Anisotropic molecules confined on a spherical or other curved surface can display coupled positional and orientational orderings, which make possible applications in physics, chemistry, biology, and material science. Therefore, controlling the order of such system has attracted much attention recently. Several distinct conformations of rod-like or chain-like molecules confined on a spherical surface have been predicted, including states such as tennis-ball, rectangle, and cut-and-rotate splay. These conformations have four +1/2 defects and are suggested to dominate over the splay conformation that has two +1 defects. For the purpose of investigating the conformations of 2-fold anisotropic molecules confined on the spherical surface, the author of this thesis utilizes the Onsager model to study the system of rigid rods and conducts Monte Carlo simulations on the bead-bond model to research the system of semiflexible polymer chains. At low surface coverage density, no particular pattern of the molecules would form. However, coupled positional and orientational ordering begins to emerge beyond a transition density. On the basis of the numerical solutions of the Onsager model of rigid rods, the splay conformation is shown to be the only stable state. On the other hand, Monte Carlo simulations on a polymer system indicate that the ordered state always accompanies the tennis-ball symmetry. With comparison to the continuous isotropic-nematic transition of a fluid of hard rods embedded in a flat two-dimensional space, the disorder-order transition for both the system of rigid rods and the system of polymer chains confined on the spherical surface has first-order phase-transition characteristics.

Significant potential for plastic hypodermic needles exists as an alternative to current steel needles, especially in developing regions where proper needle disposal is problematic. Needle reuse causes tens of millions of hepatitis and HIV infections each year. Plastic needles may reduce reusability and increase the opportunities for safe disposal. Plastic needles also will help with medical waste disposal, by removing metal from the waste stream, hence making it easier to reprocess needles and syringes into useful products such as car battery cases and pails. This thesis presents the design and testing of one type of plastic hypodermic needle. The buckling and penetration characteristics of the needles were modeled and analyzed analytically and by finite element analyses. Experimental penetration tests using steel and plastic hypodermic needles and skin mimics, specifically polyurethane film and pig skin, were performed to determine penetration and friction forces. Penetration tests also were conducted to determine whether the needles could penetrate butyl rubber stoppers that cover drug vials. Various lubricants, including silicone oil and a medical grade silicone dispersion, were also used. In addition, the needles underwent perpendicular bending tests and cannula stiffness tests. Finally, fluid flow tests were conducted to determine fluid flow rates through the needles. Experimental results were compared to each other and finite element analyses and discussed. The research presented in this thesis demonstrates that with further design modifications, plastic needles may become suitable for mass replacement of steel needles, thus helping to eradicate the many health and environmental risks brought upon by steel needles.

In this study, the film-cooling effectiveness in different regions of gas turbine blades was investigated with various film hole/slot configurations and mainstream flow conditions. The study consisted of three parts: 1) turbine blade span film-cooling, 2) turbine platform film-cooling, and 3) blade tip film-cooling. Pressure sensitive paint (PSP) technique was used to get the conduction-free film-cooling effectiveness distribution. Film-cooling effectiveness is assessed in terms of cooling hole geometry, blowing ratio, freestream turbulence, and coolant-to-mainstream density ratio. Blade span film-cooling test shows that the compound angle shaped holes offer better film effectiveness than the axial shaped holes. Greater coolant-to-mainstream density ratio prevents coolant to lift-off. Higher freestream turbulence causes effectiveness to drop everywhere except in the region downstream of suction side. Results are also correlated with momentum flux, compound shaped hole has the greatest optimum momentum flux ratio, and then followed by axial shaped hole, compound cylindrical hole, and axial cylindrical hole. For platform purge flow cooling, the stator-rotor gap was simulated by a typical labyrinth-like seal. Two different film-cooling hole geometries, three blowing ratios and density ratios, and two freestream turbulence are examined. Results showed that the shaped holes present higher film-cooling effectiveness and wider film coverage than the cylindrical holes, particularly at higher blowing ratios. Moreover, the platform film-cooling effectiveness increases with density ratio but decreases with turbulence intensity. The blade tip study was performed in a blow-down flow loop. Results show that a blowing ratio of 2.0 is found to give best results on the tip floor. Lift-off of the coolant jet can be observed for the holes closer to the leading edge as blowing ratio increases from 1.5 to 2.0. A stator vane suction side heat transfer study was conducted in a partial annular cascade. The heat transfer coefficients were measured by using the transient liquid crystal technique. At X/L=0.15, a low heat transfer region where transition occurs. The heat transfer coefficients increase toward the trailing edge as flow accelerates; a spanwise variation can be found at neat tip and hub portions due to passage and horseshoe vortices.

Dissertation (Ph.D.)--Auburn University, / Abstract. Vita. Includes bibliographic references.

Thesis (M.S.)--Auburn University, 2008. / Abstract. Vita. Includes bibliographical references (p. 86-99).

Cette thèse décrit dans un premier temps la synthèse entièrement régiosélective de phtalocyanines tétra-(endo-alcoxy)-fonctionnalisées puis la formation de leurs complexes avec des ions métalliques. Dans un second temps sont étudiées leurs propriétés magnétiques, l'induction de mésophases colonnaires dans des gammes de températures convenables et avec des tailles modérées de substituants, ainsi que leur utilisation dans des diodes organiques. L'approche synthétique à suivre est la cyclo-tétramérisation de 3-(2-alkylalcoxy)-phtalonitriles suivie de la coordination d'un ion métallique. La symétrisation des chaînes aliphatiques dans le précurseur 3-alcoxy-phtalonitrile, en allant de 2 butyloctyl à 2-pentylheptyl, maintient la régiosélectivité et le mésomorphisme, tandis que les courtes chaînes 2-butylhexyl mènent à la formation d'un mélange de phtalocyanines régioisomères et à une plus grande tentance à la crystallisation. La combinaison de températures de clarification raisonnables avec un empilement colonnaire à température ambiante et avec une proportion assez importante de centres conjurés au sein de la masse moléculaire rend les deux premières séries de matériaux, c'est-à-dire MPc(OCH2CHBuHex)4, and MPc(OCH2CHPent2)4, potentiellement utiles comme transporteurs de charges uniformément orientables dans des dispositifs électroniques organiques. Nous démontrons que ces matériaux phtalocyanines tétra-α-alcoxy-substitués, représentés par H2Pc(OCH2CHBuHex)4, NiPc(OCH2CHBuHex)4 et CuPc(OCH2CHBuHex)4, mènent à des performances originales des dispositifs quand ils sont utilisés comme couche active organique dans des structures simples de diode ITO/PEDOT :PSS/PC/Al. Un redressement prononcé du courant est obtenu dans des diodes malgré l’alignement planaire prépondérant des colonnes dans les couches. Le ligand Pc tétra-α-alcoxy-substitué très soluble donne des molécules-aimants mononucléaires originales par coordination avec MnIII et DyIII. Remarquablement, l’isomère de symétrie C4h du complexe sandwich octa-alcoxy se forme sélectivement grâce aux subsistants encombrants sur les deux cycles Pc. / This thesis describes the fully regioselective synthesis of symmetric all-endo tetra-alkoxy-functionalized phthalocyanines and their metal ion complexes accompanied by induction of columnar mesophases in convenient temperature ranges at moderate substituent sizes, as well as their use in organic diodes and the study of their magnetic properties. The synthetic approach to follow is lithium-induced macrocyclization of 3-(2-alkylalkoxy)-phthalonitriles prior to transition meatl ion insertion. Symmetrization of the aliphatic chains in the 3-alkoxy-phthalonitrile precursor from 2-butylocytyl to 2-pentylheptyl maintains both the regioisomeric mixture during the cyclo-tetramerization and to a somewhat greater tendency to crystallization. The combination of attainable clearing temperatures with room temperature columnar stacking and with a relatively high content of conjugated core within the molecular mass makes the first two series of materials, i.e. MPc(OCH2CHBuHex)4, and MPc(OCH2CHPent2)4, potentially useful as uniformly orientable charge transposters in organic electronic devices. We establish that these tetra-α-alkoxy substituted phthalocyanine materials, as exemplified with H2Pc(OCH2CHBuHex)4, NiPc(OCH2CHBuHex)4 and CuPc(OCH2CHBuHex)4, lead to original device performances when applied as an active organic layer in simple ITO/PEDOT:PSS/PC/Al diode structures. A pronounced current rectification of the diodes is obtained despite the preponderantly planar alignment of the columns in the films. The highly soluble tetra-α-alkoxy-substituted Pc ligand, when combined with MnIII and DyIII, gives rise to original mononuclear single molecule magnets. Remarkably, the C4h-symmetric isomer of the octa-alkoxy double decker complex is formed selectively due of presence of the bulky substituents on both Pc rings.

Made available in DSpace on 2014-06-11T19:29:48Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-02-18Bitstream added on 2014-06-13T20:39:34Z : No. of bitstreams: 1 carvalho_fc_me_arafcf.pdf: 1754741 bytes, checksum: 4a8a4b7a238f2102f29af99ef9ae762d (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / 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... / 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.

Neste trabalho foi feito o estudo do efeito de orientação de moléculas de cristal líquido (5CB) em superfícies recobertas com fotopolímeros. Estudamos o processo de alinhamento fotoinduzido às moléculas de cristal líquido, de forma a caracterizar a intensidade de energia de ancoramento em função da energia de luz incidente e da concentração de cromóforos nos fotopolímeros. Foi realizado um estudo do efeito de competição entre duas direções distintas induzidas por fotoalinhamento, através da gravação de microtexturas periódicas. Neste trabalho, foi utilizado um modelo teórico para explicar como se dá a transição orientacional conforme se muda o período da textura periódica gravada. Foi feito também a gravação de grades de relevo nesses materiais, utilizando luz polarizada com alta potência incidente através da técnica de interferência de luz. O objetivo principal deste trabalho seria uma tentativa de se realizar o efeito de competição de alinhamento entre os processos fotoinduzidos: um efeito de fotoalinhamento, levando em conta a orientação das cadeias poliméricas, e outro de relevo, levando em conta a deformação da superfície tratada. Um resultado obtido foi a impossibilidade de se realizar este estudo, pois as intensidades de energia de ancoramento induzidas envolvidas diferem entre si de um fator de duas ordens de grandeza, mostrando que a direção de fotoalinhamento sempre acaba prevalecendo. Para contornar este problema, foi estudada a competição de fotoalinhamento com a técnica de rubbing, tendo em vista que as intensidades de energia de ancoramento estudadas eram compatíveis entre si. / In this work we performed a study of the orientacional effect of the liquid crystals molecules in substrates coated with azopolymers films. We studied the photoalignment induced to liquid crystals molecules to determine the behavior of the magnitude of anchoring energy as a function of incident energy and azodyes concentration in the polymer. Then we performed a competition study of the competition of photoalignment effect by recording a microtexture pattern on the azopolymer surface, with two directions of alignment. In this work, we also introduced a theoretical model to explain the orientacional transitions observed as we changed the period of the patterned microtexture. Another technique utilized was the Surface Relief Grating recording, by using polarized light with enough power and creating an interference pattern in the azopolymer surface, we were able to create a topological structure in the surface. The main objective of this work was supposed to investigate the competition between these two photoinduced effects, when one is caused by a photoalignment of the polymer chains, and the other is due to topological issues. We concluded that it was not possible to have competition between these two effects, mainly because the magnitude of the anchoring energy induced by SRG was found to be a hundred times smaller than the photoinduced one. As an alternative to this approach, we studied, then, the competition between the rubbing process and the photoalignment effect, as the magnitude of these two effects was found to be compatible.

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.

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.