CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Este trabalho apresenta um estudo do comportamento e eficÃcia de antioxidantes aditivados ao biodiesel do Ãleo de soja. Os antioxidantes mais utilizados sÃo de estrutura fenÃlica, deste modo, sintetizar, comparar e estudar a aÃÃo destes antioxidantes avaliando as possÃveis causas que os levam a serem mais eficazes traz-nos informaÃÃes para a sÃntese de compostos com melhor atuaÃÃo antioxidante. Para uso como substrato orgÃnico, foi sintetizado o biodiesel a partir do Ãleo de soja, uma vez que à a partir deste, a produÃÃo de 81 % do biodiesel produzido no Brasil. Outro fator para o uso do Ãleo de soja à que este possui majoritariamente em sua composiÃÃo Ãcido linolÃico e olÃico, Ãcidos insaturados, altamente suscetÃveis à oxidaÃÃo. O biodiesel foi sintetizado atravÃs da reaÃÃo de transesterificaÃÃo com Ãlcool metÃlico, razÃo molar Ãlcool/Ãleo de 1:6 e hidrÃxido de sÃdio 0,5 % (m/m). As amostras de biodiesel foram aditivadas com os antioxidantes comerciais (BHT e ionol) e da biomassa (cardanol hidrogenado e cardanol alquilado) nas concentraÃÃes de 300, 600, 900, 1200, 1500, 2000, 3000 e 4000 mg/kg e armazenadas em frasco Ãmbar em uma temperatura de 22,  3 ÂC. Todas as amostras foram analisadas em teste de oxidaÃÃo acelerada (Rancimat), no tempo zero (momento logo apÃs a aditivaÃÃo) e apÃs 2, 4, 6, 9 e 12 meses de armazenamento. Durante o monitoramento observou-se a variaÃÃo do tempo de induÃÃo via rancimat em funÃÃo do tempo de armazenamento das amostras. As anÃlises tÃrmicas foram realizadas com o biodiesel do Ãleo de soja, BHT, ionol, cardanol hidrogenado, cardanol alquilado, e do biodiesel aditivado com estes antioxidantes nas concentraÃÃes de 300, 900, 1500, 3000 e 4000 mg/kg, na taxa de aquecimento de 10 ÂC/min, em atmosfera de nitrogÃnio, com faixa de aquecimento de 30 ÂC â 600 ÂC. AtravÃs da anÃlise tÃrmica verificaram-se o comportamento das amostras quando submetidas a temperaturas elevadas. As anÃlises por UV-vis foram realizadas com o intuito de avaliar o processo de autoxidaÃÃo das amostras apÃs 12 meses de armazenamento. Os experimentos via rancimat revelaram que os antioxidantes comerciais sÃo melhores que os da biomassa, os experimentos termogravimÃtricos e via UV-vis auxiliaram na constataÃÃo de que para otimizar antioxidantes fenÃlicos deve-se adicionar substituintes de baixo peso molecular nas posiÃÃes orto e para. AtravÃs dos resultados via Rancimat foi desenvolvido um software para a prediÃÃo do tempo de estabilidade oxidativa em funÃÃo do antioxidante utilizado, quantidade adicionada deste, tempo de armazenamento, bem como, realizar uma anÃlise econÃmica do custo de utilizaÃÃo de cada antioxidante. / This paper presents a study of the behavior and effectiveness of antioxidants additives for biodiesel from soybean oil. The most commonly used antioxidants are ofphenolic structure, thereby synthesizing, examining and comparing the antioxidant action for evaluating possible causes for a structure to be more effective when compared to another, brings forth necessary tools in the search for better performance antioxidant compounds. For use as an organic substrate, it was synthesized biodiesel from soybean oil, since this oil is from producing about 81 % of biodiesel produced in Brazil. Another factor for the use of soybean oil is that it has in its composition mainly oleic and linoleic acids, unsaturated acids highly susceptible to oxidation. The biodiesel was synthesized by the transesterification reaction with methyl alcohol, the molar ratio alcohol / oil of 1:6 and sodium hydroxide 0.5% (m / m). The biodiesel samples were doped with antioxidants (BHT and ionol), and biomass (hydrogenated cardanol and cardanol alkylated) at concentrations of 300, 600, 900, 1200, 1500, 2000, 3000 and 4000 mg.kg-1 and stored in an amber vial at a temperature of 22,  3  C. All samples were analyzed in an accelerated oxidation test (Rancimat), at the beginning (immediately after the moment additives) and after 2, 4, 6, 9 and 12 months storage. During monitoring the observed variation via Rancimat induction time as a function of storage time of the samples. The thermal analyzes were performed with biodiesel from soybean oil, BHT, ionol, hydrogenated cardanol, cardanolalkylated, and biodiesel doped antioxidants at concentrations of 300, 900, 1500, 3000 and 4000 mg.kg-1 rate heating to 10  C / min in a nitrogen atmosphere with heating range of 30  C - 600  C.Through thermal analysis verified the behavior of the samples when exposed to elevated temperatures. The analysis by UV-vis were conducted in order to evaluate the process of autoxidation of the samples after12 months of storage. The experiments via rancimat revealed that the commercial antioxidants are better than those of biomass, and to the thermogravimetric experiments via UV-vis the finding that helped to optimize phenolic antioxidants should be added low molecular weight substituent at the ortho and para positions. Through the results via Rancimat software was developed to predict the time depending on the oxidative stability of the antioxidant used, this added amount, time of storage and, perform an economic analysis cost of use of each antioxidant.

La présence d’un métabolisme actif des bactéries lactiques dans le vin logé en fûts de chêne induit une augmentation de la concentration des composés volatils du bois. Ce phénomène a récemment été attribué à l'activité glycosidique des bactéries. Le glucoside précurseur d'un composé majeur de l’arôme boisé (whiskylactone) a déjà été identifié et quantifié dans le bois de chêne. Mais aucune donnée n'était disponible jusqu’à présent concernant l’identification formelle des précurseurs pour d’autres arômes du bois de chêne.Un premier travail a permis de montrer que les précurseurs monoglycosides n'existaient pas dans le bois de chêne, dans les spiritueux et dans le vin. L'étude a été réalisée à l’aide de la technique UPLC-FT/MS, en utilisant la vanilline-β-D-glucopyranoside, la vanilline-β-D-xylopyranoside, et la coniféraldéhyde-β-D-glucopyranoside, synthétisées par réaction par transfert de phase. Dans un deuxième temps, une purification des précurseurs glycosidiques complexes a été réalisée à l’aide de la Chromatographie de Partage Centrifuge (CPC) à partir d’un extrait de bois de chêne. Le choix du système de solvants a été basé sur une égale répartition dans les deux phases de la libération d’arômes par hydrolyse enzymatique. Cela a conduit à la détermination du nouveau concept de coefficient de partage d’activité Kca. Après purification et fractionnement, la vanilline galloylglucoside, le triméthoxyphénol-galloyl-glucoside et le macarangioside E ont été isolés du bois et identifiés par HPLC-ESI-MS et RMN. Ces précurseurs ont été quantifiés dans différentes espèces de chêne par HPLC-QqQ-MS. Ces trois composés sont les précurseurs respectivement de la vanilline, du 3,4,5-triméthoxyphénol et du 3-oxo-α-ionol. Par dégradation thermique, le macarangioside E peut conduire à la mégastigmatriénone et à la 4-oxo-isophorone, dont les notes aromatiques sont le tabac et l’encens. Ces composés complètent la connaissance que nous avons de l’arôme boisé du vin et contribuent ainsi à une meilleure compréhension de la genèse du bouquet tertiaire. / The presence of lactic acid bacteria (LAB) in oak barrels induces an increase in wood volatile compounds concentration. This phenomenon could be due to the glycosidic activity of LAB. The glucosidic precursor of a major woody aroma compound (oak lactone) was identified and quantified in oak wood but no data was available concerning the presence of other flavor precursors in oak wood. This study showed that monoglycosidic precursors did not exist in oak, in spirits and in wines. The study was performed by UPLC-FT/MS, using vanillin-β-D-glucopyranoside, vanillin-β-D-xylopyranoside, and coniferaldehyde-β-D-glucopyranoside as standards. These molecules were synthesized by phase transfer reaction. Purification of a vanillin glycoside precursor was done by centrifugal partition chromatography (CPC). The choice of the solvent system was based on an equal distribution in both phases of the aromas released by enzymatic hydrolysis. This led to the determination of the new concept, the activity partition coefficient Kca. After purification and fractionation, vanillin galloylglucoside, trimethoxyphenol-galloylglucoside and macarangioside E were isolated from wood and identified by HPLC-ESI-MS and NMR analysis. These precursors were quantified in different oak species by HPLC-QqQ-MS. These three compounds are precursors of vanillin, 3,4,5-trimethoxyphenol and 3-oxo-α-ionol respectively. The macarangioside E can lead by thermal degradation, to megastigmatrienone and 4-oxo-isophorone which have aromatic notes of tobacco and incense. These compounds are involved in the woody aroma of the wine and the genesis of the bouquet.