Movimentos coletivos prestam um papel fundamental na dinâmica e energética de biomoléculas em solução. Estes movimentos permitem o acoplamento de regiões significativamente distantes, apresentando considerável influência, por exemplo, no alosterismo para a formação de complexos macromoleculares e no funcionamento integrado de proteínas multidomínios como \"máquinas moleculares\". Neste trabalho de doutoramento, serão apresentados os resultados referentes à aplicação conjunta de técnicas experimentais biofísicas, de modelagem estrutural e de dinâmica molecular no estudo de dois sistemas para os quais estes movimentos coletivos demonstram considerável importância funcional. Para a interação do receptor nuclear do ácido 9-cis-retinóico com seu elemento responsivo específico no DNA (HRE), a comparação de estudos de dinâmica molecular com ensaios de afinidade por anisotropia de fluorescência sugere que a resistência inicial para a associação do monômero, seguida da acentuada colaboratividade na associação do dímero é regida por um impedimento da associação do domínio de ligação ao DNA (DBD) para o primeiro à sequência responsiva devido, em última análise, a uma não complementaridade dos modos coletivos mútuos. Este impedimento para a associação monomérica inicial é mais acentuado para o monômero 5\' (para o qual a menor especificidade de ligação à seqüência específica já é bem documentada), devido aos efeitos conjuntos de um \"defeito\" natural no empacotamento de bases da seqüência responsiva, que se manifesta mais significativamente na interface entre o meio-sítio 5\' e a seqüência espaçadora, e dos modos vibracionais entre os dois sítios decorrentes de seu faseamento relativo na topologia do DNA na seqüência responsiva, caracterizando um mecanismo \"chave e fechadura\" para a interação obrigatoriamente simultânea dos dois monômeros ao DNA. No segundo caso, um estudo integrado utilizando a técnica experimental de espalhamento de raios X a baixos ângulos e uma abordagem de modelagem estrutural baseada em dinâmica molecular foi realizado para a celobiohidrolase I de Trichoderma harziannum. Este estudo permitiu tanto a elaboração de um modelo estrutural de maior resolução para esta enzima de alto potencial biotecnológico como a constatação dos possíveis mecanismos moleculares a partir dos quais as glicosilações no peptídeo conector impõem restrições à orientação e modos vibracionais entre seus dois domínios de forma condizente com sua ação concertada na interação e no deslize da enzima sobre a superfície celulósica, ambos de fundamental importância para a processividade da enzima na hidrólise do substrato microcristalino. / Collective motions play a fundamental role in solution biomolecule dynamics and energetics. These movements can couple very distant regions in the protein structures affection, for instance, allosteric mechanisms, the establishment of macromolecular complexes, and on the integrated function of multidomain proteins as molecullar machines. In this thesis, we present results concerning to the joint use of experimental biophysical techniques, structural modeling and molecular dynamics simulations on the study of two systems for which these collective motions have substantial importance. First, we study the interaction of the nuclear retinoid X receptor with its specific DNA hormone response element (HRE) using a combination of molecular dynamics simulations and affinity assays performed by using fluorescence anisotropy. We find out that collective motions mediate the low binding affinity of monomers and the high cooperative binding of HRE dimers. The lower binding affinity of the monomer is more prominent for 5´ monomers. This occur due to an natural ineffective stacking of the last base pair step at the 5´-half-site and to the phasing of the two binding half-sites in the DNA topology, that impose a collective motions that tends to occlude the 5´ binding site. This behavior, in turn, is concurrent with the well known 3´ polarity and the decreased binding specificity to the 5´ half site for the hRXRα monomer. This same pattern impose a lock-and-key mechanisms dependent on the binding of the full dimer. Second, an integrated Small angle X ray scattering and molecular dynamics based structural modeling was used to comprehend the interdomain motions of cellobiohydrolase I of Trichoderma harziannum. We manage to build a refined model for this enzime, with important biotechnological potential. We also provide insights into molecular mechanisms of linker and glycosylation imposed restraints on the orientation and vibrational modes of the full-length enzyme, supporting a mechanism of sliding of on the cellulose surface. This mechanism is fundamental for the high processivity on the hydrolysis of microcrystalline cellulose.

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.

Apesar de ser utilizado há muito tempo como solvente para espécies orgânicas e inorgânicas, bem como carreador de fármacos, muitos aspectos relativos à auto-associação intermolecular do dimetil sulfóxido (DMSO) e às suas interações com espécies iônicas são ainda motivos de controvérsia na literatura. No presente estudo, a estrutura e ambiente local de dimetil sulfóxido (DMSO) em diferentes meios iônicos foram estudados por meio de três abordagens diferentes. Na primeira abordagem, o efeito de não-coincidência Raman (NCR) observado na banda atribuída ao modo ν(S=O) do DMSO, ca. 1050 cm-1, foi investigado para o líquido puro e em soluções de tetracloreto de carbono (CCl4) e água. Além disso, foi investigado o efeito de espécies iônicas (Kl, KSCN, KBr, TBAN3, TBAOCN, LiClO4, Mg(ClO4)2) na frequência ν(S=O), bem como no NCR das soluções. Os resultados de NCR juntamente com as técnicas de infravermelho, RMN e de medidas de propriedades físico-químicas mostraram que essas espécies iônicas não somente afetam a estrutura de associação do DMSO, como são capazes de interagir fortemente com o solvente. Na segunda abordagem, com a finalidade de modular as propriedades de um líquido iônico, fez-se a análise estrutural das misturas envolvendo DMSO e água como solventes e o líquido iônico EAN como soluto por meio das técnicas de espalhamento de raios-X e de nêutrons. Os resultados mostraram que a estrutura cátion-ânion do EAN é afetada pela presença de DMSO e, que em ambos os solventes são evidentes fortes ligações de hidrogênio entre o cátion EA+ e os oxigênios do solvente e do ânion nitrato. As moléculas de água não afetam drasticamente a estrutura do EAN, pois seu caráter doador/aceptor de LH e seu tamanho permite a formação de pontes entre cátion e o ânion, no entanto, EAN consegue distorcer a rede tridimensional de ligação de hidrogênio da água. Por outro lado, as moléculas de DMSO afastam os ânions da região polar do EA+ na competição pela formação de LH com o cátion e o EAN, por sua vez, provoca a ruptura das estruturas de associação do DMSO. Na terceira abordagem, misturas envolvendo três diferentes SEPs (uma classe de líquidos iônicos); Relina, MUCHCl e DMUCHCl; com DMSO foram investigadas por meio de suas propriedades físico-químicas e por espectroscopia Raman, tendo em vista modular as propriedades dos SEPs. Neste caso, os resultados não apontaram para interações fortes e específicas envolvendo as espécies iônicas e o DMSO, mas a um maior empacotamento do sistema, onde os desvios de suas propriedades físico-químicas com relação à idealidade são negativos e sua mobilidade iônica juntamente com a análise dos espectros vibracionais não evidenciaram interações específicas. No entanto, as viscosidades e densidades diminuíram nas misturas e a mobilidade iônica foi favorecida. / Although it has long been used as a solvent for organic and inorganic species, as well as drug carriers, many aspects concerning the intermolecular self-association of dimethyl sulfoxide (DMSO) and their interactions with ionic species are still controversial in the literature. In the present study, the structure and local environment of dimethyl sulfoxide (DMSO) in different ionic media were studied using three different approaches. In the first approach, the Raman non-coincidence effect (NCE) observed in the band assigned to the DMSO ν(S = O) mode, ca. 1050 cm-1, was investigated for the pure liquid and in its solutions of carbon tetrachloride (CCl4) and water. In addition, the effect of ionic species (K1, KSCN, KBr, TBAN3, TBAOCN, LiClO4, Mg (ClO4)2) on the frequency ν(S = O) as well as the NCE of the solutions were investigated. The results of NCR together with the infrared, NMR and physico-chemical properties measurements showed that these ionic species not only affect the association structure of DMSO, but are also capable of interacting strongly with the solvent. In the second approach, with the purpose of modulating the properties of an ionic liquid, the structural analysis of the mixtures involving DMSO and water as solvents and the ionic liquid EAN as a solute were carried out by X-ray and neutron scattering techniques. The results showed that the cation-anion structure of the EAN is affected by the presence of DMSO and that in both solvents strong hydrogen bonds between the EA+ cation and the oxygen from solvent and from nitrate anion are evident. The water molecules do not affect the structure of the EAN drastically, because its LH donor/acceptor character and its size allows the formation of bridges between cation and anion, however, EAN can distort the hydrogen bonding three-dimensional network in water. On the other hand, the DMSO molecules repels the anions from the polar head of EA+ in the competition in forming LH with the cation, however EAN break down DMSO association structures. In the third approach, mixtures involving three different SEPs (a class of ionic liquids); Relina, MUCHCl and DMUCHCl; with DMSO were investigated by means of their physicochemical properties and by Raman spectroscopy, in order to modulate the properties of SEPs. In this case, the results did not point to strong and specific interactions involving the ionic species and DMSO, but to a greater packaging of the system, where the deviations of its physicochemical properties with respect to the ideality are negative and its ionic mobility together with the analysis of the vibrational spectra showed no specific interactions. However, the viscosities and densities decreased in the mixtures and the ionic mobility was favored.

Eletrônica utilizando polímero em substituição ao silício é uma área de pesquisa recente com perspectivas econômicas promissoras. Compósitos de polímeros com partículas metálicas apresentam interessantes propriedades elétricas, magnéticas e ópticas e têm sido produzidos por uma grande variedade de técnicas. Implantação iônica de metais utilizando plasma é um dos métodos utilizados para obtenção desses compósitos condutores. Neste trabalho é realizada implantação de íons de ouro de baixa energia em PMMA utilizando plasma. O PMMA tem grande importância tecnológica sendo largamente utilizado como resiste em litografias por feixe de elétrons, raios-X, íons e deep-UV. Como resultado da implantação iônica de baixa energia em PMMA há formação de uma camada nanométrica de material condutor. Esse novo material, denominado compósito isolante-condutor, permite criar micro e nanodispositivos através de técnicas largamente utilizadas em microeletrônica. Medidas elétricas são realizadas in situ em função da dose de íons metálicos implantada, o que permite um estudo das propriedades de transporte desses novos materiais, que podem ser modeladas pela teoria da percolação. Simulações utilizando o programa TRIDYN permitem obter a profundidade e o perfil da implantação dos íons. São mostradas caracterizações importantes tais como Microscopia Eletrônica de Transmissão, Microscopia de Varredura por Tunelamento, Espalhamento de Raios-X a Baixos Ângulos, Difração de Raios-X e Espectroscopia UV-vis. Essas técnicas permitem visualizar e investigar o caráter nanoestruturado do compósito metal-polímero. Ainda como parte deste projeto, as camadas condutoras formadas no polímero são caracterizadas quanto à manutenção das suas características de elétron resiste. / Electronics using polymers instead of silicon is a recent research area with promising economic perspectives. Polymer with metallic particles composites presents interesting electrical, magnetic and optical properties and they have been produced by a broad variety of techniques. Metal ion implantation using plasma is one of the used methods to obtain conductor composites. In this work it is performed low energy gold ion implantation in PMMA by using plasma. PMMA has great technological importance once it is broadly used as resist in electron-beam, X-ray, ion and deep UV lithography. As a result of low energy ion implantation in PMMA, a nanometric conducting layer is formed. This new material, named insulator-conductor composite, can allow the creation of micro and nanodevices through well known microelectronics techniques. Electrical measurements are performed in situ as a function of metal ions implanted dose, which allows the investigation of electrical transport of these new materials, which can be modeled by the percolation theory. Simulations using TRIDYN computer code provide the prediction of depth profile of implanted ions. Important characterizations are showed such as Transmission Electron Microscopy, Scanning Tunneling Microscopy, Small Angle X-Ray Scattering, X-Ray Diffraction and UV-vis Spectroscopy. These techniques allow to visualize and to investigate the nanostructured character of the metal-polymer composite. Still as a part of this project, the conducting layers formed are characterized in relation to the maintenance of their characteristics as electron-beam resist.

Les rhabdovirus, dont les virus de la stomatite vésiculaire (VSV) et de la rage (RAV) constituent des prototypes, sont des virus enveloppés dont le génome est constitué d'une seule molécule d'ARN simple brin de polarité négative qui font partie de l'ordre des Mononegavirales (MNV). La machinerie de transcription/réplication de ces virus est constituée de l'ARN génomique et de trois protéines qui sont communes à tous les virus de l'ordre des MNV, la (N) qui encapside le génome viral, la grande sous-unité de l'ARN polymérase ARN dépendante (L) et la phosphoprotéine (P) qui est un cofacteur non-catalytique de la L et sert de chaperonne à la N. Le premier objectif de mon travail de thèse consistait à déterminer la structure cristallographique du domaine de dimérisation de la phosphoprotéine du virus de la rage. La P des rhabdovirus est une protéine modulaire qui contient deux régions intrinsèquement désordonnée, un domaine central responsable la dimérisation et un domaine C-terminal responsable de la fixation sur la matrice N-ARN. Le modèle atomique obtenu à une résolution de 1.5A montre que la structure est très différente de celle du domaine correspondant chez VSV. Le second objectif de mon travail était la caractérisation structurale de la grande sous-unité L de la polymérase du virus de la stomatite vésiculaire. Cette enzyme de 2109,aa, possède six régions conservées. Le domaine conservé III comprend les régions impliquées dans l'activité de polymérisation et les domaines V et VI sont responsables de la formation de la coiffe des ARNm. Plusieurs stratégies ont été envisagées successivement. (1) Sur la base de prédictions de structures secondaires et de prédictions de désordre, nous avons essayé d'exprimer différents fragments en système d'expression bactérien. Les constructions testées se sont avérées insolubles et certaines d'entre elles fixaient GroEL, indiquant un problème de repliement. (2) Nous avons alors essayé d'exprimer la L seule ou en complexe avec la P en système d'expression eucaryote. La purification s'est avérée impossible, la protéine L restant toujours associées à des protéines cellulaires visibles par coloration au bleu de Coommassie. (3) Finalement nous avons réussi à purifier la polymérase à partir de virus entier. La préparation de la polymérase était très homogène et a permis d'entreprendre une caractérisation par microscopie électronique. Une classification d'images a permis de construire un premier modèle à basse résolution. Le modèle révèle la présence d'un domaine annulaire avec plusieurs domaines structurés attachés au coeur de la polymérase. La cryo-microscopie électronique et la tomographie permettront d'obtenir plus de détails sur cette protéine. / Rhabdoviruses, including vesicular stomatitis virus (VSV) and rabies virus (RAV), are enveloped viruses which genome is made of a single molecule of negative-sense RNA and are classified in the order Mononegavirales (MNV). The transcription/replication machinery of these viruses consists of the genomic RNA and of three proteins, which are common to all other viruses of the order MNV, a nucleoprotein (N) that encapsidates the viral genome, a large subunit of the RNA-dependent RNA polymerase (L) and a phosphoprotein (P) that acts as a non-catalytic cofactor of L and a chaperone of N. The first goal of my research project was to determine the crystallographic structure of the dimerization domain of the rabies virus phosphoprotein. The P protein of the rhabdoviruses is a modular protein, which contains two intrinsically disordered regions, a central dimerization domain and a C-terminal domain involved in binding to the N-RNA template. The atomic model obtained at a resolution of 1.5 A showed that the structure is different from that of the corresponding domain of VSV. The second goal was the structural characterization of the large subunit L of VSV polymerase. The enzyme of 2109 aa has six conserved regions. Conserved region III includes the residues involved in the RNA synthesis activity, whereas domains V and VI are involved in mRNA capping formation. Three strategies were successively developed: (1) On the basis of secondary structure and disorder predictions, we tried to express different fragments in bacterial expression systems. These constructions appeared to be insoluble and some of them bound GroEL suggesting a folding problem; (2) We tried to express L alone or co-express it with P in eukaryotic expression system. The purification appeared to be impossible, the L protein always remaining associated with host-cell proteins in amounts detectable by Coommassie staining; (3) We succeeded in purifying the L protein from the virus. The L samples were homogenous and allowed a characterization by electron microscopy. Image classes allowed the reconstruction of a first low-resolution model. This model revealed the presence of a large ring-like domain and several globular domains. Cryo-electron microscopy and tomography should lead to a more detailed description of this protein.

Orientador: Maria Virgínia Costa Scarpa / Coorientador: Marlus Chorilli / Banca: Renata Fonsenca Vianna Lopez / Banca: Leila Aparecida Chiavacci / Resumo: Amplamente utilizado no tratamento de vários tipos de câncer e na psoríase, o metotrexato (MTX) é um quimioterápico, estruturalmente análogo do ácido fólico, que apesar de sua eficácia apresenta uma série de efeitos adversos, sendo a hepatotoxicidade o mais grave. Atualmente os sistemas nanoestruturados líquido-cristalinos de fase lamelar estão sendo utilizados como dispositivos para liberação modificada de fármacos, sendo vantajosos na liberação tópica de várias substâncias, conforme suas características de interação com o estrato córneo e as outras camadas da pele, evitando assim efeitos adversos sistêmicos. Os objetivos deste trabalho foram desenvolver sistemas nanoestruturados líquido-cristalinos de fase lamelar, acrescidos de MTX, caracteriza-los do ponto de vista físico, realizar a análise estrutural das formulações, através de microscopia de luz polarizada (MLP), espalhamento de raios-X a baixo ângulo (SAXS) e suas propriedades reológicas, executar os testes de estabilidade preliminar (TEP) das formulações, validar o método analítico para a quantificação de MTX por CLAE e executar ensaios de liberação, permeação e retenção in vitro. As formulações preparadas a partir da mistura do poliéter funcional siloxano (Dow Corning® 5329) como tensoativo, com silicone fluido de co-polímero glicol (Dow Corning® 193C) como fase oleosa titulados em fase aquosa, composta por tampão fosfato de potássio monobásico 0,01M pH 7,4, apresentaram fases líquido-cristalinas do tipo lamelar, confirmados pelos ensaios de MLP e SAXS. Os TEPs evidenciaram que as formulações A, B e C mantiveram-se estáveis durante o período do estudo. Os estudos do comportamento reológico das formulações apresentaram-se como fluidos pseudoplásticos não-newtonianos tixotrópicos ... / Abstract: Widely used in the treatment of some types of cancer, the methotrexate (MTX) is a chemotherapeutic, structurally analog of the folic acid, although its effectiveness, presents a series of adverse effect, being the most serious hepatotoxicity. Currently, the liquid crystal lamellar phase is being used of devices for modified release of drug demonstrated to be advantageous in the release topic of some substances, given to the characteristics of interaction with the stratum corneun and other layers of the skin, avoiding systemic adverse effects. The aims of this research had been to develop and to characterize liquid crystalline nanostructure systems of lamellar phase, increased of MTX of the physical point of view, also carry through the structural analysis of the formulations through by polarized light microscopy (PLM), small-angle X-ray scattering (SAXS) and rheological properties. Perform stability studies of the chosen formulations, validate the analytical method of quantification of MTX for High Performance Liquid Chromatography (HPLC) and carry through release assay, cutaneous permeation and skin retention in vitro for the chosen formulations. The formulations prepared by the mixture of polyether functional siloxane as surfactant, with silicone polyether copolymer as oily phase and phosphate buffer 0,01M pH 7,4 as aqueous phase demonstrating lamellar liquid-crystalline phases, confirmed by assays of PLM and SAXS. The stability studies showed that formulations A, B and C remained stable throughout the period of the study. The study of the rheological behavior of the formulations presented as not Newtonian pseudoplastic fluid and thixotropic ... / Mestre

Le contrôle de la microstructure des matériaux organiques est crucial pour des applications pratiques telles que la photonique, la biomédecine ou encore le domaine très dynamique de l'électronique organique. Les études récentes ont montré une possibilité de contrôler la structure des polymères à l'échelle nanométrique en utilisant l'auto-assemblage supramoléculaire sous confinement spatial. Bien que de nombreuses études ont déjà été effectuées dans ce domaine, plusieurs questions essentielles restent ouvertes. En particulier, il est important de comprendre comment les différents processus de formation structurale tels que la cristallisation, la formation d`une phase cristal liquide et la séparation de phases se déroulent sous confinement. Dans le présent travail, nous abordons l'effet du confinement à 1D et à 2D sur la formation de la structure pour une variété de systèmes, y compris les copolymères segmentés de poly(éther-ester-amide) (PEEA), les polymères cristaux liquides (CL) dont la chaîne principale appartient à la famille des poly(di-n-alkylsiloxane)s et des copolymères à bloc cristaux-liquides /semicristallins formés par complexation de poly(2-vinylpyridine-b-oxyde d'éthylène) (P2VP-PEO) avec un ligand cunéiforme, l'acide 4'-(3'',4'',5''-tris(octyloxy) benzamido) propanoïque. Pour être capable de traiter de façon adéquate la morphologie complexe de ces systèmes sous confinement, le travail a été effectué en utilisant une batterie de méthodes expérimentales. Les techniques principales opérationnelles dans l'espace direct et réciproque que nous avons employées sont décrites dans le chapitre 2. [...] / Controlling the micro-structure of organic materials is crucial for a variety of practical applications such as photonics, biomedicine or the rapidly growing field of organic electronics. Recent studies have shown a possibility of tailoring the polymer structure on the nanoscale using supramolecular self-assembly under spatial confinement. Despite extensive studies already performed in this field, many questions remain open. In particular, it will be important to understand how different structure formation processes such as crystallization, LC-phase formation, microphase separation, and others occur under confinement. In the present work, we address the effect of 1D- and 2D-confinement on the structure formation for a variety of systems including segmented poly(ether-ester-amide) (PEEA) copolymers, main-chain liquid-crystalline (LC) polymers belonging to the family of poly(di-n-alkylsiloxane)s and liquid-crystalline/semicrystalline block copolymers formed through complexation of poly (2-vinylpyridine-b-ethylene oxide) (P2VP-PEO) with a wedge-shaped ligand, 4'-(3'',4'',5''-tris(octyloxy) benzamido) propanoic acid. In order to reveal the morphological diversity of the studied systems under confinement, the work was carried out on bulk materials and on thin films employing a battery of experimental methods. The main experimental techniques operational in direct and reciprocal space applied in my work are described in chapter 2. [...]

Pour comprendre l'origine de la torsion lamellaire dans le poly(triméthylène téréphtalate), PTT, une étude a été entrepris sur la structure des sphérolites à bandes de PTT en utilisant la micro-diffraction des rayons-X sur une source synchrotrone. Nous avons démontré que les pics de diffraction de la maille triclinique de PTT révèlent une variation périodique de l'intensité en fonction de la distance jusqu'au centre sphérolitique lorsque nous effectuons un balayage avec un micro-faisceau de rayons X. Cela indique que la torsion lamellaire est strictement uniforme et régulière. Celte derrière observation est plus compatible avec le modèle expliquant la torsion comme résultat de contraintes surfaciques que des dislocations-vis géantes. En outre, les données expérimentales montrent que les polymères achiraux ne sont pas indifférents par rapport à l'inversion de la chiralité lamellaire, et que le changement de la chiralité est nécessairement accompagné d'un changement de signe du vecteur de croissance. En plus, nous avons observé que l'inclinaison globale de la chaîne (c'est à dire, l'inclinaison du paramètre c de la maille dans le plan perpendiculaire à la direction de la croissance rapide) n'affecte pas la vitesse et le sens de la torsion. Cela remet en question la seconde hypothèse du modèle de Keith et Padden. Par contre, l'inclinaison des segments de la chaine à l'interface du cristal lamellaire peut être identifiée comme le facteur clé déterminant les contraintes superficielles qui provoquent la torsion lamellaire. Avec la variation de l'épaisseur du cristal la chiralité lamellaire change, ce qui dû au changement de l'angle des segments polymères à l'interface. / To address the origin of the lamellar twisting in polytrimethylene terephthalate (PTT) an in-depth micro-focus X-ray scattering study was correlated to the data derived using conventional polarized optical microscopy to study the banded spherulite texture for PTT. It is shown that the diffraction peaks of the triclinic lattice of PTT show a periodical pattern as a function of the distance from the spherulite center when scanned with the micro focus X-ray beam. This indicates that the lamellar twist has a strictly uniform and regular nature. The latter observation is more compatible with the model explaining the twist as a result of unbalanced surface stresses than the giant screw dislocations. Moreover, the data shows that achiral polymers are in fact not indifferent to the inversion of the lamellar handedness, and that a change in handedness is necessarily accompanied by a change in the sign of the growth vector. At the same time, we show that the overall chain tilt (i.e., the inclination of the c-parameter of the unit cell in the plane perpendicular to the fast growth direction) does not affect the rate and sense of twisting. This calls into question the second premise of the KP-mod el. Instead, the local inclination of the terminal segment of the crystalline stem protruding the lamellar surface can be identified as the origin of the surface stresses and forcing the lamellar ribbon to twist. With the variation of the crystal thickness as a function of crystallization temperature the angle and direction of this segment is changed, resulting in a change of the lamellar ribbon chirality.

Aluminas have had some form of chemical and industrial use throughout history. For little over a century corundum (α-Al2O3) has been the most widely used and known of the aluminas. The emerging metastable aluminas, including the γ, δ, η, θ, κ, β, and χ polymorphs, have been growing in importance. In particular, γ-Al2O3 has received wide attention, with established use as a catalyst and catalyst support, and growing application in wear abrasives, structural composites, and as part of burner systems in miniature power supplies. It is also growing in importance as part of the feedstock for aluminium production in order to affect both the adsorption of hydrogen fluoride and the feedstock solubility in the electrolytic solution. However, much ambiguity surrounds the precise structure of γ-Al2O3. Without proper knowledge of the structure, understanding the properties, dynamics and applications will always be less than optimal. The aim of this research was to contribute towards settling this ambiguity. This work was achieved through extensive computer simulations of the structure, based on interatomic potentials with refinements of promising structures using density functional theory (DFT), and a wide range of supporting experiments. In addition to providing a more realistic representation of the structure, this research has also served to advance knowledge of the evolution of the structure with changing temperature and make new insights regarding the location of hydrogen in γ-Al2O3. / Both the molecular modelling and Rietveld refinements of neutron diffraction data showed that the traditional cubic spinel-based structure models, based on m Fd3 space group symmetry, do not accurately describe the defect structure of γ-Al2O3. A more accurate description of the structure was provided using supercells of the cubic and tetragonal unit cells with a significant number of cations on c symmetry positions. These c symmetry based structures exhibited diffraction patterns that were characteristic of γ-Al2O3. The first three chapters of this Thesis provide a review of the literature. Chapter One provides a general introduction, describing the uses and importance of the aluminas and the problems associated with determining the structure of γ-Al2O3. Chapter Two details the research that has been conducted on the structure of vi γ-Al2O3 historically. Chapter Three describes the major principles behind the computational methods employed in this research. In Chapter Four, the specific experimental and computational techniques used to investigate the structure of γ-Al2O3 are described. All preparation conditions and parameters used are provided. Chapter Five describes the methodology employed in computational and experimental research. The examination of the ~ 1.47 billion spinel-based structural possibilities of γ-Al2O3, described using supercells, and the selection of ~ 122,000 candidates for computer simulation, is detailed. This chapter also contains a case study of the structure of κ-Al2O3, used to investigate the applicability of applying interatomic potentials to solving complex structures, where many possibilities are involved, and to develop a systematic procedure of computational investigation that could be applied to γ-Al2O3. Chapters Six to Nine present and discuss the results from the experimental studies. / Preliminary heating trials, performed to determine the appropriate preparation conditions for obtaining a highly crystalline boehmite precursor and an appropriate calcination procedure for the systematic study of γ-Al2O3, were presented in Chapter Six. Chapter Seven details the investigation of the structure from a singletemperature case. Several known structural models were investigated, including the possibility of a dual-phase model and the inclusion of hydrogen in the structure. It was demonstrated that an accurate structural model cannot be achieved for γ-Al2O3 if the cations are restricted to spinel positions. It was also found that electron diffraction patterns, typical for γ-Al2O3, could be indexed according to the I41/amd space group, which is a maximal subgroup of m Fd3 . Two models were presented which describe the structure more accurately; Cubic-16c, which describes cubic γ-Al2O3 and Tetragonal-8c, which describes tetragonal γ-Al2O3. The latter model was found to be a better description for the γ-Al2O3 samples studied. Chapter Eight describes the evolution of the structure with changing calcination temperature. Tetragonal γ-Al2O3 was found to be present between 450 and 750 °C. The structure showed a reduction in the tetragonal distortion with increasing temperature but at no stage was cubic γ-Al2O3 obtained. Examination of the progress of cation migration indicates the reduction in the tetragonal nature is due to ordering within inter-skeletal oxygen layers of the unit cell, left over from the breakdown of the hydroxide layers of boehmite when the transformation to γ-Al2O3 occurred. Above 750 °C, δ-Al2O3 was not observed, but a new phase was identified and designated γ.-Al2O3. / The structure of this phase was determined to be a triple cell of γ-Al2O3 and is herein described using the 2 4m P space group. Chapter Nine investigates the presence of hydrogen in the structure of γ-Al2O3. It was concluded that γ-Al2O3 derived from highly crystalline boehmite has a relatively well ordered bulk crystalline structure which contains no interstitial hydrogen and that hydrogen-containing species are located at the surface and within amorphous regions, which are located in the vicinity of pores. Expectedly, the specific surface area was found to decrease with increasing calcination temperature. This trend occurred concurrently with an increase in the mean pore and crystallite size and a reduction in the amount of hydrogen-containing species within the structure. It was also demonstrated that γ-Al2O3 derived from highly crystalline boehmite has a significantly higher surface area than expected, attributed to the presence of nano-pores and closed porosity. The results from the computational study are presented and discussed in Chapter Ten. Optimisation of the spinel-based structural models showed that structures with some non-spinel site occupancy were more energetically favourable. However, none of the structural models exhibited a configuration close to those determined from the experimental studies. Nor did any of the theoretical structures yield a diffraction pattern that was characteristic of γ-Al2O3. This discrepancy between the simulated and real structures means that the spinel-based starting structure models are not close enough to the true structure of γ-Al2O3 to facilitate the derivation of its representative configuration. / Large numbers of structures demonstrate migration of cations to c symmetry positions, providing strong evidence that c symmetry positions are inherent in the structure. This supports the Cubic-16c and Tetragonal-8c structure models presented in Chapter Seven and suggests that these models are universal for crystalline γ-Al2O3. Optimisation of c symmetry based structures, with starting configurations based on the experimental findings, resulted in simulated diffraction patterns that were characteristic of γ-Al2O3.

The techniques of small-angle x-ray scattering (SAXS) and grazing-incidence small-angle x-ray scattering (GISAXS) have successfully been used for many years in the analysis of nanostructures in non-crystalline samples, e.g., polymers, metallic alloys, ceramics, and glasses. In many specimens, however, the nanostructure is not distributed homogeneously, but instead varies as a function of position in the sample. Conventional SAXS or GISAXS measurements on such heterogeneous samples merely yield an averaged scattering pattern of all the different structures present along the x-ray beam path. In this thesis, scanning tomography is combined with SAXS and GISAXS, revealing the individual local scattering cross section at each position on a virtual section through the sample. The technique thereby offers unique analytical possibilities in heterogeneous specimens. A brief review of the physics of x rays and x-ray scattering is given, before the methods of tomographic SAXS and GISAXS are introduced. Experimental requirements and limitations of both methods are discussed, including aspects of sampling, local rotational invariance and x-ray beam coherence. Experiments performed at the beamline BW4 at HASYLAB at DESY, Hamburg, Germany are described, illustrating the capabilities of the method. Finally, an outlook on possible future developments in tomographic small-angle x-ray scattering is given. / Die Methoden der Röntgenkleinwinkelstreuung (SAXS) und Röntgenkleinwinkelstreuung unter streifendem Einfall (GISAXS) werden seit vielen Jahren erfolgreich eingesetzt zur Analyse von Nanostrukturen in nicht-kristallinen Proben, z.B. Polymeren, metallischen Legierungen, Keramiken und Gläsern. In vielen Proben ist die Nanostruktur allerdings nicht homogen verteilt, sondern variiert als Funktion des Ortes in der Probe. Konventionelle SAXS- oder GISAXS-Messungen an solch heterogenen Proben liefern lediglich ein über alle unterschiedlichen Strukturen entlang des Röntgenstrahls gemitteltes Streubild. In dieser Arbeit wird Rastertomographie mit SAXS und GISAXS kombiniert und so der lokale Streuquerschnitt an jedem Ort auf einem virtuellen Schnitt durch die Probe gewonnen. Diese Technik bietet so einzigartige Analysemöglichkeiten von heterogenen Proben. Es wird zunächst ein kurzer Überblick über die Physik der Röntgenstrahlung und Röntgenstreuung gegeben, bevor die Methoden der SAXS- und GISAXS-Tomographie eingeführt werden. Die experimentellen Anforderungen und Grenzen beider Methoden werden besprochen, wobei Aspekte der Abtastung, der lokalen Rotationsinvarianz und der Kohärenz im Röntgenstrahl eine Rolle spielen. Experimente, die an der Messstrecke BW4 am HASYLAB bei DESY, Hamburg, durchgeführt wurden, werden beschrieben, um die Möglichkeiten der Methode zu illustrieren. Schließlich wird ein Ausblick auf mögliche zukünftige Entwicklungen der Kleinwinkelstreutomographie gegeben.