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.

Metal oxide thin films serve as critical components in many modern technologies, including microelectronic devices. Industrial state-of-the-art production utilizes vapor-phase techniques to make high-quality (dense, smooth, uniform) thin film materials. However, vapor-phase techniques require large energy inputs and expensive equipment and precursors. Solution-phase routes to metal oxides have attracted great interest as cost-effective alternatives to vapor-phase methods and also offer the potential of large-area coverage, facile control of metal composition, and low-temperature processing. Solution deposition has previously been dominated by sol-gel routes, which utilize organic ligands, additives, and/or solvents. However, sol-gel films are often porous and contain residual carbon impurities, which can negatively impact device properties. All-inorganic aqueous routes produce dense, ultrasmooth films without carbon impurities, but the mechanisms involved in converting aqueous precursors to metal oxides are virtually unexplored. Understanding these mechanisms and the parameters that influence them is critical for widespread use of aqueous approaches to prepare microelectronic components. Additionally, understanding (and controlling) density and composition inhomogeneities is important for optimizing electronic properties. An overview of deposition approaches and the challenges facing aqueous routes are presented in Chapter I. A summary of thin film characterization techniques central to this work is given in Chapter II. This dissertation contributes to the field of solution-phase deposition by focusing on three areas. First, an all-inorganic aqueous route to high-κ metal oxide dielectrics is developed for two ternary systems. Chapters III and IV detail the film formation chemistry and film properties of lanthanum zirconium oxide (LZO) and zirconium aluminum oxide (ZAO), respectively. The functionality of these dielectrics as device components is also demonstrated. Second, the impact of steam annealing on the evolution of aqueous-derived films is reported. Chapter V demonstrates that steam annealing lowers processing temperatures by effectively reducing residual counterion content, improving film stability with respect to water absorption, and enhancing dielectric properties of LZO films. Third, density and composition inhomogeneities in aqueous-derived films are investigated. Chapters VI and VII examine density inhomogeneities in single- and multi-metal component thin films, respectively, and show that these density inhomogeneities are related to inhomogeneous metal component distributions. This dissertation includes previously published coauthored material.

Pour contrôler les systèmes chimiques complexes, les outils de la chimie supramoléculaire s’avèrent puissants et représenteront certainement une des technologies clef du 21e siècle. En effet, la réversibilité intrinsèque des liaisons chimiques impliquées dans la formation d'assemblages supramoléculaires apporte à ces systèmes un caractère "adaptatif", capable de réorganiser leur structure en fonction des conditions environnementales. Ce comportement s’avère totalement inédit malgré le grand nombre d’études effectuées sur cette famille de molécules du fait de ses propriétés photoactives. Au cours des dernières années, notre groupe a synthétisé de nombreux dérivés de triarylamines (TAAs), qui ont été utilisés pour produire des architectures supramoléculaires multifonctionnelles. En fonction des différents groupements qui substituent ce coeur TAA, diverses morphologies ont pu être observées et les propriétés physiques de ces auto-assemblages produits dans des solvants non polaires tels que les solvants chlorés ou le toluène se sont également révélées variées (propriétés cristal-liquide, conductrices, plasmoniques...). A partir de ces travaux, mon projet de thèse consistait en deux objectifs: a) étudier l'auto-assemblage et les propriétés de ces composés TAA dans des solvants polaires comme l'eau ou le méthanol. Pour cela, comme tenu du caractère hydrophobe des TAAs, il s'avérait nécessaire de synthétiser de nouvelles molécules incorporant des groupements latéraux favorisant la solubilité dans de tels solvants; b) stabiliser les auto-assemblages de triarylamine par polymérisation covalente et étudier les propriétés physiques associées à ces nouvelles structures. Pour cela, il convenait de synthétiser de nouvelles molécules incorporant des groupements polymérisables sur les chaines latérales, qui n'influençaient pas les propriétés d'auto-assemblages des TAAs. [...] / Based on the unique directionality and reversibility of non-covalent interactions, supramolecular self-assembly works as an elegant methodology to construct multifunctional hierarchical architectures. Inspired by nature, where water provides a vital environment for biological process such as biomacromolecular folding, water-soluble supramolecular polymers have been prepared and studied so as to mimic related biological systems. On the other hand, owing to the dynamic nature of their non-covalent bonds, supramolecular polymers often lack mechanical robustness. Thus, cross-linking strategies have been developed in order to combine highly ordered molecular arrangement inherent to the sef-assembly and mechanical robustness of the covalent backbone, which might bee promising to reach functional materials for practical applications. In this thesis, we focus on well-designed triarylamine molecules which are known to self-assemble into supramolecular polymers with excellent physical properties, as discovered by our group. In particular, molecules studied in this manuscript are based on tris-amide triarylamine scaffold known to produce self-assemblies with metallic conductivity and self-healing behavior. First, we studied the self-assemblies of three novel tris-amide triarylamine derivatives decorated with either poly(ethylene glycol) (PEG), peptide or cyanine dyes side chains on the three amide positions in polar solvents, i.e. either water or methanol. Characterizations by various physico-chemical techniques (NMR, UV-Vis absorption, fluorescence, infrared spectroscopies, microscopies, scatterings) demonstrated the formation of fibrillar aggregates for all molecules in such polar environments. Overall, this study suggest that the triarylamine core act as the main driving force for the self-assembly into columnar aggregates while side chains ensure solubility in these solvents and/or favor the formation of chiral architectures. In a second study, we investigated the formation of tris-amide triarylamine supramolecular polymers decorated with norbornene and siloxane end side chains, which could be further used to freeze the self-assembled structures by ring opening metathesis polymerization and sol-gel methods, respectively. [...]

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Bibliography: leaves 59-62. / by John Luigi Battaglioli. / M.S.

Para o estudo usou-se uma coluna de vidro, com 2,75 m de altura e 3,7 cm de diâmetro interno, contendo 29 pratos perfurados (diâmetro dos furos, 0,3 cm e área livre de 35 %), com espaçamento de 9,35 cm. O solvente percorria a coluna no sentido ascendente e a fase contínua, no contrário. A pulsação era fornecida ao sistema líquido por uma biela ligada excentricamente a uma polia, de um lado, e a uma junta de expansão, do outro. A frequência variou de 0 a 2,8 s-1 e a amplitude, de 0,6 a 2,3 cm. Uma primeira série de ensaios foi feita com o sistema binário acetato de n-butila-água, pois, para ele, há dados disponíveis para comparação. Dos resultados obtidos, concluiu-se ser conveniente o desempenho do equipamento. Em seguida, usou-se (a) o sistema metil isobutil cetona-água para levantar curvas de inundação e retenção da fase dispersa para várias condições de operação e (b) o sistema metil isobutil cetona-fenol-água para obter dados de transporte de massa, ou seja, altura equivalente a um estágio de equilíbrio e eficiência da remoção do fenol. Os resultados foram comparados, quando possível, com outros da literatura e com correlações existentes; em alguns casos, obtiveram-se correlações próprias. Os resultados alcançados são reprodutíveis e, para propriedades físicas e geométricas semelhantes, comportam-se de modo compatível com os da literatura. O processo é razoavelmente eficiente na remoção do fenol. / The extraction of phenol from aqueous solutions using a pulsed perforated-plate column was studied. The glass column, 2.75 m high and 3.7 cm internal diameter contains 29 perforated plates (0.3 cm holes and 35% of free area). The solvent flows upwards and the continuous phase, downwards. The pulsation was obtained by the expansion and compression of an expansion joint. Frequency varied from 0 to 2.8 s-1 and amplitude, from 0.6 to 2.3 cm. The initial tests were undertaken with the binary system n-butyl acetate-water because, for this system, there are data for comparison. It was shown that the equipment leads to convenient results. Then, the system methylisobutylketone-water was used to obtain flooding curves and dispersed phase hold-up and the system MIBK-phenol-water to study height equivalent to a theoretical stage and the phenol separation efficiency. The results were compared, whenever possible, with data from the literature and with existing correlations; specific correlations were obtained in certain cases. Results are reproducible and, for similar geometries and physical properties they are compatible with those of literature. The equipment is rather efficient in removing the phenol from the solution.

Made available in DSpace on 2016-04-28T20:17:28Z (GMT). No. of bitstreams: 1 2008 - Alexander Santos.pdf: 2028526 bytes, checksum: 5876d3f1d1f305df3af598f0bef1531d (MD5) Previous issue date: 2008-04-15 / This work was developed in the Department of Microbiology and Immunology of the Institute of Veterinary Rural Federal University of Rio de Janeiro in Serop?dica-RJ. We evaluated the antifungal activity plant Cymbopogon citratus (lemon-grass), Peumus boldus (boldo) and Shinus terebinthifolia (aroeira), inhibition of growth of species of the genus Aspergillus (A. flavus, A. niger, A. ochraceus, A. Parasiticus and A. carbonarius. Using the method of minimum inhibitory concentration in agar, with the technique of dilution plate (Pour-Plate), were held dilutions of different extracts, resulting in the final concentrations of 5%, 2.5% and 1.25%. Testing of commercial sensitivity to antifungal - ketoconazole were made in a final concentration of 1933.18 ? g /mL, as recommended by the National Committee for Clinical Laboratory Standards (NCCLS). The results obtained in the experiments have shown that aqueous extracts of C. citratus and S. terebinthifolia, after 24 hours of incubation, were able to inhibit the growth of A. flavus and A. carbonarius, respectively. The other extracts being studied and tested in the concentrations were not able to inhibit the growth of mycelial species of the genus Aspergillus. / Este trabalho foi desenvolvido no Departamento de Microbiologia e Imunologia do Instituto de Veterin?ria da Universidade Federal Rural do Rio de Janeiro, em Serop?dica-RJ. Foram avaliadas a atividade antif?ngica das plantas Cymbopogon citratus (capim-lim?o), Peumus boldus (boldo) e Shinus terebinthifolia (aroeira), na inibi??o do crescimento de esp?cies do g?nero Aspergillus (A. flavus, A. niger, A. ochraceus, A. parasiticus e A. carbonarius). Utilizando o m?todo da concentra??o inibit?ria m?nima em ?gar, com a t?cnica de dilui??o em placa (Pour-Plate), foram realizadas dilui??es dos diferentes extratos, obtendo-se as concentra??es finais de 5%, 2,5% e 1,25%. Testes de sensibilidade ao antif?ngico comercial - cetoconazol foram realizados numa concentra??o final de 1933,18 ?g/mL, conforme recomendada pelo National Committee for Clinical Laboratory Standards (NCCLS). Os resultados obtidos nos experimentos demonstraram que os extratos aquosos de C. citratus e S. terebinthifolia, ap?s 24 horas de incuba??o, foram capazes de inibir o crescimento de A. flavus e A. carbonarius, respectivamente. Os demais extratos em estudo e nas concentra??es testadas, n?o foram capazes de inibir o crescimento micelial das esp?cies do g?nero Aspergillus.

Híbridos poliuretano-acrílicos foram sintetizados via polimerização em emulsão, utilizando uma dispersão de poliuretano base poliol poliéster como semente para a polimerização dos monômeros acrílicos, no caso, acrilato de butila e ácido metacrílico. As propriedades das dispersões híbridas resultantes foram avaliadas por espalhamento dinâmico de luz, teor de sólidos, pH e potencial Zeta. Os polímeros resultantes da secagem das dispersões aquosas foram caracterizados por cromatografia por exclusão de tamanho, calorimetria exploratória de varredura, análise dinâmico-mecânica, dureza, microscopia ótica do processo de cristalização, microscopia de força atômica, microscopia eletrônica de transmissão. A influência do método de síntese na morfologia dos híbridos foi avaliada. / PU-acrylic hybrids were prepared via emulsion polymerization, using an aqueous polyurethane dispersion as a seed for the acrylic monomers polymerization. Different quantities of acrylic monomers (butyl acrylate and methacrylic acid) were polymerized. The properties of the resulting hybrid dispersions were evaluated through dynamic light scattering, solid content, pH and Zeta potential. The resulting polymers obtained from dried dispersions were characterized via size exclusion chromatography, differential scanning calorimetry, dynamic mechanical analysis, optical microscopy of the crystallization process, atom force microscopy and transmission electron microscopy. The influence of the synthetic method on the morphology of the hybrids was evaluated.

Neste trabalho foram estudadas duas abordagens para a obtenção de novos metabólitos secundários a partir de fungos. Na primeira, o ácido hidroxâmico suberoilanilida (SAHA) e cinco análogos foram sintetizados. Sua atividade como modificadores epigenéticos foi avaliada em oito linhagens fúngicas do ambiente marinho. Os fungos Penicillium sp. e Acremonium sp. apresentaram modificações no seu perfil metabolómico quando foram crescidos em pequena escala em presença do derivado 4F-SAHA, enquanto Microphaeropsis sp. apresentou modificação em presença do 3AM-SAHA. O fungo P. decaturense foi crescido em maior escala e os compostos de interesse foram isolados. Na segunda abordagem, uma nova estratégia de extração utilizando mistura de resinas XAD 2-4-7 permitiu a extração e posterior isolamento de seis novos alcaloides peptídicos (72-77) e dois peptídeos (78-79) a partir da fração aquosa do meio de cultivo do fungo antártico Penicillium solitum IS1-A. Utilizando a mesma metodologia, o metabolismo secundário do fungo antártico Thelebolus globosus E2 foi estudado. A partir de seu extrato metanólico do meio liquido PDB foram isoladas a ciclopenina (86) e o ciclopenol (87) e foram detectados os alcaloides viridicatina (88) e viridicatol (89). O fungo Thelebolus globosus mostrou-se produtor de estatinas, sendo isoladas como composto majoritário a mevastatina (90). / In this work two approaches to obtain new secondary metabolites from fungi were studied. Suberoylanilide hydroxamic acid (SAHA) and five analogues were synthesized and assessed as epigenetic modifiers in eight marine-derived fungi. The fungus Penicillium sp. and Acremonium sp. presented changes in their metabolomic profile when they were grown on a small scale in presence of 4F-SAHA derivative and Microphaeropsis sp. presented a modification in the presence of the 3 AM-SAHA. In the second approach a new extraction strategy using XAD 2-4-7 resin mixture allowed the extraction and subsequent isolation of six new peptide alkaloids (72-77) and two peptides (78-79) from the aqueous fraction of the culture medium of the Antarctic fungus Penicillium solitum IS1-A. Using the same methodology, the secondary metabolism of the Antarctic fungus Thelebolus globosus E2 was studied. From the methanolic extract of the PDB liquid medium cyclopenine (86) and cyclopenol (87) were isolated and the viridicatine (88) and viridicatol (89) alkaloids were detected. The fungus Thelebolus globosus was shown to be a producer of statins, mainly of mevastatin (90).

Bromelina é um nome coletivo para enzimas proteolíticas encontradas no talo, fruto e folhas do abacaxi (Ananas comosus Merr). A bromelina possui propriedades anti-inflamatórias, de debridamento, entre outras. Para a produção da bromelina deve-se, preferencialmente, usar resíduos do abacaxi, visto que os produtos do fruto têm aplicação comercial. Este trabalho teve como objetivo a extração de bromelina a partir de cascas de abacaxi através de sistema de duas fases aquosas (SDFA), e sua aplicação em hidrogel polimérico. Foram realizados estudos de estabilidade da bromelina comercial, em que se observou maior estabilidade em pH 5,0 com menor perda da atividade relativa em todas as temperaturas estudadas (20, 30, 40 e 50°C). O estudo da extração da bromelina em SDFA formado por polietileno glicol (PEG) e ácido poliacrílico (PAA) (com auxílio da análise de variância de parâmetros como rendimento, fator de purificação e coeficiente de partição) proporcionou rendimento de 335% e fator de purificação de 25,8. Os hidrogéis poliméricos à base de PEG estudados apresentaram-se flexíveis, com pouca elasticidade e taxa de absorção superior a 1000%. Hidrogel carreado de bromelina pelo método de turgescência proporcionou a maior liberação da enzima, assim como a maior atividade (80% da bromelina liberada em 24 h e 278 ± 89 U/mL). / Bromelain is a collective name for the proteolytic enzymes found in the stem, fruit and leaves of pineapple (Ananas comosus Merr.). Bromelain possesses anti-inflammatory properties, debridement, among others. For bromelain production one should preferably use the waste materials, whereas pineapple fruit products have commercial application. This study aimed to extract bromelain from pineapple peels using aqueous two-phase system (ATPS), and its application in polymeric hydrogels. Stability studies of commercial bromelain were performed, which found greater stability at pH 5.0 with minor loss of relative activity at all temperatures studied. The study of bromelain extraction in ATPS composed by polyethylene glycol (PEG) and poly acrylic acid (PAA) (with assistance of variance analysis of parameters such as yield, purification factor and partition coefficient) showed yield 335% and purification factor of 25.8. The PEG-based hydrogels studied presented flexibility, low elasticity and swelling ratio higher than 1000%. Hydrogel containing bromelain, loading by embedding (solvent sorption) method, yielded the highest enzyme release, as well as the highest activity (80% bromelain released over 24 h and 278 ± 89 U / mL).

The enthalpies of solution, HS, of carbon dioxide in aqueous methyldiethanolamine were measured with an isothermal flow calorimeter over wide ranges of temperature, pressure, weight percent MDEA, and loading (gmole CO2/gmole MDEA). The values of HS (kJ/gmole CO2) were found to be constant up to the saturation concentration of CO2 in the aqueous solution. In addition, experimental data showed that HS was independent of the total pressure over the solution, but linearly dependent upon both temperature and weight percent MDEA as was given by a correlation. A computer program based upon basic thermodynamic quantities was developed to model HS of CO2 in MDEA solutions. The values of K and ΔH for each of the chemical reactions (except the MDEA protonation reaction) were fitted values from the literature. Activity coefficient correlations used in the program were also obtained from the literature. Using these data, the program was first used to find the values of K and ΔH for the MDEA protonation reaction which gave the minimum error between the model and the experimental data. Finally, the values of HS predicted by the program were compared to the experimental data and the differences were discussed.