Au cours de cette thèse, plusieurs approches de fonctionnalisation anti-bactérienne passive, de type"bactériostatique" utilisant des espèces hydrophobes, et active (selon un standard ISO), de type"bactéricide" utilisant des nanoparticules d’argent métallique ou des espèces à base d’ammoniumquaternaire, ont été testées sur des tissus textiles. Des solutions liquides ont été élaborées par voie sol-gelet photochimique, en association ou non. Elles ont tout d’abord été caractérisées d’un point de vuephysico-chimique, morphologique et structural, afin d’optimiser leur formulation et les caractéristiquesdes espèces en solution vis-à-vis de différents cahiers des charges industriels. Ce travail d’optimisation aen particulier conduit à des solutions stables permettant leur utilisation reproductible au cours du temps.Les solutions ont ensuite été imprégnées sur des échantillons textiles, par un dispositif simplifié de "padcoating"mis au point au cours de la thèse, afin de tester la fonction anti-bactérienne des textiles traités.Selon la nature des espèces imprégnées, l’optimisation des solutions conduit à une fonctionnalité antibactériennepassive ou active respectant l’aspect visuel du textile et ne dénaturant pas son toucher. Destests de lavage de laboratoire ou de lavage ménager en conditions réelles ont également montré unaccrochage notable des espèces imprégnées sur les textiles. Des options ont finalement été proposées pouraccroître cet accrochage afin de répondre à des conditions de lavage industriel. En conclusion, ce travail met en évidence le potentiel des approches d’élaboration par chimie douce en vue de fonctionnaliser des textiles, en permettant en particulier de proposer des méthodologies originales et simplifiées en adéquation avec des impératifs industriels. / In this thesis, several approaches have been tested for the passive ("bacteriostatic") and active (as definedby an ISO standard, "bactericidal") anti-bacterial fonctionalization of textile fabrics by using hydrophobicspecies and nanoparticles of metallic silver or quaternary ammonium species, respectively. Liquidsolutions were prepared by sol-gel and photochemistry methods, in association or not. Physicochemical,morphological and structural characterizations have first been realized to optimize the solutionformulations and the characteristics of active species in solutions towards various industrialspecifications. This optimization study has in particular led to stable solutions allowing their use inreproducible conditions over time. The optimized solutions were then imparted to textile samples, using asimplified "pad-coating device implemented during the thesis, in order to test the anti-bacterial functionof treated textiles. Depending on the nature of the species present on textiles, the optimized solutions ledto a passive or active anti-bacterial function while keeping the visual aspect and hand feeling of textiles.Laboratory washing tests or laundering washings in real conditions also showed a significant attachmentof impregnated species on textiles. Different options have finally been proposed to enhance thisattachment in order to fulfill industrial washing criteria. In conclusion, this thesis work highlights thepotential of soft chemistry approaches to functionalize textiles supports and enable us to propose originaland simplified methodologies in adequacy with industrial requirements.

<p><em>Size exclusion chromatography</em> (SEC) was applied for purification of psychoactive biomolecules from plants. These molecules are in the same molecular weight range, but do not necessarily share other chemical properties, that makes the SEC technique efficient. By applying SEC as a first purification step much of the co-extractives from the plants can easily be removed. Large amounts of target substance can be obtained with little effort if the system is automated. Combining SEC with a second purification step, consisting of normal phase chromatography, provides high purity of the target substance.</p><p>Both known and unknown psychoactive biomolecules can easily be purified using the purification method developed in this Master's Thesis. Purifications that previously required long time and much "hands-on" can be completed much faster and with less manual work.</p><p>The method developed was tested on cannabis, coffee and 'Spice' with good results.</p>

Size exclusion chromatography (SEC) was applied for purification of psychoactive biomolecules from plants. These molecules are in the same molecular weight range, but do not necessarily share other chemical properties, that makes the SEC technique efficient. By applying SEC as a first purification step much of the co-extractives from the plants can easily be removed. Large amounts of target substance can be obtained with little effort if the system is automated. Combining SEC with a second purification step, consisting of normal phase chromatography, provides high purity of the target substance. Both known and unknown psychoactive biomolecules can easily be purified using the purification method developed in this Master's Thesis. Purifications that previously required long time and much "hands-on" can be completed much faster and with less manual work. The method developed was tested on cannabis, coffee and 'Spice' with good results.

Many attempts have been made to control water conformance. It is very costly to produce, treat and dispose of water, and produced water represents the largest waste stream associated with oil and gas production. The production of large amounts of water results in: (a) the need for more complex water?oil separation; (b) corrosion of wellbore and other equipment; (c) a rapid decline in hydrocarbon production rate and ultimate recovery; and (d) consequently, premature abandonment of a well or field, leaving considerable hydrocarbons unproduced. Sometimes water production results from heterogeneities in the horizontal direction, which leads to uneven movement of the flood front and subsequent early breakthrough of water from high permeability layers. This problem is exacerbated if there is (vertical) hydraulic communication between layers so that crossflow can occur. One of the novel technologies in chemical enhanced oil recovery (EOR) is a gel type called deep diverting gel (DDG), which describes material that functions by plugging thief zones deep from the well where they were being injected. To evaluate the performance of this new treatment method, we will (1) model the treatment methods, (2) conduct economic analysis, and (3) compare different EOR methods. We have conducted relevant literature review about the development, design, modeling and economics of the enhanced oil recovery methods. Schlumberger's Eclipse simulator software has been used for modeling purposes. Modeling runs have demonstrated that placement of a DDG in a high permeability zone provided a blockage that diverted water into lower permeability areas, thus increasing the sweep of target zones. Research results demonstrated that, although higher recovery can be achieved with a polymer flood, the combination of delayed production response and large polymer amounts cause such projects to be less economically favorable than deep gel placement treatments. From results of several sensitivity runs, it can be concluded that plug size and oil viscosity are two determining factors in the efficiency of DDG treatments. For the assumed case, economic analysis demonstrated that DDG has the most positive net present value (NPV), with polymer flooding second and simply continuing the waterflood to its economic limit the least positive NPV.

The distinctive architecture of the stratum corneum with its unique nature of an interstitial lipoidal environment plays the major role in regulating the barrier function of the skin. The major problem with the transdermal delivery of 5-fluorouracil or idoxuridine is the permeation of sufficient amounts to the deeper layers of the skin and into the systemic circulation. In an attempt to enhance the transdermal permeability of 5-fluorouracil and idoxuridine, the aim of this study was to evaluate two lamellar gel phase systems (Physiogel dermaquadrille® and Physiogel NT®) and Emzaloids® as transdermal delivery vehicles for the two actives. Lamellar gel phase systems (LGPS) and Emzaloids® are both novel drug delivery systems. The epidermis of female abdominal skin was used in vertically mounted Franz diffusion cell experiments. An average amount of 250 mg of the 1% m/m LGPS was applied to cover the entire diffusion area of 1,075 cm2 of the skin, which contained 2,5 mg of the active. Samples of the actives in Emzaloids® were prepared and applied in the same way. The control solutions of the actives in water were prepared so that 1 ml of the applied solution contained the same amount of drug that was applied to the experimental cells. The entire receptor phase of the cells was removed at 2,4,6, 8, 10, 12 and 24 hours and was replaced with fresh 37°C receptor phase. The amount of active in the receptor phase was determined by HPLC analysis. Graphs of the cumulative amount of the active that permeated the skin over the 24 hour period were drawn and the slope of the graphs represented the flux in µg/ml/h. The average flux values of six experimental cells and six control cells were compared. Entrapment of the actives in the Emzaloid® vesicles was confirmed with the use of confocal laser scanning microscopy. Results for the LGPS indicate an enhancement ratio in the order of 4,2 for 5-fluorouracil and 1,7 for idoxuridine when compared to the control cells. There were no viscosity changes in the LGPS samples containing 1% m/m of the active when compared with the blank LGPS samples, suggesting that no change in the internal structure of the LGPS occurred after the addition of the actives to it. There were also no significant changes in the pH of the samples. Entrapment of the actives in the Emzaloid® vesicles occurred readily. The Emzaloid® vehicle showed a lower rate of release for idoxuridine than the LGPS did during the VanKel dissolution experiments. This suggests that higher flux values would be obtained with the LGPS for idoxuridine than with the Emzaloid® formulation, since more drug was available for permeation through the skin. This was, however, not the case. The Emzaloid® formulation showed much higher flux values, showing that even with a smaller amount of active available to permeate the skin higher flux values were obtained. Enhancement ratios of 20,33 and 3,50 were achieved with the Emzaloid® formulation for 5-fluorouracil and idoxuridine respectively. The internal LGPS structure which mimics the skins lipid components remained unchanged after the addition of the actives. Greater success might be achieved with the LGPS for different model drugs, since the drugs' physicochemical properties play an important part in its permeation through the skin. The Emzaloid® formulation, which is closely related to liposomes and transfersomes, showed great potential for commercially marketable formulations for the drugs tested but further research on the formulation has to be done. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2005.

The distinctive architecture of the stratum corneum with its unique nature of an interstitial lipoidal environment plays the major role in regulating the barrier function of the skin. The major problem with the transdermal delivery of 5-fluorouracil or idoxuridine is the permeation of sufficient amounts to the deeper layers of the skin and into the systemic circulation. In an attempt to enhance the transdermal permeability of 5-fluorouracil and idoxuridine, the aim of this study was to evaluate two lamellar gel phase systems (Physiogel dermaquadrille® and Physiogel NT®) and Emzaloids® as transdermal delivery vehicles for the two actives. Lamellar gel phase systems (LGPS) and Emzaloids® are both novel drug delivery systems. The epidermis of female abdominal skin was used in vertically mounted Franz diffusion cell experiments. An average amount of 250 mg of the 1% m/m LGPS was applied to cover the entire diffusion area of 1,075 cm2 of the skin, which contained 2,5 mg of the active. Samples of the actives in Emzaloids® were prepared and applied in the same way. The control solutions of the actives in water were prepared so that 1 ml of the applied solution contained the same amount of drug that was applied to the experimental cells. The entire receptor phase of the cells was removed at 2,4,6, 8, 10, 12 and 24 hours and was replaced with fresh 37°C receptor phase. The amount of active in the receptor phase was determined by HPLC analysis. Graphs of the cumulative amount of the active that permeated the skin over the 24 hour period were drawn and the slope of the graphs represented the flux in µg/ml/h. The average flux values of six experimental cells and six control cells were compared. Entrapment of the actives in the Emzaloid® vesicles was confirmed with the use of confocal laser scanning microscopy. Results for the LGPS indicate an enhancement ratio in the order of 4,2 for 5-fluorouracil and 1,7 for idoxuridine when compared to the control cells. There were no viscosity changes in the LGPS samples containing 1% m/m of the active when compared with the blank LGPS samples, suggesting that no change in the internal structure of the LGPS occurred after the addition of the actives to it. There were also no significant changes in the pH of the samples. Entrapment of the actives in the Emzaloid® vesicles occurred readily. The Emzaloid® vehicle showed a lower rate of release for idoxuridine than the LGPS did during the VanKel dissolution experiments. This suggests that higher flux values would be obtained with the LGPS for idoxuridine than with the Emzaloid® formulation, since more drug was available for permeation through the skin. This was, however, not the case. The Emzaloid® formulation showed much higher flux values, showing that even with a smaller amount of active available to permeate the skin higher flux values were obtained. Enhancement ratios of 20,33 and 3,50 were achieved with the Emzaloid® formulation for 5-fluorouracil and idoxuridine respectively. The internal LGPS structure which mimics the skins lipid components remained unchanged after the addition of the actives. Greater success might be achieved with the LGPS for different model drugs, since the drugs' physicochemical properties play an important part in its permeation through the skin. The Emzaloid® formulation, which is closely related to liposomes and transfersomes, showed great potential for commercially marketable formulations for the drugs tested but further research on the formulation has to be done. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2005.

Zugl.: Berlin, Humboldt-Univ., Diss., 2009

Neste trabalho foram obtidos filmes de óxido de tungstênio pelo método sol-gel modificado, tendo como precursor o tungstato de sódio dihidratado (Na2WO4.2H2O) e como agente estruturante o surfactante cloreto de dodeciltrimetilamônio (DTAC). O comportamento dos sistemas em meio aquoso foi avaliado por medidas de pH, condutividade e viscosidade. Foram avaliadas duas metodologias de obtenção dos filmes de óxido de tungstênio: a primeira consistiu na obtenção de filmes de tungstato de sódio, através de sistemas contendo 10 mmol.L-1 de Na2WO4.2H2O em diferentes concentrações de DTAC, por casting, e conversão do tungstato de sódio a óxido de tungstênio pela acidificação dos filmes; a segunda metodologia consistiu na conversão dos sistemas aquosos contendo 20 mmol.L-1 de Na2WO4.2H2O, em diferentes concentrações de DTAC, em ácido tungstico, obtenção dos filmes por spin coating e, calcinação em presença de ar. Os filmes foram obtidos em substratos de silício (100) recobertos com dióxido de silício e avaliados por Difração de Raios-X, Espectrometria de retroespalhamento Rutherford, Espectroscopia Raman, Microscopia Eletrônica de Varredura e ensaios fotocatalíticos. As alterações na concentração precursor e agente estruturante não afetaram significativamente o pH e a viscosidade dos sistemas precursores. A determinação da concentração micelar crítica (cmc) do DTAC, obtida através da condutividade, foi de 13 mmol.L-1 e 9,88 mmol.L-1 para os sistemas contendo 10 e 20 mmol.L-1 de Na2WO4.2H2O, respectivamente. Em ambas metodologias o produto final foi o óxido de tungstênio em forma de disco e placas. As espessuras dos filmes obtidos na primeira metodologia variaram de 4 a 5 μm e as estruturas tiveram diâmetros médios de 4,37 μm e 114 nm. Na segunda metodologia as espessuras foram de 0,5-1,0 μm e as estruturas obtidas tiveram diâmetros médios em torno de 95-103 nm. Os filmes obtidos apresentaram atividade fotocatalítica, uma vez que duplicaram a velocidade da reação de degradação do corante alaranjado de metila em relação ao sistema sem o filme. / In this work tungsten oxide films have been obtained bymodified sol-gel method, with sodium tungstate dehydrate (Na2WO4.2H2O) as the precursor and the cationic surfactant dodecyltrimethylammonium chloride (DTAC) as structuring agent.The behavior in aqueous media of precursor/structuring agent systems was characterized by pH, conductivity and viscosity measurements. Two methods for obtaining tungsten oxide films were evaluated: the first consisted in obtaining sodium tungstate films from the systems containing 10 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations, by casting, converting the sodium tungstate to tungsten oxide; the second method consisted in the conversion of the aqueous systems containing 20 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations to tungstic acid, obtaining the films by spin coating and, posteriorly, calcination in the presence of air. The films were obtained on silicon substrate (100) with a 50 nm layer of silicon dioxide and were characterized by X-ray diffraction, Rutherford backscattering spectrometry, Raman spectroscopy, Scanning Electron Microscopy and photocatalytic tests. The precursor concentration and structuring agent do not affect significantly the pH and the viscosity of the precursor systems in aqueous media.The values of critical micelle concentration (CMC) of DTAC, obtained by the conductivity, were of13 mmol.L-1 and 9,88 mmol.L-1, for the systems containing 10 and 20 mmol.L-1 de Na2WO4.2H2O, respectively.In both adopted methods the final product is the tungsten oxide, with nano and micrometric structures in the form of discs and plates. The thickness of the films obtained in the first method varied from 4 to 5 μm and the structures presented an average diameter around 4,37 μm and 114 nm. The thickness of the films obtained with the second methodvariedfrom0,5to 1 μm and the structures presented an average diameter from 95 to103 nm.The obtained tungsten oxide films presented photocatalytic activity, since doubled the reaction rate of methyl orange dye degradation with respect to the system without the film.

Ce travail de thèse porte sur une meilleure compréhension de la croissance de nanoparticules d'oxyde de zinc élaborées à partir d'une approche organométallique. Au cours de ce travail, une analyse de la taille des nanoparticules en utilisant un outil simple basée sur une représentation bidimentionnelle couplée à une analyse statistique multivariée. Elle permet d'extraire la corrélation éventuelle entre la longueur et la largeur des nanoparticules. Cette approche permet de traiter un ensemble de nanoparticules homogène ou hétérogène en taille et en forme. Comparée à l'approche statistique usuelle qui analyse individuellement la distribution de la longueur et celle de la largeur, notre démarche met très facilement en évidence les différents types de nanoparticule et leur anisotropie (ou non). Pour chaque classe de nano-objets considérée, la relation entre la longueur et la largeur, c'est-à-dire les corrélations fortes ou faible entre ces deux paramètres, fourni des informations concernant le(s) mécanisme(s) de nucléation-croissance des nanoparticules. Par exemple, cette approche permet de suivre l'effet sur la taille et la forme de nanoparticules préparées par différents procédés (chimiques ou physique). A partir de différentes images de microscopie électronique extraites de la bibliographie ou de nos travaux de recherche, nous avons démontré l'efficacité et la simplicité de cette approche. De plus, nous avons pu revisiter la synthèse organométallique de nanoparticules de ZnO à la lumière de cette nouvelle méthode de traitement des données. Les nanoparticules anisotropes obtenues par hydrolyse du dicyclohexyl zinc comme précurseur organométallique en présence d'alkyl amine uniquement ont donc été analysées. Le mécanisme de formation a été étudié par analyse systématique des images de microscopie électroniques à transmission et une croissance par attachement orienté a pu être mise en évidence. De plus, nous avons montré que la taille des nanabatonnets d'oxyde de zinc peut être facilement contrôlée en modulant la vitesse d'hydrolyse, le temps de maturation du mélange précurseur organométallique et ligand alkyl amine avant le début de l'hydrolyse, la nature du ligand et la quantité d'eau introduite. Enfin, pendant ce travail, nous avons observé la gélification des milieux réactionnels. L'étude de ce phénomène a permis de développer une approche originale permettant de mettre en forme des matériaux hybride organique-inorganiques. En effet, à partir d'un ensemble d'expériences utilisant la rhéologie, la RMN, la MET, des calculs théoriques, le WAXS ... nous avons pu mettre en évidence une réaction d'oligomérisation entre le précurseur organométallique et les ligands alkyl amine. Cette oligomérisation entre les centres métalliques conduit à la formation de gels, qui peuvent être mise en forme en utilisant des seringues, des tampons ou encore des moules. Des matériaux hybrides d'oxydes métalliques sont ensuite obtenus par hydrolyse du gel. Cette nouvelle approche a été développée pour l'oxyde de zinc puis a été étendue aux oxydes d'étain et de fer. Il s'agit donc d'une approche générale qui ouvre des perspectives intéressantes dans l'utilisation de ces matériaux notamment comme couches sensibles pour des capteurs de gaz. / This work is focused on the better understanding of the formation of zinc oxide anisotropic nanoparticle through an organometallic synthesis. To start on this project, the development of a statistical tool to analyze nanoparticle sizes and shapes was mandatory. A simple 2D plot with a multivariate statistical analysis is proposed in order to extract, in particular, the correlation between length and width in a collection or a mixture of anisotropic particles. Compared to the usual statistics on the length associated to a second and independent statistical analysis of the width, this simple plot easily points out the various types of nanoparticles and their (an)isotropy. For each class of nano-objects, the relationship between width and length (i.e. the strong or weak correlations between these two parameters) may suggest information concerning the nucleation-growth processes. It allows one to follow the effect on the shape and size distribution of physical or chemical processes such as simple ripening. Various electronic microscopy pictures from the literature or from our own syntheses are used as examples to demonstrate the efficiency and simplicity of such an analysis. Furthermore, following the organometallic approach, well defined crystalline zinc oxide nanorods are obtained through the hydrolysis reaction of dicyclohexyl zinc precursor without solvent in presence of primary fatty amine only. Their mechanism of formation is studied through a multivariate analysis of TEM results and an oriented attachment process is demonstrated. Taking advantage of this mechanism, the size of the ZnO nanorods can be easily adjusted tuned by controlling adjusting the hydrolysis rate, the aging time before hydrolysis, the nature of ligand, and/or the amount of water. During such experiments, a gelification of the chemical media are for the first time observed. This is the origin of the last part of our work, which put forward an original approach for outstanding processable and reshapable hybrid materials. Indeed, we unequivocally demonstrate through various complementary experiments (rheology, NMR, TEM, theoretical calculation, WAXS...) the formation of oligomeric structures in a mixture of fatty amine with organometallic compounds. This oligomerization reaction between the metallic centers induces the formation of a gel which can be processed into fibers, stamped patterns or molded pieces. Metal oxide hybrid materials are obtained merely by hydrolysis of the organometallic gel, which are furthermore liquid crystal. This unprecedented route towards easily processable hydrid and metal oxide materials is demonstrated for zinc oxide and extended to other metal oxides such as tin oxide and iron oxide, proving the universality of the method and paving the way, for example, to new sensitive gas sensors layers.

Orientadora: Marileda Bonafim Carvalho / Banca: Julieta Rodini Engracia Moraes / Banca: Aguemi Kohayagawa / Resumo: Para este estudo foram avaliados 20 cães adultos sadios (10 machos e 10 fêmeas) e 24 cães adultos (16 machos e 8 fêmeas) com insuficiência renal crônica (IRC), com o objetivo de estudar a proteinúria. Foram empregadas técnicas para determinação quantitativa de proteína da urina e para a separação de suas frações por meio de SDS-PAGE. As quantidades de proteínas presentes na urina de cães sadios foram pequenas, mas o estudo dos perfis eletroforéticos mostrou haver diferenças entre machos e fêmeas. Apesar da ampla variação das concentrações de proteínas entre os animais, o grupo dos portadores de IRC apresentou proteinúria intensa. Os resultados dos portadores de IRC foram agrupados de acordo com o sexo ou em função do tipo de lesão renal predominante, para comparação dos eletroforetogramas. As análises revelaram que os perfis eletroforéticos seguem um padrão para os machos e outro pra as fêmeas. Ainda, o padrão o perfil eletroforético observado quando há predomínio de lesões glomerulares difere do observado quando há predomínio de lesões túbulo-intersticiais. / Abstract: This trial was conducted in 20 adult health dogs (10 male and 10 female) and in 24 adult dogs (16 male and 8 female) in chronic renal failure (CRF), in order to study urinary protein loss. Determination of total urinary proteins and their separation with SDS-PAGE were employed. The results show that CRF dogs had higher proteinuria when compared to controls and the amount of detected protein had large difference among them. In the CRF there are different patterns of protein bands occurrence and distribution according to the patient sex and predominant renal lesion. The difference between protein bands occurrence of male and female already exists in normal dogs. / Mestre