Ce travail de thèse consiste en l'étude détaillée des conséquences matérielles et ondulatoires de l'application d'un faisceau laser sur l'orientation d'un film de cristal liquide nématique dans un cadre bien particulier, dénommé la réorientation optique "topologique". Cela correspond en pratique à une situation où la lumière donne naissance à un défaut d'orientation pour le champ de directeur, dont la nature dépend des caractéristiques du champ lumineux excitateur (polarisation, phase, intensité). Après avoir introduit la notion de réorientation optique topologique, identifié et discuté les conditions expérimentales permettant son apparition, le rôle de l'état de polarisation est étudié. Le cas d'un faisceau singulier, structuré en phase ou en polarisation, est ensuite traité. Enfin, la mise en évidence de nouveaux effets nonlinéaires, statique et dynamique, est démontrée. / This thesis deals with a detailed study of the material an optical waves aspects of the lightinducedreorientation of a nematic liquid crystal film in a particular framework, called the optical“topological” reorientation. In practice, it corresponds to a situation where a laser beaminduces an orientational topological defect for the director field, whose nature depends on thecharacteristics of the excitation light field (polarization, phase, intensity). First, the concept oftopological optical reorientation is introduced and the experimental conditions for its appearanceare discussed and experimentally verified. Then, the role of the polarization state of a Gaussianlight beam excitation is investigated, followed with the more complex situation of singular lightbeams with structured phase or polarization. Finally, we report on self-induced nonlinear opticalmanifestations of the topological reorientation, which include the experimental identificationand discussion of novel singular phenomena such as nonlinear spin-orbit interaction of light andself-induced vortex beam precession.

Nous avons analysé par cryomicroscopie électronique la morphologie et la structure de longues chaines d’ADN condensées par un polycation tétravalent, la spermine (polyamine). Les expériences ont été réalisées i) avec des solutions de chaînes diluées et ii) avec des chaines isolées confinées dans la capside d’un virus.Les expériences ont été réalisées avec de l’ADN Lambda (48kbp) en solution diluée (0.03 mM Ph) et à faible concentration ionique (10 mM Tris HCl, 1 mM EDTA, pH 7.6). Nous avons exploré une large gamme de concentrations en spermine, allant du seuil de précipitation (0.05 mM sp) jusqu’à la limite de re-solubilization et au-delà (400 mM sp). Seize minutes après mélange de l’ADN et de la spermine, les échantillons sont piégés en film mince et vitrifiés à basse température pour garder intactes les conditions ioniques, puis imagés à basse température sous faibles doses d’électrons (cryoMET). La plupart des chaînes d’ADN forment des agrégats de tores de structure hexagonale avec des interdistances entre hélices de 2.93, 2.88, et 2.95 nm pour des concentrations en spermine respectivement égales à 0.05, 1 et 100 mM spermine, ce qui est en bon accord avec les données collectées précédemment par diffraction des rayons X. A concentration plus élevée en spermine (200mM), les tores hexagonaux sont remplacés par des faisceaux cholestériques de structure plus lâche (3.32 nm entre hélices). Nous en déduisons que la forme comme la structure des condensats cristallins liquides ADN-sp sont liées aux interdistances entre hélices et déterminés par les conditions ioniques i.e. par l’énergie cohésive entre chaînes d’ADN. En dehors du domaine de précipitation (400mM sp), les molécules d’ADN forment un réseau soluble de fines fibres (4-6nm de diamètre) qui nous amènent à reconsidérer l’état de ces chaiînes en présence de spermine. Nous avons également conçu des expériences pour visualiser les agrégats formés 6 à 60 sec après addition de la spermine dans les mêmes conditions de tampon. Parmi les nombreuses formes originales que nous avons observées (absentes après 16 min), la présence de fibres étirées ou en hélice, visibles seulement après 9sec, nous conduit à proposer que les chaines d’ADN soient immédiatement étirées après addition de spermine puis relaxent sous forme de fibres hélicoïdales qui donnent naissance à de petits toroids (comprenant quelquefois moins d’une chaine) qui grandissent et fusionnent. Nous avons également analysé les dimensions de l’ensemble des tores observés et montré l’existence de contraintes géométriques qui restent à élucider. Puisqu’il était généralement impossible de prévenir l’agrégation des chaines d’ADN, nous avons choisi une autre approche pour analyser le collapse de chaines d’ADN individuelles. Nous avons utilisé une population de virus T5 contenant une fraction de leur génome initial (12-54 kbp). La molécule d’ADN, initialement confinée dans le petit volume de la capside (de de 80nm diamètre) est collapsée par addition de spermine. Par comparaison avec le premier jeu de données, nous avons travaillé à concentration plus élevée en ADN (0.45 mM Phosphates dans l’ensemble de l’échantillon) et la concentration en spermine a été ajustée entre 0.05 et 0.5 mM (ce qui correspond à des rapports de charges +/- bien inférieurs). Ces expériences ont donc été réalisées au voisinage de la ligne de précipitation, dans la « région de coexistence », entre le domaine où les chaines sont en condition de pelote et le domaine ou les chaines sont toutes collapsées sous forme de tores. Nous avons montré l’existence de formes intermédiaires entre ces deux états que nous appelons « tores chevelus » dans lesquels une partie de la molécule est condensées dans le tore alors que l’autre partie reste non condensée. Les distances entre hélices ont également été mesurées. Elles sont plus grandes dans ces structures intermédiaires que dans les tores formés à plus forte concentration en spermine. Ces deux séries d’expériences montrent l’intérêt des méthodes de cryo-microscopie pour étudier la structure locale des phases condensées de l’ADN. Nous avons montré comment le confinement modifie le comportement de l’ADN en solution et l’intérêt d’étudier ces effets compte tenu de son importance dans le contexte biologique. / By using cryo-electron microscopy, we analyzed the morphology and structure of long double-stranded DNA chains condensed upon addition of varying amounts of the tetravalent polycation spermine (polyamine). Experiments have been performed i) with chains diluted in the bulk and ii) with individual chains confined in a virus capsid.Bulk experiments have been done with lambda DNA (48.5 kbp) at low concentration (0.03 mM Ph) and in low salt conditions (10 mM Tris HCl, 1 mM EDTA, pH 7.6). We explored a wide range of spermine concentration, from the onset of precipitation (0.05 mM sp) up to above the resolubilization limit (400 mM sp). Sixteen min after mixing spermine and DNA, samples have been trapped in thin films and vitrified in liquid ethane to keep ionic conditions unchanged, and imaged at low temperature with low doses of electrons (cryoTEM). DNA chains mostly form large aggregates of toroids in which DNA chains are hexagonally packed with interhelical spacings of 2.93, 2.88, and 2.95 nm at 0.05, 1 and 100 mM spermine, respectively, in agreement with previous X-ray data. At higher spermine concentration (200 mM), hexagonal toroids are replaced by cholesteric bundles with a larger interhelical spacing (3.32 nm). We conclude that the shape and the structure of the liquid crystalline sp-DNA condensates are linked to the DNA interhelix spacing and determined by the ionic conditions i.e. by the cohesive energy between DNA strands. Outside of the precipitation domain (400 mM spermine), DNA chains form a soluble network of thin fibers (4-6 nm in diameter) that let us reconsider the state of these DNA chains in excess of spermine. We also designed experiments to visualize condensates formed 6-60 sec after mixing Lambda DNA with 0.05 mM spermine, under identical buffer conditions. Among multiple original shapes (not found after 16 min), the presence of stretched and helical elongated fibers seen only 9sec after addition of spermine let us propose that DNA chains are immediately stretched upon addition of spermine, relax into helical structures and finally form small toroids (containing in some cases less than one Lambda chain) that further grow and aggregate. We also analyzed the dimensions and structural details of the complete collection of toroids, and reveal the existence of geometric constraints that remain to be clarified. Since it was only exceptionally possible to prevent the aggregation of DNA in dilute solution, we used another approach to observe the collapse of single DNA chains. We handled a population of T5 viruses containing a fraction of their initial genome (12-54 kbp long). The Na-DNA chain, initially confined in the small volume of the capsid (80nm in diameter) is collapsed by the addition of spermine. Compared to the first set of experiments, we explored a higher DNA concentration range (0.45 mM Phosphates in the whole sample) and the spermine concentration was varied from 0.05 to 0.5 mM (which corresponds to much lower +/- charge ratios). Experiments are thus performed close to the precipitation line, in the coexistence region, between the region where all chains are in a coil conformation, and the region where all chains are collapsed into toroids. We describe the existence of intermediate states between the coil and the toroidal globule that were not reported yet. In these “hairy toroids”, part of the DNA chain is condensed in the toroid and the other part stays uncondensed outside of it. The interhelical spacing was also measured; it is larger in these partly-condensed toroids than in the fully organized toroids formed at higher spermine concentration.These two series of experiments show the interest of cryoEM to analyze the structural polymorphism and local structure of spermine-DNA aggregates. We also demonstrated how the confinement interferes with DNA condensation and the interest to investigate such effects that are important in the biological context.

Apesar da aparente acessibilidade, a pele é bem protegida contra a absorção de materiais estranhos. Esta função barreira é exercida principalmente pelo estrato córneo. Dessa forma, a administração cutânea de fármacos precisa transpor esta barreira para atingir uma concentração efetiva. Uma maneira de tornar o tratamento eficaz é o uso de injeções, forma de administração muito invasiva e desconfortável para o paciente. A administração tópica é uma forma simples e confortável para a administração cutânea de fármacos. As doenças cutâneas, em geral, são doenças estigmatizadas. Assim, o desenvolvimento de uma formulação capaz de transpor as barreiras impostas a esta via de administração e um novo tratamento para estas doenças complexas, com componentes genéticos, devem ser estudados. O siRNA veiculado com nanocarreadores foi aplicado a esta via de administração. O nanocarreador possibilita um maior tempo de permanência na superfície da pele devido às propriedades adesivas, além de proteger o siRNA contra a degradação. O siRNA visa o bloqueio específico da expressão de genes, por isso é capaz de agir em diferentes caminhos de uma doença. A maior limitação para o uso de siRNA é a incapacidade de difundir-se através das membranas celulares devido a carga negativa, o que gera uma repulsão eletrostática da membrana celular. Portanto, a complexação com um carreador torna a liberação do siRNA no interior celular mais efetiva. É amplamente aceito que o desenvolvimento de um sistema de liberação eficiente é um dos principais obstáculos para transformar siRNA em terapêutica. Consequentemente, o objetivo deste trabalho foi o desenvolvimento farmacotécnico de um nanocarreador capaz de liberar o siRNA de maneira efetiva na aplicação tópica cutânea, respeitando as peculiaridades desta via. As formulações de monoleína (MO), polietilenoimina (PEI) e diferentes concentrações de vitamina E TPGS, contendo ou não ácido oléico (AO), foram caracterizadas como fases líquido cristalinas com tamanho de partícula e potencial zeta desejado, mostrando-se eficazes em complexar o siRNA. As nanodispersões desenvolvidas foram efetivas na complexação do siRNA, na estabilização deste ácido nucléico frente a degradação enzimática, e na efetiva internalização celular in vitro em células de fibroblastos de camundongos L929. As nanodispersões contendo maior quantidade de vitamina E TPGS, ou contendo o AO foram as formulações que promoveram um maior aumento da penetração cutânea de siRNA in vitro em peles de modelo animal. Logo, os resultados obtidos permitiram concluir que as formulações desenvolvidas são sistemas de liberação nanotecnológicos, contendo cristais líquidos, promissores para a administração tópica de siRNA, no tratamento de patologias cutâneas na terapia gênica / Despite its apparent easy accessibility, the skin is, in fact, well protected against the absorption of foreing materials. The barrier function is imposed, mainly, by the stratum corneum. Thus, the cutaneous administration of drugs needs to overcome this barrier to reach an effective concentration. One way to make an effective treatment is the use of injections, mode of administration very invasive and uncomfortable for the patient. Topical administration is simple and comfortable for cutaneous administration of drugs. Skin diseases, in general, are stigmatized diseases. Therefore, the development of a formulation capable of overcoming the barriers of this route of administration and a new treatment for these complex diseases, with the genetic components, shall be studied. The siRNA in nanocarriers has been applied to this route of administration. The nanocarrier allows siRNA to stay longer on the skin surface because of its adhesive properties, while also protects siRNA against degradation. The siRNA is directed for producing gene-specific inhibition, so it is able to act in different ways to the same disease. The most critical factor limiting the use of siRNA as therapeutics is delivering siRNA to its intracellular target site due to their negative charge, which cause an electrostatic repulsion of the cell membrane. Therefore, complexation with a carrier makes the release of siRNA inside the cells more effective. It is widely accepted that the development of an efficient delivery system is a major obstacle to change siRNA into therapeutics. Consequently, the objective of this work was the pharmacotechnical development of a nanocarrier capable of releasing the siRNA effectively in topical skin, respecting the peculiarities of this pathway. The formulations of monoolein (MO), polyethylenimine (PEI) and different concentrations of vitamin E TPGS, with or without oleic acid (OA), were characterized as liquid crystalline phases with particles size and zeta potential desired, proving to be effective in complexing the siRNA. The nanodispersions developed were effective for the complexation of siRNA, for the stabilization of nucleic acid against enzymatic degradation, and for the effective in vitro cellular uptake into cells of mouse fibroblast L929. The nanodispersions containing higher amounts of vitamin E TPGS, or containing OA, have been the formulations which promoted a greater increase in skin penetration of siRNA in vitro in animal model skin. Therefore, the results obtained allowed one to conclude that the formulations developed are delivery systems based on nanotechnology, with liquid crystalline phase, promising for topical administration of siRNA, for the treatment of cutaneous diseases in gene therapy

Resumo: A zidovudina (AZT) é o fármaco antiretroviral mais utilizado no tratamento da AIDS, porém possui baixa biodisponibilidade, pois sofre intenso metabolismo hepático. Para alcançar concentrações plasmáticas efetivas são requeridas doses altas e freqüentes, as quais podem chegar a níveis tóxicos. A via nasal tem sido proposta como uma rota alternativa para administração de fármacos que sofrem metabolismo pré-sistêmico, pois favorece a absorção direta para circulação sanguínea; porém, ela possui mecanismos de depuração mucociliar, os quais podem eliminar rapidamente a formulação da cavidade nasal. Sistemas de liberação mucoadesivos podem promover o contato prolongado entre a formulação e os sítios de absorção da cavidade nasal, retardando a depuração mucociliar. Alguns sistemas estabilizados por tensoativos, capazes de formar diferentes estruturas liotrópicas líquido cristalinas, têm sido propostos para aumentar o tempo de contato de formulações com as mucosas. Estes sistemas, ao entrar em contato com os fluidos aquosos que compõem o muco, se ordenam em cristais líquidos (CLs), formando uma matriz de liberação do fármaco. O objetivo deste trabalho foi desenvolver sistemas capazes de formar CLs, como potenciais sistemas mucoadesivos para administração intranasal do AZT. A caracterização por microscopia de luz polarizada e SAXS mostrou que microemulsões (MEs) formadas por AC205/ácido oléico/água formam CLs com a adição tanto de água como de fluído nasal simulado (FNS). As MEs foram capazes de incorporar cerca de 50 mg.g-1 de AZT. A mucoadesão foi avaliada por ensaios de reologia oscilatória, em que a adição de fase aquosa aumentou os módulos elásticos dos sistemas, e pela medida da força para remover as formulações a partir de um disco de mucina, obtidas através de um analisador de textura. Ensaios de liberação in vitro em... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Zidovudine (AZT) is the most widely used drug in AIDS treatment; however, AZT shows low oral bioavailability, since it suffers extensive hepatic metabolism. In order to maintain therapeutic levels, large doses have to be given frequently, which may reach toxic levels. The nasal route has been exploited as an alternative route of drugs that suffer first pass metabolism, as it ensures the direct drug absorption to blood circulation; however, the nasal route has mucociliary clearance mechanisms which can quickly remove the formulation of the nasal cavity. Mucoadhesive drug delivery systems can improve residence time of formulation in the nasal cavity absorption sites, delaying mucociliary clearance. Some surfactants systems which are able to form different liotropic liquid crystalline structures have been explored as a strategy to increase formulation residence time on the mucosa. When these systems are placed in physiologic aqueous environment, they can form a drug delivery matrix. The aim of this work was to develop systems capable of forming CLs as potential intranasal AZT mucoadhesive systems. The polarized light microscopy and SAXS characterization showed that microemulsions (MEs) composed by AC205/oleic acid/water form CLs with the addition of either water or simulated nasal fluid (FNS). The MEs were able to incorporate about 50 mg.g-1 of AZT. The mucoadhesion was evaluated both by oscillatory rheology, in which aqueous phase addition increased the elastic modulus of the systems, and by measurement of the necessary force to remove the formulations from mucin disc, obtained through texture analyzer. In vitro Franz' Cell drug release assay showed, according to the Weibull model, that phase transition sustained AZT release. These results suggest that the systems in hand have great potential for nasal AZT administration. / Orientador: Maria Palmira Daflon Gremião / Coorientador: Victor Hugo Vitorino Sarmento / Banca: Maria Palmira Daflon Gremião / Banca: Marcela Longhi / Banca: Rosângela Itri / Mestre

O desenvolvimento de formulações cosméticas multifuncionais tem sido cada vez mais crescente na indústria cosmética. A elaboração de uma formulação que contém diferentes ativos com propósitos diferentes podendo agir sinergicamente, muitas vezes, confere resultados cosméticos eficazes e até mesmo terapêuticos ao usuário. Nesta pesquisa foram desenvolvidas emulsões cosméticas apresentando formação de fases líquido cristalinas à base de manteiga de cupuaçu (Theobroma grandiflorum), manteiga de cacau (Theobroma cacau), o agente hidratante Hidraskin? e aditivos estabilizantes tais como álcool cetoestearílico, lanolina polietoxilada e carbômero. O desenvolvimento das formulações deu-se pelo método de inversão de fases. Estas foram caracterizadas quanto à formação de mesofases líquido cristalinas e avaliadas quanto à estabilidade física. Foram selecionadas quatro emulsões, duas com manteiga de cupuaçu (com e sem Hidraskin?) e duas com manteiga de cacau (com e sem Hidraskin?) que apresentaram maior estabilidade física e formação de fases líquido-cristalinas mais abundante. A adição do ativo hidratante (Hidraskin?) não alterou as características morfológicas das fases líquido cristalinas, identificadas como fase lamelar e a adição de lanolina polietoxilada como aditivo estabilizante promoveu maior estabilidade fisico-química das emulsões, principalmente quando submetidas à temperaturas em torno de 40ºC também sem alteração das fases líquido cristalinas. / Development of multifunctional cosmetic formulations has been growing each day in cosmetic industry. Elaboration of formulations, which presents many actives with different purposes acting together, many times give good and therapeutic results to customers. In this research cosmetic emulsions with liquid crystals were developed based on cupuaçu (Theobroma grandiflorum) or (Theobroma cacau) butter, Hidraskin? as a moisturizer active and actives for stabilization such as cetostearil alcohol, poliethoxilated lanolin and carbomer. Formulations were prepared by the Emulsion Phase Inversion method and characterized on the liquid crystal assembly and evaluated for physical stability. Four emulsions were chosen, two formulated with cupuaçu butter (one with and the other without Hidraskin?) and two with cocoa butter (one with and the other without Hidraskin?), which presented the highest amount of liquid crystals. Addition of Hidraskin? did not change the morphological aspects of liquid crystals, identified as lamellas. Also addition of polyethoxilatted lanolin increased the physical stability of all emulsions prepared, especially when they were submitted to increase of temperature (40ºC).

A terapia gênica por interferência de RNA (RNAi) trata-se de um processo de silenciamento pós-transcricional capaz de suprimir a expressão de um determinado gene. A RNAi é uma proposta terapêutica promissora para o tratamento de muitas doenças severas que ainda não possuem cura ou terapias bem definidas. Porém, é necessário o desenvolvimento de sistemas de liberação clinicamente adequados, seguros e eficazes para se viabilizar essa nova terapêutica, uma vez que obstáculos na administração e distribuição in vivo comprometem o uso clínico dos siRNAs (small interfering RNA). Paralelamente, a liberação tópica de siRNAs surge como uma alternativa promissora para o tratamento de patologias cutâneas. Neste contexto, a presente pesquisa teve como objetivo o desenvolvimento de um sistema de liberação baseado em nanotecnologia para a liberação tópica de siRNAs, visando introduzir a terapia gênica como nova abordagem para o tratamento de patologias cutâneas. Como sistema de liberação, foram desenvolvidas nanodispersões líquido-cristalinas aquosas, compostas por monoleína (MO), um lipídeo polar biocompatível, associadas ou não com ácido oléico (AO). Foram incorporados a esses sistemas os adjuvantes catiônicos polietilenoimina (PEI) e oleilamina (OAM) para obtenção das nanodispersões. Dentre as nanodispersões aquosas desenvolvidas, foram escolhidas as preparações com as menores concentrações de adjuvantes catiônicos, a saber: MO e OAM a 0,4%, MO e PEI a 0,4%, MO, AO e OAM a 2,5% e MO, AO e PEI a 1,0%. Estas formulações apresentaram: reduzido tamanho médio das partículas, baixa polidispersividade, valores de potencial zeta positivos (característica interessante para interação com as moléculas de siRNA que apresentam carga negativa), baixa citotoxicidade in vitro e foram capazes de complexar o siRNA na concentração final de 2,5 ?M. A análise de difração de raios X caracterizou a fase líquido-cristalina desses sistemas como hexagonal, exceto a nanodispersão MO e PEI a 0,4% que foi caracterizada como uma mistura de fase hexagonal e cúbica. As nanodispersões obtidas foram capazes de aumentar a penetração cutânea de siRNA in vitro. Face aos resultados obtidos, podemos concluir que as formulações desenvolvidas são sistemas de liberação de base nanotecnológica promissores para administração tópica de siRNA para o tratamento de patologias cutâneas na terapia gênica. / Gene therapy by RNA interference (RNAi) is a post-transcriptional silencing process that can suppress the expression of a particular gene. The RNAi is a promising therapeutic approach for the treatment of many severe diseases that have no cure or well-defined treatments. However, the development of clinically appropriate, safe and effective delivery systems is necessary to enable this new therapy, since obstacles in the in vivo administration and distribution committed the clinical use of siRNAs (small interfering RNA). In addition, the topical delivery of siRNAs appears as a promising alternative for the treatment of cutaneous pathologies. In this context, this research aimed to develop a delivery system based on Nanotechnology for the topical delivery of siRNAs, aiming to introduce gene therapy as a new approach for the treatment of skin disorders. As a delivery system, liquid-crystalline nanodispersions, composed by monoolein (MO), a polar biocompatible lipid, associated or not with oleic acid (OA) were developed. The cationic adjuvants polyethylenimine (PEI) and oleylamine (OAM) were incorporated into these systems to obtain the nanodispersions. Among the aqueous nanodispersions developed, preparations with lower concentration of cationic adjuvant were chosen, these consisting of: MO and OAM at 0.4%, MO and PEI at 0.4%, MO, OA and OAM at 2.5% and MO, OA and PEI at 1.0%. These formulations presented: reduced average particle size, low polydispersity, positive values of zeta potential (an interesting feature for interacting with the siRNA molecules that have a negative charge), low cytotoxicity in vitro and they were able to complex the siRNA at a final concentration of 2.5 ?M. The X-ray diffraction analysis characterized the liquid crystalline phase of these systems as hexagonal, except the nanodispersion MO and PEI at 0.4% which was characterized as a mixture of cubic and hexagonal phases. The nanodispersions obtained were able to increase the skin penetration of siRNA in vitro. With the results obtained, we can conclude that the formulations developed are delivery systems based on nanotechnology, promising for topical administration of siRNA for the treatment of cutaneous diseases in gene therapy.

O poli (sulfeto de p-fenileno) - (PPS) é um termoplástico de engenharia de elevada resistência térmica e química com uma crescente importância industrial. já que pode ser utilizado na fabricação de filamentos, filmes e moldados por injeção. Este polímero tem mostrado grande habilidade de ser dopado para a produção de um material eletricamente condutivo (σ = 10 S/cm, na dopagem com AsF5), porém sua estrutura morfológica é bastante destruída quando dopado com estes fortes agentes oxidantes. Neste trabalho. o PPS foi dopado com agentes dopantes mais fracos como o tetracianoquinodimetano (TCNQ), para que não ocorresse a destruição da morfologia e assim, a sua influência pudesse ser melhor estudada. Diversas morfologias de PPS com TCNQ foram produzidas variando as condições de processamento. Foi analisado o efeito da adição de um segundo polímero, um cristal líquido termotrópico (TLCP), nas características microscópicas e na orientação do PPS e, conseqüentemente, no efeito destes parâmetros sobre a condutividade final das misturas destes dois polímeros. Foi verificado um efeito negativo do TLCP sobre a condutividade do PPS, já que o primeiro teve sua condutividade diminuída com a dopagem. Além disso, o LCP só induziu orientação no PPS a concentrações acima de 80% de TLCP na blenda. Verificou-se para o PPS que não é a orientação, mas sim a cristalinidade, o fator importante na sua condutividade final. O mecanismo de condução apresentado pelo PPS e blendas tanto puro quanto dopados com TCNQ, é o de salto de portadores entre níveis de impurezas (\'\'hopping\"). / Poly (p-phenylene sulphide) (PPS) is an engineering thermoplastic, with high thermal and chemical resistance, and. with a growing industrial importance, due to its easy processability in the form of films, fiaments and injection molded articles. It also can be chemically doped and. therefore be a conductive polymer (σ = 10 S/cm, by doping with AsF5); however, when doping with strong oxidative agents, its morphology is destroyed. In this work, PPS was doped with a weaker doping agent, tetracyanoquinodimethane (TCNQ) in order to preserve its initial morphology and to study its influence on the final conductivity values. Different PPS/TCNQ morphologies were produced by varying the processing conditions. It was also studied the influence the blending of PPS/TCNQ with a liquid crystalline polymer (LCP) has on the microstructure and orientation of the PPS and on its conductivity. It was observed that this addition has a negative effect on the PPS conductivity. Orientation of the PPS by the LCP was only achieved at 80% wt LCP. It was concluded that, for the PPS, the major influence on its electrical conductivity is given by its amount of crystallinity, not by its orientation. The conduction mechanism of the PPS and its blends with the LCP doped with TCNQ is a hopping mechanism.

Neste trabalho, várias técnicas foram utilizadas para estudar mesofases constituídas por laurato de potássio, cloreto de decilamônio, água e sulfato de brucina. Este sistema foi eleito por apresentar a fase colestérica biaxial, cuja caracterização continua se constituindo um problema digno de investigação. Foram efetuadas medidas reológicas sobre sistemas nemáticos e colestéricos, em diferentes composições e condições. Os valores das viscosidades aparentes foram calculados e o comportamento caracterizado. Para os estudos de RMN, introduziu-se nas amostras uma molécula probe, o racêmico dl alanina, procurando-se verificar se havia diferença na interação dos enantiômeros d e I com a matriz colestérica. Os espectros foram obtidos com variação de temperatura. Compararam-se os dados de variação do parâmetro de ordem, obtidos dos acoplamentos diretos, com a semi largura da linha larga dos espectros de próton, para obter informações sobre o comportamento da alanina e das micelas colestéricas. Todas as fases foram acompanhadas por estudos de microscopia sob luz polarizada, técnica simples e eficiente utilizada para caracterizar tipos de fases de cristais líquidos. / In this work, several techniques were used to study mesophases constituted by potassium laurate, decylammonium chloride, water and brucine sulfate. This system was chosen for presenting a cholesteric biaxial phase, whose characterization continues to be worthy of investigation. Rheological measurements were made on nematic and cholesteric systems, in different compositions and situations. The values of apparent viscosity were calculated and the behaviour was characterized. For the RMN studies, a probe moIecule, the racemic form of dl alanine, was introduced in the sampIes trying to verify difference between in interaction of the enantiomers d and I with the main cholesteric matrix. The spectra were obtained with temperature variation. It was compared the data of variation of the order parameter, obtained from the direct couplings, with the half width of the wide line of the proton spectra, to obtain information about the behaviour of the alanine and of the cholesteric micelles. All the phases were accompanied by microscopy studies under polarized light, simple and efficient technique to characterize types of liquid crystal phases.

Three-dimensional (3D) displays project 3D images that give 3D perceptions and mimic real-world objects. Among the rich varieties of 3D displays, multiview displays take advantage of light’s various degrees of freedom and provide some of the 3D perceptions by projecting 2D subsampling of a 3D object. More 2D subsampling is required to project images with smoother parallax and more realistic sensation. As an additional degree of freedom with theoretically unlimited state space, orbital angular momentum (OAM) modes may be an alternative to the conventional multiview approaches and potentially project more images. This research involves exploring the possibility of encoding/decoding off-axis points in 2D images with OAM modes, development of the optical system, and design and development of a multiview colour display architecture. The first part of the research is exploring encoding/decoding off-axis points with OAM modes. Conventionally OAM modes are used to encode/decode the on-axis information only. Analysis of on-axis OAM beams referenced to off-axis points suggests representation of off-axis displacements as a set of expanded OAM components. At current stage off-axis points within an effective coding area are possible to be encoded/decoded with chosen OAM modes for multiplexing. Experimentally a 2D image is encoded/decoded with an OAM modes. When the encoding/decoding OAM modes match, the image is reconstructed. On the other hand, a dark region with zero intensity is shown. The dark region suggests the effective coding area for multiplexing. The final part of the research develops a multiview colour display. Based on understandings of off-axis representation of a set of different OAM components and experimental test of the optical system, three 1 mm monochromatic images are encoded, multiplexed and projected. Having studied wavelength effects on OAM coding, the initial architecture is updated to a scalable colour display consisting of four wavelengths.

Um dos veículos de grande utilização para ativos cosméticos são os sistemas emulsionados, que são constituídos de duas fases líquidas imiscíveis e agentes tensoativos, obtidos por diferentes metodologias de emulsificação. Devido à sua excelente capacidade de solubilizar compostos hidrofílicos e lipofílicos a importância comercial e científica das emulsões entre os diversos sistemas coloidais é inquestionável. O delineamento desses sistemas exige conhecimento dos principais fatores que influenciam sua formação, propriedades físico-químicas e, consequentemente, estabilidade e performance. O uso de óleos vegetais na iensdpúésctrieias vfaergmeataciês uotliecaa gien ocsoassm, péotidcae mtoosrn cai-taser oc baadrau (vDeizp temryaxis a laattraa tVivoog. .)D, neanttirvea daos Bioma Cerrado e cujas sementes contêm um óleo com alto grau de insaturação cseonntdeor qousa nátcididaodse sg rsaixgonsif icoalenitceos teo cloinfoelreóiicso e ofsit oceosntesrtóituisi,n treesp rmesaejonrtaitánrdioos i,m aploérmta ndtee fonte de agentes capazes de atuar no combate aos processos oxidativos diretamente ligados ao envelhecimento e às doenças degenerativas. O objetivo duteilsiztaa npdeos cqoumisao ffaosi eo o ldeeossean ovo ólvleimoe enxtotr aeíd oc adraasc tesreimzaeçnãtoe s ddee sbisatreum (aDs. adliastpae).r sAoss etapas envolvidas no desenvolvimento dos sistemas estão listadas a seguir: 1) Obtenção e caracterização da matéria prima vegetal (óleo); 2) Desenvolvimento das fboarrmu u(lDaç. õaelas:t ae);s teusdtou ddoo dEaq culialísbsrieo dHeid treónfisloo aLtiivpoósfi;l oc o(EnHstLru) çrãeoq udeor iddoia gpraarma ao tóelrenoá rdioe; coabrtaidcotes;r iz3a) çEãnos afíiosisc oin-q vuiítmroi:c aA vea liaeçsãtuod doas s dme uedsatnaçbailsid easdteru tduoras iss mistiecrmoascsó pdiicsapse rdsooss sistemas dispersos mediante simulação da evaporação do produto final após aplicação na pele; estudo do efeito dos sistemas dispersos na dinâmica da membrana de estrato córneo por Ressonância Paramagnética Eletrônica. Os resultados encontrados sugerem que os sistemas dispersos desenvolvidos são potenciais alternativas na liberação de fármacos ou ativos cosméticos ou ainda, podem ser considerados produtos finais de interesse para recuperação da camada lipídica da pele. O uso de metodologia de emulsificação com baixo gasto de energia (emulsificação por inversão de fases) permitiu a obtenção de dois sistemas emulsionados estáveis: um com presença de fase gel lamelar e outro com partículas de tamanho nanométrico. O estudo das propriedades físico-químicas das formulações mostrou inexistência de quaisquer sinais de instabilidade das formulações durante o período de armazenamento em condições de temperatura específicas. A utilização de espectroscopia de Ressonância Paramagnética Eletrônica (RPE) forneceu informações acerca da dinâmica molecular do estrato córneo frente a aplicação do óleo e das formulações, demonstrando o potencial dos mesmos em atuar como veículos de fármacos ou ativos cosméticos visto que os espectros obtidos revelaram diferenças significativas na fluidez dos lipídios do estrato córneo, principal barreira na permeação cutânea. / The commercial and scientific importance of emulsions among the colloidal systems is unquestionable. These systems consist of two immiscible phases that could be obtained by different methods of emulsification. Emulsions have excellent ability to solubilize hydrophilic and lipophilic compounds, so, are widely used as vehicules for drugs and cosmetics. The rational design of these systems requires studies of the main factors that influence their formation, physicochemical properties and, consequently, stability and performance. Nowadays, the use of vegetable oils in the pharmaceutical and cosmetic industries becomes attractive. Dipteryx alata Vog is an oleaginous plant specie native to Cerrado. The seeds of this specie contain an oil with a high degree of unsaturation (oleic and linoleic fatty acids are the major constituents) and significant amounts of tocopherols and phytosterols, representing an important source of agents capable of acting to combat the oxidative processes directly related to aging and degenerative diseases. The objective of this research was the development and characterization of dispersed systems using the oil extracted from the seeds of D. alata (baru). The steps involved in the development of the systems were: 1) Preparation and characterization of vegetable raw material (oil); 2) Development of formulations: Study of Hydrophilic and Lipophilic Balance (HLB) required for baru oil; study of surfactant class; Construction of the ternary diagram; physicochemical characterization and stability studies of dispersed systems obtained; 3) In vitro assays: Evaluation of microscopic structural change of dispersed systems by simulating the evaporation of the final product after application on the skin; study of the effect of dispersed systems in the dynamics of the stratum corneum membrane by Electron Paramagnetic Resonance. The use of low energy emulsification method allowed the development of two stable emulsions: one with presence of lamellar gel phase and another with nanometric size particles. The study of physicochemical properties of the formulations showed absence of any signs of instability of the formulations during the storage period. The use of Electron Paramagnetic Resonance (EPR) spectroscopy provide information about the molecular dynamics of the stratum corneum facing the implementation of oil and formulations, demonstrating the potential of them to act as drug or cosmetic active vehicles