A multidisciplinary literature survey revealed that copolymeric nanoparticles could be applied in various technologies such as the production of paint, adhesives, packaging material and lately especially drug delivery systems. The specialized application and investigation of copolymers in drug delivery resulted in the synthesis of two series of copolymeric materials, i.e. poly(styrene-co-methyl methacrylate) (P(St-co-MMA)) and poly(styrene-co-ethyl methacrylate) (P(St-co-EMA)) were synthesized via the technique of o/w microemulsion copolymerization. These copolymers have not as yet been utilized to their full potential in the development of new drug delivery systems. However the corresponding hydrophobic homopolymer poly(styrene) (PS) and the hydrophilic homopolymer poly(methyl methacrylate) (PMMA) are known to be biocompatible. Blending of homopolymers could result in novel applications, however is virtually impossible due to their unfavorable mixing entropies. The immiscibility challenge was overcome by the synthesis of copolymers that combined the properties of the immiscible homopolymers. The synthesized particles were analyzed by gel permeation chromatography combined with multi-angle laser light scattering (GPC-MALLS) and attenuated total reflectance Fourier infrared spectroscopy (ATR-FTIR). These characterizations revealed crucial information to better understand the synthesis process and particle properties i.e. molecular weight, nanoparticle size and chemical composition of the materials. Additionally, GPC-MALLS revealed the copolymer chain conformation. These characterizations ultimately guided the selection of appropriate copolymer nanoparticles to develop a controlled-release drug delivery system. The selected copolymers were dissolved in a pharmaceutically acceptable solvent, tetrahydrofuran (THF) together with a drug, rifampin. Solvent casting of this dispersion resulted in the evaporation of the solvent and assembly of numerous microscale copolymer capsules. The rifampin molecules were captured in these microcapsules through a process of phase separation and coacervation. These microcapsules finally sintered to produce a multi-layer film with an unusual honeycomb structure, bridging yet another size scale hierarchy. Characterization of these delivery systems revealed that both series of copolymer materials produced films capable of controlling drug release and that could also potentially prevent biofilm adhesion. / Thesis (Ph.D. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2008.

Abstract The Generalized Predictive Controller in transfer function representation is proposed for the cascade control task. The recommended cascade GPC (CGPC) applies one predictor and one cost function that results in several advantageous features: The disturbance regulations of the inner and the outer loops can be totally decoupled; The inner disturbance regulation is well damped, the typical overshoot of the traditional cascade control structure is avoided; The robustness properties of the inner and the outer loops can be designed separately; The anti-windup properties of the CGPC are exactly as perfect as in the case of the simple SISO GPC. The typical problem of the saturation in the inner loop, resulting in modeling error for the outer loop, is prevented. The CGPC was applied as the oxygen controller of a pilot fluidized bed boiler. The investigation is based on simulation experiments and on experiments on a pilot scale boiler. In another simulation experiment, the CGPC was applied as the temperature controller of at a steam superheater stage. The results of the experiments well illustrated the power of the proposed cascade control algorithm.

Introdução: A Locomoção tem como uma das características básicas a ritmicidade. Entre os mecanismos que envolvem seu controle destaca-se o conceito de um gerador de padrão central (GPC) capaz de gerar atividades neurais e musculares rítmicas. A técnica de treino locomotor com suspensão de peso na esteira (TLSP) utiliza esse conceito e emerge como uma estratégia terapêutica efetiva após a lesão medular (LM) em humanos em função do alto nível de automatismo do sistema nervoso, podendo ser esperadas diferentes respostas em lesões completas e incompletas. Portanto, uma análise detalhada das respostas biomecânicas obtidas durante o TLSP pode servir como base para compreensão do controle neural da locomoção humana. Objetivos: Caracterizar, a partir de parâmetros biomecânicos, a marcha com suspensão parcial de peso e assistência manual em indivíduos com lesões medulares completas e incompletas. Método: 40 indivíduos (20 com LM e 20 sem lesão) foram divididos em quatro grupos: Lesão Medular ASIA A (GLA), Lesão Medular ASIA B (GLB), Lesão Medular ASIA C e D (GLC) e Grupo Controle (GC) composto por sujeitos sem lesão. Durante o TLSP, ambos os grupos foram submetidos ao mesmo protocolo, com suspensão do peso corporal, duração total do treino e velocidades pré-definidas. Foram coletados dados de eletromiografia de superfície e a análise cinemática foi realizada por meio de 7 centrais inerciais. As análises foram realizadas por meio de análise de variância múltipla (MANOVA) Resultados: Em relação às variáveis cinemáticas o GC apresentou menor tempo de apoio em relação ao GLA não havendo diferenças entre os outros grupos com lesão medular. Quanto à ativação muscular o GLA e GLB apresentaram maior atividade de músculos proximais com co-contrações, GLC atividade proximal similar à GLA, GLB e distal similar ao GC que apresentou níveis mais baixos de atividade muscular com maior atividade distal em relação a proximal. Para o momento do pico de atividade, o GC apresentou momento antecipado para músculos proximais, atrasado para músculos distais em relação aos grupos com LM. Conclusão: Quando comparados ao GC, os grupos com LM apresentaram maiores amplitudes de sinal eletromiográfico, provavelmente pelo fato de o GC realizar a tarefa de forma mais eficiente com menor demanda de ativação muscular. Não foi possível reconhecer padrões rítmicos de ativação nos grupos com LM / Introduction: The locomotion has a characteristic the rhythmicity. Concerning the understanding of the mechanisms involving its control, the concept of a central pattern generator (GPC) capable of generating neural and muscular rhythmic activities stands out. The body weight support treadmill training (BWSTT) technique uses this concept and emerges as an effective therapeutic strategy after spinal cord injury (LM) in humans due to the high level of automatism of the nervous system, and different responses can be expected in complete and incomplete injuries. Therefore, a detailed analysis of the biomechanical responses obtained during BWSTT may serve as a basis for understanding the neural control of human locomotion. Objectives: To characterize, from biomechanical parameters, treadmill gait with body weight support in individuals with complete and incomplete spinal cord injury. Method: 40 individuals (20 with LM and 20 without lesion) were divided into four groups: ASIA A (GLA), ASIA B (GLB), ASIA C and D (GLC) and Control Group (GC) composed of subjects without injury. During BWSTT, both groups were submitted to the same protocol, with pre-defined body weight suspension, total training duration and speeds. Surface electromyography data were collected and kinematic analysis was performed by means of 7 inertial power plants. The analyzes were performed through multiple variance analysis (MANOVA). Results: In the kinematic variables, the CG presented less support time in relation to the GLA and there were no differences between the other groups with spinal cord injury. As for muscle activation, GLA and GLB presented higher activity of proximal muscles with co-contractions, GLC presented similar proximal activity similar to GLA, GLB and distal similar to GC, which presented lower levels of muscular activity with greater distal activity in relation to proximal muscles. For the moment of peak activity, the GC presented early moment for proximal muscles, delayed to distal muscles in relation to the groups with LM. Conclusion: When compared to CG, the groups with LM presented higher amplitudes of electromyographic signal, probably because the CG performed the task more efficiently with less demand for muscle activation. It was not possible to recognize rhythmic patterns of activation in the LM groups

Cette thèse a pour objectif la modélisation et la commande d'un robot parallèle actionné pneumatiquement destiné à des applications de prise et dépose d'objets. Les actionneurs pneumatiques sont des actionneurs à bas coût et ayant des rapports poids/puissance plus importants que les actionneurs électriques. Ceci a pour avantage de réduire le coût de revient du robot en augmentant sa capacité de charge. Cependant, du fait des fortes non linéarités qui les caractérisent (compressibilité de l'air, caractéristique de la valve, frottement, hystérésis ...), le principal obstacle à leur utilisation en robotique est leur commande de façon précise et robuste. C'est pour cela que plusieurs stratégies de commande ont été proposées et implémentées expérimentalement sur un banc d'essai utilisant trois types d'actionneurs pneumatiques: deux vérins et des muscles artificiels travaillant en mode antagoniste. Ces stratégies sont des schémas en cascade qui –après une linéarisant exacte obtenue sur la base du système non linéaire- combinent un contrôleur externe de position et une boucle interne de force (équivalente à la différence de pression) dans le cas des vérins pneumatiques. Pour les muscles artificiels, le même principe est utilisé sauf que la boucle interne de force est remplacée par une boucle qui régule le couple en contrôlant les pressions de chacun des deux muscles. Un contrôleur prédictif généralisé (GPC) est synthétisé pour la boucle de position permettant ainsi de réduire sensiblement les temps de réponse. Pour la boucle interne de pression, un contrôleur robuste multi-objectif combinant des performances H infinie avec des contraintes de placement de pôle a été synthétisé. L'utilisation d'inégalités matricielles affines (LMI) a permis de combiner les objectifs du contrôleur de façon très intuitive. Le choix de ce contrôleur robuste est motivé par la nécessité de rejeter les fortes variations de charge qui caractérisent les applications de prise-et-dépose d'objets. Deux autres stratégies pour la commande prédictive en effort ont été synthétisées sur les vérins et les muscles et ont donné des résultats très encourageants. Les résultats expérimentaux obtenus ont montré l'apport de ces lois de commande en termes de performances (réduction des temps de réponse, erreurs de suivi faibles) et de robustesse (bon rejet des perturbations). Une étude comparative des trois actionneurs testés a conduit au choix du vérin à double effet standard car offrant le meilleur compromis entre performances, robustesse et coût de l'actionneur. En se basant sur ce choix, un nouveau prototype de robot parallèle à deux degrés de liberté utilisant les vérins standards a été conçu, modélisé et commandé en utilisant les différentes stratégies en cascade proposées. L'implémentation expérimentale des algorithmes de commande a conduit à des résultats encourageants en termes de qualité de suivi et de rejet de perturbations. / The thesis objective is the control of a parallel robot driven with pneumatic actuators for pick-and-place applications. The advantage of using pneumatic actuators rather than electrical ones is that they are cheaper and have a bigger power-to-weight ratio which can increase the payload abilities of the robot. However, due to their strong nonlinearities such as air compressibility, valve characteristic, friction, and hysteresis, they are still difficult to control precisely and in a robust way.That is why the main contribution of the thesis is in the control area where different control schemes have been proposed and experimentally implemented on a test bench that involves three types of pneumatic actuators: two cylinders and agonist/antagonist artificial muscles. After the modeling and identification of the nonlinear models, different strategies have been developed: for cylinders, a cascade scheme which uses an outer position control loop and an inner force (or pressure difference) loop is used. For muscles, the inner force loop is replaced by a torque loop controlled by acting on the pressures in each muscle. For position, a Generalized Predictive Controller (GPC) is synthesized reducing sensibly the time responses. For the inner pressure loop, an LMI based multi objective controller is synthesized combining H infinity performances and pole placement constraints. The choice of a robust controller is motivated by the necessity of rejecting load variation disturban ces that characterize pick-and-place applications. On the other hand, two predictive control strategies with feedback linearization were implemented showing very encouraging results.The different experimental results have shown the interest of such strategies in terms of performances (time response reduction, good dynamic tracking) and robustness (disturbance rejection). The comparison of the three tested actuators led to the choice of the standard double acting cylinder because it offers the best compromise in terms of performances and cost. This cylinder was then used to design a planar parallel robot and the implementation of the proposed cascade strategies. The experimental tests showed encouraging results in terms of disturbance rejection and ability of tracking dynamic references and performing pick-and-place cycles.

Introdução: A Locomoção tem como uma das características básicas a ritmicidade. Entre os mecanismos que envolvem seu controle destaca-se o conceito de um gerador de padrão central (GPC) capaz de gerar atividades neurais e musculares rítmicas. A técnica de treino locomotor com suspensão de peso na esteira (TLSP) utiliza esse conceito e emerge como uma estratégia terapêutica efetiva após a lesão medular (LM) em humanos em função do alto nível de automatismo do sistema nervoso, podendo ser esperadas diferentes respostas em lesões completas e incompletas. Portanto, uma análise detalhada das respostas biomecânicas obtidas durante o TLSP pode servir como base para compreensão do controle neural da locomoção humana. Objetivos: Caracterizar, a partir de parâmetros biomecânicos, a marcha com suspensão parcial de peso e assistência manual em indivíduos com lesões medulares completas e incompletas. Método: 40 indivíduos (20 com LM e 20 sem lesão) foram divididos em quatro grupos: Lesão Medular ASIA A (GLA), Lesão Medular ASIA B (GLB), Lesão Medular ASIA C e D (GLC) e Grupo Controle (GC) composto por sujeitos sem lesão. Durante o TLSP, ambos os grupos foram submetidos ao mesmo protocolo, com suspensão do peso corporal, duração total do treino e velocidades pré-definidas. Foram coletados dados de eletromiografia de superfície e a análise cinemática foi realizada por meio de 7 centrais inerciais. As análises foram realizadas por meio de análise de variância múltipla (MANOVA) Resultados: Em relação às variáveis cinemáticas o GC apresentou menor tempo de apoio em relação ao GLA não havendo diferenças entre os outros grupos com lesão medular. Quanto à ativação muscular o GLA e GLB apresentaram maior atividade de músculos proximais com co-contrações, GLC atividade proximal similar à GLA, GLB e distal similar ao GC que apresentou níveis mais baixos de atividade muscular com maior atividade distal em relação a proximal. Para o momento do pico de atividade, o GC apresentou momento antecipado para músculos proximais, atrasado para músculos distais em relação aos grupos com LM. Conclusão: Quando comparados ao GC, os grupos com LM apresentaram maiores amplitudes de sinal eletromiográfico, provavelmente pelo fato de o GC realizar a tarefa de forma mais eficiente com menor demanda de ativação muscular. Não foi possível reconhecer padrões rítmicos de ativação nos grupos com LM / Introduction: The locomotion has a characteristic the rhythmicity. Concerning the understanding of the mechanisms involving its control, the concept of a central pattern generator (GPC) capable of generating neural and muscular rhythmic activities stands out. The body weight support treadmill training (BWSTT) technique uses this concept and emerges as an effective therapeutic strategy after spinal cord injury (LM) in humans due to the high level of automatism of the nervous system, and different responses can be expected in complete and incomplete injuries. Therefore, a detailed analysis of the biomechanical responses obtained during BWSTT may serve as a basis for understanding the neural control of human locomotion. Objectives: To characterize, from biomechanical parameters, treadmill gait with body weight support in individuals with complete and incomplete spinal cord injury. Method: 40 individuals (20 with LM and 20 without lesion) were divided into four groups: ASIA A (GLA), ASIA B (GLB), ASIA C and D (GLC) and Control Group (GC) composed of subjects without injury. During BWSTT, both groups were submitted to the same protocol, with pre-defined body weight suspension, total training duration and speeds. Surface electromyography data were collected and kinematic analysis was performed by means of 7 inertial power plants. The analyzes were performed through multiple variance analysis (MANOVA). Results: In the kinematic variables, the CG presented less support time in relation to the GLA and there were no differences between the other groups with spinal cord injury. As for muscle activation, GLA and GLB presented higher activity of proximal muscles with co-contractions, GLC presented similar proximal activity similar to GLA, GLB and distal similar to GC, which presented lower levels of muscular activity with greater distal activity in relation to proximal muscles. For the moment of peak activity, the GC presented early moment for proximal muscles, delayed to distal muscles in relation to the groups with LM. Conclusion: When compared to CG, the groups with LM presented higher amplitudes of electromyographic signal, probably because the CG performed the task more efficiently with less demand for muscle activation. It was not possible to recognize rhythmic patterns of activation in the LM groups

Ces travaux de thèse sur le fractionnement des produits pétrolier a pour but de mieux caractériser certaines espèces métalliques, principalement le Nickel et le Vanadium. Dans un premier temps, ils ont permis de démontrer que les composés contenant du V et Ni présents dans ces matrices complexes sont essentiellement concentrés dans les fractions les plus polaires, à savoir, les résines et les asphaltènes. En ce qui concerne les composés soufrés, on a constaté qu'ils se concentrent dans les fractions résines et les aromatiques. Il a également été constaté que la teneur en composés contenant du V et Ni qui précipite avec les asphaltènes est linéairement lié au paramètre de solubilité du solvant utilisé pour la précipitation. Et pour des solvants aux paramètres de solubilité proche de 16 MPa0.5, le pourcentage d’asphaltènes soluble est augmenté. On conclut que le pourcentage réel des asphaltènes présents dans un brut est égal au pourcentage d'asphaltènes insolubles, plus un pourcentage d’asphaltènes soluble. On a constaté que ces types d’asphaltènes ont une distribution de poids moléculaire similaire à celle des asphaltènes insolubles, et non un poids moléculaire plus faible. En ce qui concerne la distribution des poids moléculaires des composés du V présents dans les échantillons évalués, au moins trois grandes distributions de poids moléculaires ont été identifiées. Il s’agit des composés de « high molecular weight », « medium molecular weight » et « low molecular weight ». Sur ces distributions, nous trouvons que les composés contenant du V, Ni et S sont, dans les asphaltènes, prédominant dans la fraction HMW et sont caractéristiques des composés nanoagrégés. En ce qui concerne les composés de type MMW, ils ont été observés dans une plus grande proportion dans les maltènes. Il est à noter la présence de composés de type HMW avec les maltènes, ce qui pour les raisons exposées ci-dessus, peut être considérée comme une preuve incontournable de la présence d’asphaltènes soluble dans les maltènes. A propos des méthodes de séparation développées, il a été possible de séparer les différentes distributions de poids moléculaires initialement identifiées chez les maltènes et les asphaltènes. Pour les maltènes, il a été possible d’extraire les différents composés contenant du V et Ni en fonction de leur poids moléculaire HMW, LMW et MMW. Cette extraction a été réalisé en utilisant des extractions liquide-liquide des maltènes dissous dans de l'heptane avec de l’ACN pour extraire les composés à bas poids moléculaire, suivie par une extraction avec du DMF pour extraire des composés MMW. La fraction restante des maltènes est composés surtout de composés HMW.Pour les asphaltènes, 11 solvants ont été évalués pour l'extraction des composés contenant du V et du Ni. Le profil des composés extraits a permis de séparer jusqu'à 4 distributions différentes de poids moléculaire avec du ACN, de l’acétone et du DMF utilisés séquentiellement. En ce qui concerne les composés de HMW, la fraction insoluble après extraction au DMF a un poids moléculaire plus élevé que la fraction soluble. Pour l'influence de la concentration sur la présence des composés contenant du Ni et V de HMW, il a été démontré que même dilué 40.000 fois, une solution asphaltènes (à 25 mg / L) contient toujours des composés de HMW et donc des nanoaggregat d’asphaltènes. Quant à la caractérisation des fractions extraite, seule la fraction correspondant aux poids moléculaires faibles (LMW) a été étudiée. La détermination de la distribution du poids moléculaire par spectrométrie de masse FT ICR MS et la comparaison du chromatogramme par GPC ICP MS suggère que ces composés contenant du V et du Ni présent dans la fraction LMW sont des métalloporphyrines libre avec des structures brutes assez simples. Ces travaux vont permettre d’ouvrir la voie à une caractérisation plus approfondie des différentes fractions obtenus et ainsi de permettre une meilleure connaissance des pétroles lourds. / This PhD work were mainly dedicated to the fractionation of crude oil and petroleum products in order to better caracterize metals compounds (mainly V and Ni) in these complex matrices. It was determined that V and Ni compounds present in the crude oils and residues are concentrated mainly in their more polar fractions, that is to say, resins and asphaltenes. Concerning sulfur compounds, it was found that they are concentrate in the resins and aromatics fractions. All these results were similar to reported in the literature.It was also found the content of V and Ni compounds that precipitate together with the asphaltenes depends linearly of solubility parameter of solvent used for the precipitation of asphaltenes, so, for solvents with solubility parameters close to 16 MPa0.5, the percentage of asphaltene soluble increases. So it can be concluded the true percentage of asphaltenes present in the crude oil is equal to the percentage of insoluble asphaltenes plus the percentage of soluble asphaltenes. For this type of asphaltenes, it was found that they have a molecular weight distribution very similar to insoluble asphaltenes, and not a lower molecular weight, as originally thought (Speight and Mitchell, 1973).With respect to the distribution of molecular weights for the V compounds present in the samples evaluated, at least three molecular weight distributions were identified. Those were identified as compounds with high molecular weight (HMW), medium molecular weight (MMW) and low molecular weight (LMW) following the nomenclature previously reported in the literature. (Desprez et al., 2014).On these distributions, we has found that compounds of V, Ni and S with HMW predominate in the asphaltenes, which is characteristic of nanoaggregate compounds. With respect to the compounds with MMW, these were observed in a greater proportion in maltenes. It should be noted the presence of compounds with HMW in all maltenes evaluated, which for the reasons discussed above, can be considered an unavoidable evidence of the presence of soluble asphaltenes.With respect to the separation/extraction methods developed, it was possible to separate the different distributions of molecular weights initially identified in maltenes and asphaltenes. In the case of maltenes, for the first time in the literature it was possible to extract the various compounds of V and Ni present in these according to their molecular weight. For the separation in maltenes, liquid-liquid extractions on maltene dissolved in heptane were developed. So, with ACN, it has been possible to extract LMW compounds, while extractions with DMF allowed extracting MMW compounds, staying in the remaining maltene mostly compounds with HMW.For the asphaltene extraction, 11 solvents were evaluated. The study of profile obtained to each extract and remanent, allowed to pose a separation scheme that enabled to get up to 4 different molecular weight distributions. These were obtained with ACN, Acetone and DMF used sequentially. It is important to mention it was found that the insoluble fraction gotten with DMF had the highest molecular weight, even in comparison with the HMW asphaltenes soluble in DMF.With respect to the influence of the concentration on the aggregated compounds, it was found that this does not influence on the presence of compounds with HMW. Nanogregate were found in a solution of asphaltenes diluted 40,000 times (25 mg / L).Regarding the characterization of the extracted fractions, only the fraction corresponding to low molecular weights was studied. Determination of the molecular weight distribution by mass spectrometry and comparison of the GPC ICP MS chromatogram with a porphyrin standards, suggests that these V and Ni compounds present in LMW fraction has a structures quite simple. A deeper characterization will be presented in later work. / Se determinó que los compuestos de V y Ni presentes en los crudos y residuos evaluados se concentran principalmente en su fracciones más polares, es decir, resinas y asfaltenos. Con respecto a los compuestos de azufre, se encontró que los mismos se concentran en las resinas y aromáticos. Todos estos resultados fueron similares a lo reportado en la literatura. Igualmente se encontró que el contenido de compuestos de V y Ni que precipitan junto con los asfaltenos depende linealmente del parámetro de solubilidad del solvente usado para la precipitación de los asfaltenos, así para solventes con parámetros de solubilidad cercanos a 16 MPa0.5, el porcentaje de se asfalteno soluble incrementa, por lo que se puede concluir que el porcentaje verdadero de asfaltenos presente en el crudo es igual al porcentaje de asfaltenos insoluble más el porcentaje de asfaltenos solubles. Sobre este tipo de asfaltenos, se encontró que los mismos poseen una distribución de pesos moleculares muy similar a la de los asfaltenos insolubles, y no un peso molecular mucho menor, como se pensaba en un principio. Con respecto a la distribución de pesos moleculares para los compuestos de V presentes en las muestras evaluadas, se identificaron al menos tres grandes distribuciones de pesos moleculares. Las mismas se identificaron como compuestos con alto peso molecular o high molecular weight (HMW en inglés), medio peso molecular o medium molecular weight (MMW en inglés) y bajo peso molecular o low molecular weight (LMW por sus siglas en inglés) siguiendo la nomenclatura reportada previamente en la literatura. Sobre estas distribuciones, encontramos que en los asfaltenos predominan compuestos de V, Ni y S con HMW, el cual es característicos de compuestos agregados. Con respecto a los compuestos con MMW, estos fueron observados en mayor proporción en los maltenos. Es de hacer notar la presencia de compuestos con HMW en todos los maltenos evaluados, la cual por las razones antes expuestas, puede ser considerada una evidencia ineludible de la presencia de asfaltenos solubles. Con respecto a los métodos de separación desarrollados, fue posible la separación de las diferentes distribuciones de pesos moleculares inicialmente identificadas en los maltenos y asfaltenos. En el caso de los maltenos, por primera vez en la literatura fue posible separar los diversos compuestos de V y Ni en función de su peso molecular en HMW, MMW y LMW. La separación si hizo empleando extracciones líquido-líquido a maltenos disueltos en heptano con acetonitrilo para la extracción de compuestos con LMW, seguido de extracciones con dimetilformamida para la extracción de compuestos con MMW, quedando en el malteno remanente de la extracción, mayoritariamente compuestos con HMW. Para los asfaltenos, se evaluaron hasta 11 solventes en la extracción de compuestos de V y Ni. El perfil de los compuestos extraídos, permitió separar hasta 4 distribuciones de pesos moleculares diferentes con ACN, acetona y DMF usados secuencialmente. Con respecto a los compuestos con HMW, se encontró que la fracción insoluble con DMF presenta un mayor peso molecular que los asfaltenos con HMW solubles en estos. Con respecto a la influencia de la concentración en la determinación de compuestos con HMW la caracterización de los compuestos de V y Ni, los mismos fueron determinados aun en una solución de asfaltenos diluida 40.000 veces (25 mg/L). En lo referente a la caracterización de las fracciones separadas, solo fue estudiada inicialmente la fracción correspondiente a bajos pesos moleculares. En la misma, la determinación de la distribución de pesos moleculares por espectrometría de masa y la comparación en el cromatograma por GPC-ICP MS de estándares porfirínicos, sugiere que estos compuestos de V y Ni con LMW son metaloporfirinas simples presentes en el crudo con estructuras bastantes sencillas. Una caracterización más profunda será presentada en trabajo posteriores para esta y las demás fracciones.

Made available in DSpace on 2016-12-12T20:27:38Z (GMT). No. of bitstreams: 1 Aldo Zanella Junior.pdf: 3746857 bytes, checksum: 7ff548689a89fd8090402ad4891a23c1 (MD5) Previous issue date: 2015-07-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work introduces the report of performed studies in order to evaluate the applicability of generalized predictive control (GPC) to several plants. The main goal is to analyze the GPC performance in processes with different features, analyzing the influence of its tuning parameters. The study is justified by the fact that GPC presents itself as a generalized solution for several classes of processes, which are becoming increasingly complex and demanding for traditional controllers to handle. For the purpose to prove this proposal of GPC, it was performed several tests with plants of different orders and response characteristics, real and simulated, varying controller tuning parameters and measuring some quality indices. It was evaluated the influence of tuning parameters and it was made a report of conclusions that was reached. Through obtained results, it is shown that GPC satisfies the proposal and presents favorable results. / Esta dissertação traz o relato do estudo realizado a fim de avaliar a aplicabilidade do controlador preditivo generalizado (GPC) em plantas diversas. O objetivo principal é analisar o desempenho do GPC em processos com diferentes características, analisando a influência dos seus parâmetros de sintonia. O estudo se justifica pelo fato de que o GPC apresenta-se como uma solução generalizada para diversos tipos de processos, os quais estão se tornando cada vez mais complexos e com maiores exigências para o controlador. A fim de comprovar essa proposta do GPC, realizou-se inúmeros ensaios com plantas com respostas e ordem diferentes, reais e simuladas, variando-se os parâmetros de sintonia do controlador e medindo-se alguns parâmetros de qualidade. Avaliou-se a influência dos parâmetros de sintonia e fez-se um relato das conclusões a que se chegou. Através dos resultados obtidos, mostra-se que o GPC corresponde ao que se propõe para as plantas testadas e apresenta resultados favoráveis.

Human immunodeficiency virus (HIV) infected patients with a history of injection opiate abuse have higher incidences of acquired immunodeficiency syndrome (AIDS) and neurological dysfunction. The use of combined anti-retroviral therapy has significantly reduced the prevalence of mortality and progression to AIDS. Due to extended life expectancy, these patients are still at a great risk for HIV-associated neurological disorders and impairment in their later life. Neural progenitor cells (NPCs) play critical roles in brain growth and repair after injury and insult. Pediatric HIV patients whose glial populations are still developing are especially at risk for central nervous system (CNS) damage. Our previous reports suggest that HIV-1 transactivator of transcription (Tat) can directly cause pathology in neural progenitors and oligodendroglia (OLs) (Hauser et al. 2009). Thus, we have hypothesized that NPCs and/or glial progenitors may be targets of HIV proteins ± opiates drugs of abuse. To determine whether progenitors are targets of HIV-1, a multi-plex assay was performed to assess chemokine/cytokine expression after treatment with viral proteins Tat or glycoprotein 120 (gp120) with/without morphine. Murine striatal progenitors released increased amount of the beta-chemokines CCL5/regulated upon activation, normal T cell expressed and secreted (RANTES), CCL3/macrophage inflammatory protein-1α (MIP-1α), and CCL4/macrophage inflammatory protein-1β (MIP-1β) after 12 h exposure to HIV-1 Tat, but no to gp120. Secreted factors from Tat-treated progenitors were chemoattractive towards microglia, an effect blocked by 2D7 anti- C-C chemokine receptor type 5 (CCR5) antibody pre-treatment. Tat and opiates have interactive effects on astroglial chemokine secretion, but this interaction did not occur in progenitors. We also examined effects of Tat and morphine on proliferation and lineage progression of NPCs in vitro and in vivo. In vitro, Tat and morphine independently reduced the proliferation and population of Sox2+ and Olig2+ cells in the absence of cell death. The interactive effects of morphine and either Tat or supernatant from HIV-1SF162 infected monocytes varied depending on outcome measure and time of exposure, but interactive effects occurred primarily on proliferation. In rare instances, viable human progenitors were associated with p24 immunolabeling suggesting that progenitors may be infected, a concept that is still controversial. To investigate effects of Tat and morphine on NPCs in vivo, we used a mouse model in which HIV-1 Tat1-86 is conditionally expressed in astroglia. In vivo results in neonatal striata were similar to those in cell cultures. We extended the experiments into adult mice with inducing Tat expression for 3 month and the effect of sexes was examined in these animals. Intriguingly, males showed more Tat-induced impairment in behavioral tests (rotarod, grip strength, light-dark box) than females. Tat+ males also showed a greater reduction in the proportion of NeuN+ cells and NeuN immunoreactivity in the striatum, accompanied by greater microglial activation (3-nitrotyrosine+/Iba-1+). Unbiased stereological estimation in Nissl staining revealed that the depletion of NeuN immunoreactivity in these mice was not due to neuron cell death or loss, because the total neuron number in striatum and total striatal volume were not affected by long-term Tat induction. Tat exposure appears to selectively reduce levels of NeuN in living neurons, although the reason is not known. Therefore, both the enhanced microglial reactivity and depletion of NeuN levels in males may help to explain sex-specific behavioral outcomes. Sox2+ and Olig2+ cells showed equivalent reduction in their population in both sexes. Overall, our findings show that CNS progenitors, including both undifferentiated NPCs and glial progenitors, are vulnerable to individual or combined effects of HIV-1 or Tat and opiates. Changes in progenitor dynamics may alter the balance of cell populations in both the developing and adult CNS. We speculate that such changes may contribute to the behavioral abnormalities that we observed in Tat+ mice and which appear to model aspects of motor, cognitive and anxiety deficits in HIV-infected patients.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Decorticated flax contains a significant amount of shive content, which limits applications of flax fibre. Separation of shives from the fibre is essential to improve the quality of flax fibre. Pneumatic method and a Sorter were implemented to meet the above objective. Terminal velocities of individual flax fibre and shive particles were investigated and their width, length, and mass were recorded. A sorting method was used for separation of short and long fibre for two grades of fibre: Grade 1 and Grade 2, with initial fibre purities of 51% and 15%, respectively. The ranges of terminal velocities for shive and fibre particles were 1.13 to 4.09 m/s and 0.51 to 1.07 m/s, respectively, which were significantly different. Fibre purity of approximately 80% for Grade 1 and 66% for Grade 2 were recorded from sorting, which were a significant improvement when compared to the initial purities. This study demonstrated the potential of the pneumatic and sorting methods for improving fibre quality. With the increase in resistant strains of microorganisms to antibiotics, researchers have started to explore plant parts to discover new antimicrobials. Since medieval times all portions of plants were used medicinally. Plant tissues, including stems, possess secondary metabolites (SMs), which have known antimicrobial properties. The purpose of this study was to investigate: the presence of antimicrobial compounds in stem extracts of canola, flax, hemp, and sweet clover; and study sorption-desorption behavior of their powdered stem material. GC-MS analysis of all extracts showed the presence of many SMs, including fatty acids, terpenoids, steroids, and sterols, etc. Many of the SMs found in the extracts have previously shown antimicrobial activity against a broad spectrum of organisms according to literature. Water sorption isotherms of stems showed a typical IUPAC Type II sigmoid curve similar to natural fibres. Equilibrium moisture content (EMC) of canola and sweet clover was significantly higher than flax and hemp at 95% RH, which were all higher than the fibre saturation point of wood (27%). The preliminary investigation via GC-MS showed promising results and water absorptivity results of stems can be used as the initial key property for many applications. / October 2015