Incorporating nanotechnology into polymers has tremendous potential to improve the functionality and performance of polymer materials for use in a wide range of biomedical and industrial applications. This research uses lyotropic liquid crystals (LLCs) to control polymer structure on the nanometer scale in order to improve material properties. The overall goal of this research is to establish fundamental methods of synthesizing polymers with controlled nanostructured architectures in order to understand and utilize useful property relationships that result from the organized polymer morphologies. This work aims to establish a fundamental understanding of the reaction conditions needed to control polymer nanostructure and determine the benefits of organized polymer network structures on mechanical and transport properties. The synthesis of nanostructured polymers for improved material performance has utilized LLCs and photopolymerization kinetics to direct polymer structure. Self-assembled LLC phases provide a useful template that may be used as a photopolymerization platform to control polymer morphology on the nanometer size scale. Photopolymerization kinetics were used as a tool to examine the thermodynamics and phase structure evolution that occurs during the polymerization reaction. Additionally, several methods were developed to control polymer morphology and prevent loss of LLC order that can occur during polymerization. LLCs were also used to generate nanocomposite polymers with two distinct polymer networks to impart improvements in material properties. Other useful property relationships including increases in mechanical integrity, greater diffusive transport, and larger water uptake were established in this research. Finally, the LLC templating process was applied to solve performance problems associated with stimuli-sensitive polymer materials. Dramatic improvements in the response rate, dynamic range, and mechanical properties were achieved using LLCs and photopolymerization to control polymer nanostructure. This work has established fundamental tools that can be used to understand and control the evolution of polymer structure during the polymerization reaction in order to improve polymer properties. Ultimately, the enhanced properties generated by the nanostructured polymer network can be used to improve the functionality of polymers.

The successful applications of nanoparticles require the ability to tune their properties by controlling size and shape at the nanoscale. In metal nanomaterial research, the optical properties have been of interest especially because of the applications to medical diagnostics and nanooptics. It is important to prepare nanoparticles of well-defined shape and size for properly characterizing the optical properties. We describe improved seed mediated synthesis of gold nanorods (GNRs) producing a high yield of NRs with low polydispersity and few byproducts. The efficient separation of GNRs from mixture of shapes is achieved by understanding the hydrodynamics of nanoparticles undergoing centrifugation. The optical properties of resulting refined GNRs are compared to predictions of existing theories, and the main parameters affecting them are discussed. GNRs with well defined aspect ratios are introduced into a polyvinyl alcohol matrix by means of solution-casting techniques. The film is drawn to induce the uniaxial alignment of GNRs to be used as color polarizing filters. We prepare GNR polarizing filter with different peak positions ranging from visible to near infra red by using different aspect ratio of NRs. To utilize GNRs to make nanoscale devices, spatial organization is required. We characterize the self-assembly of GNRs observed on a TEM grid. The drying process is accompanied by complex hydrodynamic and thermodynamic events, which create rich range of patterns observed. Being anisotropic in shape, the rods can form liquid crystal (LC) assemblies above a certain concentration. We observed LC phase of GNRs by resorting to an evaporation of aqueous NR solution. The convective flow caused by the solvent evaporation carries NRs from the bulk solution to solid-liquid-air interface, which makes the solution locally very concentrated driving the phase transition of NRs. We calculate the order parameter from various assemblies observed, and compare the observed phase behavior to the one expected on the basis of theory.

Conjugated polymers are semiconducting materials that are currently being researched for numerous applications from chemical and biological sensors to electronic devices, including photovoltaics and transistors. Much of the novel research on conjugated polymers is performed in academic settings, where scientists are working to prepare conjugated polymers for commercially viable applications. By offering numerous advantages, inherent in macromolecular materials, conjugated polymers may hold the key to cheap and environmentally friendly manufacturing of future electronic devices. Mechanical flexibility, and solvent-based coating processes are two commonly cited advantages. Transitions in the backbone conformation of polythiophenes (PT) in organic solvents have been widely observed to influence thin-film morphology. However, conformational transitions of water-soluble PT derivatives, with respect to their intramolecular versus intermolecular origin, remain largely obscure. Here, conformational transitions of a water- soluble polythiophene in aqueous ionic surfactants are investigated by means of Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), polarizing optical microscopy (POM), ultraviolet-visible (UV-Vis) absorption and fluorescence spectroscopy, and various X-ray scattering techniques. As-prepared complexes exist as stable hydrogels. Upon dilution, a significant time-dependent chromism occurs spontaneously. A coil-to-rod conformational transition is identified in this mechanism and verified using small-angle x-ray scattering (SAXS). Study into the corresponding kinetics demonstrates an inverse first-order rate law. It is found that the conformational transition is thermally reversible and concentration-independent. The critical transition temperature is largely dependent on the surfactant formulation. A theoretical model is presented to explain this new phenomenon and the mechanisms behind its influence on the optoelectronic and solid-state morphological properties. A relationship between the dilute-solution processing with surfactants and the final properties of the system is substantiated.

The twin screw extrusion technique has been explored to produce lyotropic liquid crystal coated powder precursor by exploiting Pluronic F127 thermoreversible gelation property to get powder precursor without granular aggregates or with less compacted granular aggregates. The highly soluble chlorpheniramine maleate loaded in Pluronic F127 solution coated MCC particles prepared through twin screw extrusion was examined to produce the cubic phase (gel) for the development of controlled release formulation and for coating of very fine particles which cannot be achieved by traditional bead coaters. Controlled release formulations are beneficial in reducing the frequency of administration of highly soluble drugs having short half life and also to address the problem of polypharmacy in old age patients by reduction of dosage frequency. An unusual refrigerated temperature (5 C) profile for twin screw extrusion was selected based on the complex viscoelastic flow behaviour of Pluronic F127 solution which was found to be highly temperature sensitive. The Pluronic F127 solution was found to be Newtonian in flow and less viscoelastic at low temperature, such that low temperature (5 C) conditions were found to be suitable for mixing and coating the MCC particles to avoid compacted aggregates. At higher temperatures (35-40 C) Pluronic F127 solution exhibited shear thinning and prominent viscoelasticity, properties which were exploited to force CPM containing Pluronic F127 solution to stick over the MCC surface. This was achieved by elevating the temperature of the last zone of the extrusion barrel. It was found that to avoid compacted aggregates the MCC must be five times the weight of the Pluronic F127 solution and processed at a screw speed of 400 RPM or above at refrigerated temperature. Processing was not found to be smooth at ambient temperature with frictional heat and high torque generation due to significant compaction of coated particles which can be attributed to the elastic behaviour of Pluronic F127 solution at temperatures between ambient to typical body temperature. PLM images confirmed the cubic phase formation (gel) by Pluronic F127 coating which was found to be thick with maximum Pluronic F127 concentration (25%). SEM images showed smoothing of surface topography, and stretching and elongation of MCC fibres after extrusion which is indicative of coating through extrusion processing. Plastic deformation was observed for the lower Pluronic F127 concentration and higher MCC proportions. There was a significant decrease in work done for cohesion by the powder flow analyser observed in the batches with more aggregates compared with batches with least aggregates. A regression analysis study on factorial design batches was conducted to investigate the significant independent variables and their impact on dependent variables for example % torque, geometric mean diameter and work done for cohesion, and to quantitatively evaluate them. From the regression analysis data it was found that the coefficient of determination for all three dependent variables was in the range of 55-62%. The pharmaceutical performance of the prepared coated LLC precursor through twin screw extrusion in terms of controlled release was found to be very disappointing. Almost 100% chlorpheniramine maleate was released within 10-15mins, defined as providing burst release. The MDSC method was developed within this work to detect Pluronic F127 solution cubic phase formation. The MDSC method was developed to consider sample size, effect of heating and cooling, sample heat capacity, and the parameters for highest sensitivity which can be followed by sample accurately without the phase lag to produce accurate repeatable results.

Misturas liotrópicas de laurato de potássio (KL)/ sulfato de potássio (K2SO4)/ álcool (CnH2n+1OH)/ água (H2O) apresentam fases no estado líquido cristalino nemático. Essas fases nemáticas foram colesterizadas através da adicão do agente quiral brucina à mistura. Este estudo foi realizado mantendo as frações molares de todos os constituintes das misturas constantes e variando o comprimento da mol´ecula de álcool entre oito (1-octanol) e dezesseis (1-hexadecanol) átomos de carbono. Três fases colestéricas foram identificadas: ChD (colestérica discótica), ChB (colestérica biaxial) e ChC (colestérica calamítica). O diagrama de fases foi construído em função do número de átomos de carbono n na molécula do álcool. As transições entre as fases colestéricas foram investigadas por medições das birrenfringências ópticas usando microscopia óptica de luz polarizada. As misturas com 9 n 12 apresentaram as três fases colestéricas como função da temperatura e uma região de crossover entre as fases ChD e ChB, com comprimento de correlação a temperatura nula maior do que as dimensões micelares típicas. Misturas com n=8 e n=13 apresentaram transição de fase de primeira ordem entre as fases ChD e ChC, sem a presença da fase ChB intermediária a elas. As misturas com n=14, 15 e 16 apresentaram somente a fase ChC como função da temperatura. Os resultados foram interpretados como consequência da nanosegregação das moléculas de álcool nas micelas com relação às moléculas do anfifílico principal. / Lyotropic mixtures of potassium laurate (KL)/ potassium sulphate (K2SO4)/ alcohol (CnH2n+1OH)/ water (H2O) present nematic liquid crystal phases. These nematic phases were cholesterized by the doping of the mixtures with the chiral agent brucine. This study was conducted by keeping constant the molar fractions of all constituents of the mixtures and varying the length of the alcohol molecule between eight (1-octanol) and sixteen (1-hexadecanol) carbon atoms. Three cholesteric phases were identified: ChD (discotic cholesteric), ChB (biaxial cholesteric), and ChC (calamitic cholesteric). The phase diagram was constructed as a function of the number of carbon atoms n in the alcohol molecule. The cholesteric-cholesteric phase transitions were investigated by measurements of the optical birefringences via polarized light microscopy. The mixtures with 9 n 12 presented the three cholesteric phases as a function of temperature and a crossover between the ChD and ChB phases, with a bare correlation length larger than the typical micellar dimensions. Mixtures with n =8 and n =13 exhibited first order phase transitions among the ChD and the ChC phases, without the presence of the intermediate ChB phase. Mixtures with n =14, 15 and 16 showed only the ChC phase as a function of temperature. These results were interpreted as a consequence of the nanosegregation of the alcohol molecules in the micelles with respect to the main amphiphilic molecules.

Com uma mistura de laurato de potássio, decanol e agua, determina-se a birrefringência induzida, na fase isotrópica, por gradientes de velocidade, no interior da amostra. Os movimentos são provocados através de vibrações periódicas nas paredes do porta amostras. O tempo de relaxação, da estrutura de rolos, e determinado experimental e teoricamente. É determinado, também, o parâmetro T AST (temperatura em torno da temperatura de transição), ate então desconhecido, em cristais líquidos liotrópicos. Como uma provável aplicação pratica, e proposta a confecção de dispositivos sensíveis a vibrações. / With a mixture of the Potassium Laurate, Decanol and water, the birefringence induced by gradient of the velocity, in the isotropic phase, is determinated. The movement are provocated through periodic vibrations of the superface of the sample holder. The relaxation time of the roll structure is determinated experimental an theorically. The temperature T* (temperature around the transition temperature), well-known in thermotropic liquid crystals, is determinated in liotropic liquid crystals. The confection of the sensible vibration dispositive is proposed.

Com uma mistura de laurato de potássio, decanol e agua, determina-se a birrefringência induzida, na fase isotrópica, por gradientes de velocidade, no interior da amostra. Os movimentos são provocados através de vibrações periódicas nas paredes do porta amostras. O tempo de relaxação, da estrutura de rolos, e determinado experimental e teoricamente. É determinado, também, o parâmetro T AST (temperatura em torno da temperatura de transição), ate então desconhecido, em cristais líquidos liotrópicos. Como uma provável aplicação pratica, e proposta a confecção de dispositivos sensíveis a vibrações. / With a mixture of the Potassium Laurate, Decanol and water, the birefringence induced by gradient of the velocity, in the isotropic phase, is determinated. The movement are provocated through periodic vibrations of the superface of the sample holder. The relaxation time of the roll structure is determinated experimental an theorically. The temperature T* (temperature around the transition temperature), well-known in thermotropic liquid crystals, is determinated in liotropic liquid crystals. The confection of the sensible vibration dispositive is proposed.

Misturas liotrópicas de laurato de potássio (KL)/ sulfato de potássio (K2SO4)/ álcool (CnH2n+1OH)/ água (H2O) apresentam fases no estado líquido cristalino nemático. Essas fases nemáticas foram colesterizadas através da adicão do agente quiral brucina à mistura. Este estudo foi realizado mantendo as frações molares de todos os constituintes das misturas constantes e variando o comprimento da mol´ecula de álcool entre oito (1-octanol) e dezesseis (1-hexadecanol) átomos de carbono. Três fases colestéricas foram identificadas: ChD (colestérica discótica), ChB (colestérica biaxial) e ChC (colestérica calamítica). O diagrama de fases foi construído em função do número de átomos de carbono n na molécula do álcool. As transições entre as fases colestéricas foram investigadas por medições das birrenfringências ópticas usando microscopia óptica de luz polarizada. As misturas com 9 n 12 apresentaram as três fases colestéricas como função da temperatura e uma região de crossover entre as fases ChD e ChB, com comprimento de correlação a temperatura nula maior do que as dimensões micelares típicas. Misturas com n=8 e n=13 apresentaram transição de fase de primeira ordem entre as fases ChD e ChC, sem a presença da fase ChB intermediária a elas. As misturas com n=14, 15 e 16 apresentaram somente a fase ChC como função da temperatura. Os resultados foram interpretados como consequência da nanosegregação das moléculas de álcool nas micelas com relação às moléculas do anfifílico principal. / Lyotropic mixtures of potassium laurate (KL)/ potassium sulphate (K2SO4)/ alcohol (CnH2n+1OH)/ water (H2O) present nematic liquid crystal phases. These nematic phases were cholesterized by the doping of the mixtures with the chiral agent brucine. This study was conducted by keeping constant the molar fractions of all constituents of the mixtures and varying the length of the alcohol molecule between eight (1-octanol) and sixteen (1-hexadecanol) carbon atoms. Three cholesteric phases were identified: ChD (discotic cholesteric), ChB (biaxial cholesteric), and ChC (calamitic cholesteric). The phase diagram was constructed as a function of the number of carbon atoms n in the alcohol molecule. The cholesteric-cholesteric phase transitions were investigated by measurements of the optical birefringences via polarized light microscopy. The mixtures with 9 n 12 presented the three cholesteric phases as a function of temperature and a crossover between the ChD and ChB phases, with a bare correlation length larger than the typical micellar dimensions. Mixtures with n =8 and n =13 exhibited first order phase transitions among the ChD and the ChC phases, without the presence of the intermediate ChB phase. Mixtures with n =14, 15 and 16 showed only the ChC phase as a function of temperature. These results were interpreted as a consequence of the nanosegregation of the alcohol molecules in the micelles with respect to the main amphiphilic molecules.

Dans ce travail nous étudions l’élaboration, la caractérisation et les applications de différents matériaux poreux. L’étude est organisée en trois parties majeures: la synthèse de zéolithes micro/mesoporeux et leur application potentielle dans l’industrie pétrochimique, l’étude théorique de mécanismes réactionnels sur des zeolites microporeux, et le design de métaux mesoporeux avec une chiralité intrinsèque de leur surface interne. Ces matériaux poreux montrent des propriétés excellentes, notamment pour des applications potentielles en catalyse et comme interfaces chirales. / In the present work, the elaboration, characterisation and applications of differentporous materials have been studied. Porous materials are divided into three categoriesdepending on the porous cavity size, namely microporous materials (pore diameter < 2nm), mesoporous materials (2 nm < pore diameter < 50 nm) and macroporous materials(pore diameter > 50 nm). The thesis work is organized in three major parts: the synthesisof hierarchical micro/mesoporous zeolites and their potential application for thepetrochemical industry, the theoretical study of reaction mechanisms on microporouszeolite and the design of mesoporous metals with intrinsic chirality at their inner surface.The hierarchical micro/mesoporous zeolite, composed of microporous andmesoporous features, has been prepared using carbon-silica (C/SiO2) composites derivedfrom a pyrolysis of hydrocarbon gas on silica gel. Our findings demonstrate that not onlythe presence of a high surface area and porosity, but also an improved efficiency of thesematerials for many petrochemical processes such as n-butene isomerization, nhexadecanecatalytic cracking and hydrocracking. The novel synthetic method is expectedto be generalized for other types of zeolites, and is considered to be a promising methodfor creating hierarchical micro/mesoporous zeolites for potential catalytic applications,especially in the petrochemical industry.In addition to the study of practical catalytic aspects, a theoretical approach hasbeen used to investigate potential reaction mechanisms such as the selective isomerizationof 1-butene into isobutene. More specifically, the monomolecular skeletal isomerizationof 1-butene into isobutene on H-FER zeolite was theoretically studied by using theONIOM approach. This process was found to involve the transformation of adsorbed 1-butene through 2-butoxide, isobutoxide, and tert-butyl cation intermediates. The ratedeterminingstep is the conversion of isobutoxide into isobutene, in which the reactionhas to proceed through the primary isobutyl cation transition state. The shape selectivitydue to the “nano-confinement” effect of the zeolite framework strongly affects theadsorption, the stability of alkoxide species and carbenium ion, as well as the skeletalisomerization mechanism of 1-butene.Moreover, the microporous and mesoporous zeolite, the generation of chiralmesoporous metal and its enantioselective recognition properties have been studied.Molecular imprinting (MI) is a major approach for generating materials withenantioselective properties. In this work, a chiral imprinted mesoporous platinum hasbeen obtained by the electrochemical reduction of platinum salts in the simultaneouspresence of a lyotropic liquid crystal phase and chiral template molecules. The resultingmaterials exhibit not only a dramatic increase in active surface area due to theirmesoporosity, but also a significant discrimination between two enantiomers of a chiralprobe, confirmed by both electrochemical and enantioselective adsorption experiments.Most importantly the porous platinum retains its chiral character even after removal of thechiral template molecule. Our findings could lead to the development of new materials,which are of potential interest for applications in areas such as chiral synthesis, sensors,separation, purification and drug development.

Neste trabalho, estudamos a dinâmica de formação e dispersão de agregados de látex quando inseridos num cristal líquido liotrópico. Esse cristal líquido é um sistema ternário composto de laurato de potássio, cloreto de decilamônia e água; e apresenta fases nemáticas uniaxiais calamítica e discótica (NC e ND, respectivamente) e biaxial (NB). As partículas de látex possuem diâmetro de 100nm e partículas com diferentes tipos de recobrimentos foram testadas. Observamos que nas fases NC e NB há formação de aglomerados de partículas, porém na transição para a fase ND as partículas se dispersam no meio. Verificamos que esse processo de aglomeração e dissociação das partículas está relacionado com a transição de fase NB - ND e foi observado em dois sistemas hospedeiros por resfriamento e por aquecimento. No intervalo de temperatura que corresponde à fase nemática biaxial para o cristal líquido puro, observa-se que há um aumento na dimensão dos aglomerados, que se tornam anemométrico e orientados na direção de orientação do meio. Dois diagramas de fases foram construídos, variando-se a concentração de partículas dispersas no meio, e a composição relativa de surfactantes do sistema hospedeiro. Experimentos de espalhamento de raios X indicam que a distância média entre as micelas que formam o meio hospedeiro não é alterado pela inserção de partículas no cristal líquido e permanece a mesma em todas as fases nemáticas. Foram também realizados estudos de reologia que mostram que a viscosidade do sistema é alterada pela presença das partículas de látex. Os fenômenos observados são interpretados levando-se em conta as flutuações de orientação das micelas nas diferentes fases nemáticas. / In this work, we studied the dynamics of agglomeration and dissociation of latex particles when inserted into a lyotropic liquid crystal. This liquid crystal is a ternary system formed by potassium laurate, decilamonium chloride and water, presenting uniaxial calamitic and discotic nematic phases (NC e ND, respectively) and a biaxial nematic phase NB. The latex particles have diameter of 100 nm and particles with different surface treatments were tested. It was observed that in the NC e NB phases the latex particles form agglomerates, however in the transition to the ND phase, the particles disperse in the medium. In the temperature domain of the biaxial nematic phase the agglomerates increase in size, become anisometric and oriented along parallel to the orientation of the medium. Two phase diagrams were built by varying the particle concentration dispersed in the liquid crystal and by varying the relative composition of surfactants of the liquid crystal. X rays diffusion experiments have shown that the average distance between the micelles in the host medium are not affected by the presence of the latex particles and remain the same in all nematic phases. Rheology studies were also performed and it was found that the viscosity of the system is affected by the presence of the particles. The observed phenomenon are interpreted taking into account the orientational fluctuations of miceles in the different nematic phases.