Ce travail de thèse s'intéresse à la relation entre la composition des phases Hydroxydes Doubles Lamellaires (HDL) et leurs propriétés structurales. La première partie de ce manuscrit est consacrée à la formation et aux propriétés structurales de ces matériaux. L'effet de la nature des cations (MgII, NiII, CoII ; AlIII, FeIII) et de leur stoechiométrie dans le feuillet (MII/MIII E [2 ; 10]) constitue les axes principaux de ces travaux. L'étude du comportement hydrolytique d'un mélange de cations divalents et trivalents en fonction de leurs proportions en solution a permis de proposer un mécanisme topotactique de formation de ces phases HDL. Il a aussi été montré que la variabilité stoechiométrique du feuillet ne dépend que de la nature des cations. Ainsi, des modèles électrostatiques ont été proposés afin de rationaliser et prédire la gamme de composition de ces phases HDL en fonction de la nature des cations. La seconde partie est dédiée aux propriétés du milieu interfoliaire. Une étude couplant des analyses par spectroscopies vibrationnelles infrarouge et Raman et par diffraction des Rayons X a permis d'apporter une description précise de l'influence de la nature des cations, et de leurs stoechiométries sur l'organisation des anions dans le milieu interfoliaire (Cl-, CO32-, NO3-, ClO4-, acides aminés). Le rôle de l'eau dans ces phases a également été étudié. Dans le cas des hybrides organo-minéraux, il a été montré que la charge dicte l'orientation des acides aminés intercalées et par conséquent, leur réactivité envers la formation de la liaison peptidique. Également, les propriétés énantioselectives du domaine interfeuillet sont mises en avant pour la formation de peptides / This manuscript is devoted to the comprehension of the relationship between the composition of Layered Double Hydroxides (LDH) and their structural properties. The first part of this manuscript is focalized on the formation and the structural properties of these materials. The influence of the cationic nature (MgII, NiII, CoII ; AlIII, FeIII) and their stoichiometries within the layer (MII/MIII E [2 ; 10]) constitutes the main axis of these investigations. The study of the hydrolytic behavior of a solution containing a mixture of divalent and trivalent cations as a function of their relative proportion allowed to propose a topotactic mechanism of formation of LDH phases. Moreover, it has been showed that the composition range is solely dependent on the nature of the cations. Thus, electrostatic models were designed to rationalize and predict the composition range as a function of the cationic nature. The second part is concerned with the properties of the interlayer domain. A joint study, coupling vibrational spectroscopies (Infrared and Raman) and X-ray diffraction allowed a detailed description of the influence of the cations and their stoichiometries on the organization of the interlayer anions (Cl-, CO32-, NO3-, ClO4-, aminoacids). The role of the interlayer water has also been investigated. Concerning hybrid organo-minerals, it has been showed that the layer charge dictates the orientation of the interlayered aminoacids, and consequently, their reactivity toward the formation of the peptide bonds. The enantioselective properties of the interlayer domain are highlighted toward the formation of peptides

Au cours du 21ème siècle, les techniques de fluorescence ont montré une expansion considérable dans l’étude du mécanisme du vivant. Un progrès majeur dans le développement, la conception et les applications de divers types de chromophores organiques ont été achevés. Bien que largement utilisés, les sondes fluorescentes les plus utilisées souffrent encore de quelques limitations qui diminuent leur étendue d'action. Les plus problématiques sont : un nombre restreint de familles de chromophores, une faible résistance au photoblanchiment, une faible solubilité aqueuse, une durée de vie de fluorescence relativement courte, etc…. A ce titre, le développement de nouveaux motifs organiques inédits, compacts et possédants des propriétés de fluorescence alternatives et/ou complémentaires aux fluorophores usuels organiques reste plus que jamais d’actualité. Dans ce contexte, les noyaux 1,3a, 6a-triazapentalènes nous sont apparus particulièrement prometteuses et encore très peu exploitées. Dans ce manuscrit, il est décrit la synthèse de noyaux tricycliques et tétracycliques comportant ce motif, obtenus par substitution nucléophiles aromatiques, suivi d’une thermolyse. La modulation de ces noyaux a ensuite été effectuée par couplage métallo-catalysé. L’évaluation photophysique de ces composés révèle des propriétés spectroscopiques remarquables comme des rendements quantiques supérieurs à 50%, des déplacements de Stokes d’environ 100 nm et des longueurs d’ondes d’émission allant de 450 à 650 nm. Le dernier volet de cette thèse a porté sur l’imagerie cellulaire, qui nous a permis d’évaluer les meilleurs fluorophores sur cellules vivantes. / Over the last two decades, fluorescence technologies have shown a spectacular spreading in biological research. Major progress in the development, design, and purposeful application of various types of organic chromophores was achieved. Although widely used, the most commonly fluorescent probes still suffer from some limitations which decrease their use in the field of life sciences. The most problematic ones are: low scaffold diversity, high sensitivity to photobleaching, low water solubility and modest Stokes Shift… In this context, the main idea of our work focuses on the development of novel organic motifs responding to the conventional fluorophores issues. The 1,3a, 6a-triazapentalene moiety represents a real interest in this field with its promising optical properties. In this manuscript, the syntheses of tricyclic and tetracyclic derivatives containing this scaffold were obtained by aromatic nucleophilic substitution followed by the thermolysis cyclization. The modulation of these cores was then allowed by various organometallic cross of these compounds provides remarkable spectroscopic properties, as quantum yields above 50%, Stokes shift around 100 nm, and emission wavelengths between 450 and 650 nm. The last part of this thesis was focused on cellular imaging, that allowed us to evaluate the best fluorophores in living cells.

La synthèse et la caractérisation de nouveaux matériaux sont des enjeux majeurs en chimie et en physique. En particulier, les réseaux organométalliques (metal –oganic frameworks : MOFs) avec deux ou plusieurs fonctionnalités couplées, encore rares, sont très attractifs en raison de leur grande variété de propriétés et de leurs applications prometteuses connectant de nombreuses disciplines.Le développement de nouveaux matériaux fascinants peut avoir un impact considérable sur notre vie quotidienne, ce qui explique en partie l'intensification de la recherche dans le cadre de la science des matériaux et de la matière condensée.Cette thèse se concentre sur la synthèse et la caractérisation des propriétés physiques de structures magnétiques basées sur le formiate de métal en utilisant la combinaison de diffraction par neutrons et par rayons X ainsi que d'autres techniques.Les réseaux de métal-formiate sont un sous-groupe spécifique des réseaux organométalliques, typiquement synthétisés en faisant réagir un ligand organique avec un sel métallique sous des conditions solvo-thermiques ou par des techniques d'évaporation ou de diffusion lente. Les centres métalliques sont liés par des molécules de formiate formant un cadre anionique qui peut être équilibré électrochimiquement par des amines protonées.Dans ce travail, j’ai étudié la structure cristalline, les transitions de phases et les propriétés magnétiques de deux familles de composés qui sont représentés par les composés hétéro-métalliques ou à valence mixtes, adoptant une structure de type niccolite et des composés homo-métalliques adoptant une structure pérovskite (ABX3). Les composés suivants ont été synthétisés et caractérisés: [(CH3)2NH3][FeIIIMII(HCOO)6] (M = Mg, Mn, Fe, Co, Ni), [(CH3)2NH3][FeIIIFeII(HCOO)6], [(CH3NH3)[M(HCOO)3] (M = Co, Mn, Fe, Ni, Cu), and [(NH4)[Mn(HCOO)3].Le choix d'utiliser des ions métalliques spécifiques a été motivé par leur configuration électronique différente et, par conséquent, par les différents comportements physiques, c'est-à-dire une grande différence bien connue dans l'anisotropie magnétique des différents ions divalents utilisés dans cette étude. Outre les effets sur les propriétés lorsque différents ions métalliques divalents sont introduits dans la structure, un autre aspect intéressant est l’effet produit en changeant la nature des contre-ions. Même s'il n'y a pas de corrélation claire entre le contre-ion sélectionné et le changement de comportement magnétique, la diffraction des neutrons permet d'élucider les différences dans la structure nucléaire et dans la structure magnétique lorsque différents contre-ions sont utilisés. Par ailleurs, ce travail, nous aide à comparer nos résultats neutroniques avec les mesures complémentaires de magnétométrie. Une variété de phénomènes magnétiques tels que le comportement ferromagnétique, l'ordre antiferromagnétique, l’angle de basculement spin ont été observés dans les composés étudiés. De plus, du point de vue de la structure nucléaire, différentes transitions de phases ont été détectées impliquant par exemple l'ordre-désordre du contre-ion employé (dans [(CH3)2NH3][FeIIIMII(HCOO)6] par exemple), ou le passage d'une phase commensureable à une phase incommensurable donnant lieu à une modulation de la structure (dans [(CH3NH3)[Co(HCOO)3] par exemple). / The synthesis and the characterization of new materials are key challenges in chemistry and physics. In particular, metal–organic frameworks (MOFs) with two or more coupled functionalities are still rare and very attractive candidates because of their wide variety of properties, and promising applications interesting many disciplines. The impact of the development of new fascinating materials on our day life might be considerable. This is also one of the reason explaining the intense increasing of the research in material science and condensed matter.This thesis is focused on the synthesis and the physical characterization of magnetic metal formate frameworks using the combination of neutron and synchrotron X-Ray diffraction as well as other techniques. Metal-formate frameworks are a specific subgroup of metal-organic frameworks, where the metal centres are linked by the formate molecules to form an anionic framework. The negative charge of the framework is balanced by a counter-cation inside the frameworks’ cavities, that can be for example protonated amines.Typically, these compounds are synthesized by reacting formate or formic acid with a metal salt under solvo-thermal conditions or by slow evaporation or diffusion techniques.In this work, I investigated the crystal structure, phase transitions and magnetic properties of two families of metal formate frameworks, which are represented by the hetero-metallic or mixed valance compounds adopting a niccolite-like structure, and the homo-metallic compounds adopting a perovskite-like (ABX3) structure.Altogether, the following compounds were synthesized and characterized: [(CH3)2NH3][FeIIIMII(HCOO)6] (M = Mg, Mn, Fe, Co, Ni), [(CH3)2NH3][FeIIIFeII(HCOO)6], [(CH3NH3)[M(HCOO)3] (M = Co, Mn, Fe, Ni, Cu), and [(NH4)[Mn(HCOO)3].The choice of using specific metal ions has been motivated by their different electronic configuration and therefore different physical behaviours, i.e. a large difference in the magnetic anisotropy is well known among the different divalent ions used in this study. Beside the effects on the properties when different divalent metal ions were introduced within the framework, the effects of the nature of the counterions was investigated.Even though there is not a clear correlation between the selected counterion and the change of magnetic behaviour, neutron diffraction allows elucidating the differences in the nuclear and in the magnetic structure when different counterions are used. Moreover, these works help us to compare our neutron results with the magnetometry measurements, which is a complementary technique.A variety of magnetic phenomena such as ferromagnetic behaviour, antiferromagnetic ordering, spin canting have been observed in the compounds studied. Furthermore, from the nuclear structure point of view many different kind of phase transitions were detected involving for instance, the order-disorder of the counter ion employed (in [(CH3)2NH3][FeIIIMII(HCOO)6] for example), or the transition from a commensurate to incommensurate phase giving rise to a modulation of the structure (in [(CH3NH3)[Co(HCOO)3] for example).

Submitted by EPITÁCIO JOSÉ DE SOUZA null (epitacio.agro@gmail.com) on 2018-03-15T22:10:40Z No. of bitstreams: 1 NANOTECNOLOGIA APLICADA A AVALIAÇÃO FÍSICA DE UM LATOSSOLO DE CERRADO SOB SISTEMAS DE SUCESSÃO DE CULTURAS EM PLANTIO DIRETO .pdf: 4786904 bytes, checksum: 2e74d65cc0fde9399a953d88dd0a155e (MD5) / Approved for entry into archive by Cristina Alexandra de Godoy null (cristina@adm.feis.unesp.br) on 2018-03-16T19:38:28Z (GMT) No. of bitstreams: 1 souza_ej_dr_ilha.pdf: 4786904 bytes, checksum: 2e74d65cc0fde9399a953d88dd0a155e (MD5) / Made available in DSpace on 2018-03-16T19:38:28Z (GMT). No. of bitstreams: 1 souza_ej_dr_ilha.pdf: 4786904 bytes, checksum: 2e74d65cc0fde9399a953d88dd0a155e (MD5) Previous issue date: 2018-01-18 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A compactação do solo em sistemas plantio direto (SPD) tem comprometido a sua sustentabilidade. Para contornar esse problema, a escarificação mecânica e a manutenção da cobertura vegetal são sugeridas como práticas de manejo a fim de restabelecer as condições ideais de cultivo. Assim, o objetivo deste trabalho foi avaliar o efeito a curto prazo da escarificação e do uso de diferentes plantas de cobertura na manutenção do SPD envolvendo as culturas do arroz de “terras altas” e feijão de “inverno”). O trabalho foi desenvolvido em Selvíria, MS em 2014/15 e 2015/16, em um Latossolo Vermelho Distrófico de textura argilosa. Utilizou-se o delineamento em blocos casualizados disposto em parcelas subdivididas, tendo nas parcelas as condições da superfície do solo em SPD (com e sem escarificação mecânica) e nas subparcelas as plantas de cobertura (pousio, Cajanus cajan, Crotalaria juncea, Urochloa ruziziensis (Syn. Brachiaria ruziziensis) e Pennisetum glaucum), com quatro repetições, cultivadas com arroz e feijão. Foram avaliadas as características fitotécnicas das culturas e atributos físicos e químicos do solo em quatro camadas (0 a 0,05; 0,05 a 0,10; 0,10 a 0,20 e 0,20 a 0,40 m). Realizou-se a análise de variância e teste de Tukey a 5%de probabilidade para comparação de médias. Além disso, na camada de 0 a 0,05 m do solo também foram analisadas as características das nanopartículas e nanoestruturas do solo. Para essas análises incluiu-se o solo de Cerrado remanescente para comparação com os tratamentos estudados. As nanopartículas (< 200nm) foram extraídas e caracterizadas por microscopia eletrônica de transmissão (MET) e espectrometria de infravermelho (FTIR). Os resultados obtidos foram avaliados por meio da análise dos componentes principais e agrupamentos hierárquicos. As plantas de cobertura e a escarificação não influenciaram a produtividade do arroz de “terras altas “e do feijão de “inverno” após dois anos de cultivo. O estudo das nanopartículas e nanoestruturas mostrou-se sensível as alterações promovidas pelo uso da escarificação e das plantas de cobertura, apresentando assim potencial para ser uma ferramenta suplementar indicadora de qualidade do solo. O fósforo (P) foi o atributo químico mais influenciado pelas práticas de manejo pela sucessão com milheto (Pennisetum glaucum) sem escarificação nas duas camadas superficiais e nas demais camadas pela sucessão Urochloa ruziziensis (Syn. Brachiaria ruziziensis). Os atributos físicos e químicos do solo combinados com a caracterização de nanopartículas permitiram identificar que o milheto (Pennisetum glaucum) sem escarificação como mudanças estáveis para a manutenção do SPD. As características geométricas e químicas das nanopartículas auxiliam na identificação de mudanças causadas pelas práticas de manejos sobre os indicadores físicos e químicos da qualidade do solo. A contribuição das plantas de cobertura para a manutenção do SPD está ligada diretamente pela adição de matéria orgânica do solo (MOS). Deste modo contribuindo para as melhorias dos atributos químicos, físicos e influenciaram no comportamento das nanopartículas e nanoestrutura do solo. / Soil compaction in no-tillage systems (NTS) affects the sustainability of this management. To overcome the problem, mechanical chiseling and maintenance of the cover crop were suggested as management practices reestablishing ideal cultivation conditions. Thus, the objective of this study was to evaluate the short-term effect of mechanical chiseling and the use of different cover crops in the maintenance of NTS involving as crops "dryland” rice and "winter" common bean. The experiment was conducted in Selvíria, state of Mato Grosso do Sul, Brazil, during the 2014/15 and 2015/16 growing season, on a typical clayey dystrophic Red Latosol, with experiment was evaluated in a randomized block design in split plots, with the main plots as SPD soil surface conditions (with and without mechanical chiseling) and in the subplots as cover crop (fallow, Cajanus cajan, Crotalaria juncea, Urochloa ruziziensis and Pennisetum glaucum), with four replications, cultivated with “dryland” rice and "winter" common bean. The agronomic characteristics of the crops and soil physical and chemical attributes in four layers (0 a 0.05; 0.05 a 0.10; 0.10 a 0.20 e 0.20 a 0.40 m). The analysis of variance and Tukey's test were performed at a 5% probability for comparison of average. In addition, treatments of the 0 to 0.05 m layer of the soil were also compared to the natural closed area, through the conventional chemical and physical properties and characteristics of its nanoparticles and nanostructures. For these analyze the remaining Cerrado soil was included for comparison with the treatments studied. As nanoparticles (<200 nm) were extracted and characterized by transmission electron microscopy (TEM) and infrared spectrometry (FTIR). The results were evaluated by principal component analysis and hierarchical groupings. Cover crops and mechanical chiseling did not influence the yield of “dryland” rice and “winter” common bean after two years of cultivation. The study of the nanoparticles and nanostructures was sensitive to the changes promoted using mechanical chiseling and the cover crops, thus presenting potential to be a supplementary soil quality indicator tool. The phosphorus (P) was the chemical attribute most influenced by management practices by succession with pearl millet (Pennisetum glaucum) without mechanical chiseling in the two superficial layers and in the other layers by the succession Urochloa ruziziensis (Syn. Brachiaria ruziziensis).The physical and chemical attributes of the soil combined with the characterization of nanoparticles allowed to identify that pearl millet without mechanical chiseling as stable changes to the maintenance of NTS. The geometric and chemical characteristics of the nanoparticles assist in the identification of changes caused by the management practices on the physical and chemical indicators of soil quality. The contribution of cover crops to NTS maintenance is directly linked by the addition of soil organic matter (SOM). Thus, contributing to the improvements of the chemical and physical attributes of soil and influenced the behavior of the nanoparticles and the nanostructure of the soil. / Projeto CNPq 471052/2013-2

Made available in DSpace on 2014-08-20T14:30:05Z (GMT). No. of bitstreams: 1 tese_Adaue_banca.pdf: 296840 bytes, checksum: 0cd98d8b2ca7a1306c82e4b8319d9e71 (MD5) Previous issue date: 2012-06-01 / The use of orthodontic devices has been associated with an increase in dental biofilm retention. In this study, the effect of hydrophobic coatings, based on (fluorinated or not) organo-silanes, on the reduction of the contact angle and early biofilm retention in orthodontic devices was tested. Two different types of hydrophobic were tested: hydrophobic solution 1 (SH1), obtained by dilution of 2.5% of hexadecyl-triethoxy-silane in ethanol, and hydrophobic solution 2 (SH2), composed of 2.5% of perfluorodecyl-triethoxy-silane diluted in dimethyl sulfoxide. The solutions were applied in ceramic and stainless steel substrates and, via sol-gel process and crosslinking, siloxane networks were formed on the surface of the devices. The effect of the coatings was evaluated in two stages. In the first stage, aiming the characterization of the surface, the water contact angle was analyzed. Stainless steel and polycrystalline alumina plates were prepared, previously applying or not alumina sandblasting as surface treatment. A significant increase in contact angle was observed with the application of both hydrophobic solutions in both substrates, with the sandblasting allowing formation of super-hydrophobic surface in the ceramic substrate (contact angle up to 155o), while hydrophobic surfaces were obtained in the steel substrate (contact angle up to 123o). In the second phase, the effect of the hydrophobic coating on the biofilm retention in orthodontic brackets was evaluated using a microscosm model. Orthodontic brackets were previously prepared according to the surface treatments that showed the best results in the phase 1 (SH1 for steel, SH2 for ceramic). The effect of the coatings on the biofilm formation was evaluated in periods of 12h and 24h (controls: uncoated substrates and sandblasted substrates). The results showed that the hydrophobic coatings did not result in significant effect in biofilm retention for the time 12h, whereas all coating treatments significantly reduced the biofilm retention in the metal and ceramic brackets compared with the control groups. A significant exponential reduction in biofilm retention at 24h was associated with the increase in contact angle. It can be concluded that application of (super)-hydrophobic crosslinked coatings via sol-gel process on the surface of orthodontic metal and ceramic brackets reduced the surface wetting of the surfaces in contact with water and had a significant effect on the retention of dental biofilm after 24h / O uso de dispositivos ortodônticos tem sido associado ao aumento da retenção de biofilme dentário. Neste estudo, foi testado o efeito de coberturas hidrófobas,baseadas em organo-silanos (flourados ou não), no aumento do ângulo de contato e redução de acúmulo de biofilme inicial em dispositivos ortodônticos. Dois tipos diferentes de soluções hidrófobas foram testadas: solução hidrófoba 1 (SH1), obtida pela diluição de 2,5% de hexadecil-trietóxi-silano em etanol, e solução hidrófoba 2 (SH2), composta por 2,5% de perfluorodecil-trietóxi-silano diluído em dimetilsulfóxido. As soluções foram aplicadas em substratos cerâmico e de aço inox e, via processo sol-gel e reticulação, foram formadas redes siloxanas na superfície dos dispositivos. O efeito das coberturas foi avaliado em duas etapas. Na primeira etapa, buscando a caracterização da superfície, foi analisado o ângulo de contato com água. Placas de aço inox e alumina policristalina foram preparadas, aplicando ou não jateamento prévio das superfícies com partículas de alumina. Foi observado aumento significativo do ângulo de contato com a aplicação das duas soluções hidrófobas em ambos substratos, sendo que o jateamento do substrato propiciou a formação de superfície superhidrófoba no substrato cerâmico (ângulo de contato de até 155o), enquanto superfícies hidrófobas foram obtidas no substrato aço (ângulo de contato até 123o). Na segunda fase do trabalho, avaliou-se o efeito da cobertura no acúmulo de biofilme em braquetes ortodônticos, através de modelo de microcosmos. Braquetes ortodônticos foram previamente preparados conforme os tratamentos de superfície que apresentaram melhores resultados na primeira fase (SH1 para aço, SH2 para cerâmica). Foi avaliado o efeito da cobertura na formação de biofilme em períodos de 12h e 24h (controles: substratos não-recobertos e substratos jateados). Os resultados mostraram que as coberturas hidrófobas não resultaram em efeito significativo no acúmulo de biofilme no tempo 12h, entretanto todos os tratamentos de cobertura reduziram de forma significativa o acúmulo de biofilme sobre os braquetes metálicos e cerâmicos comparados aos grupos controle no período 24h. Foi observada relação de redução exponencial significativa entre ângulo de contato e acúmulo de biofilme para o tempo 24h. Dessa forma, conclui-se que a aplicação de coberturas (super)-hidrófobas reticuladas via processo sol-gel na superfície de dispositivos ortodônticos metálicos e cerâmicos reduziu o molhamento das superfícies em contato com a água e teve efeito significativo na retenção de biofilme bucal sobre esses dispositivos após 24h

Endlosfaserverstärkte Thermoplaste werden oftmals als imprägnierte und konsolidierte Halbzeuge angeboten. Solche thermoplastischen Prepregs werden üblicherweise als Organobleche bezeichnet. Die thermoplastische Matrix ermöglicht unter anderem die Warmformbarkeit und Schweißbarkeit von Organoblechen. Organobleche sind, durch die ausschließliche Möglichkeit sie mittels Thermoformen umzuformen, in ihrer Formgebung auf halbschalige Strukturen beschränkt, welche begrenzte Torsions-, Verwindungs- und Beulsteifigkeiten aufweisen. Um die Steifigkeiten dieser schalenförmigen, offenen Bauteile zu erhöhen, können z. B. versteifende Rippen oder Verstärkungssegmente eingebracht werden. Aufgrund des Thermoformprozesses sind mit Organoblechen, verglichen mit duroplastischen Systemen, jedoch nur kleine und einfache Bauteilgeometrien realisierbar. Um neben der Steifigkeitserhöhung auch größere und komplexere Bauteile herzustellen, können die schalenförmigen Organobleche während des Umformvorgangs gefügt werden. Auf diese Weise werden Hohlkörper in Doppelhutprofilform gefertigt. So werden, auch ohne Einbringung von Rippen o. ä., hohe Bauteilsteifigkeiten erreicht. Die Doppelhutprofilform hat jedoch eine nicht optimale Nutzung der Faserverstärkung über die Fügeebene hinweg zur Folge, da die Fasern von der Belastungsrichtung abweichend umgelenkt werden. Im vorliegenden Beitrag wird daher das überlappende Infrarotschweißen von Organoblechen behandelt, was eine Faserverstärkung über die Fügeebene hinweg ermöglicht. Die Prozess- und Werkstoffeinflüsse auf die Verbindungseigenschaften werden beschrieben und Möglichkeiten zur Optimierung der Schweißnahteigenschaften dargestellt. Des Weiteren werden Optimierungskriterien für überlappende Infrarotschweißungen an den untersuchten Organoblechen festgelegt. Die im Verlauf der Forschungsarbeiten umzusetzenden Verfahrensvarianten zur Herstellung von Hohlkörperbauteilen aus Organblechen werden zudem vorgestellt.

Les substrats structurés aux échelles micrométriques et nanométriques sont intéressants pour des applications biomédicales, par exemple dans des puces à ADN/protéines, pour la miniaturisation des « lab-on-chip » ou pour préparer des implants permettant le contrôle de l'adhésion de cellules. Dans la dernière décennie des études ont montrées, que les cellules vivantes peuvent détecter la présence de nano-structures sur les substrats sur lesquels elles adhèrent. Bien que ces mécanismes soient étudiés depuis une dizaine d'années, les mécanismes fondamentaux sont encore en cours d'études. Tant pour une étude au niveau fondamental que dans le but d'applications concrètes, il est important de développer des techniques simples pour structurer des substrats sur de grandes surfaces. Nous avons réalisé une nouvelle méthode alliant un faible coût de fabrication et la biocompatibilité pour structurer et biofonctionnaliser des substrats à l'échelle nanométrique en utilisant des membranes d'alumine poreuses comme masque. Les membranes d'alumine poreuses, préparées par électrochimie, sont naturellement organisées en un réseau hexagonal sur une surface de quelques cm². Nous les utilisons comme masque pour la structuration de surfaces. Des trous réguliers sont gravés dans le substrat à travers les membranes d'alumine poreuses. Ce substrat est ensuite utilisée lors d'une application biologique : une bicouche lipidique est déposée sur le substrat structuré pour imiter les hétérogénéités de la membrane cellulaire. La mobilité de la bicouche est étudiée par corrélation de spectroscopie de fluorescence à rayon variable. Une autre série d'expériences est faite en utilisant des membranes d'alumine poreuses comme masque d'évaporation pour créer des réseaux organisés d'îlots d'organo-silanes. Deux molécules sont utilisées elles possèdent soit une fonction amine réactive soit une longue chaîne carbonée inerte. La bio-fonctionnalisation est ensuite effectuée en utilisant la fonction amine pour accrocher un anticorps. Des études sont effectuées en parallèle, sur des substrats bio-fonctionnalisés à l'échelle micrométrique grâce au micro-contact printing. Le but de cette étude est de mettre au point une biochimie de surface permettant le contrôle de l'adhésion de cellules immunitaires, avec le but de transférer ensuite la biochimie à l'échelle nanométrique. / Substrates patterned at the micro-scale and nano-scale are interesting for biomedical applications, for example, in DNA/protein nano-arrays, for miniaturized lab-on-chip applications or for making smart implants that can control adhesion of cells. In the last decade, some studies showed that living cells can detect nano-scale structures on substrates to which they adhere. Although this behaviour has been observed now for over a decade, the fundamental detection mechanism is still under investigation. Both for fundamental studies and for applications, it is important to develop facile techniques to pattern substrates on a large scale. We have realized a novel technique for patterning and bio-functionalizing substrates at the nano-scale using porous anodic alumina membranes as masks. The ordered porous anodic alumina membranes, prepared by classical electro-chemistry, are naturally organized in an hexagonal array over surface area of few square centimeters. Here we use them as mask for surface patterning. To create an array of nano holes, the substrate is dry etched through the alumina pores. In a biologically relevant application, a lipid bilayer is deposited on the patterned substrate to mimic a heterogeneous cell membrane. The mobility of the bilayer is studied by fluorescent correlation spectroscopy. In a different set of experiments, the porous alumina membranes are used as evaporation mask to create an organized array of alkyl-silane islands - either with a short carbon chain and with a reactive amine group or with a long carbon chain and non-reactive. Afterwards, biochemical functionalization is achieved by exploiting the amino-function of the amino-silane to bind an antibody. In parallel, we have started some studies of adhesion on a pattern substrate at micro-scale with immunological cells. The substrate is pattern by micro contact printing and the cell adhesion is observed by RICM. The aim of this studies is to prepare the biochemistry for the immunological cells adhesion, with the aim or transferring this to the nano-scale.

Orientador: Newton Luiz Dias Filho / Banca: Andre Henrique Rosa / Banca: Wagner Luís Polito / Resumo: A combinação de diferentes tipos de materiais para obtenção de novas propriedades tem despertado grande interesse em vários campos da ciência de materiais. Em processos de separação, é de considerável interesse o uso de materiais com propriedades básicas extremamente diferentes. Entre os suportes mais usados está a sílica gel, um material com tamanho de partículas e porosidade bem definidas, elevada área superficial, e estabilidades mecânica, química e térmica elevadas. Neste contexto, a sílica gel modificada com grupos organofuncionais pode ser utilizada para a adsorção de íons metálicos em soluções aquosas e não aquosas, pré-concentração e separação de íons metálicos. Neste trabalho, a sílica gel 60 (Merck), com tamanho de partículas entre 0,2 e 0,05 mm e área superficial específica de 486 m2.g-1, foi quimicamente modificada em duas etapas. Primeiro, a sílica gel foi quimicamente modificada com 3-cloropropiltrimetoxisilano, resultando o 3-cloropropil sílica gel (CPSG). Na segunda etapa, o produto resultante, CPSG, reagiu com 2-mercaptopirimidina e 4-amino-2-mercaptopirimidina, resultando os materiais sólidos 2-mercaptopirimidina-propil sílica gel (MPSG) e 4-amino-2-mercaptopirimidinapropil sílica gel (AMSG). As quantidades de grupos funcionais conectados na superfície da sílica gel, N0, foram 7,007 x 10-4 mols e 7,416 x 10-4 mols de moléculas por grama de sílica, para MPSG e AMSG, respectivamente. Conhecendo a área superficial específica e assumindo que as moléculas cobrem uniformemente a superfície, a densidade média, d, das moléculas ancoradas e a distância intermolecular média, l, podem ser calculadas aplicando as equações d = N0 N/SBET e l = (l/d) 1/2 , onde N é o número de Avogadro. Os valores calculados são d = 1,42 moléculas.nm2 e l = 0,979 nm, e d = 1,166 moléculas.nm2 e l = 0,926 nm, para MPSG e... (Resumo completo, clicar acesso eletrônico abaixo). / Abstract: The combination of different type of materials for achieving novel properties has always been of high interest in many fields of the materials sciences. The use of materials with extremely different basic properties, like organic and inorganic compounds, is of considerable interest in separation processes. Among the supports the most used is silica gel, a material of well-established particle sizes and well-define porosity, high surface area, and high mechanical, chemical, and thermal stability. In this context, silica gel modified with organofunctional groups has been used for adsorption of metal ions from aqueous and non-aqueous solutions, pre-concentration and separation of metallic ions. In this work, silica gel 60 (Merck) having secondary particles sized between 0,2 and 0,05 mm and specific surface area of 486 m2.g-1 was modified using a two step approach. First, the silica gel was chemically modified with 3- chloropropyltrimetoxysilane, resulting the 3-chloropropyl-silica gel (CPSG). Second, the resultant product, CPSG, reacted with 2-mercaptopyrimidine and 4-amino-2- mercaptopyrimidine, resulting the solid materials 2-mercaptopyrimidine-propyl-silica gel (MPSG) and 4-amino-2-mercaptopyrimidine-propyl-silica gel (AMSG). The quantities of functional groups attached on the silica gel surface, No, were 7,007 x 10-4 mols e 7,416 x 10-4 mols .g-1 of molecules per gram of silica, for MPSG and AMSG, respectively. It being known the specific surface area and assuming that the molecules uniformly cover the surface, the average density, d, of the attached molecules and the average intermolecular distance, l, can be calculated by applying the equations: d = N0 N /SBET and l = (l/d)1/2, where N is Avogadro's number. The calculated values were d = 1,042 molecules.nm-2 and l = 0,979 nm and d = 1,166 molecules.nm-2 and... (Complete abstract click electronic address below). / Mestre

Plant roots are critical weathering agents in deep soils, yet the impact of resulting mineral transformations on the vast deep soil carbon (C) reservoir are largely unknown. Root-driven weathering of primary minerals may cause the formation of reactive secondary minerals, which protect mineral-organic associations (MOAs) for centuries or millennia. Conversely, root-driven weathering may also transform secondary minerals, potentially enhancing the bioavailability of C previously protected in MOAs. Here we examined the impact of root-driven weathering on MOAs and their capacity to store C over pedogenic time scales. I compared soil that experienced root-driven weathering, resulting in the formation of discrete rhizosphere zones in deep soil horizons (100-160 cm) of the Santa Cruz Marine Terrace chronosequence (65 ka-226 ka), with adjacent soil that experienced no root growth. Using a combination of radiocarbon, mass spectrometry, Mössbauer spectroscopy, and X-ray spectromicroscopy approaches, we characterized MOA transformations in relation to changes in C content, turnover and chemistry across four soils ranging in age (65 ka-226 ka). We found that the onset of root-driven weathering (65-90 ka) increased the amount of C associated with poorly crystalline iron (Fe) and aluminum (Al) phases, particularly highly-disordered nano-goethite. The increase in C coincided with greater overall C concentrations, longer C residence times, and a greater abundance of microbially-derived C. Continued root-driven weathering (137-226 ka) did not significantly change the amount of C associated with crystalline Fe and Al phases, but resulted in a decline in the amount of C associated with poorly crystalline metal phases. This decline in C associated to poorly crystalline phases coincided with a decrease in C concentrations and potential turnover rates, and a shift toward plant-derived C. In contrast, soil not affected by root-driven weathering showed low amounts of C bound to poorly crystalline Fe and Al phases regardless of soil age and, correspondingly, lower C concentrations and estimated residence times. My results demonstrate that root-driven formation and disruption of poorly crystalline Fe and Al phases directly controls both C accrual and loss in deep soil. Hence root impacts on soil C storage are dependent on soil weathering stage, a consideration critical for predictions of the vulnerability of deep soil C to global change.

The diploma thesis is focused on the issue of sedimentation stability of magnetorheological fluids, whis represents one of the most important characteristics determining the reliability of these fluids. Higher sedimentation stability can by achieved in several ways. Methods that are further examined in the thesis include particle polymerization and the addition of clay mineral additives. Both achieve positive results by schowing increased sedimentation stability. However, in the case of additives, the effect is much higher. In particular, the CLAYTONE 40 additive achieves a lower particle sedimentation rate while maintaining the same viscosity as the commercial LORD-122ED. The results provide significant knowledge in the field and can bring magnetorheological fluids closer to wider commercial use.