Cette thèse porte sur la synthèse de nouveaux complexes binucléaires à ponts cyanures de type {Fe(μ-CN)Co}, qui reproduisent au sein d'une seule molécule les propriétés originales du réseau de coordination d'analogue de bleu de Prusse AxCo[Fe(CN)6]y•nH2O (A=ions alcalins), i.e. un transfert d'électron intramoléculaire thermo- et photo-induit à l'état solide. Au sein de ce travail, nous nous sommes intéressés à l'étude des propriétés physiques des paires moléculaires Fe/Co, avec l’objectif de comprendre les mécanismes du phénomène de transfert d'électrons. Le chapitre I contient les exemples les plus représentatifs des réseaux de coordination d'analogues de bleu de Prusse et de leurs analogues moléculaires Fe/Co, en se concentrant sur les techniques utilisées pour comprendre leurs propriétés photomagnétiques et les stratégies synthétiques employées pour contrôller leur dimensionnalité et obtenir ces analogues moléculaires. Les bases théoriques du transfert d'électron ainsi que la motivation de ce travail sont décrites à la fin du chapitre. Après une introduction sur l’utilisation des briques moléculaires employées au cours de ce travail à travers l’étude de leurs potentiels redox, le chapitre II est consacré à la synthèse et la caractérisation de nouveaux composés dinucléaires à ponts cyanures Fe/Co. Des études structurales, spectroscopiques, magnétiques, photomagnétiques, diélectriques et d’absorption des rayons-X révèlent qu'un transfert d’électron métal-métal peut être déclenché à l'état solide en faisant varier la température et par application de la lumière. Dans le chapitre III est présenté l'influence de l'environnement des complexes binucléaires Fe/Co, à savoir les contre-ions, sur le transfert d’électron thermo- et / ou photo-induit à l'état solide. Enfin le chapitre IV porte sur la possibilité de transférer le phénomène de transfert d'électron des paires Fe/Co étudiées de l'état solide à la solution / This thesis is dedicated to the synthesis of new dinuclear cyanido-bridged Co/Fe complexes, which mimics on a single molecule the original properties of the coordination network of Prussian Blue Analogues AxCo[Fe(CN)6]y•nH2O (A= alkaline ions), i.e. intramolecular thermal and photo-induced electron transfer in the solid state. We focus on the study of the physical properties of the simplest Fe/Co PBA, a dinuclear complex, with the hope to understand the fundamental concepts of this fascinating phenomenon. Chapter I contains the most representative examples of Fe/Co PBAs, focusing on the synthetic strategies employed in order to obtain Fe/Co PBAs of different dimensionalities and the techniques used to understand their photomagnetic properties. The theoretical background of the electron transfer phenomenon and the motivation of our work are described in the end of the chapter. After introducing the choice of the building blocks used in this work through the study of their redox potential properties, chapter II is devoted to the synthesis and the characterization of a novel dinuclear Fe/Co cyanido-bridged complex, which exhibits metal-to-metal electron transfer properties in solid state triggered by temperature and light. The ET phenomenon has been also studied by X-ray absorption spectroscopy and dielectric measurements. In Chapter III is illustrated the influence of the environment content of the dinuclear Fe/Co complexes, such as the counter ions, on the occurrence of the thermally and/or photo-induced electron transfer in solid state, thus highlighting the versatility of these molecular materials. Finally in chapter IV, the possibility of transferring the electron transfer phenomenon of the studied Fe/Co pairs from solid state to solution is investigated.

Made available in DSpace on 2014-12-17T14:07:00Z (GMT). No. of bitstreams: 1 AuristelaCM_DISSERT.pdf: 1278248 bytes, checksum: cbdcf9cab5a2fc14113da4b21bc60b64 (MD5) Previous issue date: 2011-11-28 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The mesoporous molecular sieves of the MCM-41 and FeMCM-41 type are considered promissory as support for metals used as catalysts in oil-based materials refine processes and as adsorbents for environmental protection proposes. In this work MCM-41 and FeMCM41 were synthesized using rice husk ash - RHA as alternative to the conventional silica source. Hydrothermal synthesis was the method chosen to prepare the materials. Pre-defined synthesis parameters were 100?C for 168 hours, later the precursor was calcinated at 550?C for 2 hours under nitrogen and air flow. The sieves containing different proportions of iron were produced by two routes: introduction of iron salt direct synthesis; and a modification post synthesis consisting in iron salt 1 % and 5% impregnation in the material followed by thermal decomposition. The molecular sieves were characterized by X ray diffraction XRD, Fourier transform infrared spectroscopy FT-IR, X ray fluorescence spectroscopy XFR, scanning electronic microscopy SEM, specific surface area using the BET method, Termogravimetry TG. The kinetic model of Flynn Wall was used with the aim of determining the apparent activation energy of the surfactant remove (CTMABr) in the MCM- 41 porous. The analysis made possible the morphology characterization, identifying the presence of hexagonal structure typical for mesoporous materials, as well as observation of the MCM41 and iron of characteristic bands. / As peneiras moleculares mesoporosas do tipo MCM-41 e FeMCM-41, s?o consideradas promissoras como suporte para metais, usadas como catalisadores em processos de refino de materiais a base de petr?leo e como adsorventes com o prop?sito de prote??o ambiental. Neste trabalho MCM-41 e FeMCM-41 foram sintetizadas utilizando a cinza da casca de arroz CCA, como alternativa para a fonte de s?lica. O m?todo escolhido foi a s?ntese hidrotermal para o preparo dos materiais, a temperatura de 100 ?C por 168 horas em estufa, posteriormente foi calcinado a 550 ?C por 2 horas sob fluxo de nitrog?nio e ar. As peneiras moleculares contendo diferentes propor??es de ferro foram produzidas por duas rotas: introdu??o do sal de ferro no gel de s?ntese e impregna??o de 1% e 5% de ferro no MCM-41 sintetizado. As peneiras moleculares foram caracterizadas por difra??o de raios X DRX, espectroscopia no infravermelho por transformada de Fourier (Fourier transform infrared spectroscopy FT-IR), espectroscopia de fluoresc?ncia de raios X FRX, microscopia eletr?nica de varredura MEV, ?rea superficial espec?fica atrav?s do m?todo BET e Termogravimetria TG. O modelo cin?tico de Flynn Wall foi utilizado com o objetivo de determinar a energia de ativa??o aparente da remo??o do surfactante (CTMABr) nos poros do MCM-41. As an?lises possibilitaram a caracteriza??o morfol?gica, identificando a presen?a da estrutura hexagonal t?pica dos materiais mesoporosos, assim como das bandas caracter?sticas do MCM41 e do ferro.

Le développement d’une troisième génération d’aciers Fe-Mn-Al-C à structure duplex, pour des teneurs en Mn et Al inférieures à 8 %mass, pourrait être une réponse prometteuse aux objectifs d’allègement de 20% des véhicules automobiles, tout en garantissant des propriétés de haute résistance mécanique et haute formabilité.Le choix des nuances et l’optimisation des conditions d’élaboration nécessitent de prévoir en particulier les compositions et proportions des phases existantes en fonction de la route métallurgique. Une base de données thermodynamiques fiable et précise est donc requise. Cependant les données de la littérature sur le système quaternaire Fe-Mn-Al-C, dans les domaines de composition envisagés, sont limitées.Ce mémoire est consacré à l’établissement des équilibres de phases ferrite-α, austénite-γ et carbure-κ (Fe,Mn)3AlC entre 700 et 1000°C par une approche couplée d’expériences ciblées et de modélisation thermodynamique. Pour appuyer l’évolution expérimentale des fractions de phases et des compositions, une modélisation cinétique (DICTRA) est proposée. La cinétique de formation de l’austénite en fonction de la composition de l’alliage et de la température de maintien dans le domaine intercritique a été caractérisée. Les phases en équilibre, caractérisées par DRX, MEB, microsonde, sont représentées sous forme de conodes α/γ, γ/κ, α/γ/κ, ce qui permet de définir les domaines de stabilité de l’austénite et du carbure κ. Ces données expérimentales sont utilisées pour affiner la description thermodynamique du système quaternaire mais il est nécessaire de réviser la modélisation du carbure κ. / A third generation of Fe-Mn-Al-C steels with a duplex structure, for Mn and Al contents less than 8%mass, could be a promising response to the 20% weight lightening of automotive vehicles, by keeping a high strength and a high formability.The knowledge of the corresponding quaternary phase diagram serves as a roadmap for the choice of compositions and the optimization of elaboration conditions. A reliable and precise thermodynamic database is therefore required. However, the literature data on the Fe-Mn-Al-C quaternary system in the targeted domains are limited.This study is devoted to the establishment of phase equilibria involving ferrite-α, austenite-γ and carbide-κ (Fe,Mn)3AlC between 700 and 1000°C by a coupled approach of experiments and thermodynamic modeling. A kinetic model (DICTRA) is proposed to support the experimental evolution of phase fraction and composition. The kinetics of austenite formation as a function of the alloy composition and of the maintaining temperature in the intercritical domain have been calculated. The phases in equilibrium, characterized by XRD, SEM, EPMA, are represented as α/γ, γ/κ, α/γ/κ tie-lines in order to specify the stability fields of γ and κ. These data are used to refine the thermodynamic description of the quaternary system but it is necessary to revise the modeling of κ carbide.

Dans le cadre de la nouvelle réglementation sur l'environnement, un objectif d'allègement de 20% des véhicules automobiles doit être atteint afin de répondre aux impératifs de réduction des émissions de CO2. Le développement d'une nouvelle génération d'aciers sous forme de composites à matrice acier Fe-TiB2 est d'un grand intérêt industriel et pourrait être une réponse prometteuse car il permet d'améliorer la rigidité de l'acier tout en diminuant sa densité. L'élaboration de tels produits nécessite une très bonne connaissance de la thermodynamique des équilibres de phases dans les systèmes concernés. Ce mémoire est consacré à l'étude thermodynamique de cette nouvelle famille de composite à matrice acier Fe-TiB2 et plus particulièrement à l'établissement des équilibres de phases liquide/solide et solide/solide dans le système ternaire Fe-Ti-B du côté riche en fer ainsi qu'à la définition du domaine de stabilité du diborure de titane dans les solutions Fe-Ti-B. La démarche employée est une approche couplée d'expériences ciblées (séparation électromagnétique de phases, analyse thermique différentielle, équilibre de phases) et modélisation thermodynamique des équilibres de phases. / To answer the imperatives of reduction of CO2 emissions, an objective of 20% weight lightening of automotive vehicles must be reached. Developing such innovative Fe-TiB2 composites of a great industrial interest could be a promising answer because it allows to improving the rigidity of the steel while decreasing its density. The development of such products requires a good knowledge of the thermodynamics of phase equilibria in the studied systems. This thesis is devoted to thermodynamic study of this new family of steel matrix composite Fe-TiB2 and particularly to the establishment of liquid/solid and solid/solid phase equilibria in the iron richer side of the ternary Fe-Ti-B system as well as to the definition of the stability domain of the titanium diboride in the Fe-Ti-B solutions. This task was performed by a coupled approach consisting in specific experiments (electromagnetic separation of phases, differential thermal analysis, phase equilibria) and thermodynamic modeling of phase equilibria.

Nous avons étudié par STM, SQUID, Réflectivité X, Diffraction des rayons X, absorption optique et XAS des échantillons de Fe(phen)2(NCS)2 et Fe{[3,5-dimethylpyrazolyl]3BH}2 déposé par évaporation thermique sur des substrats de Cu(100), Co(100) et SiO2, et comparé avec des échantillons en poudre. Nous avons confirmé l'existence de l'effet de piégeage d'état de spin induit par les rayons X (SOXIESST), et étudié ses propriétés, en particulier dynamiques. Celui-ci dépend de l'intensité et de la structure du faisceau X appliqué, et est non-résonant. Nous suggérons que son efficacité est influencée également par les états de transfert de charge métal-ligand (MLCT). L'étude des molécules isolées a montré que l'on pouvait les faire transiter par une impulsion électrique, et construire ainsi des dispositifs memrésistifs, mais seulement si l'influence du substrat est suffisamment réduite. À l'aide d'un modèle thermodynamique simple, nous avons alors étudié les couches minces et montré que la coopérativité est réduite et que la température de transition est modifiée (plus grande pour la Fe-phen, plus faible pour la Fe-pyrz). Enfin, nous utilisons ces résultats pour construire des dispositifs multicouche verticaux Au/Fe-phen/Au dont les propriétés électriques, d'après nos résultats préliminaires, sont dépendantes des stimuli extérieurs (température, champ magnétique). Notamment, ils présentent un effet « diode » à la transition de spin. / We have studied by STM, SQUID, X-ray reflectivity, X-ray diffraction, optical absorption and XAS Fe(phen)2(NCS)2 and Fe{[3,5-dimethylpyrazolyl]3BH}2 samples deposited by thermal evaporation on Cu(100), Co(100) and SiO2 substrates, and compared with results on powder samples. We have confirmed the existence of the soft X-ray induced excited spin state trapping (SOXIESST), and investigated its properties, in particular dynamic aspects. The effect is sensitive to the intensity and the structure of the applied X-ray beam, and is non-resonant. We suggest that its efficiency is also governed by metal-ligand charge transfer states (MLCT). The study of single molecules has revealed that they could be switched by voltage pulses, and by this way building memristive devices, but only if the influence of the substrate is sufficiently reduced. We have then investigated thin films with the help from a simple thermodynamic model, and evidenced that the cooperativity was reduced and the transition temperature is modified (higher for Fe-phen, and lower for Fe-pyrz). Finally, we use these results to build multilayer vertical devices Au/Fe-phen/Au, and its electrical properties depends, according to our preliminary results, on the external stimuli (temperature, magnetic field). Notably, they present a “diode” effect at the spin transition.

Orientadores: Roberto Perez Xavier, Lena Virginia Soares Monteiro / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociencias / Made available in DSpace on 2018-08-14T22:53:15Z (GMT). No. of bitstreams: 1 Torresi_Ignacio_M.pdf: 10387814 bytes, checksum: 10ae1f36fa8d66f6046d5f1bb6d6a4aa (MD5) Previous issue date: 2009 / Resumo: O depósito de óxido de ferro-cobre-ouro (IOCG) Alvo 118 (170 Mt @ 1,0 wt% Cu, 0,3 g/t Au), junto aos depósitos de classe mundial de Sossego e Cristalino, situam-se no setor sul da Província Mineral de Carajás (PMC) alinhados e uma zona de cisalhamento subvertical regional, de direção WNW-ESE, e 60 km de extensão, próximo ao contato do Supergrupo Itacaiunas, uma sequência metavulcano-sedimentar (~2,76 Ga), com o embasamento arqueano (Complexo Xingu; ~3,0 Ga). A mineralização de Cu-Au no deposito Alvo118 e hospedada por rochas vulcanicas máficas e intermediarias, corpos de granitos e gabbros, que foram sujeitos a seguinte sequência de alteração hidrotermal em direção ao minério de Cu: (1) alteração sódica representada por albita e escapolita, o que indica circulação de fluidos quentes (>500°C) e salinos; (2) alteração potássica dominada pela presença de biotita e k-feldspato, respectivamente, nas rochas máficas e intermediarias, acompanhada de formação de magnetita e silicificação; (3) alteração a clorita, espacialmente associada brechas quartzo-carbonaticas mineralizadas a calcopirita e stockworks de veios que normalmente apresentam estruturas de preenchimento de espaço; (4) alteração a quartzo-sericita tardia a mineralizacao. A assembléia mineral da mineralizacao e dominada por calcopirita (80%), acompanhado de bornita (10%), magnetita (10%), hematita (10%), e traços de teluretos de Au-Ag, galena e cassiterita. Diferente de outros depósitos do tipo IOCG da PMC, onde ETRL estão presentes em apatita, allanita e monazita, no Alvo 118 o enriquecimento e em ETRP. Neste deposito os ETRP estão concentrados principalmente em apatite e em um mineral pobre em alumínio, um silicato de Be-B-ETRP do grupo da gadolinite, que nunca foi descrita em qualquer deposito do tipo IOCG do mundo. Estudos de inclusões fluidas em quartzo e calcite apontam pra um regime de fluidos, em que soluções hipersalinas e quentes, representada por inclusões trifásicas, fossem progressivamente esfriadas e diluídas por fluidos de baixa salinidade, representada por inclusões bifásicas, que dominam na mineralizacao do Alvo 118. Valores de d18OH2O em equilíbrio com calcita (-1.9¿ a 10.7¿ a 300°C) sugerem forte interação entre os fluidos mineralizantes e as rochas hospedeiras, como também prolongada mistura com fluidos meteóricos. A composição de d34S em calcopirita (5.1¿ a 6.3¿) difere daquela de fonte mantélica/magmática, reforçando a possibilidade de fontes de enxofre mais pesado (sulfatos de evaporitos?) para os sulfetos da brecha e dos veios mineralizados. A alteração sódica de alta temperatura, a sobreposição de alteração potássica e a alteração a clorita proximal, a brecha de quartzo-carbonatica mineralizada e os valores de d18O indicam que o Alvo 118 e um sistema IOCG que evoluiu em níveis estruturais superiores, nível crustal raso, envolvendo o influxo de águas meteóricas. / Abstract: The Alvo 118 iron oxide-copper-gold (IOCG) deposit (170 Mt @ 1,0 wt% Cu, 0,3 g/t Au), together with the world-class Sossego and Cristalino deposits, lie in the southern sector of the Carajas Mineral Province (CMP) along a steeply-dipping, WNW-ESE-striking, 60 km-long shear zone, close to the contact of the Itacaiunas Supergroup metavolcano-sedimentary sequence (~2,76 Ga) and the basement (Xingu Complex; ~3,0 Ga). The Cu-Au mineralization at the Alvo 118 is hosted by mafic and felsic metavolcanic rocks and crosscutting granitoid and gabbro bodies that have been subjected to the following hydrothermal alteration sequence towards the ore zones: (1) sodic alteration represented by albite and scapolite, indicating the circulation of hot (>500°C) and highly saline fluids; (2) potassium alteration dominated by biotite or Kfeldspar, respectively, in mafic and felsic volcanic and intrusive rocks, accompanied by the formation of magnetite and silicification; (3) chlorite alteration spatially associated with carbonate-quartz ore breccia and vein stockworks that commonly display open-space filling textures; (4) local post-ore quartz-sericite alteration. The ore assemblage is dominated by chalcopyrite (80%), accompanied by bornite (10%), magnetite (10%), hematite (10%), and traces of Au-Ag tellurides, galena and cassiterite. Dissimilar from other IOCG deposits of the CMP where LREEs are commonly enriched in apatite, allanite and monazite, the Alvo 118 ore displays enrichments of HREEs. In this deposit the HREEs are mainly concentrated in apatite and in an Al-poor, Be-B-HREE silicate of the gadolinite group which has never been reported in IOCG systems worldwide. Fluid inclusion studies in quartz and calcite point to a fluid regime in which hot brine solutions, represented by < 10 vol.% of salt-bearing aqueous inclusions, were progressively cooled and diluted by lower temperature, low-salinity (< 10 wt% NaCl eq.) aqueous fluids defined by two-phase aqueous inclusions, by far the dominant type. d18OH2O values in equilibrium with calcite (- 1.9¿ to 10.7¿ at 300°C) suggest strong interaction between ore fluids and the host rocks, as well as prolonged mixing with meteoric fluids. The d34S composition of chalcopyrite (5.1¿ to 6.3¿) differs from a mantle/magmatic source adding the possibility of heavier sulfur sources (e.g., evaporite sulfate?) for the ore breccia and vein sulfides. The restricted high temperature sodic alteration, the pervasive overprinting of the potassic alteration minerals (biotite and K-feldspar) by chlorite proximal to the ore zones, quartz-calcite-chlorite ore breccias/veins with open-space filling textures in brittle structures, and the d18O data collectively indicate that the Alvo 118 IOCG system developed at structurally high levels and experienced the influx of evolved meteoric water. / Mestrado / Mestre em Geociências

Made available in DSpace on 2016-08-19T12:56:36Z (GMT). No. of bitstreams: 1 MIRELA GHISI.pdf: 1324849 bytes, checksum: 5d9ca5c5a49c366f3bf4959e2e942a14 (MD5) Previous issue date: 2011-05-16 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / The metals content in biodiesel is directly related with the raw material used and also with the utilized biodiesel production method. In this work, an evaluation of the main metals present in biodiesel samples from different sources was done. The qualitative analysis of the metal content was assessed using the Inductively Coupled Plasma Mass Spectrometry technique after sample digestion in microwave oven. The main metals identified in the analyzed biodiesel samples were Al, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr and Zn. Metals like Ag, As, Ba, Cd, Co, Tl and V have not significant presence in the samples. Among these, Cu and Fe were selected due to their relevance and importance in oxidative process of biodiesel, to the development of an analytical methodology to be used in the determination by Electrothermal Atomic Absorption Spectrometry, and also evaluate the effect of these metals over the oxidative stability of the soy biodiesel. The samples were prepared with tetramethylammonium hydroxide (TMAH), and the pyrolysis and atomization temperatures were optimized pyrolysis and atomization curves. The high pyrolysis temperature adopted, 1000 oC, certainly minimized potential interferences, but calibration had to be carried out with aqueous standard solutions in the presence of the TMAH. The detection limits in the sample (3s, n=10), were quite low 15 ng g-1 and 24 ng g-1 for Cu and Fe, respectively. Seven biodiesel samples, produced from different raw materials, including vegetable seed, waste frying oil and animal fat were analyzed. Accuracy was validated by applying the recovery test (recoveries from 105% to 120%) and through comparison with the obtained results by High Resolution Continuum Source Electrothermal Atomic Absorption Spectrometry. The precision, expressed by the relative standard deviation, was better than 3% for Cu and than 7% for Fe. Copper could be quantified in two and Fe in three of the seven samples. The biodiesel sample from fodder turnip was especially rich in the analytes in comparison to the other samples. The influence of metals Cu and Fe on soy biodiesel oxidative stability was evaluated by Rancimat method through induction period, according with the Standard EN 14112. The metals Cu2+ and Fe3+ were added to the biodiesel samples in the form of theirs salts, and different storage times of the samples were evaluated. Due to the catalytic behaviour of these metals, the oxidative stability of the samples was affected, even under low metal concentrations. Compared to Cu2+, the effect over the biodiesel stability was higher when Fe3+ was added. / A presença de metais no biodiesel está diretamente relacionada com a matéria-prima utilizada e também com o processo utilizado para a obtenção do biodiesel. Neste trabalho realizou-se uma avaliação dos principais metais presentes em amostras de biodiesel provenientes de diferentes fontes. A análise semi-quantitativa nas amostras de biodiesel foi realizada utilizando a técnica de Espectrometria de Massa com Plasma Indutivamente Acoplado após a digestão das amostras em micro-ondas. Os principais metais identificados nas amostras de biodiesel analisadas são Al, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr e Zn. Metais como Ag, As, Ba, Cd, Co, Tl e V não estão presentes em concentrações significativas nessas amostras. Em função de sua relevância e importância em processos oxidativos do biodiesel, selecionou-se Cu e Fe para o desenvolvimento de uma metodologia analítica para a determinação destes por Espectrometria de Absorção Atômica com Atomização Eletrotérmica e também a avaliação do efeito destes metais sobre a estabilidade oxidativa do biodiesel de soja. As amostras foram preparadas com hidróxido de tetrametilamônio (TMAH), e as temperaturas de pirólise e atomização foram otimizadas através de curvas de pirólise e atomização. A alta temperatura de pirólise adotada, 1000 oC, certamente ajudou a minimizar possíveis interferências; porém, a calibração teve de ser realizada com padrões aquosos na presença de TMAH. Os limites de detecção (3s, n = 10), na amostra, foram baixos, 15 ng g-1 e 24 ng g-1 para Cu e Fe, respectivamente. Sete amostras de biodiesel, produzidas de diferentes matérias-primas, incluindo óleos vegetais, óleo de fritura e gordura animal foram analisadas. A exatidão foi avaliada através do teste de recuperação (recuperações de 105% a 120%) e através da comparação com os resultados obtidos por Espectrometria de Absorção Atômica de Alta Resolução com Fonte Contínua e Atomização Eletrotérmica. A precisão, expressa pelo desvio padrão relativo foi melhor que 3% para Cu e que 7% para Fe. Cobre pôde ser quantificado em duas e Fe em três das sete amostras. A amostra de biodiesel proveniente do nabo forrageiro era especialmente rica nos analitos comparada às outras amostras. A influência dos metais Cu e Fe sobre a estabilidade oxidativa do biodiesel de soja foi avaliada pelo método Rancimat através do período de indução, de acordo com a Norma EN 14112. Os metais Cu2+ e Fe3+ foram adicionados nas amostras de biodiesel na forma de seus sais, e foram avaliados diferentes tempos de armazenamento das amostras. Devido ao efeito catalítico destes metais, a estabilidade oxidativa das amostras analisadas foi reduzida mesmo na presença de baixas concentrações dos metais. O efeito do Fe3+ sobre a estabilidade do biodiesel foi significativamente maior quando comparado ao Cu2+.

[pt] A presente Dissertação de Mestrado consiste na análise do problema filosófico de Deus na obra do espanhol Xavier Zubiri (1898-1983). Em sua compreensão da inteligência humana, Zubiri descobre a realidade não como o existente ou o além da intelecção, mas como a formalidade na qual as coisas ficam atualizadas na inteligência. Assim, o homem se realiza na realidade, que tem um caráter de fundamento último, possibilitante e impelente, e à qual o mesmo se encontra religado pelo poder do real. Mas a realidade não é nenhuma das coisas reais, e nos lança a buscar e inteligir o fundamento do poder do real, a realidade absoluta na qual se funda a realidade das coisas reais: Deus. Assim, o problema de Deus não é um problema que o homem poderia ou não se propor, mas uma dimensão de nossa realidade: a dimensão teologal. / [es] La presente Tesis de Master consiste en la análise del problema filosofico de Dios en la obra del español Xavier Zubiri (1898-1983). En su compreensión de la inteligencia humana, Zubiri descubre la realidade no como lo existente ou lo allende la intelección, sino como la formalidad en que las cosas quedan actualizadas en la inteligencia. Entonces, el hombre se realiza en la realidad, que tiene um caracter de fundamento último, posibilitante e impelente, y a la cuál el mismo se encuentra religado por el poder del real. Pero la realidad no és ninguna de las cosas reales, y nos lanza a buscar y inteligir el fundamento del poder del real, la realidad absoluta en la cuál se funda la realidad de las cosas reales: Dios. Entonces, el problema de Dios no és un problema que el hombre podría o no plantearse, pero una dimensión de nuestra realidad: la dimensión teologal.

Over the past few decades, inorganic nanostructured materials have elicited a lot of interest due to their high surface-to-volume ratio and many size dependent properties which stem from their nanoscale dimensions. Owing to these distinct properties, they have found applications in widespread fields like catalysis, energy storage, electronics, and biotechnology. In the field of biotechnology, nanotubes and mesoporous materials are attractive vehicles for drug delivery because of their hollow and porous structures and facile surface functionalization. Their inner void can take up large amounts of drug as well as act as gates for the controlled release of drug. These hollow structures can also be used for confining biomolecules like proteins and peptides. The study on protein conformation in biocompatible materials is very important in materials sciences for the development of new and efficient biomaterials(sensors, drug delivery systems or planted devices). Titania(TiO2)has been widely explored for applications in photovoltaic cells, batteries, desalination, sensing, and photocatalysis, to name only a few. The work presented in this thesis focuses on titania based nanostructures for drug delivery and protein confinement. First part of the work focusses on synthesis and characterization of Fe-doped TiO2 nanotubes. Fe-doped TiO2 nanotubes were demonstrated as controlled drug delivery agents. In vitro cytotoxic effects of Fe-doped titania nanotubes were assessed by MTT assay by exposing Hela cell line to the nanotubes. Second part of the work focusses on synthesis and characterization of TiO2 nanotubes by two synthesis procedures, namely hydrothermal and sol-gel template synthesis. Myoglobin, a model globin protein was encapsulated in hydrothermally synthesized TiO 2 nanotubes(diameter 5 nm) and sol-gel template synthesized TiO2 nanotubes(diameter 200 nm). Effect of encapsulating myoglobin these nanotubes was studied. The electrochemical activity and structure of myoglobin were studied by cyclic voltammetry and circular dichroism respectively. Direct electron transfer was found to be enhanced upon confinement in 200 nm diameter nanotubes. No such enhancement was observed upon encapsulation in hydrothermally synthesized nanotubes. In addition to this, the thermal stability of myoglobin was found to be enhanced upon confinement inside 200 nm diameter TiO 2 nanotubes.

O cinturão Fíngoè é uma unidade tectônica do Supercontinente Gondwana Oeste composta por rochas supracrustais formadas há aproximadamente 1.33 Ga. Essas rochas são portadoras de mineralizações de Au, Cu, Zn, Pb e Fe. Com cerca de 150 km de comprimento, e orientado WSW-ENE, este cinturão estende-se desde o Monte Atchiza a oeste até cerca de 30 km para leste da vila de Fíngoè no norte de Moçambique e consiste de uma extensa variedade de rochas metassedimentares e metavulcânicas. O cinturão Fíngoè apresenta especialização metalogenética para Au e Cu, que já foram explotados no passado em diversos locais. Muitos destes registros estão associados com magnetita e malaquita. Atualmente trabalhos de prospecção e pesquisa mineral têm sido realizados pela empresa de mineração African Queen Mines Ltda, através do projeto denominado de King Solomons, localizado na parte central do mesmo. A geologia da área abrangida pelo prospecto Mankombiti, mostra uma predominância de rochas carbonáticas, granitos e gabros. As rochas carbonáticas são consideradas importantes na gênese de depósitos tipo skarn e depósitos de substituição de metais de base e Au devido à sua natureza fortemente reativa. Os dados geocronológicos realizados neste trabalho indicaram uma idade precisa para a rocha intrusiva granítica associada à mineralização de 1079,1 ± 8,2 Ma, que poderia ser a idade da formação do skarn e consequentemente desta mineralização. Entretanto a idade obtida para o processo de alteração hidrotermal que afetou o gabro, na ordem de 657 ± 36 Ma e a idade modelo Pb-Pb sugerida pelo modelo de Stacey e Kramers (1975) para a calcopirita da mineralização principal de 725 Ma, sugerem que a mineralização, do prospecto Mankombiti é neoproterozóica. Para melhor entendimento dos processos que estiveram envolvidos na formação deste depósito skarn, duas hipóteses são consideradas: (i) poderia ser admitida a presença de corpos graníticos intrusivos em 700 Ma, situados em profundidade, que não foram ainda caracterizados, como responsáveis pela fonte de calor necessária, (ii) pode ser admitida ocorrência de um evento distensional em 700 Ma que produziria um adelgaçamento da litosfera e a consequente ascensão da astenosfera, produzindo uma elevação do fluxo térmico gerando os fluidos mineralizantes necessários. / The Fíngoè belt is a tectonic unit of West Gondwana Supercontinent, comprised of supracrustal rocks formed at approximately 1.33 Ga. These rocks are carriers of Au, Cu, Zn, Pb and Fe mineralization. With about 150 km long and oriented WSW- ENE, this belt extends from west of the Atchiza Mount to about 30 km east of the Fíngoè village in the north Mozambique, and consists of an extensive variety of metasedimentary and metavolcanic rocks. The Fíngoè metallogenic belt provides specialization for Au and Cu, which have been exploited in the past in various locations. Many of these records are associated with magnetite and malachite. Currently, the prospecting and mineral exploration have been conducted by the African Queen Mines Ltd mining company, through a project called the King Solomons, located in the central part of it. The geology of the studied area shows a predominance of carbonate rocks, granites and gabbros. The carbonate rocks are considered important in the genesis of the skarn deposits type and deposits of replacement for base metals and Au due to its highly reactive nature. The geochronological data performed in this work indicate a precise age of the 1079.1 ± 8.2 Ma for the intrusive granitic rock associated with mineralization, which could be interpreted as the age of the skarn and consequently of the mineralization. However the age obtained for the hydrothermal alteration that affected the gabbro at about 657 ± 36 Ma and the Pb-Pb model age suggested by the model of Stacey and Kramers (1975) for primary chalcopyrite mineralization at 725 Ma, suggesting that the mineralization of the Mankombiti prospectus was developed during the Neoproterozoic time. For understanding the processes that were involved in the skarn-type mineralization processes, two hypotheses are here considered: (i) could be admitted the presence of i ntrusive granitic rocks at 700 Ma, situated in depth, which have not yet been characterized, as responsible for the heat source required, (ii) may be admitted occurrence of an extensional event at 700 Ma to produce a thinning of the lithosphere and the uplift of the asthenosphere, producing high thermal flows generating the mineralization fluids.