Myocilin, expressed in the trabecular meshwork of the eye, has been linked to inherited primary open-angle glaucoma (POAG). The biological function of myocilin is unknown, but mutant myocilin exhibits a gain-of-function mechanism, aggregating within the endoplasmic reticulum of human trabecular meshwork cells, causing cell stress and eventually apoptosis. After apoptosis occurs, the trabecular meshwork is compromised, leading to an increase in intraocular pressure, a symptom of glaucoma. In this thesis, I have expressed and purified the wild-type olfactomedin (OLF) domain and 24 reported disease-causing variants. I developed a facile thermal stability assay using differential scanning fluorimetry, which follows the unfolding of a protein through the fluorescence of a dye sensitive to hydrophobic regions of a protein. Also in this thesis I have determined melting temperatures for the wild-type and for each of the disease-causing mutants. I have tested the stability of the mutants in the presence of seven osmolytes, with sarcosine and trimethylamine-N-oxide restoring the melting temperature closest to wild-type. Additionally, I expressed and purified three reported single nucleotide polymorphisms (SNPs) (E352Q, E396D, K398R), which are considered benign variants. Variants were also compared by circular dichroism, revealing high b-sheet content and wild-type structure. When compared to previous studies, there is a positive correlation between the melting temperature, and previously reported qualitative assays, which measure the mutant myocilin solubility in detergent, secretion from mammalian cells, and aggregation propensity. Taken together, these data give insight into the relationship between glaucoma genotypes and phenotypes.

Absorption-stripping with aqueous, concentrated piperazine (PZ) is a viable retrofit technology for post-combustion CO2 capture from coal-fired power plants. The rate of thermal degradation and oxidation of PZ was investigated over a range of temperature, CO2 loading, and PZ concentration. At 135 to 175 °C, degradation is first order in PZ with an activation energy of 183.5 kJ/mole. At 150 °C, the first order rate constant, k1, for thermal degradation of 8 m PZ with 0.3 mol CO2/mol alkalinity is 6.12 × 10-9 s-1. After 20 weeks of degradation at 165 °C, 74% and 63%, respectively, of the nitrogen and carbon lost in the form of PZ and CO2 was recovered in quantifiable degradation products. N-formylpiperazine, ammonium, and N-(2-aminoethyl) piperazine account for 57% and 45% of nitrogen and carbon lost, respectively. Thermal degradation of PZ likely proceeds through SN2 substitution reactions. In the suspected first step of the mechanism, 1-[2-[(2-aminoethyl) amino]ethyl] PZ is formed from a ring opening SN2 reaction of PZ with H+PZ. Formate was found to be generated during thermal degradation from CO2 or CO2-containing molecules. An analysis of k1 values was applied to a variety of amines screened for thermal stability in order to predict a maximum recommended stripper temperature. Morpholine, piperidine, PZ, and PZ derivatives were found to be the most stable with an allowable stripper temperature above 160 °C. Long-chain alkyl amines or alkanolamines such as N-(2-hydroxyethyl)ethylenediamine and diethanolamine were found to be the most unstable with an allowable stripper temperature below 120 °C. Iron (Fe2+) and stainless steel metals (Fe2+, Ni2+, and Cr3+) were found to be only weak catalysts for oxidation of PZ, while oxidation was rapidly catalyzed by copper (Cu2+). In a system with Fe2+ or SSM, 5 kPa O2 in the inlet flue gas, a 55 °C absorber, and one-third residence time with O2, the maximum loss rate of PZ is expected to 0.23 mol PZ/kg solvent in one year of operation. Under the same conditions but with Cu2+ present, the loss rate of PZ is predicted to be 1.23 mole PZ/kg solvent in one year of operation. Inhibitor A was found to be effective at decreasing PZ loss catalyzed by Cu2+. Ethylenediamine, carboxylate ions, and amides were the only identified oxidation products. Total organic carbon analysis and overall mass balances indicate a large concentration of unidentified oxidation products. / text

<p><font face="Times-Roman"> <p align="left">The growth of the Internet has led to many interesting developments for both educational and commercial purposes. In this project an attempt was made to use the Internet for a research purpose to facilitate the determination of the thermal stability of diffusion barriers. Another purpose of this thesis is to investigate the teaching and training use of the Internet through the development of online interactive tools and activities as well as materials. The training aspects are mentioned as it is hoped that this thesis can serve as a form of documentation of the use of the Internet, while the central part was the determination of thermal stability of TiN, TaN and TiW diffusion <font face="Times-Roman">barriers on Ag.</font></p> </font></p>

An experimental apparatus was designed and built to study the thermal autoxidative carbon deposition, or coking, in the fuel injection nozzles of small gas turbine engines. The apparatus is a simplified representation of an aircraft fuel system, consisting of a preheating section and a test section, which is a passage that simulates the geometry, temperatures, pressures and flow rates seen by the fuel injection nozzles. Preliminary experiments were performed to verify the functionality of the apparatus. Pressure drop across the test section was measured throughout the experiments to monitor deposit buildup, and an effective reduction in test section diameter due to deposit blockage was calculated. The preliminary experiments showed that the pressure drop increased more significantly for higher test section temperatures, and that pressure drop measurement is an effective method of monitoring and quantifying deposit buildup.

An experimental apparatus was designed and built to study the thermal autoxidative carbon deposition, or coking, in the fuel injection nozzles of small gas turbine engines. The apparatus is a simplified representation of an aircraft fuel system, consisting of a preheating section and a test section, which is a passage that simulates the geometry, temperatures, pressures and flow rates seen by the fuel injection nozzles. Preliminary experiments were performed to verify the functionality of the apparatus. Pressure drop across the test section was measured throughout the experiments to monitor deposit buildup, and an effective reduction in test section diameter due to deposit blockage was calculated. The preliminary experiments showed that the pressure drop increased more significantly for higher test section temperatures, and that pressure drop measurement is an effective method of monitoring and quantifying deposit buildup.

Novel solutions to offset thermal degradation of polyamide-6 (PA-6) and organoclay (organically modified layered silicates) nanocomposites during melt compounding have been investigated. In this research, a novel chain extender (Joncryl ADR 3400) has been used to improve thermal stability of PA-6 and PA- 6/organoclay nanocomposites during melt compounding. The materials were compounded using a linear twin extruder and various laboratory scale mixers. The effects of organoclay and chain extender were studied using both processing methods. In order to replicate large scale production used in industry, a comprehensive plan of experimental work was carried out under different processing conditions (extrusion temperature and screw speed), organoclay and chain extender loading using a linear twin screw extruder. Rheology, mechanical and thermal properties were analysed and selected samples were also characterised by TEM and FTIR. Process induced degradation of PA-6 during the melt compounding was found to have significant influence on the rheological and mechanical properties. Rheological and mechanical characterisation clearly showed showed that incorporation of the chain extender minimised thermal degradation of PA-6 and nanocomposites during melt processing. Visual analysis of selected nanocomposites using TEM confirmed that chain extender increased the dispersion of nanoclays in the PA- 6 matrix. The crystallinity of the PA-6 was slightly affected by addition of organoclay and chain extender. The samples obtained by linear twin screw extrusion showed higher rheological properties than the samples from laboratory scale mixers suggesting better mixing and less thermal degradation during extrusion.

The research described in this thesis seeks to explore a concept that has the potential to make a step-change for the control of the properties of energetic materials (sensitivity, long-term storage, processability, performance, etc.), resulting in safer munitions with enhanced performance. This concept is co-crystallisation and involves crystallisation of the energetic material with one or more molecular components in order to modify the properties of the composition. The concept has been demonstrated in the pharmaceutical sector as a successful means of altering the physical properties of active pharmaceutical ingredients, e.g. solubility, bioavailability, stability to humidity. This project therefore aims to exploit the concepts of crystal engineering and co-crystallisation as applied to selected energetic materials in order to achieve the following objectives: (i) develop an enhanced understanding of how structure influences key properties such as sensitivity, (ii) control the sensitivity of existing, approved energetic materials, and (iii) identify new energetic materials with enhanced properties, e.g. reduced sensitivity, higher performance, and increased thermal stability. The compound 3,5-nitrotriazolone (NTO) was crystallised with a selection of co-formers to produce salts and co-crystals. The structure properties of these materials were explored using single-crystal and powder X-ray diffraction, and structural features were correlated with properties such as crystal density, difference in pKa of co-formers, thermal properties, and sensitivity to impact. Detonation velocities of the co-crystals were calculated based on densities, chemical composition, and heats of formation. Co-former molecules included a series of substituted anilines, substituted pyridines (including 4,4’-bipyridine, 2-pyridone), and substituted triazoles. A co-crystal was formed between NTO and 4,4’-bipyridine on crystallisation from ethanol, whilst a salt was formed when crystallised from water. Upon heating the salt to 50ºC, the co-crystal was formed. Structural differences between the salts formed by NTO with 3,5-DAT and 3,4- DAT were correlated with structural features. 3,5-DAT.NTO is substantially less impact sensitive than 3,4-DAT.NTO, and this is attributed to the layered structure of 3,5-DAT.NTO. An investigation into triazole-based NTO salts under high pressure was conducted. A new polymorph of 3,5-DAT.NTO was discovered upon increasing the pressure to 2.89 GPa. The high-pressure phase appears to retain the layered structure and remains in this phase up to 5.33 GPa, although it was not recoverable upon decompression to atmospheric pressure. The compression behaviour of the unit cell volume for phase I of 3,5-DAT.NTO has been fitted to a 3rd-order Birch- Murnaghan equation of state (EoS) with V0 = 957.7 Å3, B0 = 8.2 GPa and B’0 = 14.7. The unit cell was found to be most compressible in the a and c directions. Under high pressure 3,4-DAT.NTO does not give any indication of a phase change occurring up to 6.08 GPa. The coefficients of the 3rd-order Birch-Murnaghan EoS have been determined to be V0 = 915.9 Å3, B0 = 12.6 GPa and B’0 = 6.5.

Submitted by Emily Colferai Bonfá null (miemilymi@hotmail.com) on 2016-03-22T01:17:39Z No. of bitstreams: 1 Mestrado-Emily Finall.pdf: 1593107 bytes, checksum: ce9ebf44b67e4020e069a84d708f2f71 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-03-22T17:56:40Z (GMT) No. of bitstreams: 1 bonfa_ec_me_sjrp.pdf: 1593107 bytes, checksum: ce9ebf44b67e4020e069a84d708f2f71 (MD5) / Made available in DSpace on 2016-03-22T17:56:40Z (GMT). No. of bitstreams: 1 bonfa_ec_me_sjrp.pdf: 1593107 bytes, checksum: ce9ebf44b67e4020e069a84d708f2f71 (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As celulases podem ser utilizadas na bioconversão da fração de celulose de resíduos agro-industriais em açúcares fermentáveis, visando a obtenção de combustíveis renováveis e produtos químicos. As β-glicosidases são cruciais para a total sacarificação da celulose, mas na maioria dos casos elas são fortemente inibidas pelo seu produto, a glicose. Portanto, o conhecimento das cinéticas de hidrólise e as respostas dessa enzima frente a diferentes substratos e produtos pode definir a eficiência de hidrólise e do processo biotecnológico no qual poderia ser incorporada. O presente trabalho teve como objetivo caracterizar a β -glicosidase de 50 kDa (BG50) produzida pelo fungo termofílico Myceliophthora thermophila M.7.7 cultivado em estado sólido, em mistura de bagaço de cana e farelo de trigo (1:1). O zimograma do extrato bruto evidenciou duas isoformas, de aproximadamente 200 e 50 kDa, as quais foram separadas por cromatografia de filtração em gel. A caracterização da BG50 mostrou atividade ótima a 60 ˚C e pH 5,0 quando usado o 4-nitrofenol-β-D-glicopiranosídeo (pNPG), enquanto com celobiose o valor da temperatura e pH ótimo foram de 50 ˚C e pH 4,5, respectivamente. Testes realizados com adição de íons e reagentes mostraram diferenças nos efeitos sobre a atividade da enzima dependendo do substrato, principalmente com a adição de Ditiotreitol (DTT) utilizando celobiose, e inibição completa com Cu2+ e Fe3+ para pNPG e celobiose. Além disso, a enzima não mostrou efeito inibitório quando testada na presença de nove compostos fenólicos, uma característica significativa. Os estudos cinéticos revelaram um perfil de inibição competitiva pela glicose quando utilizado pNPG com valor de KI=1,5 mM e um Km significativamente menor (0,52 mM) pelo pNPG do que pela celobiose (Km=8,50 mM). Os parâmetros termodinâmicos mostraram que a BG50 é bastante estável, destacando seu tempo de meia vida de 855,6 minutos a 60 °C, porém desnatura facilmente acima dessa temperatura. Os resultados enfatizam a importância de investigar potencialidades de β-glicosidases baseadas na celobiose, uma vez que no processo industrial a enzima atuará sobre o substrato natural, além da compreensão da termoestabilidade da enzima. / Cellulases can be used in bioconversion of cellulose from agro-industrial waste into fermentable sugars in order to obtain renewable fuels and chemicals. The β-glucosidases are crucial to the overall saccharification of cellulose, but in most cases, they are strongly inhibited by its product, glucose. Therefore, knowledge of the hydrolysis kinetics of the enzyme and its responses against different substrates and products can set the hydrolysis efficiency and possible incorporation in biotechnological process. This study aimed to characterize the 50 kDa β-glucosidase (BG50) produced by the thermophilic fungus Myceliophthora thermophila M.7.7 grown in solid state, in a mixture of sugarcane bagasse and wheat bran (1:1). The zymogram of the crude extract showed two isoforms of 200 and 50 kDa, which were separated by gel filtration chromatography. The characterization of BG50 showed optimal activity at 60 °C and pH 5.0 when used pNPG, whereas using cellobiose the values of the optimal temperature and pH were 50 °C and pH 4.5, respectively. Tests with addition of reactants and ions showed differences in the effects on enzyme activity depending on the substrate, especially with the addition of dithiothreitol (DTT) utilizing cellobiose, and complete inhibition with Cu2+ and Fe3+ for 4-nitrophenyl-β- D-glucopyranoside (pNPG) and cellobiose. Furthermore, the enzyme showed no inhibitory effect when tested in the presence of nine phenolic compounds, a remarkable characteristic. Kinetic studies showed a profile of competitive inhibition by glucose when using pNPG with Ki = 1.5 mM and Km significantly lower (0.52 mM) with pNPG than using cellobiose (Km = 8.50 mM). The thermodynamic parameters show that BG50 is quite stable, highlighting its half life of 855.6 minutes at 60 ° C, but above this temperature easily denatured. The results emphasize the importance of investigating β-glucosidases’ potential based on cellobiose, since for the industrial processes the enzyme will function with its natural substrate, in addition to understanding the thermal stability of the enzyme.

abstract: Lithium ion batteries have emerged as the most popular energy storage system, but they pose safety issues under extreme temperatures or in the event of a thermal runaway. Lithium ion batteries with inorganic separators offer the advantage of safer operation. An inorganic separator for lithium ion battery was prepared by an improved method of blade coating α-Al2O3 slurry directly on the electrode followed by drying. The improved separator preparation involves a twice-coating process instead of coating the slurry all at once in order to obtain a thin (~40 µm) and uniform coat. It was also found that α-Al2O3 powder with particle size greater than the pore size in the electrode is preferable for obtaining a separator with 40 µm thickness and consistent cell performance. Unlike state-of-the-art polyolefin separators such as polypropylene (PP) which are selectively wettable with only certain electrolytes, the excellent electrolyte solvent wettability of α-Al2O3 allows the coated alumina separator to function with different electrolytes. The coated α-Al2O3 separator has a much higher resistance to temperature effects than its polyolefin counterparts, retaining its dimensional integrity at temperatures as high as 200ºC. This eliminates the possibility of a short circuit during thermal runaway. Lithium ion batteries assembled as half-cells and full cells with coated α-Al2O3 separator exhibit electrochemical performance comparable with that of polyolefin separators at room temperature. However, the cells with coated alumina separator shows better cycling performance under extreme temperatures in the temperature range of -30°C to 60°C. Therefore, the coated α-Al2O3 separator is very promising for application in safe lithium-ion batteries. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2016

Submitted by Luanna Matias (lua_matias@yahoo.com.br) on 2015-03-23T15:26:24Z No. of bitstreams: 2 Dissertação - Rangel Magalhães Luzin - 2011.pdf: 5253417 bytes, checksum: 4a3879b95b6b8e88185d667c72771ed4 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luanna Matias (lua_matias@yahoo.com.br) on 2015-03-23T15:29:27Z (GMT) No. of bitstreams: 2 Dissertação - Rangel Magalhães Luzin - 2011.pdf: 5253417 bytes, checksum: 4a3879b95b6b8e88185d667c72771ed4 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-03-23T15:30:11Z (GMT). No. of bitstreams: 2 Dissertação - Rangel Magalhães Luzin - 2011.pdf: 5253417 bytes, checksum: 4a3879b95b6b8e88185d667c72771ed4 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2011-12-20 / This work describes the thermal and photoelectric stability investigation of commercial sunscreens benzophenone-3, octyl methoxycinnamate and octyl salicylate. The purpose was determining thermal and photoelectric (resistance to sunlight) stability. For thermal stability evaluation, thermal ramp was set up in attempt to get closer to conditions which sunscreen could be submitted in manufacture or in people using. In this test each filter was exposed to temperature variations from 30 to 65 °C, in times and speeds of heating, under synthetic air atmosphere. A solar simulator was used for photoelectric stability evaluation. The measures were not performed with samples irradiated at a specific wavelength, but exposed to all wavelengths emitted by the sun, extending from the ultraviolet to infrared, with high reproducibility. The samples were exposed to simulated solar light in five different times, ranging from 30 to 120 minutes. This change aims to understand how the filter behaves with the increased exposure time. Infrared, ultraviolet and NMR spectroscopies were used on structural characterization of the compounds submitted to thermal and photoelectrical evaluation. This study has demonstrated that sunscreens evaluated are thermally stable but photoelectrically unstable. This instability was observed by formation of minor compounds derivative of sunscreens studied. The shift in the chemical equilibrium producing higher concentrations of minor compounds was also observed. These factors change the absorptive capacity of the sunscreens, causing loss of stability in solar protection. Octyl methoxycinnamate and benzophenone 3 have the higher molar absorptivity (23,300 and 14,380, respectively) and presented the higher loss of efficiency, overcoming 20% in 2 hours of exposure. On the other hand octyl salicylate has lower molar absorptivity value (4.130) and presented lower loss of efficiency, overcoming 10% in 2 hours of exposure. The used methodologies have low cost and are viable, representing an interesting tool in stability evaluation of sunscreens already established in cosmetic market or in development. This study also emphasizes the importance of NMR technique that enabled us to identify and quantify all structures modified without any previous separation. The correlation between UV and NMR techniques was also effective to demonstrate that lower losses in molar absorptivity are directly related to lower differences on NMR spectra, as observed in octyl salicylate. / Neste trabalho avaliaram-se as estabilidades térmica e fotoelétrica dos filtros solares benzofenona-3, metoxinamato de octila e salicilato de octila. Para verificação da estabilidade térmica, estabeleceu-se a rampa térmica apropriada, por intermédio de análise térmica, buscando se aproximar de condições reais, as quais o produto final poderia ser submetido. Neste teste cada filtro suportou variações de temperatura de 30 a 65°C, em tempos e velocidades de aquecimento determinados, sob atmosfera de ar sintético. Para a verificação da estabilidade fotoelétrica de filtros solares, utilizou-se de forma inovadora um simulador solar. Portanto, as medidas não foram realizadas com amostras irradiadas em um comprimento de onda ou faixa específica, mas sim, expostas a todos os comprimentos de onda emitidos pelo sol, se estendendo desde o ultravioleta até o infravermelho, com alto grau de reprodutibilidade. Todas as amostras foram submetidas à luz solar simulada com diferentes tempos de exposição, variando de 30 a 120 minutos. Assim, foi avaliado o comportamento do filtro de acordo com o tempo de exposição. Conclui-se deste estudo, que os filtros solares aqui trabalhados são estáveis termicamente, porém instáveis fotoeletricamente. A instabilidade foi observada através da formação de subprodutos derivados dos filtros estudados, bem como deslocamento no equilíbrio químico entre as estruturas envolvidas, aumentando a concentração de produtos minoritários. Estes fatores alteram a capacidade absortiva do filtro, fazendo com que os mesmos não sejam tão estáveis quanto antes da exposição fotoelétrica. O metoxinamato de octila e a benzofenona 3 são os filtros com maiores absortividades molares 23300 e 14380 respectivamente e foram os que apresentaram maior perda de eficiência, aproximando-se dos 20% no período de 2 horas. Por outro lado, o salicilato de octila cuja absortividade molar é de 4130 e sua perda foi próxima aos 10%. As técnicas de infravermelho (IV), ultravioleta (UV) e Ressonância Magnética Nuclear (RMN) foram utilizadas para caracterizar as alterações estruturais, efetividade absortiva e deslocamentos de equilíbrio, resultantes das avaliações térmica e fotoelétrica. Essas metodologias foram eficientes, de fácil aplicação e com observação direta dos resultados. Foram viáveis e de baixo custo, podendo ser aplicadas na caracterização e verificação de estabilidade de filtros já consolidados no mercado de cosméticos ou em desenvolvimento. Destaca-se a importância da técnica de RMN, que possibilitou identificar e quantificar todas as estruturas modificadas, sem métodos de separações prévias. A correlação entre UV e RMN foi efetiva para demonstrar que as menores perdas de absortividade estão também ligadas às menores diferenças no RMN, como observado para o salicilato de octila.