La present Tesi Doctoral es basa en la preparació, caracterització i assaig de catalitzadors suportats. Els materials preparats són híbrids orgànico-inorgànics derivats de silici. S'han utilitzat diferents mètodes de preparació, principalment el procés sol-gel. En primer lloc, s'han obtingut materials derivats d'un complex de Pd de tipus bipiridínic que s'han utilitzat com a catalitzadors en reaccions de Suzuki, Heck i Sonogashira, mostrant una elevada activitat i un bon reciclatge. També s'han sintetitzat materials derivats de sals d'imidazoli i de dihidroimidazoli que ens han permès, per una banda, preparar complexos de Ru suportats derivats de catalitzadors de Grubbs. Aquests catalitzadors s'han assajat en reaccions de ring closing metathesis de diens i enins. L'activitat i el reciclatge en aquest cas van ser baixos. Els mateixos híbrids orgànico-inorgànics, juntament amb Pd(OAc)2, s'han assajat en reaccions de Suzuki, Heck i Sonogashira, amb una bona activitat i s'han pogut reutilitzar. Finalment, aquests materials han resultat ser actius i reciclables com a organocatalitzadors en condensacions de Knoevenagel. Amb els lligands bi- i trisililats derivats de sals d'imidazoli amb cadenes hidrocarbonades llargues s'ha estudiat l'autoestructuració de materials híbrids orgànico-inorgànics. Algunes de les sals d'imidazoli no sililades que s'han sintetitzat han resultat ser cristalls líquids iònics. S'han estudiat les seves propietats mesomòrfiques i les seves possibles aplicacions. / The present Doctoral Thesis is based on the preparation, characterization and assay of supported catalysts. We focused on organic-inorganic hybrid silica materials. Different methods have been used in the preparation of these materials, mainly the sol-gel process. Firstly, materials derived from a bipyridinic Pd complex have been obtained which have been tested as catalysts in Suzuki, Heck and Sonogashira reactions, showing a high activity and a good recycling. Materials derived from imidazolium and dihydroimidazolium salts have been also synthesized which serve us to prepare Ru supported complexes derived from Grubbs catalysts. These catalysts have been tested in diene and enyne ring closing metathesis reactions. The activity and recycling in this case was low. The same organic-inorganic hybrid materials, with Pd(OAc)2, have been tested in Suzuki, Heck and Sonogashira reactions, with a good activity and they have been reused. Finally, these materials were active and recyclable as organocatalysts in Knoevenagel condensations. The self-structuration of new organic-inorganic hybrid materials prepared with bis- and trisilylated ligands derived from imidazolium salts with long hydrocarbonated chains have been studied. Some of the non-silylated imidazolium salts were ionic liquid crystals. Their mesomorphic properties and their possible applications have been studied.

En el presente trabajo se distinguen dos partes claramente diferenciadas, a saber, una primera parte en la que se estudian diferentes sistemas pigmentantes y una segunda parte en la que se estudia la influencia del praseodimio en circonas estabilizadas con calcio, itrio y magnesio.Los sistemas pigmentantes estudiados son el amarillo de Pr-ZrSiO4, el sistema Pr-ZrO2 y el sistema Pr-(Ca-ZrO2). El pigmento amarillo de Pr-ZrSiO4 se estudia el mecanismo de síntesis de dicho pigmento mediante la utilización de métodos de síntesis no convencionales, haciendo énfasis en los procedimientos sol-gel.En el sistema Pr-ZrO2 y Pr-(Ca-ZrO2) se pretende optimizar el pigmento amarillo con dicha red huésped en función de los precursores, métodos y polimorfo de circona estabilizado.El praseodimio no estabiliza a temperatura ambiente la circona cúbica/tetragonal. La circona cúbica estabilizada con óxido de calcio y dopada con praseodimio presenta una coloración amarilla, en la que el praseodimio sustituyendo a un ion estructural: formación de una disolución sólida.En la segunda parte de la tesis se estudia el efecto del praseodimio sobre la estabilización, reactividad y sinterizabilidad de circonas tetragonales y cúbicas estabilizadas en función del método de síntesis: cerámica, coloide, resina de citratos y gel polimérico.En el sistema Pr-(Ca-ZrO2) se siguen dos tratamientos: estabilización-sinterización simultánea y estabilización-sinterización sucesiva. Los resultados indican que para obtener buenos densificados y un adecuado control composicional los mejores polvos son los del tipo citrato o coloide tratados por el procedimiento de estabilización ­sinterización simultánea.En función de lo comentado anteriormente se compararon diferentes sistemas estabilizantes (Ca, Y, Mg) cuando son tratados por el procedimiento simultáneo.Por último, dichos materiales son caracterizados desde el punto de vista mecánico, microestructural y de propiedades eléctricas.

La bioinformatique constitue un outil de choix dans l'étude des plantes. Lorsqu'utilisées efficacement, la gestion ainsi que l'analyse informatique des données biologiques permettent de réduire considérablement la durée des expériences ainsi que les coûts liés à la recherche tout en élargissant le spectre d'analyses pouvant être effectuées. L'objectif de cette recherche est de définir un protocole efficace utilisant les outils actuels et mettant en oeuvre de nouvelles approches, dans le but de faire le prétraitement, le clustering et l'assemblage d'un ensemble d'EST. Ce mémoire traite des algorithmes et des techniques informatiques utilisés dans l'étude de l'expression différentielle à partir des EST. Les particularités du projet de FGAS sont présentées et une attention particulière est portée sur la manière dont les résultats ont été analysés. À travers la classification en sous-groupes fonctionnels et de l'analyse différentielle digitale, l'identification des gènes potentiellement impliqués dans le phénomène d'acclimatation du blé au froid est effectuée. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Bioinformatique, Clustering, Assemblage, Expressed Sequence Tags, Tolérance au froid.

La demande énergétique mondiale sans cesse croissante pousse au développement d'autres sources d'énergie, de préférence durables, encouragé par nos gouvemements. Les cellules photovoltaïques à jonction p-n au silicium permettent de convertir directement l'énergie solaire en électricité. En raison du coût élevé de ce type de dispositif, notre laboratoire travaille à la conception d'une cellule photovoltaïque électrochimique, utilisant des films minces, dont la configuration est n-CulnS₂ couple redox thiolate/disulfure incorporé dans un gel verre | conducteur (lTO)-CoS. Pour optimiser la performance de la cellule, un couple redox ayant une structure aromatique, quasi-transparent en solution et possédant de bonnes propriétés électrochimiques est recherché. La synthèse de deux nouvelles espèces thiolates (forme réduite), soit le 4-cyanobenzènethiolate de potassium et celui de tétraméthylammonium, a été mise au point. Chaque thiolate a été mélangé avec la forme disulfure (espèce oxydée), également synthétisée dans notre laboratoire, pour former les couples redox respectifs A et B. La conductivité ionique, la viscosité, les propriétés électrochimiques et optiques des couples redox ont été étudiées dans deux milieux, soit le mélange de solvants DMF/DMSO: 60/40 (v/v) contenant 200 mM du sel support perchlorate de tétrabutylammonium (PTBA) (milieu 1) et le liquide ionique bis(trifluorométhylsulfonyl)imidure de l-éthyl-3-méthylimidazolium (EMlTFSI) (milieu 2). Chaque espèce a été caractérisée par spectroscopie RMN ¹H, ¹³C et IRTF. La voltampérométrie cyclique à une électrode de platine a permis d'optimiser les rapports molaires forme réduite:forme oxydée (Red:Ox) et les concentrations. Pour les milieux électrolytiques contenant le couple A, le rapport Red:Ox optimal est de 1:1 à une concentration totale de 500 mM dans le milieu 1, alors que cette concentration est doublée à 1 M en utilisant le couple B, avec le même rapport Red:Ox, ce qui permet d'obtenir des densités de courant et des conductivités beaucoup plus grandes du milieu électrolytique. Dans le milieu 2, les milieux électrolytiques préparés avec le couple A montrent un rapport Red:Ox optimal de 1: 1 avec une concentration totale de 20 mM. En utilisant le couple B, la concentration totale atteint 70 mM et le rapport Red:Ox a été optimisé à 3: 1. La catalyse des processus électrochimiques est supérieure sur une électrode de carbone vitreux comparée à une électrode de platine. L'ajout du groupement CN en para du cycle aromatique à six atomes de carbone, pour la forme thiolate, permet d'augmenter le potentiel standard apparent (E0=0,17 V vs ENH comparé à -0,24 V sans CN), indicateur d'un rendement accru de la pile solaire utilisant un semi-conducteur de type n, mais non la réversibilité. Des gels électrolytiques ont aussi été préparés en incorporant, aux solutions jugées optimales, 20% massique de poly(difluorure de vinylidène) (PVDF) aux électrolytes du milieu 1 et 7% à ceux préparés dans le milieu 2. Ces gels ont permis d'obtenir généralement des propriétés électrochimiques supérieures en densité de courant à celles des électrolytes liquides correspondants. Les mesures de résistance ont permis de constater une baisse de la conductivité des gels par rapport aux milieux liquides correspondants. La viscosité accrue des gels affecte le coefficient de diffusion des espèces électroactives. Le PVDF étant un polymère incolore, les gels électrolytiques possèdent les mêmes propriétés optiques que celles des milieux liquides. Le remplacement du groupement NO₂ par un CN en para du cycle aromatique a permis de diminuer la coloration des électrolytes. Les milieux électrolytiques contenant les couples redox ont une légère coloration jaunâtre translucide comparée aux milieux électrolytiques contenant le couple 4-nitrobenzènethiolate de potassium et sa forme disulfure, qui sont d'un rouge très foncé et opaque. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : 4-cyanobenzènethiolate, Disulfure de 4-cyanophényle, Cellule photovoltaïque électrochimique (CPE), Gel redox, Voltampérométrie cyclique.

In this work two different solution based methods have been used for synthesis ofoxide-wires and homogeneous heterometallic oxides of transparent conductingmaterials. The first method used is an aqueous chemical growth (ACG) method for synthesis ofmicrorods and nanowires of zinc oxide and tin dioxide useful for detection of toxicgases. No desired films have been obtained but some new interesting structures withnew surfaces at the a,b-plane, especially for zinc oxide where a jagged surface hasbeen observed. For low metal-concentrations of zinc, a band-like structure with 120 °angles has been observed to grow along the a- and b-axis instead of the preferredc-axis. The rod- and wire films have been characterized by SEM and XRD. The other solution-based method used is an inorganic sol-gel type where aheterometallic oxide of 80 mol% zinc and 20 mol% tin manufactured for CIGS solarcells acts as an absorption layer. The alkoxide was prepared by first synthesizing a zincmethoxy-ethoxide solution from diethylzinc and methoxy-ethanol and then mixing itwith tin tert-butoxide to get a heterometallic alkoxide solution. Films and powderhave been prepared either in humidified argon atmosphere or in air and characterizedby SEM, TGA and XRD. The XRD pattern just show the two expected phases of zincoxide and the heterometallic zin-tin oxide which improves the homogeneity of theheterometallic oxide. But the TGA show that some carbonating species formed. This method seems promising for large scale manufacturing of absorption layer toCIGS solar cell for commercially use due to low-cost materials, low temperatures andcheap equipment.

Sol-gel (solution-gelation) method was used to prepare Ni-Ti and Ni-Ti-Al catalysts for reforming of methane with carbon dioxide. This method, after optimizing the parameters such as hydrolysis and acid/alkoxide ratio, is able to make a Ni-Ti catalyst with a surface area as high as 426m2/g when calcined at 473K; but calcination at higher temperature lead to dramatic decrease in surface area. XRD, XPS, TEM and SEM were used to understand this change. Using a packed bed reactor, the catalysts were evaluated with the reforming reaction. It was found that the activity of the Ni-Ti catalyst increases with the Ni loading in the range of 1-10wt%. The reduction temperature has strong effect on activity of the reduced catalyst. Up to 973K, the activity increases with the reduction temperature; but after 973K, the activity decreases and become 0 when the temperature is over 1023K. The Ni-Ti catalyst also deactivated as 15% after 4h of time on stream. The XRD analysis shows that Ti3O5 formed in the catalyst after higher-temperature reduction as well as after the reaction for a period of time. The formation of Ti3O5 may render the catalyst to loss its activity. However, further study is expected to understand the mechanism. TG/DTA analysis shows that both Ni-Ti and Ni-Ti-Al catalysts had carbon deposition; but the latter maintained higher activity in a longer period of time.

A series of sol-gel based photopolymerizable silica glass for holographic storage have been synthesized via a facile chemical design in an effort to overcome the cracking problem incurred during the irradiation stage. The holographic composite material includes a low molecular weight polydimethylsiloxane (PDMS) with end-capped hydroxyl groups, an epoxide-containing coupling agent, a photopolymerizable acrylate monomer, and the sol-gel-derived silica matrix. Inclusion of PDMS provides improved compression stress and strain and toughness over the original unmodified samples, without deterioration on the diffraction efficiency (£b). A plateau value of £b ~ 40 % can be found under a beam power of 5.02 mW. Correlation between the molecular weight of acrylate polymer and £b of the holographic composite material is described and the discrepancies analyzed. The premature saturation of polymerization in the holographic system is attributed to the retarded free radical polymerization within the silica matrix. Minor variation of £b with photoinitiator concentration is observed, indicating that only moderate molecular weight is required for a reasonably high £b. The crack-free mechanism is based on the chemical and physical interactions within the material system. We also investigated the pore size and volume effect for optical properties, especially in studies of diffraction efficiency. With mixing rubber additives, the pore characteristics change via measurement of BET technique. The results indicated that moderate pore size made high diffraction efficiency for porous matrix and some characterizations also were presented. On the other hand, the optical application of this recording medium was described via 3D projected fringes profilometry (PFP) measurement. We recorded coded pattern on medium by employing fiber devices as light source. Using endoscope as image-derived tool, we get double-projected fringe images on tiny object. By PFP technique, a performed retrieved image can be achieved.

A series of photopolymerizable silica for optical storage has been prepared using sol-gel process in this study. The inorganic-organic hybrid materials were based on methacroloxy-propyl-trimethoxysilane (MPTS) and tetraethylorthosilicate (TEOS). Thin films of the hybrids were prepared using spin coating, knife coating, and the closed-mold methods, while the knife coating showing better film flatness and controlled film thickness. Results indicate crack-free polymerizable silica can be obtained using a recipe with 1 wt% photoinitiator. Samples after irradiation shows increased transmittance, suggesting that photopolymerization did take place with the aid of photoinitiators. Spectroscopic study from FTIR indicates C=C conversion in the acrylic part of MPTS reaches 57.51%. The grating period is observed by the optical microscopy. The maximum diffraction efficiency is 48.21%, as obtained from the sample of pure MPTS. From BET measurements, the pore size of the polymerizable silica increases with the increasing amount of MPTS, consistent with the results from measurements of apparent density. Factors affecting the diffraction efficiency are analyzed; these include sample flatness, sample thickness, the conversion of monomer, and concentration of the photoinitiator. Formation mechanism of the periodic grating is proposed based on this study. Addition of MPTS can greatly alleviate problem of phase separation; yet, movement acrylic segment in MPTS is severely limited. On the other hand, samples with more TEOS tend to be densified more with decreased diffraction efficiency

In the coming decades, the world will require additional supplies of natural gas to meet the demand for energy. Tight gas reservoirs can be defined as reservoirs where the formation permeability is so low (< 0.1 md) that advanced stimulation technologies, such as large volume fracture treatments, are required before a reasonable profit can be made. Hydraulic fracturing is one of the best methods to stimulate a tight gas well. Most fracture treatments result in 3-6 fold increases in the productivity index. However, if one computes the effective fracture length of most wells, we usually find that the effective length is less than the designed propped fracture length. The “propped length” is the distance down the fracture from the wellbore where proppants have been placed at a high enough concentration to “prop open” the fracture. The “effective length” is the portion of the propped fracture that cleans up and allows gas flow from the reservoir into the fracture then down the fracture to the wellbore. Whenever the effective length is much shorter than the designed propped length, several reasons must be evaluated to determine what might have occurred. For example, the difference could be caused by one or more of the following issues: insufficient fracture fluid cleanup, proppant settling, proppant embedment, proppant crushing, or poor reservoir continuity. Although all these causes are possible, we believe that fracture fluid cleanup issues may be the most common reason the industry fails to achieve the designed propped fracture length in most cases. In this research, we have investigated fracture fluid cleanup problems and developed a better understanding of the issues involved which hopefully will lead to ways to improve cleanup. Fracture fluid cleanup is a complex problem, that can be influenced by many parameters such as the fluid system used, treatment design, flowback procedures, production strategy, and reservoir conditions. Residual polymer in the fracture can reduce the effective fracture permeability and porosity, reduce the effective fracture half-length, and limit the well productivity. Our ability to mathematically model the fundamental physical processes governing fluid recovery in hydraulic fractures in the past has been limited. In this research, fracture fluid damage mechanisms have been investigated, and mathematical models and computer codes have been developed to better characterize the cleanup process. The codes have been linked to a 3D, 3-phase simulator to model and quantify the fracture fluid cleanup process and its effect on long-term gas production performances. Then, a comprehensive systematic simulation study has been carried out by varying formation permeability, reservoir pressure, fracture length, fracture conductivity, yield stress, and pressure drawdown. On the basis of simulation results and analyses, new ways to improve fracture fluid cleanup have been provided. This new progress help engineers better understand fracture fluid cleanup, improve fracture treatment design, and increase gas recovery from tight sand reservoirs, which can be extremely important as more tight gas reservoirs are developed around the world.

The hydraulic fracturing treatment is an essential tight sand gas reservoir stimulation that employs viscous fluid to break the formation rock to create a fracture and transport the propping agent to support the fracture from naturally healing. Despite proven economic benefit, the hydraulic fracture fluid damages the producing formation and the propped fracture. To analyze the gel damage effect quantitatively, the filter cake thickness is used as a parameter that has not been measured before. This project was divided into two stages. The first stage built up a filter cake and measured the filter cake thickness by a laser profilometer. A correlation between leakoff volume and filter cake thickness was produced. The second stage eroded the filter cake by flowing original fracturing fluid through the core sample to study the fracturing fluid shear clean up effect on filter cake thickness. The filter cake was built up in the lab and the thickness was measured with different methods. The profilometer has been tested as an effective tool to measure the filter cake thickness. A correlation for crosslinked guar fracture fluid filter cake thickness was produced. An experiment setup used to shear erode the filter cake was built and tested. The results showed the filter cake was not eroded at 200 s-1 shear rate.