The discovery of superconductivity in ceramic materials by Bednorz and Müller [2, 3] in early 1987, immediately followed by Wu et al. [4, 5] who showed that YBa2Cu3O7−x (YBCO) becomes superconducting (92K) well above the boiling point of nitrogen (77K) created a great excitement in superconductivity research. Potential applications of high Tc-superconductors require large critical currents and high-applied magnetic fields. Effective ways to increase the critical current density at high magnetic fields in YBCO are the introduction of nanoparticles and chemical substitution of yttrium by other rare earth elements. Since low costs and environmental compatibility are essential conditions for the preparation of long length YBCO films, the cost effective chemical solution deposition (CSD) procedure was selected, given that no vacuum technology is required. To reveal the flexibility and the good optimization possibilities of the CSD approach two main processes were chosen for comparison: a fluorine-free method, namely the polymer-metal precursor technique, and a fluorine-based method, the metalorganic deposition (MOD) using the trifluoroacetates (TFA) technique. Sharp transition temperature widths DTc of 1.1K for the polymer metal method, 0.8K for TFA method and critical current densities Jc of _3.5MA/cm2 shows that high quality YBCO thin films can be produced using both techniques. Especially interesting is the magnetic field dependence of the critical current density Jc(B) of the Y(Dy)BCO (80 %) films showing that for the lower magnetic fields the critical current density Jc(B) is higher for a standard YBCO film, but at fields higher than 4.5T the critical current density Jc(B) of Y(Dy)BCO is larger than that for the YBCO. Above 8T, Jc(B) of the Y(Dy)BCO film is more than one order of magnitude higher than in pure YBCO film. / Die Entdeckung der Supraleitung in keramischen Materialien durch Bednorz und Müller 1987 und die kurz darauf folgende Beobachtung von Wu et al., dass YBa2Cu3O7−x (YBCO) supraleitende Eigenschaften deutlich oberhalb (92K) des Siedepunktes von Stickstoff (77K) aufweist, führten zu einer enormen Intensivierung der Forschung hinsichtlich neuer supraleitender Materialien sowie deren Eigenschaften und möglichen Einsatzgebieten. Potentielle Anwendungsgebiete für diese neuen Hochtemperatur-Supraleiter erfordern hohe kritische Stromdichten und hohe kritische Feldstärken. Effektive Wege zur Erhöhung der kritischen Stromdichte in starken Magnetfeldern in YBCO sind der Einbau von Nanoteilchen oder die chemische Substitution von Yttrium durch ein anderes Seltenerd-Element. Da niedrige Kosten und gute Umweltverträglichkeit wichtige Voraussetzungen für die Herstellung von YBCO-Schichten großer Länge darstellen, werden in dieser Arbeit die Vorteile und Einsatzmöglichkeiten der Chemischen Lösungsabscheidung (chemical solution deposition - CSD) untersucht. CSD Prozesse sind besonders gut geeignet, weil sie keine Vakuum-Technologie erfordern und einen hohen Grad an Flexibilität garantieren. Zur Demonstration der guten Optimierbarkeit werden zwei wichtige CSD-Verfahren miteinander verglichen: die Polymer-Metall Precursor Technik - eine Fluor-freie Methode - und die metallorganische Abscheidung mittels Trifluoroacetat (TFA-MOD), bei der Fluor zum Einsatz kommt. Scharfe supraleitende Übergänge (Polymer-Metall Precursor Technik: DTc = 1.1K; TFA -MOD: DTc = 0.8K) sowie hohe kritische Stromdichten von ca. 3.5MA/cm2 (B= 0 T) zeigen, dass mit beiden Verfahren dünne YBCO-Schichten hoher Qualität hergestellt werden können. Außerdem bieten CSD-Verfahren durch die hervorragende Kontrollierbarkeit der Stöchiometrie des Precursors die Möglichkeit Yttrium teilweise oder vollständig durch andere Seltenerd-Metalle zu ersetzen und damit die kritische Stromdichte in hohen Magnetfeldern deutlich zu erhöhen. In dieser Arbeit wird gezeigt, dass besonders die TFA-Methode besonders geeignet ist, um (RE)BCO-Schichten (RE: rare earth) herzustellen. Untersucht wurden verschiedene Zusammensetzungen mit Sm, Dy und Ho. Außerordentlich interessant sind dabei die Ergebnisse für Y(Dy)BCO-Schichten. Schichten mit einem Dy-Gehalt von 80 % zeigen oberhalb von 4.5T deutlich höhere kritische Stromdichten als reine YBCO Schichten. Bei Magnetfeldern größer als 8T beträgt der Unterschied mehr als eine Größenordnung.

<p>Aminoglycoside antibiotics are commonly used to treat bacterial infections but are highly susceptible to chemical modification, leading to resistance. Chemical modification can be hindered through the use of small molecule inhibitors that target bacterial enzymes involved in resistance, most notably kinases. Current methods for the discovery of small molecule inhibitors of kinases and related “kinase-like” enzymes are limited in throughput and utilize slow, tedious, and expensive assays. This thesis is focused on the development of highly versatile and scaleable kinase and “kinase-like” screening platforms for the discovery of small molecule inhibitors of these drug targets. The work begins with the validation of a matrix-assisted laser desorption/ionization tandem mass spectrometry (MALDI-MS/MS) platform utilizing phosphorylation of kanamycin, an aminoglycoside antibiotic, by aminoglycoside phosphotransferase 3ʹIIIa (APH 3ʹIIIa) as a model system. Using a product-to-substrate signal ratio as an internal standard, the assay was used to functionally screen over 200 compounds, combined into mixtures to enhance assay throughput. Moreover, the assay was used to determine inhibitory dissocation constants for newly discovered modulators. Throughput was further increased to a novel dual-kinase assay targeting a bacterial enzyme, APH 3ʹIIIa and a human kinase, protein kinase A (PKA), which was validated using the previous small molecule library. Alternative assay development platforms were also studied using imaging mass spectrometry of reaction microarrays and the fabrication of sol-gel derived bioaffinity chromatography columns. The MS-based kinase assays developed herein are highly amenable to high throughput screening, and have the potential to be extended to other important therapeutic targets.</p> / Doctor of Philosophy (PhD)

Une organisation contrôlée de la porosité offre l’opportunité de combiner les avantages structuraux des macropores (diamètres supérieures à 50 nm), assurant l’intégrité et l’interconnectivité de l’ossature du matériau, avec ceux des pores plus étroits (méso- et micropores), déployant des surfaces spécifiques réactives importantes. L’élaboration de telles architectures, dites « hiérarchisées », à l’échelle du laboratoire représente un véritable défi physico-chimique. Dans ce contexte, ce travail de thèse s’intéresse à l’élaboration de matériaux poreux fonctionnels avancés, s’inscrivant dans le concept de chimie intégrative, en combinant matière molle (mésophases lyotropes, émulsions directes concentrées, auto-assemblages organique-organique, etc.), procédé sol-gel, polymérisation organique et principe de l’empreinte « dure ». Dans une première approche générale, des monolithes hybrides macrocellulaires à base de silice ont été fonctionnalisés par greffage covalent post-synthèse ou par co-condensation de précurseurs organosilanes appropriés. Dès lors, l’encapsulation de complexes luminescents (ions europium), de catalyseurs métalliques piégés dans une phase liquide ionique supportée (sels ou nanoparticules de palladium), ou d’entités biologiques (enzymes hydrosolubles : lipases) a offert une modulation rationnelle des propriétés optiques, catalytiques ou biocatalytiques induites in fine. Dans une seconde approche générale, l’utilisation de monolithes de silice macrocellulaires comme empreintes dures « sacrificielles » a permis la genèse de composés carbonés poreux, associée à un contrôle structural sur plusieurs échelles. Dès lors, une surface spécifique développée et une porosité hiérarchisée, conjuguées à des propriétés intrinsèques opportunes (stabilités thermique et chimique, conductivité électrique), ont offert un large champ d’applications, comme électrodes pour systèmes de stockage de l’énergie électrochimique (batteries Li-ion et condensateurs à double couche électrochimique), sites de nucléation de borohydrures de lithium (LiBH4) pour le stockage de l’hydrogène, ou encore comme électrodes enzymatiques pour biopiles. / Mainly induced by the wide scope of expected applications, designing hierarchical porous architectures appears today as a strong and competitive field of research. The opportunity to combine the structural advantages of both macropores (diameters larger than 50 nm), providing interconnected framework while reducing the diffusion low kinetic issue, with those of the more narrow pores (meso and micropores), generating high surface reactive areas, has induced a need for novel synthetic routes to achieve hierarchical structures. In this view, by combining soft mater (lyotropic mesophases, concentrated direct emulsions or organic-organic self-assemblies, etc.), sol-gel process, organic polymerization and hard-template approaches, we have generated new functional porous materials, fitting with the transversal integrative chemistry concept. In a first general approach, organically grafted silica foams have been designed, either by a grafting method or a one-pot co-condensation route of organosilane derivatives, to encapsulate luminescent complexes (europium ions), metallic catalysts entrapped into supported ionic liquid phase (palladium salts or nanoparticules) or bio-related entities (water-soluble enzymes: lipases), dealing with promising optical, catalytic or biocatalytic properties. In a second synthetic pathway, using siliceous foams as “sacrificial” hard templates, carbonaceous foams have been obtained addressed through a structural design over several length scales. Due to inherent high surface area, chemical inertness, thermal stability and good conductivity, this new foams series has offered a large field of applications, such as electrodes for electrochemical energy storage devices (Li-ion batteries and electrochemical double-layer capacitors), host sites for hydrogen storage through LiBH4 nucleation, as well as advanced porous electrodes for enzyme-based biofuel cells.

Les composites carbone/carbone présentent de propriétés thermomécaniques à hautes températures qui les rendent particulièrement adaptés à l’ablation ou à la friction. Leur sensibilité à l’oxydation dès 400°C a conduit à envisager leur dopage en éléments réfractaires inoxydables ou à température d’oxydation élevée. Le procédé sol-gel a permis d’introduire environ 1 % volumique d’oxyde ou de nitrure de titane ou d’aluminium dans leur matrice. Les nitrures sont obtenus par nitruration carbothermique des films d’oxydes. Deux types de sols ont été utilisés : des sols « standard » et des sols enrichis en saccharose. Le saccharose est ajouté pour prévenir la consommation du pyrocarbone lors de la nitruration. Il a par ailleurs une influence sur l’avancement de la nitruration. Les composites chargés sont ensuite densifiés par voie gazeuse, ce qui induit des transformations de phases prévues par la thermodynamique : les films de nitrure de titane sont partiellement carburés (formation de carbonitrure), et les films d’oxyde de titane sont réduits (formation d’oxycarbure). Les dépôts à base d’aluminium sont plus stables et ne subissent aucune transformation. La diffusivité thermique des composites réalisés est faiblement impactée par les charges introduites, alors que les résistances en traction/compression sont sensiblement augmentées. Par ailleurs, une rigidification des composites est observée. Leur cinétique d’oxydation est ralentie. Les composites enrichis en alumine et nitrure d’aluminium présentent des vitesses de perte de masse divisées par 2 par rapport à la référence C/C. Toutes ces propriétés sont liées directement ou non à la composition des sols, et plus particulièrement à sa teneur en saccharose. Il a en effet été montré que les sols qui en contiennent ont tendance à gélifier en surface du composite, ce qui gêne la diffusion des gaz précurseurs au cœur du composite lors de la densification. La porosité finale s’en trouve modifiée. Cette dernière a une influence non négligeable sur le comportement en compression, la diffusivité thermique et la cinétique d’oxydation des composites élaborés. / Carbon/carbon composites exhibit excellent mechanical and thermal properties at high temperature that make them espe-cially suitable for ablation or friction pieces. Their sensitivity toward oxidation above 400°C has lead to the will of doping them with refractory ceramics that are nonoxidizable or with a high oxidation temperature. The sol-gel process allowed to introduce 1 % in volume of titanium or aluminum oxide or nitride in the matrix. Nitrides are obtained by carbothermal nitridation of the oxide films. Two types of sols were used: the “standard” ones and those with extra sucrose. Sucrose is added to prevent pyrocarbon consumption during the nitridation. Furthermore, it was shown that it has an impact on the nitridation rate. Charged composites are then densified by Chemical Vapor Infiltration, which induces phases transforma-tions that were predicted by thermodynamics: titanium nitride films are partially carburized (formation of titanium carbonitride) and titanium dioxide films are reduced (formation of titanium oxycarbide). Aluminum-based films are more stable and don’t undergo any transformation. Thermal diffusivity of the as-synthesized composites is not much modified by the addition of these ceramics while the tensile and compressive strength are slightly increased. By the way, composites are hardened. Their oxidation kinetics is slowed down. Aluminum-rich composites exhibit a weight loss divided by two compared to the C/C reference. All those properties are directly, or not, linked to the composition of the sols, in particular to their sucrose content. Indeed, it was shown that sucrose-containing sols rather jellify on the surface of the composite, thus preventing the diffusion of precursor gases to the heart of the pieces. The final porosity is then modified. The porosity has an important impact on the compressive strength, thermal diffusivity and oxidation kinetics of the synthesized composites.

Un procédé sol-gel développé au laboratoire a été appliqué à des précurseurs hétéroleptiqueset/ou hétérométalliques pour l’élaboration de nouveaux matériaux hybrides et/ou dopés.Des nanoparticules de TiO2 dopées par le gadolinium et l’europium ont été obtenues sous formede nanocristallites d’anatase par ce procédé basse température. Leurs performancesmagnétiques et luminescentes ont été évaluées afin de pouvoir les utiliser comme agents decontraste pour l’imagerie médicale. L’utilisation d’un précurseur hétérométallique ethétéroleptique contenant à la fois du titane, du gadolinium et du PABA a pu conduire à laformation de matériaux dopés et hybrides en une seule étape. L’utilisation future de cesmatériaux dans le domaine biomédical est envisagée.La deuxième partie de ce travail a consisté en l’élaboration de supports hybrides TiO2(citrate) en appliquant le même procédé de co-hydrolyse à un nouvel alcoxyde de titane comportant le ligand citrate. Plusieurs degrés de fonctionnalisation organique de surface ont été obtenus par la modification des quantités relatives des précurseurs de départ. En mettant simplement en présence ces supports avec des solutions aqueuses de sels d’or ou d’argent, les fonctions citrates ont permis la formation de particules métalliques directement à la surface des supports. Ces matériaux M/TiO2 ont été utilisés en tant que catalyseurs dans l’époxydation du transstilbène en phase liquide et ont permis d’améliorer la connaissance des mécanismes de cette réaction aérobie. / A new and relevant sol-gel process has allowed us to prepare new hybrid materials. Titania nanoparticles with lanthanides doping agent (gadolinium and europium) were obtained as anatase nanocrystallites via our low-temperature process. Their magnetic and luminescent properties have been tested in order to use them as contrast agent in medical imaging. A doped and hybrid material has also been obtained and its NH2 groups at the surface will be used in thebio-medical field. The second part of this work has consisted in the preparation of TiO2(citrate) hybrid supports viaa new titanium alkoxide that contains a citrate ligand. Several surface citrate density had been obtained by changing the precursor’s initial relative amounts. Then the simple contact between these hybrid supports and aqueous solutions of silver or gold ions led to the formation of metallic particles directly on the surface support thanks to the presence of the citrate groups, which are known to be reducing agent. These M/TiO2 materials were then tested as catalysts in the aerobic epoxidation of trans-stilbene in the liquid phase. Through this study, we were able to improve our knowledge in this reactionmechanism.

Esse trabalho de tese descreve a síntese e a caracterização de materiais amorfos e cristalinos na forma de pó e de filmes finos pertencentes ao sistema Er2O3-Y2O3-Al2O3-B2O3. O principal objetivo do trabalho foi o de obter filmes finos amorfos contendo íons Er3+ próximo à composição YAI3(BO3)4 (YAB), visando sua aplicação como amplificador em dispositivos ópticos integrados. Na síntese das amostras foi empregado o método dos precursores poliméricos e o método sol-gel. Uma vez estabelecida às condições de síntese das resinas e de sóis estáveis, diferentes parâmetros foram otimizados visando à deposição de filmes relativamente espessos e amorfos. As propriedades térmicas, estruturais e ópticas de amostras cristalinas ou amorfas, na forma de pó e na forma de filmes finos, foram caracterizadas através das técnicas de análise termogravimétrica, calorimetria exploratória diferencial, difração de raios X, espectroscopia vibracional na região do infravermelho com transformada de Fourier, espectroscopia Raman e microscopia eletrônica de varredura de alta resolução, microscopia de força atômica, espectroscopia \"m-line\", medidas de espectros de luminescência. Baseado na análise térmica e estrutural das amostras na forma de pó, foi possível realizar a síntese de amostras na forma de filmes finos de composição Y1-xErxAl3(BO3)4 que apresentaram características estruturais, microestruturais e ópticas adequadas à aplicação desejada. Através do estudo das propriedades térmicas e estruturais, foi observado que as amostras preparadas através do método dos precursores poliméricos e do método sol-gel apresentam respectivamente uma temperatura de transição vítrea (Tg) à 723 &#176C e à 746 &#176C e uma temperatura de cristalização (Tc) à 814 &#176C e à 830&#176C. O tratamento térmico à aproximadamente 1150 &#176C da amostra amorfa na forma de pó de composição Y0,9Er0,1Al3(BO3)4 contendo boro em excesso levou a obtenção de uma solução sólida cristalina de composição Y0,9Er0,1Al3(BO3)4. No que se refere às propriedades dos filmes finos, as melhores condições de densificação, homogeneidade, eficiência de guiamento, emissão luminescente e tempo de vida foram observadas quando os filmes de composição Y0,9Er0,1Al3(BO3)4 foram tratados entre as temperaturas de Tg e Tc. Os filmes amorfos de composição Y0,9Er0,1Al3(BO3)4 se comportam como guias monomodos, apresentando alta emissão luminescente e um tempo de vida comparável a outros sistemas amorfos a base de boro. Esse comportamento mostra a viabilidade de aplicação desses filmes amorfos como amplificadores ópticos planares. / This work specifies the synthesis and the characterization of amorphous and crystalline powder and thin films materials belonging to the Er2O3-Y2O3-Al2O3-B2O3 system. The main objective of this work was to develop amorphous thin film samples near the YAI3(BO3)4 composition with yttrium partially substituted by erbium Y1-xErxAl3(BO3)4 with the aim of applying these thin films as waveguide amplifiers in integrated optical systems. The polymeric precursor and the sol-gel methods were applied in order to produce such thin films. After the first step where the conditions to obtain very stable resins and sols was established, different parameters were adjusted aiming the deposition of thick and stable thin films. To well define the best conditions to obtain amorphous and dense thin films, the powder samples of the same compositions were first characterized by thermal analysis techniques, X-ray diffraction, IR and Raman spectroscopies, high resolution electron microscopy and atomic force microscopy. From thermal analysis and structural results, it was observed that the samples prepared from the polymeric precursor and sol-gel methods exhibit glass transition temperatures, Tg, at 723 and 746 &#176C and cristallisation temperatures, Tc, at 814 and 830 &#176C, respectively. The heat treatment at around 1150 &#176C of Y0,9Er0,1Al3(BO3)44 powder sample containing a smaller amount of boron in excess produced by both methods lead to the formation of a crystalline solid solution of the same composition without the presence of secondary phases. These results show that dense, free of cracks, thick and homogeneous thin films could be obtained when they were submitted at a heat treatment in temperatures between Tg and Tc. From the \"m-line\" spectroscopy technique and luminescence measurements we observed that the Y0,9Er0,1Al3(BO3)4 amorphous thin films can be considered as monomode waveguides showing a high luminescence intensities and a lifetime similar to other amorphous borate systems. These results show the potentiality to apply such amorphous thin films as optical planar amplifiers.

Das Hauptaugenmerk dieser Arbeit liegt auf einer Pilotstudie zur Darstellung von Eisen(III)fluorid (FeF3) unter Verwendung von Sol-Gel-Syntheserouten. Eine modifizierte fluorolytische Sol-Gel-Synthese wurde entwickelt um bi-acide auf FeF3 basierende Materialien zu erhalten. Die Synthese erzeugt Hydroxygruppen, die potentiellen Brønsted-sauren Zentren, auf der Oberfläche der klassischen Lewissäure FeF3. Im Anschluss wurde Magnesiumfluorid (MgF2) als Matrix eingesetzt. Verglichen mit FeF3 zeigen ternäre FeF3-MgF2 bemerkenswert hohe Oberflächen und verbesserte Porosität. Das Wichtigste jedoch ist, das hauptsächlich starke Lewis- und mittelstarke Brønsted-saure Zentren auf der FeF3-MgF2 vorhanden sind. Des Weiteren wurden, unter Verwendung anderer Erdalkalimetallfluoride (CaF2 oder SrF2) und Zinkfluorid (ZnF2) als Matrix, Serien ternärer Fluoridmaterialien synthetisiert und systematisch untersucht. Durch Charakterisierung der FeF3-MF2-Oberflächen konnten systematische Veränderungen hinsichtlich Größe der Oberfläche, Porosität und Azidität festgestellt werden. Mit abnehmender Atomnummer (von Sr zu Mg) erhöht sich die Stärke der sauren Zentren, während die mittlere Porengröße dramatisch abnimmt. Darüber hinaus führt ein größeres M-zu-Fe-Verhältnis generell zu kleineren Porengrößen und höheren Oberflächen. Diese Ergebnisse implizieren, dass die Eigenschaften ternärer FeF3-MF2 durch Veränderung der MF2-Matrix oder des M-zu-Fe-Verhältnisses einstellbar sind. Schlussendlich konnte anhand einer Modellreaktion, der Isomerisierung von Citronellal zu Isopulegolen, die katalytische Aktivität der bi-aziden Zentren der auf FeF3 basierenden Materialien nachgewiesen werden. Zusätzlich wurde in dieser Arbeit diskutiert wie Oberfläche, Porosität und Azidität gemeinsam die katalytische Aktivität von FeF3-MgF2 bestimmen. Diese Arbeit beweist damit die Realisierbarkeit der Synthese neuer nanoskopischer Metallfluoride mit gewünschten Oberflächeneigenschaften. / This work serves as a pilot study on the development of iron(III) fluoride (FeF3) based materials with surface bi-acidity. A modified fluorolytic sol-gel route was established to prepare the bi-acidic FeF3-based materials. The synthesis procedure introduced hydroxyls, the potential Brønsted acid sites, on the surface of a classic Lewis acid, FeF3. Subsequently, magnesium fluoride (MgF2) was used as matrix. Comparing with FeF3, the ternary FeF3-MgF2 showed remarkable high surface area and enhanced porosity. Most importantly, strong Lewis and medium strong Brønsted acid sites were found predominant on the FeF3-MgF2 surface. Next a series of ternary fluoride materials were synthesised and studied systematically, using other alkaline earth metal fluorides (CaF2 or SrF2) as well as zinc fluoride (ZnF2) as matrices. Surface characterisation of FeF3-MF2 revealed systematic changes in their surface area, porosity, and surface acidity. With decreasing atom numbers (from Sr to Mg), strengths of surface acidic sites and surface area increased, while the average pore size decreased drastically. Moreover, higher M-to-Fe ratio generally resulted in smaller pore size and larger surface area. These findings imply that the properties of ternary FeF3-MF2 are tunable by changing the MF2 matrix or the M-to-Fe ratio or both. Last but not least, in the model reaction, isomerisation of citronellal to isopulegols, FeF3-based materials were highly active due to their bi-acidity. Finally this work discussed how surface area, porosity, and surface acidity jointly determined the catalytic activity of FeF3-MF2. In conclusion, this work demonstrates the feasibility to synthesise novel nanoscopic metal fluorides with desirable surface properties.

Estudos sistemáticos utilizando a técnica de SAXS foram realizados no síncrotom do LURE (Orsay) com feixe intenso de geometria pontua:, para descrever a cinética e as estruturas obtidas durante as etapas de transformação sol -> gel úmido -> gel seco -> vidros de sílica . As análises foram feitas em termos de uma lei de potência I = q-? cujo expoente está relacionado a dimensão fractal de massa ou de superfície das estruturas. Devido a polidispersividade das unidades espalhadoras as dimensões fractais verificadas podem ser resultados de dimensões reais encobertas por uma distribuição de tamanhos. As curvas obtidas para a cinética de gelificação e envelhecimento dos géis úmidos mostram expoentes que indicam fractalidade de massa e, posteriormente, de superfície. Uma microestrutura composta, que pode resultar de uma agregação limitada por difusão (DLA) seguido de agregação de agregados (C-C) foi observado nas soluções básicas. Por outro lado, os agregados ácidos parecem surgir do crescimento contínuo de cadeias até atingir a interligação com outros agregados com uma cinética que pode ser descrita pelo modelo DLA. No estado de aerogeis outras técnicas como picnometria de mercúrio e hélio, microscopia eletrônica de transmissão e adsorção de gás de nitrogênio, foram também aproveitadas. Nestes materiais encontramos em uma faixa estreita de escala, um expoente indicando fractalidade de massa, embora com superfície lisa. Os resultados estão de acordo com um modelo de estrutura que tem uma matriz de SiO2 densa. A estrutura fractal desaparece durante o tratamento térmico de densificação devido ao rearranjo estrutural. / Systematic SAXS studies have been performed at the LURE synchrotron (Orsay) using an intense beam of point-like cross-section to describe the kinetic and the structure obtained during the sol-> humid gel -> dry gel ->silica glass. The analysis were done in terms of a power law, I = q-? , whose exponent is related to mass and surface fractal dimensions of the structures. Due to polidispersity of the scattering units the found fractal dimensions can be \"smeared\" dimensions that result from a size distribution. All the kinetic and aging humids curves showed evidenced of fractal structures. A composed microstructure that can be originated by clustering of clusters (C-C) of primary units grown by diffusion limited-aggregation (DLA), was observed for basic gels. By other hand, the acidic cluster seems to grow continuously reaching gelation through crosslinking of the clusters. The DLA model seems to describe this process. In the aerogels study others techniques like density measurements using Hg and He, TEM and adsorption of N2 gas were done along with SAXS measurements. Here we could find a narrow range in which the system is a mass fractal, although its surface has been already smoothened. The results agree with a dense SiO2 matrix model. During the densification no fractal structure was verified due to structural rearrangements at high temperature.

Dans ce manuscrit, un travail multidisciplinaire, de la synthèse de précurseurs métalliques à la caractérisation des matériaux est présenté. La première porte sur l’élaboration de poudres d’oxyde TiO2 dopé Nb5+ et d’oxydes mixtes SnO2-TiO2 dopé Nb5+ par une approche Sol-Gel. Leur mise en forme sous forme de pastille par une méthode moderne de frittage flash (SPS) a permis d’étudier leurs propriétés physiques vibrationnelles et thermoélectriques. La deuxième partie de cette étude présente l’élaboration de nouveaux précurseurs d’étain et de tantale adaptés au procédé de dépôt de couches minces par DLI-MOCVD. Afin de répondre aux exigences de ce procédé, des dérivés moléculaires à base de ligand beta-aminoalcool fluoré ou pas ont été élaborées. Les complexes métalliques ont ensuite été entièrement caractérisés à l’état solide et en solution. Le bon comportement thermique (stabilité et volatilité) de certains de ces composés ont conduit à l’élaboration et à la caractérisation de couches minces de SnO2 et SnO2:F / In this manuscript, a multidisciplinary work, from the synthesis of metal precursors to the characterization of materials, is presented. The first concerns the development of Nb5+ doped TiO2 oxide powders and Nb5+ doped SnO2-TiO2 mixed oxides by a Sol-Gel approach. Their shaping into a pellet form by a modern flash sintering method (SPS) made it possible to study their physical, vibrational and thermoelectric properties. The second part of this study presents the development of new tin and tantalum precursors adapted to the DLI-MOCVD thin film deposition process. In order to meet the requirements of this process, molecular derivatives based on fluorinated or non-fluorinated beta-aminoalcohol ligand have been developed. The metal complexes were then fully characterized in solid state and in solution. The good thermal behaviour (stability and volatility) of some of these compounds has led to the development and characterization of thin layers of SnO2 and SnO2:F

Biocere verkörpern eine neue Klasse von keramischen Funktionswerkstoffen, deren Eigenschaften entscheidend von den konkreten Herstellungsbedingungen beeinflusst werden. Am Beispiel ausgewählter Biocere mit immobilisierten vegetativen Zellen und Sporen von Bacillus sphaericus JG-A12 wurden im Rahmen der vorliegenden Arbeit Zusammenhänge zwischen Gefügeausbildung und Funktionalität, besonders unter dem Gesichtspunkt metallbindender Eigenschaften, untersucht. Mit Hilfe von Fluoreszenzfarbstoffen konnte die räumliche Verteilung der Biokomponente in der Matrix, die Überlebensfähigkeit der immobilisierten vegetativen Zellen und das Verhalten von Bakteriensuspensionen in Gegenwart von verschiedenen Metallionen untersucht werden. Mit ionensensitiven Fluoreszenzfarbstoffen wurde die Aufnahme von Kupfer(II) und Nickel(II) in lebende Bakterien unter Kontrolle des physiologischen Status der Zellen verfolgt. Es wurde nachgewiesen, dass die Aufnahme von Metallionen von der Erhöhung des intrazellulären Ca2+-Spiegels begleitet und die Aufnahmeraten sowie die Ca2+-abhängige Zellantwort stammspezifisch und von der Konzentration der Metallsalzlösung abhängig sind. Durch Immobilisierung bakterieller Sporen in dünnen Sol-Gel-Schichten konnten langzeitlagerfähige Biokeramiken erzeugt werden, die sich durch die Aktivierung mit einem 1:1 Komplex aus Ca2+ und Dipicolinsäure gezielt aus Ruhephasen in biologisch aktive Zustände schalten ließen. Im Durchschnitt führt die vorherige Aktivierung der Sporen mit Ca2+-DPA zu einer fünf- bis achtfach erhöhten Keimungsrate. Mit Hilfe einer kapazitiven Messanordnung wurden darüber hinaus an diesen Schichten während der Keimung auftretende mechanische Spannungszustände nachgewiesen und quantifiziert. Biocere unterliegen während ihrer Nutzung als Filtermaterialien überwiegend durch mikrobielle Einflüsse hervorgerufenen Materialveränderungen, die mit licht- und rasterelektronenmikroskopischen Untersuchungen nachgewiesen wurden. Diese Untersuchungen sind als Teil eines Monitoring-Systems zur kontinuierlichen Überwachung von Filtersystemen denkbar. / Biocers embody a new class of ceramic functional materials in which the properties are mainly determined by the specific production conditions. The interplay between structure formation and functionality of selected biocers containing immobilised vegetative cells and spores of Bacillus sphaericus JG-A12 was investigated under special consideration of metal binding properties. Spatial distribution of the bio-component inside the matrix, the viability of the immobilised vegetative cells, as well as the behaviour of cell suspensions in the presence of different metal ions were examined using fluorescence dyes. The uptake of copper(II) and nickel(II) ions into the living cells while monitoring of their physiological state were detected using different ion-sensitive fluorescence dyes. As expected, the uptake of metal ions was thereby accompanied by an increase of the intracellular Ca2+ level. Further, the uptake rate of metal ions and the Ca2+ dependent cellular reaction are strain-specific and depend on the metal ion concentration. Bioceramics suitable for long-term storage were produced through immobilisation of bacterial spores in thin sol-gel layers. The switch from the metabolic inactive to the active state of the bio-component was achieved by the activation with a 1:1 ratio of the chelate of Ca2+ and dipicolinic acid. The average germination rate after activation with Ca2+-DPA was increased by five- to eightfold. The mechanical stress conditions during the germination of spores inside these silica layers were measured and quantified using a capacitive deflection measurement. As filter materials, biocers are affected by microbial determined degrading impacts. Material alterations could be detected by light and scanning electron microscopic methods. Such investigations should be considered part and parcel of monitoring systems required for continuous checks of filter systems.