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La géothermie est considérée comme une source d'énergie propre et inépuisable à échelle humaine. Actuellement, le rendement des centrales géothermiques est limité à l'exploitation de fluides de températures inférieures à 300°C. L'association de l'activité tectonique et volcanique aux dorsales océaniques fait de l'Islande un lieu où l'extraction de fluides supercritiques (T°>400°C) peut être envisagée. Cette exploitation pourrait multiplier par dix la puissance électrique délivrée par les puits géothermiques. Ces fluides peuvent-ils circuler dans la croûte océanique ? Ce travail propose de contraindre les observations géophysiques et de prédire le fonctionnement des réservoirs hydro-géothermaux de très haute température par l'étude des propriétés physiques des basaltes. La première approche est focalisée sur l'étude de roches ayant accueilli une circulation hydrothermale par le passé. L'étude de ces roches au site ODP 1256, montre que leur porosité est associée à la présence de minéraux d'altération hydrothermale du faciès amphibolite (T°>500°C ). La seconde approche a consisté à recréer en laboratoire les conditions des systèmes hydrothermaux à très haute température afin de prédire les propriétés mécaniques et électriques des basaltes dans ces conditions. Les résultats mécaniques indiquent que la transition fragile/ductile, souvent associée à une forte décroissance de perméabilité, intervient à une température d'environ 550°C. La mise en place d'une cellule de mesure de la conductivité électrique de haute températures a fournit les premiers résultats utiles à l'analyse des données géophysiques. Appliqués aux conditions de la croûte basaltique Islandaise, ces résultats indiquent que des fluides hydrothermaux pourraient circuler au moins transitoirement à l'état supercritique jusqu'à ~ 5 km de profondeur. / Geothermal energy is considered as a green and infinite energy source at human scale. Currently, the yield of geothermal power plants is limited to temperatures of the operating fluid which 300 °C. From tectonic and volcanic activity at mid-ocean ridges, Iceland is a locuswhere supercritical fluid extraction (T > 400° C) can considered for the near future. Exploiting such fluids could theoretically multiply by a factor of ten the electrical power delivered by geothermal wells. Can such fluids circulate at the base of brittle oceanic crust? This work investigates the petrophysical properties of basalts in order to constrain geophysical observations in Iceland and predict the behavior of very high temperature hydro-geothermal reservoirs. The first approach consisted in studying the physical properties of rocks that have hosted deep hydrothermal circulations at oceanic ridges. The study of these rocks at ODP Site 1256 shows that the porosity mea sured both in the field and in the lab is associated with amphibolite facies alteration minerals (T > 500° C). The second approach was to recreate in the laboratory the conditions of pressure, temperature and pore fluid pressure of high temperature to supercritical hydrothermal systems to predict the mechanical and electrical properties of basalts under these conditions. The mechanical results indicate that the brittle/ductile transition occurs at a temperature of about 550° C, where a strong permeability decrease is expected. The implementation and calibration of a new cell for measuring electrical conductivity at high temperature provide the first results for the interpretation of geophysical data. When applied to basaltic crustal conditions in Iceland, these results indicate that hydrothermal fluids could circulate, at least temporarily, in a supercritical state up to 5 km depth.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Steven J. Eckels / The current research presents the experimental investigation of the effect of tube pitch on enhanced tube bundles’ performance. The typical application of this research is flooded refrigerant evaporators. Boosting evaporator’s performance through optimizing tube spacing reduces cost and energy consumption. R-134a with the enhanced tube Turbo BII-HP and R-123 with Turbo BII-LP were used in this study. Three tube pitches were tested P/D 1.167, P/D 1.33, and P/D 1.5. Each tube bundle includes 20 tubes (19.05 mm outer diameter and 1 m long each) constructed in four passes. The test facility’s design allows controlling three variables, heat flux, mass flux, and inlet quality. The type of analysis used is local to one location in the bundle. This was accomplished by measuring the water temperature drop in the four passes. The water-side pressure drop is included in the data analysis. A new method called the EBHT (Enthalpy Based Heat Transfer) was introduced, which uses the water-side pressure drop in performing the heat transfer analysis. The input variables ranges are: 15-55 kg/m².s for mass flux, 5-60 kW/m² for heat flux, and 10-70% for inlet quality. The effect of local heat flux, local quality, and mass flux on the local heat transfer coefficient was investigated. The comparison between the bundle performance and single tube performance was included in the results of each tube bundle. The smallest tube pitch has the lowest performance in both refrigerants, with a significantly lower performance in the case of R-134a. However, the two bigger tube pitches have very similar performance at low heat flux. Moreover, the largest tube pitch performance approaches that of the single tube at medium and high heat fluxes. For the R-123 study, the smallest tube bundle experienced quick decease in performance at high qualities, exhibiting tube enhancement dry-out at certain flow rates and high qualities. The flow pattern effect was demonstrated by the dry-out phenomena. At medium and high heat fluxes, as the tube pitch increases, the performance approaches that of the single tube. All tube bundles experience quick decrease in performance at high qualities. Evidently, P/D 1.33 is the optimum tube pitch for the studied refrigerants and enhanced tubes combinations.

Dans cette thèse, nous présentons une approche modélisatrice multi-échelles au sein de la théorie de la fonctionnelle densité (DFT) de différentes classes de complexes à propriétés magnétiques commutables essentiellement à base de Fe(II) (3d6). Le manuscrit est organisé en trois grandes parties : la première a été consacrée à la présentation de la chimie théorique (concepts et méthodes). Le magnétisme moléculaire été examiné au travers du calcul de la constante de couplage et discuté dans la partie II. L’analyse de la constante de couplage, du magnétisme, des structures électroniques et des liaisons chimiques a été présentée. D’autre part, l’étude des valeurs thermodynamiques pour [Fe(btz)2(NCS)2] ainsi que la famille de complexes à transition de spin [Fe(L)2(NCS)2] a formée la troisième partie. De deux approches complémentaires sont utilisées: i-moléculaire où l’entité isolée est examinée en utilisant des codes de calcul ciblés moyennant différentes fonctionnelles d’échange corrélation et bases ; ii-« tout solide » prenant en compte la structure cristalline étendue. Les résultats sont également appuyés par une étude semi-empirique au sein de la dynamique moléculaire / In this thesis, we present an multiscale approaches based on theoretical modeling within density functional (DFT) of different classes of complex magnetic properties switched from predominantly Fe(II) (3d6). The manuscript is organized into three main parts: the first was devoted to the presentation of theoretical chemistry (concepts and methods). The molecular magnetism was examined through the calculation of the coupling constant and discussed in Part II. The analysis of the coupling constant, magnetism, electronic structure and chemical bonds was presented. In the third Part, the study of thermodynamic values for [Fe(btz)2(NCS)2] and the family of spin crossover complexes [Fe(L)2(NCS)2] has formed the third party. Two complementary approaches are used: i-“molecular” which considers a fragment entity or isolated molecule using different computer codes targeted through various exchange correlation functional and basis; ii-"solid state" taking into account the extended crystal structure. The results are also supported by a semi-empirical study through molecular dynamics.

Au cours des deux dernières décennies, le contexte économique a changé de manière significative en raison de la hausse des prix de l'énergie. Le bâtiment étant devenu le principal secteur consommateur d'énergie, la réduction de celle-ci est devenue un objectif économique, sociétal et environnemental. Ce sujet mobilise de nombreux travaux de recherche. Les Matériaux à Changement de Phase (MCP) représentent une solution innovante qui pourrait contribuer à améliorer la performance énergétique des bâtiments. Ils sont principalement utilisés pour la régulation de température, et leur forte capacité de stockage est un moyen de réduire la consommation d'énergie. Notre étude vise à caractériser, via une approche expérimentale et numérique, le comportement d'un PCM (l’Octadécane). Pour cela, nous avons développé et mis en œuvre un modèle numérique qui corrobore les résultats expérimentaux, et ainsi améliore la prédiction de la performance du MCP considéré.Dans ce travail, notre principale préoccupation est de mettre en évidence les erreurs ou simplifications présentes dans le modèle numérique traditionnel pouvant entraîner un écart global par rapport au comportement réel du MCP. Ces différences conduisent à une estimation erronée des temps de fusion et de la quantité d'énergie stockée. L'amélioration significative de notre modèle est la prise en compte de la convection naturelle, de la surfusion, et l'utilisation des courbes réelles d'enthalpie du MCP considéré. La relation température-enthalpie réelle tient compte de la présence d'une fraction d'impuretés solubles dans le matériau. L’originalité de ce travail est de traiter ces phénomènes physiques via la méthode de Boltzmann réseau (connue sous l'acronyme LBM) avec des fonctions de distribution doubles couplée à une formulation enthalpique. Une telle approche permet de passer outre la non-linéarité des équations régissant l'écoulement et le transfert de chaleur. Sa simplicité de mise en œuvre et son caractère local permettent d'affiner le modèle. Ainsi, on peut couvrir les problèmes de changement de phase, y compris ceux pouvant avoir lieu dans des matrices poreuses ou fibreuses. Ce dernier point a été couvert dans cette thèse.Enfin, il s'est avéré que l'approche numérique adoptée ici pour traiter les problèmes de changement de phase corrobore à la fois nos résultats expérimentaux et ceux disponibles dans la littérature. / Over the past two decades, the economic context has changed significantly due to the rise in energy prices. The building sector has become the main consumer of energy. Thereby, reducing the latter is now an economic, societal and environmental necessity. Accordingly, this topic mobilizes many researches. Phase Change Materials (PCMs) represent an innovative solution, which could improve buildings' energy performance. They are primarily used for temperature regulation, and their high storage capacity can reduce energy consumption.Our study aims at characterizing, via a complementary approach of experimental and numerical simulation, the behavior of a PCM (n-Octadecane). For this, we have developed and implemented a numerical model that corroborates the experimental results, and hence improves the prediction of the PCM performance.In this work, our main concern is to highlight the common errors or simplifications taken in the traditional numerical model, which can result in an overall discrepancy compared to the actual behavior of PCMs. Those discrepancies lead to wrong estimation of the fusion times and amount of energy stored. The major improvement of our model is the consideration of the natural convection, the supercooling, and the use of real enthalpy curves of the considered PCM. The actual temperature-enthalpy relationship takes into account the presence of a fraction of soluble impurities in the material. The originality of this work is to handle these physical phenomena via a lattice Boltzmann method (known by the acronym LBM), which leans on double distribution functions and coupled with the enthalpy formulation. Such an approach overcomes the non-linearity in the governing equations of fluid flow and heat transfer. Its simplicity and local character allow adding complexity to the model. Thereby, one can cover up the phase change problems, including those, which may occur in heterogeneous matrices. This last point has been also covered in this thesis.Finally, it turned out that the approach implemented here for phase change problems supports both, our experimental results and those available in the literature.

Made available in DSpace on 2017-07-21T18:53:22Z (GMT). No. of bitstreams: 1 Polyana Silveia Hornung.pdf: 3542822 bytes, checksum: 8024b84822411cfd8c223c8836b7d0d8 (MD5) Previous issue date: 2014-08-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The starch in its native form does not always have the appropriate physicochemical properties for processing. The chemical and physical changes has been widely studied in order to promote change in these characteristics. The work aimed to study the effects of ultraviolet radiation-induced oxidation of cassava starch. Cassava starch samples were oxidized with sodium hypochlorite and hydrogen peroxide in combination with exposure to ultraviolet light for 1 hour action. The samples were analyzed by Thermogravimetry and Derivative Thermogravimetry (TG / DTG), Differential scanning calorimetry (DSC), Viscoamilograph Analysis (RVA), X Ray Diffraction Powder, Non-contact Atomic Force Microscopy method (NC-AFM) and Color characteristics were analyzed by Reflectance Spectrophotometry. The modified samples showed higher thermal stability compared to the sample of cassava starch unmodified. The results of DSC of the samples modified with H2O2 showed little influence on the enthalpy of gelatinisation, but the modification with sodium hypochlorite considerably decreased the enthalpy of gelatinisation. Similarly, there was a decrease of the peak viscosity and final viscosity and setback, demonstrating the high degree of modification which occurred by treatment with NaClO. The micro-images revealed a significant increase of depressions and projections for the samples treated with NaClO and significant changes were obtained in the mean diameter of the granules of treated samples with H2O2. The two oxidation processes altered the relative crystallinity of the starch samples. The Colorimetry confirmed the bleaching action of NaClO and the mild action of H2O2. Therefore, the two-way modification had effects on the properties of cassava starch. / Os amidos podem ser provenientes de diferentes fontes botânicas mas, em sua forma nativa possuem algumas propriedades que nem sempre são adequadas às necessidades industriais.Assim, muitas alterações podem ser realizadas de diferentes maneiras, cujas propriedades físico-químicas podem tornar-se adequadas para o seu uso. As modificações químicas e físicas vem sendo muito estudadas a fim de promover a alteração destas características. O presente trabalho teve como objetivo estudar os efeitos da radiação ultravioleta na oxidação induzida de amido de mandioca. Amostras de amido de mandioca foram oxidadas com hipoclorito de sódio e peróxido de hidrogênio em ação combinada à exposição à luz ultravioleta por 1 hora. As amostras foram analisadas por Termogravimetria e Termogravimetria Derivada (TG/DTG), Calorimetria Exploratória Diferencial (DSC), Análise Viscoamilográfica (RVA), Difração de raios X pelo método do pó, Microscopia de Força Atômica pelo método não contato (NC-AFM) e as características de Cor foram analisadas por Espectrofotometria de Refletância. As amostras modificadas demonstraram maior estabilidade térmica em relação à amostra de amido de mandioca não modificada. Os resultados de DSC das amostras modificadas por H2O2 demostraram pouca influência sobre a entalpia de gelatinização, mas a para a modificação por hipoclorito de sódio diminuiu significativamente a. Da mesma forma, ocorreu a diminuição dos valores de viscosidade de pico e viscosidade final e setback, demonstrando o alto grau de modificação ocorrida pelo tratamento por NaClO. As micro-imagens revelaram um aumento significativo das depressões e saliências para as amostras tratadas por NaClO e alterações expressivas foram obtidas no diâmetro médio dos grânulos das amostras tradadas por H2O2. Os dois processos oxidativos alteram a cristalinidade relativa das amostras de amido. A colorimetria confirmou a ação de branqueamento do NaClO e a ação branda do H2O2. Portanto, as duas vias de modificação exerceram efeitos sobre as propriedades do amido de mandioca.

Made available in DSpace on 2015-04-14T13:35:46Z (GMT). No. of bitstreams: 1 450558.pdf: 2693787 bytes, checksum: e4ffe9234a98b2ddfc9bc350c708c01c (MD5) Previous issue date: 2013-06-28 / Tuberculosis (TB), one of the oldest recorded human afflictions, is still one of the biggest killers among the infectious diseases. The HIV co-infection and the emergence of multidrug resistant TB have provided a very alarming challenge to global health and led us to focus on the research for new and more effective therapeutics against the disease. The modern approach to the development of new chemical compounds against complex diseases, especially the neglected endemic ones, such as TB, is based on the use of defined molecular targets. Enzymes from the pyrimidine biosynthesis pathway have been considered potential targets for identification or development of novel anti-mycobacterial agents since in bacteria, pyrimidine nucleotide interconvertion pathways are important in a number of essential processes, including DNA, RNA, and phospholipid biosynthesis. Cytidine 5 -monophosphate kinase from Mycobacterium tuberculosis (MtCMK) catalyzes the ATP-dependent phosphoryl group transfer preferentially to CMP and dCMP. Here, initial velocity studies and Isothermal Titration Calorimetry (ITC) measurements showed that MtCMK follows a random-order kinetic mechanism of substrate binding, and an ordered mechanism for product release. The thermodynamic signatures of CMP and CDP binding to MtCMK showed favorable enthalpy and unfavorable entropy, and ATP binding was characterized by favorable changes in enthalpy and entropy. The contribution of linked protonation events to the energetics of MtCMK:phosphoryl group acceptor binary complex formation suggested a net gain of protons. Values for the pKa of a likely chemical group involved in proton exchange and for the intrinsic binding enthalpy were calculated. The Asp187 side chain of MtCMK is suggested as the likely candidate for the protonation event. Data on thermodynamics of binary complex formation were collected to evaluate the contribution of 2 -OH group to intermolecular interactions. The data are discussed in light of functional and structural comparisons among CMP/dCMP kinases and UMP/CMP ones. / A tuberculose (TB), uma das doen?as mais antigas da humanidade, ainda ? uma das principais causas de morte entre as doen?as infecciosas. A coinfec??o com o HIV e a emerg?ncia de TB resistente a m?ltiplas drogas representam um desafio ? sa?de p?blica e tem estimulado a pesquisa por novos e mais efetivos agentes terap?uticos contra a doen?a. Novas abordagens para o desenvolvimento de compostos contra doen?as complexas, especialmente doen?as end?micas negligenciadas, s?o baseadas no uso de alvos moleculares definidos. Enzimas envolvidas no metabolismo de pirimidinas tornam-se alvos moleculares interessantes para compostos inibidores, uma vez que em bact?rias, as rotas de interconvers?o de nucleot?deos pirimid?nicos s?o importantes em in?meros processos essenciais, incluindo a bioss?ntese de DNA, RNA e fosfolip?dios. A citidina 5 -monofosfato quinase de Mycobacterium tuberculosis (MtCMK) em estudo, catalisa a transfer?ncia revers?vel de um grupamento fosforil a partir de ATP, preferencialmente para CMP e dCMP. Neste trabalho, os estudos de velocidade inicial e experimentos de Calorimetria de Titula??o Isot?rmica (ITC) demonstraram que a adi??o dos substratos (CMP e ATP) ? MtCMK segue um mecanismo cin?tico sequencial aleat?rio, e que a libera??o dos produtos ocorre de forma ordenada, onde o ADP ? o primeiro produto a ser liberado. As assinaturas termodin?micas da liga??o do CMP e do CDP ? MtCMK mostraram varia??es favor?veis da entalpia e desfavor?veis da entropia, e, a liga??o do ATP foi caracterizada por mudan?as favor?veis da entalpia e da entropia. As contribui??es energ?ticas oriundas dos eventos de protona??o, associados ? forma??o do complexo bin?rio MtCMK:receptor do grupamento fosforil, sugerem um ganho l?quido de pr?tons. Al?m disso, foram calculados os valores de pKa de um prov?vel grupo envolvido na troca de pr?tons, e da entalpia de liga??o intr?nseca. A cadeia lateral do Asp187 da MtCMK ? sugerido como prov?vel candidato para o evento de protona??o. As medidas termodin?micas da forma??o do complexo bin?rio foram coletados a fim de avaliar a contribui??o do grupo 2 -OH da pentose nas intera??es intermoleculares. Os dados obtidos foram discutidos comparando-se as caracter?sticas estrutural e funcional entre as CMKs j? estudadas e a UMP/CMP quinase humana.

Les variations de température à la surface externe d'une conduite peuvent provoquer la solidification du fluide en écoulement interne, induisant la formation de dépôts solides sur les parois en contact avec le fluide. Ces dépôts peuvent s'avérer néfastes au bon fonctionnement du système intégrant cette conduite ce qui motive l'étude de ces phénomènes physiques afin de comprendre les mécanismes qui les gouvernent et de permettre leur prévention. Ce genre de situations peuvent être rencontrées dans le domaine pétrolier, par exemple lors du transport en pipeline d'huiles chargées de paraffines, d'hydrates ou d'asphaltènes ; dans le domaine agroalimentaire pour la circulation de produits liquides dans des tubes refroidis ou bien tout simplement pour des canalisations d'eau subissant un refroidissement. Dans la majorité des cas le fluide en écoulement dans les conduites pétrolières est un matériau à changement de phase (MCP) complexe et sa composition multiple avec des interactions entre la rhéologie, la constitution et la température impactant la thermo-hydrodynamique de l'écoulement et la cinétique de transition de phase. Dans le cadre de cette thèse nous proposons de nous pencher sur ces aspects par voie de modélisation. Dans la première partie de ce travail, nous avons développé un modèle physique basé sur la méthode enthalpique pour étudier l’impact de la convection naturelle sur des écoulements et des transferts thermiques avec transition de phase solide liquide dans différentes géométries (cavité carré, cylindre, sphère, autour d’un faisceau de cylindre, …). L'effet du maillage et de l'ordre de précision des schémas numérique est aussi présenté. Le même modèle a été utilisé pour analyser la cristallisation d’un mélange de deux paraffines dans des cellules calorimétriques (Differential Scanning Calorimetry). Pour cette étude, le modèle a été validé à l’aide des résultats expérimentaux de la technique DSC. Le problème de l’écoulement d’un mélange de deux paraffines dans une conduite cylindrique a été aussi abordé afin de prédire la cristallisation du mélange sur la paroi interne de la conduite. Une étude paramétrique a été effectuée pour analyser l’influence de différents paramètres (nombre de Reynolds, concentration initiale de la solution binaire, température de la paroi, …) sur la cinétique de la cristallisation du mélange. La deuxième partie de la thèse a été consacrée à l’étude de l’écoulement avec changement de phase liquide-solide d’un brut paraffinique dans des conduites pétrolières. En effet, la cristallisation des paraffines dans les bruts engendre un équilibre phase thermodynamique liquide/solide. Un modèle thermodynamique rendant compte de cet équilibre a été développé (et validé à l’aide de résultats expérimentaux disponible dans la littérature). Ce modèle nous a permis de prédire la température de cristallisation commençante (Wax Appearance Temperature), ainsi que la quantité de paraffines cristallisées. Ce modèle thermodynamique a été couplé avec un modèle physique reposant sur les équations de conservation de la masse, de la quantité de mouvement, de l'énergie et des espèces pour décrire l’écoulement d’un brut paraffinique avec changement de phase liquide-solide dans des conduites pétrolières. Le modèle physique a été validé à l’aide de résultats expérimentaux disponibles dans la littérature. / Temperature change at the outer surface of a pipe can cause solidification of the fluid flowing internally, inducing the formation of solid deposits on the walls in contact with the fluid. This kind of phenomena can be encountered in many situations in the industrial context such as petroleum industries, for example when transporting pipeline oils with paraffins, hydrates or asphaltenes; food industry for the flow of liquids in cooled tubes or simply for water pipes undergoing cooling.The rheology of the transported fluid, its composition and temperature are among the key factors that influence the thermo-hydrodynamics of the flow and the kinetics of the formation of the deposits. The analysis of their impact is required to enhance the understanding of these mechanisms in order to avoid their undesirable effects as fouling or complete blockage of pipes.In this thesis we propose to study these mechanisms by numerical modelling. We will focus on the modelling of phase change and especially on the description of liquid-solid interfaces by models able to integrate the thermodynamics of physical phenomena such as diffuse interface methods. We seek the two-dimensional numerical resolution of the equations of flow, heat and mass transfer while taking into account the coupling between rheology, composition and temperature in the liquid phase as well as at the interface. The work will be undertaken in the basis of the in-house computational fluid dynamics (CFD) code developed in the laboratory.

Made available in DSpace on 2014-06-11T19:30:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-06-01Bitstream added on 2014-06-13T20:01:03Z : No. of bitstreams: 1 capitao_rc_dr_sjrp.pdf: 1458333 bytes, checksum: fd4e34f8fc16fc7f141646298640bdcc (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A hemoglobina (Hb) e uma proteina tetramerica cuja principal funcao e o transporte de oxigenio. As moleculas de O2 se ligam cooperativamente a proteina, com afinidade crescente com a saturacao. O favorecimento a energia de ligacao se deve a mudanca da estrutura quaternaria da proteina, ou seja, da conformacao T de baixa afinidade para a conformacao R de alta afinidade, induzida pela ligacao do ligante. Decorrente desta mudanca conformacional ha um aumento da area de superficie proteica acessivel ao solvente (ASA), na transicao do estado totalmente desoxigenado (T) para o estado totalmente oxigenado (R). Esta variacao de ASA pode ser medida, em solucao, utilizando-se o metodo de estresse osmotico (COLOMBO et al., 1992). Neste trabalho, determinamos o numero de moleculas de agua ( nw) que se liga a diferentes especies de Hb na transicao desoxiHb oxiHb. Este valor varia de especie para especie, e dentro de cada especie e maior na presenca de NaCl do que na ausencia deste sal. A ligacao preferencial do anion cloreto a conformacao T da Hb altera sua estrutura terciaria, o que reflete em mudancas no valor de nw de oxigenacao medidos na ausencia e na presenca deste anion. Como referenciado, os valores de nw de oxigenacao foram determinados em solucao pelo metodo de estresse osmotico, isto e, a partir da determinacao da dependencia de P50 com a atividade de agua (aw). Mostramos que diferentes especies de Hb, em diferentes condicoes de solucao, alem de terem valores de nw de oxigenacao distintos, apresentam valores diferentes de H de oxigenacao ( Hobservado). Os valores de nw e de Hobservado, determinados para as especies de Hb Equina adulta (HbEq), Bovina adulta (HbBovad) e fetal (HbBovfet) em diferentes condicoes experimentais, em conjunto com valores de nw e Hobservado para as hemoglobinas das especies Humana (HbA0) e do molusco Scapharca inaequivalvis (HbI)... / Hemoglobin (Hb) is a tetrameric protein whose main function is oxygen transport. Four O2 molecules bind cooperatively to the protein. The cooperative stepwise increasing in O2-affinity with protein saturation is bound to the change in the protein's quaternary structure from the low O2- affinity conformation (T-state) to the high O2-affinity conformation (R-state) induced by ligand binding. Upon the T'R transition, the water accessible surface area (ASA) of the protein increase, with a consequent binding of extra water molecules to the protein. The change in hydration associated with the ASA can be determined in solution using the osmotic stress method (COLOMBO et al., 1992). In this work, we determined the number of water molecules ( nw) that bind to different Hb specie in the T'R transition. This value changes from specie to specie, and is larger in presence of NaCl than in absence for all specie. In this work we had also determined the enthalpy change of Hb oxygenation ( Hobs) for the different specie and at varied conditions where the value of nw of oxygenation were observed to vary. nw and Hobs values determined for the Equine adult (HbEq), Bovine adult (HbBovad) and fetal (HbBovfet) Hb in different experimental conditions, and nw and Hobs values previously determined for Human (HbA0) and for the mollusk Scapharca inaequivalvis (HbI) hemoglobins, we correlated and analyzed in order to determine the enthalpy and entropy changes associated with the binding of extra water molecules to the newly exposed protein surface upon oxygenation. We have found that 'ÂHsol, the heat change of protein hydration, is approximately -0,57Kcal/mol.H2O. This parameter represents the enthalpic cost of protein hydration in aqueous solution. The entropic cost, ÂSsol, was estimated as approximately -2,89cal/mol.K.H2O. At 298K, the free energy...(Complete abstract click electronic access below)

L'exfoliation en phase liquide du graphite est l'une des méthodes les plus prometteuses pour augmenter la production et la disponibilité commerciale du graphène. Le processus d'exfoliation peut être décrit, de manière conceptuelle, en quatre étapes: le contact du graphite avec le liquide, l'intercalation du solvant entre les feuillets de graphène, la dispersion du matériau à deux dimension et sa stabilisation en phase liquide. Comme les liquides ioniques peuvent être facilement obtenus avec différentes structures moléculaires et donc des propriétés physicochimiques modulables, ils ont été utilisés dans cette thèse comme milieux liquides pour l'exfoliation du graphite. Notre objectif est d'optimiser l'exfoliation du graphite à travers la compréhension des mécanismes moléculaires et des interactions impliquées dans chaque étape du processus. Les énergies interfaciale graphite-liquide ont été calculées à partir de tensions de surface et d'angles de contact mesurées entre des liquides ioniques et du graphite pour déterminer l'affinité de différents liquides à la surface du graphite. Afin d'étudier cette interface liquide - solide, des simulations en dynamique moléculaire ont été menées pour analyser l'organisation des liquides ioniques à la surface du graphite. De même, l'énergie libre nécessaire pour créer des cavités au sein du liquide ionique a été calculée.Des simulations moléculaires ont également été réalisées pour modéliser l'exfoliation d'un feuillet de graphène à partir de graphite en apportant une vue microscopique de l'intercalation des molécules de solvant. L'énergie nécessaire à l'exfoliation a pu être calculée en présence de différents liquides. Des composés polyaromatiques ont été considérés comme des modèles pour le graphène car ils peuvent être facilement obtenus purs, sans variabilité de structure, défauts ou groupes fonctionnels non contrôlés. Les enthalpies de dissolution du naphtalène, anthracène et pyrène dans différents liquides ioniques ont été mesurées par calorimétrie en solution et liées à leur solubilité. L'organisation des ions autour de ces composés modèles a été étudiée par simulation moléculaire et spectroscopie Infra-Rouge.Après l'exfoliation, les échantillons de graphène en suspension dans différents liquides ioniques ont été caractérisés expérimentalement en termes de taille de feuillets (microscopie électronique à transmission et microscopie à force atomique), nombre de couches de graphène (microscopie à force atomique, spectroscopie Raman), concentration totale (spectroscopie UV-visible) et pureté du matériau exfolié (spectroscopie de photoélectrons~X). Vingt liquides ioniques différents à base de cations imidazolium, pyrrolidinium et ammonium et d'anions bis (trifluorométhylsulfonyl)imide, triflate, dicyanamide, tricyanométhanide et méthylsulfate ont été testés. Les interactions moléculaires permettant d'établir de règles de conception pour les liquides ioniques capables d'exfolier les matériaux carbonés ont été identifiées. Le cation pyrrolidinium a montré des résultats prometteurs dans toutes les étapes du processus d'exfoliation, par rapport au cation imidazolium ou ammonium. La sélection d'un grand anion flexible a réduit l'énergie interfaciale avec le graphite, dispersé les nanocarbones en augmentant l'entropie du système et stabilisé le graphite exfolié en plus grande quantité. Un petit anion tel que le triflate semble être favorable à l'obtention de graphène, même si la taille des couches et leur quantité sont réduites. Un liquide ionique ayant une partie apolaire importante facilitera l'insertion et la dispersion du nanomatériau de carbone. Pour la stabilisation du graphite, les interactions alkyle-π et π- π sont décisives. / The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. The exfoliation process can be conceptually described in four steps: the contact of the graphite with liquid, the intercalation of the solvent between layers, the dispersion of the two dimensional material, and its stabilization in the liquid-phase. Because ionic liquids can be easily obtained with chosen molecular structures and tunable physicochemical properties, they were used in this study as liquid media for the exfoliation of graphite. Our aim is to optimize the exfoliation of graphite through the understanding of the molecular mechanisms and of the interactions involved in each step of the process.The liquid-graphite interfacial energies from measured surface tensions and contact angles, between ionic liquids and pristine graphite surface, were used to determine the affinity of different liquids at the surface of graphite. In order to investigate this interface, molecular dynamics simulations were conducted to analyse the ordering of ionic liquids at the surface of graphite. The free energies necessary to create cavities inside the bulk ionic liquid have also been studied.Molecular simulations were also used to study the exfoliation of one graphene layer from a stack of graphite and hence provide a microscopic view of the intercalation of solvent molecules. The energies involved in the process have been calculated.Polyaromatic compounds were regarded as models for graphene as they can be easily obtained pure, without structure variability, defects or uncontrolled functional groups. Enthalpies of dissolution of polyaromatic hydrocarbons (naphthalene, anthracene and pyrene) in different ionic liquids were measured by solution calorimetry and related with their solubility. The ordering of the ions around this model compounds were studied by molecular simulation and spectroscopy Infra-Red.After exfoliation, samples of suspended graphene in different ionic liquids have been characterized experimentally in terms of flake size (using transmission electron microscopy and atomic force microscopy), number of layers (atomic force microscopy, spectroscopy Raman), total concentration (UV-visible spectroscopy) and purity of the exfoliated material (X-ray photoelectron spectrometry).Twenty different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate have been tested. The molecular interactions have been identified thus allowing the establishment of design rules for ionic liquids capable of exfoliating carbon materials. The pyrrolidinium cation has shown promising results in all the steps of exfoliation process, compared to the imidazolium or ammonium cation. Selecting a large and flexible anion reduced the interfacial energy with graphite, dispersed the nanocarbons by increasing the entropy of the system and stabilized the exfoliated graphite in larger quantity. A small anion such as triflate appears to be favorable for obtaining graphene, whereas the size of the layers and their quantity is reduced. An ionic liquid having an important apolar portion will facilitate the insertion and dispersion of graphene layers. For the stabilization of graphite, the alkyl-π et π -π interactions are decisive.