Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-09T11:39:47Z No. of bitstreams: 1 2012 - Filipe Arantes Furtado.pdf: 4817236 bytes, checksum: 027c11b973e31fc0617693a998446e3e (MD5) / Made available in DSpace on 2017-05-09T11:39:47Z (GMT). No. of bitstreams: 1 2012 - Filipe Arantes Furtado.pdf: 4817236 bytes, checksum: 027c11b973e31fc0617693a998446e3e (MD5) Previous issue date: 2012-07-26 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / The main objective of this work was the development of a methodoly using the Solid Phase Microextraction (SPME) on determinations of thermodynamic equilibrium data of liquid and polymeric mixtures. Three methodologies were proposed for determination of infinite dilution activity coefficient of solutes in liquid mixtures (??). The ?? values were determined for 9 hydrocarbons in the solvent furfural at temperatures of 25, 35 and 45 ?C. The liquid-gas partition coefficients were also determined in each studied temperature. On the experiments involving liquid mixtures, high sorption of solvent was observed, which may lead to swelling the polymer coating phase. Statistical tests were conducted after each experiments to measure possible damages on fiber coatings. There was also proposed a methodology using the SPME to determine the Flory Huggins parameter of the nine hydrocarbons used as solutes in polydimethylsiloxane (PDMS) and polyacrylate (PA). The Flory parameter were determined at temperature range of 25 to 80 ?C for the PDMS and 50 to 90 ?C for the PA. The proposed methodologies were evaluated through comparison of the obtained data with literature. All the results agreed with literature data. The Hildebrandt solubility parameter for PA was not available on literature and was determined on these experiments for the first time / O principal objetivo deste trabalho foi o desenvolvimento de uma nova metodologia para determina??o de dados de equil?brio termodin?mico em misturas l?quidas e polim?ricas. Tr?s metodologias foram propostas utilizando a Microextra??o em Fase S?lida (SPME) para determina??o dos coeficientes de atividade em dilui??o infinita (??) de sistemas l?quidos. Os valores de ?? de 9 hidrocarbonetos foram determinados em furfural nas temperaturas de 25, 35 e 45 ?C. Foram determinados valores de coeficiente de parti??o l?quid-g?s (KLg) em cada uma das temperaturas estudadas. Nos experimentos envolvendo as misturas l?quidas, foi observada uma alta taxa de sor??o de solvente podendo ocasionar o inchamento e poss?vel quebramento das fibras de SPME. Para verificar o poss?vel inchamento, foram conduzidos testes estat?sticos antes e depois de cada amostragem. Foi proposto ainda uma metodologia para determinar os par?metros de Flory em polidimetilsiloxano (PDMS) e poliacrilato (PA) utilizando a SPME. Nesse caso, os mesmos 9 hidrocarbonetos tiveram seus par?metros de Flory determinados na faixa de temperatura 25 a 80 ?C para o PDMS e de 50 a 90 ?C para o PA. As metodologias foram avaliadas atrav?s da compara??o dos dados obtidos com dados da literatura. Todos os resultados foram satisfat?rios, sendo ainda obtidos os valores dos par?metros de solubilidade de Hildebrandt, que para o poliacrilato, eram inexistentes na literatura

Este estudo utilizou os princípios da glacioquímica para determinar e analisar as variações nas concentrações aniônicas de um testemunho de neve e firn obtido pela perfuração no manto de gelo da antártica ocidental no verão austral de 2004/05. O testemunho IC-6 (81°03'S, 79°51'W), de 34,65 m de profundidade, obtido a 750 m de altitude, foi subamostrado em sala limpa (CLASE 100), usando um sistema de derretimento contínuo desenvolvido pela equipe do Climate Change Institute (CCI) da Universidade do Maine (EUA). Esse processo gerou 1.368 amostras para análises por cromatografia iônica, cerca de 58 amostras por metro, permitindo detalhamento sazonal da variabilidade das concentrações dos íons majoritários. O testemunho representa 66 ± 3 anos de dados ambientais, segundo a datação baseada na variação sazonal dos íons Cl-, Na+, Mg+2 e SO4-2. O testemunho de 23,61 m em equivalente d’água, corrigido para variações em densidade, representa uma acumulação liquida média anual de 0,36 m (em equivalente d’água). Assim, a camada ao fundo foi formada no ano de 1938 (± 3 anos). As concentrações iônicas médias medidas no IC-6, são: [(Na+= 66,92 ± 2,32 μg L-1), (K+= 3,31 ± 0,18 μg L-1); (Mg+2= 10,07 ± 0,25 μg L-1); (Ca+2 = 16,93 ± 0,38 μg L-1); (Cl- = 155,74 ± 4,40 μg L-1); (NO3- = 56,01 ± 0,80 μg L-1); (SO4 2 = 55,65 ± 1,36 μg L-1); e (CH3SO3 (MS) = 14,11 ± 1,19 μg L-1)]. As maiores concentrações de Na+, Cl-, e Mg+2 foram interpretadas como picos de invernos, associadas diretamente ao aerossol dos mares circundantes em respostas, provavelmente, a advecção mais intensa de massas de ar (marinho) sobre as plataformas de gelo, e portanto são também traçadores marinhos. Já o perfil (série) de sulfato está em antifase, em relação às variações nas espécies Na+, Cl- e Mg+2. De origem predominantemente marinha, o sulfato total apresentou maiores concentrações durante a primavera e verão (períodos de maior atividade biológica nos mares circumpolares), possivelmente marcando a variação sazonal da atividade biológica na região. Embora em alguns intervalos essa ―antifase‖ não fique tão clara, é o que ocorre na maior parte do testemunho IC-6, condição que auxiliou na interpretação da variação sazonal observada principalmente na série do cloro. O perfil de excesso de sulfato apresenta perfil similar ao de sulfatos total, com picos concomitantes. Além da forte correlação com o íon SO4-2, também é observada uma correlação fraca a moderada com o íon nitrato. Picos concomitantes deste íon com o excesso de sulfato representam eventos episódicos como é o caso das erupções vulcânicas de grande magnitude. A variabilidade da concentração de nitrato não esta associada ao aerossol marinho, como aponta a falta de correlação entre esse ânion e o Cl-, Na+ e Mg2+. Porém, série de nitrato apresenta muitos períodos bem marcados e correlacionados com as concentrações de excesso de sulfato, devendo representar a ocorrência de eventos episódicos, como erupções vulcânicas. Entretanto, a análise de íons maiores nesse estudo não possibilitou a identificação de eventos específicos, será necessário o uso de técnicas complementares para determinação de elementos traços. Sugere-se que o nitrato seria transportado e depositado por massas de ar provenientes da estratosfera ou da alta troposfera e que grandes concentrações dessa espécie poderiam estar associadas ao registro de ocorrências de eventos vulcânicos. Essa característica parece ser coerente com os picos correlacionáveis nos perfis (séries) de nitrato e sulfatos. Além da variação sazonal (observada principalmente no perfil de cloro), foram identificados outros padrões recorrentes no tempo (ciclos), principalmente nas séries de dos íons Na+, Cl- e Mg2+ (origem marinha) e NO3-. O principal ciclo identificado, de aproximadamente 17,3 anos, necessita melhor investigação. A secundária, em torno de 10 anos, estaria associada ao ciclo solar (de 10,7 anos). Também são observados ciclos com períodos entre 2 a 5 anos, que poderiam estar associados ao fenômeno ENOS (El Niño - Oscilação Sul). Ao comparar as concentrações médias do IC-6 com de outros sítios no interior da Antártica, observa-se uma abrupta redução ao atravessar as montanhas Transantárticas em direção ao Polo Sul geográfico. Sugere-se que cordilheira esteja barrando o transporte dos aerossóis marinhos para o interior do continente devido a um efeito orográfico sobre a precipitação. / This study employed glaciochemical principles to determine and analyze the variation of anionic concentrations of a firn and snow core obtained from the Western Antarctic Ice Sheet, in the summer of 2004/05. The IC-6 core (81°03'S, 79°51'W), reaching 34.65 m in depth, was extracted at 750 m above sea level. This core was subsampled in a Class 100 clean room, employing a discrete continuous melting system developed by the team at the Climate Change Institute (CCI), University of Maine, USA. This process produced 1,368 samples for ionic chromatographic analyses, approximately 58 samples per meter, permitting a seasonal-scale resolution of the main ion concentrations and variabilities. This core represents 66 ± 3 years of environmental data, according to Cl-, Na+, Mg+2 e SO4-2 ion seasonal variations. The 23.61 m core, in water equivalent, corrected for the density variation, represents an annual net accumulation average rate of 0.36. The deepest layer was deposited in 1938 (± 3 ). Core mean ionic concentrations are: [(Na+= 66,92 ± 2,32 μg L-1); (K+= 3,31 ± 0,18 μg L-1); (Mg+2= 10,07 ± 0,25 μg L-1); (Ca+2 = 16,93 ± 0,38 μg L-1); (Cl- = 155,74 ± 4,40 μg L-1); (NO3- = 56,01 ± 0,80 μg L-1); (SO4 2 = 55,65 ± 1,36 μg L-1); and (CH3SO3 (MS) = 14,11 ± 1,19 μg L-1)]. The largest concentrations of Na+, Cl-, e Mg+2 were interpreted as winter peaks, directly associated with the aerosols from the surrounding seas, probably, in response to the intensification of marine air mass advection on the ice shelves, and, thus, also being marine tracers. The sulphate profile (series) presents an antiphase, with relation to Na+, Cl- e Mg+2 species variations. Predominantly of marine origin, total sulphates presented greater concentrations during Spring and Summer (periods of greater biologic activity in the Southern Ocean), possibly marking the seasonal variation of biologic activity in the region. Although in some intervals of this ―antiphase‖ are not clearly evident, they are consistent throughout most of the IC-6 core, assisting with the interpretation of the observed seasonal variations, particularly when related to chlorine data series. The sulphate excess profile is similar to total sulphate profile, showing concomitant spikes. Besides the strong correlation to tSO4-2 ion, a weak to moderate correlation was observed for nitrate ions. Coinciding peaks for this ion with excess sulphate may represent episodic events, such as presented by volcanic events of great magnitude. The nitrate concentration variability is not associated to marine aerosols, as shown by the lack of correlation between this anion and Cl-, Na+ e Mg2+. The nitrate series presents many well marked periods and seem to be correlated to excess sulphate concentrations, possibly representing the occurrence of episodic events, such as volcanic eruptions. Even so, the major ions analyses proposed by this work did not make the identification of such episodic events clear. Such events need to be addressed with complementary techniques to determine the specific trace elements. These results suggest that nitrate is transported and deposited by stratospheric or high tropospheric air masses, and that great concentrations of this species could be associated to the recorded volcanic events. This characteristic appears to be coherent with the spikes in the nitrate and sulphate profiles. Besides the seasonal variation (observed, principally, in the chlorine profile), other time cycle/patterns were identified, mainly those related to Na+, Cl- e Mg2+ ion series (of marine origin) and NO3-. The main identified cycle, approximately 17.3 years, ensues to be better investigated. A second cycle, presenting a 10 year period, is possibly associated to the solar cycle (10.7 years). Shorter cycles of 2 and 5 year periods could possibly be related to the ENSO phenomenon. On comparing average concentrations of the IC-6 core with other sites, farther within the Antarctic continent, an abrupt reduction was observed, from the Trans-Antarctic mountains to the Geographic South Pole, suggesting that this mountain range could be a barrier for marine aerosol transport to the interior of the continent, due to an orographic effect on the precipitation.

A adição de vitaminas aos produtos industrializados tornou-se prática comum para as indústrias de alimentos e os teores adicionados devem obedecer à legislação brasileira durante toda a vida de prateleira dos produtos. Sabendo da sensibilidade das vitaminas a fatores como oxigênio, luz e calor, é essencial conhecer o comportamento destes compostos no alimento frente aos fatores críticos. Informações confiáveis sobre teores de vitaminas somente podem ser obtidas com métodos analíticos validados. Neste trabalho foi desenvolvido e validado um método de análise para vitaminas B1, B2, B6 e PP em leite em pó/fórmulas infantis, cereais e bebidas instantâneas por cromatografia líquida de alta eficiência com uma única etapa de extração que apresentou recuperações de 90 a 120% dependendo do teor e da matriz analisada. Após a validação do método analítico, foi avaliada a estabilidade das vitaminas em amostras submetidas a diferentes condições de estocagem durante 10 meses. Os resultados mostram que a principal causa de perda das vitaminas B2 e B6 é a exposição à luz, que pode ser agravada pela temperatura e/ou presença de oxigênio no meio, enquanto as vitaminas PP e B1 mostraram-se bem estáveis sob as diferentes condições e no tempo estudado. / Food fortification with vitamins is a very common practice in food industry and the added content must be in compliance with Brazilian Legislation during the whole product shelf life. Due to the vitamins sensibility to light, temperature and oxygen it\'s necessary to know the behavior of these compounds when submitted to these critical conditions. Trustful information about the vitamins content just can be obtained from validated analytical methods. In this work it was developed and validated a HPLC method for determination of vitamins B1, B2, B6 e PP in milk/infant formula, cereals and beverage powders with the same extract which presented recoveries within 90 and 120% depending on the matrix and the vitamins level. After method validation, the vitamins stability in different samples was evaluated during 10 months under different storage conditions. The results showed the high sensitivity of vitamins B2 and B6 to light exposure that can become worse when samples were exposed to high temperature and oxygen. Vitamins PP and B1 had very stable behavior under the studied conditions and for the period of this study.

No description available.

It has been shown in previous studies that when sulfite is absorbed by rabbits via either inhalation of SO2 or oral exposure to sulfite, the hydrated form, bisulfite, interacts with plasma disulfides where it is suspected to be in the form, cysteine-S-sulfonate. A rapid and specific gas chromatographic analysis procedure for cysteine-S-sulfonate has been developed to better study the distribution of sulfite in biological systems. Sulfonated proteins are enzymatically hydrolyzed to ensure stability of the acid labile S-sulfonate disulfide. The hydrolysate is then applied to a 6 cm cation-exchange column and eluted with 0.1 N HCl which elutes the acidic cysteine-S-sulfonate with the void volume of the column leaving behind any remaining cysteine. the silylated derivatives of the column effluent are prepared using Tri-Sil/BSA. These derivatives are injected into a gas chromatograph equipped with a flame-photometric detector operating in the sulfur mode, 2% 0v-101 on Chromosorb W/HP 1/4 inch glass column, oven temperture 140°C, and carrier flow rate of 86 ml/min. The presence of cysteine-S-sulfonat in the sulfite treated rabbits had been directly determined by the described method.

This study was concerned with development of chromatographic methods suitable for determination of plant sugars. The resultant methodology was applied to the comprehensive study of plant carbohydrates as they vary during plant growth. Plant cell walls were isolated with boiling water followed by delignification with acid chlorite. The soluble portions were hydrolyzed with 2N sulfuric acid and the total sugars and individual monosaccharides were quantified using gas chromatography and colorimetry. The insoluble residues were hydrolyzed with 72% sulfuric acid followed by dilution with water to 2N and further hydrolysis. The effects of duration of delignification and acid hydrolysis were interpreted in terms of carbohydrate yield monitored colorimetrically and with gas chromatography. The rapid derivation of sugars was perfected using N-methyl-imidazole as an acetylation catalyst. This catalyst was also employed for the derivatization of lactonized aldonic acids, enabling the gas chromatographic quantitation of uronic acids. The growth of reed canarygrass was interpreted with empirical and non-empirical methodology. the empirical procedures provided little insightinto plant cell wall composition. The non-empirical methodology which included DMSO extraction and gas-liquid chromatography revealed the possible presence of a branched galactoarabinoxylan and a linear arabinoxylan in reed canarygrass hemicellulose. The presence of β-glucan was also confirmed using selective enzymatic hydrolysis. As the plants matured, the proportion of linear xylan increased. The occurence of galactose, mannose, fucose and rhamnose in cell wall extracts may be the result of acid catalyzed degradations and transformations of other cell wall sugars. The results revealed the value of chromatography as it is applied to interpretation of plant growth and composition. Gas-liquid chromatography was proposed as a tool for the evaluation of forage digestibility and forage quality.

Bibliography: leaves 151-166. This thesis describes the development of two novel and complementary analytical approaches for assaying cyanoalanine non-protein amino acids. These assays are used to determine the distribution of these compounds both within and between plants and to identify accessions of common vetch which contain low levels of the cyanoalanine non-protein amino acids in germplasm collections. These analytical tools are used to correlate toxicity observed in animal feeding experiments with the cyanoalanine content. This thesis covers also the first report of the use of diffuse reflectance using dispersive infrared spectrometry for the "in situ" quantification of specific organic components from plant tissue as well as the first use of micellar electrokinetic chromatography for the quantitative analysis of 9-fluorenylmethyl chloroformate (FMOC) derivatised and non-derivatised components of extracts from plant material.

University of Macau / Institute of Chinese Medical Sciences

University of Macau / Institute of Chinese Medical Sciences

No description available.