A irradiação de alimentos frescos pós-colheita tem como interesses principais: inibir a brotação, aumentar a vida útil de prateleira, reduzir ou retardar os danos causados por insetos e doenças, atuando como fungicidas ou inseticidas. Atualmente, há uma grande expansão no interesse por alimentos minimamente processados e a manipulação para preparação destes produtos em estado fresco, incluindo muitos processos (descascamento, limpeza, entre outros) que podem alterar as características essenciais para proteger a saúde pública, ou seja, para que o produto não cause danos à saúde do consumidor. Em razão deste fato, este trabalho teve como objetivo avaliar os efeitos da radiação gama em ervilhas em grão (Pisum sativum L.) in natura, a fim de inibir a brotação e aumentar a vida de prateleira. As ervilhas foram divididas em quatro grupos (n=4 amostras/ grupo), de acordo com a intensidade da radiação: 0 (controle), 150, 300 e 450 Gy. Utilizou-se um irradiador de pesquisa 60Co e após irradiação as ervilhas foram armazenadas a uma temperatura 8 °C e seu aspecto visual, de amadurecimento (sólidos solúveis totais, acidez total titulável e razão entre eles), perda de massa fresca, coloração, textura, pH, umidade e cinzas foram avaliados durante os períodos de 1, 7, 14 e 21 dias após a irradiação. A avaliação do aspecto visual mostrou que a irradiação não alterou significativamente a vida de prateleira dos grãos, e que a dose de 300 Gy aumentou significativamente a germinação das ervilhas. As análises de: aspecto visual, perda de massa fresca, coloração e pH, sofreram interferência devido o processo natural de maturação dos grãos e não pela radiação ionizante. Observou-se que, as doses de radiação gama não influenciaram no teor de cinzas, umidade e textura durante o armazenamento e que a dose de 450 Gy foi insuficiente para inibir a brotação das ervilhas. Assim, com base nos resultados encontrados neste trabalho, conclui-se que doses de radiação gama até 450 Gy não foram suficientes para melhorar a vida útil de prateleira e/ou inibir o brotamento de ervilhas. Portanto, recomenda-se que futuros trabalhos sejam realizados com doses de radiação gama maiores que 450 Gy. / The irradiation of fresh post-harvest foods has as main interests: inhibit sprouting, increase shelf life, reduce or delay damage caused by insects and diseases, acting as fungicides or insecticides. Currently, there is a greater interest in minimally processed foods and handling for the preparation of these products in a fresh state, including many processes (peeling, cleaning, among others) that can alter the characteristics essential to protect public health, product does not cause harm to the consumer\'s health. The objective of this work was to use gamma radiation, where the product was irradiated with final packaging to avoid manipulation of the product to the consumer and to evaluate the effects of the same on peas in grains (Pisum sativum L.), in to sprout and increase shelf life. The peas were submitted to 4 treatments: 0 (control), 150, 300 and 450 Gy, in a 60Co research irradiator, after irradiation stored at 8 °C, being evaluated at 1, 7, 14 and 21 days after irradiation, for the following analyzes: assessments of visual appearance, maturation (total soluble solids, titratable total acidity and ratio), fresh weight loss, coloring, texture, pH, water and ash. By visual evaluation it was observed that the irradiation did not significantly change the shelf life of the grains, and that the dose of 300 Gy increased the germination of the peas. The visual appearance, coloring and pH had interference due to the natural process of grain maturation. The fresh weight loss and increase of soluble solids were proportional to the increase of gamma radiation doses, but the doses of gamma radiation did not influence the content of ash, water and texture during storage and that dose of 450 Gy was not sufficient to inhibit the sprouting of the peas. It is possible to conclude that, with this work, a recommendation that, for the later works, in which one wishes to define the shelf life or to inhibit pea budding, initiate the irradiation of its samples with values above 450 Gy.

Conscients de la raréfaction progressive et l’augmentation continue du coût du pétrole et aussi des volumes importants des tensioactifs produits et éliminés chaque année, l’industrie chimique s’intéresse de plus en plus aux ressources issues de la biomasse. Cependant, dans le marché européen des tensioactifs, la part des produits d’origine végétale par rapport aux dérivés pétrochimiques est estimée à seulement 20%. Compte-tenu de ces enjeux, de nouvelles stratégies de synthèse pour produire des tensioactifs ayant des structures originales issus d’agro-ressources sont nécessaires. Dans le cadre d’une collaboration de recherche, l’ITERG (Pessac) et l’ICBMS (équipe COB-INSA) de Lyon se sont associées pour développer la synthèse de nouveaux glycolipides amphiphiles obtenus par fonctionnalisation d’huiles végétales époxydées. Les enjeux synthétiques ont concerné la compétition entre les deux fonctions réactives des huiles époxydées (ester et époxyde) et la multifonctionnalité des sucres et autres polyols utilisés comme substrats nucléophiles. Plusieurs séries de composés originaux ont été préparées, et leurs propriétés physico-chimiques ont été évaluées en regard des applications industrielles visées. Parmi les produits synthétisés, quelques uns ont également été évalués en tant que monomères biosourcés. / Aware of the irreversible scarcity and graving increase in oil prices, as well as large amounts of surfactants produced and disposed of each year, the chemical industry more and more focuses on resources from biomass. However in Europe, plant derived from plants only represent 20%. New strategies to produce surfactants with novel structures derived produced of the surfactants from agricultural resources are thus synthetic challenges.. As part of a research collaboration, ITERG (Pessac) and ICBMS (COB-INSA in Lyon) have joined forces to develop the synthesis of new amphiphilic glycolipids obtained by functionalization of epoxidized vegetable oils. Synthetic issues concerned the competition between the two reactive groups of epoxidized oils (ester and oxirane) and multifunctionality of sugars and other polyols used as nucleophilic substrates. Several series of novel compounds were prepared and their physicochemical properties were assessed for targeted industrial applications. Among the synthesized products, some were also evaluated as biobased monomers.

The general aim of this thesis was to evaluate a newly designed and constructed miniaturized rotating disk apparatus for in vitro dissolution rate measurements of different drug substances from all of the classes in the Biopharmaceutical Classification System (BCS). The new equipment is based on a low volume flow-through cell of Plexiglas, a gold plated magnetic bar and a special designed press. The disk of drug substance (approx. 5 mg) is placed eccentrically in the bar. Rotation speeds were set with a graded magnetic stirrer. An external HPLC pump delivered a continuous flow of aqueous medium to the flow-through cell during dissolution testing. A reversed phase high-performance liquid chromatography system using diode array detection (RP-HPLC-DAD) was coupled online to the new equipment. The injections from the miniaturized rotating disk outlet into the quantifying HPLC system were controlled by a six-position switching valve. The injection volumes from the valve and the autosampler, used for the external standards, were statistically evaluated to match each other volumetrically. No analyses were longer than three minutes, using isocratic mode. A traditional USP rotating disk apparatus was used as a reference system and the two instruments were shown to be statistically dissimilar in the numerical dissolution rate values probably due to different hydrodynamics, but had approximately the same precision/repeatability. When correlating the logarithmic values of the in vitro dissolution rate (G) with the apparent solubility (S), using shake-flask methodology in the solubility studies, the two apparatuses gave the same correlation patterns. Further correlation studies were done where the media components were altered by the use of different buffer species or additives into the buffers, such as inorganic salts. Chemometric tools, e.g. orthogonal partial least squares (OPLS), were used to better evaluate the most influential factors for G and S in different media. The most significant factor for a model basic drug substance (terfenadine) was pH, followed by the ionic strength (I) and added sodium chloride in one of the media. However, the surfactants in the Fasted State Simulated Intestinal Fluid (FaSSIF-V2) were found to be insignificant for G and S in this study (using a 95% confidence interval). The new miniaturized apparatus is a promising prototype for in vitro dissolution rate measurements both for early screening purposes and in dissolution testing during drug development, but needs further instrumental improvements.

In this thesis technical nonionic surfactants are studied using multivariate techniques. The surfactants studied were alkyl ethoxylates (AEOs) and alkyl polyglucosides (APGs). The aquatic toxicity of the surfactants towards two organisms, a shrimp and a rotifer, was examined. The specified effect was lethality, LC50, as indicated by immobilisation. In a comparative study, the LC50 values obtained were used to develop two different types of model. In the log P model the toxicity was correlated to log P alone, while in the multivariate model several physicochemical variables, including log P, were correlated to the toxicity. The multivariate model gave smaller prediction errors than the log P model. Further, the change in reactivity when a surfactant mixture was added to dissolving pulp under alkaline conditions was studied, using the amount of residual cellulose as a measure of the reactivity. Ten AEO/APG mixtures were tested, and the mixture with greatest potential was studied in more detail. An optimum in the amount of added surfactant was found that seems to coincide, according to surface tension measurements, with the CMC.

The aim of the work was to design, manufacture, and characterize targeted multi-component dry powder aerosols of (non-destructive) mucolytic agent (mannitol), antimicrobial drug (tobramycin or azithromycin), and lung surfactant mimic phospholipids (DPPC:DPPG=4:1 in molar ratio). The targeted dry powder for inhalation formulation for deep lung delivery with a built-in rationale of specifically interfering several disease factors of chronic infection diseases in deep lungs such as cystic fibrosis, pneumonia, chronic bronchitis, and etc. The dry powder aerosols consisting of selected chemical agents in one single formulation was generated by using spray drying from organic solution. The physicochemical properties of multi-component dry powder inhaler (DPI) formulation were characterized by a number of techniques. In addition, the in vitro aerosol dispersion performance, storage stability test, and in vitro drug release of selected spray-dried (SD) multi-component systems were conducted. The physicochemical study revealed that multi-component aerosol particles possessed essential particle properties suitable for deep lung delivery. In general, the multi-component particles (typically 0.5 to 2 µm) indicated that the designed SD aerosol particles could potentially penetrate deep lung regions (such as respiratory bronchiolar and alveolar regions) by sedimentation and diffusion, respectively. The essential particle properties including narrow size distribution, spherical particle and smooth surface morphologies, and low water content (or water vapor sorption) could potentially minimize interparticulate interactions. The study of in vitro aerosol dispersion performance showed that majority of SD multi-component aerosols exhibited low values (less than 5µm) of MMAD, high values (approximately above 30% up to 60.4%) of FPF, and high values (approximately above 90%) of ED, respectively. The storage stability study showed that azithromycin–incorporated multi-component aerosol particles stored at 11 and 40% RH with no partial crystallization were still suitable for deep lung delivery. Compared to SD pure azithromycin particles, the azithromycin-incorporated multi-component particles exhibited an enhanced initial release. The targeted microparticulate and nanoparticulate multi-component dry powder aerosol formulations with essential particle properties for deep lung pulmonary delivery were successfully produced by using spray drying from organic solution. The promising experimental data suggest the multi-component formulations could be further investigated in in vivo studies for the purpose of commercialization.

The broad objective of the study was to determine feeding behaviour and gut health of pigs fed different fibres at varying inclusion levels. Maize cob, maize stover, sunflower hulls, veld grass, sawdust, lucerne and dried citrus pulp were used in growing and finishing pig diets to provide a wide range of physicochemical properties. Time spent eating, drinking, lying down, sitting/standing and other activities was observed using video cameras. Blood samples were collected at the end of the trial for both growing and finishing pigs for analysis of glycated haemoglobin, albumin, globulin, total protein, creatine kinase, urea and uric acid. Intestinal segments were collected at the end of trial for growing pigs to determine mucosal architecture of the intestines. Digestible energy (DE), bulk density (BD), acid detergent fibre (ADF) and water holding capacity (WHC) were the most important variables predicting time spent on different behavioural activities in growing pigs (P < 0.001). Water holding capacity, neutral detergent fibre (NDF) and ADF were the most important variables involved in predicting time spent on different behavioural activities in finishing pigs (P < 0.001). Physicochemical properties influenced time spent on different behavioural activities and they provided relationships with time spent on different behavioural activities in both growing and finishing pigs. Glycated haemoglobin, albumin, globulin, total protein and uric acid were factors that influenced time spent eating in growing pigs (P < 0.05). In finishing pigs, only serum total protein was selected as the best predictor variable influencing time spent eating (P < 0.05). The blood metabolites were correlated with time spent eating and drinking. They provided threshold values with time spent eating and drinking by pig. Hence, they can also be used as potential biomarkers that modulate neuronal pathways which reduce time spent eating and drinking. In this study, bulk density (BD) and NDF were the best predictor variables influencing villi height (VH) and apparent villi surface area (AVSA) in pigs (P < 0.05). Grouped pigs fed fibrous diet spent more time eating, lying down, standing, walking and fighting (P < 0.05). Skin lesions appeared the most on neck and shoulder region followed by chest, stomach and hind leg region, and finally head region (P < 0.05). Fibrous diet did not reduce aggressive behaviours, rather aggressive behaviours emanated out of frustration when queuing at the feeder. It was concluded that physicochemical properties of fibrous diets and nutritionally-related blood metabolites influence feeding behaviour. Mucosal architecture was also influenced by physicochemical properties of the fibrous diets. / Ph.D. University of KwaZulu-Natal, Pietermaritzburg 2013.

Submitted by Deyse Queiroz (deysequeirozz@hotmail.com) on 2018-06-13T14:15:26Z No. of bitstreams: 1 JOSÉ DIVÂNIO PEREIRA DE OLIVEIRA - DISSERTAÇÃO PPGEA 2011..pdf: 15315292 bytes, checksum: e9b24518134206b0e9339d2a725d179a (MD5) / Made available in DSpace on 2018-06-13T14:15:26Z (GMT). No. of bitstreams: 1 JOSÉ DIVÂNIO PEREIRA DE OLIVEIRA - DISSERTAÇÃO PPGEA 2011..pdf: 15315292 bytes, checksum: e9b24518134206b0e9339d2a725d179a (MD5) Previous issue date: 2011-09 / O consumo de carne congelada é cada vez maior, sobretudo nas grandes cidades, tornando-se imprescindíveis estudos mais detalhados dos processos de congelamento e sua influência no produto destinado ao consumidor. O principal objetivo deste trabalho foi determinar a cinética de congelamento e avaliar as alterações físico-químicas do lombo da carne caprina e ovina, submetido a quatro temperaturas de congelamento: -22,5 e -45 °C (freezer comercial), -170 °C (vapor de nitrogénio líquido) e -196 °C (imersão no nitrogénio líquido). Foram realizadas as análises físico-químicas de teor de água, pH, acidez, cinzas e proteínas, de acordo com o Instituto Adolfo Lutz enquanto para os atributos textura, ruptura da fibra e resistência de corte, as amostras foram realizadas em texturômetro da marca TA.XT plus. O lombo da carne ovina a -22,5 e -45 °C congelou mais rapidamente que a do lombo da carne caprina, cujos tempos foram iguais a 10200 e 10800 segundos; 6240 e 6480 segundos, respectivamente; Já nas temperaturas de -170 e -196 o lombo da carne apresentou ligeira diferença no tempo de congelamento com a carne caprina congelando de maneira mais rápida em aproximadamente 1920 segundos com relação à carne ovina, que foi de 1940 segundos e 120 e 125 segundos, respectivamente. As difusividades efetivas médias (am) do lombo da carne caprina e ovina apresentaram tendência de aumento com a diminuição da temperatura de congelamento. Os maiores valores de teor de água, pH, acidez e proteínas do lombo da carne caprina foram iguais a 76,8447% (-45°C); 5,756 (-45 °C), 5,733 (-90 °C) e 5,770 (-196 °C); 0,052% (-90 °C); e 23,490% (-170 °C), respectivamente; por outro lado, teores de água, pH, acidez e proteínas, foram iguais a 71,6773% (-90 °C), 5,530 (-22,5 °C), 0,032% (-170 °C) e 18,390 (-196 °C), respectivamente. No lombo da carne caprina os maiores e menores valores para o teor de água foram iguais a 77,6433 (-22,5 °C) e 70, 5390 (-90 °C); pH iguais a 5,753 (-196 °C) e 5,610 (-22,5 °); acidez iguais a 0,047, 0,045, 0,044 % (-22,5, -45 e -170°C)e 0,040 (- 196 °C); proteínas iguais a 20,643 e 20,953 % (-45 e -90 °C) e 18,923 e 18,720 (-22,5 e - 170 °C), mas as cinzas não apresentaram alterações significativas. A redução da temperatura de congelamento proporcionou tendência de diminuição da força de corte e ruptura das fibras do lombo da carne caprina e ovina. / Frozen meat consumption has increased especially in large cities, calling for more exhaustive rescarch concerning the freezing process and its influence on consumer products. The main objective of present study is to determine the freezing kinetics and evaluate the physical and chemical changes that occur in the lamb loin and goat meat. Both the lamb loin and goat meat were exposed to four freezing temperatures, -22.5 and - 45 C (freezer trade), -170 C (liquid nitrogen vapor) and -196 ° C (immersion in liquid nitrogen). A physical-chemical water content analysis, including pH, acidity, ash and protein content was conducted in conformity with the Instituto Adolfo Lutz's, norms whereas for texture attributes of fiber rupture and resistance, samples cutting were done in brand texturometer TA . XT plus. The lamb loin -22.5 and -45 ° C froze faster than the goat meat , whose times were equal to 10200 and 10800 / 2, 6240 and 6480 / 2, respectively. At temperatures of -170 and -196 °C, the loin meat exhibited a slight difference in freezing weather, with freezing goat meat quickly, in about 1920 / 2, in relation to lamb, which was 1940 / 2 and 120 125 seconds, respectively. The mean effective diffusivities (am) of loin meat goats and sheep tended to increase with decreasing freezing temperature. The highest values of water content, pH, acidity and protein loin of goat meat were equal to 76.8447% (-45 ° C) 5.756 (-45 ° C), 5.733 (-90 C) and 5.770 (-196 ° C), 0.052% (-90 C) and 23.490% (-170 ° C), respectively. While the lower water content, pH, acidity and protein were equal to 71.6773% (-90 C), 5.530 (-22.5 C), 0.032% (-170 ° C) and 18.390 (-196 degrees C), respectively. On the back of the goat meat, the highest and lowest values for water content were equal to 77.6433 (-22.5 C) and 70, 5390 (-90 C), pH equal to 5.753 (-196 ° C) and 5.610 (-22.5 °); acidity equal to 0.047, 0.045, 0.044% (-22.5, -45 and - 170 ° C) and 0.040 (-196 ° C), protein equal to 20.643 and 20.953% (-45 and -90 C) and 18.923 and 18.720 (-22.5 and - 170 ° C), while the ash did not change significantly. The reduction of the freezing temperature gave a trend of cutting force and rupture of the fibers of the loin of lamb and goat meat.

Neste trabalho, foi avaliado o comportamento de alguns flavonóides e do adjuvante tecnológico celulose microcristalina (CMCr) no estado sólido, em relação ao tipo de interação e sua intensidade, quando existente, utilizando misturas físicas equiponderais e na proporção ponderal 1:2, respectivamente, através da calorimetria exploratória diferencial (DSC), análise termogravimétrica e espectroscopia no infravermelho (FTIR). A relação estrutura-propriedade de interação dos flavonóides estudados foi determinada nas possíveis interações sólido-sólido com a celulose microcristalina, correlacionando os padrões de hidroxilação nos anéis A, B e C dos flavonóides com: 1) a intensidade de variação (IV - %) entre as entalpias observada e esperada, 2) a energia do sistema conjugado do anel aromático relativa à banda I, 3) o pKa dos flavonóides e 4) os cálculos do campo de força da mecânica molecular 2 (MM2) para a energia de interação do sistema flavonóide-CMCr. Os flavonóides avaliados foram canferol, fisetina, luteolina, miricetina, morina e quercetina. Os resultados da DSC evidenciaram interações de natureza física do tipo ligações de hidrogênio, com variação de entalpia para todas as misturas dos flavonóides com a CMCr, mas que não puderam ser confirmadas por FTIR, devido à sobreposição de bandas com os flavonóides. O potencial de interação (PI) mostrou-se proporcional ao número de hidroxilas e apresentou a ordem de importância de posição e presença das hidroxilas nos anéis: B>C>A. A miricetina apresentou a menor energia do sistema conjugado do anel aromático relativa à banda I, relacionado ao maior PI entre os flavonóides estudados. Na avaliação do pKa dos flavonóides em relação à IV, não foi possível estabelecer uma correlação entre estas variáveis, não apresentando uma tendência de aumento ou diminuição do valor de pKa em relação ao aumento do PI. Os cálculos de MM2 para a energia de interação do sistema flavonóide-CMCr, considerando as dez interações propostas, demonstraram que a CMCr determinou a melhor orientação do flavonóide para obter a conformação de menor energia, não sendo possível estabelecer um padrão de conformação mais estável de interação para estes flavonóides. / In this work was evaluated the behavior of some flavonoids and of technological adjuvant microcrystalline cellulose (MCC) in solid state, in relation to the type of interaction and its intensity, when existing, using equiponderal physical mixtures and in 1:2 ratio, respectively, through of differential scanning calorimetry (DSC), thermogravimetric analysis and infrared spectroscopy (FTIR). Structure-property of interaction relation was determined to studied flavonoids in possible solid-solid interactions with MCC, correlating standard hydroxylation in A, B and C rings of flavonoids with: 1) intensity variation (IV-%) between observed and hoped enthalpies, 2) energy of the conjugated system of aromatic ring relative to band I, 3) pKa value of flavonoids and 4) molecular mechanics 2 (MM2) force field calculations for interaction energy of system flavonoid-MCC. Evaluated flavonoids were fisetin, kaempferol, luteolin, morin, myricetin and quercetin. DSC results evidenced physical interactions hydrogen bonds type, with enthalpy variation for all mixtures of flavonoids with MCC, but could not be confirmed by FTIR, due to overlapping with flavonoids bands. Interaction potential (IP) showed to be proportional to the number of hydroxyls and presented in order of importance of position and presence of hydroxyls in rings: B>C>A. Myricetin presented the lowest energy of the conjugated system of aromatic ring relative to band I, related with the highest IP among studied flavonoids. In the evaluation pKa value of flavonoids in relation to IV, it was not possible to establish a correlation between these variables, not presenting a trend of increase or decrease of pKa value in relation to the increase of IP. MM2 force field calculations for interaction energy of system flavonoid-MCC, considering ten proposed interactions, demonstrated that MCC determined the best orientation of flavonoids to get the lowest energy conformation, not being possible to establish the steadiest standard conformation of interaction for these flavonoids.

[pt] Para substituir parcialmente a demanda em óleo diesel de origem fóssil, reduzir os elevados custos de importação e respeitar as normas ambientais, políticas sustentáveis já levaram a substituir parcialmente óleo diesel por biodiesel. Entretanto, outras tecnologias, como as misturas diesel-biodiesel-etanol, estão sendo investigadas. O principal desafio dessas misturas consiste em melhorar a miscibilidade e a estabilidade do álcool no óleo diesel. No presente trabalho, formulou-se um aditivo original, a partir de compostos renováveis, que permitiu melhorar a faixa de concentração de etanol anidro dentro de óleo diesel com 15 por cento em volume de biodiesel e de temperatura onde observa-se misturas estáveis. Diversas propriedades físico-químicas das misturas aditivadas foram medidas em uma larga faixa de concentração de etanol para avaliar os aspetos de consumo, qualidade da combustão, comportamento a baixa temperatura, interação entre fluido e superfície, e segurança. Os resultados obtidos mostraram que misturas com, pelo menos, 1,0 por cento em volume de aditivo e até 20 por cento em volume de etanol anidro são estáveis para temperaturas superiores a 10 graus Celsius e respeitam a maioria das especificações brasileiras atuais para óleo diesel. Ensaios experimentais em um motor de ignição por compressão MWM 4.10 TCA (Euro III) foram realizados com estas misturas. Os resultados obtidos mostraram que a substituição do óleo diesel altera as características da combustão: o crescente teor de etanol leva ao aumento do atraso de ignição, à liberação de calor mais rápida e à diminuição da pressão máxima. Mesmo nessas condições não otimizadas de injeção e de combustão, os resultados mostraram uma melhor conversão da energia química no etanol para produzir potência efetiva, comparado com os valores encontrados nos motores flex fuel de ciclo Otto, além de um pequeno aumento no rendimento térmico do motor. / [en] In order to partially replace the demand of fossil diesel fuels, to reduce high import costs and to comply with environmental standards, sustainable policies have led to partially replace diesel fuel by biodiesel. However, other technologies, such as diesel-biodiesel-ethanol mixtures, are being investigated. The major challenge of these mixtures is to improve the miscibility and the stability of alcohol in diesel fuel. In this study, an original additive, from renewable compounds, improved the miscibility of anhydrous ethanol in diesel fuel with 15 per cent by volume of biodiesel and temperature in which stable mixtures were observed. Several physicochemical properties of the additivated mixtures were measured in a large range of ethanol concentration to evaluate aspects of consumption, combustion quality, behavior at low temperature, interaction between the fluid and the surface, and safety. The results showed that blends with, at least 1.0 per cent, by volume of additive and 20 per cent by volume of anhydrous ethanol are stable at temperatures above 10 degrees Celsius and respected most of the current Brazilian specifications for diesel fuel. Experimental tests on a compression ignition engine MWM 4.10 TCA (Euro III) were performed with these mixtures. The results showed that the diesel fuel substitution alters the characteristics of combustion: the increased ethanol content implied an increase of the ignition delay, a faster heat release and a decrease of maximum pressure. Despite these non-optimized conditions for injection and combustion, results showed a better conversion of ethanol chemical energy into brake power, in comparison to the values found in flex fuel spark ignition engine, in addition to a small increase in the indicated efficiency of the engine.

Os métodos computacionais da química quântica foram empregados para estudar as estruturas moleculares e as energias de interação de cátions e ânions que são componentes de alguns líquidos iônicos funcionalizados, derivados do imidazólio. O estudo teve como objetivo comparar e relacionar os efeitos da presença de funcionalização nos substituintes das posições 1 e 3 do cátion imidazólio, nas propriedades desses líquidos iônicos. Essa funcionalização pode ocorrer pela presença de insaturações, grupos aromáticos, éteres, álcoois, tióis, aminas, nitrilas entre outros grupos nas cadeias dos substituintes. Nesta tese são reportados os estudos dos complexos formados por ânions tetrafluorborato e cátions imidazólio substituídos por grupos metila, etila, propila, butila, isobutila, vinila, propargila, alila, crotila e metalila, observando assim o efeito da presença de substituintes contendo cadeias insaturadas em comparação com os de cadeias saturadas nas estruturas, distribuições de carga, energias de interação e propriedades físico-químicas desses sistemas. Nesses sistemas foram observados intensos efeitos de polarização e transferência de carga ânion-cátion. Foram encontradas diversas relações entre volumes iônicos, energias de interação dos íons e as propriedades de transporte dos respectivos líquidos iônicos. / The methods of computational quantum chemistry have been used to study the molecular structures and the interaction energies of cations and anions which are components of some functionalized ionic liquids derived from imidazolium. The objective of this study is comparing and relating the effects of the presence of functionalization of the side chains of the imidazolium with the properties of these ionic liquids. This functionalization can occur by the presence of unsaturated side chains, aromatic groups, ether, alcohols, thiols, amines, nitriles among other groups in the side chains. In this thesis are reported the studies of the complexes formed of tetrafluorborate anions and imidazolium cations with side chains methyl, ethyl, propyl, butyl, isobutyl, vinyl, propargyl, allyl, crotyl and methallyl, thus observing the effects of the presence of unsaturated side chains compared to saturated ones on the structures, charge distributions, interaction energies and physicochemical properties of these systems. It was observed in these systems strong effects of polarization and anion-cation charge transfer. It was found several relations between ionic volumes, interation energies of the ions and the transport properties of the respective ionic liquids.