L’étude de l’adsorption et de la mobilité des ions dans les argiles est importante pour mieux appréhender de nombreux processus géochimiques et environnementaux, de même que pour prédire le comportement des radionucléides dans les conditions du stockage géologique. A cause de leurs tailles très petites (< 2μm), il n’est pas toujours évident d’étudier les argiles à l’aide des méthodes et techniques expérimentales existantes. L’une des alternatives à ce problème consiste alors à utiliser la modélisation moléculaire pour les étudier. En plus de leurs tailles fines, les argiles présentent également des structures complexes, qui peuvent survenir en raison de la multiplicité de possibilités de distributions et d’arrangements des substitutions isomorphiques dans leurs couches. Il a été clairement démontré qu’il existe une corrélation entre la distribution des substitutions dans les couches des argiles et les propriétés de ces dernières. En revanche, ceci reste à démontrer en ce qui concerne l’arrangement de ces substitutions dans les couches de l’argile. Dans ce travail, la modélisation moléculaire est utilisée pour déterminer et comparer les propriétés d’hydratation, ainsi que la structure et la mobilité des ions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ni²⁺, UO₂²⁺) et de l’eau dans l’espace interfoliaire de trois modèles de montmorillonite, différents entre eux par l’arrangement des substitutions isomorphiques dans les couches de l’argile.L’adsorption et la diffusion des cations cités plus haut et de l’eau sont également étudiées à la surface de la montmorillonite et les résultats sont comparés à ceux obtenus dans l’espace interfoliaire à 298 K et à 363 K. Les résultats obtenus dans ce travail s’accordent bien avec les observations expérimentales, et font ressortir une corrélation plus ou moins importante entre le modèle d’argile utilisé et le type de propriété calculée. Cette corrélation dépend également de la nature du cation présent dans la structure de la montmorillonite et de sa teneur en eau. / The study of adsorption and ion mobility in clay minerals is important for a better understanding of many geochemical and environmental processes, as well as to predict the behavior of radionuclides in geological storage conditions. Because of their very small size (<2μm), it is not always easy to study clays by using the existing experimental methods and techniques. One alternative to this issue is to use computational molecular modeling to carry out clay studies. In addition to their tiny size, clays minerals also have complex structures, which can appear due to various possibilities in the distribution and arrangement of isomorphic substitutions in their layers. It has been clearly demonstrated that there is a strong correlation between the distribution of substitutions in the clay layers and their properties. However, this remains to be shown regarding the arrangement of the substitutions in the layers of the clay. In this work, computational molecular modeling techniques are used to determine and compare the hydration properties, as well as the structure and mobility of ions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Ni²⁺,UO₂²⁺) and water in the interlayer space of the three models of montmorillonite, that differ from each other by the arrangement of isomorphic substitutions in the clay layers.The adsorption and diffusion of the previously listed cations and water are also studied on the surface of montmorillonite clay and the results are compared to those obtained in the interlayer space both at 298 K and at 363 K. The data generated in this work agree well with experimental observations, and show a more or less significant correlation between the clay model used and the type of property calculated.

Les mélanges de ciment sulfoalumineux et de ciment Portland sont des liants hydrauliques innovants permettant de moduler les propriétés des bétons, telles que la vitesse de montée en résistance ou la stabilité dimensionnelle. Les performances du liant peuvent ainsi être ajustées pour de nombreuses applications. Au-delà de cet avantage, les émissions de dioxyde de carbone liées à la production du ciment sulfoalumineux sont significativement réduites comparées à celles du ciment Portland traditionnellement utilisé. La diversité des propriétés de ces liants résulte de la variété des mélanges pouvant être réalisés à partir des deux constituants de base. Chaque mélange présente alors une cinétique d'hydratation et des propriétés qui lui sont propres. Par exemple, certains liants sont expansifs mais présentent une montée en résistance progressive, tandis que d'autres sont stables dimensionnellement alors que leur résistance stagne après quelques jours d'hydratation. L'identification et le contrôle des paramètres à l'origine de ces comportements sont donc nécessaires pour garantir des propriétés spécifiques à un usage donné : chape, mortier de réparation, élément préfabriqué, etc. C'est l'objectif de cette étude qui s'attache à déterminer la cinétique, la minéralogie et les propriétés associées à l'hydratation de trois mélanges contenant 85 %, 70 % et 40 % de ciment Portland. Les essais entrepris ont aussi permis d'aboutir à une modélisation thermodynamique des mécanismes d'hydratation. L'impact de la composition du ciment Portland est également étudié. Enfin, il est montré que l'anhydrite et la chaux sont deux leviers qui modifient radicalement le processus d'hydratation et permettent ainsi d'adapter les propriétés d'un mélange aux exigences de son utilisation / Blends of ordinary Portland cement and sulfoaluminate cement are innovative hydraulic binders allowing control of concrete properties such as hardening speed or dimensional stability for specific applications. Moreover, carbon dioxide emissions linked to sulfoaluminate cement are significantly reduced compared to ordinary Portland cement. The binder properties can be adjusted due to the diversity of blends conceivable with these two constituents. Each blend has its own hydration kinetic and properties. For example, some blends are expansive and the hardening is progressive whereas other mixtures are dimensionally stable but their strength stagnates after few days. Identification and control of the parameters responsible of these comportments are necessary in order to guaranty specific properties for each application: screed, repairing mortar, etc. This is the aim of this study which described the hydration kinetic, the properties and composition of three blends containing 85 %, 70 % and 40 % of Portland cement. These experiments are completed by thermodynamic modeling of the hydration mechanisms. The effect of the Portland cement composition has also been tested. Finally, it's shown that anhydrite and calcium hydroxide are two key parameters which modify radically the hydration process and allow the properties adjustment required for the blend used

Water is “the matrix of life” for its fascinating properties. The well-known simple water molecule consists of one oxygen atom and two hydrogen atoms, covering most of planet earth’ssurface. It is the most studied element in science; however, its properties are still not fully understood. Another essential building block of life is proteins, which manifest naturally in aqueous environments. The protein activity is controlled by the protein folding process that is dependent on the surrounding environment. It is hypothesized that the hydrogen bond network of water plays an important role in the folding process. Here, we investigate the protein lysozyme in liquid water as well as in the crystalline state ice Ih, exploring various temperatures, using FT-IR and XRD. Our main finding is that a transition occurs at approximately T=210 K, indicative of the hypothesised protein dynamic “glass” transitionobserved by previous studies in supercooled water at similar temperatures.

Atualmente doenças ocupacionais manifestadas nas mãos, como hiperqueratinização, escamação, desidratação e fissuras profundas são frequentemente relatadas por profissionais como médicos, enfermeiros, dentistas, mecânicos e donas de casa. O uso frequente de luvas e o contato constante com substâncias químicas como detergentes e sabões são as principais causas. O tratamento é feito pelo uso de corticóides tópicos, o que a longo prazo pode causar aumento das infecções no local de aplicação, devido ao efeito colateral de inibição do sistema imune destes fármacos. Isto exposto, fica evidenciada a importância da profilaxia e boa hidratação como alternativas de tratamento. O emprego de matérias-primas vegetais em formulações cosméticas atende ao apelo de sustentabilidade e biocompatibilidade tão buscado pelas empresas do setor. Óleos como o de andiroba e copaíba são tradicionalmente empregados pois podem apresentar potencial antibiótico e antiinflamatório. As manteigas de cacau e cupuaçu possuem alto teor de ácidos graxos, o que lhes confere potencial poder hidratante. Óleos e manteigas vegetais apresentam ainda potencial na formação de estruturas lamelares, as quais melhoram a estabilidade e aumentam o poder hidratante da formulação onde estão presentes. Esta pesquisa teve como objetivo o desenvolvimento de um creme à base de matérias primas vegetais, destinado à profissionais acometidos de doenças ocupacionais nas mãos. Foram manipuladas formulações com os óleos de copaíba e andiroba, aditivadas de manteigas de cacau e cupuaçu. Diversos pares de tensoativo foram pesquisados a fim empregar aquele que produzisse melhor estabilidade e permitisse a formação de estruturas lamelares. Quando empregados os tensoativos PEG-80 Sorbitan Laurate / Steareth-2 em emulsões com valores de EHL final 7 e 9, foi obtida boa estabilidade preliminar e observada presença de estruturas lamelares. Foi avaliado o comportamento destas frente à evaporação da água e foi observado que mesmo em pequenas concentrações ou após evaporação da água livre do sistema, as estruturas lamelares se mantêm presentes, sugerindo armazenamento de água entre as lamelas. A caracterização por difração de raios-X em alto ângulo (WAXS) permitiu observar que as cadeias carbônicas que compõem a bicamada ao redor dos glóbulos internos da emulsão estão dispostas em um estado ordenado denominado fase gel. A análise por difração de raio-X a baixo ângulo (SAXS) confirmou que os tensoativos estão organizados em multicamadas lamelares intercaladas por camadas de água que se mantiveram estáveis mesmo após três meses de envelhecimento em temperatura ambiente. A avaliação reológica mostrou comportamento pseudo-plástico com tixotropia e ligeiro aumento da viscosidade com o tempo, porém, não confirmou boa estabilidade. Por meio dos testes in vivo observou-se que as formulações desenvolvidas promoveram aumento da hidratação a qual foi prolongada em relação à formulação de mercado. / Currently occupational diseases manifested in the hands, as hyperkeratinazation, scaling, dehydration and deep fissures are frequently reported by professionals such as doctors, nurses, dentists, mechanics and housewives. The frequent use of gloves and constant contact with chemical such as detergents and soaps are the main cause. The treatment is done by the use of topical steroids, which in the long term may cause increased infections in the application site, due to side effect of inhibiting the immune system of these drugs. This exposed, the importance of proper hydration as prophylaxis and treatment alternatives is evidenced. The use of vegetable raw materials in cosmetic formulations attends the sustainability and biocompatibility appeal so sought by the cosmetics business sector. Oils such as Andiroba and Copaiba are traditionally used for their antibiotic and anti-inflammatory potential. Cocoa and Cupuassu butters have high levels of fatty acids, giving them potential moisturizing power. Vegetable oils and butters have yet a potential in formation of lamellar structures, which improve stability and increase the moisturizing power of the formulations where they are present. This research aimed to develop a cream based on vegetable raw materials destined to professionals suffering from occupational disease in the hands. Formulations were manipulated with Copaiba and Andiroba oils added with Cocoa and Cupassu butter. Several pairs of surfactant were investigated to employ one that produces better stability and allow the formation of anisotropic lamellar structures. When employed the following pair of surfactants PEG-80 Sorbitan Laurate / Steareth-2 in emulsions with required HLB of 7 and 9, good preliminary stability was obtained and lamellar structures were observed. We evaluated their behavior against water evaporation and we observed that even in small concentrations or after free water evaporation, lamellar structures are still present, suggesting water storage between the lamellae. Characterization by X-ray diffraction at wide angle (WAXS) elucidated that he carbon chains composing the bilayer around the emulsions internal globules are disposed in an ordered state called gel phase. The analysis by small angle X-ray diffraction (SAXS) confirmed that the surfactants are arranged in multilayered lamellae intercalated by layers of water that remained stable even after three months aging at room temperature. The rheological evaluation showed pseudo-plastic behavior with thixotropy and slight increase in viscosity with time, however, not confirmed good stability. The in vivo tests showed that the formulations caused an increase in hydration which was prolonged in relation to the formulation from the market.

Le ligand Rim3, constitué d’une cavité resorcinarène fonctionnalisée par 3 groupements méthylimidazole a été synthétisé et étudié. Ce ligand est capable de coordiner différents métaux de transitions comme le zinc et le cuivre. Ces complexes possèdent des propriétés hôte-invité intéressantes et une sélectivité avec la taille de la cavité. La complexation d’invités acides nécessite l’addition d’une base exogène. De plus, la présence de base peut être nécessaire pour réaliser des réactions d’hydratation ou d’hydrolyse. Dans ce manuscrit sont présentés différents ligands cavitaires resorcinarène avec 4 imidazoles greffés. Chaque ligand et complexe associé présente des solubilités différentes. Nous étudierons d’abord la synthèse et la caractérisation des systèmes en milieu organique ou aqueux. Les études de complexation montreront la forte affinité associée à ces complexes en milieu organique. L’étude des propriétés hôte-invité montre que le complexe est capable de coordiner un invité acide de manière quantitative dans les conditions RMN. Cette coordination ne nécessite pas l’addition de base. Le 4e imidazole joue le rôle de base intramoléculaire et n’est pas nécessaire à la coordination. Deux positions labiles en cis sont également disponibles, attesté par la coordination de ligands bidentes. Le complexe zincique [Rim4ZnII(EtOH)](ClO4)2 montre des propriétés d’hydratation des nitriles. Dans l’acétonitrile avec 35% d’eau à 70°C, le complexe forme de l’acétamide de manière catalytique. L’addition de base n’est pas nécessaire et le pH n’évolue pas avec la réaction. Dans l’eau avec 10% d’acétonitrile, [WRim(OH)44 Zn(H2O)](NO3)2 catalyse l’hydratation en acétamide mais est inhibé par l’hydrolyse successive en acétate. / In this manuscript, we present the synthesis and caracterisation of three tetradentate bowlshaped ligand. These ligands are resorcin[4]arene functionnalized by four methylimidazole. Each ligand is soluble in a different medium, such as organic solvent, water and mixed solvent. The four methylimidazoles are able to coordinate several metal ions, such as zinc, copper and iron. We then present the host-guest properties of the complexes. The complexes are able to coordinate acidic guests without addition of an exogenous base, thanks to the fourth imidazole. Two labiles positions are avalaible in cis, and bidentate ligands are able to coordinate the metal ions. Finally, we present the reactivity of the complexes. The zinc complex, [Rim4Zn]2+ catalyses the acetonitrile hydration with 35% water at 70°C. In an aqueous media with 10% water,[WRim(OH)44 Zn(H2O)](NO3)2 catalyses not only the acetonitrile hydration but also it’s subsequent hydrolysis into acetate.

A presente Tese tem por objetivo estudar alguns aspectos das interações água-detergente que são importantes para o entendimento das propriedades fisico-químicas da própria micela. além das interações que ocorrem na pseudo-fase micelar. Estas interações foram estudadas utilizando-se duas técnicas: RMN de 1H, para avaliar o efeito de micelas aquosas iônicas, zwitteriônicas e não-iônicas sobre a estrutura da água; e o estudo cinético da hidrólise espontânea de um éster do ácido carbônico, para determinar a reatividade cinética desta água além de, possivelmente, esclarecer alguns aspectos da questão da penetração da água na micela. Foi determinado o efeito da concentração do detergente e a presença de deutério no solvente sobre os deslocamentos químicos dos prótons da água. Foi usada a seguinte série de detergentes: dodecilsulfato de sódio (SOS, aniônico), dodecilbenzenossulfonato de sódio (SDBS, aniônico), perfluoroctanoato de sódio (SPFO, aniônico), cloreto de cetiltrimetilamônio (CTACl, catiônico), éter octilfenil(9,5)polioxietilênico (TX-100) e dodecildimetilamônio-3-propanossulfonato (DDAPS, zwitteriônico). O deslocamento químico dos prótons da água. depende linearmente da concentração de detergente e os coeficientes angulares das retas são sinsíveis à concentração de deutério no solvente. A partir destas correlações foram calculados os fatores de fracionamneto deutério/prótio,&#966; cujas magnitudes dão uma idéia quantitativa do efeito do detergente sobre a estrutura da água. Para averiguar a origem micelar do fracionamento observado, foram determinados também os fatores de fracionamento para compostos modelos. Estes são constituídos de cadeias carbônicas curtas que não formam agregados mas que possuem os mesmos grupos hidrofílicos dos detergentes. Foram usados os seguintes compostos como modelos: butilsulfato de sódio (modelo para SDS), p-tolouenossulfonato de sódio (modelo para SDBS), perfluorobutirato de sódio (modelo para SPFO) e brometo de butiltrimetilamônio (modelo para CTACl). Os resultados obtidos mostram que estes compostos perturbam pouco a estrutura água e são diminuidores da sua estrutura. Os detergentes, com a excessão de DDAPS e TX-100, claramente aumentam a estrutura da água devido a efeitos eletrorrestritivos. Interações inter e intramoleculares entre os íons do DDAPS resultam numa neutralização interna das cargas e explicam o seu pequeno efeito (aumento) sobre a estrutura do solvente. Nao é fácil oferecer uma explicação simples para a diminuição da estrutura da água na presença de TX-100, pois existe a interferência de fatores cujos efeitos sobre o fracionamento não podem ainda ser avaliados. Entre estes destacamos o enrolamento das cadeias oxietilênicas do detergente. a presença de água fisicamente presa entre estas cadeias e o fato de que a distruibição das moléculas de água entre as unidades de oxietileno não é homogênea. Foram determinadas as constantes de velocidade, os parâmetros de ativação e o efeito isotópico cinético do solvente para a hidrólise independente do pH de carbonato de bis(2,4-dinitrofenila) , na presença de SDS, CTABr, CTACl, TX-100 de cetildimetilamônio-3-propanossulfonato (HDAPS) . O efeito micelar foi analisado em termos da transferência do éster do seio aquoso para água micelar, e do efeito salino acoplado a fatores eletrostáticos das micelas iônicas. Como modelo para o efeito da transferência do meio, a reação foi estudada em misturas de água e acetonitrila. O efeito salino foi avaliado estudando a reação em presença de alguns dos compostos-modelo acima mencionados. Houve mudanças marcantes na entropia e na entalpia de ativação da reação somente em presença de grandes quantidades de acetonitrila no solvente (fração molar de 0,55 a 0,90). O efeito salino foi pequeno. Todos os detergentes, especialmente o SDS, diminuiram velocidade da reação devido a fatores entálpicos desfavoráveis. Para ter uma idéia do sítio da solubilização do éster nas micelas usadas, estudamos o efeito de acetato e decanoato de p-nitrofenila (compostos usados como modelo para CDNF), sobre os deslocamentos químicos dos grupos de cada detergente. Os resultados mostram que o sítio de solubilização destes ésteres não está predominantemente na região da superfície da micela. Os ésteres movimentam-se rapidamente (em relação à escala do tempo da RMN), em todo volume da micela. Efetuamos um cálculo simples mostrando que a penetração da água até os primeiros dois grupos metilênicos pode dar origem a um volume hidratado da micela de mais de 50%. Uma consideração dos parâmetros de ativação, dos resultados de RMN de 1H e do significado do cálculo do volume micelar efetuado, nos levou a concluir que nossos dados cinéticos podem ser explicados sem a necessidade de assumir uma micela extensivamente hidratada, como por exemplo aquela proposta pelo modelo de aglomeração poros (porous cluster model). / Study of micelle-water interactions is relevant to the physical chemistry of the micelle itself, and for a better understanding of the interactions occuring therein. In the present thesis two aspects of these interactions were studied: the effect of the organized assembly on the structure of water at the micellar interface, and on the kinetic reactivity of water as probed by examining the pH-independent (spontaneous) hydrolysis of a carbonate ester. The effect of the following surfactants on the structure of water was studied: sodium dodecylsulphate (SDS, anionic) sodium dodecylbenzene sulphonate (SDBS, anionic), sodium perfluorooctanoate (SPFO, anionic), cetyltrimethylammonium chloride (CTACl, cationic), polyoxyethylene (9.5) octylphenyl ether (TX-100, nonionic), dodecyldimethylammonio-3-propane sulphonate (DDAPS, zwitterionic). The dependence of the chemical shift of the water protons on the surfactant concentration, and on the deuterium content of the solvent was used to calculate the deuterium/protium fractionation factor, &#966;. The magnitude of the latter (relative to unity, the fractionation factor for bulk water) gives a quantitative idea of the solvent structure perturbation by the micellar pseudophase. In order to ascertain that the observed D/H fractionation is micelle-induced, the fractionation factors for model compounds were also determined. These were short-chain, i.e., non-aggregating compounds bearing the same head-groups as the surfactants. The following model compounds were used: sodium butylsulphate (model for SDS), sodium p-toluenesulphonate (model for SDBS), sodium perfluorobutyrate (model for SPFO) and butyltrimethylammonium bromide (model for CTACl). The following conclusions were drawn from the determined fractionation factors: whereas the short-chain compounds perturb the structure of water only slightly, and are usually water structure breakers, the presence of the micelles clearly enhances the structure of the solvent. Exceptions are zwitterionic DDAPS (marginal structure enhancement) and nonionic TX-100 (water structure decrease). The behavior of the zwitterionic surfactant was explained based on the negligible electrostrictive effect of the micelle due to inter and intramolecular interactions between the head-ions. A simple rationale for the case of TX-100 is not easy because of can complicate such interpretation: the followino factors that coiling of the oxyethylene chains, physical trapping of water between the chains, noneven distribution of the water molecules along the oxyethylene chains. Rate constants, activation parameters, solvent kinetic isotope effect were determined for the pH-independent hydrolysis of 2,4-dintrophenyl carbonate in the presence of SDS, CTABr, CTACl. TX-100 and cetyldimethylammonio-3-propane sulphonate (HDAPS). The micellar effect was analyzed in terms of a transfer Effect, a salt and an electrostatic effect. The first refers to the transfer of the ester form bulk water to \"micellar\" water, and was mimicked by studying the reaction in water-acetonitrile mixtures. Salt effect was evaluated by conducting the hydrolysis in the presence some of the above mentioned short-chain compounds. For the reaction in aqueous acetonitrile the entropy and enthalpy of activation showed sizable changes only at high mole fraction (0.55 to 0.90) of the organic solvent. Salt effect was negligible. The tested detergents, specially SDS, slow the reaction rate due to unfavorable enthalpy. The solubilization site of the ester in the micelles was assesed by 1H NMR. using p-nitrophenyl acetate and decanoate as models. This study showed that the ester in the micelles is not localized at, or very near, to the micelle/water interface, but is rapidly moving (on the NMR time-scale) all over the micellar volume. Analysis of the obtained activation parameters, coupled with the 1H NMR data, and with the result of simple geometric calculation led us to conclude that deep water penetration in the micelle (e.g ., according to the porous cluster model) is not essential to rationalize our data.

A soja é uma leguminosa com alto valor nutricional, devido principalmente a seu alto conteúdo protéico. Dentre a cultura de grãos, a soja caracteriza-se como a mais importante do país, o que representa um incentivo ainda maior para o consumo desse alimento. Porém, este alimento ainda sofre restrições por parte dos consumidores ocidentais, devido, principalmente a seu odor e sabor característicos, conhecidos como beany flavor, que é proporcionado pela ação da enzima lipoxigenase. A ação catalítica exercida por esse tipo de isoenzima sobre ácidos graxos poliinsaturados, ácido linolênico e linoléico, dos grãos de soja é um dos principais fatores responsáveis pelo aparecimento dos compostos carbonílicos, os quais causam o sabor desagradável em grãos. Para melhorar as características organolépticas da soja, pesquisadores desenvolveram novas cultivares, sem a presença da lipoxigenase. O objetivo deste trabalho foi avaliar diferenças físicas, químicas e sensoriais entre as cultivares de soja com lipoxigenase e sem lipoxigenase (cultivar BRS 232 e BRS 257, da Embrapa, respectivamente) e analisar as possíveis alterações promovidas por diferentes doses de radiação (0, 4 e 8 kGy) nos grãos de soja crus e cozidos. As análises físicas realizadas foram o tempo de cocção e o tempo de hidratação dos grãos. As análises químicas realizadas foram a composição centesimal, digestibilidade da proteína, fatores antinutricionais, teor de isoflavonas e capacidade antioxidante (DPPH e ABTS). Os aspectos sensoriais foram determinados por análise sensorial realizada aplicando-se métodos analíticos de diferenciação para seleção de provadores, e método descritivo para determinar a qualidade da soja. Ao final, foi realizada análise estatística fatorial 3x2x2 (doses de irradiação x cultivares x tratamentos) para análise, comparação e discussão dos resultados obtidos. Os resultados mostraram diferenças nas medidas das análises físicas com a irradiação e com as diferentes cultivares. Além disso, as diferentes cultivares apresentaram diferenças na composição centesimal, digestibilidade, teor de fenólicos, isoflavonas e inibidor de tripsina. A cocção promoveu diferença em todos os componentes estudados, com exceção da digestibilidade protéica dos grãos. Por outro lado, a irradiação afetou os compostos antinutricionais, a digestibilidade protéica e o teor de isoflavonas agliconas. Os dados da análise sensorial mostraram que o sabor e a textura das amostras não diferiram entre os cultivares e não foram afetadas pela irradiação. / The soybean is a vegetable with high nutricional value, mainly due to its high protein content. Among the culture of grains, the soybeam is the most important in Brazil, what represents a greater incentive for the consumption of this food. However, a great claim of occidental consumer is its characteristic odor and flavor, known as beany flavor, which is provided by the action of lipoxigenase enzyme. The catalytic action exerted by this type of isoenzime on pollyunsaturated fatty acids, linolenic and linoleic acid of the soy grains, is one of the main factors responsible for the appearance of the carbonyl compounds, which cause the unpleasant flavor in grains. To enhance the organoleptic characteristics of soybeans, researchers have developed new cultivars, without the presence of lipoxigenase. The objective of this study was tof evaluate physical, chemical and sensorial differences between the two soy cultivar, with and without lipoxygenases (cultivars BRS 232 and BRS 257, of Embrapa, respectively) and to analyze the possible changes promoted by different radiation doses (0, 4 and 8 kGy) in raw and cooked soybean grains. The physical analyses were: time of cooking and hydration of the grains. The chemical analyses were: centesimal composition, protein digestibility, antinutritional factors, isoflavone content and antioxidant capacity (DPPH and ABTS). The sensory aspects were determined by sensorial analysis performed by appling analytical methods of differentiation for selection of panelists, and descriptive method to determine the quality of the soybean. At the end, factorial statistical analysis was performed 3x2x2 (irradiation doses X cultivars x treatment) for analysis, comparison and discussion of the obtained results. The results showed differences in physical analyses with the irradiation and between the two cultivars. Besides, the cultivars presented differences in the centesimal composition, digestibility fenolic content, isoflavone content and tripsin inhibitor. Cooking promoted difference in all the studied components, except for the proteic digestibility of the grains. On the other hand, the irradiation affected the antinutritional contents, the proteic digestibility and the content of aglicone isoflavones. Data from sensory analysis showed that the taste and the texture of the samples didn\'t differ between the cultivars and were not affected by the irradiation.

Esta pesquisa trata da estabilização de misturas de agregados reciclados por meio da ativação de seus finos, cujas composições possibilitam a ocorrência de reações químicas de cimentação. Para o desenvolvimento da pesquisa foram utilizados dois tipos de agregados reciclados: um proveniente de resíduo de demolição de natureza cimentícia e outro da indústria de cerâmica vermelha. O uso dos materiais foi feito por meio de dosagens para obtenção de misturas cujas combinações de materiais pudessem, quimicamente, potencializar a ocorrência de hidratação do cimento anidro existente nos finos do agregado reciclado cimentício e de reação pozolânica pela pozolanicidade da cerâmica vermelha. Com isso foram obtidas cinco misturas, compostas pelos agregados reciclados em estudo misturados entre si e com a adição de aglomerantes hidráulicos, sobre as quais foram realizados ensaios em laboratório para verificação da ocorrência das reações químicas esperadas com consequente estabilização das misturas, de modo a influenciar nos respectivos comportamentos mecânicos. Também foi realizada a avaliação de características do empacotamento dos grãos como forma de verificar se o arranjo físico, neste caso, exerce influência significativa na melhora do comportamento mecânico das misturas estudadas. Os resultados obtidos indicaram que, de fato, ocorreram as reações químicas esperadas, comprovadas pelos resultados dos ensaios de termogravimetria e difração de raios x, realizados em três diferentes idades de cura. Verificou-se, também, a melhora no comportamento mecânico das misturas por meio do aumento da resistência à compressão simples e do módulo de resiliência com a evolução da cura, além de baixa deformabilidade aos 91 dias de cura. Com isso foi comprovada a estabilização das misturas em estudo, com a consequente melhora de seus desempenhos, sendo devida, principalmente, à ocorrência das reações químicas de hidratação do cimento anidro e pozolânica. A pesquisa demonstrou a possibilidade de se estabilizar misturas de agregados reciclados cimentícios e de cerâmica vermelha por meio da ocorrência de reações químicas de cimentação promovidas pela combinação destes materiais. / This research deals with the stabilization of mixtures constituted by recycled aggregates through the activation of its fines portions, whose components enable the occurrence of chemical cementation reactions. In order to develop this research, two types of recycled aggregates were used: one from demolition waste with cementitious origin, and the other one from the red ceramic industry. The use of these materials was done through mix designs to obtain mixtures whose combinations of materials could chemically increase the occurrence of hydration of the anhydrous existing in fine portion of the recycled cementitious aggregates, and pozzolanic reactions due to the pozzolanicity of red ceramics. Thus, five mixtures were obtained, and they were composed by the studied recycled aggregates, mixed together and with the addition of hydraulic binders, on which laboratory tests were performed in order to verify the occurrence of the expected chemical reactions with consequent stabilization of the mixtures, in order to influence their mechanical behavior. Furthermore, it was performed the evaluation of packing characteristics of the particles to verify if the physical arrangement, in this case, has any significant influence on improving the mechanical behavior of the mixtures studied. The results obtained indicated that in fact the expected chemical reactions occurred, which was verified by the results from thermogravimetry and X-ray diffraction tests performed at three different times of curing. The improvement of the mixtures mechanical behavior by increasing of their compressive strength and their resilient modulus was also verified as the mixtures were cured, in addition to low deformability at 91 days of curing. Thus, the stabilization of the mixtures studied was confirmed, which was mainly due to the occurrence of chemical hydration reactions of the anhydrous cement and pozzolanic reactions. The study demonstrated the possibility of stabilizing mixtures of recycled aggregates cementitious waste and red ceramic by the occurrence of cementing chemical reactions promoted by combination of these materials.

The present work had as objective to study the hydration process of grains and its possible enhancement using the ultrasound technology. For that, it was studied the hydration kinetics of different grains (Andean lupin, Adzuki beans, sorghum grains and corn kernels) correlating the morphology with mathematical models and the mass transfer mechanisms. Moreover, the effect of the soaking water temperature and the grain initial moisture content were studied to complement the description of this process. The ultrasound application was studied for improving the hydration process, describing the possible mechanisms (direct and indirect effects) that improve the mass transfer process. Therefore, it was established the way by how water enters in the studied grains, demonstrating that the water transfer into the grains is a complex phenomenon and takes place not only due to diffusional mechanisms, but also by capillarity. In addition, suitable mathematical models were proposed and used to explain the processes, describing their parameters according to the grains morphology and the mass transfer mechanisms. Further, it was determined how ultrasound enhances the mass transfer and in which conditions the direct (inertial flow and sponge effect) and the indirect effects (micro channels formation by acoustic cavitation) take place in the process, maximizing the effect of this technology. Finally, it was demonstrated that the ultrasound technology enhanced the hydration process for corn kernels, reducing significantly the process time in approximately 35 %, without modifying the thermal, structural and rheological properties of their starch. In conclusion, the present work improved the description of the grain hydration phenomenon and proved that the ultrasound technology can be used to enhance this process without changing its main industrial component. It is highlighted that the obtained results are thus high desirable for both the industrial and academic point of view. / O presente trabalho teve como objetivo estudar o processo de hidratação de grãos e sua possível melhora usando a tecnologia do ultrassom. Estudou-se a cinética de hidratação de diferentes grãos (tremoço andino, feijão Adzuki, grãos de sorgo e grãos de milho) correlacionando a morfologia com modelos matemáticos e os mecanismos de transferência de massa. Também foi estudado o efeito da temperatura e o conteúdo de umidade inicial do grão para complementar a descrição deste processo. Estudou-se a aplicação do ultrassom no processo de hidratação descrevendo-se os possíveis mecanismos (efeito diretos e indiretos) que melhoram a transferência de massa. Como resultado, foi estabelecida a forma como a água entra nos grãos estudados, demostrando que a transferência de água dentro dos grãos é um fenômeno complexo e que acontece por difusão e capilaridade. Foram propostos e utilizados modelos matemáticos apropriados para explicar os processos, descrevendo os parâmetros de acordo com a morfologia dos grãos e os mecanismos de transferência de massa. Ainda, determinou-se como o ultrassom melhora a transferência de massa e em que condições do processo acontecem os efeitos diretos (fluxo inercial e efeito esponja) e efeitos indiretos (formação de micro canais pela cavitação acústica), maximizando o efeito dessa tecnologia. Finalmente, demonstrou-se que a tecnologia do ultrassom melhora o processo de hidratação de grãos de milho, diminuindo significativamente o tempo do processo em cerca de 35 % sem alterar as propriedades térmicas, reológicas e estruturais do seu amido. Como conclusão, o presente trabalho melhorou a descrição de como os grãos são hidratados, demonstrando que o ultrassom pode ser usado para melhorar o processo de hidratação de grãos sem alterar os seus principais produtos industriais. Ressalta-se que os resultados obtidos são desejáveis tanto do ponto de vista acadêmico quanto industrial.

Les roches mantelliques exposées sur le plancher océanique et/ou en contact avec l’atmosphère au niveau d’une ophiolite, sont en déséquilibre et s’altèrent, via les réactions de serpentinisation (i.e. d’hydratation et oxydo-réduction) et les réactions de carbonatation. Ces réactions d’altération jouent un rôle important dans les échanges chimiques entre la Terre profonde et les enveloppes externes, en particulier dans le cycle des volatils (C, H et O) via la minéralisation du CO2 atmosphérique, la production d’hydrogène et la formation d’hydrocarbures et de molécules prébiotiques. L’ophiolite d’Oman est un « laboratoire naturel » idéal pour étudier ces réactions depuis l’hydrothermalisme océanique jusqu’à l’altération continentale actuelle.Cette thèse présente les résultats d’une étude multi-technique et multi-échelle réalisée sur une série de péridotites serpentinisées et carbonatées échantillonnées sur deux sites, Wadi Dima et Batin (Massif de Wadi Tayin), considérés comme représentatifs des processus d’altération affectant l’ophiolite d’Oman. Ces travaux combinent caractérisations (micro-)structurales (EBSD, µ-tomographie), pétrographiques et minéralogiques (Raman, Cathodoluminescence, (3D-)XANES), et analyses géochimiques (EPMA, (LA)-ICPMS) et isotopiques (isotopes du O, C micro-bulk et in-situ).L’étude des harzburgites de Wadi Dima a permis d’identifier la succession des épisodes de serpentinisation et de carbonatation qui ont affecté les péridotites lors du refroidissement de la lithosphère jusqu’à la mise en place de l’Ophiolite d’Oman. La serpentinisation commence en domaine océanique (appauvrissement en REE, anomalie négative en Ce) durant le refroidissement initial de la lithosphère océanique et/ou au début du détachement intra-océanique à < 200-220°C, par la formation des veines de lizardite. Cette serpentinisation continue avec la formation de chrysotile au centre de la structure maillée, remplaçant l’olivine. Le dernier stade de serpentinisation a lieu simultanément au premier stade de carbonatation et engendre l’altération complète de la péridotite à < 100°C. Le système est contrôlé par des hétérogénéités locales (anomalies en Ce et variation de la composition isotopique en carbone). La carbonatation continue à < 50°C lors de la transition en domaine continental. Des veines de carbonates se forment par interaction avec des fluides issus des sédiments durant la convergence et avec des fluides de surface et de sub-surface durant l’altération actuelle de l’ophiolite. Ce processus marque le passage d’un régime hydrothermal océanique dont la chimie est dominée par la composition de la roche, à un régime hydrothermal continental dont la chimie est contrôlée par la composition du fluide dans des fractures. Paradoxalement, la structure initiale du manteau contrôle l’orientation et la distribution des veines de carbonate.Le site de Batin se distingue par sa structure complexe avec la présence de nombreux filons de gabbros et de pyroxénites et des évidences d’imprégnation magmatique. La serpentinisation y est marquée par la formation de textures atypiques en anneau ("fingerprint") caractérisées par des variations des teneurs en Fe-Mg et du redox à micro-échelle et par des compositions isotopiques en oxygène en déséquilibre. Ces caractéristiques sont interprétées comme résultant de déséquilibres locaux dans les processus de transport-nucléation-réaction pouvant être liés à plusieurs paramètres : forts gradients de température, redox, composition du fluide, et de perméabilité.Cette thèse apporte de nouvelles données vis-à-vis des relations temporelles et spatiales entre les réactions de serpentinisation et de carbonatation, les hétérogénéités chimiques à micro-échelle et l’impact de ces réactions d’altération sur les bilans globaux des volatils (C, H et O) en Oman. Elle met particulièrement en évidence la possibilité de stocker du CO2 et de produire de l’H2 simultanément lors de l’altération du plancher océanique. / Mantle rocks exposed in seafloor and/or directly in contact with atmosphere in ophiolite system are thermodynamically and chemically in disequilibrium. Mantle alteration is driven by serpentinization (ie, hydration and oxidation-reduction reactions) and carbonatization reactions. These reactions play an major role in the chemical exchanges between the deep mantle and the outer envelops, especially in the global mass budget of volatiles (C, H and O) via CO2 mineralization, hydrogen production and formation of hydrocarbons and prebiotic molecules. Oman ophiolite is an ideal "natural laboratory" for studying alteration reactions in mantle rocks from ocean hydrothermalism to modern continental weathering.This thesis presents the results of a multi-technical and multi-scale study on carbonate-hosted serpentinized peridotites in two sites, Wadi Dima and Batin (Wadi Tayin massif), considered representative of the alteration processes affecting the Oman ophiolite. This work combines (micro-) structural (EBSD, µ-tomography), petrographical (EPMA), mineralogical (Raman, Cathodoluminescence, (3D-)XANES), geochemical ((LA)-ICPMS) and isotopic studies (O, C in situ and micro-bulk).Studies in Wadi Dima harzburgites have highlighted successive episodes of serpentinization and carbonatization in Oman peridotites from oceanic lithosphere cooling to Oman Ophiolite emplacement. Serpentinization occurs in oceanic setting (REE depletion, negative Ce anomalies), probably during the onset of the oceanic lithosphere cooling and / or of the intra-oceanic detachment, at < 200-220°C, driven by the formation of lizardite veins constituting the mesh structure. Serpentinization continues at lower temperature with the formation of chrysotile in the center of the mesh structure, replacing olivine. The last stage of serpentinization is concurrent with early carbonatization and generates the complete peridotite alteration at < 100°C. In this rock-dominated system, fluid flow paths are controlled by nano-porosity (etch pits), by pore scale weakness and by local heterogeneity in permeability, generating local chemical heterogeneities (Ce anomalies variability and carbon isotope heterogeneity). Carbonatization continues at < 50°C during the transition in continental setting. Carbonate veins are formed during interaction with sediment-derived fluids during intra-oceanic detachment at the onset of obduction and with surface and sub-surface fluids during modern continental Ophiolite weathering. This process records the transition from oceanic diffuse-flow rock-dominated to cooler continental fluid-focused-flow fluid-dominated hydrothermal systems. Paradoxically, initial mantle structure controls orientation and distribution of carbonate veins.Batin site is distinguished by its complex structure with the presence of abundant gabbros and pyroxenites dikes, evidence of magmatic impregnation peridotites. Serpentinization is charcheterized by the formation of an uncommon texture in rings ("fingerprint") at the expense of olivine, marked by chemically variation in Fe-Mg and redox at microscale and by disequilibrium oxygen isotopic composition. These features are interpreted as resulting from local disequilibrium in the transport-nucleation-reaction processes that may be related to several parameters: high temperature gradient, redox, fluid composition, and permeability.This thesis brings new constraints on temporal and spatial relations between serpentinization and carbonatization reactions, on local chemical heterogeneities at micro-scale and on the global chemical budget of volatiles (C, H and O) in Oman peridotites. It has highlighted the possibility to store CO2 and producing H2 simultaneously during subseafloor alteration.