Ce travail de thèse constitue une nouvelle approche de l’étude du comportement des bactéries immobilisées dans des matrices inorganiques centrée sur l’influence d’un champ magnétique sur le comportement cellulaire. Des nouveaux gels incorporant des nanoparticules de magnétite ont été élaborés par voie sol-gel dans des conditions cytocompatibles et caractérisés par diffraction des rayons X, sorption d’azote, microscopie électronique en transmission (MET) et mesures magnétiques. Après une étude de viabilité des bactéries modèles Escherichia coli immobilisées, le procédé d’encapsulation a été étendu aux bactéries magnétotactiques Magnetospirillum magneticum. L’effet d’un champ magnétique statique sur ces deux types de microorganismes a été étudié. Enfin, les processus de biominéralisation intracellulaire chez les bactéries magnétotactiques ont été suivis en présence et en absence d’un champ magnétique statique sur des cellules immobilisées et en suspension. Cette approche nous a permis de comprendre les phénomènes liés à l’encapsulation et à l’exposition à un environnement magnétique extérieur. Des effets originaux du champ magnétique continu sur la cinétique de production des magnétosomes et sur la dynamique collective des chaînes de magnétosomes à l’intérieur des cellules encapsulées ont pu être mis en évidence. / This work constitutes a new approach to the study of the behavior of immobilized bacteria in inorganic matrices focusing on the influence of a magnetic field on cell behavior. Novel gels incorporating magnetite nanoparticles were prepared by the sol-gel process in cytocompatible conditions and were characterized by X-ray diffraction, nitrogen sorption, transmission electron microscopy (TEM) and magnetic measurements. After studying the viability of immobilized model bacteria Escherichia coli, the encapsulation process was extended to magnetotactic bacteria Magnetospirillum magneticum. The effect of a static magnetic field on these two types of microorganisms was studied.Finally, the process of intracellular biomineralization in magnetotactic bacteria was followed in the presence and absence of a static magnetic field on the immobilized cells and suspension. This approach allowed us to understand the phenomena related to encapsulation and exposure to an external magnetic environment. New effects of the continuous magnetic field on the kinetics of magnetosome production and on the collective dynamic of magnetosome chains within the encapsulated cells are described.

Ce travail de thèse s'inscrit dans la problématique de la préparation et l'intégration des matériaux diélectriques poreux à très faible permittivité (ULK) dans les interconnexions des puces microélectroniques. Cette étude porte sur le développement de couches minces hydrophobes ULK à porosité organisée et isolée, préparées par voies sol-gel et PECVD. Elle vise une amélioration des propriétés mécaniques et une diminution de la diffusion de polluants au cœur des films. Des matériaux hydrophobes mésostructurés et ULK (k < 2,2) ont ainsi été obtenus par voie sol-gel, après retrait d'un porogène par traitement thermique, ou pour la première fois sous UV. Les caractéristiques mésostructurales et microstructurales des couches ont été reliées aux caractéristiques de porosité et aux propriétés mécaniques. Les mesures électriques et de perméation de gaz de ces matériaux sont également discutées en vue de leurs applications en tant que matériaux ULK ou comme membranes de séparation de gaz. En PECVD, des matériaux polymère plasma à base de styrène ont été synthétisés et également caractérisés en termes de propriétés mécaniques et de séparation de gaz. / This thesis is dealing with the challenging preparation and integration of porous dielectric materials with ultra low permittivity (ULK) for interconnections in microelectronic devices. This study focuses on synthesis of hydrophobic ULK thin layers with ordered and isolated porosity obtained by sol-gel. An improvement in mechanical properties and a decrease of the impurities migration in the heart of the bulk are expected. Hydrophobic and mesostructured ULK (k < 2.2) materials have been obtained by sol-gel after removal of porogen mesophases by thermal treatment and for the first time under UV irradiation. Mesostructural and microstructural properties of the layers were discussed with regard to the porosity and mechanical properties. The electrical and gas permeation measurements were also discussed in the framework of their possible applications as ULK materials and gas separation membranes, respectively. Using PECVD, styrene-based polymers, have been synthesized and also characterized in terms of mechanical and gas separation properties.

Dans cette thèse, le développement de nouveaux matériaux organiques-inorganiques pour deux enjeux technologiques majeurs est présenté : (1) le développement de phosphores sans métal pour l'éclairage ; (2) l'évaluation du potentiel de matériaux hybrides contenant des lanthanides comme concentrateurs solaires luminescents. En outre, un autre objectif, de nature fondamentale, est de comprendre l'effet de modifications légères dans le fragment organique de matériaux hybrides (changements de régioisomère, utilisation des thiourées à la place des urées) et de les mettre en forme (des poudres vers les films) pour moduler leurs nanostructures et photoluminescence. Ce manuscrit est divisé en 4 parties : (I) une introduction bibliographique décrivant les concepts de base de cette thèse : les mécanismes de luminescence et les réactions sol-gel sont d'abord décrits. La photoluminescence des sels de lanthanides est introduite. Finalement, les organosilices contenant des sels de lanthanides sont étudiées. (II) La synthèse, les caractérisations et les applications potentielles de différents silsesquioxanes pontés provenant de différents isomères (n,n'-diuréido-2,2'-bipyridine) et contenant des sels de lanthanides ou en l'absence complète de métal, sont décrits. Les propriétés des matériaux provenant des différents isomères sont comparées afin de mieux comprendre la coordination des ions lanthanides. (III) Cette partie s'intéresse à la mise en forme des précurseurs utilisés précédemment pour obtenir les matériaux correspondants sous forme de films minces. Les propriétés de ces dépôts sont comparées à celles des poudres précédentes. (IV) La substitution systématique des groupements urées par des thiourées dans des silsesquioxanes pontés bien connus a été réalisé : (1) Les propriétés structurales de matériaux synthétisés sous différentes conditions et à base de groupements thiourées sont étudiées ; (2) Les propriétés de photoluminescence des matériaux des isomères n,n'-dithiouréido-2,2'-bypiridine sont présentées. / In this thesis, the development of new organic-inorganic materials for two technological challenges is presented : (1) developing metal-free phosphors for solid state lighting ; (2) investigating the potential of lanthanide-containing materials as luminescent solar concentrators. Moreover, a fundamental objective is to understand the effect of minor modifications in the organic fragment of the hybrid materials (changing the regioisomer, using urea or thiourea crosslinks) and of the processing (from powders to films) to modulate their nanostructure and pholuminescence. This manuscript is divided in four parts : (I) a bibliographic introduction describing the basic concepts of this thesis : the luminescence mechanisms and the sol-gel reactions are first described. The photoluminescence of lanthanide salts is introduced ; finally, the organosilicas containing lanthanide salts are studied. (II) The synthesis, characterisations and potential applications of different bulk pristine and lanthanide-containing bridged silsesquioxanes derived from different n,n'-diureido-2,2'-bipyridine isomers are described. The properties of the material derived from the different isomers are compared to get insights into the coordination of the lanthanide ions. (III) The third part deals with the processing of the former sols to obtain the corresponding materials as thin films ; the properties of these coatings and of the formerly obtained powders are compared. (IV) The systematic substitution of urea by thiourea groups in the composition of well-known urea cross-linked bridged silsesquioxanes is performed. This fourth part is divided in two parts : (1) the structural features of simple thiourea-based materials synthesised under different conditions are investigated ; (2), the photoluminescence properties of n,n'-dithioureido-2,2'-bypiridine isomers are studied.

Orientador: Flavia Maria Netto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-04T01:03:16Z (GMT). No. of bitstreams: 1 Paz_JanaiCristianeSantosNascimento_M.pdf: 1327387 bytes, checksum: 694e3264c81a1a8b6a29d69943a20d23 (MD5) Previous issue date: 2004 / Resumo: A influência do pH (3,5 e 7,0); da temperatura de aquecimento (80 e 95 ºC) e da concentração de proteína (8 a 14%) na obtenção de géis de isolados protéicos comerciais de soja (IPS) e de soro de leite (IPSL) foi estudada em sistemas simples e mistos, nas proporções de IPS : IPSL 100 : 0; 80 : 20; 60 : 40; 40 : 60; 20 : 80; 0 : 100. Os géis simples e mistos formados em pH 3,5 foram do tipo coágulo, opacos, com grande exudação de água e quando a concentração de IPSL foi maior que a de IPS, os géis apresentaram separação de fase dos dois sistemas protéicos. Os géis preparados em pH 7,0, com 12 e 14% de proteína e temperatura de 80ºC eram extremamente moles e, com 12% de proteína e temperatura de aquecimento de 95ºC, eram formados géis incapazes de manter a sua forma. Os géis simples e mistos preparados em pH 7,0, com 14% de proteína, e temperatura de aquecimento 95ºC eram firmes e elásticos, sendo que nos géis mistos essas características tiveram intensidade intermediária a dos géis simples de IPS e IPSL. As propriedades físico-químicas, estruturais e funcionais dos géis foram estudadas pela análise da solubilidade dos componentes protéicos dos géis em diferentes meios de extração, caracterização dessas frações solúveis por SDS-PAGE e da microestrutura por microscopia diferencial de varredura. A capacidade de retenção de água (CRA) e os parâmetros de textura dureza, coesividade e elasticidade também foram determinados. Os resultados mostraram que houve aumento na dureza dos géis com o aumento da proporção de IPSL na mistura em ambos os pHs estudados e em pH 7,0, géis com dureza igual (p = 0,05) à do gel de IPSL foi obtido quando a substituição foi de 20%. A mistura IPS:IPSL também favoreceu o aumento da coesividade dos géis de pH 7,0 e da elasticidade dos géis de pH 3,5, quando comparados ao gel simples de IPS. Os géis de filamentos finos e estrutura compacta, obtidos em pH 7,0, apresentaram maior CRA que os géis de estrutura grosseira obtidos em pH 3,5. A substituição parcial de IPS por IPSL na obtenção de géis com pH 3,5 favoreceu a formação de uma microestrutura mais compacta, menos porosa, que a do gel simples de IPS. A analise de solubilidade indicou que os géis foram mantidos principalmente por interações hidrofóbicas e pontes de hidrogênio em ambos os pHs estudados. O perfil indica que a a-lactalbumina, b-lactoglobulina, proteínas do soro de leite, e o polipeptídeo ácido da fração 11S, foram estabilizados principalmente por interações eletrostáticas. A fração 7S e o polipeptídeo básico da fração 11S, foram mantidos principalmente por ponte de hidrogênio e interações hidrofóbicas / Abstract: The influence of pH (3.5 and 7.0); heating temperature (80 and 95ºC) and protein concentration (8 to 14%) on gelation properties of commercial soy protein isolate (SPI), whey protein isolate (WPI) was tested in isolation and when mixed in ratios 100:0; 80:20; 60:40; 20:80; 0:100 SPI:WPI. The simple and mixed gels obtained in pH 3.5 were clot gels, opaque, with high loss of water, and when the concentration of WPI was larger than the concentration of SPI, the gels showed phase separation of the two protein systems. In pH7.0 with protein concentration of 12 and 14% and 80ºC, the gels were very soft and when the protein concentration was of 12% and the heating temperature was 95ºC the gels were unable to keep their shape. In pH 7.0, 14%, 95ºC, the simple and mixed gels were firm and elastic, and the mixed gels showed these characteristics in an intermediate intensity when compared to simple gel obtained from SPI or WPI. These gels¿ physical-chemical, structural, and functional properties were studied by determination of solubility of the gel proteinic components, characterization of the soluble fractions by SDS-PAGE and of the microstructure by scanning electron microscopy (SEM). The water-holding capacity (WHC) and parameters of texture (hardness, cohesiveness and elasticity) were also determined. The results showed that the hardness increased when the amount of WPI was higher than the amount of SPI in the mixture in both pH studied, and in pH 7.0 the gels as hard as (p=0.05) the simple gel of WPI were obtained when the substitution of SPI to WPI was of 20%. The mixture SPI:WPI favored the increase of cohesiveness of the gels with pH 7.0 and the elasticity of the gels with pH 3.5, when compared to the simple gel of SPI. The gels that showed fine strand and compact structure, pH 7.0, had higher WHC than the gels with coarse structure, pH 3.5. The partial change of SPI for WPI in the gels pH 3.5 made the microstructure more compact and less porous than the microstructure of the simple gel of SPI. Solubility assays indicated that the main responsible forces for the maintenance of the gel structure in these pHs are hydrophobic and H bindings. It is possible that the a-lactalbumin, b-lactoglobulin, whey prtein, and the acid polypeptide of the 11S globulin was maintenanced main for eletrostatic forces. The 7S globulin and the basic polypeptide of the 11S globulin was maintenanced main for hydrophobic and H binding / Mestrado / Mestre em Alimentos e Nutrição

Orientador: Fabio Augusto / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T13:57:50Z (GMT). No. of bitstreams: 1 Silva_RaquelGomesdaCosta_D.pdf: 2096184 bytes, checksum: a4a32e68eebe713c6f80bc5415484d51 (MD5) Previous issue date: 2009 / Resumo: Esse trabalho apresenta o desenvolvimento de materiais sorventes com impressão molecular, para utilização na Extração em Fase Sólida (SPE) a partir da tecnologia sol-gel. No capítulo 1 foi preparado um material com impressão molecular seletivo para metilxantinas, utilizando-se o processo sol-gel. Posteriormente, esse material foi aplicado na extração de cafeína em águas e urina humana, seguido de análise cromatográfica. No capítulo 2, foi sintetizado um ormosil (sílica organicamente modificada) seletivo para fenobarbital. Nessa etapa, como molécula molde foi utilizado um análogo estrutural (ácido barbitúrico) ao analito alvo. O material foi aplicado na determinação de fenobarbital em plasma humano, demonstrando ser seletivo para esse composto. No capítulo 3 foi relatado o preparo de um ormosil impresso molecularmente seletivo para compostos triazínicos. Esse material foi aplicado com sucesso na determinação de simazina, propazina e atrazina em amostras de caldo de cana. Paralelamente, o material preparado em laboratório foi comparado ao material comercial seletivo para triazinas. Ambos materiais demonstraram ser seletivo para esses compostos. Os materiais preparados a partir do processo sol-gel apresentaram potencialidade na determinação de diferentes analitos alvo. / Abstract: This work presents the development of sorbent materials with molecular imprinting for use in Solid Phase Extraction (SPE) through sol-gel technology. In chapter 1, a molecularly imprinted material selective for methylxanthines was prepared, using the sol-gel process. Subsequently, this material was used in the extraction of caffeine from water and human urine, followed by chromatographic analysis. In Chapter 2, an ormosil (organically modified silica) selective for phenobarbital was synthesized. For this, a analogue structural was used as template (barbituric acid) for the target analyte. The material was applied to the determination of phenobarbital in human plasma, proving to be selective for this compound. In Chapter 3 the preparation of a imprinted ormosil selective for triazine is reported. This material has been successfully applied for the determination of simazine, atrazine and propazine in samples of sugar cane juice. In addition, the material prepared in the laboratory was compared to commercial material selective for triazines. Both materials were shown to be selective for these compounds. The materials prepared by the sol-gel process showed potential for the determination of different target analytes. / Doutorado / Quimica Analitica / Doutor em Ciências

Submitted by Rafael Santana (rafael.silvasantana@ufpe.br) on 2017-07-25T19:46:06Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Dissertacao PRONTA.compressed-2.pdf: 7340420 bytes, checksum: 27358d102b9b7c405f37c9e2a0ceb516 (MD5) / Made available in DSpace on 2017-07-25T19:46:06Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Dissertacao PRONTA.compressed-2.pdf: 7340420 bytes, checksum: 27358d102b9b7c405f37c9e2a0ceb516 (MD5) Previous issue date: 2015-07-02 / Neste trabalho foi feito um estudo das propriedades estruturais e magnéticas de filmes granulares de cromita de cobalto sobre substrato de silicio. Aqui os filmes foram fabricados a partir do método químico sol‐gel, técnica de centrifugação spincoating e Tratamento térmico apropriado. Toda família de filmes foi fabricada sobre substrato de silício (100) e submetida a tratamento termico. A diferença de um filme para outro esta na quantidade de material depositado. Isto possibilitou o estudo das propriedades supracitadas em função da quantidade de material depositado para fabricação do filme. A cristalinidade de todas as amostras obtidas foi confirmada por difração de raios-X (XRD). A microscopia eletrônica de varredura (MEV) mostrou filmes granulares com boa homogeneidade e que a espessura de todas as amostras aumenta com a quantidade de gotas depositadas durante o spin‐coating. As propriedades magnéticas foram medidas usando magnetometria de amostra vibrante (VSM). O campo aplicado durante a medicao foi orientado paralelo ao plano do filme e observou‐se uma alta coercividade e que esta diminui quase linearmente com o aumento de temperatura. / In this work we have made a study of the structural and magnetic properties of cobalt chromite granular films over silicon substrate. Here the films were fabricated by the chemical method sol‐gel, spin coating technique and ppropriate heat treatment. The entire Family was deposited over silicon substrate (100) and submitted to heat treatment. The difference between a film to another is the quantity of deposited Material. This allowed the study of the above properties as a function of the deposited material. The crystallinity of all samples obtained was confirmed by X‐ray diffraction (XRD). The scanning electron microscopy (SEM) showed granular films with good homogeneity and the thickness of all samples increases when the number of drops increases during spin‐coating. The magnetic properties were measured using vibrating sample magnetometry (VSM). The applied field during the measurement was Oriented parallel to the film plane and observed a high coercivity and that decreases pproximately linearly with increasing temperature.

O presente trabalho consiste na preparação e caracterização de filmes finos de óxido nióbio (Nb2O5) dopados com trifluoro metano sulfonato de lítio (CF3SO3Li). A adição do sal de lítio tem como objetivo verificar a influência do mesmo nas performances opto-eletroquímicas dos filmes de óxido de nióbio. Os sóis para deposição dos filmes foram preparados pelo processo sol-gel submetendo a mistura de NbCl5, butanol, ácido acético e o sal de lítio à irradiação ultra-sônica por alguns minutos. Em seguida, os filmes foram depositados pela técnica dip-coating sobre um substrato de vidro recoberto com camada condutora (ITO-Asahi). Os filmes foram então submetidos a um tratamento térmico entre 400&#176C e 600&#176C durante alguns minutos em atmosfera de ar. A reversibilidade eletroquímica destes filmes foi estudada através de voltametria cíclica e cronoamperometria. As medidas de transmissão ótica foram realizadas in-situ na região entre 350 e 800nm (ultravioleta ao visível). Análises microscópicas (MEV, EDX, AFM) foram feitas para verificar a textura, composição e a topografia dos filmes. Foram feitas também, medidas de espectroscopia de infravermelho para a caracterização dos sóis e análises térmicas (DTA/TGA) e difração de raios-X para os precipitados. O possível uso destes filmes em sistemas eletrocrômicos para aplicação em arquitetura foi estudado através de comparação com os resultados de transmissão ótica de vidros comuns. / Present work shows the preparation and characterization of niobium (V) oxide films (Nb2O5) doped with lithium trifluoromethanesulfonate (CF3SO3Li). The main objective of lithium salt addition was to verify its influence on the opto-electrochemical performance of the niobia films. Sols to deposition of the films were prepared by sol-gel process. The mixture of NbCl5 butanol, acetic acid and lithium salt was submitted to ultrasonic irradiation for some minutes. After, films were deposited by dip-coating on glass substrate re-covered with conductor layer (ITO-Asahi). Films were submitted to the thermal treatment between 400 and 600&#176C during some minutes in air atmosphere. The electrochemical reversibility of these films was studied by cyclic voltammetry and chronoamperometry. Their optical transmission measurements were performed in-situ in the UV-VIS range (between 350 and 800nm). Microscopic analysis (SEM, EDX, AFM) was made to check the texture, composition and topography of the films. Infrared spectroscopy measurements were made to sols characterizations and thermal analyses (TGA/ DTA) and X-ray diffraction to the precipitates. The possible use these films in architecture was studied by comparing with the optic transmission results of the common glass.

Este trabalho apresenta resultados da preparação e caracterização de filmes finos de pentóxido de nióbio (Nb2O5) dopados com isopropóxido de zircônio (IV) Zr[O(CH2)2CH3]4, obtidos via processo sol-gel. A adição do precursor dopante teve como finalidade estudar a sua influência sobre as propriedades eletroquímicas destes filmes. Os sóis destinados à deposição destes filmes foram preparados a partir da mistura de pentacloreto de nióbio (NbCl5 anidro), n-butanol e ácido acético e sua submissão à ação de irradiação ultrasônica. A obtenção das camadas delgadas de Nb2O5:Zr, com diferentes espessuras (1 a 6 camadas), sobre um substrato de vidro recoberto com camada condutora eletrônica (ITO), fez-se pelo processo sol-gel juntamente com a técnica de imersão vertical (dip-coating). Os filmes foram submetidos a um tratamento térmico entre 450ºC e 560ºC, em atmosfera de ar, por 5 e 10 minutos. O estudo efetuado revelou que estes filmes finos de Nb2O5:Zr, apresentaram influência de concentração de zircônio, número de camadas e tempo de tratamento térmico nas propriedades eletroquímicas. As medidas de voltametria cíclica demonstraram que o processo de inserção/extração é reversível, enquanto medidas cronoamperométricas, demonstraram que o processo de intercalação atinge o seu valor máximo (35 mC/cm2) em 30s à -1,8V, para filmes dopados numa razão molar de 0,5% e com 5 camadas e tratamento térmico de 450°C por 10 minutos. Estes filmes também apresentaram nas análises microscópicas por MEV uma morfologia muito uniforme, lisa e sem rachaduras. Além disso, foi comprovada por análises EDX a presença de zircônio nos filmes. Todos estes resultados mostraram que os filmes de Nb2O5:Zr são promissores e excelentes candidatos à substituir filmes de WO3.em aplicações eletroquímicas. / This work consists of the preparation and characterization of niobium (V) oxide films (Nb2O5) doped with zirconium (IV) isopropoxide Zr[O(CH2)2CH3]4, was obtained by sol-gel process. The main objective of dopant addition was to study its influence on eletrochemical properties of these films. The sols used to deposition of these films were prepared from the mixture of niobium (V) (NbCl5), butanol and acetic acid by ultrasonic radiation action. The obtaining of the thin layers of Nb2O5:Zr with different thick (from 1 to 6 layers), on a glass substrate recovered with conductor layer ( ITO) was carried out by sol - gel process and dip-coating technique. The films were subjected to a thermal treatment between 450ºC and 560ºC, during some minutes in air atmosphere for 5 and 10 minutes. The study performed showed that these thin films of Nb2O5:Zr, presented influence of zirconium concentration, numbers of layers and time of termic treatment in the electrochemical properties. The measures of cyclic voltammetry showed that the process of insertion and extraction is reversible whereas the chronoamperometry measures showed the intercalation process has as maximum values (35mC/cm2) in 30s at -1,8V to doped films in a molar ration of 0,5% and with 5 layers and termci treatment of 450oC for 10 minutes. These films also presented in microscopic analysis by SEM a morphology very consistent, smooth and without cracks. Besides, it was proved by analysis by EDX the zirconium presences in the fims. All these results showed that the films of Nb2O5:Zr are promising and excellent application to replace films of WO3 in electrochemical application.

Les organosilices sont des matériaux en plein essor, qui combinent les propriétés des fragments organiques et ceux de la matrice siliciée. Ces matériaux hybrides ont trouvé des applications dans les domaines de la catalyse, de l'optique, de l'électronique etc. Ils peuvent être préparés par le procédé sol-gel à partir d'organosilanes contenant des fragments organiques à propriétés désirées. Pour former ces matériaux, il est essentiel de simplifier la préparation des organosilanes fonctionnels en réduisant le nombre d'étapes réactionnelles. Aussi, l'un des buts de cette thèse est de développer une méthode de préparation sélective, universelle et à spectre large pour les organo(trialcoxy)silanes. Dans ce but, la réaction Click de CuAAC, connue comme une approche simple de couplage, a été adaptée pour les composés sensibles à l'eau. En utilisant des azotures ou des alcynes contenant la fonction triéthoxysilane avec des partenaires organiques, nous avons réussi à préparer des séries de précurseurs silylés par réaction Click. La réaction est rapide, quantitative et sélective, et tolère une gamme étendue de substrats. De plus, de nouveaux alcynes et azotures comportant deux fonctions triéthoxysilyle ont été préparés, afin d'être clickés sur différentes molécules organiques. Ces précurseurs bissilylés sont des organo(triéthoxy)silanes clickables, précurseurs de silsesquioxanes pontés. En utilisant des molécules fonctionnelles comportant un seul site de dérivatisation, des organosilanes pontés peuvent être obtenus, présentant un fragment organique pendant. De plus, un précurseur contenant une fonction alcyne protégée a été obtenu, ce qui permettra la formation de matériaux multifonctionnels. Certains des précurseurs sol-gel obtenus ont été transformés en matériaux hybrides par le procédé sol-gel. Ceux contenant des fragments organiques connus comme des ligands chiraux actifs ont été choisis pour des tests en catalyse asymétrique. Par ce biais, des ligands chiraux supportés ont été formés, et testés pour quelques réactions bien connues. De plus, cette thèse s'est intéressée à la nano-structuration de matériaux. Des molécules contenant des systèmes aromatiques et des fonctions urée, capables de s'auto-assembler grâce à des interactions non covalentes, ont été conçues et préparées. Dans certains cas, en particulier les systèmes à base de Binol avec des fonctions urée, des nanostructures régulières ont été observées sur des surfaces localisées. En conclusion, les travaux présentés dans cette thèse ont apporté de nouvelles possibilités pour la synthèse d'organo(triéthoxy)silanes, ainsi que des matériaux hybrides à propriétés et applications ciblées. / Organosilicates are attracting considerable attention, owing to the combined properties of the organic fragment and inorganic silica matrix. These hybrid materials have found application in catalysis, optics, electronics, etc. They can be prepared by the sol-gel hydrolysis of functional organosilanes with the desired properties. To apply these materials in industry, it is essential to make the preparation of these silylated precursors easier and more efficient by reducing the number of reaction steps. Therefore one of the aims of this thesis is to develop a universal, wide scope and selective method of preparation for trialkoxyorganosilanes. For this purposes the “CuAAC reaction”, known for its simple approach, has been adapted for water-sensitive substrates. Using a silylated azide or silylated alkyne with an organic counterpart, we were able to prepare a series of clicked sol-gel precursors. The reaction is quantitative, fast, and selective and tolerates a wide range of substrates. Moreover, new bissilylated alkynes and azides which can be clicked to various organic molecules were prepared. They represent new families of bridged organotrialkoxysilanes to which a desired organic molecule, bearing only one bonding site, can be incorporated as a pending group with a targeted functionality. Furthermore, a bissilylated precursor bearing a protected alkyne function was prepared, allowing the synthesis of bifunctional materials. Some of the prepared precursors were transformed into hybrid silicas by the sol-gel process. Those containing organic molecules known as active chiral ligands for enantioselective reactions were chosen. By this way, supported chiral ligands were formed and we tested their activity according to known reactions. Additionally, in this thesis the structuring of the materials was also attempted. Molecules bearing aromatic systems and urea functions, which are capable of self-organization thanks to the weak non-covalent bonding interactions, were designed and prepared. In some cases, especially Binol systems with urea function, regular nanostructures on localized areas have been observed. Overall, this thesis brings new possibilities in the synthesis of both trialkoxyorganosilanes precursors and hybrid materials with desired properties and applications.

Les aciers inoxydables austénitiques sont très utilisés dans l’industrie. Reconnus pour leur résistance à la corrosion, ils le sont également pour leur forte susceptibilité à l’usure adhésive (grippage). Cela a pour conséquence une dégradation accélérée des matériaux, ce qui conduit à des pannes brutales, à des pertes de performances et à une augmentation des coûts d’exploitation. Le CETIM et le CIRIMAT explorent des solutions basées sur des revêtements protecteurs afin de diminuer le coefficient de frottement et le volume d’usure. Des sols chargés en carbone sont élaborés et déposés par trempage-retrait sur des substrats en acier inoxydable 304L. Après gélification et traitement thermique en atmosphère inerte, des revêtements carbone-céramique d’une épaisseur d’environ 2 à 7 μm sont obtenus. Deux matrices (alumine et alumine-silice) sont étudiées, ainsi que différentes charges carbonées: du graphite commercial et des nanotubes de carbone (NTC) dont le nombre de parois moyen est égal à 2, 8 ou 20. Des essais tribologiques rotatifs bille-plan réalisés selon la norme ASTM G99 (bille en acier, charge normale 2N, vitesse 10 cm/s, 250 m de glissement) ont montré que les revêtements graphite-alumine présentent un plus faible coefficient de frottement et une plus faible usure que les revêtements alumine et NTC-alumine. Nous montrons que la surface totale de carbone disponible dans l’échantillon est le paramètre pertinent et que l’exfoliation progressive du graphite en graphène oligocouche (2-5) pendant l’essai permet de générer in situ de nouvelles surfaces, tandis que les NTC ne subissent pas d’endommagement majeur. Nous mettons en évidence la formation d’un tribofilm lubrifiant au contact bille/revêtements composites. Nous nous sommes donc orientés vers la pré-exfoliation du graphite dans le sol par différentes méthodes. Nous mettons en évidence qu’une méthode impliquant de grandes contraintes de cisaillement permet la pré-exfoliation efficace du graphite, la surface de carbone étant alors 1300 fois plus grande qu’avec la dispersion par sonde à ultrasons. Nous montrons que ce sont les échantillons GBC-alumine qui présentent les plus faibles volumes d’usure (0,0023 mm3) et coefficient de frottement (0,14) de ce travail. Le dernier chapitre est consacré à l’étude de l’adhérence du revêtement au substrat et du comportement tribologique des revêtements lors d’un essai industriel sévère (ASTM G133). Il est notamment mis en évidence que les revêtements à matrice alumine-silice présentent une meilleure adhérence que ceux à matrice alumine. / Austenitic stainless steels are widely used in industry. Recognized for their resistance to corrosion, they are also known for their high susceptibility to adhesive wear (seizure). This results in accelerated material degradation leading to sudden failures, loss of performance and increased operating costs. CETIM and CIRIMAT are actively exploring solutions based on protective coatings in order to reduce the friction coefficient and the wear volume. Carbon-loaded sols are prepared and deposited by dip-coating on 304L stainless steel substrates. After gelation and heat-treatment in an inert atmosphere, carbon-ceramic coatings about 2 to 7 μm thick are obtained. Two matrices (alumina and alumina-silica) are studied, as well as different carbonaceous fillers: commercial graphite and carbon nanotubes (CNT) with an average number of walls equal to 2, 8 or 20. Rotative friction tests performed according to the ASTM G99 standard (steel ball, normal load 2N, velocity 10 cm/s, distance 250 m) have shown that the graphite-alumina coatings show a lower friction coefficient and a lower wear than the alumina- and CNT-alumina coatings. We show that the total available carbon surface area in the sample is the relevant parameter and that the progressive exfoliation of graphite to flew-layered-graphene (2-5) during the test generates new surfaces in situ whereas the CNT do not sustain any major damage. We bring to light the formation of a lubricating tribofilm in the contact between the friction ball and the composite coating. Therefore, we have focused on the pre-exfoliation of graphite in the sol by different methods. We show that a method involving high shear stresses allows an efficient pre-exfoliation of graphite, the carbon surface area being 1300 times higher than when performing the dispersion using an ultrasonic probe. We show that the BLG-alumina samples have the lowest wear volumes (0.0023 mm3) and friction coefficient (0.14) reported in this work. The last chapter is devoted to the study of the adhesion of the coating to the substrate and to the tribological behavior of the coatings in a severe industrial test (ASTM G133). It is notably demonstrated that the alumina-silica matrix coatings show a better adhesion than the alumina-matrix ones.