Orientador: Flávio Luis Schmidt / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-16T15:12:47Z (GMT). No. of bitstreams: 1 Martins_BrunodeAndrade_D.pdf: 17768602 bytes, checksum: d9a4daf666aa8a8349c5b37f0a160fe1 (MD5) Previous issue date: 2010 / Doutorado / Doutor em Tecnologia de Alimentos

Neste trabalho foi estudado a influência da água na estabilização da estrutura e conformação da mioglobina (Mb) e hemoglobina (Hb) através de mudanças no centro ativo (grupo heme), detectadas por Ressonância Paramagnética Eletrônica (RPE). Utilizou-se os derivados meta Mb e nitrosil-Mb de baleia, meta Mb eqüina, meta Hb humana e meta Hb bovina. Amostras com diferentes graus de hidratação (0 a 0,50g H2/g proteína) foram submetidas as medidas de RPE, a T= -160&#176C, acompanhando o sinal do íon ferro (III) nas metas Mb (e Hb) e do grupo NO na nitrosil-Mb. A fração populacional dos complexos formados foram obtidos a partir da integral dupla do espectro de RPE. Na desidratação da meta Mb 65% das moléculas perderam a água da sexta coordenação do ferro (III) dando origem a outros complexos. Um desses complexos foi o hemicromo H (bi-histidina) onde um átomo de nitrogênio da histidina distal E7 se coordena ao ferro, com a hélice E se movimentando em direção ao heme. Adicionalmente a formação do hemicromo observou-se uma diminuição de 40% de moléculas detectáveis por RPE, na desidratação, e sugeriu-se a formação de moléculas com ferro reduzido [Fe (II)] como explicação para essa redução. Foi observado também um alargamento da linha com g &#8776 6 para as amostras com graus de hidratação menores que 0,20g H2O/g Mb devido a desvios da simetria axial em torno do íon ferro (III). Esses desvios de simetria foi proposto originar-se de distorções conformacionais nas amostras com baixa hidratação. Em níveis de hidratação acima de 0,20g H2O/g Mb observou-se um aumento considerável de centros detectáveis por RPE com a recuperação de moléculas com a forma meta. Na meta Hb somente 5% das moléculas permaneceram com a água da sexta coordenação do ferro após a desidratação. As outras 95% das moléculas deram origem a dois tipos de hemicromos (55%) e moléculas de Fe2+ (40%). Foram formados o hemicromo H e principalmente o hemicromo P (o 5&#176 ligante do ferro deve ser o átomo de enxofre da cisteína da cadeia &#946 posição 93 (&#94693), vizinho da histidina proximal &#94692 que é deslocada, e o 6&#176 ligante é proposto ser o nitrogênio da histidina distal E7). Em um nível de hidratação em torno de 0,40g H2O/g Hb há um aumento considerável de moléculas que voltam a ter a água na 6&#176 coordenação do ferro com o concomitante decréscimo da quantidade de hemicromos e de moléculas com ferro (II). Na adição do gás NO nas amostras de meta Mb de baleia com diferentes graus de hidratação houve a formação significante do complexo Fe2+ - NO somente abaixo de 0,25g H2O/g Mb. Em valores superiores de hidratação (até 0,50g H2O/g Mb) as amostras tornaram-se praticamente diamagnética, após a adição do NO, com a formação do complexo Fe2+ - NO+. Os resultados foram interpretados supondo que o NO reage diretamente com íons Fe2+ disponíveis abaixo de 0,25g H2O/g Hb formando o complexo Fe2+ - NO paramagnético. Em hidratações superiores como praticamente não há mais íons Fe2+ disponíveis o NO reduz o Fe3+ parando no intermediário Fe2+ - NO+ - diamagnético. O espectro tripleto observado para o NO em baixa hidratação na Mb é associado a um complexo onde o ferro (II) está pentacoordenado. Isso indica que a histidina proximal F8 se afastou do heme tornando possível a entrada de um novo grupo em seu lugar / In this work the role of water was studied in the stabilization of structure and conformation of myoglobin (Mb) and hemoglobin ( Hb) by changes in the active center (heme group), detected by Electron Paramagnetic Resonance (EPR). Whale met Mb and nitrosyl-Mb, equine met Mb, human and bovine met Hb were used. Samples with differents hydration degrees (0 to 0,50 g H2O/g protein) were measured by EPR, T= -160&#176C, analysing the iron (III) signal in the met Mb (and Hb) and NO signal in the nitrosyl-Mb. The populational fractions of complexes were obtained by double integration of EPR spectrum. In the dehydration of met Mb 65% of molecules lost the water molecule coordinated to the iron (II) giving origin to other complexes. One of these complexes was the hemichrome H (bishistidin) where the nitrogen atom of the E7 distal histidin binds to the iron (III). For this to occur the E helix must be close to the heme group. A percentual of 40% of the molecules were not detected by EPR in the dehydration and we suggest the reduction of iron (III) to iron (II) in these molecules. We also observed an increase of line width of g &#8764 6 signal in the samples with hydration degree below 0,20g H2O/g Mb, due to changes in the axial symmetry around at iron(III) ion. These symmetry changes were suggested to occur due to conformational distortions in the samples at low hydration. For hydrations levels above 0,20g H2O/g Mb a considerable increase was observed in the groups detectable EPR with recuperation of molecules in the met form. In met Hb only 5% of molecules remained with the water molecule coordinated to the iron after dehydration. The other 95% of molecules gave origin to two types of hemicromes (55%) and molecules with iron (II) (40%). The hemichromes observed were the bi-histidin and hemichrome P (the proximal histidin 92 was deslocated with the coordination of sulphur atom of cystein 93). For hydration levels around 0,40 g H2O/g Hb there is a considerable increase of molecules that return to met form. There is for the same hydration level a decrease of quantities of hemichromes and molecules with iron (II). In the NO gas addition to whale met Mb sample with differents hydration degrees we observed significant formation of Fe (II) - NO complex only below 0,25 g H2O/g Mb. For higher hydration levels (until 0,50 g H2O/g Mb) after the NO addition, the samples were pratically diamagnetic, with the formation of Fe (II) NO+ complex. The results were interpreted supposing that NO binds directly to Fe (II) ion that is present below 0,25 g H2O/g Hb with the formation of a paramagnetic complex Fe (II) - NO. For higher hydrations there is no iron (II) available and the NO reduces the iron (III) with the formation of intermediate diamagnetic complex Fe (II) NO+. The triplet spectrum displayed by NO at low hydration in Mb is associated with a complex where the iron (II) is pentacoordinated. This result indicates that F8 proximal histidin moves away from the heme group possibilitating the coordination of a new group in this place

Actualmente los materiales cementicios suplementarios como el metacaolín, son comúnmente empleados en la industria cementera y de la construcción, debido a factores ambientales, económicos y técnicos. La mayoría de estudios que evalúan la influencia del metacaolín en sistemas cementicios, se enfocan en aspectos de desempeño y de resistencia mecánica, en edades avanzadas. Existen pocos estudios que evalúan la etapa inicial de hidratación. Por tanto, este trabajo tiene como propósito entender mejor la influencia que tiene la sustitución parcial de metacaolín en pastas de cemento Portland, durante las primeras 72 horas de hidratación. Normalmente para evaluar la cinética de hidratación se analiza el calor liberado, usando un calorímetro de conducción isotérmico. Sin embargo, otra técnica relativamente nueva usada en este estudio, es medir la retracción química en forma continua; en Brasil son raros los estudios que usen retracción química para obtener la cinética de hidratación. Para tal fin se elaboraron pastas utilizando reemplazos de metacaolín de 5, 10 y 20% en masa, además de una pasta de referencia, usando una relación constante agua/sólido de 0.5. La retracción química fue medida en forma continua automatizando el método de la dilatometría, también se evaluó la cinética de hidratación usando un calorímetro isotérmico. Adicionalmente, el desarrollo de los productos hidratados fue estudiado por análisis termogravimétrico y difracción de rayos X. Los resultados obtenidos muestran que existe una excelente relación entre la retracción química y la calorimetría y que la adición de metacaolín produce cambios en la cinética de hidratación, que también afectan a la retracción química. / Currently the supplementary cementitious materials such as metakaolin are commonly used in the cement and construction industry, due to environmental, economic and technical factors. Most studies evaluating the influence of metakaolin in cementitious systems focus on aspects of performance and mechanical strength at older ages. There are few studies evaluating the initial stage of hydration. Therefore, this paper aims to better understand the influence of the partial replacement of metakaolin in Portland cement pastes during the first 72 hours of hydration. Normally to evaluate the kinetics of hydration heat released is analyzed using an isothermal calorimeter. Nevertheless, another relatively new technique used in this study is to measure the chemical shrinkage continuously; in Brazil are rare studies using chemical shrinkage to obtain hydration kinetics. This study shows the influence of partial replacement of Portland cement by metakaolin in the hydration reactions and chemical shrinkage of cementitious pastes. For this, pastes were prepared using metakaolin replacements of 5, 10 and 20% by mass, and a reference paste, using a constant water/solid ratio of 0.5. Chemical shrinkage was measured continuously automating the method of dilatometry, hydration kinetics was evaluated using an isothermal conduction calorimetry. Additionally, the development of hydrated products was studied by thermogravimetric analysis and X-ray diffraction. The results show that there is an excellent relationship between chemical shrinkage and calorimetry and the addition of metakaolin leads to changes of the hydration kinetics, which also affect the chemical shrinkage.

Os anfíbios são organismos típicos dos ambientes de água doce e com vários representantes de hábitos terrestres e estão caracterizados por uma elevada permeabilidade da pele. Este atributo faz com que tanto no sistema aquático quanto no terrestre o fluxo de água através da pele seja considerado uma característica relevante. Nos ambientes aquáticos os animais ganham água como resultado do gradiente osmótico entre o animal e o meio, e o excesso de água é eliminado pelo sistema excretor através da produção de urina. Em meios com elevada salinidade os animais perdem água, portanto são susceptíveis de desidratação. Um dos efeitos negativos da desidratação é o aumento da concentração dos fluidos corporais dado o efeito desnaturante dos íons sobre as proteínas. O aumento da concentração também pode responder a entrada dos íons devido ao gradiente de concentração desses osmólitos entre o meio e o animal. Estes efeitos sobre os anfíbios fazem parte das explicações do por que estes organismos estão menos representados nos ambientes costeiros marinhos do que em outros ambientes. Porém, há um número elevado de espécies que usam este ambiente e pouco se sabe como se ajustam aos efeitos da elevada salinidade ambiental. Ao mesmo tempo, dado que o ambiente costeiro está caracterizado pela maresia assim como pelos ventos que vem do mar, os indivíduos que ocupam esta região também estariam expostos a perdas de água por evaporação que poderiam implicar riscos de desidratação. Relacionado com a perda de água por evaporação, a resistência cutânea é uns dos atributos que mostra variação entre as espécies, sendo mais elevada naquelas que por seus hábitos e as características dos ambientes que ocupam são propensas a perder água por evaporação e correr com o risco de desidratação. As taxas de desidratação também mostram variação entre espécies e populações com taxas mais baixas naqueles organismos que ocupam ambientes que promovem a perda de água por evaporação. Também existem evidências que indicam que as taxas de hidratação são mais elevadas nos indivíduos que ocupam ambientes ou que apresentam hábitos que facilitam a perda de água por evaporação do que os que ocupam ambientes úmidos ou têm hábitos aquáticos. Thoropa taophora é um bom modelo para avaliar se a tolerância à salinidade, resistência cutânea e as taxas de desidratação e hidratação fazem parte das vias de ajuste ao ambiente costeiro porque ocupa os costões rochosos da costa marinha do Litoral do Estado de São Paulo e regiões rochosas associadas a cachoeiras afastadas da costa em ambiente de Mata Atlântica. Através da comparação de uma população costeira localizada na região de Ubatuba e uma não costeira localizada na região de Picinguaba abordamos esses fatores. Como resultados gerias do presente trabalho podemos dizer que a população costeira não apresenta tolerância à salinidade comparável ao do grupo de espécies mais tolerantes à salinidade representadas por Fejervarya cancrivora, Xenopus laevis e Bufote viridis. Pelo contrário parece se tolerar níveis de salinidade similar à mais frequentemente reportadas para os anfíbios. Também não apresentou resistência cutânea por encima dos valores mais frequentes registrados na literatura. Por outro lado, detectamos que a tolerância à salinidade, a taxa de desidratação e taxa de hidratação fariam parte do ajuste a este tipo de ambiente. Neste sentido encontramos maior tolerância à salinidade, menor taxa de desidratação e maior taxa de hidratação nos indivíduos da população de Ubatuba do que nos de Picinguaba. Os resultados sugerem que a tolerância à salinidade e a taxa de desidratação estariam relacionados, o que permitiria elaborar hipóteses sobre outros ambientes que possam exibir variação na salinidade, como acontece com a salinização de corpos de água como consequências de práticas agrícolas, e variação na umidade do ambiente como consequência das variações do clima / Amphibians are typically found in freshwater environments and include various species of terrestrial habits all characterized by having a high skin permeability. In both terrestrial and aquatic environments, this attribute makes the water flow through the skin a featured system worth to be studied. In aquatic environments animals gain water as a result of the osmotic gradient between the animal and the environment, and the excess water is eliminated through the excretory system as urine. In environments where the salinity is high, animals lose considerable volumes of water which may lead to dehydration. One of the negative effects of dehydration is the raise of the osmotic concentration of body fluids due to the denaturing effect of the ions on the proteins. The increased concentration may also take place by the entrance of ions into the body, following the osmotic gradient between the medium and the animal. For these reasons, amphibians are seldom found in coastal marine environments. However, there are a large number of species that inhabit coastal areas and little is known about the physiological adjustments associated to the high environmental salinity. The skin resistance is one of the traits that show variation among species, being higher in those who inhabit environments where the risk of dehydration is higher. Dehydration rates also show variation among and within species with lower rates in those organisms which occupy environments that promote water loss by evaporation. The hydration rates of the organisms occupying such environments, or species whose habits facilitate the loss of water by evaporation, are higher than in those animals inhabiting humid environments or that are not exposed to this type stress. Thoropa taophora is a good model to evaluate if salt tolerance, skin resistance, and dehydration and hydration rates are part of the adjustments to coastal environment as it occupies the rocky marine coast of São Paulo and rocky outcrops associated with the waterfalls in the Atlantic Forest biome. We address these questions by comparing a coastal population located in the Ubatuba region and an inland population in the Picinguaba region. The results suggest that the coastal population has no extraordinary attributes associated to salinity tolerance in comparison with other coastal species such as Xenopus laevis and Bufote viridis. The values for skin resistance did not exceeded the once reported in the literature either. An increase of the tolerance to salinity, and lower dehydration and hydration rates were found in the individuals from Ubatuba than in the specimens from Picinguaba which suggests that tolerance to salinity, and dehydration and hydration rates may represent adjustments to different environments. Tolerance to salinity and dehydration rate appeared to be related, which could allow to draw assumptions on populations inhabiting other environments that may exhibit variations in salinity as a consequence of anthropogenic activities or climate change

A pele é constituída por duas camadas: a epiderme e a derme sendo que a camada mais superficial da epiderme, o estrato córneo, camada mais superficial da pele é responsável pela sua função de barreira. Os hidratantes são formulações destinadas a manter o conteúdo de água na pele, uma vez que a hidratação é essencial para manter a função barreira íntegra. Assim, emulsões fluídas e semi-fluídas como as nanoemulsões, que apresentam glóbulos na faixa de 20-200 nm estão sendo amplamente utilizadas como veículos em produtos cosméticos por apresentarem vantagens em relação às macroemulsões, como melhor espalhabilidade e penetração, além de possuírem uma maior estabilidade cinética. O emprego de óleos vegetais como constituintes das nanoemulsões tem sido cada vez mais notório, uma vez que esses óleos são capazes de repor as frações lipídicas da pele hidratando-a. Desta forma, o presente trabalho tem como objetivo obter e caracterizar nanoemulsões O/A a base de óleo de framboesa, maracujá e pêssego e avaliar as propriedades cosméticas da formulação. A atividade antioxidante dos óleos foi avaliada por meio do método do DPPH. O EHL da fase oleosa foi então determinado utilizando-se os tensoativos lipofílicos monolaurato de sorbitano e mono-oleato de sorbitano e os tensoativos hidrofílicos polissorbato 20 , polissorbato 80 e PEG 36 castor oil combinados entre si de modo a originar 5 sistemas binários. A nanoemulsão foi obtida pela metodologia EPI (Emulsion phase inversion), utilizando-se os tensoativos lipofílicos monooleato de sorbitano e PEG-15 castor oil e os tensoativos hidrofílicos PEG-30, PEG-36, PEG-40 e PEG-54 castor oil combinados entre si, e as características físico-químicas da nanoemulsão foram determinadas. A nanoemulsão estável e com menor tamanho de glóbulo foi aditivada de (i) lanolina etoxilada e (ii) lanolina acetilada em diferentes concentrações e as alterações nas características físico-quimicas das nanoemulsões foram avaliadas. As nanoemulsões aditivadas de lanolina acetilada e lanolina etoxilada foram submetidas a testes de estabilidade preliminar e acelerada e a avaliação da influência dos derivados de lanolina na hidratação, oleosidade, valor de pH cutâneo e formação de eritema foram avaliados. A mistura dos óleos apresentou maior atividade antioxidante que os óleos separadamente. O EHL requerido para a fase oleosa da emulsão foi igual a 9 e nanoemulsões com menor tamanho de glóbulos foram obtidas com o par de tensoativos monooleato de sorbitano e PEG 36 castor oil. A lanolina tanto etoxilada quanto acetilada provocou alterações nas propriedades físico-químicas da nanoemulsão inicial. Frente aos testes de estabilidade, a formulação aditivada de lanolina etoxilada mostrou-se mais estável que a formulação aditivada de lanolina acetilada. As nanoemulsões aditivadas de derivados de lanolina provocaram maior hidratação da pele e aumento da oleosidade quando comparada a nanoemulsão não aditivada, não havendo alteração no valor de pH cutâneo e formação de eritema quando as formulações (tanto aditivadas quanto não aditivada) foram aplicadas. / The skin consists of two layers: the epidermis and dermis. The most superficial layer of the epidermis, the stratum corneum is responsible for barrier function, so moisturizing formulations are designed to maintain the water content in the skin, since hydration is essential for maintaining the barrier function intact. Thus, fluid and semi-fluid emulsions as the nanoemulsions that present droplets in the range of 20-200 nm are widely used in cosmetics as vehicles because they present advantages over macroemulsões as better spreadability and penetration, and they have greater stability kinetics. The use of vegetable oils as components of the nanoemulsion has been increasingly clear, since these oils are able to replace the lipid fractions of skin moisturizing it, and they have other activities of cosmetic concern. Thus, this study aims to obtain and characterize O/W nanoemulsions composed by raspberry, passion fruit and peach oils and evaluate the cosmetic properties of the formulation. The antioxidant activity of the oils was evaluated by the DPPH method. The HLB of the oil phase was then determined using the lipophilic surfactants sorbitan monolaurate and sorbitan monooleate and the hydrophilic surfactants polysorbate 20, polysorbate 80 and PEG 36 castor oil combined among themselves in order to create five binary systems. The nanoemulsion was obtained by the methodology EPI (Emulsion phase inversion), using the lipophilic surfactants sorbitan monooleate, PEG-15 castor oil and hydrophilic surfactants PEG-30, PEG-36, PEG-40 and PEG-54 castor oil combined among themselves, and the physicochemical characteristics of the nanoemulsion was determined. The stable nanoemulsion and with smaller droplet size was additivated (i) ethoxylated lanolin and (ii) acetylated lanolin in different concentrations and changes in physico-chemical properties of nano-emulsions were evaluated. Nanoemulsions were tested for primary and accelerated stability and the influence of derived from lanolin in hydration, skin pH, oily skin and training erythema were evaluated. The mixture of the oils showed higher antioxidant activity than oils separately. The required HLB for the oil phase of emulsion was equal to 9 and nanoemulsion with smaller droplet size were obtained with the pair of surfactants sorbitan monooleate, PEG 36 castor oil. Ethoxylated an acetylated lanolin caused changes in physico-chemical properties of nanoemulsions. The formulation additivated of ethoxylated lanolin was more stable than the formulation additivated of acetylated lanolin front accelerated stability testing. Nanoemulsions additivated of lanolin derivatives caused a higher skin hydration and increase oily skin when compared to the nanoemulsion without additives, with no change in the value of skin pH and erythema formation when the formulations (both with additives and without additives) were applied.

Introdução - A relação da atividade física e da alimentação com a saúde é estudada há muitos anos e os resultados confirmam que a prática regular de exercício físico e uma alimentação equilibrada atuam diretamente na prevenção de doenças. Objetivo - Identificar os fatores associados ao comportamento alimentar dos frequentadores de academias de ginástica do município de Taubaté, SP, segundo idade, gênero e estado nutricional. Métodos - Estudo transversal, quantitativo e com uma amostra não probabilística, constituída por 160 frequentadores de academias do município de Taubaté-SP. Para a obtenção dos dados utilizou-se questionário padronizado de múltipla escolha com questões demográficas, socioeconômicas, comportamentais, nutricionais e sobre saúde; o teste Como está a sua alimentação? do Guia Alimentar de bolso do Ministério da Saúde; o Questionário Internacional de Atividade Física IPAQ; e para avaliação do estado nutricional, informações do peso e da altura para cálculo do IMC (índice de massa corporal) e aferição de dobras cutâneas para a estimativa do percentual de gordura corporal ( por cento GC). Empregou-se análise descritiva, teste do qui-quadrado de Pearson para avaliar associação e análise de cluster. Resultados - A idade média dos frequentadores é de 39,4 anos (DP = ±13,1 anos). Há uma predominância do gênero feminino, alto grau de escolaridade e elevada renda familiar. O IMC médio é de 25,5 kg/m², a maioria encontra-se eutrófico e apresenta por cento GC normal. Fazem uso de complementos nutricionais e os mais jovens consomem os proteicos e BCAA, enquanto os mais velhos as vitaminas e minerais. No teste Como está sua alimentação? 59,4 por cento apresentavam alimentação saudável. A alimentação não se apresentou equilibrada em todos os grupos, segundo recomendação do Guia Alimentar. A maioria relata se preocupar com a composição da alimentação e refere ter mudado algo na dieta nos últimos meses. E em relação à hidratação, 48,8 por cento relata ingerir 500 ml de água durante o período das atividades na academia. Os motivos citados para a realização de exercícios físicos são saúde, prazer e controle de peso. E para o nível de atividade física, segundo o IPAQ, os frequentadores foram classificados a partir irregularmente ativo A. Conclusão - O presente estudo permitiu identificar que a idade e o estado nutricional estão associados a pratica de atividade física (frequência, modalidade, motivação), e a fatores relacionados à dieta, como o uso de complemento, a hidratação e a qualidade da alimentação. Frequentar academias não assegurou o comportamento alimentar adequado desses indivíduos de Taubaté. / Introduction - The relationship between physical activity and food with health have been studied for many years and the results confirm that the regular practice of physical activity and a balanced diet influence directly in disease prevention. Objective - To identify the factors associated with eating behavior of users of fitness centers from Taubaté city, SP, according to age, gender and nutritional status. Methods - There was a cross-sectional study with a non-probabilistic sample involving 160 users of fitness centers from Taubaté city, SP. Data were collected using a questionnaire containing demographic, socioeconomic, behavioral, nutritionals and about health multiple choice questions. Furthermore, they were used the test Whats your diet like?, present in the pocket edition of the Brazilian Dietary Guideline from the Health Ministry, and the International Physical Activity Questionnaire IPAQ. For anthropometric assessment were used weight and height to calculate the BMI (Body Mass Index) and skinfolds thicknesses to estimate the percentage of body fat ( per cent BF). It was used the chi-square test to determine the association and cluster analysis. Results - The average age users of fitness centers was 39.4 years old (SD = 13.1). There was predominance of the feminine gender, high schooling and high family income. The averages of BMI was 25.5 kg/m2, the most of them were found eutrophic and presents normal per cent BF. They use nutritional complements and the younger users were the ones who most consume the protein complements and BCAA, meanwhile the vitamins a minerals are mainly consumed among the elders. According to the test classification Whats your diet like?, 59.4 per cent presented healthy eating . The food did not appear balanced in all groups, as recommended by the Food Guide. The majority related to worry about composition of food and refers that had changed something in the diet in the last months. Regarding to hydration, 48,8 per cent of the users mentioned to ingest 500 ml of water during the period of activities at the gym. The reasons to the realization of physical activities were health, enjoyment and weight control. And to the level of physical activity, according to IPAQ, the users of fitness center were classified as from irregular active A. Conclusion - The present research permits to identify that the age and the nutritional status were associated to physical activity (frequency, modality, motivation) and to factors related to the diet, as the use of complements, to hydration and the quality of food. Attend gyms did not ensure the adequate eating behavior of these individual from Taubaté city.

Aujourd'hui le béton est l'option la plus attrayante pour le secteur de la construction. Ceci est du au fait que le béton est un matériau peu couteux et que sa fabrication nécessite peu d'énergie et a un faible impact environnemental En outre, les structures en béton sont durables et performantes mais le béton nécessite d’être associé à des armatures d’acier, car le il présente une faible résistance à la traction.Du point de vue de la chimie, le point faible provient de l’origine de la cohésion du ciment utilisé pour la fabrication du béton. Des expériences à l’échelle nanométrique et des simulations numériques ont montré que la cohésion de la pâte de ciment résulte de forces de courte portée qui s'exercent entre les surfaces de silicates de calcium hydratés (C-S-H) dans la solution interstitielle.Cette thèse explore l'ingénierie de la liaison entre les grains de ciment en vue d'améliorer les propriétés mécaniques des matériaux cimentaires. Nous visons à introduire en plus de celles déjà existantes, des forces de cohésion à longue portée entre les grains à l’aide de liaisons chimiques pour conduire à une augmentation de la résistance à la traction et de la ténacité. La stratégie choisie a été de greffer différents silanes organo-fonctionels sur le ciment anhydre. Deux méthodes possibles de silanisation ont été étudiées et les produits modifiés ont été caractérisés.La première méthode a consisté à mélanger directement la poudre de ciment avec les silanes. Il a été montré que, ce faisant, pâtes de ciment et de mortiers présentent une maniabilité améliorée. En outre, il a été observé que les silanes influent fortement l'hydratation, principalement en retardant l'hydratation des silicates et en réduisant leur degré d'hydratation. En conséquence, une perte sévère de résistance a été constatée dans tous les tests mécaniques standards effectués. Ceci est lié à la dose excessive de silane incorporée au ciment pour atteindre l'homogénéité du mélange au cours de l’hybridation.Une deuxième méthode de silanisation a été développée afin de permettre la diminution du dosage des silanes en gagnant en homogénéité. Elle consiste à mélanger le ciment dans une solution de silane dans un solvant non aqueux. Cette méthode à permis en outre d’obtenir des données quantitatives relatives à l’adsorption des silanes utiles à une meilleure compréhension des interactions silane-ciment. Elles constituent en effet des moyens indirects aidant à caractériser les substrats modifiés. Il a été constaté que les interactions silane-ciment dépendent fortement du type de solvant utilisé. La couverture de la surface a également été calculée et est loin d'être une monocouche. Elle est constituée d’espèces chimiquement et physiquement adsorbées qui influencent les propriétés des ciments modifiés.En termes de vitesse d'hydratation, les plus forts effets de ralentissement sur l’hydratation des silicates sont toujours associés aux silanes affichant une plus faible affinité avec la surface, mais fortes de liaisons avec cette dernière. En termes de rhéologie, tous les silanes améliorent grandement la capacité des pâtes à résister à une charge au-dessus de la limite élastique. Il en résulte une augmentation de résistance à la flexion jusqu'à 35% par rapport au ciment pur. / Nowadays concrete is the most attractive option for the construction sector. This is because concrete itself is a low cost, low energy and low environmental impact material. Moreover, concrete structures are very durable and high load bearing. This is achieved by incorporating steel, because concrete itself is a very low tensile strength material. Chemically, the weakness originates in the cohesive nature of cement used for concrete making. Nanoscale experimental investigations and numerical simulations showed that cohesion of cement paste is caused by short range surface forces acting between calcium silicate hydrates (C-S-H) in the interstitial solution. This thesis addresses the possibility of engineering the bonding between hydrates in order to tune the mechanical properties of cementitious materials. We aim at introducing long range cohesion forces between hydrates in addition to the existing ones. This should potentially lead to an increase in strength and toughness. The strategy chosen was to hybridize the cement prior to hydration with organofunctional silanes. Two possible methods of silanization were investigated and the modified products have been characterized. The first method consisted in dry blending cement powder to silanes. It is shown that by doing so, cement pastes and mortars exhibit improved workability. In addition, we have observed that silane agents strongly affect the hydration kinetics, mainly by retarding the hydration of silicates and reducing their degree of hydration. As a consequence, severe strength loss was evidenced in all standard mechanical tests. This was related to excessive dosage of silane to cement imposed to reach good mix homogeneity during hybridization.A second silanization methodology was developed in order to allow diminishing the dosage of silane without facing inhomogeneity mix issues. It is shown that by adsorbing silane from organic solvents we gain a better understanding of silane-cement interactions. In addition, the adsorption data provide indirect means to help characterize the modified substrates. It was found that silane-cement interactions strongly depend on the type of the solvent used as vehicle media. The surface coverage has also been calculated and is far from being monolayer because both chemically bonded and physically adsorbed species are assumed to be present. This further influences the properties of the modified cements. In terms of hydration kinetics, stronger retarding effects of silicates hydration are always associated to silanes displaying lower surface affinity, but stronger surface bonding. In terms of rheology, all silanes greatly improved the ability of pastes to withstand load above the critical deformation. This results in increased bending strength by up to 35% compared to neat cement.

Le manque de connaissance sur les interactions existantes entre les adjuvants organiques et les phases minérales ainsi que leur influence sur les mécanismes d’hydratation du Ciment Portland Ordinaire (CPO) limite le développement de nouvelles molécules organiques avec des propriétés améliorées et contrôlées. Ici, le but de ces travaux était de comprendre pourquoi et comment des adjuvants organiques modifient le temps de prise du CPO en faisant varier progressivement les caractéristiques de molécules organiques simples comme leur charge, leurs groupes fonctionnels (hydroxyle, hydroxy-carboxylate, carboxylate, sulfonate et phosphonate) et la stéréochimie de leurs groupes hydroxyles.Les différents retards induits par les molécules organiques étudiées sur l’hydratation du composé minéral responsable des propriétés finales du CPO, le silicate tricalcique, ont été reliés aux caractéristiques des composés organiques. Les interactions de ces derniers dont leur adsorption sur du silicate de calcium hydraté (C-S-H) ainsi que leur complexation avec les ions calcium, hydroxyde et/ou silicates en solution ont été identifiées dans des systèmes à l’équilibre et corrélées au retard généré par les molécules organiques sur l’hydratation du silicate tricalcique.L’impact des hexitols qui varient uniquement en fonction de la stéréochimie de leurs groupes hydroxyles sur le processus de dissolution-précipitation de l’hydratation du silicate tricalcique a été étudié. L’influence de ces polyols sur l’hydratation d’un mélange luminatesulfate de calcium a été expliquée par leur adsorption sur l’ettringite, les AFm et par leur complexation ionique en solution. Pour finir, cette étude s’est focalisée sur les conséquences des interactions des hexitols avec l’ettringite et les ions aluminate en solution sur l’hydratation des phases silicates présentes dans le CPO. / The current limited knowledge on the interactions between organic admixtures and mineral phases as well as their influence on the hydration mechanisms of the Ordinary Portland Cement (OPC) represents a real limitation in the development of new organic products with improved and controlled properties. Here, this study intended to understand why and how organic admixtures modify the setting time of OPC by progressively varying the characteristics of simple organic molecules such as their charge, functional groups (hydroxyl, hydroxy-carboxylate, carboxylate, sulfonate and phosphonate) and the stereochemistry of their hydroxyl groups.The different retardations induced by the organic molecules studied on the hydration of the mineral compound responsible of the final properties of OPC, tricalcium silicate, were related to the characteristics of the organic admixtures. The interactions of these organic compounds such as their adsorption on calcium silicate hydrate (C-S-H) and their complexation with calcium, hydroxide and/or silicate ions in solution were identified in systems at equilibrium and correlated to the retarding effect generated by the organic molecules on the hydration of tricalcium silicate.The impact of hexitols which differ from one another in the stereochemistry of their hydroxyl groups on the dissolution-precipitation process of the hydration of tricalcium silicate was studied. The influence of these polyols on the hydration of a calcium aluminate and calcium sulfate mixture was explained by their adsorption on ettringite and AFm as well as by their ionic complexation in solution. Finally, this study focused on the consequences of the interactions of hexitols with ettringite and aluminate ions in solution on the hydration of the silicate phases present in OPC.

La zone d'enrobage des aciers des structures en béton armé est soumise au cours de la vie de l'ouvrage à l'action de divers agents agressifs (ions chlorure, dioxyde de carbone, etc.) qui sont susceptibles d'entraîner la corrosion des armatures. Dans le cadre de la maintenance de l'ouvrage, une réparation du béton dégradé est généralement imposée afin d'assurer l'intégrité et la sécurité de la structure, et d'en allonger la pérennité. Cette étude s'attache à explorer les transferts hydriques qui limitent l'efficacité de la réparation au cours de l'hydratation du mortier de réparation. L'évolution microstructural et les profils hydriques sont obtenus par des techniques non-destructives comme l'imagerie résonance magnétique (IRM) et la gamma-densimétrie (GD) depuis très jeune âge à 28 jours. La durabilité du béton réparé est concernée. L'effet du séchage est évité dans cette étude. Le mortier isolé d'une même formulation est préparé pour la comparaison du comportement d'hydratation avec le mortier de réparation. Des diverses techniques classiques aident de compléter les résultats obtenus par IRM et GD. Donc le système de réparation est désigné. Les transferts hydriques à l'interface sont visualisés pendant la réparation (0 - 28 jours), afin de permettre une exploration en profondeur sur les mécanismes des couplages physico-chimiques. La réparation plus efficace donc est déterminée par cette méthodologie, en étudiant divers matériaux de réparation, divers états de support (saturé ou séché) et divers conditions environnementaux, etc. De plus, après la réparation (1 - 2 mois), la porosité totale est mesurée par GD ou la porosimétrie par l'intrusion de mercure (PIM). La distribution poreuse est aussi examinée par PIM selon la hauteur du système de réparation. Les indicateurs de durabilité (Cl- et CO2) après la réparation (> 2 mois) présentent l'empêchement de pénétration des ions chlorures et un effet non-évident pour la pénétration du dioxyde de carbone. L'évolution est suivie au fur et à mesure pendant la pénétration, afin d'explorer l'efficacité de la réparation qui s'adresse à une vie de service prolongée. Cette méthodologie pourra être appliquée aussi sur des autres systèmes, où il existe des transferts hydriques. Par exemple, une couche de protection en Béton Fibré à Ultra-haute Performance (BFUHP) sur le béton ordinaire. En conclusion, cette méthodologie en combinant des techniques non-destructifs et destructifs, est un outil d'étudier le système de réparation par un moyen systématique et quantitatif. C'est intéressant de comparer des divers cas. L'efficacité de réparation est étudiée afin d'assurer une durabilité à long terme / The coating area of steel reinforced concrete structures is subjected during service life time to various aggressive agents (carbon dioxide, chloride ions, etc.), which causes corrosion of steel rebars. Concerning the maintenance, repair works of degraded concrete cover are generally imposed to ensure its integrity and structural safety, and to extend long-term durability. This research aims in exploring moisture transfers which limit the efficiency of repair work during mortar hydration. Microstructure evolution and water profiles are obtained by non-destructive techniques such as Magnetic Resonance Imaging (MRI) and Gamma-Ray Attenuation (GRA) since casting until 28 days. The durability of repaired concrete is involved after the repair procedure. The effect of drying is avoided in this research. Sealed mortar of the same formula is prepared to compare its hydration performance with the repair mortar. Various conventional techniques help to supplement the results obtained by MRI and GRA. The configuration of designed repair systems is shown. Moisture transfers at the interface between the repair mortar and the old concrete are investigated during the repair procedure (0 - 28 days), which allows exploring the mechanisms of physico-chemical couplings. Efficient repair work can be determined for various repair materials, various substrates (initially-saturated or initially-dried), various environmental conditions, etc. Furthermore, total porosity is measured by GRA or by Mercury Intrusion Porosimetry (MIP) after the repair procedure (1 - 2 months). Pore size distribution (PSD) is also investigated by MIP at different positions within the repair systems. Durability indicators (Cl- and CO2) after the repair procedure (> 2 months) present a prevention of chloride penetration and a non-evident influence on carbonation. Evolution is followed during penetration, in order to explore repair efficiency during prolonged service life time. This methodology could also be applied on various systems where exist moisture transfers. For example, a protective layer of Ultra High Performance Fiber-Reinforced Concrete (UHPFRC) on conventional concrete. In conclusion, this methodology is a tool to investigate the repair systems in a systematic and quantitative way, by combining non-destructive and destructive techniques. It is interesting to compare aforementioned systems. Repair efficiency is investigated in order to ensure a long-term durability

The hydration behavior of the calcium aluminates as a function of the glass content, the curing temperature, and the water-solid ratio was investigated. In order to keep them from influencing the results, the free-lime content and the surface area of all samples were kept constant, whenever possible. Samples were hydrated with a water-solid ratio of 10/1 for periods of 1 to 90 days. Three curing temperatures were studied; 2°C, 25°C, and 50°C. Samples were hydrated in tightly sealed polyethylene containers to prevent reactions with atmospheric carbon dioxide. The hydration was followed by X-ray diffraction and thermal analysis. Only two samples, Hexacalcium Tetra-alumino Magnesium Silicate and Tricalcium Magnesium Dialuminate, were successfully prepared in an amorphous form. These compounds were used to investigate the effect of glass content on the hydration behavior. Results indicate that when the glass content is increased a corresponding increase is found in the percent combined water. Samples hydrated at 25°C were influenced by changes in the glass content to a greater degree than were those hydrated at either 2°C or 50°C. The effect of the water-solid ratio on the hydration behavior of the calcium aluminates was studied using the compounds; Hexacalcium Tetra-Alumino Magnesium Silicate/ and Dodecacalcium Hepta-Aluminate. In general, samples that were hydrated with large water-solid ratios reacted more completely than did those hydrated with small water-solid ratios. The presence of sufficient water to theoretically hydrate the samples to completion did not guarantee that the sample would do so. The curing temperature influenced the hydration behavior to a greater degree than did the glass content or the water-solid ratio. Increasing the curing temperature not only increased the rate of hydration, but, in some cases, also changed the hydration products.