Conselho Nacional de Desenvolvimento Científico e Tecnológico / The sulfur compounds have been studied for many years due to their importance in chemical, biological and industrial areas. These compounds can also be found in matrices of oil and its derivatives, and among the groups, the most important are the sulfides, thiophenes and benzothiophenes. The determination of these compounds in asphalt has great importance since they are considered precursors of oxidation reactions and are directly related to its aging, which reflects the durability of pavements. Therefore, various methods for determining these compounds have been described, although there is a lack of information in the literature about studies of sulfur compounds employing voltammetry and gold electrode. Thus, the aim of this study was to develop an electrochemical method for determining organo-sulfur compounds in asphalt oil cement samples (CAP) using differential pulse voltammetry in non-aqueous medium, a gold electrode as working electrode, an Ag/AgCl reference electrode modified with LiCl saturated in ethanol and 0.1M NaClO4 in DMSO and a platinum wire as counter electrode, as a supporting electrolyte was used a 0.1M NaCl4 solution in DMSO. / Os compostos de enxofre têm sido estudados há muitos anos devido à sua importância em áreas químicas, biológicas e industriais. Esses compostos podem ser encontrados também em matrizes de petróleo e seus derivados, e entre as principais classes destacam-se os sulfetos, tiofenos e benzotiofenos. A determinação destes compostos em asfaltos é de grande importância uma vez que são considerados precursores das reações de oxidação e estão diretamente relacionados com o seu envelhecimento, o que reflete na durabilidade dos pavimentos. Em vista disso, diferentes métodos para a determinação desses compostos têm sido descritos, porém a literatura não contém muitos relatos de estudos de compostos sulfurados empregando voltametria e eletrodo de ouro. Assim, o objetivo deste trabalho foi desenvolver um método eletroquímico para determinar compostos organo-sulfurados em amostras de cimento asfáltico de petróleo (CAP) utilizando a voltametria de pulso diferencial em meio não aquoso, um eletrodo de ouro como eletrodo de trabalho, um eletrodo de referência de Ag/AgCl modificado com LiCl saturado em etanol e NaClO4 0,1M em DMSO e um fio de platina como contra-eletrodo, como eletrólito de suporte foi utilizado uma solução de NaClO4 0,1M em DMSO.

Magister Pharmaceuticae - MPharm / Syzygium cordatum is a medicinal plant indigenous to South Africa and Mozambique, commonly used to treat stomach aches, diabetes, respiratory problems and tuberculosis. In spite of the folklore use, adequate scientific data to credit its widespread traditional use is lacking. The objectives of this study were: to evaluate and validate scientifically the successful therapeutic claims by traditional medicine practitioners that Syzygium cordatum is effective in treating diarrhoea and diabetes; to determine the effects of the plant extract on gastrointestinal transit of a charcoal meal in mice; to determine the effects on castor oilinduced intestinal fluid accumulation; to determine the safety profile of the plant by carrying out acute toxicology study and to carry out preliminary screening of the active compounds present in the plant using standard phytochemical analytical procedures. The aqueous leaf extract of Syzygium cordatum (3.125 -50mg/kg, p.o) significantly reduced the faecal output caused by castor oil (0.7ml). All the doses used, reduced faecal output from 100% produced by castor oil to between 40 and 61%. S.cordatum (6.25 – 50mg/kg, p.o) significantly and in a dose dependent manner, delayed the onset of castor oil-induced diarrhoea. / South Africa

L'oxydation des composés organiques émis dans l'atmosphère est progressive et conduit à la formation d'une multitude de composés organiques secondaires. Ces composés organiques secondaires (COS) peuvent être hydrosolubles et donc réagir dans la phase aqueuse atmosphérique. La communauté scientifique s'intéresse actuellement à l'impact environnemental de la réactivité de la matière organique atmosphérique en phase aqueuse. Des études récentes montrent par exemple que ces modifications pourraient entraîner une augmentation de la production d'aérosol organique secondaire (AOS). Pour explorer les effets de la réactivité aqueuse, une modélisation détaillée de la dissolution des COS et de leur oxydation aqueuse a été menée dans ce travail. Cette modélisation repose sur l'extension du générateur de schémas chimiques explicites GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere).La fraction soluble des COS est peu connue. Il est donc nécessaire de la quantifier en fonction du contenu en eau liquide. GECKO-A permet de générer des schémas explicites d'oxydation en phase gazeuse. Pour intégrer la dissolution des composés organiques formés, leurs constantes de Henry ont été documentées. Le faible nombre de données disponibles (600) comparé au très grand nombre d'espèces secondaires formées (>103) demande d'estimer empiriquement la majorité des constantes de Henry. Nous avons eu recours à une méthode d'estimation de type structure-propriété développée au LISA, GROMHE (GROup contribution Method for Henry's law Estimates). Ceci a permis de décrire le transfert de masse de toutes les espèces solubles générées lors de l'oxydation de trois précurseurs d'intérêt atmosphérique : l'isoprène, l'octane et l'α-pinène. Pour un contenu en eau liquide typique d'un aérosol déliquescent, seule une très faible fraction des COS est dissoute. Cependant, nous avons montré qu'une proportion significative des COS est susceptible de se dissoudre dans une phase aqueuse nuageuse. La dissolution et la réactivité des COS issus de l'oxydation des composés à chaîne longue doivent donc être représentées dans les modèles. Pour décrire la réactivité aqueuse des composés organiques dissous, un module de réactivité aqueuse a été ajouté à GECKO-A. La génération des mécanismes d'oxydation aqueuse repose sur l'écriture d'un protocole d'oxydation systématique. En s'appuyant sur les connaissances disponibles, ce protocole définit les règles d'oxydation et d'estimation des constantes inconnues. Implémenté dans GECKO-A, il permet dorénavant d'écrire des schémas d'oxydation multiphasique explicites pour les composés organiques. Pour l'instant, les espèces précurseur sont limitées en longueur de chaîne carbonée à cause de la taille des schémas générés. Le traitement de l'octane et de l'α-pinène est par exemple impossible. Néanmoins, à partir du mécanisme généré pour l'isoprène, le modèle a été utilisé pour explorer l'impact de la réactivité aqueuse sous différentes conditions environnementales. La réactivité aqueuse modifie significativement la distribution du carbone entre les phases ainsi que la spéciation de la matière organique dans les deux phases. Nous avons en particulier montré une production importante de diacides carboxyliques, espèces régulièrement identifiées dans la phase particulaire lors de mesures de terrain. Le mécanisme généré permet pour la première fois d'identifier environ 360 voies de formation différentes pour l'acide oxalique / The atmospheric oxidation of organic compounds is progressive and leads to the formation of a myriad of secondary organic compounds. These secondary organic compounds (SOC) can be hydrosoluble and react in the atmospheric aqueous phase. The scientific community is currently interested in the environmental impact of the atmospheric organic matter aqueous phase reactivity. For example, recent studies show that these modifications could increase the secondary organic aerosol (SOA) production. In order to explore effects of the aqueous reactivity, this work consists of a detailed modeling study of the SOC dissolution and their aqueous oxidation. The modeling is based on the extension of the explicit chemical schemes generator GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere).There is little known about the soluble fraction of SOC. It is thus needed to quantify it as a function of the liquid water content. GECKO-A enables the generation of explicit oxidation schemes for the gas phase. To integrate the dissolution of produced organic compounds, their Henry's law constants have been documented. The low number of available data (600) compared to the large number of formed secondary species (>103) requires the empirical estimate of the majority of Henry's law constants. We relied on an estimate method based on a structure-activity relationship developed at LISA, GROMHE (GROup contribution Method for Henry's law Estimates). This allowed us to describe the mass transfer of every soluble species generated during the oxidation of three precursors of atmospheric interest: isoprene, octane and α-pinene. For a liquid water content typical of a deliquescent aerosol, only a very small fraction of SOC is dissolved. However, we showed that a significant proportion of SOC could dissolve in a cloud aqueous phase. Dissolution and reactivity of SOC produced from the oxidation of long chain compounds need to be represented in models. In order to describe the aqueous reactivity of dissolved organic compounds, a aqueous reactivity module was added to GECKO-A. The generation of aqueous oxidation mechanisms is based on the writing of a systematic oxidation protocol. Supported by available knowledge, this protocol defines rules for oxidation and estimates of unknown constants. Implemented in GECKO-A, it now enables us to write multiphase explicit oxidation schemes for organic compounds. For now, precursor species are limit in the carbon skeleton length by the size of generated schemes. Treatment of octane and α-pinene is for example impossible. Nevertheless, from the mechanism generated for isoprene, the model has been used to explore the aqueous reactivity impact under different environmental conditions. Aqueous reactivity modifies significantly the carbon distribution between phases as well as the organic matter speciation in both phases. In particular, we showed an important production of carboxylic diacids, species that are regularly identified in the particulate phase during field measurements. For the first time, the generated mechanism allows the identification of approximately 360 different formation pathways for oxalic acid

Le combustible nucléaire usé, après avoir été débarrassé de l'uranium, du plutonium et potentiellement du neptunium par le procédé PUREX, est encore constitué d'environ la moitié des éléments du tableau périodique. Au sein de ceux-ci, l'américium est majoritairement responsable des émissions thermiques à long terme des colis de déchets. En le recyclant, la compacité des sites de stockage pourrait être significativement améliorée. Le procédé d'extraction liquide-liquide EXAm, dont l'étape clé est la séparation Am/Cm, a donc été développé afin de séparer l'Am seul. Pour ce faire, un mélange d'extractants est utilisé conjointement au TEDGA (N,N',N,N'-tétraéthyl-diglycolamide), un complexant aqueux. Ce dernier permet en effet d'améliorer la séparation Am/Cm en maintenant préférentiellement le curium en phase aqueuse, mais sa relation structure sélectivité est encore mal comprise. Ces travaux de thèse concernent donc la synthèse et l'évaluation d'analogues structuraux du TEDGA afin de mieux comprendre l'influence de sa structure sur la sélectivité Am/Cm dans le procédé EXAm. Durant cette étude, 14 analogues du TEDGA ont été synthétisés et 17 molécules ont été évaluées en extraction liquide-liquide. Plusieurs modifications structurales ont été étudiées : la longueur et l'encombrement stérique des chaines alkyle portées par les azotes, la taille de l'espaceur, ainsi que l'utilisation d'amides secondaires. Ainsi, ces travaux ont montré qu'à partir des chaines tétrabutyle, il n'est plus possible de maintenir les molécules en phase aqueuse et que l'ajout d'encombrement stérique sur les chaines alkyles ou la modification de la balance hydrophilie/lipophilie diminue systématiquement la sélectivité des ligands. L'introduction d'amides secondaires (-CONHR) donne des ligands extractibles par le solvant (formation de liaison hydrogène avec les extractants) ce qui les rend inutilisables dans le procédé EXAm. Quant à l'espaceur, il joue un rôle prépondérant sur la sélectivité : le raccourcir (malonamides) entraine la disparition du caractère complexant de la molécule à forte acidité, et l'allonger entraine une préférence du ligand pour l'Am au lieu du Cm (inversion de sélectivité). L'ensemble de l'étude met en lumière la particularité de la sélectivité apportée par le TEDGA face aux autres diglycolamides ainsi que la difficulté d'améliorer le procédé en utilisant cette famille de molécules. Néanmoins la meilleure compréhension de sa chimie a permis d'affiner sa modélisation dans le procédé et l'étude de sa relation structure sélectivité montre qu'une amélioration de la sélectivité des ligands pourrait encore être envisagée en rigidifiant l'espaceur. / After the reprocessing of uranium, plutonium and eventually neptunium by the PUREX process, the spent fuel is still composed of half of the periodic table. Among these elements, the main responsible for the heat of the wastes is americium. Its reprocessing could allow improving the compactness of deep geological storage of the wastes. Thus the liquid-liquid extraction process called EXAm was developed in order to recover the americium alone. The key step of the process is the Am/Cm separation. An extractant mixture is used with an aqueous complexing agent: TEDGA (N,N',N,N'-tetraethyl-diglycolamide). It allows to enhance the Am/Cm separation by keeping preferentially curium in the aqueous phase, but its structure selectivity relationship is not well known yet. Therefore, the purpose of this thesis is to synthesize and evaluate some structural analogues of TEDGA, in order to better understand the impact of its structure on the Am/Cm selectivity in the EXAm process.During this study, 14 analogues of TEDGA were synthesized and 17 molecules were evaluated in liquid-liquid extraction. Several structural modifications were studied: length and steric hindrance of the N-alkyl chains, size of the spacer, and the introduction of secondary amide functions. This work shows that it is not possible to maintain the ligand in the aqueous phase from tetrabutyl derivatives, and the addition of steric hindrance, or modification of hydrophilicity/lipophilicity balance, systematically decreases the selectivity of ligands. The addition of secondary amide functions (-CONHR) makes the molecules extractible by the solvent (formation of hydrogen bonds with the extractants), therefore they are unsuitable to be used in the EXAm process. The spacer has the main impact on the selectivity: the complexation capacity in high acid medium disappears when it is shortened (malonamide), whereas the ligand has a preference for Am instead of Cm (inversion of selectivity) when it is lengthen (TEDOODA and TETOUDA derivatives).This whole study shows the peculiar selectivity given by the TEDGA in comparison with other diglycolamides, and the difficulties to enhance the process using this family of ligands. Nevertheless, a better understanding of its chemistry has allowed to define more clearly its modeling in the process and the studying of its structure/selectivity relationship has shown that the enhancing of the ligands selectivity probably requires spacer preorganization.

En réponse aux attentes actuelles des consommateurs pour des produits de haute qualité nutritionnelle et environnementale, et face aux impératifs industriels conduisant à minimiser les risques et l’impact environnemental lors de l’extraction à l'hexane de l’huile de la graine de colza, l’étude de l’extraction aqueuse avec assistance enzymatique de cette huile a été reprise avec 2 objectifs principaux : déterminer les enzymes et mélanges d'enzymes adaptés à la meilleure déstructuration du tissu adipeux végétal, et d'autre part étudier les propriétés et la déstabilisation de l'émulsion formée. De l'optimisation de ces 2 séquences du process dépendent les rendements finaux en huile de l'extraction et les propriétés du tourteau, qui constituent les clés économiques de l'émergence de cette nouvelle technologie. Pour cela, après caractérisation physicochimique des constituants de la graine, protéases et polysaccharides hydrolases ont été testées seules ou en combinaison afin d’optimiser le rendement en huile libre et en huile contenue dans l’émulsion engendrée lors de l’extraction et obtenue par centrifugation. Après caractérisation de l’émulsion (rhéologie, diffusion statique de la lumière, pH, conductivité), des tests de déstabilisation physicochimiques ou thermo-mécaniques ont été mis en œuvre afin de séparer les constituants de l’émulsion formée, et obtenir ainsi la libération de l'huile. Les tests réalisés ont permis de retenir trois procédés de déstabilisation: l’addition de talcs, l’inversion de phase par addition d’huile exogène en présence de NaCl dans la phase aqueuse, et les cycles de congélation/décongélation. Afin d’apporter les premiers éléments de l’optimisation de ce dernier procédé, une étude par planification expérimentale a été mise en œuvre / Consumer's concerns about the quality and environmental impact of the products as well as the industrial requirements regarding the risk assessment and the environmental and health repercussions of the solvent extraction of rapeseed oil using hexane led us to work on the optimisation of the aqueous enzymatic extraction of this oil. The study has been carried out to determine the best combination of enzymes able to achieve the disruption of the vegetal adipose tissue, and to characterize the emulsion obtained after centrifugation. The final objective was to maximize the yields of the oil extraction and to obtain adequate nutritional properties of the cake. After the physicochemical characterization of the rapeseed raw material, several proteases and polysaccharide hydrolases have been tested individually and in combination in order to optimize the removal of free oil and the emulsion oil yield occurring during the aqueous extraction process. The physicochemical properties of the emulsion have been determined: rheological properties, pH, conductivity, spectroscopy by Short Angles Light Scattering). Thereafter some physicochemical and thermo-mechanical treatments have been carried out to destabilize the oil-in-water emulsion obtained after the centrifugation, which contained a large part of the total oil of the reaction mixture. Three destabilization processes appeared particularly interesting to increase the free oil removal from the emulsion: talc addition before centrifugation, phase inversion by addition of exogenous oil in presence of NaCl in the aqueous phase, and freezing/thawing cycles. Finally, an optimisation trial of the freezing/thawing process using a Doehlert experimental design has been done as an example

The proposed human intestinal absorption prediction model is applied to over 900 pharmaceuticals and has about 82.5% true prediction power. This study will provide a screening tool that can differentiate well absorbed and poorly absorbed drugs in the early stage of drug discovery and development. This model is based on fundamental physicochemical properties and can be applied to virtual compounds. The maximum well-absorbed dose (i.e., the maximum dose that will be more than 50 percent absorbed) calculated using this model can be utilized as a guideline for drug design, synthesis, and pre-clinical studies.

L'extraction d'huile de graines d'oléagineux en milieu aqueux a pour principal objectif la suppression des solvants utilisés dans les industries de trituration. Pour extraire l'huile des graines, les mélanges enzymatiques et de nombreux paramètres physico-chimiques ont été étudiés. Deux plans d'expériences consécutifs, réalisés sur le M.I.A. ont permis de formuler des mélanges d'enzymes efficaces, constitués de 3 ou 4 préparations enzymatiques commerciales parmi les 25 retenues initialement. Cette démarche permet de réaliser des mélanges optimaux pour la dégradation des parois des graines étudiées. Les extractions d'huile font apparaître 4 phases après séparation par centrifugation : résidu solide, émulsion, phase aqueuse et huile libre. Les effets de différents paramètres physico-chimiques ont été évalués (broyage, temps, température, agitation, séparation...). Au final, l'huile libérée des graines à l'aide des mélanges formulés (85% de l'huile totale pour le colza, 92% pour le tournesol), la quantité de sucres fermentescibles produite (entre 60 et 80 g/l en fonction des conditions) ou encore la concentration de protéines solubilisées (supérieure à 30g/l) sont les résultats marquants de cette étude. Cette étude décryptant les conditions à mettre en œuvre pour maximiser l'extraction d'huile en phase aqueuse constitue un socle de connaissances permettant d'envisager le développement futur d'un bioraffinage complet des graines de colza grâce à la valorisation de chacun des co-produits huiles, protéines (napines du colza) et sucres fermentescibles. / The extraction of oil from oilseed in an aqueous medium aims to remove the solvents used in the crushing industry. To extract oil from seeds, the enzymatic mixtures and numerous physico-chemical parameters have been studied. Two consecutive experimental designs, realized on the A.I.M. prepared from treated seeds, allowed to select effective enzyme mixtures, consisting of 3 or 4 commercial enzyme preparations out of the 25 originally selected. This original approach, based on the use of statistical tools, allows to achieve optimal mixtures for the degradation of the walls of studied seeds. The extraction of oil shows 4 phases after separation by centrifugation: solid residue, emulsion, aqueous phase and free oil. The effects of different physico-chemical parameters were evaluated (grinding time, temperature, agitation, separation...). Finally, the oil released from seeds using enzymatic mixtures made (85% of the total oil for rapeseed, 92 % for sunflower), the amount of fermentable sugars produced (60 and 80 g/l depending on conditions) or the concentration of solubilized protein (greater than 30g/l) are the landmark results of this study. This study, decrypting the conditions to implement the maximization of oil extraction in aqueous phase, is an important whole of knowledge to contribute the future development of a complete biorefining of rapeseed and sunflower with the use of each co-products : oils, proteins (napins from rape) and fermentable sugars.

The electrochemical oxidation of CoCl2(PPh3)2 was investigated in a mixture of acetonitrile and pentanol (1:1) at a platinum disk working electrode using Cyclic Voltammetry (CV) and Chronoamperometry. Elemental Analysis and Infrared Spectroscopy were used to characterise the synthesized compounds i.e. CoCl2(PPh3)2 and CoCl(PPh3)3. Cyclic Voltammetry was utilised for the examination of different working electrode materials that could be used for the anodic voltammetric studies of CoCl2 (PPh3)2, to characterise the reactants and products of each electrode reaction, to investigate the chloride binding ability to a CoCl(PPh3)3 complex, and to evaluate the electrocatalytic substitution of chloride by PPh3 from the complex CoCl2(PPh3)2. Use of ferrocene as an internal standard during the anodic studies of CoCl2(PPh3)2 was also evaluated. The number of electron involved in the electrode process, CoII to CoIII from CoCl2(PPh3)2 and diffusion coefficient of ferrocene in a mixture of acetonitrile and pentanol (1:1) were determined using Chronoamperometry. Ultraviolet-Visible (UV-Vis) and 31P Nuclear Magnetic Resonance (31P NMR) spectra were used to assist with the characterisation of the electrode reactions involved during oxidation of CoCl2(PPh3)2. / Dissertation (MSc (Chemistry))--University of Pretoria, 2008. / Chemistry / unrestricted

Orientador: Vital Paulino Costa / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Ciências Médicas / Made available in DSpace on 2018-08-24T05:19:20Z (GMT). No. of bitstreams: 1 Santana_AlanaMendonca_M.pdf: 2805390 bytes, checksum: 9512111e988de78a1ffde9d9f877658b (MD5) Previous issue date: 2014 / Resumo: O objetivo deste trabalho foi investigar os efeitos das combinações fixas dos análogos de prostaglandinas com timolol sobre a barreira hematoaquosa, a espessura macular central e a pressão intraocular (PIO), em pacientes pseudofácicos com glaucoma primário de ângulo aberto. Neste ensaio clínico randomizado, com observador mascarado e duração de 6 meses, os pacientes foram tratados uma vez por dia (20:00 horas) com lubrificante (grupo controle) ou com a combinação fixa de maleato de timolol 0,5% e latanoprosta 0,005% (CFLT), maleato de timolol 0,5% e bimatoprosta 0,03% (CFBT) ou maleato de timolol 0,5% e travoprosta 0,004% (CFTT). Foi incluído no estudo apenas um olho de 61 pacientes: CFLT (n=16), CFBT (n=15), CFTT (n=15) e grupo controle (n=15). A barreira hematoaquosa foi avaliada por meio do &quot;laser flare meter¿ antes do início do uso das medicações e após 15 dias, 1,2,3,4,5 e 6 meses de tratamento. A PIO foi medida sempre às 9:00 horas, nas mesmas ocasiões. A espessura macular central foi avaliada por meio da tomografia de coerência óptica antes do uso das medicações, após 1 e 6 meses de tratamento ou na hipótese de piora da acuidade visual. Não houve aumento estatisticamente significante nos valores médios de &quot;flare¿ em comparação aos valores iniciais em todos os grupos (p>0,05) em todas as visitas, exceto no grupo CFTT no primeiro mês (p=0,0476) e no grupo CFLT (p=0,0129) no terceiro mês de seguimento. Não houve diferença estatisticamente significativante entre os valores médios de &quot;flare¿ entre os grupos durante o estudo (p>0,05). A média dos valores da espessura macular central aumentou significativamente nos grupos CFLT (p=0,012) e CFTT (p=0,0419) no primeiro mês de tratamento em relação aos valores iniciais. Não houve aumento estatisticamente significante nos valores médios da espessura macular central em relação aos valores iniciais em todos os grupos após 6 meses de tratamento (p>0,05) e não ocorreu diferença estatisticamente significante entre os grupos durante o estudo (p>0,05). A PIO média inicial foi significativamente menor no grupo controle (p=0,0000). Todas as combinações fixas reduziram significativamente a PIO em todas as visitas (P<0,0001), com efeito hipotensor semelhante entre si (p=0,816). Estes resultados indicam que o uso das combinações fixas de análogos de prostaglandinas com timolol não aumentou significativamente a média dos valores de &quot;flare¿ ou a média da espessura macular após 6 meses de tratamento nesta população / Abstract: The aim of this study was to investigate the effects of prostaglandin analogues and timolol fixed-combinations on the blood-aqueous barrier, central macular thickness and intraocular pressure (IOP) in pseudophakic patients with primary open angle glaucoma. In this randomized, masked-observer, 6-month clinical trial, patients were treated once daily (8 pm) with lubricant eye drops (control group), 0,5% timolol and 0,005% latanoprost fixed-combination (LTFC), 0,5% timolol and 0,03% bimatoprost fixed-combination (BTFC) or 0,5% timolol and 0,004% travoprost fixed-combination (TTFC). One eye of 61 patients were included in the study: LTFC (n=16), BTFC (n=15), TTFC (n=15) and control group (n=15). The blood-aqueous barrier status was assessed using the laser flare meter before the medications were started and after 15 days, 1, 2, 3, 4, 5 and 6 months of treatment. The IOP was measured always at 9 am, at the same intervals. The central macular thickness was evaluated with optical coherence tomography before medications were started, after 1 and 6 months of follow-up or if a patient showed decreased visual acuity at any time during follow-up. There was no significant increase in mean flare measurements from baseline in all groups (p>0.05) in all visits, except TTFC group at 1 month (p=0,0476) and LTFC group at 3 months (p=0,0129). There were no significant differences in mean flare values among the groups (p>0.05). Mean central macular thickness values were significantly higher in LTFC (p=0,012) and TTFC groups (p=0,0419) at 1 month of follow-up. There was no significant increase in mean central macular thickness values from baseline in all groups (p>0.05) after 6 months and no significant differences among the groups (p>0.05) during follow-up. At baseline, mean IOP was significantly lower in control group (p=0,0000). All fixed-combinations significantly reduced IOP in all follow-up visits, with similar lowering effect (p=0,816). These findings indicate that the use of prostaglandin analogues and timolol fixed-combinations didn't significantly increased mean flare values or mean central macular thicknes measurements after 6 months of follow-up in this population / Mestrado / Oftalmologia / Mestra em Ciências Médicas

A partição das enzimas glicose-6-fosfato desidrogenase (G6PD) e uroquinase (UK) em sistemas micelares de duas fases aquosas foi investigada, teórica e experimentalmente. Inicialmente, a partição de G6PD em sistema micelar de duas fases aquosas composto pelo tensoativo não-iônico C10E4 (óxido de n-deciltetraetileno) foi estudada. Observou-se uma partição governada primariamente por interações repulsivas estéricas, do tipo \"volume de exclusão\", sendo a G6PD recuperada preferencialmente na fase inferior do sistema, pobre em micelas, resultando em valores de KG6PD inferiores a 1,0. Os tensoativos catiônicos CnTAB (brometos de alquiltrimetilamônio, n = 8, 10 e 12) foram adicionados ao tensoativo C10E4, de modo a formar sistemas micelares mistos (não-iônico/catiônico) de duas fases aquosas e atrair a G6PD de carga efetiva negativa para a fase superior, rica em micelas positivamente carregadas. Os coeficientes de partição obtidos nos sistemas C10E4/CnTAB/tampão foram no mínimo 2,5 vezes maiores que os correspondentes no sistema C10E4/tampão mantendo-se o volume de exclusão constante. De uma forma geral, o sistema micelar misto C10E4/C10TAB/tampão forneceu o melhor KG6PD = 7,7, com um rendimento de G6PD na fase superior de 71%. A adição de ligantes de afinidade (inibidores enzimáticos) ao sistema de duas fases aquosas C10E4/tampão para purificação de UK e G6PD também foi estudada. Não foram observadas diferenças significativas no perfil de partição da UK na presença ou não do ligante p-aminobenzamidina, o qual apresentou partição uniforme entre as duas fases do sistema, sendo obtidos valores de KUK ~ 0,70 em ambos os casos. Para a G6PD, um pequeno incremento no KG6PD foi observado na presença dos ligantes de afinidade cibacron blue e procion red, porém resultando ainda em valoresfnferiores a 1. Portanto, a utilização de inibidores enzimáticos livres em solução como ligantes de afinidade para purificação de UK e G6PD em sistema micelar C10E4/tampão de duas fases aquosas não resultou em diferenças significativas no perfil de partição das enzimas. Por fim, um sistema de purificação em dois estágios, sendo o primeiro constituído de sistema micelar não-iônico (C10E4) de duas fases aquosas e o segundo de sistema micelar misto (C10E4/ C10TAB) de duas fases aquosas foi aplicado para a purificação de G6PD presente em homogeneizado celular de Saccharomyces cerevisiae, sendo obtido um rendimento final de G6PD de 59%, com um fator de purificação de 1,3. / The partitioning of the hydrophilic enzymes glucose-6-phosphate dehydrogenase (G6PD) and urokinase (UK) in two-phase aqueous micellar systems was investigated, both experimentally and theoretically. Initially, the partitioning of G6PD in two-phase aqueous micellar system composed of the nonionic surfactant C10E4 (n-decyl tetra(ethylene oxide) was studied. It was observed a partitioning behavior governed primarily by repulsive, steric, excluded-volume interactions, which drove the enzyme preferentially to the bottom, micelle-poor phase, resulting in KG6PD values smaller than one. The cationic surfactants CnTAB ((alkyltrimethylammonium bromide, n = 8, 10, and 12) were mixed wíth the nonionic surfactant C10E4 to form two-phase aqueous mixed (nonionic/cationic) micellar systems. The measured G6PD partition coefficients in the C10E4/CnTAB/buffer systems were at least 2.5 times larger than those in the corresponding C10E4/buffer system, clearly demonstrating that the net negatively charged G6PD was attracted electrostatically to the top, mixed micelle-rich phase, containing a greater number of positively-charged C10E4/CnTAB mixed micelles. Overall, the two-phase aqueous mixed (C10E4/C10TAB) micellar system yielded the highest KG6PD = 7.7, with a G6PD yield in the top phase of 71%. The addition of affinity ligands (enzyme inhibitors) to the two-phase C10E4 /buffer systems was studied for UK and G6PD purification. No significant differences in the UK partitioning behavior was observed in the presence or not of the ligand p-aminobenzamidine, since the ligand was found to partition evenly between the two phases of the system. Partition coefficient values of about 0.70 were obtained in both cases. For the G6PD, the partition coefficient was found to be slightly higher in the presence of either cibacron blue or procion red as affinity ligand, however still smaller than one. Therefore, the use of competitive inhibitors free in solution as affinity ligands for UK and G6PD purification in two-phase C10E4 /buffer systems did not provide significant differences in the enzymes partitioning behaviors. Finally, a two-step purification process, combining a two-phase aqueous nonionic (C10E4) micelar system, followed by a two-phase aqueous mixed (C10E4/C10TAB) micellar system, was employed for the purification of G6PD present in a Saccharomyces cerevisiae cell homogenate. It was obtained a G6PD final yield of 59%, and a purification factor of 1,3.