High performance multifunctional epoxy resin systems are becoming increasingly important as matrix materials for the advanced composites used in aerospace, electronics, automotive and other industries. In a composite based on epoxy resin systems, a three-dimensional network of the matrix is formed around the reinforcing fibre as a result of the chemical reaction between the resin and the curing agent. This chemical process, known as curing, is an important event to he considered in the production of composite components made up of these resin systems. Two process parameters namely viscosity and chemical conversion are of paramount significance in the production of composite materials Curing studies of the resin systems based on these two parameters, would therefore assume great importance in deciding the performance reliability of the end product. The objectives of the present investigation are 1. to study the cure kinetics of three thermoset resin systems, viz., i) epoxy novolac (EPIT)/ diamino diphenyl methane{DDM), ii) trigylcidyl para- ammo phenol (TGPAP)/toluene diamine (TDA) and iii) tetraglycidyl diamino diphenyl methane (TGDDM)/pyridine diamine(PDA) using the cure kinetic models based on chemical conversion (α), Theological conversion (β) and viscosity. 2.to develop a correlation between a and viscosity (η) and modify an existing autocatalytic model based on α, to the viscosity domain and 3.to investigate the cure behaviour of these systems in terms of the TTT cure diagram and its associated models. EPN/DDM, TGPAP/PDA and TGDDM/PDA resin systems were chosen for the studies to represent a range of functionalities, The cure was monitored using differential scanning calorimetry (DSC), fourier transform infrared (FTIR) and dynamic mechanical analysis (DMA) techniques by following the changes in enthalpy, functional groups and rheology, respectively. The kinetic parameters namely, order of reaction and activation energy were estimated from dynamic DSC data using the methods of Freeman-Carroll and Ellerstein using nth rate expression. Barton, Kissinger and Osawa methods were employed to find out the activation energy from the peak/equal conversion at different heating rates. Isothermal DSC data were also analyzed using nth order model and it was observed that the data could be fitted satisfactorily only for higher temperatures The results obtained from the analysis of both dynamic and isothermal DSC data using nth order model clearly indicate that this model is inadequate for describing the cure behavior. The isothermal DSC data was analyzed by the autocatalytic models of Hone and Kamal Good correlation was observed with Hum and Kamal models up to 60-70%, 25% and 45% conversions for EPN/DDM, TGPAP/TDA and TCDDM/PDA systems respectively. However, the parameters m and n in Kamal model were found to be temperature dependent for EPN/DDM and TCPAP/TDA systems. The limited applicability of the autocatalytic models IK attributed to the counter-effect offered by the intra-molecular bonding taking place. The primary amine and epoxy groups conversions obtained from FTIR were analyzed using autocatalytic model and the kinetic parameters were calculated. The reactivity ratio of the primary amine and the secondary amine with epoxy was found to be dependent on temperature in agreement with the recent findings reported m the literature. The existing models that relate the cure kinetics and the rheological changes, are dual Arrhenius nth order model and autocatalytic model The nth order kinetic model was used to evaluate the kinetic parameters using the viscosity data at different cure temperatures under isothermal conditions As the storage modulus, G' is proportional to the chemical cross links and becomes significant only after the g<4 point, it was used to follow the changes in conversion known as rheoconversion after the gel point The rheoconversion was found by normalizing the G' data with G1^, the storage modulus of the fully cured resin It was used to study the cuie kinetics using an autocatalytic model The kinetic parameters such as rate constant, acceptation and retardation parameters were evaluated and that temperature dependence was established. While the existing models relate viscosity and conversion only up to gel point the new proposed model, termed VISCON model takes into account the changes up to vitrification. The relation so developed is used to modify the autocatalytic cure model based on chemical conversion. The parameters appearing in this model were evaluated using Levenberg-Marquardt error minimization algorithm. The kinetic parameters obtained are comparable with the values estimated using the DSC data. All the models cited above represent the microkinetic aspects. The models based on the information of TTT cure diagrams, however, represent the macrokinetic aspects of the cure, as they are based on the cure stages such as gelation and vitrification TTT diagram relates the cure characteristics like cure temperature, cure time, Ta and, indirectly, chemical conversion Hence the ultimate properties of the composite could he predicted and established with the help of the models based on TTT cure diagrams The changes in the storage modulus, G1 and loss modulus, G", were followed to identify the gel and vitrification points of the resin systems at different cure temperatures Gel point and vitrification point were used to generate gelation and vitrification hues in the construction of TTT cure diagrams for EPN/DDM, TGPAP/TDA and TGDDM/PDA resin systems Theoretical TTT diagrams were generated and IBO-T, contours were established using the TTT diagram-based models The cure schedule for the resin systems investigated could be determined from the TTT diagram and the respective rheological data.

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Dans les réacteurs industriels ou dans la nature, l'écoulement de fluides peut être couplé à des réactions chimiques. Dans de nombreux cas, il en résulte l'apparition de structures complexes dont les propriétés dépendent entre autres de la géométrie du système.<p><p>Dans ce contexte, le but de notre thèse a été d'étudier de manière théorique et sur des modèles réaction-diffusion-convection simples les propriétés de dynamiques spatio-temporelles résultant du couplage chimie-hydrodynamique. <p>Nous nous sommes focalisés sur les instabilités hydrodynamiques de digitation visqueuse et de densité qui apparaissent respectivement lorsqu'un fluide dense est placé au-dessus d'un fluide moins dense dans le champ de gravité et lorsqu'un fluide visqueux est déplacé par un fluide moins visqueux dans un milieu poreux.<p><p>En particulier, nous avons étudié les problèmes suivants:<p>- L'influence d'une réaction chimique de type A + B → C sur la digitation visqueuse. Nous avons montré que les structures formées lors de cette instabilité varient selon que le réactif A est injecté dans le réactif B ou vice-versa si ces réactifs n'ont pas un coefficient de diffusion ou une concentration initiale identiques.<p>- Le rôle de pertes de chaleur par les parois du réacteur dans le cadre de la digitation de densité de fronts autocatalytiques exothermiques. Nous avons caractérisé les conditions de stabilité de fronts en fonction des pertes de chaleur et expliqué l'apparition de zones anormalement chaudes lors de cette instabilité.<p>- L'influence de l'inhomogénéité du milieu sur la digitation de densité de solutions réactives ou non. Nous avons montré que les variations spatiales de perméabilité d'un milieu poreux peuvent figer ou faire osciller la structure de digitation dans certaines conditions.<p>- L'influence d'un champ électrique transverse sur l'instabilité diffusive et la digitation de densité de fronts autocatalytiques. Il a été montré que cette interaction peut donner lieu à des nouvelles structures et changer les propriétés du front.<p><p>En conclusion, nous avons montré que le couplage entre réactions chimiques et mouvements hydrodynamiques est capable de générer de nouvelles structures spatio-temporelles dont les propriétés dépendent entre autres des conditions imposées au système.<p>/<p>In industrial reactors or in nature, fluid flows can be coupled to chemical reactions. In many cases, the result is the emergence of complex structures whose properties depend among others on the geometry of the system.<p>In this context, the purpose of our thesis was to study theoretically using simple models of reaction-diffusion-convection, the properties of dynamics resulting from the coupling between chemistry and hydrodynamics.<p><p>We focused on the hydrodynamic instabilities of viscous and density fingering that occur respectively when a dense fluid is placed above a less dense one in the gravity field and when a viscous fluid is displaced by a less viscous fluid in a porous medium.<p><p>In particular, we studied the following issues:<p>- The influence of a chemical reaction type A + B → C on viscous fingering. We have shown that the fingering patterns observed during this instability depends on whether the reactant A is injected into the reactant B or vice versa if they do not have identical diffusion coefficients or initial concentrations.<p>- The role of heat losses through the reactor walls on the density fingering of exothermic autocatalytic fronts. We have characterized the conditions of stability of fronts depending on heat losses and explained the appearance of unusually hot areas during this instability.<p>- The influence of the inhomogeneity of the medium on the density fingering of reactive solutions or not. We have shown that spatial variations of permeability of a porous medium may freeze or generate oscillating fingering pattern under certain conditions.<p>- The influence of a transverse electric field on the Rayleigh-Taylor and diffusive instabilities of autocatalytic fronts. It was shown that this interaction may lead to new structures and may change the properties of the front.<p><p>In conclusion, we showed that the coupling between chemical reactions and hydrodynamic motions can generate new space-time structures whose properties depend among others, on the conditions imposed on the system. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Le régulateur transcriptionnel BAP1 est une déubiquitinase nucléaire (DUB) dont le substrat est l’histone H2A modifiée par monoubiquitination au niveau des residus lysines 118 et 119 (K118/K119). Depuis les dernières années, BAP1 emerge comme un gene suppresseur de tumeur majeur. En effet, BAP1 est inactivé dans un plethore de maladies humaines héréditaires et sporadiques. Cependant, malgré l’accumulation significative des connaissances concernant l’occurrence, la pénétrance et l’impact des défauts de BAP1 sur le développement de cancers, ses mécanismes d’action et de régulation restent très peu compris. Cette étude est dédiée à la caractérisation moléculaire et fonctionnelle du complexe multi-protéique de BAP1 et se présente parmi les premiers travaux décrivant sa régulation par des modifications post-traductionnelles. D’abord, nous avons défini la composition du corps du complexe BAP1 ainsi que ses principaux partenaires d’interaction. Ensuite, nous nous sommes spécifiquement intéressés a investiguer d’avantage deux principaux aspects de la régulation de BAP1. Nous avons d’abord décrit l’inter-régulation entre deux composantes majeures du complexe BAP1, soit HCF-1 et OGT. D’une manière très intéressante, nous avons trouvé que le cofacteur HCF-1 est un important régulateur des niveaux protéiques d’OGT. En retour, OGT est requise pour la maturation protéolytique de HCF-1 en promouvant sa protéolyse par O-GlcNAcylation, un processus de régulation très important pour le bon fonctionnement de HCF-1. D’autre part, nous avons découvert un mécanisme unique de régulation de BAP1 médiée par l’ubiquitine ligase atypique UBE2O. en effet, UBE2O se caractérise par le fait qu’il s’agit aussi bien d’une ubiquitine conjuratrice et d’une ubiquitine ligase. UBE2O, multi-monoubiquitine BAP1 au niveau de son domaine NLS et promeut son exclusion du noyau, le séquestrant ainsi dans le cytoplasme. De façon importante, nos travaux ont permis de mettre de l’emphase sur le rôle de l’activité auto-catalytique de chacune de ces enzymes, soit l’activité d’auto-déubiquitination de BAP1 qui est requise pour la maintenance de sa localisation nucléaire ainsi que l’activité d’auto-ubiquitination d’UBE2O impliquée dans son transport nucléo-cytoplasmique. De manière significative, nous avons trouvé que des défauts au niveau de l’auto-déubiquitination de BAP1 due à des mutations associées à certains cancers indiquent l’importance d’une propre regulation de cette déubiquitinase pour les processus associés à la suppression de tumeurs. / BAP1 is a nuclear deubiquitinating enzyme (DUB) that acts as a transcription regulator and a DUB of nucleosomal histone H2AK119. In the recent years, it has become clear that BAP1 is a major tumor suppressor, inactivated in a plethora of hereditary and sporadic human malignancies. Although, we now accumulated a significant body of knowledge in respect to the occurrence, penetrance and impact of BAP1 disruption in cancer, its mechanism of action and regulation remained poorly defined. This work is dedicated to the biochemical and functional characterization of the BAP1 multiprotein complex and presents one of the first cases regarding its regulation by post-translational modifications. First, we defined the initial composition of the BAP1 complex and its main interacting components. Second, we specifically focused on two aspects of BAP1 regulation. We described the cross regulation between the two major components of the complex namely HCF-1 and OGT. We found that HCF-1 is important for the maintenance of the cellular levels of OGT. OGT, in turn, is required for the proper maturation of HCF-1 by promoting O-GlcNAcylation-mediated limited proteolysis of its precursor. Third, we discovered an intricate regulatory mechanism of BAP1 mediated by the atypical ubiquitin ligase UBE2O. UBE2O multi-monoubiquitinates BAP1 on its NLS and promotes its exclusion from the nucleus. Importantly, our work emphasises the role of the autocatalytic activity of both enzymes namely the auto-deubiquitination activity of BAP1, required for the maintenance of nuclear BAP1 and the auto-ubiquitination of UBE2O implicated in its nucleocytoplasmic transport. Significantly, we found that auto-deubiquitination of BAP1 is disrupted by cancer-associated mutations, indicating the involvement of this process in tumor suppression.

Motivated by the existence of complex behaviors arising from interactions between chemistry and fluid dynamics in numerous research problems and every-day life situations, we theoretically investigate the dynamics resulting from the interplay between chemistry, diffusion, and fluid motions in a reactive aqueous solution. As a chemical reaction induces changes in the temperature and in the composition of the reactive medium, such a reaction can modify the properties of the solution (density, viscosity, surface tension,…) and thereby trigger convective motions, which in turn affect the reaction. Two classes of convective flows are commonly occurring in solutions open to air, namely Marangoni flows arising from surface tension gradients and buoyancy flows driven by density gradients. As both flows can be induced by compositional changes as well as thermal changes and in turn modify them, the resulting experimental dynamics are often complex. The purpose of our thesis is to gain insight into these intricate dynamics thanks to the theoretical analysis of model systems where only one type of convective flow is present. In particular, we numerically study the spatio-temporal evolution of model chemical fronts resulting from the coupling between reactions, diffusion, and convection. Such fronts correspond to self-organized interfaces between the products and the reactants, which typically have different density and surface tension. Fluid motions are therefore spontaneously induced due to these differences across the front.<p><p>In this context, we first address the propagation of a model autocatalytic front in a horizontal solution layer, in the presence of pure Marangoni convection on the one hand and of pure buoyancy convection on the other hand. We evidence that, in both cases, the system attains an asymptotic dynamics characterized by a steady fluid vortex traveling with the front at a constant speed. The presence of convection results in a deformation and acceleration of the chemical front compared to the reaction-diffusion situation. However we note important differences between the Marangoni and buoyancy cases that could help differentiate experimentally between the influence of each hydrodynamic effect arising in solutions open to the air. We also consider how the kinetics and the exothermicity of the reaction influence the dynamics of the system. The propagation of an isothermal front occurring when two diffusive reactants are initially separated and react according to a simple bimolecular reaction is next studied in the presence of chemically-induced buoyancy convection. We show that the reaction-diffusion predictions established for convection-free systems are modified in the presence of fluid motions and propose a new way to classify the various possible reaction-diffusion-convection dynamics./En induisant des changements de composition et de température, une réaction chimique peut modifier les propriétés physiques (densité, viscosité, tension superficielle,…) de la solution dans laquelle elle se déroule et ainsi générer des mouvements de convection qui, à leur tour, peuvent affecter la réaction. Les deux sources de convection les plus courantes en solution ouverte à l’air sont les gradients de tension superficielle, ou effets Marangoni, et les gradients de densité. Comme ces deux sources sont en compétition et peuvent toutes deux résulter de différences de concentration ou de température, les dynamiques observées expérimentalement sont souvent complexes. Le but de notre thèse est de contribuer à la compréhension de telles dynamiques par une étude théorique analysant des modèles réaction-diffusion-convection simples. En particulier, nous étudions numériquement l’évolution spatio-temporelle de fronts chimiques résultant du couplage entre chimie non-linéaire, diffusion et hydrodynamique. Ces fronts constituent l’interface auto-organisée entre les produits et les réactifs qui typiquement ont des densités et tensions superficielles différentes. Des mouvements du fluide peuvent dès lors être spontanément initiés dus à ces différences au travers du front.<p> <p>Dans ce contexte, nous étudions la propagation d’un front chimique autocatalytique se propageant dans une solution aqueuse horizontale, d’une part en la seule présence d’effets Marangoni, et d’autre part en présence uniquement d’effets de densité. Nous avons montré que dans les deux cas, le système atteint une dynamique asymptotique caractérisée par la présence d’un rouleau de convection stationnaire se propageant à vitesse constante avec le front. Ce front est à la fois déformé et accéléré par les mouvements convectifs par rapport à la situation réaction-diffusion. Nous avons mis en évidence d’importantes différences entre les deux régimes hydrodynamiques qui pourraient aider les expérimentateurs à différencier les effets de tension superficielle de ceux de densité générés par la propagation de fronts chimiques en solution. Nous avons également considéré l’influence de la cinétique de réaction ainsi que de l’exothermicité sur la dynamique de ces fronts. Enfin, nous avons étudié la propagation en présence de convection d’un front de réaction impliquant deux espèces de densités différentes, initialement séparées et réagissant selon une cinétique bimoléculaire. Nous avons montré que la convection modifie les propriétés réaction-diffusion du système et nous proposons de nouveaux critères pour classifier les dynamiques réaction-diffusion-convection.<p><p><p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished