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Los sistemas poliméricos multifásicos han recibido una considerable atención en las últimas décadas. En particular, los copolímeros bloque presentan un marcado interés no sólo desde el punto de vista académico sino también desde el tecnológico, porque permiten obtener nuevos materiales con propiedades específicas cuya principal característica es la presencia de dos o más fases en estado sólido en la escala de los nanómetros. En la mayoría de los casos, los copolímeros bloque están constituidos por segmentos termodinámicamente incompatibles que se encuentran unidos químicamente en una sola molécula. Algunos ejemplos son: combinación de bloques hidrofóbicos con hidrofílicos, para aplicaciones como espesan-tes, absorbentes o compatibilizantes para la industria cosmé-tica. Por otra parte los copolímeros bloque presentan proce-sos de separación en microfases o formación de estructuras auto-ensambladas que los convierte en excelentes candidatos para aplicaciones en nanotecnología y electrónica. En esta Tesis se sintetizaron y caracterizaron copolímeros bloque en base siloxano, con estructura definida, empleando polimeri-zación aniónica en alto vacío. En particular se sintetizaron copolímeros de estireno-dimetilsiloxano, butadieno-dimetilsi-loxano, metil-metacrilato-dimetilsiloxano y estireno--caprolac-tona con estructuras y composiciones definidas con el objeti-vo de encontrar condiciones de reacción adecuadas para la síntesis de estos materiales. Los copolímeros obtenidos fueron caracterizados química y térmicamente empleando numerosas técnicas analíticas tales como Cromatografía por Exclusión de Tamaños (SEC); Resonancia Magnética Nuclear de hidrógeno (1H-NMR), Espectroscopia Infrarroja con Transformada de Fourier (FTIR), Difracción de Rayos X de bajo ángulo (SAXS), Calorimetría Diferencial de Barrido (DSC), Análisis Termogra-vimétrico (TGA) y Microscopía Óptica de luz Polarizada (POM) entre otras. Todos los copolímeros mostraron tener un control adecuado de las masas molares, presentando bajos índices de polidispersión para un amplio rango de masas molares y compo-siciones, además los resultados permitieron corroborar la formación de nanoestrucuras tanto en masa como en solución. Los resultados informados en esta Tesis constituyen un apor-te de interés respecto a la síntesis y caracterización de copo-límeros de estructura molecular definida basados en siloxano y ε-caprolactona. En tal sentido, los resultados obtenidos per-miten ampliar y profundizar la información existente en cuanto a la morfología en masa y en solución de copolímeros bloque basados en siloxano, y a las características térmicas de copo-límeros con un bloque semicristalino de poli(ε-caprolactona). / In the last decades, multiphase polymer systems have received widespread attention. In particular, block copolymers are of both academic and technological interest because they can generate new materials with enhanced or specific properties. These materials are usually characterized by the presence of two or more polymeric phases in the solid state at the nanometer scale. In all cases, block copolymers are made of thermodynamically incompatible segments chemically bonded. Some examples are: combination of hydrophobic and hydrophilic blocks for applications such as thickeners, absor-bents or compatibilizers for cosmetics industry. Moreover, block copolymers exhibit microphase separation processes given self-assembled structures which are excellent candida-tes for nanotechnology and electronic applications. This Doc-toral Thesis reports the results for well-defined synthesis and characterization of block copolymers based on siloxane using high vacuum anionic polymerization techniques. Particularly, several synthesis reactions were performed during the course of the experimental research and styrene-dimethylsiloxane, butadiene-dimethylsiloxane, methylmetacrylate-dimethylsilo-xane, and styrene--caprolactone copolymers were obtained with well-defined molar mass and narrow polydispersity. Obtained block copolymers were chemically and thermally characterized by Size Exclusion Chromatography (SEC), Nuclear Magnetic Resonance (1H-NMR), Fourier Transform Infrared Spectroscopy (FTIR), Small Angle X-ray Scattering (SAXS), Differential Scanning Calorimetry (DSC), and Polarized Optical Microscopy (POM), among others. All the copolymers showed a well-defined molar mass and narrow polydispersity for a wide range of molar masses and compositions, which allows the study of nanostructures obtained both in mass and in solution. Reported results are an interesting contribution regarding the synthesis and characterization of well-defined copolymers based on siloxane and ε-caprolactone. In these sense, the obtained information extend and to deepen the existing information on both mass and solution morphology of siloxane based block copolymers and thermal characteristics of semicrystalline poly(ε-caprolactona).

A primeira etapa do projeto foi realizar testes para usinagem controlada e otimizada de vidro ótico de borosilicato (BK7) por laser de femtossegundos. Parâmetros como energia, pulsos sobrepostos e a variação da posição focal foram investigados para controle da taxa de remoção do material e extensão da cratera ablacionada. Especial atenção foi dada à condição física e topográfica da superfície resultante da usinagem para torná-la menos rugosa e evitar a retenção de reagentes que possam contaminar e alterar as reações pretendidas. Microcanais, microválvulas, microbombas, misturadores, microrreatores, aquecedores e outros componentes foram desenvolvidos para compor sistemas microfluídicos. Os microcanais construídos sobre a superfície de vidro BK7 vedados por uma lâmina de polidimetilsiloxano (PDMS) são a base dos sistemas microfluídicos. O controle de fluxo de reagentes é feito por miniválvulas pneumáticas controladas por um microcontrolador Arduino através de uma plataforma Labview. Este trabalho mostra os componentes desenvolvidos e dois sistemas microfluídicos criados. O primeiro contém um circuito capaz de replicar ensaios imunoenzimáticos (ELISA) com um custo muito menor de insumos. O segundo é um sistema para a produção de nanocristais fluorescentes de NaYF4 especialmente utilizados como marcadores em imagens de sistemas biológicos. / The first stage of the project was to perform tests for controlled and optimized machining of borosilicate optical glass (BK7) by femtosecond laser. Parameters such as energy, number of overlapped pulses, and the focal position variation were investigated for a better extraction of material. Microchannels, microvalves, micropumps, mixers, reactors, heaters and other components were developed to compose applied microfluidic systems. Microchannels built on the surface of BK7 glass sealed by a polydimethylsiloxane (PDMS) sheet form the basis of the microfluidic circuits. The reagents flow control is done by pneumatic mini-valves controlled by an Arduino microcontroller through a Labview platform. This work shows the components developed and two microfluidic systems created. The first contains a microfluidic circuit capable of replicating enzyme-linked immunosorbent assays (ELISA) with a much lower cost of materials. The second has a microfluidic circuit for the production of NaYF4 fluorescent nanocrystals specially used as markers in images of biologic systems.

A monitorização terapêutica tem sido descrita como valioso recurso clínico, na individualização do regime de dosagem, de acordo com a concentração do fármaco e/ou de seus produtos de biotransformação, em amostras de plasma ou soro, coletadas com base no contexto clínico e nos princípios da farmacocinética. Em razão da complexidade dos fluidos biológicos e da baixa concentração dos fármacos nestas matrizes, a etapa de preparo de amostra, extração, pré-concentração dos analitos e eliminação dos interferentes, têm sido requerida para o desenvolvimento de métodos cromatográficos com alta sensibilidade e seletividade analítica. A extração sortiva em barra de agitação (SBSE), recente técnica de preparo de amostra, baseia-se no equilíbrio de sorção do analito entre as fases: extratora (polidimetilsiloxano) e amostra aquosa. A fase extratora PDMS é a única disponível no mercado, o que tem limitado a sensibilidade e a seletividade analítica da técnica SBSE. O uso de polipirrol (PPY) como fase extratora está relacionado às diferentes interações de seus grupos funcionais (hidrofóbica, -, com o grupo funcional polar, troca iônica, ácido-básica, dipolo-dipolo e dipolo induzido-dipolo.) com os analitos. Neste trabalho, uma nova fase extratora SBSE, com o revestimento misto PDMS/PPY foi avaliada para análises de antidepressivos em amostras de plasma, por cromatografia líquida de alta eficiência. A otimização das variáveis SBSE: tempo e temperatura de extração, tempo de dessorção e pH da matriz biológica, baseada no equilíbrio de sorção dos analitos entre as fases: polimérica (PDMS/PPY) e fluido biológico, permitiu a determinação dos analitos em concentrações plasmáticas que contemplam o intervalo terapêutico. A presença de estrutura porosa (PPY) e não porosa (PDMS) na superfície polimérica da barra extratora SBSE-PDMS/PPY foi confirmada através de análises por Microscopia Eletrônica de Varredura (MEV). De acordo, com os resultados obtidos nas análises de MEV e nas análises (individuais e simultâneas) de amostras de plasma enriquecidas com os analitos, os mecanismos de retenção dos fármacos junto à superfície PDMS/PPY ocorreram através dos processos de adsorção (PPY) e absorção (PDMS). A validação analítica foi realizada segundo as normas da Agência Nacional de Vigilância Sanitária. O método padronizado apresentou linearidade no intervalo de concentração plasmática que variou dos limites de quantificação a 500 ng mL-1, coeficientes de determinação maiores que 0,994, precisão inter ensaios com coeficientes de variação menores que 15% e exatidão de 96% a 106%. Os valores de limites de quantificação obtidos são congruentes com a menor concentração plasmática do intervalo terapêutico preconizado. O método SBSE-PDMS/PPY padronizado e validado foi utilizado para determinações dos antidepressivos, sertralina, duloxetina e fluoxetina em amostras de plasma de pacientes, em terapia com estes fármacos. Desta forma, o método SBSE-PDMS/PPY poderá ser empregado para fins de monitorização terapêutica. / Therapeutic drug monitoring has been described a valuable clinical resource for the customization of the dosage regimen, in accordance with the drug concentration and/or its biotransformation products, in of plasma or serum samples, collected on the basis of clinical context and pharmacokinetics principles. Due the complexity of biological fluids and the low concentration of the drug in these matrices, an stage of sample preparation, extraction, pre-concentration of the analytes and elimination of the interferents has been required for the development of chromatographic methods with high sensitivity and analytical selectivity. Stir bar sorptive extraction (SBSE), a recent sample preparation technique, is based on the sorption equilibrium of the analytes between the polydimethylsiloxane (PDMS) and aqueous phases. PDMS is the only commercially available extraction phase (SBSE), which has limited the analytical sensitivity and the selectivity of the SBSE technique. The use of polypyrrole (PPY) as extraction phase is related to the different interactions of its functional groups (- interactions, polar groups interactions, acid-base, dipole-dipole, dipole-induced-dipole) and the analytes. In this work, a new SBSE extraction phase, with a PDMS/PPY coating was evaluated for the analysis of antidepressants in plasma samples by High Performance Liquid Chromatography. The optimization of the SBSE variables extraction time and temperature, dessorption time and pH of the biological matrix based on the sorption equilibrium of the analytes between the polymeric (PDMS/PPY) and biological fluid phases, allowed determination of the analytes in plasmatic concentrations that correspond to the therapeutic interval. The presence of a porous structure (PPY) as well as no none, porous (PDMS), on the polymeric surface of SBSE-PDMS/PPY was confirmed by Scanning Electron Microscopy (SEM) analyses. In agreement with the results obtained by SEM analyses and individual and simultaneous analyses of the plasma samples spiked with the analytes, the mechanisms of drugs retention on the surface of PDMS/PPY occur through adsorption (PPY) and absorption (PDMS). Analytical validation was carried through according to the norms of the National Agency of Sanitary Vigilance. The standardized method presented linearity in the plasmatic interval concentrations that varied from the limits of quantification to 500 ng mL-1, the determination coefficients were higher than 0.994, inter precision assays with coefficients of variation lower than 15%, and accuracy from 96% to 106%. The quantification value limits were in agreement with the lowest plasmatic concentration of the established therapeutical interval. The standardized and validated SBSE-PDMS/PPY method was used for determination of sertraline, duloxetine and fluoxetine in plasma patient samples under therapy with these drugs. Thus, the SBSE-PDMS/PPY method could be used for therapeutic drug monitoring.

L' Imagerie médicale par Résonance Magnétique (IRM) constitue un outil puissant pour le diagnostic et le suivi de pathologies dans le cadre des modèles développés sur petit animal en neurosciences. Cette application requiert une haute résolution spatiale et un Rapport Signal à Bruit(RSB) élevé, rendus possibles par l’utilisation d’un haut champ magnétique (7 T) et d’une antenne miniature à forte sensibilité, implantée à proximité de la zone d’intérêt. Le design monolithique de l’antenne, appelé Résonateur Multi-tours à Lignes de Transmission (RMLT), permet la miniaturisation en dessous du centimètre et sa réalisation par les technologies de microfabrication en salle blanche.Afin de réduire l’aspect invasif de l’implantation, l’antenne a été réalisée sur support souple :FEP Téflon® ou PDMS. Pour résoudre les problèmes d’adhérence liés à ces matériaux polymères, des traitements plasmas spécifiques ont été mis en œuvre pour le FEP Téflon® tandis qu’un procédé de transfert de motifs dédié au PDMS a été élaboré. Outre la fiabilité mécanique, l’épaisseur du revêtement PDMS assurant la bio compatibilité de l’antenne a été optimisée pour limiter le couplage diélectrique avec les tissus et ainsi conserver des caractéristiques électromagnétiques appropriées à l’IRM à 7 T lorsque l’antenne est implantée. L’ensemble de ces travaux a permis la réalisation des premières images du cerveau du rat acquises in vivo avec une micro-antenne souple implantée. Ces images ont démontré un RSB amélioré d’un facteur 5, comparées à celles acquises avec une antenne commerciale quadrature. D’autres applications et perspectives dans le domaine biomédical sont ouvertes par ces travaux comme des capteurs pour la détermination des propriétés diélectriques des tissus, et des microbobines et des capteurs de pression intégrés dans les canaux microfluidiques. / Magnetic Resonance Imaging (MRI) is a powerful tool for the diagnosis and the monitoring of diseases in the frame of research models developed on small animal in neurosciences. This application requires a high spatial resolution and a high Signal to Noise Ratio (SNR) using a high magnetic field (7 T) and a highly sensitive miniaturized coil, implanted near the interest area. The coilmonolithic design, called Multi-turn Transmission Lines Resonator (MTLR), allows theminiaturization below the centimeter scale and the clean-room technology. To reduce the invasive aspect of implantation, the coil was fabricated on a flexible substrate: FEP Teflon® or PDMS. To overcome adhesion issues related to these polymers, specific plasma treatments were applied to FEPTeflon® while a transfer process dedicated to PDMS was developed. Besides mechanical reliability, the thickness of the PDMS coating ensuring the coil biocompatibility, was optimized to limit the dielectric coupling with tissues and thus to keep suitable electromagnetic characteristics for 7 T MRI when the coil is implanted. This work allowed the achievement of the first images of the rat brain acquired in vivo using an implanted soft coil. These images have shown a 5-fold enhanced SNRcompared with the ones acquired using a commercial quadrature coil. Other applications in the biomedical field are open by this work: sensors for the dielectric characterization of tissues, integrated microcoils and pressure sensors in microfluidic channels.

Le potentiel du polydiméthylsiloxane (PDMS), élastomère transparent et déformable réversiblement en temps réel, est mis en avant dans ce travail comme substrat fonctionnel dans le domaine de l’optique et du mouillage. Dans une première partie, nous avons développé des surfaces de PDMS ridées à l’aide d’instabilités de flambage, de longueurs d’onde (λ) et d’amplitude (A) variables et contrôlées, puis nous avons organisé sélectivement des nano-objets sur cette texturation de surface avec afin d’en moduler la physico-chimie. Dans une seconde partie, la génération, in situ, de nano-plots/nanoparticules d’or et d’argent à la surface de verre et de PDMS a été étudiée et caractérisée d’un point de vue optique. / The polydimethylsiloxane (PDMS), a transparent and stretchable elastomer, is put forward in this work as a functional substrate in the field of optics and wetting. In the first part, we have developed wrinkled PDMS surfaces via controlled buckling instabilities. We were able to tune both the wavelength (λ) and the amplitude (A) of the structuration on a large length scale. We have then selectively organized some nanoparticles the textured surfaces in order to modulate its physical-chemistry. In the second part, in situ generation of gold and silver nanoparticles/plots has been developed and studied both on glass PDMS surfaces and subsequently characterized optically.

A primeira etapa do projeto foi realizar testes para usinagem controlada e otimizada de vidro ótico de borosilicato (BK7) por laser de femtossegundos. Parâmetros como energia, pulsos sobrepostos e a variação da posição focal foram investigados para controle da taxa de remoção do material e extensão da cratera ablacionada. Especial atenção foi dada à condição física e topográfica da superfície resultante da usinagem para torná-la menos rugosa e evitar a retenção de reagentes que possam contaminar e alterar as reações pretendidas. Microcanais, microválvulas, microbombas, misturadores, microrreatores, aquecedores e outros componentes foram desenvolvidos para compor sistemas microfluídicos. Os microcanais construídos sobre a superfície de vidro BK7 vedados por uma lâmina de polidimetilsiloxano (PDMS) são a base dos sistemas microfluídicos. O controle de fluxo de reagentes é feito por miniválvulas pneumáticas controladas por um microcontrolador Arduino através de uma plataforma Labview. Este trabalho mostra os componentes desenvolvidos e dois sistemas microfluídicos criados. O primeiro contém um circuito capaz de replicar ensaios imunoenzimáticos (ELISA) com um custo muito menor de insumos. O segundo é um sistema para a produção de nanocristais fluorescentes de NaYF4 especialmente utilizados como marcadores em imagens de sistemas biológicos. / The first stage of the project was to perform tests for controlled and optimized machining of borosilicate optical glass (BK7) by femtosecond laser. Parameters such as energy, number of overlapped pulses, and the focal position variation were investigated for a better extraction of material. Microchannels, microvalves, micropumps, mixers, reactors, heaters and other components were developed to compose applied microfluidic systems. Microchannels built on the surface of BK7 glass sealed by a polydimethylsiloxane (PDMS) sheet form the basis of the microfluidic circuits. The reagents flow control is done by pneumatic mini-valves controlled by an Arduino microcontroller through a Labview platform. This work shows the components developed and two microfluidic systems created. The first contains a microfluidic circuit capable of replicating enzyme-linked immunosorbent assays (ELISA) with a much lower cost of materials. The second has a microfluidic circuit for the production of NaYF4 fluorescent nanocrystals specially used as markers in images of biologic systems.

Thesis (MSc.) (Physics) --University of Limpopo, 2007 / Molecular dynamics simulations have been carried out in order to examine the mechanism of diffusion of molecules in amorphous polymer matrix. PDMS model was folded in to a periodic cell, generated by rotational isomeric state (RIS) method at a prescribed temperature and density. Molecular dynamics was used to study transport properties of cyclic PDMS oligomers (hexa-methylcyclotrisiloxane (D3), octa-methylcyclotetrasiloxane (D4) and deca-methylcyclopentasiloxane (D5) using Dreiding and COMPASS force fields. Diffusion coefficients were calculated from the Einstein relation. Only D3 penetrant reached the long time limit from which the Einstein relation is satisfied. Analysis of displacement versus time for all the penetrants in PDMS matrix indicates that the penetrant motion is characterized by relatively long periods interspersed with fairly long and small jumps. Transport of solvent molecules occurs by jumps between individual sections of free volume (cavity/hole) through temporarily open channels. / The National Research Foundation (NRF) and Eskom

Dans ce mémoire, une étude des conditions de contrôles d’écoulements aérodynamiques par des réseaux de générateurs de tourbillons fluidiques pulsés est menée pour établir un cahier des charges des micro-actionneurs instrumentés de faible coût, indispensables à la réalisation de ce type de contrôle actif à l’échelle industrielle. Une discussion des problématiques rencontrées dans la mise en place de ces dispositifs permet de définir des solutions techniques pertinentes. Une micro-valve encapsulée, constituée d’un canal micro-fluidique en silicium dont l’ouverture est contrôlée par un résonateur annulaire en PDMS, actionnée par différents dispositifs macroscopiques magnétiques, est alors modélisée, fabriquée et caractérisée. Le dispositif permet de générer des jets d’air pulsés complètement contrôlés jusqu’à des vitesses de 150m/s sur la gamme de fréquence [0 ; 500 Hz]. Des réseaux de ces micro-actionneurs polyvalents sont ensuite utilisés en soufflerie pour démontrer sur différents profils aérodynamiques classiques l’intérêt du contrôle par jet pulsé. Le recollement du flux d’air décollé est obtenu sur chacune de ces maquettes pour des conditions réalistes et avec un rendement fluidique supérieur à celui des jets continus.Un débitmètre massique composé d’un capteur de température, d’un capteur de frottement pariétal et d’un capteur de pression de type Pirani, réalisés dans le même procédé de fabrication, est intégré au micro-actionneur. Il permet de caractériser in-situ les jets d’air produits.Enfin un prototype répondant complètement au cahier des charges industriel est obtenu. Sa taille est minimisée par l’optimisation de l’actionneur grâce à un algorithme génétique / This thesis starts with a study of aerodynamic flow control conditions by arrays of pulsed fluidic vortex generators. Detailed specifications are synthesised for the conception of low cost, sensors equipped, micro-actuators required to manage industrial scale active flow control experiments. Devices implementation is discussed to define relevant technical solutions.A packaged micro valve is modelled, fabricated and characterized. It is composed of a micro fluidic channel modulated by an annular membrane resonator made of PDMS. The membrane is controlled by different kinds of magnetic actuation. Fully controlled pulsed air jets are obtained in the frequency range [0; 500 Hz] with velocities up to 150 m/s. Arrays of these micro actuators are used in wind tunnel experiments to demonstrate the ability of pulsed jet to manage control on a wide range of classical separated flows. Reattachment is achieved under industrial flow conditions with improved fluidic yield compared to continuous jets.A mass flow meter constituted of a thermal sensor, a shear flow sensor and a Pirani pressure sensor, all of them built in a single fabrication step, is integrated in the micro-actuator. It allows in-situ characterization of the produced air jets.Finally, a fully satisfying demonstrator is obtained. Its sized is minimized through the use of a genetic algorithm