Os depósitos de tipo Cu-Au (Mo) pórfiro de Água Rica e Bajo de la Alumbrera, NW argentino, estão geneticamente associados às atividades do Complexo Vulcânico Farallón Negro, no Mioceno. Estes depósitos de classe mundial estão inseridos no contexto geotectônico dos Andes Centrais, Província Geológica das Serras Pampeanas Ocidentais e são do tipo Cu-Au (Mo) pórfiro, embora o depósito de Água Rica possua uma série de características epitermais e uma fase de enriquecimento supergênico. Estudos isotópicos e geocronologia de alta resolução foram propostos para os dois depósitos, objetivando investigar a fonte da mineralização e a influência crustal em sua gênese, além de idades para os pórfiros de Água Rica. Os isótopos de Pb mostram que as amostras de rocha total de Bajo de la Alumbrera são menos radiogênicas, com valores de razões muito próximos e apresentam-se menos radiogênicas do que as amostras de rocha total de Água Rica. As amostras de rocha total de Água Rica mostram maior dispersão, mas de certo modo alguma relação com o material analisado (pirita, ou rocha total). As amostras de pirita, de ambos os depósitos apresentam valores de razões similares, o que permite agrupá-las. As composições isotópicas de Pb em sulfetos e em rochas hospedeiras para os depósitos de Água Rica e Bajo de la Alumbrera indicaram que, apesar da diferença nas litologias presentes nos dois depósitos, os valores obtidos são próximos e muito homogêneos. As amostras de sulfetos de Bajo de la Alumbrera apresentam razões \'ANTPOT.206 Pb\'/ \'ANTPOT.204 Pb\', \'ANTPOT.207 Pb\'/ \'ANTPOT.204 Pb\' e \'ANTPOT.208 Pb\'/ \'ANTPOT.204 Pb\' muito próximas das razões de rocha total, porém com discreto enriquecimento em Pb radiogênico. As amostras de sulfetos de Água Rica apresentam distribuição pouco mais variável, no entanto, observa-se que as amostras de pirita de diorito e pirita do metarenito encaixante ficam próximas entre si e próximas das razões de pirita de Bajo de la Alumbrera Isto pode ser interpretado como fonte e condições de formação similar para estes sulfetos. Os isótopos de Sr e Nd obtidos e combinados com dados da literatura podem sugerir mais evidências na fonte dos magmas e fluidos para estes depósitos, onde as rochas foram divididas em grupos por afinidades isotópicas. Percebe-se que há rochas de padrão juvenil, incorporadas durante a orogenia Andina, mas também há rochas que indicam a presença de contaminação crustal, não homogênea, com variações nos valores de épsilon Nd(t) positivos e negativos. Idades de U-Pb em zircão SHRIMP-IIe nos pórfiros Trampeadero e Quebrada Seca, do depósito de Água Rica, apresentaram idades de 6,20±0,16 Ma e 5,66±0,22 Ma, respectivamente. Estas idades indicam um intervalo tempo muito curto, de cerca de 0,54 Ma, entre as intrusões que contém as mineralizações de maior teor e sendo as primeiras idades obtidas para as intrusões de Água Rica, por meio de datação por U-Pb SHRIMP em zircão. Estas idades sugerem que as intrusões associadas a mineralizações do depósito Água Rica são as mais jovens das que ocorrem na área do Complexo Farallón Negro. Uma isócrona Re-Os obtida em pirita para o depósito de Água Rica de 6,4±2,8 Ma é condizente com a história evolutiva deste depósito. Esta idade, combinada com a idade U-Pb em zircão condiz com a principal fase magmática ocorrida neste depósito e que é tida como a fase principal da mineralização. Com base nos dados, sugere-se que a gênese do depósito de Água Rica ocorreu concomitantemente aos estágios magmáticos finais de Bajo de la Alumbrera, e que esta marca as idades mais jovens para as rochas do Complexo Vulcânico Farallón Negro. Além disso, a participação crustal foi significativa durante a gênese desses depósitos, com uma componente maior no depósito de Água Rica, devido a maior interação dos fluidos magmáticos e mineralizantes com o embasamento Paleozoico. Com base neste estudo, indicamos que em zonas de subducção com baixo ângulo de mergulho, os depósitos minerais gerados podem apresentar maior interação com fluidos crustais do que aqueles em áreas de com placa de alto ângulo. / The Agua Rica and Bajo de la Alumbrera Cu-Au (Mo) porphyry-type deposits, NW Argentina, are genetically associated with the Farallón Negro Volcanic Complex, Miocene age. These world-class deposits of Bajo de la Alumbrera and Agua Rica, located into the tectonic context of the Central Andes, Geological Province of the Sierras Pampeanas, are Cu-Au (Mo) porphyry-type, although the Agua Rica deposit has a number of epithermal features and a supergene enrichment phase. Isotopic studies and high-resolution geochronology were carried out for the two deposits, aiming to investigate the source of the mineralization and crustal influence in its genesis, and ages for the Agua Rica porphyries. Pb isotopes show that the whole-rock samples from Bajo de la Alumbrera are less radiogenic than those from Agua Rica, with close ratio values. The whole-rock samples from Agua Rica show higher dispersion compared to Bajo de la Alumbrera. The pyrite samples from both deposits present similar ratios, which allows grouping them. The Pb isotopic compositions of sulfides and host rocks for the Agua Rica deposit and Bajo de la Alumbrera indicated that, despite the difference in the lithology present in the two deposits, the values obtained are close and very homogeneous. Sulfide samples from Bajo de la Alumbrera show ratios of \'ANTPOT.206 Pb\'/ \'ANTPOT.204 Pb\', \'ANTPOT.207 Pb\'/ \'ANTPOT.204 Pb\' and \'ANTPOT.208 Pb\'/ \'ANTPOT.204 Pb\' very close to the whole-rock ratios, but with a slight enrichment in radiogenic Pb. Sulfide samples from Agua Rica present variable distribution, however, the pyrite samples from diorite and from metasandstone present ratios close to the pyrite from Bajo de la Alumbrera. This ratios similarity could be interpreted as similar conditions and sources to these sulfides. The Sr and Nd isotopes obtained and combined with literature data may suggest more evidence on the source of magmas and fluids for these deposits. Rocks with juvenile pattern, incorporated during the Andean orogeny, are one group observed, but there are also rocks that indicate the presence of crustal contamination, not homogeneous, with variations in Epsilon Nd(t) positive to negative. U-Pb SHRIMP-IIe zircon ages in the porphyries Trampeadero and Quebrada Seca, from the Agua Rica deposit, presented ages of 6.20 ± 0.16 Ma and 5.66 ± 0.22 Ma, respectively. These ages indicate a short time interval between these intrusions, of about 0.54 Ma, and represent the youngest ages obtained for Agua Rica by U-Pb SHRIMP zircon. A Re-Os isochron obtained in pyrite to the Agua Rica deposit of 6.4 ± 2.8 Ma is consistent with the evolution of this deposit. This age, combined with the U-Pb SHRIMP zircon ages matches the main magmatic phase and shows that the main mineralization phase is coeval to the intrusions. Based on these data, it is suggested that the genesis of the Agua Rica deposit was coeval to the last magmatic stages of Bajo de la Alumbrera, and this marks the youngest ages to the Farallón Negro Volcanic Complex rocks. In addition, the crustal participation was significant in the genesis of these deposits, with a major component in the Agua Rica deposit, because the fluids interaction with the Paleozoic basement. Based on this study, we indicated that in flat-subduction zones, the mineral deposits generated present more significant interaction with the crustal fluids than those normal subduction zones.

Les roches vulcanogéniques de la Mine de Seival appartiennent à la Formation Hilário du Bassin de Camaquã, d’âge Néoprotérozoique. Ces roches contiennent six mines inactives avec diverses prospections de cuivre–argent. Les minéralisations semblent associées à un contrôle structurel intense du régime ruptile. La compréhension de la transformation chimique de l’hydrothermalisme associé aux paléo-contraintes est assez faible dans la région. Nous proposons de caractériser la chimie des minéraux des phases magmatiques, tardi–magmatiques et hydrothermales ainsi que de comprendre les contraintes structurales et la géochimie des veines tardives de barytine et calcite. Pour ce faire, nous avons effectué des analyses minéralogiques, et chimiques des phases magmatiques et d’altération. La chimie minérale associée à la modélisation thermodynamique a permis de caractériser l’altération comme tardi– magmatique. L’albitisation (650 à 350 °C) s’est produite en association avec une chloritisation (312 à 120 °C) et avec de la pyrite et de la chalcopyrite. Les températures les plus basses (150 à 50 °C) ont été reliées à la formation de smectite et d’inter-stratifié de chlorite/smectite et avec de la chalcocite–covellite, chalcocite–bornite ou barytine. Nous effectuons les analyses structurales des mesures de cinématique et de la direction des failles/fractures. L’analyse structurale a montré trois contraintes principales survenant dans la Mine Seival et dans le District Minier de Lavras do Sul : compression NW–SW ; compression NE–SW ; distension ENE–SWS. La contrainte NW–SE est la principale direction de contrainte associée à la minéralisation et aux filons minéralisés dans ces deux régions. / The volcanogenic rocks of the Seival Mine belong to Hilário Formation from Camaquã Basin, with ages Neoproterozoic. These rocks contain six inactive mines with various prospects of copper-silver. Mineralization are associated with intense structural control in brittle regime. Chemical transformation of hydrothermal alteration associated with paleostress is not very well understood in the region. We propose a characterization of mineral chemistry of the magmatic phases, tardi–magmatic and hydrothermal as well as understand the paleostress and geochemistry of late veins. For this, we realized analyses of mineral chemistry of magmatic and alteration phase. Mineral chemistry coupled with thermodynamic modeling allowed to characterize the alteration as tardi–magmatic. The albitization (650 to 350 °C) occurred in association with chloritization (312 to 120 °C), and with pyrite and chalcopyrite. The lowest temperatures (150 to 50 °C) were related to formation of smectite and interlayered chlorite/smectite, and with chalcocite–covellite, chalcocite–bornite or barite. We perform structural analyzes through kinematic measures and failure/fracture directions. The analysis on faults, fractures and mineralization showed three main stresses occurring in the Seival Mine and Lavras do Sul Mining District: NW–SE compression; NE–SW compression; ENE–SWS distension. The NW–SE paleostress is the main effort related to the dikes and mineralization in both areas.

La mucoviscidose est la maladie génétique la plus fréquente dans la population caucasienne. Le genre Scedosporium se situe au deuxième rang parmi les champignons filamenteux isolés des expectorations dans ce contexte. Au niveau pulmonaire, les colonisations/infections entraînent le recrutement de phagocytes qui induisent un stress oxydatif normalement délétère pour les pathogènes. Pour se défendre, ceux-ci ont développé des systèmes antioxydants, notamment diverses enzymes. Ce travail de thèse visait à étudier la réponse au stress oxydatif chez Scedosporium. Tout d’abord, la capacité à germer en présence d’oxydants a été évaluée. Par la suite, trente-trois gènes potentiellement impliqués dans la défense contre le stress oxydatif ont été identifiés. Leur expression en présence d’oxydants et en co-cultures avec des phagocytes suggère un rôle majeur, notamment pour une catalase, une peroxyrédoxine et deux thiorédoxine réductases. Par ailleurs, un mutant défectif pour un gène codant une superoxyde dismutase (SOD) pariétale et spécifique des spores a été produit. L’auranofin, un inhibiteur des thiorédoxine réductases, présente une activité vis-à-vis des Scedosporium et un effet additif avec des triazolés. Un test ELISA a été développé pour le sérodiagnostic des scédosporioses, utilisant une catalase et une Cu/Zn-SOD recombinantes. Ce test sensible et spécifique permet de distinguer les infections à Scedosporium de celles à Aspergillus fumigatus et des colonisations à Scedosporium. Au final, ces résultats indiquent un rôle majeur des enzymes antioxydantes chez Scedosporium, qui pourraient être de véritables facteurs de virulence et donc de nouvelles cibles thérapeutiques. / Cystic fibrosis (CF) is the most common genetic disease in Caucasian populations. The Scedosporium genus ranks the second among the filamentous fungi colonizing the airways of CF patients. In the respiratory tract, colonizations/infections lead to the recruitment of phagocytes which produce an oxidative stress, usually deleterious for pathogens. To defend themselves, pathogens have developed protective antioxidant systems, especially various enzymes. This thesis aimed to study the oxidative stress response in Scedosporium species. First, capacity of several Scedosporium isolates to germinate upon oxidative stress conditions was evaluated. Then, thirty-three genes potentially involved in protection against the oxidative stress were identified. Their overexpression in response to oxidants and in co-cultures with phagocytes suggested a crucial role, especially for one catalase, one peroxiredoxin and the two thioredoxin reductases. A mutant defective for the gene encoding a superoxide dismutase (SOD) anchored to the cell wall and specific for the conidia was produced. Auranofin, a thioredoxin reductase inhibitor, exhibits little anti-Scedosporium activity and an additive effect with triazole drugs. An ELISA was developed for serodiagnosis of scedosporiosis, using recombinant proteins derived from one catalase and a Cu/Zn-SOD. This sensitive and specific assay allows to differentiate Scedosporium infections from Aspergillus fumigatus infections and Scedosporium colonizations. Finally, these results indicate a crucial role of antioxidant enzymes in Scedosporium species, which could therefore be considered as virulence factors and as possible new therapeutic targets.

Le procédé de soudage par friction malaxage (FSW) entraîne, d’une manière générale, une importante chute de dureté à travers le joint soudé. Dans le but de concevoir des structures aéronautiques soudées par FSW en fatigue, il est nécessaire de connaître l’impact de cette chute de dureté dans le comportement mécanique global de la soudure. Dans ces travaux, l’alliage d’aluminium à durcissement structural 2198-T8 est considéré. Une chaîne de calcul de durée de vie en fatigue d’une structure soudée par FSW est mise en place. Elle intègre un couplage de calculs et d’expériences grâce auxquels le comportement mécanique de la structure est modélisé. Dans un premier temps, le gradient de comportement mécanique de la soudure est étudié. Des essais mécaniques de traction et cycliques sont réalisés à température ambiante. La méthode de corrélation d’images numériques (DIC) est utilisée dans le but de mesurer les champs de déplacements localement dans et au voisinage du joint soudé. À partir des résultats expérimentaux, les paramètres mécaniques d’un modèle de comportement sont identifiés à partir d’un élément de volume, zone par zone à travers le joint soudé. En parallèle, une quantification des précipités durcissants T1 (Al2CuLi) est menée dans différentes zones du joint soudé à l’aide d’un Microscope Electronique en Transmission (MET). Un lien entre l’évolution de la microstructure à travers la soudure et l’évolution des paramètres mécaniques est recherché. Le modèle de comportement mécanique est utilisé sur des calculs de structure utilisant la méthode des éléments finis pour simuler le joint soudé. En parallèle, des essais de fatigue sont réalisés sur des éprouvettes uniaxiales et cruciformes soumises à des chargements uniaxiaux et multiaxiaux. À l’aide des simulations du gradient de comportement mécanique du joint soudé ainsi que des résultats mesurés en fatigue, les paramètres d’un modèle d’endommagement sont identifiés. Ce modèle est utilisé pour prédire les durées de vie en fatigue et les zones d’amorçages de fissure pour une structure soudée soumise à des chargements multiaxiaux. / The Friction Stir Welding (FSW) process generally induces a critical hardness decrease inside the welded joint. To design aeronautical structure welded by FSW in fatigue, it is then necessary to know the impact of this hardness drop on the constitutive behaviour of the junction. In this study, the hardening structural aluminium alloy 2198-T8 is considered.A fatigue lifetime assessment loop of a welded structure is implemented. It integrates a calculations and experiments coupling which is used to model the structure’s mechanical behaviour. The gradient mechanical behaviour of the weldment is initially studied.Monotonic and cyclic mechanical tests are carried out to room temperature. Digital Image Correlation (DIC) is used to measure local displacement fields around the junction. Based on this experimental data, mechanical parameters for a constitutive model are identified on a volume element, zone by zone across the welded joint. In parallel, a quantification of the T1 (Al2CuLi) strengthening precipitates is realized in different region of the joint with a Transmission Electron Microscope. A connection between the microstructure evolution and the mechanical parameters is researched. The gradient mechanical behaviour of the joint is assessed on a 3D structure by Finite Element Analysis. Furthermore, fatigue tests are carried out on uniaxial and multiaxial loadings welded specimen. Thanks to the mechanical behaviour model and the fatigue lifetime measured, a damage model is used to predict the fatigue lifetime and the crack initiation zone for a welded structure which is subjected to higher multiaxial loads.

Ces travaux abordent, d'une part l'étude de la coordination du cuivre(II) et nickel(II) avec un ligand heptadenté tripode, et d'autre part la synthèse et la caractérisation de liquides ioniques dérivés de la bétaïne.Tout d'abord, le ligand heptadenté, le tris[(L)-alanyl-2-carboxamidoéthyl]amine (H3trenala), a été synthétisé sous forme de sel de chlorure ; ses constantes de protonation ainsi que les constantes de stabilité des complexes de Cu(II) et de Ni(II) ont été déterminées par potentiométrie. Des espèces complexes mononucléaires dans lesquels le ligand est protonné ([Cu(H5trenala)]4+, [M(H4trenala)]3+), neutre ([M(H3trenala)]2+) ou déprotonné ([M(H2trenala)]+, [M(Htrenala)]) (M = Cu2+ ou Ni2+) ont été mises en évidence. Seul le Cu(II) donne des espèces dinucléaires dans lesquels le ligand est uniquement déprotonné ([Cu2(H2trenala)]2+, [Cu2(Htrenala)]2+, [Cu2(trenala)]+, [Cu2(trenala)(OH)]). A l'état solide, deux complexes dinucléaires de cuivre(II) ont pu être isolés et caractérisés (IR, UV-Vis, masse électrospray, ATG). L'étude des propriétés catalytiques de ces deux complexes montre une faible activité vis-à-vis de la réaction d'oxydation du catéchol.La seconde partie de ce travail présente la synthèse de liquides ioniques constitués par des synthons cationiques dérivés d'ester de glycine-bétaïne {trialkyl(2-éthoxy-2-oxoéthyl)ammonium (alkyl = éthyl, n-propyl et n-butyl), N-(1-méthylpyrrolidyl-2-éthoxy-2oxoéthyl)ammonium} et des anions inorganiques {bis(trifluorosulfonyl)imide (NTf2-), dicyanamide (Dca-), tétrafluoroborate (BF4-)}. Les influences de la longueur de la chaîne alkyle portée par l'atome d'azote ammonium et de la nature de l'anion associé sur les propriétés physicochimiques telles que la densité, les températures de fusion, de transition vitreuse et de décomposition, la viscosité et les fenêtres électrochimiques, ont été déterminées. De plus, des sels fondus ont pu être générés à partir de ces cations organiques associés aux anions tetrafluoroborate, dicyanamide, hexafluorophosphate (PF6-) et perchlorate (ClO4-), et leurs propriétés physicochimiques ainsi que leurs structures cristallines ont été déterminées.Ensuite, les liquides ioniques hydrophobes sont utilisés pour l'extraction des cations métalliques [Cu(II), Ni(II), Cd(II) et Pb(II)] en phase aqueuse. Cette étude montre que les rendements d'extraction d'ions métalliques, déterminés par mesure de la concentration résiduelle en métal en phase aqueuse, dépendent de la longueur de la chaîne alkyle portée par l'atome d'azote ammonium et des propriétés chélatantes de l'anion. Les rendements les plus élevés ont été obtenus avec les liquides ioniques dont l'anion possède des propriétés chélatantes. L'étude du transfert du métal montre qu'il est dépendant de l'hydrophobicité du synthon cationique. Une augmentation de l'hydrophobicité du synthon cationique conduit à une augmentation du rendement d'extraction, tout en limitant l'échange ionique et en privilégiant une extraction par paires d'ions. Enfin, l'électrodéposition en phase liquide ionique et la désextraction liquide-liquide des ions métalliques ont été étudiées. / This work deals with copper(II) and nickel(II) complexation of a polydentate tripodal ligand and with, on a second part, the synthesis and characterization of ionic liquids derived from betaine and their use in liquid-liquid extraction.On the first part, a heptadentate ligand, tris[(L)-alanyl-2-carboxamidoethyl]amine (H3trenala), has been synthesized as its tetrahydrochloride salt; its protonation constants and the stability constants of the copper(II) and nickel(II) chelates have been determined by potentiometry. Mononuclear species with protonated, neutral, or deprotonated forms of the ligand, [Cu(H5trenala)]4+, [M(H4trenala)]3+, [M(H3trenala)]2+, [M(H2trenala)]+, and [M(Htrenala)] (M=Cu2+ and Ni2+) have been detected in all cases, while only Cu2+ gives dinuclear [Cu2(H2trenala)]2+, [Cu2(Htrenala)]2+, [Cu2(trenala)]+, and [Cu2(trenala)(OH)] species. Two dinuclear copper(II) complexes have been prepared and characterized by spectroscopic techniques (IR, UV-Vis, mass electro-spray) and thermogravimetric analysis. These two dinuclear copper(II) complexes have revealed weak catalytic activity in catechol oxidation.On the second part, a series of salts based on ethyl ester betaine derivatives[trialkyl(2-ethoxy-2-oxoethyl)ammonium or N-(1-methylpyrrolidyl-2-ethoxy-2-oxoethyl)ammonium cations] with alkyl chains [ethyl, n-propyl and n-butyl] have been synthesized. These cations generate hydrophobic ionic liquids with bis(trifluoromethylsulfonyl)imide, tetrafluoroborate or dicyanamide anions. The influence of the alkyl chain length and the chemical nature of the counteranion on physicochemical properties such as density, melting point, glass transition and decomposition temperatures, viscosity, and electrochemical window have been investigated. In addition, molten salts have been generated from these organic cations with hexafluorophosphate, perchlorate, tetrafluoroborate or dicyanamide anions. Their physicochemical properties and crystal structure have been investigated.The extraction of the different metal cations (Cu2+, Ni2+, Cd2+ and Pb2+) in aqueous solution by hydrophobic ionic liquids synthesized was performed. The extraction yields, determined by the measurements of the residual metal concentration in aqueous solution, depend not only the length of the alkyl chain of the ammonium but also on the nature of the associated anion. The most promising results are obtained with ILs whose anion has a chelating ability. The mechanism of metal transfer has been studied and was related to the hydrophobicity of the cationic synthon. Increasing the hydrophobicity of the cationic synthon leads to an increase of extraction yield, thus limiting the ion exchange and promoting ion pairing extraction. Electrodeposition in ionic liquid phase and liquid-liquid desextraction of metallic ions have also been investigated.

Os fármacos antiinflamatórios não-esteróides (FAINEs) são amplamente utilizados no combate a processos inflamatórios e dores, mas apresentam restrição de uso em razão de sérios efeitos colaterais sobre o trato gastrointestinal. A atividade biológica de complexos metálicos tem sido objeto de pesquisa de grande interesse na área de metalofármacos e compostos do tipo Cu(II)-FAINEs apresentam boa atividade antiinflamatória e efeitos colaterais reduzidos em relação aos fármacos orgânicos. Nesse trabalho, com o objetivo de contribuir para ampliar os estudos sobre o desenvolvimento de alternativas aos FAINEs, foram preparados e caracterizados complexos cobre(lI) com ibuprofeno, indometacina, naproxeno, sulindaco, meloxicam. Os compostos foram imobilizados em Hidrotalcita, um hidróxido duplo lamelar (HDL) de magnésio e alumínio (Mg/AI = 3) que é biocompatível e tem uso como antiácido estomacal. As interações dos metalofármacos com o HDL geraram materiais híbridos bioinorgânicos do tipo Cu-FAINElHDL, nos quais os complexos podem estar presentes de duas maneiras: intercalados entre as Ia meias ou adsorvidos nas superfícies externas do hidróxido duplo lamelar, dependendo do solvente utilizado. A intercalação de complexos neutros é favorecida em solvente misto álcooVamida no qual a Hidrotalcita sofre esfoliação promovida por um processo de hidrólise da amida. A estabilidade alguns dos complexos e dos materiais híbridos em condições gástricas simuladas (pH e temperatura) e as atividades antiinflamatória, analgésica e ulcerogênica in vivo dos sistemas contendo indometacina (Indo) foram investigadas. A intercalação do complexo Cu-Indo no HDL favorece sua estabilização, contribuindo para potencializar a sua atividade farmacolágica. Os materiais híbridos bioinorgânicos obtidos neste trabalho apresentam propriedades interessantes com vistas a potencial aplicação como sistemas de liberação controlada de fármacos. / Non-steroidal anti-inflammatory drugs are widely consumed to treat inflammatory diseases and pain but their clinical use are limited due to serious side-effects on the gastrointestinal tract. The bioactivity of metal complexes exhibits great interest in metal-based drug research. Cu(II)-NSAID compounds show good anti-inflammatory property and decreased side-effects compared to their organic parent drugs. This work aimed to contribute for development of alternative NSAIDs. Cu-NSAlD compounds containing the drugs Ibuprofen, Indomethacin, Naproxen, Sulindac and Meloxicam were synthesized and characterized. The compounds were also immobilized on Hydrotalcite, a layered double hydroxide (LDH) of magnesium and aluminum (Mg/Al = 3), that is biocompatible and used as stomach antacid. The interactions of the copper drugs with LDH led to Cu-NSAID/LDH- bioinorganic hybrid materiais. Two kinds of complex-LDH interactions were observed by changing the solvent: intercalation between LDH layers or adsorption on the LDH external surfaces. The intercalation of neutral complexes is favored in an alcohollamide solvent mixture where Hydrotalcite undergoes exfoliation process promoted by the amide hydrolysis. The stability of some complexes and their correspondent hybrid materials under gastric conditions (pH and temperature) and also in vivo anti-inflammatory, analgesic and ulcerogenic activities for Indomethacin (Indo)-containing systems were investigated. The stabilization of the Cu-Indo structure is promoted by intercalation of the complex into the LDH layers, contributing to increase its pharmacological activity. The bioinorganic hybrid materials here investigated also exhibit interesting properties for applications as controlled drug delivery systems.

[pt] As ligas metálicas têm sido amplamente estudadas, visando atender aplicações onde propriedades físicas e químicas diferenciadas se fazem necessárias. Nesse sentido, merecem destaque as ligas voltadas ao recobrimento de substratos metálicos, tendo-se como objetivo a proteção do substrato em ambientes corrosivos. Sendo assim, a presente pesquisa propõe abordar um método de síntese de ligas de Cu-Ni em substratos de cobre através da decomposição térmica do nitrato de níquel, e subsequentemente a redução do óxido NiO formado, mediante redução com H2 a 350 graus Celsius e tratamento térmico na mesma atmosfera a 800 graus Celsius, com tempos variados (3, 4 e 5h), para estimular a difusão do níquel produzido no interior da matriz de Cu. Os filmes serão caracterizados via microscopia eletrônica de varredura (MEV), tanto em sessões transversais, quanto panorâmico, além da difração de raios-x (DRX) com incidência rasante, visando-se identificar a liga Cu-Ni produzida. Os resultados sugerem que o processo proposto foi bem-sucedido, permitindo um amplo recobrimento do substrato e a subsequente difusão do Ni produzido, o que permitiu a identificação, em todas as amostras, da liga de interesse. As amostras selecionadas serão futuramente utilizadas para ensaios de microdureza, bem como de eletro-corrosão, sendo o comportamento medido comparando-se com o substrato puro. Espera-se que a presença do recobrimento eleve a resistência à abrasão, bem como dificultar a corrosão do cobre presente. / [en] Metal alloys has been extensively studied to light upon applications where differentiated physical and chemical properties are required. In this context, its value highlighting the alloys for the coating of metallic substrates with the objective of protecting the substrate in corrosive environments. The present work proposes to approach a method of synthesis of Cu-Ni alloys in copper substrates through the thermal decomposition of nickel nitrate and subsequently to discount the NiO oxide formed by reduction with H2 at 350 degrees Celsius and heat treatment in the same atmosphere at 800 degrees Celsius with (3, 4 and 5h) to stimulate the diffusion of the nickel produced inside the Cu matrix. The films were then characterized by scanning electron microscopy (SEM) in both cross-sectional and panoramic sessions, in addition to X-ray diffraction (XRD) with low incidence, aiming to identify Cu-Ni alloy produced. The results suggest that the proposed process was successful, allowing a wide coating of the substrate and subsequent diffusion of Ni produced, which allowed the identification in all samples of the alloy of interest. Selected samples will be used in the future for microhardness tests, as well as for electro-corrosion, and the measured behavior is compared to that observed for pure substrate. The presence of the coating is expected to raise the abrasion resistance as well as to hinder the corrosion of the copper present.

Whist copper (Cu) is an essential element for plants, when this element is present in excess quantities it can cause irreversible damage. This metal induces excessive production of reactive oxygen species (ROS), which damages organelles causing dysfunction. A possible means for the promotion of metal tolerance in plants is the adition of the element silicon (Si). The current study was conducted with the aim of evaluating the role of Si (0, 1 and 3 mmol L-1) on the morphologic, nutritional, metabolic and physiological responses of Panicum maximum cv. Tanzania under different Cu rates (0.3, 250, 500 and 750 μmol L-1). The grass was grown in a greenhouse under hydroponic conditions for two growth periods (33 and 30 days). Thirteen days after sowing, the seedlings were transplanted to a nutrient solution and supplied just with the Cu rate of 0.3 μmol L-1 and the set Si rates for 25 days. The remaining Cu rates were only added for a seven day period during the first growth stage. The second harvest took place 31 days after the first harvest. The experiment had six randomized blocks: three for yield, morphology and nutritional analyses and three for metabolic and physiological analyses. Plant yield, morphology and metabolic parameters were quantified in shoots and roots. Chlorophyll content index (SPAD values) and gas exchange parameters were determined in diagnostic leaves (DL), and Cu and Si concentrations were analysed from the DL and roots. The calculation of Cu and Si contents took into account the whole plant biomass. Plants exposed to Cu rates above 0.3 μmol L-1 showed low values of plant yield, morphologic parameters and SPAD, in both growth periods. Silicon supplied plants showed lower Cu concentration and content, and higher values of plant yield, morphlogic parameters and SPAD than the ones with no Si application. Silicon concentration and content were higher in plants exposed to excess Cu compared to those exposed to the control rate (0.3 μmol L-1). Gas exchange parameters in plants of the first growth were positively affected by Si supply and negatively affected by Cu rates. In the second growth, an eustress event was observed, in which plants exposed to stressing rates of residual Cu showed the highest values of gas exchange parameters and the lowest values of stress indicators. The activities of antioxidant enzymes were reduced with the increment in Cu rates. Silicon supply resulted in an increment in superoxide dismutase (SOD) activity. Tanzania guinea grass supplied with Si was able to better deal with Cu toxicity, showing increases in plant yield, morphologic and gas exchange parameters. Silicon supplied plants reduced their absorption of Cu and consequently, plants exposed to high Cu rates were still able to produce considerable biomass in the regrowth. / O cobre (Cu) é um elemento essencial para as plantas, porém, quando em excesso, pode causar danos irreversíveis às plantas. Este metal induz a produção excessiva de espécies reativas de oxigênio (ERO), que danificam organelas causando a disfunção delas. Uma possível maneira de aumentar a tolerância de plantas aos metais é o fornecimento de silício (Si). Um experimento foi conduzido com o objetivo de avaliar o papel do Si (0, 1 e 3 mmol L-1) nas respostas morfológicas, nutricionais, metabólicas e fisiológicas do Panicum maximum cv. Tanzânia sob doses de Cu (0,3, 250, 500 e 750 μmol L-1). Esse capim foi cultivado hidroponicamente em casa de vegetação por dois períodos de crescimento (33 e 30 dias). Treze dias após a semeadura, plântulas foram transplantadas para solução nutritiva, fornecendo-se apenas as doses de Si por 25 dias. A exposição ao cobre foi realizada apenas no primeiro crescimento das plantas e durou sete dias. O segundo corte ocorreu 31 dias após o primeiro corte. O experimento consistia de seis blocos completos ao acaso: três para avaliações de produção, morfologia e análises nutricionais e três para análises metabólicas e fisiológicas. A produção, a morfologia e o metabolismo das plantas foram quantificados na parte aérea e nas raízes. O índice de conteúdo de clorofila (valores SPAD) e as análises fisiológicas foram determinados nas lâminas diagnósticas (LD), e as concentrações de Cu e Si nas LD e nas raízes. Para o cálculo dos acúmulos de Cu e Si levou-se em consideração toda a biomassa da planta. Plantas expostas a doses de Cu acima de 0,3 μmol L-1 apresentaram menores valores de produtividade, parâmetros morfológicos e de SPAD. Plantas supridas com Si apresentaram menor concentração e acúmulo de Cu, e maiores valores de produtividade, parâmetros morfológicos e SPAD do que aquelas que não receberam o fornecimento de Si. A concentração e o acúmulo de silício foram maiores nas plantas expostas ao excesso de Cu do que nas expostas à dose controle de Cu (0,3 μmol L-1). Os parâmetros de trocas gasosas das plantas no primeiro crescimento foram afetados positivamente pelo Si e negativamente pelo incremento nas doses de Cu. No segundo crescimento, observou-se evento de eustresse em que plantas expostas à dose de Cu residual apresentaram os valores mais altos de parâmetros de troca gasosa e os valores mais baixos de indicadores de estresse. As atividades de enzimas antioxidantes foram reduzidas com o incremento nas doses de Cu. O suprimento de silício resultou em incremento na atividade da superóxido dismutase (SOD). O capim tanzânia suplementado com Si foi capaz de suportar melhor a toxicidade do Cu, mostrando um aumento na produção de biomassa da planta, e em parâmetros morfológicos e de trocas gasosas. As plantas suplementadas com Si reduziram a absorção de Cu e, consequentemente, plantas expostas a altas taxas de Cu e suplementadas com Si ainda foram capazes de produzir uma biomassa apreciável na rebrota.

Bacterial infections caused by the formation of a biofilm on the implant aftersurgery is a severe problem affecting the implants long term function and often leading to implant failure. Copper is a natural trace element found in the human body, and has recently become a possible alloying element with strongantibacterial properties. In this master thesis, copper bearing titanium alloys with different concentrations of Cu (1, 3, 5 and 10 wt.% Cu) were prepared using two different heat treatments (T1 and T2) in order to kill the bacteria and prevent the formation of biofilms causing these infections. The antibacterial performance andCu ion release rate of the Ti-Cu alloys were investigated in order to determine their applicability as a biomaterial. The results from the experimental investigations showed that the addition of Cu provided the alloys with an antibacterial effect against Staphylococcus epidermidis. The alloys with 5 and 10 wt.% Cu had improved antibacterial properties, and the alloys with highest Cu content exhibited the strongest antibacterial ability with an antibacterial rate of 42% for the 10- Cu(T2) alloy and 48% for the 10-Cu(T1) alloy, after 6 hours. The Cu ion release rate of the Ti-Cu alloys with 1, 3 and 5 wt.% Cu were far below the daily recommended allowance according to WHO, while the alloys with 10 wt.% Cu showed Cu ion release rates substantially over the daily limit. For this reason, Ti- Cu alloys with less Cu content (>10 wt.%) are recommended. Nevertheless, Ti-Cu alloys have a promising future as a medical implant with antibacterial properties.

Les nanostructures magnétiques peuvent avoir des propriétés très différentes de celles des matériaux massifs. Une des méthodes pour élaborer de petits objets est l'évaporation sur un substrat nanostructuré tel qu'une surface vicinale présentant des marches à l'échelle atomique. La compréhension des propriétés magnétiques de ces systèmes nécessite une caractérisation précise de leur structure et de leur morphologie afin d'évaluer les effets dus aux contraintes épitaxiales et aux dimensions réduites. Nous avons étudié les films de cobalt déposés sur des surfaces de Cu(1 1 11) et Cu(115) par trois techniques. Leur magnétisme a été sondé par effet Kerr magnéto-optique tandis que leur morphologie et leur structure cristallographique ont fait l'objet de mesures respectivement par microscopie à effet tunnel et EXAFS de surface. Les mesures par effet Kerr montrent une anisotropie uniaxiale magnétique avec un axe de facile aimantation parallèle aux bords de marches. L'anisotropie mesurée sur Cu(115), le substrat ayant les terrasses les moins larges, est plus importante. Les expériences de STM montrent la forte mobilité du cuivre dès les faibles taux de couverture ainsi qu'une grande évolution de la morphologie en fonction de la quantité de cobalt déposée. Grâce à l'EXAFS, nous avons montré que dès 3 monocouches (MC) de cobalt sur Cu(1 1 11) et 5 MC sur Cu(115), la structure est quasiment identique à celle observée sur Cu (001) i.e. tétragonale à faces centrées et que la présence de terrasses étroites n'engendrent pas d'anisotropie dans le plan (001). Des simulations de l'anisotropie magnétique prenant en compte les liaisons manquantes à la surface et en bord de marche (modèle de Néel) ainsi que les effets magnétoélastiques induits par la tétragonalisation de la maille montrent que l'anisotropie uniaxiale est très majoritairement due à la morphologie des films et que la distorsion de la maille de cobalt y contribue très peu.