Dans ce travail de thèse nous nous sommes intéressés aux phénomènes de transport au sein du réseau lacuno-canaliculaire (RLC) et de l'ostéon dans le tissu osseux cortical. Pour étudier la mécanotransduction ostéocytaire amenant au remodelage osseux, nous avons développé un modèle à trois échelles où sont pris en : l'électrcompte ostatique (modélisée par l'équation de Poisson Boltzmann), l'écoulement du fluide (représenté textit{via} une équation de Stokes modifiée et la conservation de la masse fluide) et le transport ionique (régi par l'équation de Nernst-Planck). L'étude de la distribution du potentiel électrique, a mis en exergue l'importance des double-couches électriques au voisinage des parois chargées des pores. Ces double-couches électriques, ainsi que la composition chimique du fluide donnent lieu à des phénomènes d'osmose et d'électroosmose intervenant dans l'écoulement du fluide interstitiel, et influençant la diffusion efficace des ions dans les pores. L'étude a démarré à l'échelle du pore canaliculaire pour être propagée à l'échelle du canalicule puis de l'ostéon, en utilisant une procédure d'homogénéisation périodique asymptotique. Une étude paramétrique nous a permis de cibler les paramètres agissant sur les phénomènes de transport et pouvant faire réagir les ostéocytes. Il est ressorti de cette étude que les effets électro-chimiques jouent rôle important. Nous avons donc choisi de nous focaliser sur la chimie et plus particulièrement sur les effets des flux ioniques physiologiques sur les ostéocytes dans le RLC. Des expériences, mises en place pour étayer ces aspects ont souligné l'importance des échanges chimiques entre les cellules et le fluide qui les entoure. Finalement, nous avons montré que les phénomènes de transports ayant lieu dans le RLC et dans l'ostéon interagissent les uns les autres, parachevant ainsi la description à trois échelles du tissu cortical / Transport phenomena appearing within the cortical bone lacuno-canalicular network (LCN) and the osteon were the objective of this study. We developped a three-scale model to investigate the osteocyte mechanotranduction which is at the origin of the bone remodeling process. This model took into account three physical phenomena : the electrostatics (through the Poisson-Boltzman equation), the interstitial fluid flow (modeled by a modified Stokes equation) and the ionic transport (governed by a Nernst-Planck equation). Analysis of the electrical potential distribution highlighted the importance of the electrical double layers close to the pore charged surface. These electrical double layers, as well as the interstitial fluid chemical composition, induce osmotic and electroosmotic fluid flows and affect the ionic effective diffusion within the pores. Using a periodic asymptotic homogeneisation procedure, the model at the canalicular pore scale was upscaled at the canalicular scale and then at the osteonal scale. A parametric study pointed out the relevant parameters acting on the transport phenomena and possibly affecting osteocyte mecanosensitivity. Our results emphasized the importance of the electro-chemical effects. We thus focused on the chemistry and more especially on the effects of the physiological ionic fluxes on the osteocyte. In vitro experiments and numrical simulations were performed to elucidate these questions. Our results underlined the importance of the chemical exchanges between the osteocyte and the surrounding fluid. Finally, we showed that fluid flow and chemical transport occuring within the LCN and the osteon interact with each other, thus achieving a three-scale description of the transport phenomena in the osteon

La vie repose sur des conversions d’énergie libre assurées par des machines moléculaires. Parmi elles, la myosine couple l’hydrolyse de l’ATP à la production de force sur l’actine par basculement d’un « bras de levier ». Compléter le cycle requiert une étape de régénération, ou recovery stroke, où le moteur retourne dans sa configuration armée et hydrolyse l’ATP. Comprendre ce couplage chimio-mécanique est critique pour révéler les principes de fonctionnement des moteurs moléculaires. Cette thèse aborde la question via des simulations moléculaires. Partant d’une nouvelle structure cristallographique de la myosine VI, nous proposons un mécanisme original pour le recovery stroke dans lequel la remise en place du bras de levier est déclenchée par les fluctuations thermiques et précède la fermeture du site actif, au contraire des modèles précédemment acceptés. / Life relies on free energy conversions performed by molecular machines. Among them, myosin couples the hydrolysis of ATP to force production on actin through a swing of a « lever-arm ». Completing the cycle requires a regeneration step, the recovery stroke, in which the motor returns to its armed configuration and hydrolyzes ATP. Understanding this chemo-mechanical coupling is critical to unravel the functioning principles of molecular motors. In this thesis, we tackle the problem using molecular simulations. Capitalizing on a new crystal structure of myosin VI, we propose an original mechanism for the recovery stroke in which the re-priming of the lever arm is driven by thermal fluctuations and precedes the closure of the active site, unlike previously accepted models.

Zielsetzung: Das Ovarialkarzinom ist die häufigste Krebstodesursache innerhalb der gynäkologischen Malignome. Im Rahmen dieser retrospektiven Arbeit werden die klinischen Ergebnissen von 84 Patientinnen dargestellt, die an Ovarialkarzinom erkrankten und im Krankenhaus im Friedrichshain in Berlin behandelt wurden. Das Ziel dieser Studie war die Analyse des Einflusses verschiedener Prognosefaktoren auf das Gesamtüberleben, Identifikation unabhängiger Prognosefaktoren und Erarbeitung von Prognoseregeln in Bezug auf das Gesamtüberleben sowie Beurteilung des Therapieerfolges und kritische Diskussion des second-look Verfahrens. Methodik: Zur Bestimmung der kumulierten Überlebensraten wurde die Kaplan-Meier-Methode verwendet, zur Identifikation unabhängiger Prognosefaktoren die multivariate Analyse. Als statistisch signifikant galten Ergebnisse mit einer Irrtumswahrscheinlichkeit von p < 0,05. Ergebnisse: Das mediane Alter zum Zeitpunkt der Erstdiagnose betrug 61 Jahre. Die kumulierte Fünfjahresüberlebensrate betrug 53 %. Die kumulierten Fünfjahresüberlebensraten lagen für die Stadien FIGO I, II, III bzw. IV bei 93 %, 83 %, 20 % bzw. 11 %. Seitens der Histologie handelte es sich überwiegend um serös-papilläre Karzinome. Die Rezidivrate lag bei 36 %. Der Median bis zum Auftreten eines Rezidivs betrug 11,5 Monate. Schlussfolgerungen: Eine gute Prognose ergibt sich bei geringem Alter bei Erstdiagnose, gutem Allgemeinzustand, normwertigem präoperativem Tumormarker CA 125, fehlendem Aszites bzw. möglichst geringer Aszitesmenge, hochdifferenzierten Tumoren, möglichst vollständiger Tumorentfernung und Lymphonodektomie. Als unabhängige Prognosefaktoren haben sich nur das FIGO-Stadium, Alter und Grading erwiesen. Anhand der unabhängigen Prognosefaktoren lässt sich die prognostizierte Überlebenswahrscheinlichkeit angeben. / Objective: Ovarian carcinoma is the most frequent reason of the cancer death among malignant gynaecological tumours. The clinical outcome of 84 patients, who had ovarian carcinoma and underwent the treatment in "The Hospital in Friedrichshain" in Berlin, is presented in this retrospective study. The objective of this study was to analyse the influence of different prognostic factors related to overall survival, to identify the independent prognostic factors, to set up prognostic rules for patients with ovarian carcinoma related to overall survival, to assess the benefit of the therapy and the critical discussion of the second-look operation. Methods: The Kaplan-Meier method was applied in order to estimate overall survival rates and multivariate analysis in order to evaluate the independent prognostic factors. The results with p < 0,05 were of statistic significance. Results: The median age at diagnosis was 61 years. The cumulated 5-year survival rate was 53 %. The cumulated 5-year survival rates for the stages FIGO I, II, III and IV were 93 %, 83 %, 20 % and 11 %, respectively. Concerning histology there were mostly serous-papillar carcinomas. The recurrence rate was 36 %. The median until the recurrence occurred was 11,5 months. Conclusions: A good prognosis is associated with lower patient age at diagnosis, good performance status, normal preoperative serum CA-125 level, absence or minimal presence of ascites, well differentiated tumours, minimal size of the residual disease after primary cytoreductive surgery and lymphadenectomy. However, on multivariate analysis, only tumour stage, patient age and tumour grade retained prognostic significance as independent prognostic factors. Due to independent prognostic factors the survival probability can be predicted.

La réaction alcali-silice est une pathologie des bétons qui se caractérise par une réaction chimique entre la silice réactive contenue dans certains granulats et les ions contenus dans la solution interstitielle. Elle entraîne la formation de gels silico-calco-alcalins, le gonflement voire la chute des caractéristiques des bétons affectés. Ce travail a pour but de fournir des outils d'aide à la compréhension et à l'expertise des ouvrages atteints. Il est composé de trois parties complémentaires. La première vise à prédire le gonflement du béton à partir de la connaissance des mécanismes réactionnels locaux. La seconde modélise l'influence de l'eau sur la réaction. La dernière vise à reproduire les effets structuraux induits par la réaction (endommagement, déplacements, chute des caractéristiques mécaniques...).

The three main components of wood, namely, cellulose, hemicellulose, and lignin, can be used in various areas. However, since lignin covalently crosslinks with wood polysaccharides creating networks that is an obstacle for extraction, direct extraction of different wood components in high yield is not an easy matter. One potential approach to overcome such obstacles is to treat the wood with specific enzymes that degrade the networks by specific catalysis. However, the structure of wood is so compact that the penetration of the wood fibers by large enzyme molecules is hindered. Thus, the pretreatment of wood prior to the application of enzymes is necessary, for “opening” the structure. One pretreatment method that was performed in this thesis is based on kraft pulping, which is a well-established and industrialized technique. For untreated wood, the wood fibers cannot be attacked by the enzymes. A relatively mild pretreatment was sufficient for wood polysaccharides hydrolyzed by a culture filtrate. A methanol-alkali mixture extraction was subsequently applied to the samples that were pretreated with two types of hemicellulases, Gamanase and Pulpzyme HC, respectively. The extraction yield increased after enzymatic treatment, and the polymers that were extracted from monocomponent enzyme-treated wood had a higher degree of polymerization. Experiments with in vitro prepared lignin polysaccharide networks suggested that the increased extraction was due to the enzymatic untying. However, the relatively large loss of hemicellulose, particularly including (galacto)glucomannan (GGM), represents a problem with this technique. To improve the carbohydrate yield, sodium borohydride (NaBH4), polysulfide and anthraquinone were used, which increased the yields from 76.6% to 89.6%, 81.3% and 80.0%, respectively, after extended impregnation (EI). The additives also increased the extraction yield from approximately 9 to 12% w/w wood. Gamanase treatment prior to the extraction increased the extraction yield to 14% w/w wood. Sodium dithionite (Na2S2O4) is an alternative reducing agent for the preservation of hemicelluloses because it is less expensive than metal hydrides and only contains sodium and sulfur, which will not introduce new elements to the recovery system. Moreover, Na2S2O4has the potential to be generated from black liquor. Na2S2O4 has some preservation effect on hemicelluloses, and the presence of Na2S2O4 also contributed to delignification. The extraction yield increased to approximately 15% w/w wood. Furthermore, Na2S2O4 has been applied in the kraft pulping process of spruce. The yield and viscosity increased, while the Klason lignin content and kappa number decreased, which represents a beneficial characteristic for kraft pulp. The brightness and tensile strength of the resulting sheets also improved. However, the direct addition of Na2S2O4 to white liquor led to greater reject content. This problem was solved by pre-impregnation with Na2S2O4 and/or mild steam explosion (STEX) prior to the kraft pulping process. Following Na2S2O4 pre-impregnation and mild STEX, the obtained kraft pulp had substantially better properties compared with the properties exhibited after direct addition of Na2S2O4 to the white liquor. The wood structure opening efficiency of mild STEX alone was also tested. The accessibility of the wood structure to enzymes was obtained even at very modest STEX conditions, according to a reducing sugar analysis, and was not observed in untreated wood chips, which were used as a reference. The mechanical effect of STEX appears to be of great importance at lower temperatures, and both chemical and mechanical effects occur at higher STEX temperatures. / <p>QC 20140903</p>

Les matériaux soumis à de grandes déformations présentes pour la plupart l’apparition de déformations inélastiques. Ce phénomène est souvent accompagné d’une localisation des déformations dans une zone étroite, précurseur de la rupture. Un cas particulier, mais très fréquent, est les bandes de cisaillement qui apparaissent pour beaucoup de géomatériaux. Ces bandes peuvent être rencontrées à des échelles allant de l’échelle kilométrique pour les zones de subduction à l’échelle micrométrique à l’intérieur des zones de faille. Etudier et modéliser la création de ces zones d’instabilité est fondamental pour décrire la rupture des géomatériaux et des phénomènes associés comme les glissements sismiques dans les zones de faille mature de la lithosphère. Les conditions de pression, de température, l’interaction de l’eau interstitielle avec un matériau finement fracturé conduisent à l’apparition de multiples processus physiques impliqués dans les glissements sismiques. Dans ce travail, nous nous attachons à modéliser la création de bandes de cisaillement à l’intérieur des gouges de faille en prenant en compte l’effet de la microstructure par l’intermédiaire des milieux continus de Cosserat, ainsi que les couplages thermo-hydro-mécanique. L’utilisation de la théorie de Cosserat permet non seulement de régulariser le problème de localisation des déformations par l’introduction d’une longueur interne dans les lois constitutives, mais en même temps de prendre en compte l’effet de la microstructure. Deux approches sont employées pour étudier le système d’équations couplées aux dérivées partielles non linéaires : L’analyse de stabilité linéaire et la méthode des éléments finis. L’analyse de stabilité linéaire permet d’examiner les conditions d’apparitions d’instabilités pour un système mécanique avec des couplages multi-physiques. Par ailleurs, des considérations sur les perturbations appliquées au système permettent aussi de déterminer l’épaisseur de la zone de cisaillement, un paramètre clé pour la compréhension du mécanisme mécanique des failles. Ces estimations sont confirmées par l’intégration numérique pour des déformations restant dans une gamme donnée. Elles sont confrontées aux observations expérimentales et in situ et présentent une bonne corrélation. D’autre part, les simulations numériques permettent d’obtenir la réponse mécanique de la gouge de faille et de donner des informations sur l’influence des différents couplages dans le budget énergétique d’un tremblement de terre / When materials are subjected to large deformations, most of them experience inelastic deformations. It is often accompanied by a localization of these deformations into a narrow zone leading to failure. One particular case of strain localization is the formation of shear bands which are the most common patterns observed in geomaterials. In geological structures, they appear at very different scales, from kilometer scale for subduction zones, to micrometric scale inside fault cores. Studying their occurrence and evolution is of key importance to describe the failure of geomaterials and model seismic slip for mature crustal faults. The pressure and temperature conditions in these faults and the interaction with the pore water inside a highly fractured materials highlight the importance of different physical processes involved in the nucleation of earthquakes. In this thesis, we study the occurrence and evolution of shear bands inside fault gouges taking into account the material microstructure by resorting to elastoplastic Cosserat continua and also the effect of thermo-hydro mechanical couplings. The use of Cosserat theory introduces information about the gouge microstructure, namely the grain size, and permits to regularize the mathematical problem of in the post-localization regime by introducing an internal length into the constitutive equations. Two approaches are used to study the coupled non-linear partial differential set of equations: linear stability analysis and finite element simulations. Linear stability analysis allows to study the occurrence of localized deformation in a mechanical system with multi-physical couplings. Considerations on the dominant wave length of the perturbations permit also to determine the width of the localized zone. This shear band thickness is confirmed by numerical integration in the post-localization regime for a certain range of deformation. The obtained widths of the localized zone are key parameters for understanding fault behavior, are in agreement with experimental and field observations. Moreover, numerical finite element computations enable to model the mechanical response of a fault gouge during seismic slip and give insights into the influence of various physical couplings on the energy budget

Le disque intervertébral est principalement composé de deux types de tissu : le nucleus pulposus au centre contenu par l'annulus fibrosus en périphérie.Le nucleus est relativement bien décrit dans la littérature contrairement à l'annulus dont la constitution bi-phasique couplée à une structure à fibres orientées reste délicate à modéliser. La caractérisation hydro-chimio-mécanique représente un point clé dans la compréhension des phénomènes qui régissent le comportement de l'organe.Pour répondre au manque d'information, deux axes de travail sont mis en place : expérimental et numérique.La réalisation de tests de traction cyclique associés à des techniques de corrélation d'images permet de fournir une base de données complète du comportement.Elle est ensuite utilisée pour identifier un modèle hydro-chimio-mécanique qui traduit le comportement non-linéaire, anisotrope, dissipatif ainsi que la sensibilité aux variations d'environnement chimique du tissu observés expérimentalement.L'intérêt majeur de cette méthode est l'identification simultanée de l'ensemble des paramètres du modèle au cours de sollicitations proches des conditions physiologiques sur chacune des éprouvettes.Ce protocole réduit ainsi les incertitudes liées aux variabilités inter-individus et inter-localisations pour obtenir des valeurs de paramètres plus fiables.La formulation identifiée permettra de proposer un modèle compréhensif des transferts de fluide impliqués dans les processus de nutrition cellulaire.Ce sujet s'intègre dans une réflexion plus large relative à la compréhension des couplages hydro-chimio-mécaniques dans les tissus biologiques.L'enjeu est de quantifier l'impact des stimuli mécaniques sur l'évolution des tissus humains et leur adaptation aux conditions environnementales. / Intervertebral disc is mainly divided into two parts : nucleus pulposus surrounding by annulus fibrosus.Nucleus is relatively well described in literature, on the other hand annulus remains difficult to model due to its bi-phasic constitution coupled with an oriented fibres structure.Hydro-chemo-mechanical characterization represent a key point to reach a better understanding of this organ.To overcome this lack of knowledge, two axes are developed in this work : experimental and numerical.Cyclic tensile tests associated to digital image correlation techniques allow to obtain a large amount of data on global tissue behaviour.It permit to identify a hydro-chemo-mechanical model which takes in account the non-linear, anisotropic and dissipative behaviours.It also highlights sensibility to chemical variations in tissue environment observed experimentally.The most important point of this work is the simultaneous parameter identification performed on each sample during solicitations similar to in vivo conditions.This protocol reduce inter-individuals and inter-localisations discrepancies and leads to an accurate bundle of parameters.The formulation aims to accurately model fluid motion inside intervertebral disc tissues which is related to cell nutrition, growth and homoeostasis.This work is involved in a larger problematic about hydro-chemo-mechanical coupling within biological tissues.It will allow to quantify mechanical stimuli influence on human tissues evolution and adaptation to environment conditions.

Le but du projet est de mettre au point de nouveaux outils enzymatiques permettant la production de chitinoligosaccharides de taille et de degré d'acétylation parfaitement contrôlés pour l'étude d'enzymes impliquées dans la biosynthèse, la biodégradation et la modification de la chitine, et pour l'étude de récepteurs protéiques d'origine animale ou végétale. Des études récentes ont montré que les oligomères de la chitine et leurs dérivés sont des molécules qui interviennent dans les phénomènes symbiotiques et de reconnaissance hôte-pathogène dans le règne végétal. Ces molécules sont utilisées en agrochimie comme biofertilisants, et potentiellement en phytosanitaire. Ils sont connus également pour posséder de nombreuses activités biologiques dans le domaine de la santé (effets antimicrobiens, anticancéreux, anti-inflammatoires, immunostimulants...). Si les activités de cette classe d'oligosaccharides sont parfaitement reconnues, leurs modes d'actions restent encore à éclaircir, ce qui nécessite de disposer de molécules pures aux structures chimiques parfaitement contrôlées. La production d'oligomères de la chitine nécessite traditionnellement la mise en œuvre d'une chimie fastidieuse, qui peut être facilitée par une approche chimio-enzymatique.Dans le cadre de cette thèse, nous souhaitons donc développer des outils enzymatiques permettant la synthèse d'une bibliothèque de molécules de taille et de degré d'acétylation contrôlés en vue d'études structure-activité biologique. Pour cela, nous chercherons à produire des N-désacétylases et des chitinases dans différents systèmes d'expression et à caractériser leur activité afin de générer une panoplie de molécules de structure moléculaire parfaitement définie à partir de fragments saccharidiques issus de la biomasse. Les molécules ainsi préparées pourront ensuite être modifiées de façon chimio-sélective afin d'obtenir des sondes photoactivables et/ou biotinylées pour la caractérisation de récepteurs, des substrats fluoro- ou chromogéniques pour le dosage spécifique d'activités enzymatiques ou encore des lipochitinoligosaccharides capables de favoriser la croissance des plantes. Les approches utilisées pour mener à bien ce projet pluridisciplinaire seront : l'ingénierie et la production de protéines recombinantes, la caractérisation biochimique d'activités enzymatiques ainsi que la synthèse chimio-enzymatique et la modification chimique d'oligosaccharides qui devront être caractérisés d'un point de vue physicochimique. Il s'agit d'un projet intégré dans une collaboration nationale financée par l'ANR réunissant des équipes de l'Université de Grenoble, de Lyon, d'Orsay, et l'entreprise Bayer CropScience. / The aim of the project is to develop new tools for enzymatic production of chitooligosaccharides size and degree of acetylation perfectly controlled for the study of enzymes involved in biosynthesis, biodegradation and modification of chitin and for the study of protein receptors of animal or vegetable origin. Recent studies have shown that oligomers of chitin and its derivatives are molecules involved in the phenomena of symbiotic and host-pathogen recognition in plants. These molecules are used as agrochemicals biofertilizers. They are also known to possess numerous biological activities in the field of health (anti-microbial, anti-cancer, anti-inflammatory, immunostimulant ...). If the activities of this class of oligosaccharides are well recognized, their modes of action remain to be clarified, which requires having pure molecules with chemical structures perfectly controlled. The production of chitin oligomers traditionally requires the implementation of a tedious chemistry, which can be facilitated by a chemoenzymatic approach.As part of this thesis, we want to develop enzymatic tools for the synthesis of a library of molecules of size and degree of acetylation controlled studies for structure-biological activity. For this, we will seek to produce N-deacetylase and chitinases in different expression systems and characterize their activity to generate a variety of molecules well-defined molecular structure from saccharide fragments derived from biomass. The molecules thus prepared can then be modified so as to achieve chemoselective photoactivatable probes and / or biotinylated for the characterization of receptors, substrates or fluoro-chromogenic assay for specific enzyme activities or lipo-chitooligosaccharides can promote plant growth. The approaches used to complete this multidisciplinary project are: engineering and production of recombinant proteins, the biochemical characterization of enzymatic activities and chemoenzymatic synthesis and chemical modification of oligosaccharides to be characterized from the point of physicochemical view. This is an integrated project in a national collaboration funded by the ANR with teams from the University of Grenoble, Lyon, Orsay, and Bayer CropScience.

This paper reports the study of composition and variation of the chemical components of essential oils of Croton species of Sergipe emphasizing its importance chemotaxonomy. Essential oils from fresh aerial parts obtnained by hydrodistillation from samples of Croton blanchetianus (CB-GA), C. campestris (CC-AML), C. heliotropiifolius collected at different locations in the Sergipe (CH-SG1, CH-SG2, CH-GA, and CH-AML), C. pedicellatus (CP-SI), C. tetradenius (CT-SG) and seven other unidentified taxa, called CSP1-CPS7, were analyzed by GC-MS and GC-FID, such analysis revealed a highly variable chemical composition. It were identified 131 components by comparing the retention indices and mass spectra of compounds with literature data and NIST and Willey mass spectra libraries. With the chemical analysis of oil of Croton were established correlations between the taxa of C. heliotropiifolius, which can be differentiated by using their main chemical markers: (E)-caryophyllene and bicyclogermacrene. For comparative analysis of the chemical composition of essential oils of Croton species, chemometric tools as Principal Component Analysis (PCA) and hierarchic Cluster Analysis (HCA) was applied, by which it was possible to differentiate the components of the essential oil of aerial parts of Croton species grouped by class of compounds according to their biosynthetic origin (monoterpene hydrocarbons, oxygenated monoterpenes, sesquiterpene hydrocarbons, oxygenated sesquiterpenes, phenylpropanoids and derivatives of fatty acids). With this analysis it was possible to form three groups (I, II and III), corroborating the comparative analysis of chromatographic profiles. To our knowledge, this is the first report on the chemical composition of essential oils of C. pedicellatus and C. tetradenius. / Este trabalho relata o estudo da composição e variação dos componentes químicos do óleo essencial das espécies de Croton do estado de Sergipe dando ênfase a sua importância quimiotaxonômica. Os óleos essenciais das partes aéreas frescas obtidos por hidrodestilação das amostras de Croton blanchetianus (CB-GA), C. campestris (CC-AML), C. heliotropiifolius coletadas em diferentes localidades do Estado (CH-SG1, CH-SG2, CH-GA, CH-SI e CH-AML), C. pedicellatus (CP-SI), C. tetradenius (CT-SG) e outros sete táxons ainda não identificados denominados (CSP1-CPS7) foram analisados por CG-EM e CG-DIC revelando uma composição química bastante variável. Foram identificados 131 componentes, baseados nos índices de retenção e na comparação de seus espectros de massas com os da literatura e com as bibliotecas de espectros de massas Willey e NIST. Com a análise química dos óleos de Croton foram estabelecidas correlações entre os táxons de C. heliotropiifolius, os quais foram diferenciados dos demais mediante a utilização de seus marcadores químicos principais: (E)-cariofileno e biciclogermacreno. Para as análises comparativas da composição química dos óleos essenciais das espécies de Croton aplicaram-se ferramentas quimiométricas de Análise dos Componentes Principais (ACP) e Análise de Agrupamentos Herarquicos (AAH), pelas quais foi possível diferenciar os componentes do óleo essencial das partes aéreas das espécies de Croton agrupados por classe de compostos de acordo com sua origem biossintética (hidrocarbonetos monoterpênicos, monoterpenos oxigenados, hidrocarbonetos sesquiterpênicos, sesquiterpenos oxigenados, fenilpropanóides e derivados de ácidos graxos). Com essas análises foi possível a formação de três grupos (I, II e III), corroborando com as análises comparativas dos perfis cromatográficos. Ao nosso conhecimento, este é o primeiro relato sobre a composição química dos óleos essenciais de C. pedicellatus e C. tetradenius.

The present work aims at studying the coupling between hydrodynamic fingering instabilities and chemical reactions at the interface between two miscible solutions. Hydrodynamic deformations of interfaces between two reactive fluids as well as flows induced by chemical reactions at the front between two initially steady fluids are encountered frequently in combustion, petroleum, chemical and pharmaceutical engineering. Most of the time, concrete applications imply a very large number of variables so that an understanding of the fundamental processes of chemo-hydrodynamic coupling is out of reach. Our goal is here to analyze a much simpler model system in which only one mechanism of hydrodynamic instability is at play and for which the chemical reactions can be modeled by a one or two-variable model. <p><p>Buoyantly unstable, autocatalytic chemical fronts, are one such model system, which can be used as prototype to study the effects of the coupling between chemical reactions and hydrodynamic fingering instabilities. Fingering processes occur whenever a fluid of high mobility displaces a less mobile one in a porous medium. The initially planar interface looses then stability and a cellular fingering deformation of the interface is observed. Such an instability has been observed, for instance, in the iodate-arsenous acid and chlorite-tetrathionate reactions, autocatalytic redox reactions known to produce a change of density across a traveling front. Fingering happens there when the heavier solution lies on top of the lighter one in the gravity field. <p> <p>Our theoretical contribution to the analysis of fingering of chemical fronts focuses on different points which we detail in this thesis along the following outline. In chapter 2, we introduce fingering phenomena occurring in porous media and distinguish the situation of viscous and density fingering of pure non reactive fluids. Chapter 3 reviews the literature on coupling between fingering and chemical reactions before studying the linear stability conditions as well as nonlinear dynamics of density fingering of isothermal iodate-arsenous acid fronts. This prototype nonlinear redox reaction is the first one on which experimental results on fingering in spatially extended set-ups have been obtained. We next analyze in chapter 4 the density fingering of another front producing autocatalytic system i.e. the chlorite-tetrathionate reaction in order to address the influence of the chemical kinetics on the dynamics observed. The influence of the exothermicity of the reaction is then presented in chapter 5. Eventually, chapter 6 analyzes what happens if the kinetics is now bistable and further compares the situation of both viscous and density fingering of bistable fronts. We then conclude and present suggestions for future work in this subject at the frontier between nonlinear chemistry, hydrodynamics and engineering. <p> / Agrégation de l'enseignement supérieur, Orientation sciences / info:eu-repo/semantics/nonPublished