Submitted by infopei ufba (infopei@ufba.br) on 2017-08-07T18:35:09Z No. of bitstreams: 1 TESE-CARINE_TONDO_ALVES.pdf: 4198906 bytes, checksum: e7a6045dd5e751079523ef43e8a9eb69 (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2017-08-09T15:32:31Z (GMT) No. of bitstreams: 1 TESE-CARINE_TONDO_ALVES.pdf: 4198906 bytes, checksum: e7a6045dd5e751079523ef43e8a9eb69 (MD5) / Made available in DSpace on 2017-08-09T15:32:31Z (GMT). No. of bitstreams: 1 TESE-CARINE_TONDO_ALVES.pdf: 4198906 bytes, checksum: e7a6045dd5e751079523ef43e8a9eb69 (MD5) / Neste estudo, o aluminato de zinco foi sintetizado através da reação de combustão e caracterizado de acordo com suas propriedades físicas e texturais. O catalisador foi utilizado na reação de transesterificação em condições subcríticas e supercríticas, via rotas metílica e etílica a partir de óleos e gorduras residuais (OGR). As condições experimentais utilizadas foram previamente estudadas através do acervo bibliográfico e fixadas em 2 horas de reação, razão molar de álcool:óleo 40:1, agitação mecânica de 700 rpm, razão de catalisador em peso com relação à quantidade inicial de óleo entre 1 e 10 % e temperatura de reação entre 60 e 200 ºC. O estudo da reação de transesterificação indicou resultados promissores para as duas metodologias utilizadas. Os resultados obtidos indicaram que o rendimento em ésteres aumentou significativamente em temperaturas amênas quando a razão de catalisador:óleo foi acrescida de 1 % para 5,5 % e 10 % de catalisador em relação à quantidade inicial de óleo para as duas metodologias avaliadas. Estes dados foram justificados pela possibilidade de formação de mais do que uma fase entre o óleo e o álcool em baixas temperaturas. Contudo, a influência desta razão decresceu à medida que se aumentou a temperatura de reação até 200 °C, sendo obtidos rendimentos em ésteres > 98 % em 30 minutos de reação em condições severas utilizando-se 1 % de catalisador e dióxido de carbono em estado supercrítico. / In this study, the zinc aluminate was synthesized by the combustion reaction and characterized according to their physical and textural properties. The catalyst was used in the transesterification reaction in supercritical and subcritical conditions, via methylic and ethylic routes from waste frying oils (WFO). The experimental conditions used were previously studied and fixed in 2 hours of reaction time, 40:1 of alcohol:oil molar ratio, 700 rpm of mechanical stirring, 1, 5.5 % and 10 % by weight of catalyst ratio and 60 to 200 º C of reaction temperature. The study of the transesterification reaction indicated promising results for both methodologies. The results indicated that the yield of esters at moderate temperatures significantly increased when the ratio of catalyst:oil was increased from 1 % to 5.5 % and 10 % of catalyst relative to the initial quantity of oil to the two methodologies evaluated. These data were substantiated by the possibility of forming more than one phase between the oil and the alcohol at low temperatures. However, the influence of this ratio is decreased as the reaction temperature increased to 200 ° C, were obtained > 98% of esters yields in 30 minutes of reaction under stringent conditions using 1 % catalyst and supercritical carbon dioxide.

No / Aqueous solutions of hen egg lysozyme (3% w/v) were dispersed and precipitated by a homogenous mixture of supercritical carbon dioxide-ethanol using the Solution Enhanced Dispersion by Supercritical fluid (SEDS) process. The effects of different working conditions, such as temperature, pressure and the flow rates of the solution and ethanol, on the particle-formation process were studied The morphology, particle size and size distribution and biological activity of the protein were determined The precipitates were examined with high-sensitivity differential scanning calorimetry (HSDSC) and high-performance cation-exchange chromatography Particle size measurements showed the precipitates to be aggregates with primary particles of size 1-5 ¿m. The similarity of HSDSC data for unprocessed and processed samples indicated that the different physical forces that stabilise the native form of lysozyme are unchanged after SEDS processing. From FT-Raman spectroscopic studies secondary structural changes were observed in certain SEDS-produced lysozyme, with most processed samples displaying a slightly more disordered secondary structure than the unprocessed sample However, SEDS samples produced at 200 bar and 40 C exhibited negligible disturbance Thus the SEDS process utilising aqueous solution was able to bring about size reduction of lysozyme with minimal loss of biological activity.

Aerogel materials have had limited utility due to their fragility, geometrical limitations, fabrication costs and protracted fabrication times. The objective of this project was to eliminate these limitations. Native, cross-linked and hybrid aerogel monoliths have been fabricated using a newly developed one-pot method without the need for solvent exchange. The key to this technique is the use of an ethanol–water azeotrope mixture, which contains 4.4% water by volume, as both a gelation and supercritical drying solvent. The small water content allows for drying at temperatures close to the supercritical temperature of the dry solvent, where reactions such as silica dissolution and polymer degradation are negligible. This improvement on conventional fabrication processes is of particular importance since it decreases the total duration of aerogel fabrication from five days to one day. Cross-linked silica aerogel monoliths were fabricated using one-pot hydrolysis-condensation wet chemistry methods as well as a rapid photogelation method. Both native silica and cross-linked aerogel components were made with a minimum dimension of up to 3.6 cm and in customizable shapes. Fabrication of homogeneous aerogels using these methods required a maximum of one day, as demonstrated in this work. Finally, LEDs and Laser irradiation were both used to selectively embed cross-linked aerogel into a larger native silica component to provide reinforcement and/or a surface which can be used for labeling or affixing the aerogel component to another surface.