Water movement in the body is determined by the osmotic forces acting on the cell membrane. Ingestion of a highly-hypertonic glycerol solution resulting in high extracellular osmolality could drive water out of the intracellular space into the vascular space resulting in reduced muscle hydration and increased blood volume. The aim of this thesis was to study the effects of altered body water distribution during exercise. In chapter 3, ingestion of a 400 ml glycerol solution (1 g·kg-1 body mass) increased serum osmolality (309 mosmol·kg-1) which was associated with a 4.0% increase in blood volume due to a 7.2% increase in plasma volume, attributed to a shift of water from the intracellular space, resulting presumably in tissue dehydration. Glycerol ingestion was then used as a means of altering body water distribution in the other studies described in this thesis. Altered body water distribution had no acute effect on force production during quadriceps muscle isometric exercise (chapter 4), or handgrip strength (chapter 5). Regarding chronic effects (chapter 5), two groups of participants exercised handgrip and initiated recovery after ingestion of either a glycerol solution or placebo over a period of 8 weeks. Maximum handgrip strength increased in both groups and there was no statistically significant difference between the two groups. In chapters 6 and 7, the subjects performed a cycling exercise protocol to fatigue. In the glycerol trial, time to fatigue decreased compared with the iso-osmotic trial during an incremental VO2max test (chapter 6) and during cycling against a constant load at 100% VO2max intensity (chapter 7). In the glycerol trial, there was an accelerated increase in blood lactate and an accelerated increase in serum potassium (chapter 7), indicating altered muscle metabolism which may have contributed to the early development of fatigue.

Rampant increases in oil prices and detrimental effects of fossil fuels on the environment have been the main impetus for the development of environmentally friendly and sustainable energy sources. Amongst the many possibilities, microalgae have been proposed as a new alternative energy source to fossil fuels, as their growth is both sustainable and ecologically safe. By definition, microalgae are unicellular photosynthetic microorganisms containing chlorophyll a. These organisms are capable of producing large quantities of oils, surpassing that of traditional oil-seed crops, which can be transformed, through chemical processes, into biofuels such as biodiesel or bio-gasoline. Thus, recent research has gone into discovering high lipid producing algal strains, optimising growth media for increased lipid production and developing metabolic engineering to make microalgae a source of biofuel that is competitive to more traditional sources of biofuel and even to fossil fuel. In this context, the research reported here focused on using a mixotrophic growth mode as a way to increase lipid production for certain strains of microalgae. In addition, nitrogen starvation combined with mixotrophy was studied to analyse its effects on lipid production. Mixotrophy is the parallel usage of two trophic modes, in our case photoautotrophy and heterotrophy. Consequently, 12 algal strains were screened for mixotrophic growth, using glycerol as a carbon source. Glycerol is a waste product of the current biodiesel industry; it is a cheap and abundant carbon source present in many metabolic pathways. From this initial screening, several strains were chosen for subsequent experiments involving nitrogen starvation. Nitrogen starvation has been shown to induce lipid accumulation. The results obtained show that a mixotrophic growth mode, using glycerol as a carbon source, enhances lipid production for certain strains. Moreover, lipid enhancement was shown for nitrogen starvation combined with mixotrophic growth mode. This was dependant on time spent under nitrogen starvation and on initial concentrations of the nitrogen source. / L’augmentation effrénée des prix du pétrole et les effets néfastes des carburants fossiles sur l’environnement sont les raisons principales pour la recherche et le développement de nouvelles sources d’énergie durables et écologiques. Parmi de grands nombres de possibilités, les micro-algues sont proposées comme une source alternative d’énergie aux carburants fossiles, étant donné que leur croissance est durable et écologique. Les micro-algues sont des organismes unicellulaires et photosynthétiques détenant comme pigment essentiel la chlorophylle a. Ces organismes sont capables de produire de grandes quantités d’huile, parfois excédant celles des cultures agricoles traditionnellement utilisées pour les biocarburants. Ces huiles peuvent être transformées en biocarburants, tel que le biodiésel et le bio-essence, par certains procédés chimiques. La recherche actuelle est basée sur la découverte de souches d’algues capables de produire un haut rendement de lipides, l’optimisation de milieux de croissance pour accroitre la production lipidique et la manipulation génomique afin de créer des souches de micro-algues dont les rendements peuvent rivaliser avec l’agriculture tradionnelle et même les carburants fossiles. Dans ce contexte, notre recherche se concentre sur l’utilisation d’un mode de croissance mixotrophe afin d’induire une augmentation dans la production lipidique de certaines souches de micro-algues. De plus, des études sur la carence en azote combinée à la croissance mixotrophe ont été entreprises pour évaluer l’effet de ces paramètres sur la production lipidique. La mixotrophie est un mode de croissance qui utilise en parallèle deux modes trophiques différents, tel que l’hétérotrophie et l’autotrophie. De ce fait, 12 souches d’algues ont été examinées pour leur capacité à croitre dans un milieu mixotrophe. Le glycérol est un produit secondaire de l’industrie du biodiésel actuelle. Cette substance est à bas prix, abondante et peut être utilisé comme substrat dans plusieurs voies métaboliques. Du criblage initial, plusieurs souches ont été choisies pour des expériences subséquentes impliquant la carence en azote. La carence en azote à été démontrer comme un déclencheur de l’accumulation de lipide chez les micro-algues dans des recherches antérieures. Les résultats obtenus démontrent que la croissance mixotrophe permet d’augmenter la production de lipide chez certaines souches. De plus, la carence en azote combinée à la croissance mixotrophe a permis d’augmenter la production lipidique. Cependant, celle-ci dépendait du temps passer en carence et des concentrations initiales de source d’azote.

Master of Science / Department of Animal Sciences and Industry / Joel M. DeRouchey / A total of 6,858 pigs were used in 6 experiments to evaluate the effects of crude glycerol, dried distillers grains with solubles (DDGS), Ractopamine HCl (RAC), NutriDense corn, and feeder adjustment on growing and finishing pig performance. In Exp. 1, pigs were fed diets with 0, 2.5, or 5% crude glycerol with 0 or 20% DDGS. Adding DDGS increased ADFI and decreased G:F with no differences for pigs fed glycerol. Neither glycerol nor DDGS affected any carcass characteristics. Pigs fed DDGS had increased iodine value in carcass fat. In Exp. 2, pigs were fed diets with 0 or 5% glycerol with 0 or 7.5 ppm RAC. Feeding RAC increased ADG and G:F and decreased ADFI while glycerol tended to improve G:F. Ractopamine HCl improved carcass traits. Loin chop drip loss worsened when glycerol and RAC were added separately, however, drip loss decreased when the combination of both were fed. Glycerol did not affect loin characteristics. Neither RAC nor glycerol influenced iodine value of carcass fat. Exp. 3 and 4 were conducted to determine the 4th limiting amino acid in diets containing NutriDense corn. In Exp. 3, pigs fed the positive control and the diet with added Ile, Trp, and Val (in combination) had greater ADG. Pigs fed added Ile or Trp had greater ADG than pigs fed the negative control indicates these amino acids were co-4th limiting for 37 to 59 kg pigs. In Exp. 4, pigs fed the positive control, added Trp, or the combination of added Ile, Trp and Val had greater ADG then pigs fed the negative control or pigs fed either Ile or Val indicates these amino acids were co-4th limiting for 77 to 100 kg pigs. Exp. 5 and 6 evaluated feeder adjustment on growth performance of finishing pigs. In Exp. 5, reducing feeder opening decreased ADFI. In Exp. 6, pigs were fed at three feeder opening and either a corn-soybean meal or byproduct-based diet. Diet type did not affect pig performance. Widening feeder openings increased ADG and ADFI. Feeder setting tended to influence G:F with the best G:F at the intermediate opening.

Orientador: Pedro Magalhães Sobrinho / Resumo: O Brasil tem uma grande capacidade para produzir biocombustíveis devido a sua extensa área territorial com grande produtividade de matéria-prima para este setor. O Governo Federal vem investindo bastante neste setor, pois além de ser estratégico economicamente, também tem grandes vantagens na luta contra o aquecimento global. Desde 2005, ano em que se iniciou a comercialização do biodiesel em caráter voluntário, até 2017 a produção cresceu de 736 m3/ano para 4291294 m3/ano. Isto se deu devido a política de aumento obrigatório da porcentagem de biodiesel misturado ao diesel de petróleo de forma gradativa até o nível de 10% (B10) em 2018. Neste trabalho propõe-se um sistema de cogeração utilizando um motor de combustão interna (queimando gás natural), um queimador suplementar e uma caldeira de recuperação para gerar energia elétrica e vapor superaquecido necessário para o processo de reforma a vapor do glicerol; comparando-o com outro sistema proposto por Galarza (2017) que utiliza microturbina à gás. Este sistema será estudado para uma planta capaz de produzir 17820 m3/ano de biodiesel operando 7920 h/ano. Foi escolhido um motor de combustão interna com potência de 200 kW e consumo de 42,9 kg/h, pois foi o motor com menor consumo, mas que mantêm o nível de temperatura dos gases de exaustão (471,8 ºC). Energeticamente o sistema se demonstrou viável, mas possui grande perda de calor na chaminé que poderia ser aproveitada, como na produção de água quente por exemplo. A análise ex... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Brazil has a large capacity to produce biofuels due to its extensive land area with high productivity of raw material for this sector. The Federal Government has been investing a lot in this sector, since besides being economically strategic, it also has great advantages in the fight against global warming. Since 2005, when the commercialization of biodiesel began on a voluntary basis, by 2017 production increased from 736 m3/year to 4291294 m3/year. This was due to the policy of mandatory increase of the percentage of biodiesel mixed with petroleum diesel gradually until the level of 10% (B10) in 2018. In this work, a cogeneration system is proposed using an internal combustion engine (burning natural gas), an additional burner and a recovery boiler to generate electrical energy and superheated steam necessary for the steam reforming process of glycerol; comparing it with another system proposed by Galarza (2017) that uses microturbine to gas. This system will be studied for a plant capable of producing 17820 m3/year of biodiesel operating at 7920 hours per year. An internal combustion engine with a power of 200 kW and a consumption of 42.9 kg/h was chosen, because it was the engine with the lowest consumption, but it maintains the level of temperature of exit (471.8 ºC). Energetically the system has proven viable, but it has great heat loss in the chimney that could be better used, as in the production of hot water for example. Exergetic analysis helps to understand the sys... (Complete abstract click electronic access below) / Mestre

Le glycérol est valorisable par déshydratation en acroléine qui est un important intermédiaire chimique et peut être converti en une multitude de produits à valeur ajoutée dont l’acide acrylique qui est la base de nombreux polymères. Cette réaction est réalisée sur des catalyseurs acides comme les zéolithes protoniques qui donnent d’importants rendements initiaux en phase gazeuse (275-325°C) et à pression atmosphérique. Cependant, le principal inconvénient de ces matériaux est la désactivation rapide au cours du temps dû à la formation de dépôts carbonés appelés « coke ». L’ajout du fer sur les zéolithes H-BEA (larges pores) et H-MFI (pores moyens) a montré un effet fortement bénéfique sur cette réaction en présence d’air avec une formation supposée d’espèces actives qui permettraient de réduire de manière importante la désactivation du catalyseur et tout en favorisant la formation directe de l’acide acrylique sur la fonction métallique. Les zéolithes MFI au fer préparées par substitution isomorphe sont les plus performantes avec un rendement maximum en acide acrylique de 40% obtenu sur H-Fe3.8-Z-45 (préparé par synthèse hydrothermale). La zéolithe Np-Fe0.6-MFI-41 (préparé par traitement post-synthèse en milieu fluorure) permet d’obtenir un rendement en acroléine de plus de 80% après 24h de réaction, reproductible après régénération. Ce catalyseur est non seulement très actif, sélectif en acroléine, stable mais aussi régénérable, ce qui le place parmi les meilleurs pour ce procédé. / Glycerol is recoverable by dehydration into acrolein, which is an important chemical intermediate and can be converted into a variety of value-added products including acrylic acid that is the basis of many polymers. This reaction is carried out over acid catalysts, such as protonic zeolites which provide significant initial yields in the gas phase (275-325° C) and at atmospheric pressure. However, the main drawback of these materials is the rapid deactivation over time because of the formation of carbonaceous deposits known as "coke". The addition of iron over H-BEA (large pore) and H-MFI (mean pore) zeolites showed a highly beneficial effect on this reaction in the presence of air with an assumed formation of active species that would reduce significantly catalyst deactivation while promoting the direct formation of the acrylic acid on the metal function. H-MFI iron zeolites prepared by isomorphous substitution are the most efficient with a maximum acrylic acid yield of 40% obtained over H-Fe3.8-Z-45 (prepared by hydrothermal synthesis). Np-Fe0.6-MFI-41 zeolite (prepared by post-synthesis treatment in a fluoride medium) gives an acrolein yield of 80% after 24 hours of reaction, reproducible after regeneration. This catalyst is not only very active, selective to acrolein and stable but also regenerable, which places it among the best for this process.

Em muitas Estações de Tratamento de Esgoto Sanitário (ETE) no Brasil, reatores anaeróbios de manta de lodo (UASB) têm sido utilizados para tratamento de esgoto doméstico, embora apresentem baixa eficiência de remoção de demanda química de oxigênio (DQO) e alta quantidade de sólidos no efluente para esse substrato. Ademais, a digestão anaeróbia do esgoto sanitário em reatores UASB tem apresentado baixa produção do biogás, em razão da baixa concentração de matéria orgânica no afluente. No entanto, a produção de biogás pode ser aumentada pelo processo de codigestão anaeróbia, com a adição de um cossubstrato para aumentar a concentração inicial de matéria orgânica. O glicerol tem se destacado como cossubstrato de elevado potencial de geração de metano devido à sua alta concentração de matéria orgânica prontamente biodegradável. Nesse trabalho foi avaliada a possibilidade de utilização do potencial de produção de metano de reatores UASB já instalados no Brasil, por meio da adição de glicerol ao esgoto afluente. A pesquisa foi realizada em duas etapas, usando reatores UASB híbrido, com volumes de 24,75 L na primeira etapa, e 1,46 L na segunda etapa. Os reatores alimentados com esgoto sanitário e efluente de reator UASB, respectivamente, mantendo-se o tempo de detenção hidráulica (TDH) constante em 8 horas e variando-se a dosagem de glicerol afluente. A melhor fase de operação considerando eficiência de remoção de DQO, produção de metano e estabilidade do sistema biológico, foi operada com COV de 2,09 ± 0,22 kgDQO.m-3.d-1 e rendimento de metano de 75 ± 68 mLCH4.gDQOremovida-1. / In many sewage treatment plants in Brazil, up-flow sludge blanket (UASB) reactors have been used to treat domestic sewage, although they have a low removal efficiency of chemical oxygen demand (COD) and high amount of solids in the effluent for this substrate. In addition, most of the installed UASB reactors has presented small biogas production due to the low influent organic matter concentration. However, biogas production can be increased by the anaerobic codigestion process, by adding a co-substrate to increase the influent organic matter concentration. Glycerol has been highlighted as a co-substrate for high methane generation potential due to its high concentration of readily biodegradable organic matter. It is intended to evaluate the possibility of using the methane production potential of UASB reactors already installed in Brazil, through the addition of glycerol to the influent sewage. The research was conducted in two stages, using UASB hybrid reactors, with volumes of 24.75 L in the first stage, and 1.46 L in the second stage. They were fed with sanitary sewage and UASB reactor effluent, respectively, maintaining the hydraulic holding time (TDH) constant at 8 hours and varying the dosage of affluent glycerol. The best phase of operation considering COD removal efficiency, methane production and biological system stability was operated with OLR of 2.09 ± 0.22 kg CODm-3.d-1 and methane yield of 75 ± 68 mLCH4.gCODremoved-1.

Este trabalho foi dividido em quatro etapas, além da introdução. A primeira parte consiste no estudo comparativo do comportamento eletroquímico de eletrodos de cobre em soluções tampão fosfato 0,10 mol L-1 com valores de pH 4,5 e 7,8, e em solução de NaOH com valores de pH 13,0 e 14,0. Mostrou-se que as espécies formadas eletroquimicamente sobre a superfície do eletrodo são dependentes do valor de pH e do potencial aplicado. Os resultados experimentais obtidos estão de acordo com aqueles reportados na literatura. A segunda parte da tese corresponde ao desenvolvimento de um sensor eletroquímico fabricado com microeletrodos de cobre para a determinação de peróxido de hidrogênio (H2O2) em amostras comerciais de antissépticos bucais e clareadores dentais. Nas condições experimentais otimizadas (solução tampão fosfato 0,10 mol L-1 (pH 7,0) e potencial de redução de -0,20 V), microeletrodos de cobre foram utilizados para a determinação de H2O2 sem a necessidade de etapas de extração, obtendo-se faixa linear de 0,015 a 6,4 mmol L-1 e limite de detecção de 2,8 µmol L-1. O método proposto mostrou-se reprodutível e a presença de interferentes na matriz da amostra analisada não alterou a resposta do sensor para H2O2. Na terceira parte, a reação de eletro-oxidação de glicerol em superfícies de cobre em soluções de NaOH foi investigada utilizando a microscopia eletroquímica de varredura (SECM) no modo de geração pelo substrato de cobre / coleta no microeletrodo de platina (tip) (SG/TC). Os experimentos com a SECM mostraram a dependência da corrente com a distância entre o gerador e a tip, assim como a dependência com a concentração da solução de NaOH. Além disso, a corrente monitorada no microeletrodo diminuiu significativamente após a adição de glicerol. A atividade eletrocatalítica de eletrodos de cobre, no que diz respeito à oxidação de glicerol em meio alcalino, permitiu o desenvolvimento de um sensor amperométrico para a determinação de glicerol em amostra de biodiesel, com um intervalo linear de 0,05 a 1,33 mmol L-1 e limite de detecção de 20 µmol L-1. A metodologia proposta foi aplicada para a determinação do analito em uma amostra de biodiesel de mamona. A quarta parte descreve a síntese, caracterização eletroquímica e utilização de nanotubos de carbono de paredes múltiplas (NCPM) decorados com nanopartículas de paládio (Pd) para a modificação da superfície de eletrodo de carbono vítreo (CV) para a oxidação de metanol, etanol e glicerol em solução de KOH 1,0 mol L-1. Os resultados mostraram que o NCPM/Pd é um bom catalisador para a eletro-oxidação de álcoois em meio alcalino e que maior atividade eletrocatalítica foi obtida para o glicerol. Em condições otimizadas, experimentos amperométricos foram realizados para o desenvolvimento do método analítico para a determinação de glicerol em biodiesel, obtendo-se um intervalo linear de 0,06 a 24 mmol L-1 e limite de detecção 30 µmol L-1. Amostras de biodiesel foram analisadas com sucesso por meio de curvas de adição de padrão utilizando o eletrodo CV/NCPM/Pd. / This thesis is divided into four parts, apart from a general introduction. Part 1 is concerned with a critical comparison of the electrochemical behaviour of copper electrodes, in 0.10 mol L-1 phosphate buffer solution (pH 4.5 and 7.8), and in NaOH solution (pH 13.0 and 14.0). The electrochemical study showed that the species formed on the surface depends on both pH and the applied potential. The experimental results are in good agreement with those reported in the literature. A second goal of the thesis was the development of an electrochemical sensor for hydrogen peroxide (H2O2) determination in commercial oral antiseptic and dental whitening samples using copper microelectrodes. With optimized experimental conditions (working potential applied = -0.20 V in 0.10 mol L-1 phosphate buffer solution pH= 7.0), copper microelectrodes can be used to detect H2O2 without any previous extraction steps, in the range of 0.015 to 6.4 mmol L-1 with a lower detection limit of 2.8 µmol L-1. In addition, the electrode exhibited an excellent reproducibility and long-term stability as well as negligible interference from sorbitol, ethanol, glycerin and saccharin. In the third part, the electrooxidation reaction of glycerol at copper surfaces in NaOH solutions was investigated using Scanning Electrochemical Microscopy (SECM) in a copper substrate generation / platinum microelectrode (tip) collection mode (SG/TC). The results showed the dependence of the current measured at the tip with respect to the distance between generator and the tip, as well as on the concentration of the NaOH solution. Other studies led to the conclusion that the current measured at the tip decreased significantly after addition of glycerol in the solution. The electrocatalytic activity of copper electrodes for the oxidation of glycerol in alkaline medium allowed the development of an amperometric method to determine glycerol in biodiesel samples in the range 0.05 to 1.33 mmol L-1 with a detection limit of 20 µmol L-1. The determination of the analyte in a castor biodiesel sample employing a single copper microelectrode was carried out. The four part of this thesis shows results on the synthesis, electrochemical characterization and use of a glassy carbon (GC) electrode modified with multi-wall carbon nanotubes (MWCNT) decorated with palladium (Pd) for the electrochemical oxidation of methanol, ethanol and glycerol in 1.0 mol L-1 KOH solution. The results showed that MWCNT/Pd is a good electrocatalyst for methanol, ethanol and glycerol oxidation in alkaline medium, with highest activity toward glycerol oxidation. With optimized experimental conditions, an amperometric method was developed for the determination of glycerol in biodiesel samples, in the range of 0.06 to 24 mmol L-1 and detection limit of 30 µmol L-1. Biodiesel samples were successfully analyzed by the standard addition method using the GC/MWCNT/Pd film electrode.

A rabdomiólise é uma causa importante de lesão renal aguda (LRA) e decorre da lise das células musculares esqueléticas, com liberação do conteúdo intracelular para o compartimento extracelular e para a circulação. O extresse oxidativo e o processo inflamatório contribui para as alterações da função e estrutura renal que ocorrem na LRA. Estudos recentes tem evidenciado a participação da Vitamina D (Vit. D) no controle do processo inflamatório e do estresse oxidativo. Este estudo avaliou o efeito do tratamento com calcitriol (1,25-dihidroxivitamina D3) na evolução das alterações de estrutura e função renal, estresse oxidativo e no processo inflamatório renal provocados pela administração de glicerol. Ratos Wistar Hannover machos foram tratados com calcitriol (6 ng/dia, s.c., osmotic pump) ou veículo (salina 0,9%) por 7 dias, sendo no 3º dia injetados com glicerol (50%; 8ml/kg, i.m.) ou salina (8ml/kg, i.m). Os animais foram divididos em 4 grupos: Controle (n=7): receberam veículo s.c. e no 3º dia, injeção i.m de salina; Controle+Vit. D (n=7): receberam calcitriol s.c. e no 3º dia, injeção i.m de salina; Glicerol (n=13): receberam veículo s.c. e no 3º dia, injeção i.m de glicerol; Glicerol+Vit.D (n=10): receberam calcitriol s.c. e no 3º dia, injeção i.m de glicerol. Quatro dias após as injeções foram coletadas amostras de urina, plasma e tecido renal para estudos de função renal, histologia, imunoistoquímica, ELISA e Western blot. Os animais do grupo Glicerol tiveram aumento dos níveis plasmáticos de creatinina, redução da taxa de filtração glomerular, aumento da fração de excreção de sódio e redução da osmolalidade urinária comparados com os dos grupos controles. A análise histológica evidenciou aumento da área intersticial relativa e do número de túbulos com necrose no córtex renal dos animais tratados com glicerol. A lesão tubular foi também constatada pelo aumento da expressão de vimentina e PCNA nos animais do grupo Glicerol, em relação aos controles e ao grupo Glicerol+ Vit. D. Essas alterações foram menos intensas no grupo Glicerol+ Vit. D. A expressão de mioglobina estava aumentada no tecido renal de ambos os grupos tratados com glicerol. O estresse oxidativo foi observado pela aumento da expressão de 8-isoprostano nos animais do grupo Glicerol, essa alteração não estava presente nos animais controles e nos animais Glicerol+Vit. D. Ambos os grupos tratados com glicerol tiveram aumento do número de macrófagos, da expressão de NF-?B e dos níveis de IL1-? no córtex renal. Essas alterações foram atenuadas pelo tratamento com Vit. D. O grupo Glicerol apresentou também maior excreção urinária de VDBP, proteína transportadora de Vit. D e menor número de túbulos com bordadura em escova marcados com cubulina, receptor de Vit. D, em comparação aos grupos Controles e Glicerol+Vit. D. Portanto, a redução do receptor e a perda do transportador, reduz a captação de Vit. D nesse modelo, comprometendo a ativação renal de Vit. D e a sua ação no processo inflamatório e no estresse oxidativo no tecido renal. Concluindo, nossos resultados mostram que o tratamento com calcitriol reduziu as alterações de função e estrutura renal provocadas pelo glicerol. Esse efeito estava associado com a diminuição do processo inflamatório e do estresse oxidativo no tecido renal dos animais tratados com Glicerol+Vit. D. / Rhabdomyolysis provoked by the lysis of skeletal muscle cells can induce acute kidney injury (AKI) with release of intracellular content to the extracellular compartment and circulation. The oxidative stress and the inflammatory process contribute to the changes in renal function and structure in AKI. Recent studies have show the effect of vitamin D (Vit. D) on inflammatory process control and in the oxidative stress. This study evaluated the effect of calcitriol (1,25- dihydroxyvitamin D3) in the renal function and structure induced by glycerol and its relationship with the inflammatory process and the oxidative stress. Male Wistar Hannover rats were treated with calcitriol (6 ng/day, s.c., administered through an osmotic pump) or vehicle (saline 0.9%) for 7 days, and injected with glycerol (50%; 8ml/kg, i.m.) or saline (8ml/kg, i.m) 3 days after the beginning of this treatment. The animals were divided into 4 groups: Control (n = 7): received vehicle s.c. and on 3rd day after an injection i.m of saline; Control + Vit. D (n = 7): received Calcitriol s.c. and 3rd day after an injection i.m of saline; Glycerol (n = 13): received vehicle s.c and on 3rd day after an injection i.m of glycerol and Glycerol + Vit. D (n = 10): received Calcitriol s.c. and 3rd day after an injection i.m of glycerol. Four days after injections, urine samples, plasma and renal tissue were collected for renal function, histology, immunohistochemistry, ELISA and Western blot studies. Glycerol injected rats presented increase in plasma creatinine levels and sodium fractional excretion, and reduction glomerular filtration rate and urinary osmolality compared to controls groups. Histological analysis showed an increase in the relative interstitial area and in the number of tubules with necrosis in the renal cortex of these animals treated with glycerol. The tubular lesion was also evidenced by increased expression of vimentin and PCNA in the animals of the Glycerol group compared to controls. These changes were less intense in the Glycerol + Vit. D group. The myoglobin expression was increased in the renal tissue of both groups of the animal treated with glycerol. The oxidative stress was observed by the increased expression of 8-isoprostane in the kidneys from Glycerol group. However, this change was not observed in the control and Glycerol + Vit. D treated rats. Both glycerol-treated groups had increased number of macrophages, NF-?B expression and IL1- ? levels in the renal cortex. These changes were less intense in Vit. D treated animals. Glycerol group also presented higher urinary excretion of VDBP and less number of tubules with brush border marked with cubilin (Vit. D receptor) compared to the Control and Glycerol + Vit. D. Therefore, the reduction of the receptor and the loss of the transporter, reduces the uptake of Vit. D in this model, compromising the renal activation of Vit. D and its action in the inflammatory process and oxidative stress in renal tissue. In conclusion, our results show that treatment with calcitriol reduced the changes in renal function and structure caused by glycerol. This effect was associated with decreased inflammatory process and oxidative stress in the renal tissue of animals treated with Glycerol + Vit. D.

O glicerol, 1,2,3-propanotriol, é o principal subproduto da indústria do biodiesel, cerca de 10% em massa. Apesar das inúmeras aplicações que o glicerol tem na indústria, a oferta desse poliálcool, devido ao grande aumento da produção de biodiesel nos últimos anos, tem crescido tanto que o produto tem se acumulado nas usinas, levando a um desequilíbrio entre produção e consumo. Dessa forma, muita pesquisa vem sendo feita na tentativa de utilizar essa abundante, barata e não tóxica matéria prima como base para a obtenção de energia e outros produtos de maior valor agregado. Dentre os vários processos para a conversão do glicerol, a eletro-oxidação recebe atenção especial devido à sua versatilidade, simplicidade e baixo custo. Neste trabalho, utilizou-se a voltametria cíclica para a análise do comportamento eletroquímico do glicerol e dos possíveis produtos obtidos pela sua eletro-oxidação sobre diversos eletrodos e a influência de variáveis experimentais, tais como, solvente, eletrólito de suporte, concentrações de substrato e eletrólito de suporte, na atividade eletrocatalítica do sistema. As técnicas de eletroforese capilar, coulometria e voltametria cíclica foram utilizadas para a determinação da taxa de conversão e análise quantitativa do glicerol e dos produtos obtidos por meio de eletrólise exaustiva e como esses parâmetros são influenciados pelas variáveis experimentais. Além disso, é importante citar que o método analítico baseado na técnica de eletroforese capilar com detecção condutométrica sem contato foi desenvolvido e otimizado durante o projeto de mestrado e tem grande relevância para este trabalho / Glycerol, 1,2,3-propanetriol, is the main by-product of biodiesel industry, around 10% w/w. Despite of several glycerol applications in industry, the offer of this polyalcohol has increased so much in the last years that it has accumulated in the mills, leading to an unbalance between its production and consumption. Thus, a lot of research has been done trying to use this abundant, cheap and non-toxic raw material as the basis for energy production and synthesis of other more value-added compounds. Among the several conversion processes, the electrooxidation has drawn attention due to its versatility, simplicity and low cost. Cyclic voltammetry is used for analyzing the electrochemical behavior of glycerol and the possible electroconversion products on several electrodes, as well as the influence of experimental variables, such as, solvent, supporting electrolyte and its concentration, substrate concentration on the electrocatalytic activity of the system. Capillary electrophoresis, coulometry and cyclic voltammetry were used for determination of rate conversion and quantitative analyses of glycerol and the obtained products through bulk electrolysis and how these parameters are influenced by experimental conditions. Besides, it is noteworthy that the analytical method based on capillary electrophoresis technique with contactless conductometric detection was developed and optimized along this Master project and it has large relevance for this work.

Ce travail vise à étudier la transestérification de l'huile de tournesol pour la production de biodiesel et le vaporeformage du glycérol pour la production d'hydrogène renouvelable. Les oxydes mixtes Mg-Al prépares par voie hydrotalcite ont été choisis comme supports catalytiques. Pour la production de biodiesel, les effets du traitement thermique et de la méthode de préparation pour l'incorporation de calcium ont été étudiés. Le catalyseur Ca600/Mg₄Al₂HT calciné à 600°C, préparé par imprégnation de 40 wt% de Ca sur le support Mg₄Al₂ non calciné, a montré les meilleures performances catalytiques en raison de ses propriétés basiques améliorées. Pour le vaporeformage catalytique du glycérol, l'activité des oxydes de métaux purs imprégnés par le Ni a d'abord été étudiée, puisque les oxydes de métaux purs sont souvent utilisés comme supports catalytiques. Le catalyseur Ni/ZrO₂ s'est révélé le plus efficace pour la production d'hydrogène. Pour le vaporeformage du glycérol en présence d'oxydes mixtes obtenus par voie hydrotalcite, les catalyseurs au Ru-Mg-Al ont été étudiés. L'effet de la méthode de préparation (imprégnation ou greffage) sur l'activité catalytique a été étudié. Le catalyseur préparé par imprégnation permettait une plus grande accessibilité à la phase active. Pour des catalyseurs Ni-Mg-Al, les supports ont été modifiés par du lanthane. Le catalyseur Ni/Mg₆Al₁.₆La₀.₄ était le plus performant en raison de sa basicité accrue et de son interaction métal-support. Les activités des catalyseurs Ni/ZrO₂ et Ni/Mg₆Al₁.₆La₀.₄ ont été comparées. Les deux catalyseurs ont produit des rendements en hydrogène similaires. Moins de coke a été produit sur le catalyseur préparé par voie hydrotalcite, en raison de sa basicité supérieure. Un test de stabilité à 600°C a montré la désactivation du catalyseur Ni/Mg₆Al₁.₆La₀.₄ après 6 heures. Lors de l'optimisation des conditions de réaction sur le catalyseur Ni/Mg₆Al₁.₆La₀.₄, une amélioration significative de la stabilité a été observée, étendant ainsi sa durée de vie à 24 heures. / This work aims to study the transesterification of sunflower oil for biodesel production and the steam reforming of glycerol for renewable hydrogen production. Mg-Al hydrotalcite derived mixed oxides were chosen as catalytic support materials given their known basicity, thermal stability and low cost. Only one active phase was studied for biodiesel production (Ca) and two different active phases (Ru and Ni) for glycerol steam reforming. The various prepared catalysts were characterized by different techniques such as X-Ray Diffraction (XRD), specific surface area determination by BET method, Fourier Transform Infrared Spectroscopy (FTIR), H₂-Temperature Programmed Reduction (H₂-TPR), CO₂-Temperature Programmed Desorption (CO₂-TPD) and Simultaneous Thermogravimetric-Differential Scanning Calorimetry (TG-DSC). For biodiesel production, the effects of thermal treatment and the preparation method for Ca incorporation were both studied. The catalyst that showed the best catalytic performance was an uncalcined Mg₄Al₂ support impregnated with 40 wt% Ca followed by a calcination at 600°C (Ca/600Mg₄Al₂HT) due to its enhanced basic properties. After several optimization steps over this catalyst, the optimum conditions for biodiesel synthesis were: a methanol to oil molar ratio of 15:1, a catalyst to oil ratio of 2.5 wt% and a reaction time of 6 hours which gave a FAME yield of 95%. The properties of the produced biodiesel were studied and found to be in good agreement with ASTM (American Society for Testing and Materials) requirements. For the catalytic steam reforming of glycerol, the activity of NI-based pure metal oxides (Ni/CeO₂, Ni/Y₂O₃, Ni/ZrO₂) was first studied as pure metal oxides are commonly used as support materials. The effect of the support was evaluated and the Ni/ZrO₂ catalyst was found to be the most efficient for hydrogen production. To study the effect of the zirconia phase, a tetragonal Ni/ZrO₂ was also prepared. The tetragonal catalyst was less active for hydrogen production compared to the monoclinic catalyst. A stability test at 600°C also showed the desactivation of the tetragonal Ni/ZrO₂ after 6 hours on stream. For the catalytic steam reforming of glycerol using Mg-Al hydrotalcite derived mixed oxides, Ru-based Mg-Al catalysts were first studied. The effect of the preparation method (impregnation vs grafting) on the catalytic activity of Ru-Mg-Al catalysts was studied. The catalyst prepared by the impregnation method resulted in a better catalytic activity than the catalyst prepared by the grafting method as it allowed a higher accessibility of the active phase. For the Ni-based Mg-Al catalysts, the hydrotalcite supports were modified with La to study the effects of promoter addition on catalytic properties and activity. The bimetallic effect (1%Ru-5%Ni) and effect of a higher Ni loading (15 wt%) were also studied. The 5 wt% Ni impregnated on a La modified Mg-Al support (Ni/Mg₆Al₁.₆La₀.₄) catalyst was the most efficient for hydrogen production due to its enhanced basicity and metal-support interaction. The activities of the most efficient catalysts, Ni/ZrO₂ and Ni/Mg₆Al₁.₆La₀.₄, were compared. Both catalysts produced similar hydrogen yields. Differences in glycerol conversion to gaseous products were attributed to a higher formation of liquid by-products over the hydrotalcite support compared to the zirconia support. Nevertheless, less coke was produced over the hydrotalcite catalyst given its higher basicity. A stability test at 600°C showed the desactivation of the Ni/Mg₆Al₁.₆La₀.₄ catalyst after 6 hours on stream. Upon optimization of the reaction conditions on Ni/Mg₆Al₁.₆La₀.₄, a significant improvement in the stability was observed as the catalyst lasted for 24 hours on steam.Therefore, Ni/Mg₆Al₁.₆La₀.₄ could be a promising candidate for industrial application.