in the north of the Paraná State are enriched in organic matter and they would be associated to mineral precipitation induced by microbial activity. Organic filaments and nanostructures may correspond to fossilized remains of extracellular polymeric substance (EPS), which are used by sulfate-reducing bacteria in the precipitation of dolomite-calcite. The wave action remobilized bottom sediments, causing constant waters agitation. This induced sedimentation of oolitic packstone-grainstone facies in shoals and the terrigenous heterolithic facies between the fair-weather and storm wave bases. Maps of isopachs and frequency of occurrences of limestones show concentration of limestones in the north flank of the Ponta Grossa Arch (PGA). The thickness of the formation increases from south to north towards the PGA. In some regions near the PGA, isopachs are parallel to the axis of this tectonic structure. The obtained results suggest that the Ponta Grossa Arch influenced the deposition of the carbonate and evaporite facies of the Teresina Formation, acting as a geographical barrier that restricted the entry of ocean waters from south. This promoted reduced terrigenous input, low water circulation and the increase of salinity in the northern flank of the PGA. Furthermore, a possible winds convergence zone, parallel to the Ponta Grossa Arch, would affected the climatic conditions in the study region during the Late Permian, difficulting the northward migration of wet air masses coming from the Panthalassa Ocean. This favored arid conditions in the study area. The tectonic and climatic significance of the carbonate and evaporite facies of the Teresina Formation have important implications for correlations between the Paraná Basin and basins from Africa, such as the Karoo and Huab basins, as well as for paleogeographic reconstructions of the Gondwana in the Permian.

Os mecanismos oxidativos pelos quais macrófagos exercem atividade microbicida permanecem em discussão, e estudos com hospedeiros animais serão essenciais para elucidar tal questão. Nesse trabalho, estudamos os mecanismos microbicidas de macrófagos in vivo comparando parâmetros de infecção nas lesões de camundongos resistentes (C57Bl/6) e suscetíveis (BALB/c) ao protozoário Leishmania amazonensis. A comparação mostrou que o controle da infecção pelos camundongos resistentes é dependente da ativação de macrófagos com expressão da enzima óxido nítrico sintase induzível, síntese de óxido nítrico e extensa nitração e hidroxilação das proteínas dos parasitas dentro dos fagolisossomos dos macrófagos. O principal agente tóxico aos parasitas parece ser derivado do peroxinitrito porque a nitração dos parasitas ocorreu na ausência virtual de células polimorfonucleares e foi acompanhada de hidroxilação. Além disso, tempol um inibidor de reações de nitração mediadas por peroxinitrito, inibiu a nitração de proteínas da lesão e aumentou o número de parasitas nelas presentes. Também, estudos com parasitas em cultura confirmaram que o peroxinitrito é citotóxico aos parasitas enquanto o óxido nítrico é citostático. O camundongo suscetível se mostrou capaz de sintetizar óxido nítrico mas o fez em estágios tardios da infecção e, provavelmente, em resposta a uma infecção secundária por bactérias. Tomados conjuntamente, os resultados indicam que o peroxinitrito e radicais dele derivados são os principais agentes leishmanicidas produzidos por macrófagos in vivo. / Macrophage oxidative microbicidal mechanisms remain debatable and their elucidation is likely to depend on studies with mammalian hosts. To examine macrophage microbicidal mechanisms in vivo, we compared infection parameters in the lesions of resistant (C57Bl/6) and susceptible (BALB/c) mice to the protozoan Leishmania amazonensis. This comparison demonstrated that infection control by resistant mice relied on macrophage activation with inducible nitric oxide synthase expression, nitric oxide synthesis and extensive nitration and hydroxylation of the proteins of the parasites inside macrophage phagolysosomes. The toxic agent to the parasite is likely to be peroxynitrite-derived because parasite nitration occurred in the virtual absence of polymorphonuclear cells and was accompanied by parasite hydroxylation. In addition, tempol, an inhibitor of peroxynitrite-mediated nitrations, inhibited protein nitration of the lesions and increased the number of parasites in them. Also, studies with parasite cultures confmed that peroxynitrite is cytotoxic to the parasites whereas nitric oxide is cytostatic. The susceptible mice were also able to synthesize nitric oxide but only at late infection time and, most likely, in response to a secondary bacterial infection. Taken together, the results indicate that peroxynitrite and derived radicals are the main leishrnanicidal agents produced by macrophages in vivo.

O objetivo do presente trabalho foi avaliar o efeito de aditivos químicos sobre as perdas de matéria seca, composição química, valor nutritivo e estabilidade aeróbia da cana-de-açúcar in natura ou ensilada. No primeiro experimento, a cana-de-açúcar foi ensilada em silos laboratoriais. O experimento foi desenvolvido em delineamento experimental inteiramente casualizado com quatro repetições por tratamento. Os tratamentos avaliados foram: L. buchneri, cal virgem e calcário em doses de 1,0 e 1,5% da MV e gesso a 1,0% da MV, diluídos em 40L de água por tonelada de massa verde. Após a abertura dos silos, foram realizadas avaliações de perdas, estabilidade aeróbia, valor nutritivo e composição química. Os tratamentos contendo fontes de CaO ou CaCO3 apresentaram maior recuperação de matéria seca e menores perdas totais e gasosas. Nesses tratamentos também foram observados menor teor de etanol e maior concentração de ácido lático e de carboidratos solúveis. Para as variáveis de valor nutritivo, as silagens tratadas com esses aditivos apresentaram alto teor de cinzas, menor teor de fibra, maior coeficiente de digestibilidade e pequena alteração da fração protéica. As silagens de cana-de-açúcar com gesso ou L. buchneri apresentaram desempenho semelhante a silagem controle para as variáveis acima mencionadas. No ensaio de estabilidade aeróbia, a silagem aditivada com 1,5% de cal virgem apresentou desempenho superior e semelhante as silagens com L. buchneri e gesso. De forma geral, durante a fase anaeróbia as silagens tratadas com fontes de CaO ou CaCO3 apresentaram desempenho superior. Entretanto, na fase aeróbia, somente o tratamento contendo 1,5% de cal virgem manteve desempenho satisfatório. O segundo experimento avaliou o tratamento em montes da cana-de-açúcar picada in natura com doses de cal virgem durante dez dias de exposição aeróbia. O experimento foi realizado em delineamento inteiramente casualizado com quatro repetições por tratamento e em arranjo fatorial 2x4 com medidas repetidas no tempo. O fatorial foi composto por dois modos de aplicação e quatro doses do aditivo (0, 0,5, 1,0 e 1,5% da MV). Durante o ensaio foram realizadas avaliações de estabilidade aeróbia, valor nutritivo e composição química. Para as variáveis de estabilidade aeróbia, a utilização de cal virgem foi efetiva em evitar o aquecimento da massa de forragem e reduzir as perdas de matéria seca. Para a avaliação químico-bromatológica, não foi constatada diferença nos teores de CHO´S entre os tratamentos. O tratamento da cana-de-açúcar com cal virgem elevou o pH e a fração mineral da forragem. Os maiores teores de proteína bruta foram observados para a forragem não aditivada, contudo os valores obtidos para os demais tratamentos estão dentro da amplitude relatada na literatura. Doses de 1,0% e 1,5% do aditivo foram efetivas em evitar a elevação nos teores de FDN e FDA da canade- açúcar. A fração hemicelulose sofreu solubilização parcial imediatamente após a aplicação do aditivo. Os maiores coeficientes de DVIVMS e DVIVMO foram observados para as doses altas do aditivo, no modo de aplicação a seco, principalmente nas primeiras horas após o tratamento. / The objective of this trial was to evaluate the effects of chemical additives over the dry matter losses, chemical composition, nutritive value and aerobic stability of green chopped and ensiled sugarcane. In the first trial, the sugar cane was ensiled in experimental silos. The trial was carried out in a completely randomized experimental design with four replicates per treatment. The treatments evaluated were: L. buchneri, CaO and CaCO3, 1.0 e 1.5% and Ca(SO4)2, 1.0% (wet basis), all of them diluted to 40L of water per ton of fresh forage. After the silos were opened, the following variables were analyzed: losses, aerobic stability, nutritive value and chemical composition. Higher recovery rates and lower dry matter losses and gaseous production were observed for the silages containing CaO or CaCO3. In these treatments were also observed lower ethanol production and higher lactic acid and water soluble carbohydrates contents. The analysis of nutritive value showed that the utilization of CaO and CaCO3 increased the ash content, diminished the fibrous portion, improved the organic and dry matter digestibility and resulted in small changes of the crude protein content. The utilization of L. buchneri and Ca(SO4)2 resulted in silages similar to the control treatment for these variables. In the aerobic stability assay, only the silage containing 1.5% of CaO maintained the best performance. The silages treated with L. buchneri or Ca(SO4)2 showed similar performance. In summary, the silages treated with CaO or CaCO3 showed the best performance in the anaerobic phase and in the aerobic assay, only the treatment containing 1.5% of CaO maintained the positive performance across both assay. In the second trial, the green chopped sugar cane was treated with doses of CaO in an aerobic assay during ten days. The trial was carried out as a completely randomized experimental design with four replicates in a factorial design with repeated measures. The factorial was composed by two application methods and by increasing doses of CaO (0, 0.5, 1.0 e 1.5% in FF). The following variables were analyzed during the assay: aerobic stability, nutritive value and chemical composition. During the aerobic assay, the treatment with CaO reduced the heating and the dry matter losses in fresh sugar cane. For the chemical composition and nutritive value, there were no differences between treatments for the water soluble carbohydrates concentration. The utilization of CaO increased the pH and ash content of forages. Higher levels of crude protein were observed for the control forage, however the utilization of CaO did not reduced significantly the crude protein value. Doses of 1.0 and 1.5% of CaO inhibited the NDF and ADF uprising contents in the fresh sugar cane. The hemicellulose portion was solubilized immediately after the addition of CaO. Higher IVDMD and IVOMD coefficients were observed for the forage treated with 1.0% of CaO applied dried, mainly during the period immediately after treatment.

Ce travail décrit la synthèse, les propriétés et la réactivité de cages moléculaires covalentes composées de deux porphyrines, synthétisées avec succès par effet template du DABCO, par CuAAC introduisant des sites périphériques triazoles permettant de contrôler la taille de la cavité grâce à différents stimuli chimiques. Ces cages se composent de porphyrines base libre ou métallées au zinc(II), à l’aluminium(III) ou au cobalt(III). La coordination réversible d’ions Ag(I) ou Cu(I) aux triazoles des cages moléculaires permet de passer d’une conformation aplatie à une conformation ouverte. La protonation des sites basiques permet l’ouverture maximale de la cage. Concernant leur réactivité, les cages aux porphyrines d’Al(III) permettent de catalyser la méthanolyse d’un triester de phosphate. Les cages aux porphyrines de Co(III) catalysent la synthèse de carbonates cycliques à partir d’époxyde et de CO2, sans formation de polycarbonates et avec une conversion totale en présence de pyridine comme co-catalyseur. Les cages bis-porphyriniques ont démontré dans ces réactions, une activité catalytique supérieure à celle des métalloporphyrines de référence. / This work describes the synthesis, properties and reactivity of porphyrinic molecular cages. The successful synthesis of these covalent cages relies on a DABCO-CuAAC templated reaction, which enables to introduce triazole as peripheral binding sites. These cages incorporate either two free base porphyrins or zinc(II), aluminium(III) or cobalt(III) metalloporphyrins. Reversible coordination of Ag(I) or Cu(I) ions to the triazoles of the cages allows to control the cavity size and to switch between a flattened and an opened conformation. Protonation of the basic sites of the cage leads to its maximal expansion. Cages with Al(III) porphyrins have shown to act as catalyst in the phosphate triester methanolysis reaction. Cages with Co(III) porphyrins catalyze the synthesis of cyclic carbonates from CO2 and epoxide without formation of polycarbonate and with total conversion upon addition of pyridine as co-catalyst. In these reactions, the bis-porphyrinic cages have shown to behave as more efficient catalysts than the metalloporphyrin monomers used as reference.

This work deals with dietary supplements intake and its impact on the performance rise and muscle mass growth of bodybuilders. Twenty-five students (bodybuilders) were chosen for the purpose of this survey; they were divided into four groups according to the dosage of creatine and other dietary supplements (proteins and maltodextrine). Changes of the measured parameters (weight; bustline; weistline; limb girth; body lipid content; creatine and urea content in the urine) were compared during the survey. The tested dietary supplements impact on the muscle mass growth was evaluated on the basis of the acquired results.

The aim of this master´s thesis was the measurement of electrical conductivity and dynamic viscosity of the electrolytes. Based on these measurements to verify Walden theorem between measured variables. Electrolytes were used on sulfolane base in combination with propylene carbonate and salt. The thesis also deals with the measuring method of dielectric properties of electrical and optical method with a refractometer. The freezing point of combination of sulfolan and propylene carbonate were determined by cryoscopy.