Dans le circuit primaire des réacteurs nucléaires à eau pressurisée, le bore participe au contrôle des réactions de fission. Le traitement de cette solution génère des déchets aqueux contenant une forte concentration en bore (de 1 à 3 mol/L). Le conditionnement de ces déchets à l'aide d'un ciment silico-calcique est compliqué par le fort pouvoir retardateur des ions borate sur l'hydratation du liant. Un traitement des déchets à la chaux est nécessaire pour précipiter les ions borate sous forme d'hexahydroborite. Cette stratégie, si elle limite le retard d'hydratation, ne le supprime pas. Par ailleurs, l'hexahydroborite est instable en milieu cimentaire et se convertit dans le temps en boroaluminate de calcium. Une autre approche pourrait consister à utiliser un ciment sulfoalumineux bélitique à forte teneur en ye'elimite. Ce liant présente en effet l'avantage de former en quantité importante des phases de type AFm et/ou AFt lors de son hydratation, phases qui peuvent incorporer des ions borate dans leur structure.Au cours de ce travail, l'hydratation de ciments sulfoalumineux par des solutions de borate de sodium a été étudiée au jeune âge et à plus long terme (sur une durée de 2 ans) dans l'objectif de préciser l'influence d'un ensemble de paramètres (pH du déchet, concentration en bore, taux de gypse du ciment) sur la vitesse d'hydratation du liant, la nature des hydrates formés, et les propriétés du matériau obtenu (résistance mécanique, stabilité dimensionnelle). Pour ce faire, une démarche analytique, procédant par complexification progressive des systèmes étudiés, a été mise en œuvre. Ainsi ont été successivement abordées la spéciation du bore en solution alcaline, l'étude des phases précipitant au sein des systèmes {CaO, B2O3, Na2O, H2O}, {CaO, B2O3, Al2O3, H2O} et {CaO, Al2O3, B2O3, SO3, H2O}, puis celle des pâtes de ciment gâchées avec une solution boratée simulant le déchet. L'approche expérimentale a été complétée par des modélisations thermodynamiques s'appuyant sur une base de données spécialement développée pour les besoins de l'étude.Il apparaît que le gypse joue un rôle primordial dans le contrôle de la réactivité du ciment. L'ajout de gypse fixe, par un mécanisme indirect, le pH de la solution interstitielle à une valeur proche de 11, ce qui favorise la précipitation transitoire d'un composé boraté faiblement cristallisé, l'ulexite. La dissolution des phases anhydres du ciment est alors fortement ralentie jusqu'à l'épuisement du gypse, conduisant ainsi à des retards de prise considérables. En l'absence de gypse, le retard à l'hydratation est de plus faible amplitude. Dans ces conditions, le pH de la solution interstitielle atteint des valeurs plus élevées, ce qui permet de déstabiliser rapidement l'ulexite. A plus long terme, les ions borate sont incorporés au sein d'une phase de type AFt, en solution solide avec les ions sulfate. Les résultats obtenus permettent de conclure que ce sont les ciments sulfo-alumineux contenant une faible teneur en gypse qui sont les plus adaptés au conditionnement de solutions à forte concentration en bore. / In the primary circuit of pressurized water reactors, boron helps controlling the fission reactions. The treatment of this solution produces aqueous low-level or intermediate-level and short lived radioactive with a high boron concentration (up to 1 to 3 mol/L). Stabilization/solidification of such wastes with calcium silicate cement is complicated by the strong retarding effect of borate ions on cement hydration. A calcium hydroxide addition is required to precipitate borate ions into hexahydroborite. With this approach, the hydration delay is limited, but not suppressed. Besides, hexahydroborite is unstable in the cement paste and is progressively converted into a hydrated calcium boroaluminate phase. Another strategy may consist in using belite calcium sulfoaluminate cement with high ye'elimite content. During hydration, this binder forms indeed large amounts of AFm and/or AFt phases which can incorporate borate ions into their structure.In this work, hydration of calcium sulfoaluminate cement by borated solutions was investigated at early age, and over a 2-year period, in order to determine the influence of a set of parameters (boron concentration and pH of the waste, gypsum content of the cement) on the hydration rate of the binder, on the phase assemblage formed, and on the properties of the resulting material (mechanical strength, volume change). An analytical approach was adopted, based on a progressive increase in the complexity of the investigated systems. The focus was successively placed on the speciation of boron in alkaline solution, on the study of the phases formed within the {CaO, B2O3, Na2O, H2O}, {CaO, B2O3, Al2O3, H2O} and {CaO, Al2O3, B2O3, SO3, H2O} systems, and on the characterization of cement pastes prepared with a borate solution which mimicked the waste. The experimental approach was completed by thermodynamic modelling using a database specially developed for the needs of the study. Gypsum appears to play a key role in controlling the reactivity of cement. The gypsum addition sets, by an indirect mechanism, the interstitial solution pH at a value close to 11, which promotes the precipitation of a poorly crystallized borated compound, ulexite. Dissolution of the anhydrous phases is strongly slowed down until the exhaustion of gypsum, and major delays are observed. Without any gypsum, the hydration delay is shorter. Under these conditions, the pore solution pH reaches higher values after mixing. Ulexite is consequently quickly destabilized. Borate anions are then incorporated into a mixed borate/sulphate AFt type phase. It appears that calcium sulfoaluminate cements with low gypsum contents should be recommended to solidify borated solutions.

Les bétons de chanvre associent un granulat végétal issu du chanvre, appelé « chènevotte », et une matrice minérale. Ce sont des matériaux isolants répondant particulièrement bien aux nouvelles problématiques environnementales du secteur du bâtiment. Pourtant, leur développement est freiné par d'occasionnels désordres de mise en œuvre et des propriétés mécaniques relativement faibles qui pourraient résulter d'interactions complexes développées entre la chènevotte et le liant. Dans ce contexte, l'objectif des travaux a été de préciser la nature de ces interactions et d'identifier par quels mécanismes celles-ci peuvent modifier la prise du liant et les propriétés finales du matériau. Pour cela, l'évolution de mélanges de matières premières (chènevottes et liants) de natures différentes a été étudiée par des techniques de biochimie, de spectroscopie, de physico-chimie et de mécanique. Cette approche multi-échelle a ainsi permis de mettre en évidence le puissant pouvoir retardateur des produits extraits de la chènevotte sur la prise des liants hydrauliques. Ce retard peut conduire à une absence totale de prise du liant, lorsque celui-ci est couplé à des phénomènes de dégradation de la chènevotte, de migration de ces produits dans la matrice et d'évaporation d'eau. En outre, il a été démontré que les caractéristiques de la chènevotte (composition chimique), la nature du liant (ciment pur ou additionné de chaux), ainsi que les conditions de cure (présence ou non de CO2) sont des facteurs pouvant moduler les effets délétères sur la prise et les propriétés mécaniques du matériau formé. Ils constituent donc des paramètres potentiels d'optimisation des bétons de chanvre. / The hemp concretes, combine a plant aggregate, called “shiv” with a mineral binder. They are insulating materials particularly suited to face the new environmental problems of the building sector. However, their development is hampered by the occasional implementation problems and their relatively low mechanical properties that could result from complex interactions between the shiv and the binder. In this context, the objective of the presented work was to clarify the nature of these interactions and to identify the mechanisms by which they can impact the setting of the binder and the final properties of the material. To do so, the evolution of mixtures of the initial components (shiv and binders) differing by their nature was studied by biochemical, spectroscopic, physical chemistry and mechanical techniques. This multi-scale approach enabled us to highlight the powerful set retarding action of shiv-extractable products on hydraulic binders. This delay can even lead to a total failure of the binder setting when this one is coupled to simultaneous degradation of the hemp aggregate, migration of the formed products in the matrix and water evaporation. Finally, it has been demonstrated that the characteristics of the shiv (chemical composition), the nature of the binder (pure cement or lime added), and the curing conditions (presence or absence of CO2) represent factors that may modulate the deleterious effects on the setting and the mechanical properties of the formed material. They hence constitute potential parameters for the optimization of hemp concretes.

Doctor of Philosophy / Department of Civil Engineering / Kyle A. Riding / Finely ground glass has the potential for pozzolanic reactivity and can serve as a supplementary cementitious material (SCM). Glass reaction kinetics depends on both temperature and glass composition. Uniform composition, amorphous nature, and high silica content of glass make ground glass an ideal material for studying the effects of glass type and particle size on reactivity at different temperature. This study focuses on how three narrow size ranges of clear and green glass cullet, 63–75 [mu]m, 25–38 [mu]m, and smaller than 25 [mu]m, as well as combination of glass types and particle sizes affects the microstructure and performance properties of cementitious systems containing glass cullet as a SCM. Isothermal calorimetry, chemical shrinkage, thermogravimetric analysis (TGA), quantitative analysis of X-ray diffraction (XRD), and analysis of scanning electron microscope (SEM) images in backscattered (BS) mode were used to quantify the cement reaction kinetics and microstructure. Additionally, compressive strength and water sorptivity experiments were performed on mortar samples to correlate reactivity of cementitious materials containing glass to the performance of cementitious mixtures. A recently-developed modeling platform called “[mu]ic the model” was used to simulated pozzolanic reactivity of single type and fraction size and combined types and particle sizes of finely ground glass. Results showed that ground glass exhibits pozzolanic properties, especially when particles of clear and green glass below 25 [mu]m and their combination were used at elevated temperatures, reflecting that glass cullet is a temperature-sensitive SCM. Moreover, glass composition was seen to have a large impact on reactivity. In this study, green glass showed higher reactivity than clear glass. Results also revealed that the simultaneous effect of sizes and types of glass cullet (surface area) on the degree of hydration of glass particles can be accounted for through a linear addition, reflecting that the surface area would significantly affect glass cullet reactivity and that the effects of SCM material interaction on reaction kinetics were minimal. However, mechanical properties of cementitious systems containing combined glass types and sizes behaved differently, as they followed the weaker portion of the two particles. This behavior was attributed to the pores sizes, distruibution, and connectiity. Simulations of combined glass types and sizes showed that more work on microstructural models is needed to properly model the reactivity of mixed glass particle systems.

La prédiction des propriétés mécaniques des matériaux cimentaires nécessite d'un modèle intégrant l'hydratation progressive du matériau, le couplage entre la consommation d'eau et les contraintes et l'historique des charges appliquées. Ceci est particulièrement important lors de la modélisation du comportement de la gaine de ciment des puits pétroliers qui est soumise, dès son plus jeune âge, à une large gamme de chargements mécaniques et thermiques qui pourraient avoir un effet négatif sur ses propriétés mécaniques. L’objectif de cette thèse est de fournir un cadre de modélisation pour le comportement hydro-mécanique d'une pâte de ciment pétrolier dès son plus jeune âge jusqu'à son état durci. Le manuscrit est divisé en deux parties. Partie I : cinétique d'hydratation L’évolution des propriétés physiques des matériaux cimentaires est contrôlée par l'avancement des réactions d'hydratation. Deux approches de modélisation sont présentées:- Un cadre théorique pour la modélisation de l'hydratation du ciment est développé comme une extension des modèles de nucléation et de croissance classiques. Le modèle multi-composants proposé considère explicitement le ciment anhydre et l'eau comme des phases indépendantes participant à la réaction. Un taux de croissance est introduit qui permet de représenter sous une forme mathématique unique la croissance linéaire ainsi que la diffusion parabolique. La formulation introduit naturellement des paramètres des mélanges cimentaires tels que la composition de la poudre de ciment, les densités des différentes phases, le rapport eau/ciment, le retrait chimique et les propriétés des hydrates. Les différents mécanismes de contrôle de la réaction sont identifiés sur la base du modèle physique proposé.- Une loi générale de la cinétique d'hydratation basée sur la théorie des transformations en phase solide est proposée. Cette formulation est comparée aux lois d'évolution trouvées dans la littérature et contribue à fournir une explication physique qui pourrait aider à la compréhension de la cinétique d'hydratation du ciment. Dans les deux cas, les modèles cinétiques sont calés sur une série de résultats expérimentaux. Partie II : loi de comportement mécanique Le comportement mécanique de la pâte de ciment est décrit dans le cadre des milieux poreux réactifs. La pâte de ciment est modélisée en tant que matériau poreux multi-phases avec une loi constitutive élasto-visco-plastique, dont les paramètres dépendent du degré d'hydratation. Le retrait chimique de la pâte de ciment et la consommation d'eau pendant l'hydratation sont pris en compte dans la détermination des déformations macroscopiques. L’évolution des paramètres poroélastiques de la pâte de ciment lors de l'hydratation est calculée à l’aide d'un modèle micromécanique. Une surface de charge asymétrique avec des seuils de compression et de traction est adoptée pour le régime plastique, avec des mécanismes d’écrouissage tenant compte à la fois des déformations plastiques accumulées et du degré d'hydratation. Le comportement visqueux est basé sur les notions de la théorie de solidification. Une courbe de rétention d'eau est introduite pour tenir compte de la désaturation potentielle du matériau lors de l'hydratation. Les paramètres du modèle pour une pâte de ciment pétrolier classe G sont évalués en simulant des expériences de chargement mécanique dans un dispositif spécialement conçu pour tester le comportement thermo-mécanique de la pâte de ciment dès le début de l'hydratation. Le modèle prédit avec une bonne précision la réponse d'une pâte de ciment en cours d’hydratation lorsqu'elle est soumise à divers chemins de chargement dès son plus jeune âge. L'importance de l'histoire de chargement est mise en évidence, ainsi que la nécessité de la détermination des contraintes effectives tout au long de la vie du matériau / The prediction of the performance of cement-based materials requires a holistic model integrating the progressive hydration of the material, the coupling between water consumption and strains, and the history of the applied loadings. This is particularly important when modelling the behavior of the cement sheath in oil wells which is subjected, from its earliest age and during its lifetime, to a wide range of mechanical and thermal loadings that could have a detrimental effect on its future mechanical properties. The aim of the present thesis is to provide a complete modelling framework for the hydro-mechanical behavior of an oil well cement paste from its earliest age to its hardened state. The manuscript is divided in two parts. Part I: Hydration kinetics The evolution of the most significant physical properties of cement-based materials is controlled by the advancement of the hydration reactions. Two different modelling approaches are presented:- A theoretical framework for the modelling of cement hydration is developed as an extension of classical nucleation and growth models. The proposed multi-component model explicitly considers anhydrous cement and water as independent phases participating in the reaction. We also introduce a growth rate that encompasses linear as well as parabolic diffusion growth in a single continuous mathematical form. The formulation naturally introduces some of the most relevant parameters of cement paste mixtures, such as the cement powder composition, mass densities of the different phases, water to cement ratio, chemical shrinkage and hydrates properties. The different rate-controlling mechanisms can be identified and interpreted on the basis of the proposed physical model.- A general hydration kinetics law based on the theory of solid phase transformations is proposed. This formulation is compared with the evolution laws found in the literature and helps providing a physical explanation that could shed light on the understanding of cement hydration kinetics. In both cases, the kinetic models are calibrated over a series of experimental results in order to properly evaluate the quality of the predictions. Part II: Mechanical constitutive law The mechanical behavior of cement paste is described in the framework of reactive porous media. The cement paste is modelled as a multi-phase porous material with an elastic-viscous-plastic constitutive law, with mechanical parameters depending on the hydration degree. Furthermore, the cement paste chemical shrinkage and pore water consumption during hydration are accounted for in the determination of the macroscopic strains. The evolution of the poroelastic parameters of the cement paste during hydration is calculated by means of a micromechanical upscaling model. An asymmetric yield surface with compressive and tensile caps is adopted for the elastoplastic regime, with hardening mechanisms considering both the cumulated plastic deformations and the hydration degree. The viscous behaviour is based on the notions of solidification theory. A water retention curve is introduced to account for the potential desaturation of the material during hydration. The model parameters for a class G cement paste are evaluated by simulating the results of mechanical loading experiments in a device specially designed for testing the thermo-mechanical behavior of cement paste from the early stages of hydration. The results show that the proposed model predicts with good accuracy the response of a hydrating cement paste when subjected to various loading paths from its early age. The importance of the loading history is outlined, as well as the need for the accurate determination of the effective stresses throughout the life of the material

The influence of temperature and hydration on the long term stability of the buffer material was studied during two experimental studies - "Mock-Up-CZ" experiment and "Long-term stability of engineering barriers" project. The objectives of these studies is to identify mineralogical, chemical and geochemical changes and describe transformation processes in the bentonite materials due to heating and interaction with various saturation media (with different chemical composition) under controlled laboratory and in situ conditions. The Rokle bentonite suitability for its use in the Czech deep repository of high-level radioactive waste was investigated. Mineralogical changes in the bentonites were evaluated by X-ray diffraction. The material of the barrier of the Mock-Up-CZ experiment is a mixture of non­activated Rokle bentonite (85 vol.%), quartz sand (10 vol.%) and graphite (5 vol.%). The barrier has been subjected to thermal stress (up to 90 řC) and synthetic granitic water for 45 months. No sample from 70 analysed samples taken at different depth levels and distances from the source of the heat and/or water showed measurable transformation of original smectites. Newly formed gypsum bordered by illite aureole was detected in the upper part of the experimental set-up (backfill samples), i.e. in the...

This Thesis had as objectives to study the hydration process of grains with sigmoidal behavior, evaluating ultrasound technology to improve it, the possible effects on germination, cooking and a possible incorporation of nutrients. The work was developed in three parts. The first part consisted of describing the hydration kinetics of many grains to have a data bank of hydration kinetics, allowing further selections. Furthermore, this part compared the differences among grains hydration kinetics, associating them with the intrinsic properties of the grains and questioning some inferences previously published in the literature. The second part was related to study the effect of ultrasound on the hydration kinetics of grains with sigmoidal behavior, being studied Andean lupin, mung beans and white kidney beans. Further, the effect of ultrasound in combination with soaking water at high temperatures was studied to demonstrate if they have additive, synergic or antagonist effect. The effect of ultrasound technology was evaluated in the water uptake, extraction of components, germination and cooking kinetics. The third part consisted of studying and describing the incorporation of a nutrient inside the grains, taking advantage of the hydration process. Further, ultrasound was used to improve this incorporation. The main results of this work corroborate that the hydration process is a complex phenomenon, and many intrinsic properties of the grains causes the kinetics differences. In addition, the fact that only legume grains have sigmoidal behavior of hydration was proved. Further, the ultrasound accelerated the hydration process of grains with sigmoidal behavior without affecting the grain starch, improving the extraction of undesirable components, enhancing or hindering the germination (depending on the grain), but without affecting the cooking process. Another result was that the higher the soaking water temperature is, the lower the ultrasound effect on hydration is. Finally, regarding nutrient incorporation, a hydrophilic nutrient (iron) was incorporated in a grain during hydration process demonstrating that it is possible. The iron incorporation had the same behavior as the water uptake, suggesting similar mechanisms and phenomena of mass flow. In addition, the incorporated iron was attached not only to the bean cotyledon, but also mostly in the seed coat. Furthermore, ultrasound technology enhanced this process. The cooking process of the studied grains was improved, and its germination was hindered by the incorporated iron. In conclusion, ultrasound technology can be used for improving the hydration process of grains with sigmoidal behavior, being also practical for nutrient incorporation into grains. / A presente Tese teve como objetivos estudar o processo de hidratação de grãos com comportamento sigmoidal de hidratação, avaliar a tecnologia de ultrassom para a sua melhora, os possíveis efeitos na germinação, cozimento e possível incorporação de nutrientes. O trabalho foi feito em três etapas. A primeira etapa consistiu em realizar uma prospecção de hidratação de diversos grãos, auxiliando na escolha dos futuros grãos a serem estudados. Ainda, comparou-se as cinéticas de hidratação associando-as com as propriedades intrínsecas dos grãos, avaliando diversas inferências publicadas sobre o processo. Na segunda etapa estudou-se o efeito do ultrassom de alta potência no processo de hidratação de três grãos com comportamento sigmoidal: tremoço andino, feijão moyashi e feijão branco. Também foi avaliado o efeito combinado do ultrassom e a temperatura da água de hidratação. O efeito da tecnologia de ultrassom foi avaliado na cinética de absorção de água, extração de compostos, germinação e cozimento. A terceira etapa consistiu em aproveitar o longo tempo do processo de hidratação para incorporar um nutriente hidrossolúvel dentro do grão. O ultrassom foi também usado para acelerar este processo. Os resultados mais importantes da Tese foram que se corroborou que a hidratação de grãos é um processo complexo e que há muita dificuldade em correlacionar as propriedades intrínsecas dos grãos com as características da hidratação. Ainda, foi demonstrado que o comportamento sigmoidal de hidratação é somente encontrado em grãos da família das leguminosas. Também foi demostrado que o ultrassom acelera a hidratação de grãos com comportamento sigmoidal e que esta tecnologia não afeta o amido dos grãos, melhora ou piora a germinação (dependendo do grão), e não afeta o cozimento. Corroborou-se que quanto maior a temperatura da água, menor é o efeito do ultrassom na cinética de hidratação. Finalmente, demonstrou-se que é possível incorporar nutrientes solúveis dentro dos grãos, aproveitando assim o longo tempo de hidratação. Encontrou-se que a incorporação de nutrientes segue mecanismo similar que a entrada de água, e que pode ser acelerado usando ultrassom. Também, foi demonstrado que o ferro foi incorporado no cotilédone e no tegumento (em maior quantidade), e que este composto melhora o cozimento do feijão, porém prejudica a sua germinação. Em conclusão, o ultrassom pode ser usado para melhorar o processo de hidratação de grãos e para a incorporação de algum nutriente.

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.

Thesis advisor: Mary F. Roberts / As the central repository of biological information and ultimate mediator of all processes underlying the activities of living organisms, nucleic acids are the sine qua non for life as we know it. Biological research over the past century and more has revealed much of the structure and function of nucleic acids, revealing in turn how life begins, changes, reproduces, and ends. We glimpse how life has become what it is and perhaps what it may become. This work seeks to understand the ramifications of altering a single nitrogen of the purine nucleoside components of nucleic acids. As will be shown, purine analogs lacking the N3 nitrogen have altered interactions with proteins, water, and other molecules. Replacement of this nitrogen with a C-H, C-CH3, or C-CH2OH functionality impacts the structure and biological interactions of a DNA duplex containing these alterations in ways not entirely foreseen when this work began over ten years ago. The synthetic effort needed to obtain purine nucleosides containing each of these modifications is significant. Along the way, new methodologies applicable both to the synthesis of purine analogs and natural purine nucleosides are described. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

O objetivo do presente trabalho foi o de estudar as relações entre as variações na hidratação inicial, no tamanho e na qualidade fisiológica das sementes de soja. Para tanto, 3 lotes (cultivar BRS-157), com qualidade fisiológica distinta, tiveram as sementes padronizadas por espessura (13/64 de polegada) e submetidas a embebições a 20ºC em períodos variáveis (3, 6, 9 e 12h). Após as embebições, as sementes foram reclassificadas por espessura e, posteriormente à estimativa da freqüência de indivíduos presentes em cada fração, submetidas às avaliações da qualidade fisiológica. Foi verificado que a qualidade fisiológica afeta o teor de água e a espessura alcançados pelas sementes de soja durante a embebição; assim, há a possibilidade de comparar o desempenho fisiológico relativo de lotes por intermédio dos dados de freqüência de espessura em sementes hidratadas. / The objective of the present work was to study the relationships among the variations in the initial hydration, size and on physiologic quality of soybean seeds. Three lots (cv.BRS-157) with different physiologic quality had the seeds standardized according to thickness (13/64 inches) and submitted to hydration at 20ºC in variable periods (3, 6, 9 and 12h). After the hydration, the seeds were classified according to thickness and subsequently the individuals' frequency in each fraction was estimated, submitted to evaluations of the physiologic quality. The physiologic quality was verified to affect the water content and the thickness reached by the soybean seeds during the hydration; therefore, it is possible to compare the relative physiologic quality of lots through the thickness frequency data in moisturized seeds.

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