CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior / O objetivo desta dissertaÃÃo foi de otimizar a reaÃÃo de esterificaÃÃo para a produÃÃo de biodiesel por meio da aplicaÃÃo de tÃcnicas de adsorÃÃo. A aplicaÃÃo da adsorÃÃo teve o intuito de remover a Ãgua formada no processo, uma vez que a mesma leva a desativaÃÃo do catalisador e desloca o equilÃbrio quÃmico para reaÃÃo de hidrolise. A presenÃa de Ãgua reduz o rendimento da reaÃÃo de esterificaÃÃo, o que torna necessÃrio a utilizaÃÃo de elevadas concentraÃÃes de Ãlcool no meio reacional. Para tanto, foi realizado dois planejamentos experimentais para as reaÃÃes de esterificaÃÃo sem e com adsorÃÃo da Ãgua formada no processo. Em ambos os planejamentos foram investigadas as variÃveis temperatura, concentraÃÃo de catalisador e razÃo molar entre o Ãlcool e o Ãcido graxo. No planejamento experimental realizado para a reaÃÃo de esterificaÃÃo sem adsorÃÃo da Ãgua formada, as variÃveis concentraÃÃo de catalisador e razÃo molar entre reagentes mostraram-se estatisticamente significativas para a resposta conversÃo a 95 % de confianÃa. O melhor resultado experimental foi obtido a temperatura de 110ÂC com uma razÃo molar de 9:1 e uma concentraÃÃo de 1% de catalisador. Jà no planejamento experimental para a reaÃÃo de esterificaÃÃo com a remoÃÃo da Ãgua formada no processo, as variÃveis temperatura e a concentraÃÃo de catalisador foram significativas estatisticamente para o intervalo de confianÃa estudado (95%). Observou-se que quanto maior a temperatura e maior a concentraÃÃo de catalisador, melhor foi o resultado experimental obtido. Os experimentos cinÃticos mostraram que ao realizar a reaÃÃo de esterificaÃÃo aplicando-se tÃcnicas de adsorÃÃo, o processo tornou-se mais sensÃvel a temperatura, uma vez que o valor de energia de ativaÃÃo aparente obtido para a reaÃÃo com adsorÃÃo de Ãgua foi de 26,66 kJ/mol e para a reaÃÃo sem adsorÃÃo da Ãgua formada foi de 18,43 kJ/mol. A anÃlise via CG/MS mostrou que o acompanhamento da reaÃÃo por meio do Ãndice de acidez à satisfatÃrio para acompanhar a dinÃmica da reaÃÃo, pois os valores de conversÃo obtidos pelos dois mÃtodos foram equivalentes. Na caracterizaÃÃo do biodiesel obtido com adsorÃÃo da Ãgua formada os parÃmetros de densidade, Ãndice de iodo e viscosidade cinemÃtica atenderam as especificaÃÃes exigidas pela ANP. Ao aplicar a metodologia desenvolvida no respectivo trabalho (aplicaÃÃo de tÃcnicas de adsorÃÃo na reaÃÃo de esterificaÃÃo), os teores de Ãsteres metÃlicos obtidos foram de 98,9 % e 99,4 % para os experimentos realizados a razÃo molar de 3:1, concentraÃÃo de 1% de catalisador e temperaturas de 90 e 100ÂC, respectivamente. / This dissertation aimed to optimize the esterification reaction for biodiesel production using an adsorption reaction system. Adsorption was applied to remove the water formed in the process, because water deactivates the catalyst and shifts the equilibrium towards the hydrolysis reaction. Water reduces the yield of the esterification reaction, which requires high concentrations of alcohol in the reaction medium. Two experimental designs were carried out for the esterification reactions. One with and one without adsorbing the water formed in the process. In both designs, the variables temperature, catalyst concentration, and molar ratio between alcohol and fatty acid were investigated. Catalyst concentration and the alcohol to FFA molar ratio were the most statistically significant responses on conversion (within a 95% level of confidence) when the reaction was carried out without the adsorption system. The best result was obtained in experimental temperature of 110ÂC with a molar ratio of 9:1 and with a concentration of 1% of catalyst. Temperature and catalyst concentration were the most statistically significant variables in the experiments carried out with the adsorption system (for the confidence level of 95%). Higher temperatures and higher catalyst concentration enhanced the yield into biodiesel. The kinetic experiments showed that with the adsorption system the process became more sensitive to temperature, since the value of the apparent activation energy of the reaction was 26.66 kJ/mol and without adsorption system the apparent activation energy was 18.43 kJ/mol. GC/MS analysis showed that acidity index was very satisfactory to evaluate the yield of biodiesel., because the conversions obtained in both methods were equivalent. Density, iodine value and kinematics viscosity were within the specifications required by ANP. The methodology developed in this study resulted in conversions of oleic acid into methyl esters of 98.9% and 99.4% for the experiments performed with a molar ratio of 3:1, concentration of 1% of catalyst and temperatures of 90 and 100  C, respectively.

Este trabalho objetivou explorar o óleo de macaúba (Acrocomia aculeata) como matéria prima para produção de biodiesel, propondo uma via através da qual se possibilite a produção do biodiesel apesar da alta acidez do óleo. O processo proposto ocorreu em duas etapas de catálise homogênea, a primeira foi a reação de esterificação etílica dos ácidos graxos livres, catalisada por H2SO4; e a segunda é a transesterificação dos triglicerídeos remanescentes catalisada por álcali (KOH). A utilização das ondas ultrassônicas também foi investigada neste trabalho como potencializador do processo. Para determinação das melhores condições reacionais foi utilizado o delineamento experimental e para validação dos resultados utilizou-se análise de variância do modelo para as variáveis respostas índice de acidez na etapa de pré-tratamento e conversão de ésteres etílicos na etapa de transesterificação alcalina. Os resultados foram avaliados utilizando o software MINITAB 16. Na etapa de pré-tratamento os resultados demonstram que utilizando quantidades de H2SO4 de 2% (em massa), razão molar óleo:etanol de1:9 e temperatura de 50 ºC o índice de acidez foi reduzido de 19,25 mgKOH/g para 1,46 mgKOH/g em 2 h de reação. Com estes resultados foi possível a aplicação da reação de transesterificação alcalina. Na etapa etapa de transesterificação alcalina com agitação mecânica as melhores condições determinadas pelo delineamento experimental foram de 1,5% (massa) de KOH, razão molar de 1:6 e temperatura de 45 ºC em 30 min de reação as conversões alcançadas foram em torno de 100%. As reações processadas em banho ultrassônico e sonda ultrassônica apresentaram como principal vantagem a redução de tempo, sendo em que 10 min foram atingidas conversões próximas a 100%. As análises efetuadas nos ésteres etílicos de amêndoa de macaúba, obtidos a partir do processo em duas etapas, mostram que a viscosidade cinemática e densidade estão dentro dos parametros estabelecidos pela ANP. Os níveis de glicerina total e livre também estão dentro do estabelecido pelas normas e indica que a purificação dos produtos de reação foi adequada. / This study aimed to explore Macauba oil (Acrocomia aculeata) as an alternative raw material to the production of biodiesel, despite the high acid value of the oil. It was proposed a two-step process of homogeneous catalysis. The first step is the ethylic esterification of free fatty acids, catalyzed by H2SO4; the second is the transesterification catalyzed by alkali (KOH). The use of ultrassonic irradiation was also investigated in this work. Factorial design was used to determine the best reaction conditions and analysis of variance was used to evaluate the mathematical model for the variable responses, such as the acid level in the pre-treatment and conversion of ethyl esters in alkaline transesterification step. The results were evaluated using the software MINITAB 16. In the first step, the acid catalyzed reaction was carried out with 9:1 molar ratio ethanol-to-oil in the presence of 2% w/w H2SO4 at 50 ºC for 2 hours and the acid value of Macauba oil was reduced from 19 mgKOH/g to 1,46 mgKOH/g. With these results, it was possible the application of alkaline transesterification reaction. In the alkaline transesterification under mechanical stirring, the optimal experimental conditions were 1.5% (mass) of KOH molar ratio of 1:6 and temperature of 45 ºC in 30min. Conversions of approximately 100 %. were achieved in this process The reactions that were processed in ultrasonic bath and probe presented as the major advantage the reduction of the time, conversions of approximately 100% were achieved in 10 min. The analysis of the ethyl esters obtained from this two-step process show that the kinematic viscosity and density are within the parameters established by the ANP. The levels of total and free glycerol are also within the established standards and indicate that purification of products were adequate.

Petrochemical and fine chemical industries face a daunting problem in recovering acetic acid from its aqueous solutions. The recovery of acetic acid could be done through esterification reaction. However, esterification is an equilibrium limited reaction. Multi-functional reactors such as chromatographic reactor (CR) and reactive distillation column (RDC) are promising technologies mainly for equilibrium limited reactions wherein reaction and separation of products are carried out in a single equipment that tends to shift the equilibrium towards the desired direction which is not possible in a classical batch reactor. Physical and chemical characterisation of ion exchange resin catalysts such as scanning electron microscopy, Brunauer-Emmett-Teller (BET) surface area measurement, pore size distribution, elemental analysis, true density and particle size distribution were carried out to access the catalysts performance for n-hexyl acetate synthesis. Esterification of acetic acid with n-hexanol was studied with both dilute and concentrated acid in the presence of cation exchange resins (macroporous and gelular) in a jacketed stirred batch reactor to synthesise a value added ester, namely n-hexyl acetate and also to study the recovery of acetic acid from the waste aqueous streams. The effect of various parameters such as speed of agitation, catalyst particle size, feed mole ratio of n-hexanol to acetic acid, reaction temperature, catalyst loading and reusability of catalysts was studied for the optimisation of the reaction condition in a batch reactor. The non-ideality of each component in the reacting mixture was accounted for by using the activity coefficient via the use of the UNIFAC group contribution method. The kinetic data were correlated with both pseudo-homogeneous (PH) and adsorption based heterogeneous reaction rate models, e.g., Eley-Rideal (ER), Langmuir-Hinshelwood-Hougen-Watson (LHHW), and the modified LHHW (ML). Pseudo-homogeneous (PH) model gave the best representation of the kinetic data found experimentally. The feasibility of reactive distillation for the recovery of acetic acid using n-hexanol was evaluated through residue curve map (RCM) determination experiments. RCM provides information to a design engineer of the existence of separation boundaries imposed by the singular points corresponding to the reactive/non-reactive azeotropes, thus provides an insight into the feasibility of reactive distillation for this purpose. A laboratory scale batch chromatographic reactor was designed and constructed. Batch chromatographic reactor experiments were carried out using different parameters such as feed flow rate, feed mole ratio of n-hexanol to acetic acid, desorbent (n-hexanol) flow rate and reaction step to maximise the formation of n-hexyl acetate as well to achieve complete conversion of acetic acid. Continuous chromatographic reactor was designed, constructed and commissioned on the basis of the results obtained from the batch chromatographic reactor experiments. The experiments carried out in continuous chromatographic reactor correlated very well with the results from the batch chromatographic reactor for the optimised condition.

Recent developments in converting biomass to bio-chemicals and liquid fuels provide a promising sight to an emerging biofuels industry. Biomass can be converted to energy via thermochemical and biochemical pathways. Thermal degradation processes include liquefaction, gasification, and pyrolysis. Among these biomass technologies, pyrolysis (i.e. a thermochemical conversion process of any organic material in the absence of oxygen) has gained more attention because of its simplicity in design, construction and operation. This research study focuses on comparative assessment of two types of pyrolysis processes and catalytic upgrading of bio-oil for production of transportation fuel intermediates. Slow and fast pyrolysis processes were compared for their respective product yields and properties. Slow pyrolysis bio-oil displayed fossil fuel-like properties, although low yields limit the process making it uneconomically feasible. Fast pyrolysis, on the other hand, show high yields but produces relatively less quality bio-oil. Catalytic transformation of the high-boiling fraction (HBF) of the crude bio-oil from fast pyrolysis was therefore evaluated by performing liquid-phase reactions at moderate temperatures using Pt/HZSM-5 catalyst. High yields of upgraded bio-oils along with improved heating values and reduced oxygen contents were obtained at a reaction temperature of 200°C and ethanol/HBF ratio of 3:1. Better quality, however, was observed at 240 °C even though reaction temperature has no significant effect on coke deposition. The addition of ethanol in the feed has greatly attenuated coke deposition in the catalyst. Major reactions observed are esterification, catalytic cracking, and reforming. Overall mass and energy balances in the conversion of energy sorghum biomass to produce a liquid fuel intermediate obtained sixteen percent (16 wt.%) of the biomass ending up as liquid fuel intermediate, while containing 26% of its initial energy.

Three dimensional printing (3DP) is one of the most important solid freeform fabrication (SFF) methods that can produce any material with desired 3D shape by using suitable powder-binder formulations. It differs from the standard molding operations in that it can produce a complicated shapes by a software driven instrument in a laminated fashion and the cost is lower. This method can be applied in a very wide area including drug release operations, biomaterial production especially for bone fixation, prototype production for all purposes, wound dressing etc. It can also be used in obtaining edible objects by using natural polysaccharides with water based binders. In this study, it is aimed to understand the gelling behaviour of some of the gelling materials, which are alginates, pectins and carageenans, and effect of various factors on the production of confectionary objects by means of 3DP process. Effect of multivalent cations, especially Ca2+ ion, on the gelling behaviour of these materials are investigated. The egg-box structure obtained between the polymer segments increases the water holding capacity of the materials and much more chewy structures can be obtained. The molecular changes are followed by Fourier Transform infrared spectroscopy (FTIR). In 3DP applications, the composition of powder and binder, pH, temperature, relative humidity (RH) and machine parameters are important factors affecting the texture of the final object. The texture of the produced specimens is examined by using a texture analyzer and maximum force values are given as g/cm at failure. Alginate and carrageenans are found to be more effective in obtaining chewy textures with Ca2+ ion content in sugar based matrices and optimization of machine parameters are performed to obtain a higher resolution on the specimens.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-08-30T14:53:05Z No. of bitstreams: 1 ADRIANO SANT'ANA SILVA - PPGEP TESE 2011..pdf: 12696755 bytes, checksum: 3f702ca1b940a9bb7e2fc2feb1499709 (MD5) / Made available in DSpace on 2018-08-30T14:53:05Z (GMT). No. of bitstreams: 1 ADRIANO SANT'ANA SILVA - PPGEP TESE 2011..pdf: 12696755 bytes, checksum: 3f702ca1b940a9bb7e2fc2feb1499709 (MD5) Previous issue date: 2011-04 / Capes / 0 biodiesel é um biocombustível proveniente de fontes renováveis, tais como óleos vegetais e gordura animal, e que foi proposto como alternativa ao óleo diesel derivado do petróleo. Normalmente, este biocombustível é obtido a partir do óleo de soja, por meio da reação de transesterificação, a qual faz uso de catalisadores homogéneos alcalinos que ao término da reação não são reutilizados e ainda exigem matéria prima refinada e isenta de água. Diante disso, o uso de catalisadores heterogéneos tem-se consolidado cada vez mais no meio académico e industrial pela possibilidade do seu reuso e por permitir o uso de diferentes fontes lipídicas. Ademais, a busca por fontes lipídicas de menor custo, como óleo de algodão, e que não concorram com outros seguimentos industriais, como a indústria de alimentos, tornou-se foco atual de diversas pesquisas. Sendo assim, o objetivo desta tese foi sintetizar, caracterizar e avaliar os catalisadores suportados M0O3-MCM-41 e NiOMCM-41 nas reações de transesterificação e esterificação, etílica e metílica do óleo de algodão, usando sistema reacional estático. O suporte MCM-41 foi obtido pelo método de síntese a temperatura ambiente. Os catalisadores foram sintetizados pelo método de dispersão física em três concentrações distintas (1, 3 e 5% em massa) e foram caracterizados por DRX, FTIR, análise textural e EDX. Por meio de um planejamento fatorial 23 avaliou-se os efeitos das variáveis independentes: temperatura, razão molar de óleo: álcool e concentração de catalisador, sobre as variáveis dependentes éster e de triacilglicerídeo, na reação de transesterificação. Na reação de esterificação avaliou-se os efeitos destas variáveis sobre a conversão dos ácidos graxos livres em éster. Os resultados de caracterização indicaram que a fase hexagonal da MCM-41 foi obtida e que o procedimento de dispersão física dos óxidos foi viável para síntese dos catalisadores em estudo. Nos testes catalíticos o catalisador 5%Mo03-MCM-41 apresentou os melhores resultados para a transesterificação etílica e metílica; e esterificação metílica, com conversão de cerca de 53, 48,1 e 78,7%, respectivamente. Para a reação de esterificação etílica o catalisador 3%Mo03-MCM-41 apresentou o maior conversão, cerca de 67,9%. O catalisador NiO-MCM-41 não apresentou atividade catalítica nas reações estudadas. A temperatura, de acordo com o planejamento experimental foi a variável de maior influência nas reações de transesterificação e esterificação. As reações conduzidas em sistema estático foram viáveis para a obtenção do biodiesel / Biodiesel is a biofuel produced from renewable sources such as vegetable oils and animal fat, which was proposed as an alternative to petroleum diesel. Typically, this biofuel is made from soybean oil, by transesterification with alkaline homogeneous catalysts that at the end of the reaction are not reused and still require refined oil. Thus, the use of heterogeneous catalysts has been increasingly in industry by the possibility of its reuse and for allowing the use of different lipid sources. Furthermore, the search for low cost lipid sources, such as cottonseed oil, has become the current focus of several studies. Therefore, the objective of this thesis was to synthesize, characterize and evaluate the catalysts M0O3-MCM-41 and NiO-MCM-41 in ethyl and methyl, transesterification and esterification reactions of cottonseed oil, using a static reaction system. The support MCM-41 was obtained by synthesis at room temperature. The catalysts were synthesized by the method of physical dispersion in three different concentrations (1, 3 and 5% in weight) and were characterized by XRD, FTIR, EDX and textural analysis. Through a 23 factorial design the effects of independent variables: temperature, molar ratio of oil: the percentage of alcohol and catalyst on the dependent variables éster and triglycerides in the transesterification reaction, were evaluated. In the esterification reaction the effects of these variables on the conversion of free fat acid was evaluated. The characterization results indicated that the hexagonal phase of MCM-41 was obtained and the procedure of physical dispersion of the oxides was viable for the synthesis of the catalysts under study. In the catalytic tests the catalyst 5%Mo03-MCM-41 showed the best results for the methyl and ethyl transesterification and for methyl esterification, with conversion of about 53, 48.1 and 78.7%, respectively. For the reaction of ethyl esterification, the catalyst 3%MoC«3-MCM-41 showed the highest conversion, about 67.9%. The catalyst NiO-MCM-41 showed no catalytic activity. The temperature, according to the experimental design, was the variable that most influenced the reactions.

118 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-11T17:50:31Z No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-14T17:22:34Z (GMT) No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) / Made available in DSpace on 2013-05-14T17:22:34Z (GMT). No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) Previous issue date: 2011 / CAPES / Devido aos inúmeros incentivos governamentais que impulsionam a produção do Biodiesel no mundo, tal combustível está sendo produzido largamente, e um fator preocupante frente a esse crescimento é o destino do glicerol excedente, já que seu uso é condicionado ao seu grau de pureza, que deve estar usualmente acima de 95%. No caso do glicerol bruto, resultante do processo de transesterificação do biodiesel, são necessários processos complexos e onerosos para que essa matéria-prima alcance as exigências em grau de pureza necessária para seu emprego. Além disso, os mercados tradicionais que o consomem (indústria de cosméticos, resinas, indústria farmacêutica, têxtil e alimentícia) têm uma capacidade limitada de absorção de quantidades maiores desse sub-produto. Sendo assim, esse trabalho tem como objetivo promover modificações estruturais na molécula do glicerol (comercial, alcalino e bruto), utilizando como agentes oxidantes os sais de bismuto (Zn(BiO3)2 e NaBiO3), NaClO e KBrO3/NaHSO3. As reações foram realizadas em ácido acético , ácido lático, acetona, água, com variação de tempo, temperatura, concentração dos reagentes e catalisadores. Essa metodologia sintética tem como finalidade gerar produtos com maior valor agregado tornando o glicerol um sub-produto mais reaproveitado e competitivo no mercado. Os melhores resultados na conversão do glicerol para os produtos mono, di e triacetilados foram alcançados utilizando 1mol% do catalisador NaBiO3 em diferentes concentrações de ácido acético glacial. Na ausência do catalisador a reação também ocorre, porém com tempo elevado. Em nenhum dos experimentos ocorreu à oxidação do glicerol. O modelo experimental realizado mostrou que é necessário excesso de ácido a fim de promover o equilíbrio na direção da conversão do glicerol e seletividade para os produtos mais valiosos comercialmente, o di e triacetilados. / Salvador

Les lysophosphatidylcholines (LPCs), molécules amphiphiles, peuvent jouer le rôle d'un vecteur pour des acides gras d'intérêt. Ces molécules peuvent être synthétisées par voie enzymatique. Ce travail a pour objectif de synthétiser des LPCs contenants des acides gras mono ou poly insaturés par voie enzymatique. La sn-3-glycerophosphatidylcholine (GPC), l'acide oléique (C18 : 1, ω9), l'acide linoléique (C18 : 2, ω6) et l'acide docosahexènoïque (C22 : 6, ω3) ont été utilisés comme substrats. Ces synthèses ont été réalisées par estérification sans solvant en utilisant une lipase immobilisée. Du point de vue cinétique, une optimisation des conditions de la synthèse de l'oléoyl-LPC a été effectuée en étudiant chaque facteur d'une façon indépendante. Les conditions optimales sont : Lipozyme RM-IM (10% par rapport la masse totale des substrats), un rapport molaire de 20 (acide oléique /GPC), ni ajout ni élimination d'eau au milieu réactionnel, une température de 50°C et une agitation à 750rpm. Ces conditions permettent d'avoir 75% d'oléoyl-LPC en 24h. L'oléoyl-LPC a été purifiée sur une cartouche de silice et caractérisée par SM pour confirmer son identité. L'optimisation de la synthèse de linoléoyl-LPC a été faite via un plan d'expériences. C'est une approche qui permet de varier simultanément les paramètres étudiés. Parmi les 17 combinaisons étudiées, une combinaison a permis d'obtenir 93% de linoléoyl-LPC en 6h. Ce résultat a été confirmé en répétant la manipulation 4 fois. Comme l'oleoyl-LPC, la linoleoyl-LPC a été purifiée et caractérisée par SM. Des essais préliminaires ont montré que la synthèse de DHA-LPC est faisable. 30% de DHA-LPC a été obtenu au bout de 72h de réaction. Enfin, il faut noter que la quantité produite de di-acyl-PC était toujours faible par rapport à celle de l'acyl-LPC. Ce dernier résultat est expliqué par une apparition faible du phénomène de la migration du groupement acyle. / The Lysophosphatidylcholines (LPCs), amphiphilic molecules, can act as a carrier for fatty acids of interest. These molecules can be synthesized enzymatically. This work aims to synthesize LPCs containing mono or poly unsaturated fatty acids enzymatically. Sn-3-glycerophosphatidylcholine (GPC), oleic acid (C18: 1, 9ω), linoleic acid (C18: 2, 6ω) and docosahexaenoic acid (C22: 6, 3ω) were used as substrates. These syntheses were performed by esterification without solvent using an immobilized lipase. From kinetic point of view, optimization of conditions for synthesis of oleoyl-LPC was carried out by studying each factor independently. The obtained optimal conditions are : Lipozyme RM-IM (10% w/w), a molar ratio of 20 (oleic acid / GPC), neither addition or elimination of water was applied to the reaction mixture, a temperature at 50° C and stirring at 750rpm. These conditions allow to obtain 75% oleoyl-LPC within 24 hours. The oleoyl-LPC was purified on a silica cartridge and analyzed by MS to confirm its identity. The optimization of linoleoyl-LPC synthesis was made using a design of experiments. This is an approach that can simultaneously vary the parameters studied. Among the 17 combinations studied, one combination allows to obtain 93% of linoleoyl-LPC in 6 hours. This result was confirmed by repeating this manipulation 4 times. Like oleoyl-LPC linoleoyl-LPC was purified and characterized by MS. Preliminary trials have shown that the syntheis of DHA-LPC is feasible. 30% of DHA-LPC was obtained after 72h of reaction. Finally, it should be noted that the produced amount of di-acyl-PC is always low compared to that of the acyl-LPC. This latter is explained by a low appearance of the phenomenon of acyl migration.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study aimed to evaluate the efficiency of supplementation in the diet of silver catfish with blend of buruti and murumuru oils, in natura or enzimatically esterified on biological responses, chemical composition, oxidative stability and sensory characteristics of fillets. Silver catfish females were fed the experimental diets for 8 weeks. The fish growth parameters were evaluated. Subsequent to slaughter, the fillets were frozen for 12 months. After slaughter, were evaluated chemical composition, volatile compounds and sensory analysis of cooked steaks. Was also evaluated influence of power silver catfish on lipid oxidation and protein of frozen fillets within 3, 6 and 12 months of storage. In addition, we assessed levels of vitamin E from the fillets. The fatty acid profile of steaks was assessed after slaughter. We evaluated degradation of fatty acid C22:6n3. Supplementation esterified Amazon oils showed the best results in growth, total length and total biomass. The different treatments did not result in changes in the chemical composition of the fillets. Fatty acids in the diet leads reflect in the composition of fillets for all supplementations. Amazon oils diet had higher MUFA fatty acids. As for sensory analysis, supplementation with Amazon oils no difference in preference for the odor of cooked fillets. A few volatile compounds were detected and the higher amount hexanal was supplemented with soybean oil. Content of conjugated dienes increased three months of storage for all treatments. For amount of peroxides, esterified Amazon oils showed lower values in comparison with other treatments. An increase in TBARS values occurred in 12 months to freeze fillets and interesterified oils showed the lowest values. After 12 months of storage, degradation was approximately 40% C22:6n3 for SO and for BM. There was a reduction in amount of carbonylated proteins after 3-6 months of storage. Sulphydryl proteins no changes over storage for all treatments. There was a decrease in hardness of fillets 12 months of storage for all treatments. In short, supplementation with blends oils (buriti+murumuru) decreases formation of lipid oxidation compounds and volatile compounds leads to lower lipid and protein oxidation. / Este trabalho teve como objetivo avaliar a eficiência da suplementação na dieta de jundiás com mistura de óleos de buruti e murumuru, in natura ou esterificado enzimaticamente, sobre respostas biológicas, composição química, estabilidade oxidativa e características sensoriais de filés. Fêmeas de jundiás foram alimentadas com as dietas experimentais durante 8 semanas. Os parâmetros de crescimento dos peixes foram avaliados. Posteriormente ao abate, os filés foram congelados pelo período de 12 meses. Após o abate, foram avaliados a composição centesimal, os compostos voláteis e análise sensorial por ordenação de preferência dos filés cozidos. Avaliou-se também a influência da alimentação dos jundiás sobre a oxidação lipídica e proteica de filés congelados no período de 3, 6 e 12 meses de congelamento. Além disso, avaliou-se o teor de vitamina E dos filés. O perfil de ácidos graxos dos filés foi avaliado após o abate. Foi avaliada a degradação do ácido graxo C22:6n3. A suplementação com óleo esterificado apresentou os melhores resultados quanto ao crescimento, comprimento total, biomassa total e crescimento específico. Os diferentes tratamentos não acarretaram em alterações na composição centesimal dos filés. Os ácidos graxos presentes na dieta se refletiram na composição dos filés para todas as suplementações. Dietas contendo óleos da Amazônia apresentaram maiores valores de ácidos graxos monoinsaturados. Quanto à análise sensorial, a suplementação com óleos da Amazônia não mostrou diferença na preferência para o odor dos filés cozidos. Poucos compostos voláteis foram detectados e hexanal teve maior quantidade na suplementação com óleo de soja. O conteúdo de dienos conjugados aumentou em três meses de congelamento para todos os tratamentos. Para o valor de peróxidos, suplementação com óleos Amazônia esterificado apresentou menores valores em comparação com os outros tratamentos. Um aumento nos valores de TBARS ocorreu em 12 meses de congelamento dos filés e BME apresentou os menores valores. Após 12 meses de congelamento, houve degradação de aproximadamente 40% de C22:6n3 para suplementações com óleo de soja e buriti+murumuru esterificado. Houve uma redução na quantidade de proteínas carboniladas após 3-6 meses de congelamento. Proteínas sulfidrílicas não alteraram ao longo do armazenamento para todos os tratamentos. Houve uma diminuição da dureza dos filés em 12 meses de congelamento para todos os tratamentos. Em suma, a suplementação com misturas de óleos (buriti+murumuru) diminui a formação de compostos de oxidação lipídica e leva a menores compostos voláteis de oxidação lipídica e proteica.

Submitted by Izabel Franco (izabel-franco@ufscar.br) on 2016-10-26T17:28:34Z No. of bitstreams: 1 TeseJBCS.pdf: 2225419 bytes, checksum: d3ec7a73f461b658739175f8e171c762 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-11-08T18:27:30Z (GMT) No. of bitstreams: 1 TeseJBCS.pdf: 2225419 bytes, checksum: d3ec7a73f461b658739175f8e171c762 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-11-08T18:27:36Z (GMT) No. of bitstreams: 1 TeseJBCS.pdf: 2225419 bytes, checksum: d3ec7a73f461b658739175f8e171c762 (MD5) / Made available in DSpace on 2016-11-08T18:27:44Z (GMT). No. of bitstreams: 1 TeseJBCS.pdf: 2225419 bytes, checksum: d3ec7a73f461b658739175f8e171c762 (MD5) Previous issue date: 2016-08-25 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Cell-associated lipases have been considered biocatalysts economically advantageous because they are produced at low cost, avoiding further recovery or purification steps. Few studies regarding Streptomyces clavuligerus lipase have reported the production of extracellular enzyme, although at first this had been considered a cell-associated enzyme. In this context, the aim of this work was the production of the cell-associated lipase from Streptomyces clavuligerus (whole-cell lipase, Sc-WCL) by submerged fermentation, the biochemical characterization of the enzyme and its use in the synthesis of butyl butyrate, an aroma ester with industrial importance. The culture conditions on rotary shaker and the operational parameters for cultivation in bioreactor were evaluated in order to establish a protocol for Sc- WCL production. The conditions for S. clavuligerus cultivation in rotary shaker that resulted in maximal hydrolytic activity of Sc-WCL (3,000 U.L-1) were: baffled flask, free-glycerol production medium, pH 6.8 and 28 °C. The operational parameters in bench reactor that resulted in maximal volumetric productivity of Sc-WCL (54 U.L-1.h-1) were agitation of 400 rpm and aeration of 1 vvm. The maximal volumetric productivity in bioreactor operated under selected conditions (52.5 U.L-1.h-1) was reached after 24 h, while similar productivity in rotary shaker (54.8 U.L-1.h -1) was achieved only after 48 h fermentation. The catalytic potential of Sc-WCL in hydrolysis reactions was comparable to the commercial lipase preparations. Sc- WCL was more active at 60 °C and pH 10.7, and stable at 30-40 °C after 1 h incubation at pH 10. For butyl butyrate synthesis catalyzed by Sc-WCL, the reaction conditions that resulted in higher ester conversion (85%) were: 5 g of Sc-WCL/ L, molar ratio of fatty acid: alcohol 1:1 in heptane and 8 h reaction. The stability at alkaline pH and organic medium (leastwise in heptane and butanol), associated with the low cost, make Sc-WCL attractive in industrial applications, such as flavors synthesis, detergent formulations, hydrolysis of vegetable oils, among others. / Lipases associadas à célula têm se destacado como biocatalisadores economicamente vantajosos, pois são produzidas a baixo custo, dispensando etapas posteriores de recuperação ou purificação. Poucos estudos sobre lipase de Streptomyces clavuligerus relatam a produção da enzima extracelular, embora esta tenha sido, a princípio, considerada uma enzima associada à célula. Neste contexto, o objetivo deste trabalho foi a produção de lipase associada à célula de Streptomyces clavuligerus (lipase “whole-cell”, Sc-WCL) por fermentação submersa, a caracterização bioquímica da enzima e sua aplicação na síntese de butirato de butila, um éster de aroma com importância industrial. As condições de cultivo em shaker e os parâmetros operacionais para cultivo em biorreator foram avaliados com o intuito de estabelecer um protocolo para a produção de Sc-WCL. As condições de cultivo de S. clavuligerus em shaker que resultaram em maior atividade hidrolítica de Sc-WCL (3.000 U.L- 1) foram: frasco aletado, ausência de glicerol no meio de produção, pH 6,8 e 28 ºC. Os parâmetros operacionais em reator de bancada que resultaram em maior produtividade volumétrica de Sc-WCL (54 U.L-1.h-1) foram: agitação de 400 rpm e aeração de 1 vvm. A máxima produtividade volumétrica em biorreator operado nas condições selecionadas foi alcançada após 24 h de cultivo (52,5 U.L-1.h-1), enquanto que produtividade similar em shaker foi obtida somente após 48 h de cultivo (54,8 U.L-1.h-1). O potencial catalítico de Sc-WCL em reações de hidrólise foi comparável ao de preparações comerciais de lipase. Sc-WCL foi mais ativa a 60 ºC e pH 10,7, e mais estável na faixa de 30 a 40 ºC após 1 h de incubação a pH 10. Na síntese de butirato de butila catalisada pela Sc-WCL, as condições reacionais que resultaram em maior conversão (85%) foram: 5 g de Sc-WCL/ L, razão molar ácido graxo/álcool 1:1 em heptano e 8 h de reação. A estabilidade em pH alcalino e em meio orgânico (pelo menos em heptano e butanol), associada ao baixo custo, tornam a Sc-WCL atrativa em aplicações de interesse industrial, tais como, síntese de aromas, formulações de detergentes, hidrólise de óleos vegetais, dentre outras.