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Etude du transport de molécules bioactives dans l'épiderme de fruits à pépins(Rosacea Juss) : mise au point et développement d'un procédé d'extraction de produits phytosanitaires / Study of the transport of bioactive molecules in the epidermis of one species of pomaceous fruits : development and improvement of an extraction process of plant-protection products.Giacinti, Géraldine 20 October 2016 (has links)
L’agriculture moderne utilise depuis plus de cinquante ans de nombreux produits phytosanitaires de traitement dans le but d’assurer les meilleurs rendements et de limiter les pathogènes néfastes pour la santé humaine ou animale. Jusqu’à peu, la quantité de résidus phytosanitaires présents dans les denrées alimentaires (fruits, légumes, céréales, plantes fourragères, produits transformés…) était certes contrôlée mais en règle générale, ne soulevait que très peu d’interrogation en terme de conséquences à plus ou moins long terme. A l’heure actuelle, des exigences de plus en plus drastiques apparaissent et se généralisent. Les produits issus des industries agricole et agroalimentaire doivent répondre à des normes de plus en plus strictes en terme de résidus pour rester compétitives. En particulier, dans le cas des pommes, dont le nombre de traitements par saison est l’un des plus élevé en France, les exigences tendent vers le zéro résidu détectable. La stratégie de cette étude repose, dans un premier temps, sur la compréhension des phénomènes de transfert à la surface du fruit. Une caractérisation physico-chimique de l’épiderme de différentes variétés de pommes a conduit à l’identification des structures impliquées dans l’interaction molécule bioactivematrice biopolymérique. Le fludioxonil a été choisi comme molécule modèle en raison de sa fréquence d’utilisation comme fongicide de conservation et de sa composition atomique (présence de fluors). Les épidermes de pommes Fuji ont servi de matrice modèle. Dans un second temps, un procédé de traitement par voie chimique des pommes a été mis au point et développé pour extraire les résidus de 12 molécules de phytosanitaires parmi les plus couramment utilisées dans les vergers de pommiers du Midi-Pyrénées. Trois variétés de pommes populaires en France ont été sélectionnées pour leurs différentes périodes de récolte correspondant à des risques de contamination variables. Les résultats ont conduit à la proposition d’un schéma de désorption des molécules bioactives dans la matrice biopolymérique, basé sur les théories de la solubilité de Hildebrandt et de Hansen. En complément, le développement d’une méthode analytique de quantification par chromatographie en phase gazeuse couplée à la spectrométrie de masse trappe d’ions (GC/MS2) des molécules phytosanitaires dans la matrice épidermique des pommes a mis en évidence que : 1- l’augmentation de la concentration des analytes d’intérêt au-dessus des limites de détection de la technique analytique appliquée favorisait la quantification des très faibles traces, voire des ultratraces ; 2- les analytes d’intérêt subissaient en parallèle des effets matrice négatifs. Une forte interaction entre certains analytes de la matrice et les phytosanitaires a été démontrée et une méthode de purification basée sur un couplage chromatographie sur couche mince haute performance avec la GC/MS2 (CCMHP/GC/MS2) a été proposée afin de minimiser les effets matrice négatifs dans / For more than fifty years, the modern agriculture uses lots of products for crop protection in order to ensure optimum yields and to limit pathogens harmful for human or animal health. Until recently, the levels of pesticides in foodstuffs (fruits, vegetables, cereals, forage crops, processed food…) were controlled but usually not problematic regarding the effects over time. Nowadays, more and more drastic requirements are appearing and becoming widespread. The products from farming and food industries must satisfy stricter and stricter standards in terms of residues for maintaining competitiveness. Particularly, for apples, whose treatments per season are among the highest in France, requirements tend to the zero detectable residue. The strategy of this work deals with, on one hand, the understanding of the transfert stages involved at the outer surface of the fruit. A physicochemical characterizations of epiderms of different apples led to the identification of the structures involved in the relationship between bioactive molecule and biopolymeric matrix. Fludioxonil was chosen for modelization for its frequency of use and for its atomic composition (fluorine). The epiderms of Fuji apples were selected as the matrix-model. On the other hand, a chemically treatment process of apples was studied and developed to release the residues of 12 pesticides among the most currently used in apple orchards of Midi-Pyrenees. Three varieties of apples among the most popular in France were selected for their different periods of harvest corresponding to variable pests risks. The results led to a possible scheme of desorption of bioactive molecules in the biopolymeric matrix, based on the theory of solubility developed by Hildebrandt and Hansen. In addition, the development of an analytical mehtod of quantitation of pesticides in the epidermal matrix of apples by gas chromatography coupled with mass spectrometry ion trap (GC/MS2) highlighted that : 1- the increase of the concentrations of the analytes of interest over the limits of detection of the applied analytical method promoted the quantitation of very low traces, even ultratraces ; 2- the analytes of interest concurrently underwent negative matrix effects. A strong interaction between some matrix analytes with pesticides was demonstrated and a mehtod of cleanup based on the hyphenation of high performance thin layer chromatography with GC/MS2 (HPTLC/GC/MS2) was suggested to minimize the negative matrix effects in that kind of concentrated matrix extracts.
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Análise da viabilidade experimental da produção de moléculas fotônicas em uma armadilha de sódio / Analysis of the experimental viability to produce photonic molecules in a sodium MOTVivanco, Franklin Adán Julca 22 February 2013 (has links)
O progresso nas pesquisas no campo de átomos a baixíssimas temperaturas tem possibilitado o estudo de fenômenos de fotoassociação e blindagem óptica. Estes dois fenômenos são tipicamente produzidos quando um campo de luz externo é incidido em um MOT. Dependendo das dessintonias das frequências dos lasers em relação à ressonância atômica, se podem realizar seletivamente estes processos. Neste trabalho, os estudos são feitos em átomos de sódio e a exploração apresentada faz parte dos estudos que envolvem a formação e detecção de moléculas fotônicas. Uma exploração dos espetros de fotoionização associativa por dois fótons na região de 0 até -30 GHz foi realizada e a identificação dos estados de longo alcance foi feita. Os níveis vibracionais identificados pertencem majoritariamente aos estados 1g, 0g e 0+u, sendo o estado 0g um estado puramente de longo alcance. Um estudo da blindagem óptica em alguns picos do espectro de fotoionização associativa foi realizada com a adição de outro laser azul de frequência ωA2, e se comprovou saturação na blindagem das colisões inelásticas quando se aumenta a potência deste laser. Com estes estudos demonstramos que os potenciais moleculares intermediários são modificados na presença de campos de luz intensos. / The progress of research in the field of atoms in low temperatures has opened the possibility to study phenomena called fotoassociation and optical shielding. These two phenomena are typically produced when an external light field is focused on a MOT. Depending on the detuning of frequencies of the laser with respect to the atomic resonance can be selectively induced these processes. In this work, the studies are made for sodium atoms, and the presented exploration has been a part of the first studies involving the formation and detection of photonic molecules. An exploration of the fotoasociation spectrum of two colors fotoionizative association between 0 and -30 GHz was performed, and a labeling of the states of long range was carried out. These vibrational levels belong mostly to the states 1g, 0g and 0+u , being the state 0g , a purely long range state. A study of optical shielding of some peaks in the fotoasociation spectrum, as identified to be important in forming the photonic molecule. With respect to the blue laser detuning frequency ωA and its intensity was performed with the addition of another blue laser frequency ωA2, and can show a saturation in the shielding for inelastic collisions when increasing the laser intensity. The studies have showed modification in the intermediary potentials in the presence of an intense light field.
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Optical Spectroscopy of Heavy Element Containing Molecules In Support of Fundamental PhysicsJanuary 2019 (has links)
abstract: Transient molecules are of great importance having proposed applications in quantum science and technology and tests of fundamental physics. In the present dissertation, the transient molecules studied are SrOH, ThF, ThCl, YbF and YbOH; each having been selected because of their proposed application. Specifically, SrOH is a candidate of constructing a molecular magneto-optical trap (MOT). The simple actinide molecules, ThF and ThCl, were selected as ligand bonding model systems to gain insight into chemical processing of Spent Nuclear Fuel. The lanthanides YbF and YbOH are venues for the determination of electron electric dipole moment (eEDM) and the studies in this dissertation provide the requisite properties for those experiments.
Intense supersonic molecular beams of these transient molecules were generated via laser ablation and spectroscopically characterized using a novel medium-resolution two-dimensional (2D) spectroscopic approach, as well as high-resolution laser induced fluorescence (LIF). The 2D medium resolution approach, which was used in the studies SrOH, ThF, ThCl and YbOH, uses a multiplexing method that simultaneously records dispersed fluorescence and excitation spectra. A significant advantage of 2D-LIF imaging is that all the electronics states can be targeted to determine the electronics states and associated vibrational spacing individually. Consequently, in the 2D spectra of ThF, ThCl and YbOH, several previously unobserved band systems have been detected in one single scan. For the DF spectra of SrOH and YbOH, the determined branching ratios show that the transitions of these molecules are diagonal (i.e. Δv=0), which is essential for the proposed potential for laser cooling. In the high-resolution of YbF, ThF, ThCl and SrOH optical spectra were recorded to an accuracy of ±30 MHz, which represents an unprecedented precision of 1:10+8.
In addition to field free spectra, optical Stark and Zeeman studies were performed to determine the most fundamental magneto-and electro-static properties. Effective Hamiltonian operators were employed to analyze the recorded spectra and determine the spectroscopic parameters. This data set also establishes a contribution toward developing new computational methodologies for treating relativistic effects and electron correlation. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2019
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Metallization of Self-Assembled DNA Templates for Electronic Circuit FabricationUprety, Bibek 01 June 2017 (has links)
This work examines the deposition of metallic and semiconductor elements onto self-assembled DNA templates for the fabrication of nanodevices. Biological molecules like DNA can self-assemble into a variety of complex 2-D and 3-D architectures without the need for expensive patterning tools. In addition, self-assembled DNA templates can be designed to controllably place functional nanomaterials with molecular precision. These characteristics make DNA an attractive template for fabricating electronic circuits from biological molecules. However, electrically conductive structures are required for electronic applications. While metallized DNA nanostructures have been demonstrated, the ability to make thin, continuous wires that are electrically conductive still represents a formidable challenge. DNA-templated wires have generally been granular in appearance with a resistivity approximately two to three orders of magnitude higher than that of the bulk material. An improved method for the metallization of DNA origami is examined in this work that addresses these challenges of size, morphology and conductivity of the metallized structure. Specifically, we demonstrated a metallization process that uses gold nanorod seeds followed by anisotropic electroless (autocatalytic) plating to provide improved morphology and greater control of the final metallized width of conducting metal lines. Importantly, growth during electroless deposition occurs preferentially in the length direction at a rate that is approximately four times the growth rate in the width direction, which enables fabrication of narrow, continuous wires. The electrical properties of 49 nanowires with widths ranging from 13 nm to 29 nm were characterized, and resistivity values as low as 8.9 x 10-7 Ω-m were measured, which represent some of the smallest nanowires and the lowest resistivity values reported in the literature. The metallization procedure developed on smaller templates was also successfully applied to metallize bigger DNA templates of tens of micrometers in length. In addition, a polymer-assisted annealing process was discovered to possibly improve the resistivity of DNA metal nanowires. Following metallization of bigger DNA origami structures, controlled placement of gold nanorods on a DNA breadboard (~100 x 100 nm2) to make rectangular, square and T-shaped metallic structures was also demonstrated. For site-specific placement of nanorods to a DNA template, we modified the surface of the gold nanorods with single-stranded DNA. The rods were then attached to DNA templates via complementary base-pairing between the DNA on the nanorods and the attachment strands engineered into the DNA "breadboard" template. Gaps between the nanorods were then filled controllably via anisotropic plating to make 10 nm diameter continuous metallic structures. Finally, controlled placement of metal (gold) - semiconductor (tellurium) materials on a single DNA origami template was demonstrated as another important step toward the fabrication of DNA-based electronic components. The combination of molecularly directed deposition and anisotropic metallization presented in this work represents important progress towards the creation of nanoelectronic devices from self-assembled biological templates.
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The role of gamma-protocadherins in interneuron survival and circuit formation in the developing spinal cordPrasad, Tuhina 01 December 2009 (has links)
Protocadherins (Pcdhs) are a large family of adhesion molecules which have structure similar to that of classical cadherins. About 60 Pcdh genes are organized into three clusters (-á,- â and- ã), which are arranged contiguously on a single chromosome in mammals. Mice in which the 22-gene Pcdh- ã locus has been deleted die within a few hours of birth and show defects in movement and reflexes, extensive neurodegeneration in the spinal cord, and loss of synapses. Further studies have shown that loss of ã-Pcdhs has a primary effect on the formation or maintenance of synapses that can be dissociated from its role in cell survival. Extensive apoptotic cell death observed during the late embryonic development period in the spinal cord of the Pcdh- ã del/del mutant mice is confined to molecularly distinct populations of spinal interneurons. Analysis of cell death patterns during development of spinal cords from wild-type, the Pcdh- ã del/del and Bax -/- mice in which cell death is blocked due to deletion of a proapoptotic protein, confirmed that loss of ã-Pcdhs exacerbates a previously undocumented normal developmental pattern of spinal interneuron apoptosis. Restricted disruption of the Pcdh- ã gene cluster within specific neuronal populations suggested that ã-Pcdhs can control neuronal survival in a non-cell autonomous manner. Loss of ã-Pcdhs also resulted in an aberrant pattern of 1a proprioceptive sensory afferent (1aPSA) terminals in the spinal cord. In Pcdh- ã del/del mice the area occupied by 1aPSA terminals per motor neuron increased by 150% over the control with a corresponding reduction of 30% in the area occupied by 1aPSA terminals on the ventral interneurons. Further analysis in the Pcdh- ã del/del; Bax-/- double mutants, as well as in mouse lines in which Pcdh- ã gene cluster disruption was confined to specific neuronal subpopulations, suggested that this aberrant pattern was a result of both the increased loss of ventral interneurons in mutants, as well as a cell autonomous requirement of ã-Pcdhs in the 1aPSA and their intermediate target ventral interneurons. These studies provide evidence that the ã-Pcdhs mediate homophilic interactions that are important for the formation of multiple neuronal circuits, and are critical molecules in the regulation of interneuron survival and CNS development.
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Développement d'une plateforme de prédiction in silico des propriétés ADME-Tox / Development in silico platform for ADME-Tox predictionCanault, Baptiste 01 October 2018 (has links)
Dans le cadre de la recherche pharmaceutique, les propriétés relatives à l’Absorption, la Distribution, le Métabolisme, l’Elimination (ADME) et la Toxicité (Tox) sont cruciales pour le succès des phases cliniques lors de la conception de nouveaux médicaments. Durant ce processus, la chémoinformatique est régulièrement utilisée afin de prédire le profil ADME-Tox des molécules bioactives et d’améliorer leurs propriétés pharmacocinétiques. Ces modèles de prédiction, basés sur la quantification des relations structure-activité (QSAR), ne sont pas toujours efficaces à cause du faible nombre de données ADME-Tox disponibles et de leur hétérogénéité induite par des différences dans les protocoles expérimentaux, ou encore de certaines erreurs expérimentales. Au cours de cette thèse, nous avons d’abord constitué une base de données contenant 150 000 mesures pour une cinquantaine de propriétés ADME-Tox. Afin de valoriser l’ensemble de ces données, nous avons dans un deuxième temps proposé une plateforme automatique de création de modèles de prédiction QSAR. Cette plateforme, nommée MetaPredict, a été conçue afin d’optimiser chacune des étapes de création d’un modèle statistique, dans le but d’améliorer leur qualité et leur robustesse. Nous avons dans un troisième temps valorisé les modèles obtenus grâce à la plateforme MetaPredict en proposant une application en ligne. Cette application a été développée pour faciliter l’utilisation des modèles, apporter une interprétation simplifiée des résultats et moduler les observations obtenues en fonction des spécificités d’un projet de recherche. Finalement, MetaPredict permet de rendre les modèles ADME-Tox accessibles à l’ensemble des chercheurs. / Absorption, Distribution, Metabolism, Elimination (ADME) and Toxicity (Tox) properties are crucial for the success of clinical trials of a drug candidate. During this process, chemoinformatics is regularly used to predict the ADME-Tox profile of bioactive compounds and to improve their pharmacokinetic properties. In silico approaches have already been developed to improve poor pharmacokinetics and toxicity of lead compounds. These predictive models, based on the quantification of structure-activity relationships (QSAR), were not always efficient enough due to the low number of accessible biological data and their heterogeneity induced by the differences in experimental assays or the significant experimental error. In this thesis, we first built a database containing 150,000 data points for about 50 ADME-Tox properties. In order to valorize all this data, we then proposed an automatic platform for creating predictive models. This platform, called MetaPredict, has been designed to optimize each step of model development, in order to improve their quality and robustness. Third,, we promoted the statistical models using the online application of MetaPredict platform. This application has been developed to facilitate the use of newly built models, to provide a simplified interpretation of the results and to modulate the obtained observations according to the needs of the researchers. Finally, this platform provides an easy access to the ADME-Tox models for the scientific community.
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Cellules solaires organiques à base de molécules bio-inspirées / Bio-inspired small molecules for organic solar cellsArchet, Florence 18 December 2018 (has links)
Face à la croissance de la demande énergétique, les énergies alternatives, telles que l’énergie photovoltaïque, représentent des solutions réalistes. Cette dernière nécessite des matériaux efficaces pour la capture des photons et leur conversion en électricité.Les cellules solaires organiques (CSOs) sont basées sur les propriétés semiconductrices de certaines molécules ou de certains polymères π-conjugués. Dans le domaine des CSOs, les efforts de recherche actuels se concentrent selon trois axes : la réduction des coûts, l’augmentation de la durée de vie des cellules solaires et l’augmentation des rendements de conversion photovoltaïque. Les récentsdéveloppements ont conduit à une complexification des architectures des CSOs ainsi que des semi-conducteurs organiques utilisés, induisant une augmentation des coûts de fabrication. Dans une logique de développement économiquement efficace et écologiquement soutenable, il est nécessaire aujourd’hui de se concentrer sur des semi-conducteurs organiques viables économiquement et dont la synthèse est respectueuse de l’environnement. Ce travail doctoral a pour but de développer de nouveaux matériaux semi-conducteurs organiques bio-inspirés et bas coût. Les molécules étudiées présentent une structure donneur-accepteur-donneur. Leur squelette est celui de la curcumine, molécule qui donne sa couleur au curcuma. Le groupement accepteur est un difluorure de bore. Les groupements donneurs quant à eux varient suivant les semi-conducteurs. Les propriétés optoélectroniques de dix-sept dérivés curcuminoïdes ont été étudiées. Plusieurs d’entre eux se sont démarqués : ceux avec des groupements anthracène, ceux avec des dérivés thiophènes, enfin et impact sur les performances photovoltaïques de la formulation de l’encre utilisée pour le dépôt de la couche a été étudié en détail. Différents matériaux accepteurs ont été testés, de même que l’utilisation de mélanges ternaires. Pour l’un de dérivés curcuminoïde en combinaison avec du PC61BM, des rendements supérieurs à 4 % ont été obtenus avec des tensions de circuit ouvert supérieures à 1,0 V. Au regard de la simplicité structurale de ce semi-conducteur, ces résultats figurent à notre connaissance parmi les meilleurs reportés dans la littérature. Les phénomènes photophysiques ont également été étudiés par spectroscopie d’absorption des espèces transitoires. Enfin, le procédé de fabrication a été rapproché des conditions industrielles en éliminant les solvants halogénés utilisés et en travaillant à l’air ambiant. Finalement, bien qu’intéressantes, les propriétés photovoltaïques restent limitées pour une application industrielle du fait de la faible mobilité des trous de ces matériaux. / To face the growing needs in energy, renewable energies like solar photovoltaic represent realistic solutions. Photovoltaic energy requires efficient materials to absorb photons and to convert them into electricity. Organic solar cells (OSCs) are based on semiconducting π-conjugated polymer or small molecules. Current research in this field focuses on three main topics: the reduction of costs, the increase of device lifetime and the increase of power conversion efficiency. This last issue led to an increase in the complexity of OSCs architecture as well as organic semi-conductors, leading to anincrease in manufacturing costs. In order to develop sustainable and eco-friendly processes, it is now important to work on cost effective semi-conductors obtained fromgreen synthetic methodology. The aim of this thesis was to develop new bio-inspired organic semi-conductors. These materials are potentially low cost. Molecules studied present donor-acceptor-donor structure. They have the skeleton of curcumine. Curcumine is a natural yellow dye present in curcuma. Acceptor group is boron difluoride. Donor groups vary depending on the curcuminoid derivative. Optoelectronicproperties of seventeen semi-conductors were studied. Several of them stood out: those with anthracene groups, those with thiophene derivatives, finally and especially, those with triphenylamine groups. For this last family, the impact on the photovoltaic performances of the ink formulation used for deposition has been deeply studied. Several acceptor materials were tested, as well as ternary blend. For one curcuminoid derivative combined with PC61BM, efficiency above 4% has been achieved with open circuit voltage up to 1.0 V. Due to the very simple chemical structure of the donor, this represents one of the best result reported in literature to our knowledge. Transient species were also studied by ultrafast spectroscopy. The fabrication process was also changed to eliminate halogenated solvent and to enable processing in ambient air like in industrial process. Finally, photovoltaic properties observed are interesting. Nevertheless, they are not sufficient for industrial application due to low hole mobility in these materials.
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Aptamer Sensors for Drugs of Abuse and Medical Biomarkers: Design, Engineering and Application in Complex SamplesRoncancio, Daniel 22 June 2018 (has links)
Aptamers are short oligonucleotide sequences (DNA or RNA) capable of high affinity and specific binding to a molecule or a family of molecules. Aptamers are lower in cost and exhibit higher reproducibility when compared to antibodies and thus are well-suited for recognition and detection of small molecular targets such as drugs of abuse and small medical biomarkers. While aptamers have been extensively utilized for development of small molecule sensors, several limitations prevent measurements of complex or real-world samples. This dissertation describes methods, technologies, and assays that were developed with the goal of producing and/or improving aptamer-based sensors for target detection in complex samples. Aptamer engineering is detailed as an important facet of maximizing aptamer-sensor sensitivity and specificity, along with adaptation to various read-out mechanisms for improved selectivity. In chapter 3, an aptamer vii sensor for cocaine is developed based on binding between the fluorophore ATMND to the cocaine aptamer which results in quenching (i.e., ‘turn-off’) of the fluorescence of ATMND. Cocaine binding results in displacement of the ATMND and recovery of the fluorescence signal. Detection of cocaine is demonstrated with an engineered cocaine aptamer with higher affinity for cocaine, permitting over a 50-fold increase in sensitivity over other aptamer-based sensors. The method can be used in dilute biological fluids (e.g., saliva) with a single step reaction (seconds) and robust signal output. In chapter 4, a new adenosine specific aptamer is identified through rational engineering of a previously reported ATP-binding aptamer. The new adenosine aptamer is utilized to develop an electrochemical sensor for detection of adenosine in undiluted serum. The method displays 40-fold higher sensitivity in undiluted serum measurements over previously reported aptamer-based sensors for adenosine but also demonstrates specificity for adenosine over ATP, ADP and AMP that has not been previously reported. In chapter 5, a nuclease-guided truncation method is developed to yield optimal structure-switching aptamer sequences for the emergent illicit drug methylenedioxypyrovalerone (MDPV) and medical biomarkers ATP and deoxycorticosterone 21-glucoside (DOG). The method intelligently removes unessential nucleotides, producing truncated aptamer sequences with structure-switching functionality. This technique will be immediately useful for simple and low-cost development of aptamer-based electrochemical sensors.
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Couplage d'un contacteur membranaire à extraction liquide-liquide avec un biorécteur pour la production de molécules hydrophobes par voie biotechnologiqueRossignol, Cindie 23 May 2013 (has links)
Le travail présenté porte sur le couplage d’un procédé membranaire à extraction liquide-liquide avec un bioréacteur impliquant des molécules hydrophobes. La bioconversion modèle utilisée est la production de cis-2-methyl-5-isopropylhexa-2,5-dienal (isonovalal) à partir d’α-pinène oxyde, instable en phase aqueuse, par des cellules entières perméabilisées de Pseudomonas rhodesiae (CIP 107491). La production d’isonovalal en milieu biphasique eau (tampon phosphate)/hexadécane présente des verrous technologiques importants, dont une inactivation de l'enzyme à l'interface eau-solvant organique ainsi que l'apparition d'une émulsion stable. L’intérêt de la membrane porte sur l'absence de formation d'émulsion et sur l’augmentation de la durée de vie du biocatalyseur en raison de l'absence de contact direct du biocatalyseur avec l'interface liquide-liquide. La nature de la membrane a été choisie à partir de l'analyse des propriétés physico-chimiques du matériau et de l’étude des affinités entre membrane et composés d’intérêt (solutés, solvants). Il a été montré que les conditions d'écoulement au voisinage de la membrane, notamment du côté aqueux, jouent un rôle prépondérant sur les vitesses de transfert. Ce résultat souligne l'importance du design et des conditions d'opération du module membranaire sur les capacités de transfert. Le couplage de l’extraction membranaire liquide-liquide et de la réaction biologique a conduit à la mise en place d’un système bi-membranaire. Le prototype développé a permis de doubler les capacités catalytiques (+ 100 % d’isonovalal par gramme de biomasse) ainsi que de la durée de vie du biocatalyseur (160 h contre 80 h) par rapport à la même bioconversion réalisée en système biphasique conventionnel. / The study deals with the combination of a membrane process based on liquid/liquid extraction with a bioreactor producing hydrophobic molecules. The bioconversion used is the production of cis-2-methyl-5-isopropylhexa-2,5-dienal (isonovalal) from α-pinene oxide (unstable in aqueous phase) by whole cells of Pseudomonas rhodesiae (CIP 107491). The production of isonovalal in two-phase medium water/organic is known about but presents important technological brakes. Membrane interest concerns the stabilization of liquid/liquid interface and capacity to increase the biocatalyst life-time. Membrane nature is chosen from the analysis of physical and chemical properties of membrane material and study of the affinities between membrane and interest compounds (solutes, solvents). Two membrane contactors are designed and implemented on laboratory scale to study transfers between liquid phases. It is shown that the hydrodynamic conditions in the membrane neighborhood, in particular on aqueous side, play a major role on transfer speeds. This result underlines the importance of design and operation conditions in membrane module about the transfer capacities. The combination of liquid/liquid membrane extraction and biological reaction with unstable substrate had been studied and lead to the implementation of a serial bi-membrane system. The developed prototype, equipped with a PTFE membrane (polytetrafluoroethylene) with 0.22 μm pores’ diameter, highlights a doubling of catalytic capacities (+ 100 % of isonovalal per gram of biomass) as well as biocatalyst life-time (160 hours against 80 hours) compared with the same bioconversion realized in conventional two-phase medium system.
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Identification and validation of small molecule inhibitors for the Tiam1/SDC1 interactionLopez, Josue Alan 01 May 2014 (has links)
No description available.
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