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Thesis (Ph. D.)--Faculty of Agriculture, University of Sydney, 1998. / Bibliography: leaves 184-218. Also available in print form.

The industrial uses of cottonseed oil are limited by its fatty acid composition. Genetic modification of cotton lipid profiles using seed-specific promoters could allow cotton growers to produce valuable new oils in the seed without adverse effects on fiber quality and yield, therefore making this crop more commercially profitable. Transgenic cotton callus harboring a diverged fatty acid desaturase gene (FADX) from Momordica charantia was characterized for production of alpha-eleostearic acid (conjugated double bonds: 18:3 D9 cis, 11 trans, 13 trans), not normally found in cotton. Gas chromatography (GC) in conjunction with mass spectrometry (MS) confirmed production of alpha-eleostearic acid in the transgenic cotton tissues. A second series of transformation experiments introduced the cotton fatty acid thioesterase B (FATB) cDNA, fused to the seed-specific oleosin promoter into cotton to promote the over-expression of FATB, to generate cotton with increased palmitate in the cottonseed. PCR amplification, as well as fatty acid analysis by gas chromatography, confirmed introduction of the FATB cDNA in transgenic tissues. Collectively, these results demonstrate the feasibility of manipulating the fatty acid composition in cotton via transgenic approaches and form the basis for continued efforts to create novel oils in cottonseed.

M.S.

Orientador: Rubens Monti / Coorientador: Ariela Veloso de Paula / Banca: Rafael Rodrigues Hatanaka / Banca: Marcel Otávio Cerri / Resumo: Objetivo: o presente trabalho teve como objetivo a síntese enzimática de lipídeos estruturados a partir dos óleos de semente de uva e algodão, especificamente os triglicerídeos dietéticos do tipo MLM (médio:longo:médio), ou seja, aqueles que possuem ácidos graxos de cadeia média (M), em posições sn-1 e sn-3, e de cadeia longa (L), na posição interna da molécula de triacilglicerol. Métodos: fez-se a caracterização das matérias primas (óleos de semente de uva e algodão) e dos TAGs (triglicerídeos) modificados em relação aos índices de acidez, peróxido, perfil em ácidos graxos por cromatografia gasosa e determinação da posição sn-2. Determinou-se as atividades de hidrólise e de esterificação das lipases empregadas. Utilizou-se um planejamento de experimentos (DCCR- Central Composite Rotatable Design) para verificar a influência de razão molar e temperatura sobre o grau de incorporação (GI) do ácido graxo de cadeia média. Por fim fez-se a caracterização hidrodinâmica do reator de leito fixo e/ou empacotado. Resultados: os resultados mostraram que as matérias primas estão dentro dos padrões de especificação (0,6 mg KOH/g para acidez e 10 meq/kg para peróxido), fornecendo valores semelhantes, independentemente do óleo analisado. Os óleos foram ainda caracterizados quanto à composição em ácidos graxos por cromatografia gasosa. Ambos apresentaram altas quantidades de ácidos graxos insaturados, ressaltando-se o essencial ácido linoleico (C18:2n6). Em seguida, foram efetuadas reações d... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Objective: the objective of the present work was the enzymatic synthesis of structured lipids from grape and cottonseed oils, specifically the MLM type dietary triglycerides, that is, those with medium chain fatty acids (M), in positions sn-1 and sn-3, and long-chain (L), in the internal position of the triacylglycerol molecule. Methods: The raw materials (grape and cottonseed oils) and the modified TAGs (triglycerides) were characterized in relation to the acid, peroxide, fatty acid profile by gas chromatography and the sn-2 position determination. The hydrolysis and esterification activities of the lipases employed were determined. A DCCR (Central Composite Rotatable Design) was used to verify the influence of molar ratio and temperature on the degree of incorporation (ID) of the medium chain fatty acid. Finally, the hydrodynamic characterization of the fixed bed reactor and / or packaged was performed. Results: The results showed that the raw materials are within the specification standards (0.6 mg KOH / g for acidity and 10 meq / kg for peroxide), providing similar values regardless of the oil analyzed. The oils were further characterized for fatty acid composition by gas chromatography. Both presented high amounts of unsaturated fatty acids, emphasizing the essential linoleic acid (C18: 2n6). Then, acidolysis reactions were carried out, aiming at the selection of the fatty acid and the biocatalyst. For the grape oil, values of degree of incorporation (ID,%) ranging from 23.62±1.34 to 34.53±0.05% were obtained. The best results were obtained using C10:0 as fatty acid and Lipozyme RM IM lipase (34.53 ± 0.05%)... (Complete abstract click electronic access below) / Mestre

A otimizaÃÃo do processo de prÃ-tratamento (refino) do Ãleo bruto de algodÃo, para obtenÃÃo de Ãleo semi-refinado, com aplicabilidade na produÃÃo de biocombustÃveis, à o principal objetivo desse trabalho. Este por sua vez à motivado pela exploraÃÃo de matÃriasprimas menos processadas e de menor custo para produÃÃo do biodiesel. Portanto, o emprego de Ãleo semi-refinado de algodÃo pode vir a contribuir para a reduÃÃo nos custos de produÃÃo do biodiesel. As variÃveis estudadas no prÃ-tratamento do Ãleo bruto de algodÃo foram escolhidas tendo como referencial o processo de refino convencional (refino quÃmico) com soda cÃustica. Os experimentos foram realizados utilizando planejamento experimental e os resultados foram interpretados de acordo com a metodologia de superfÃcie de resposta. As variÃveis estudadas foram: concentraÃÃo e excesso de soda cÃustica (soluÃÃo de NaOH), temperatura inicial e final. As respostas foram avaliadas em funÃÃo de alguns dos mais importantes parÃmetros de qualidade do Ãleo semi-refinado obtido (cor, acidez e teor de sabÃo) e da quantidade do co-produto de refino (borra) produzido. O excesso de soda cÃustica e a temperatura inicial foram Ãs variÃveis que influenciaram de modo mais significativo as respostas analisadas, dentro do alcance experimental estudado. A eficiÃncia na conversÃo a Ãsteres metÃlicos mostrou-se dependente da qualidade (cor, acidez e sabÃo) do Ãleo semirefinado de algodÃo utilizado. A concentraÃÃo do pigmento gossipol que està diretamente relacionado à cor do Ãleo de algodÃo, sugere que o mesmo pode estar influenciando na conversÃo da reaÃÃo de transesterificaÃÃo alcalina, por estar consumindo parte do catalisador. As condiÃÃes Ãtimas determinadas experimentalmente foram: concentraÃÃo e excesso de soda cÃustica 25 % (p/p) e 100 % (p/p), temperatura inicial e final 40ÂC e 60ÂC, respectivamente. Nessas condiÃÃes otimizadas o Ãleo semi-refinado obtido alcanÃou conversÃo de 94 % (p/p) a Ãsteres metÃlicos. Entretanto, o Ãleo obtido nas condiÃÃes otimizadas, por apresentar ainda uma elevada concentraÃÃo de sabÃo, foi submetido à lavagem com Ãgua, o qual reduziu seu teor de sabÃo. Assim, com esse Ãleo lavado/seco, apÃs reaÃÃo de transesterificaÃÃo, alcanÃouse conversÃo de 96% (p/p) em metil-ester. Esse biodiesel, submetido a uma segunda reaÃÃo de transesterificaÃÃo conseguiu-se atingir uma conversÃo mÃxima de 98% (p/p), ficando dentro das especificaÃÃes estabelecidas pela ANP (AgÃncia Nacional de PetrÃleo, GÃs Natural e BiocombustÃveis) / The optimization of the pre-treatment (refining) of crude cottonseed oil, in order to obtain semi-refined oil, its applicability in the production of biofuels is the main objective of this work. This objective is motivated by the investigation of less processed or cheaper raw materials, for instance, semi-refined cotton oil, in order to reduce the cost of biodiesel production. The conditions of pre-treatment studied for the cotton crude oil of were chosen based on the conventional caustic soda refining process (chemical refining). The proposed process of biodiesel production was evaluated and the optimal operating conditions range was identified by application of the factorial design and response surface methodology. The studied variables were concentration and the caustic soda excess (solution NaOH), initial and final temperatures. The responses were evaluated according some of the most important quality parameters of semi-refined oil obtained (color, acidity and content of soap) and the amount of co-product of refining (soapstock) produced. The caustic soda excess and initial temperatures are the variables that most significantly influenced the responses analyzed within the experimental range studied. The efficiency of conversion to methyl esters was dependent on the quality (color, acidity and concentration of soap) in the semi-refined cotton oil used. Gossypol concentration was found to be highly correlated with color cottonseed oil,suggesting that it may influence the conversion in the alkaline transesterification reaction,consuming part of the catalyst. The best result for laboratory-scale reactions was 94% (wt/wt)of ester conversion in optimum conditions, determined experimentally: concentration and caustic soda excess 25 % (wt/wt) and 100 % (wt/wt), initial and final temperatures 40  C and 60  C, respectively. These conditions the optimized semi-refined oil obtained conversion reached 94 % (wt/wt) of esters. However, the oil obtained under the conditions optimized for present a high concentration of soap, was subjected to washing with water, which reduced its content of soap. Then with the oil washed / dry, after transesterification reaction reached 96 % (wt/wt) of ester conversion. This biodiesel was again transesterificated reaching a conversion of 98 % (wt/wt), which, therefore, is within specifications established by the ANP

Ce travail de thèse porte sur l'étude d'un procédé d'époxydation et de carbonatation par CO₂ des huiles végétales ce qui permet de valoriser à la fois les huiles et le CO₂ .Un modèle cinétique passant par la formation in situ de l'acide performique est construit pour l'époxydation de l'acide oléique et de l'huile de coton, en couplant les bilans de matière et d'énergie. Une stratégie permettant de réduire le nombre de paramètre à estimer est adoptée. Ce modèle est potentiellement transposable aux autres huiles ayant une structure similaire, car la réactivité de chaque type d'acide gras est déterminée. Pour la réaction de carbonatation, une étude cinétique est réalisée, et la solubilité et le coefficient de transfert de matière du CO₂ dans la phase liquide sont mesurés en tenant compte de la non idéalité des conditions à l'aide de l'équation d'état de Peng-Robinson. L'utilisation du carbonate obtenu est enfin examinée dans la synthèse de polyuréthanes sans isocyanates (NIPUs). / This thesis focuses on the process aspect of the first two steps in the synthesis of non-isocyanates polyurethanes (NIPUs) from vegetable oils, i.e. epoxidation and carbonation reaction. This process adds value to both vegetable oil and CO₂. A kinetic model by using performic acid formed in-situ is built for epoxidation of oleic acid and cottonseed oil, by coupling the mass balance and energy balance. This model is potentially transferable to other oils with similar structure as the reactivity of each type of fatty acid is determined. For the carbonation reaction, a kinetic study is carried out, and the solubility and the CO₂ mass transfer coefficient in the liquid phase is measured under non-ideal condition using the Peng-Robinson equation of state.

Deux types de revêtements constitués d'environ 80% d'huile végétale ont été élaborés par chimie thiol-X sous UV. Le premier a été obtenu sous UV à partir d'huiles de lin native et standolisées en présence de 0,5 équivalent (SH/ène) de divers thiols, sous air, sans photoamorceur ni solvant. L'effet bénéfique de l'oxydation des acides gras sur la réaction d'addition thiol-ène et les propriétés finales des revêtements a été démontré. Ces matériaux présentent des propriétés équivalentes à celles des films obtenus par oxydation de l'huile de lin, faisant de ce procédé une alternative intéressante à la siccativation des huiles. Le deuxième type de revêtement a été obtenu sous UV à partir d'une huile de coton époxydée en présence de 0,25 équivalent (SHlépoxy) de 7- mercapto-4-méthyl coumarine et d'un photogénérateur de base permettant d'amorcer, sous air, la réaction d'addition thiol-époxy et l'homopolymérisation des fonctions époxy. Ces revêtements sont autoréparables sous UV. / Two types of coatings constituted about 80 wt% of vegetable oil were prepared by photoinitiated thiol-X chemistry. The first one has been prepared by crosslinking of native and stand linseed oil triglycerides in the presence of 0.5 equivalent of various thiols (SH/ene) under air and UV radiation, without photoinitiator or solvent. The oxidation of fatty acids has shown a beneficial effect on the thiol-ene addition as well as on the final properties of coatings. This process is thus an interesting alternative for the drying of oils. The second type of coating has been obtained by photocrosslinking triglycerides of epoxidized cottonseed oil in the presence of 0.25 equivalent (SH/epoxy) of 7-mercapto-4-methyl coumarine and a photobase generator under air. This latter initiated both thiol-epoxy addition and homopolymerization of epoxy functions. This coating could be auto-healable under UV exposure.

The dissertation thesis deals with the analysis of prospective environmentally compatible electrical insulating fluids for electrical engineering in relation to their chemical structure. The thesis starts with the overview of the current state of the art and of the latest trends in the use of synthetic and biodegradable natural oils. In the experimental part were studied these oils: mineral oils, rapeseed oil, sunflower oils, soybean oil, methyl oleate, peanut oil, MCT oil, castor oil and other. Dielectric properties were measured using LRC meter Agilent 4980A including dielectric liquid test fixture Agilent 16452A and also by the Novocontrol Alpha-A analyzer. Electrical properties are presented in the frequency range 10 mHz – 1 MHz range in the temperature interval 253 K to 363 K. The work goes on with the study of the suitability of individual oils for lower temperature, including the impact of the chemical structure and formulation on electrical properties.