This diploma thesis deals with chemical recyclation polylactide to lactide. In the theory is summarized actual state of knowledge about chemical recyclation of polylactides, their properties, preparations a possibilities of characterization. Experimental part of work verify ethanolysis of PLA withthe samples of granulate, waste filaments and textiles. In the experimental work is suggested an optimalization of alcoholysis to direct yield of oligomer suitable for depolymerization to lactide. This method was verified for 5 different samples of PLA, which 4 of them was made of waste PLA. The time needed for depolymerization was evaluated and the effect of catalysis. Lactide and PLA recyclates was further analyzed by NMR, FTIR, DSC and GPC.

Ethyl iodide and ethyl chloride have been used as reactants to produce ethyl fragments on the stoichiometric α-Cr₂O₃ (1012) surface by means of thermal dissociation. Ethyl iodide is dissociated giving iodine adatoms and ethyl fragments bound to surface Cr cation sites, while ethyl chloride is dissociated giving chlorine adatoms and ethyl fragments. No oxygenated products are observed in thermal desorption, suggesting the 3-coordinate lattice oxygen on the stoichiometric α-Cr₂O₃ (1012) surface is very stable, and no nucleophilic attack occurs at the carbon atoms on surface ethyl fragments. For both reactants, the only reaction products observed are ethylene gas (CH₂=CH₂), ethane gas (CH₃-CH₃), hydrogen gas (H₂) and halogen adatoms (Cl_ads or I_ads). In thermal desorption experiments, all the gas phase products from ethyl chloride are produced in a reaction-limited, high temperature desorption feature attributed to a rate limiting β-hydride elimination from surface ethyl fragments. Similar product desorption features are observed for the reaction of ethyl iodide. However, the reaction of ethyl iodide also produces ethylene and ethane via a low temperature, desorption-limited reaction channel. It is postulated that I adatoms produced in the reaction of ethyl iodide thermal desorption might somehow promote a low temperature route to products that Cl adatoms do not. / Master of Science

A legislação brasileira estabelece o limite de 150 µg/L para os teores de carbamato de etila (CE ou uretana) em aguardentes. O presente trabalho indica que os teores de carbamato de etila em aguardentes podem ser reduzidos em até 92% do teor original após as aguardentes serem submetidas a uma nova destilação. Para amostras de aguardente recém destiladas (coletadas in loco) foi possível constatar que o CE também se forma após a destilação, e que a formação completa-se após 10 dias. A luz difusa não influenciou, quer na constante de velocidade quer na concentração de CE final. Esta, entretanto demonstrou-se dependente da temperatura. Observou-se que a reação ocorre com kobs de (6,4 ± 0,5) x 10-6 /s, a 25°C e pH 4,5, sendo este valor independente da origem da aguardente e da radiação luminosa. Os parâmetros de ativação para esta reação foram ΔH‡ 34 kcal/mol, ΔS‡ - 69 cal/K e ΔG‡ 54 kcal/mol. Foi possível estimar que o teor de uretana formado no interior do destilador foi inferior a 60% do CE total. Estudos com aguardente nas quais foi adicionado KOCN, indicaram que ocorre a formação de uretana com kobs (8,60 ± 0,4) x 10-5 /s, a 25°C, pH 4,5, com ΔH‡ 20,6 kcal/mol, ΔS‡ - 96,1 cal/K e ΔG‡ 48,7 kcal/mol. Esta reação não foi influenciada pela radiação luminosa (250 a 500 nm), bem como pelo teor alcoólico da aguardente (0,29 a 15,7 mol/L). O rendimento no teor de CE aumentou em função do teor alcoólico do meio, atingindo um valor máximo a 60% v/v. Cálculos quânticos sugeriram que o HNCO é a molécula reativa. Os resultados experimentais colhidos até o momento sugerem a existência de uma reação paralela consumindo parte do HNCO e, portanto limitando kobs e a relação [CE]teórico / [CE]experimental. A adição de NaCN à aguardente também conduz a formação de uretana, mas com constante de velocidade inferior a observada para o KOCN. / Brazilian law establishes the limit of 150 µg/L for ethyl carbamate (EC, urethane) contents in sugar cane spirits. The present work indicates that the levels of ethyl carbamate in spirits may be reduced up to 92% of the original content after undergoing a new distillation. It was observed that EC is also formed after distillation in recent distillated samples collected in loco and that the EC formation is completed after 10 days. The light did not influence either the rate constant or the final EC concentration. However, the rate constant proved to be temperature dependent. It was observed that the reaction occurs with kobs (6.4 ± 0.5) x 10-6 /s at 25°C and pH 4.5, which value is independent of the spirits origin and light radiation. The activation parameters for this reaction were ΔH‡ 34 kcal/mol, ΔS‡ - 69 cal/K and ΔG‡ 54 kcal/mol. It was estimated that the concentration of urethane formed inside the distiller was less than 60% of total EC. Studies adding KOCN in sugar cane spirits indicated that the formation of urethane occurs with kobs (8.60 ± 0.4) x 10-5 /s at 25°C, pH 4.5, with ΔH‡ 20.6 kcal/mol, ΔS‡ - 96.1 cal/K and ΔG‡ 48.7 kcal/mol. This reaction was not influenced by light radiation (250 to 500 nm), as well as the alcohol content of spirits (0.29 to 15.7 mol/L). The yield on EC content increased according to the alcohol content of the medium; reaching a maximum value of 60% v/v. Quantum calculations have suggested that HNCO is the reactive molecule. The experimental results collected so far suggest the existence of a parallel reaction which consumes part of HNCO and therefore limits kobs and the relationship [CE]theorical / [EC]experimental. The addition of NaCN to sugar cane spirits also leads to urethane formation, although with lower rate constant compared to the one observed for KOCN.

No limiar do ano de 2012 a população humana chegou a 7 bilhões de pessoas. Há apenas 12 anos atrás, 6 bilhões de seres humanos habitavam nosso planeta. O crescente e acentuado aumento da população tem exigido um uso exacerbado de bens naturais, principalmente do recurso solo, principal via para produção de alimentos. Para aumentar a produção de alimentos, sem aumentar a área cultivada, frequentemente faz-se o uso de pesticidas. Hoje, os herbicidas são os pesticidas mais comercializados, correspondendo à metade do mercado. Dentre seus grupos químicos mais comuns, há um destaque para as sulfonilureias, segunda classe de herbicida mais consumida em todo o mundo, contudo pouco investigada no âmbito da química analítica e ambiental. Uma vez no ambiente, o princípio ativo das sulfonilureias pode se tornar um risco para todo o ecossistema. Nos sedimentos, a sorção dos herbicidas determina quanto destes ficarão retidos na matriz e quanto estará disponível na solução do solo, contaminando os recursos hídricos. Neste sentido, o presente trabalho teve como objetivo realizar estudos que visam a determinar a dinâmica do herbicida etilclorimuron (exemplar da família das sulfonilureias) no ambiente. Estes estudos foram realizados via cinética e isotermas de adsorção em sedimentos. Compararam-se sedimentos com diferentes características em função do uso dado à terra (amostras Zona Agrícola, Zona Pecuária e Estação Ecológica). Para as três amostras, o modelo cinético obtido foi de pseudo-segunda-ordem. A amostra Zona Pecuária foi a que apresentou maior retenção (37,97.102 ug kg-1), logo uma dinâmica mais lenta. As demais amostras não apresentaram diferenças significativas para o processo sortivo (retenção de 29,07.102 e 31,67.102 ug kg-1 para as amostras Zona Agrícola e Estação Ecológica). Todos os sedimentos adsorveram de acordo com o modelo de Freundlich e suas isotermas foram classificadas como sendo do tipo C. A adsorção ocorreu com a formação de multicamadas e interações de natureza física (fisiossorção). O herbicida foi determinado via HPLC-UV. O método analítico foi validado de acordo com os documentos do INMETRO e da ANVISA e quando cabível de valores orientativos, os resultados obtidos se encontram em concordância. / On the threshold of 2012 the human population reached 7 billion of people. Only 12 years ago, 6 billion of human beings inhabited our planet. The growing and accentuated increase of the population has required an overuse of natural resources, especially the soil, main via for food production. Intending to increase the food production, without increasing the area under cultivation, pesticides are often used as an alternative. Nowadays herbicides are the pesticides most commonly traded, corresponding to a half of its market. Among the most common chemical groups, sulphonylureas have a noteworthy, the second most used class of herbicides throughout the world, however little studied in the context of analytical and environment chemistry. Once in the environment, the active principles of sulphonylureas may become a risk to the entire ecosystem. The sorption of herbicides in sediments determines how these will be retained in the matrix and how much will be available in soil solution, contaminating water resources. In this sense, this study aimed to realize studies for determinate the dynamics of chlorimuron ethyl (example of sulphonylurea herbicide family) in the environment. These studies were performed via kinetic and isotherm of absorptions in sediments. Sediments were compared with different characteristics depending of the use of earth (samples: Agricultural Zone, Farming Zone and Ecological Station). For all three samples, the obtained kinetic model was pseudo-second order. The farming Zone showed highest retention (37.97x102 ug kg-1), therefore a slower dynamic. The remaining samples didn\'t showed significant differences for the sorption process (retention of 29.07x102 and 31.67x102 ug kg-1 for Agricultural Zones and Ecological Stations). All sediments adsorbed according to Freundich\'s model and their isotherms were classified as C type. Adsorption occurred with the formation of multilayer and interactions were of physical type (physisorption). The herbicide was determined by HPLC-UV. The analytical method was validated in according with the INMETRO and ANVISA documents and, when appropriated of references values, the results have been in agreement.

A produção de biodiesel etílico é uma questão estratégica para a política energética nacional, uma vez que o Brasil é um dos maiores produtores de oleaginosas do mundo e o segundo maior produtor de etanol, álcool de origem renovável. Neste sentido, o presente trabalho buscou promover a transesterificação de óleos vegetais por etanol assistido por líquidos Iônicos sob diferentes fontes de aquecimento. O glicerol foi transformado em compostos de valor agregado e de interesse industrial. O mesmo foi modificado in situ após a reação de transesterificação gerando biodiesel aditivado pelos derivados da glicerina, conforme esquema 1. (Ver arquivo) / The production of ethyl biodiesel is a strategic issue for the national energy policy, because Brazil is one of the largest producers of oilseeds and the second largest producer of ethanol, a renewable alcohol. In this way, this work aimed to promote the transesterification of vegetable oils with ethanol assisted by ionic liquids under different heat sources. Glycerol was transformed into valuable compounds of industrial interest. It was also modified in situ after the transesterification reaction generating additive ethyl biodiesel, as shown below. (See file)

A produção de biodiesel etílico é uma questão estratégica para a política energética nacional, uma vez que o Brasil é um dos maiores produtores de oleaginosas do mundo e o segundo maior produtor de etanol, álcool de origem renovável. Neste sentido, o presente trabalho buscou promover a transesterificação de óleos vegetais por etanol assistido por líquidos Iônicos sob diferentes fontes de aquecimento. O glicerol foi transformado em compostos de valor agregado e de interesse industrial. O mesmo foi modificado in situ após a reação de transesterificação gerando biodiesel aditivado pelos derivados da glicerina, conforme esquema 1. (Ver arquivo) / The production of ethyl biodiesel is a strategic issue for the national energy policy, because Brazil is one of the largest producers of oilseeds and the second largest producer of ethanol, a renewable alcohol. In this way, this work aimed to promote the transesterification of vegetable oils with ethanol assisted by ionic liquids under different heat sources. Glycerol was transformed into valuable compounds of industrial interest. It was also modified in situ after the transesterification reaction generating additive ethyl biodiesel, as shown below. (See file)

No limiar do ano de 2012 a população humana chegou a 7 bilhões de pessoas. Há apenas 12 anos atrás, 6 bilhões de seres humanos habitavam nosso planeta. O crescente e acentuado aumento da população tem exigido um uso exacerbado de bens naturais, principalmente do recurso solo, principal via para produção de alimentos. Para aumentar a produção de alimentos, sem aumentar a área cultivada, frequentemente faz-se o uso de pesticidas. Hoje, os herbicidas são os pesticidas mais comercializados, correspondendo à metade do mercado. Dentre seus grupos químicos mais comuns, há um destaque para as sulfonilureias, segunda classe de herbicida mais consumida em todo o mundo, contudo pouco investigada no âmbito da química analítica e ambiental. Uma vez no ambiente, o princípio ativo das sulfonilureias pode se tornar um risco para todo o ecossistema. Nos sedimentos, a sorção dos herbicidas determina quanto destes ficarão retidos na matriz e quanto estará disponível na solução do solo, contaminando os recursos hídricos. Neste sentido, o presente trabalho teve como objetivo realizar estudos que visam a determinar a dinâmica do herbicida etilclorimuron (exemplar da família das sulfonilureias) no ambiente. Estes estudos foram realizados via cinética e isotermas de adsorção em sedimentos. Compararam-se sedimentos com diferentes características em função do uso dado à terra (amostras Zona Agrícola, Zona Pecuária e Estação Ecológica). Para as três amostras, o modelo cinético obtido foi de pseudo-segunda-ordem. A amostra Zona Pecuária foi a que apresentou maior retenção (37,97.102 ug kg-1), logo uma dinâmica mais lenta. As demais amostras não apresentaram diferenças significativas para o processo sortivo (retenção de 29,07.102 e 31,67.102 ug kg-1 para as amostras Zona Agrícola e Estação Ecológica). Todos os sedimentos adsorveram de acordo com o modelo de Freundlich e suas isotermas foram classificadas como sendo do tipo C. A adsorção ocorreu com a formação de multicamadas e interações de natureza física (fisiossorção). O herbicida foi determinado via HPLC-UV. O método analítico foi validado de acordo com os documentos do INMETRO e da ANVISA e quando cabível de valores orientativos, os resultados obtidos se encontram em concordância. / On the threshold of 2012 the human population reached 7 billion of people. Only 12 years ago, 6 billion of human beings inhabited our planet. The growing and accentuated increase of the population has required an overuse of natural resources, especially the soil, main via for food production. Intending to increase the food production, without increasing the area under cultivation, pesticides are often used as an alternative. Nowadays herbicides are the pesticides most commonly traded, corresponding to a half of its market. Among the most common chemical groups, sulphonylureas have a noteworthy, the second most used class of herbicides throughout the world, however little studied in the context of analytical and environment chemistry. Once in the environment, the active principles of sulphonylureas may become a risk to the entire ecosystem. The sorption of herbicides in sediments determines how these will be retained in the matrix and how much will be available in soil solution, contaminating water resources. In this sense, this study aimed to realize studies for determinate the dynamics of chlorimuron ethyl (example of sulphonylurea herbicide family) in the environment. These studies were performed via kinetic and isotherm of absorptions in sediments. Sediments were compared with different characteristics depending of the use of earth (samples: Agricultural Zone, Farming Zone and Ecological Station). For all three samples, the obtained kinetic model was pseudo-second order. The farming Zone showed highest retention (37.97x102 ug kg-1), therefore a slower dynamic. The remaining samples didn\'t showed significant differences for the sorption process (retention of 29.07x102 and 31.67x102 ug kg-1 for Agricultural Zones and Ecological Stations). All sediments adsorbed according to Freundich\'s model and their isotherms were classified as C type. Adsorption occurred with the formation of multilayer and interactions were of physical type (physisorption). The herbicide was determined by HPLC-UV. The analytical method was validated in according with the INMETRO and ANVISA documents and, when appropriated of references values, the results have been in agreement.

During alcoholic fermentation Saccharomyces cerevisiae metabolizes L-arginine to ornithine and urea. S. cerevisiae can metabolize urea through the action of urea amidolyase, encoded by the DUR1,2 gene; however, DUR1,2 is subject to nitrogen catabolite repression (NCR) in the presence of high quality nitrogen sources during fermentation. Being cytotoxic at high concentrations, urea is exported into wine where it spontaneously reacts with ethanol, and forms the carcinogen ethyl carbamate (EC). Urea degrading yeast strains were created by integrating a linear cassette containing the DUR1,2 gene under the control of the S. cerevisiae PGK1 promoter and terminator signals into the URA3 locus of the Sake yeast strains K7 and K9. The ‘self-cloned’ strains K7EC- and K9EC- produced Sake wine with 68% less EC. The Sake strains K7EC- and K9EC- did not efficiently reduce EC in Chardonnay wine due to the evolutionary adaptation of said strains to the unique nutrients of rice mash; therefore, the functionality of engineered yeasts must be tested in their niche environments as to correctly characterize new strains. S. cerevisiae possesses an NCR controlled high affinity urea permease (DUR3). Urea importing yeast strains were created by integrating a linear cassette containing the DUR3 gene under the control of the PGK1 promoter and terminator signals into the TRP1 locus of the yeast strains K7 (Sake) and 522 (wine). In Chardonnay wine, the urea importing strains K7D3 and 522D3 reduced EC by 7% and 81%, respectively; reduction by these strains was equal to reduction by the urea degrading strains K7EC- and 522EC-. In Sake wine, the urea degrading strains K7EC- and 522EC- reduced EC by 87% and 84% respectively, while the urea importing strains K7D3 and 522D3 were significantly less capable of reducing EC (15% and 12% respectively). In Chardonnay and Sake wine, engineered strains that constitutively co-expressed DUR1,2 and DUR3 did not reduce EC more effectively than strains in which either gene was expressed solely. Uptake of 14C-urea under non-inducing conditions was enhanced in urea importing strains; parental strains failed to incorporate any 14C-urea thus confirming the functionality of the urea permease derived from the integrated DUR3 cassette.

Diacetyl (2,3-butanedione) is an important flavour active, oxidative compound that has significant impact on cellular health as well as financial impact in industrial fermentations. The presence of diacetyl in certain fermented beverages, such as beer, results in an unpleasant butterscotch-like flavour and its concentration needs to be reduced by yeast to below the taste threshold prior to filtration and packaging. This results in significant process inefficiency. Furthermore, diacetyl negatively impacts cellular health and has been associated with neurodegenerative diseases and general cell aging amongst others. The reduction of this compound is therefore essential for cellular health. / Several yeast cell enzymatic mechanisms responsible for diacetyl reduction were identified and characterised, including Old Yellow Enzyme (OYE) isoforms and D-Arabinose Dehydrogenase (ARA1). OYE isoforms displayed different micromolar affinities and catalytic turnover rates for diacetyl and catalysed diacetyl reduction in a biphasic manner. ARA1 catalysed diacetyl reduction in a monophasic manner with a millimolar Michaelis constant. / Knowledge gained in these studies was applied in investigations of diacetyl production and reduction in industrial brewing operations and the enzymatic systems further exploited for the development of a novel enzyme based assay to determine diacetyl concentrations in beer samples. Concentrations as low as 0.2 muM were detectable with high repeatability.

During alcoholic fermentation Saccharomyces cerevisiae metabolizes L-arginine to ornithine and urea. S. cerevisiae can metabolize urea through the action of urea amidolyase, encoded by the DUR1,2 gene; however, DUR1,2 is subject to nitrogen catabolite repression (NCR) in the presence of high quality nitrogen sources during fermentation. Being cytotoxic at high concentrations, urea is exported into wine where it spontaneously reacts with ethanol, and forms the carcinogen ethyl carbamate (EC). Urea degrading yeast strains were created by integrating a linear cassette containing the DUR1,2 gene under the control of the S. cerevisiae PGK1 promoter and terminator signals into the URA3 locus of the Sake yeast strains K7 and K9. The ‘self-cloned’ strains K7EC- and K9EC- produced Sake wine with 68% less EC. The Sake strains K7EC- and K9EC- did not efficiently reduce EC in Chardonnay wine due to the evolutionary adaptation of said strains to the unique nutrients of rice mash; therefore, the functionality of engineered yeasts must be tested in their niche environments as to correctly characterize new strains. S. cerevisiae possesses an NCR controlled high affinity urea permease (DUR3). Urea importing yeast strains were created by integrating a linear cassette containing the DUR3 gene under the control of the PGK1 promoter and terminator signals into the TRP1 locus of the yeast strains K7 (Sake) and 522 (wine). In Chardonnay wine, the urea importing strains K7D3 and 522D3 reduced EC by 7% and 81%, respectively; reduction by these strains was equal to reduction by the urea degrading strains K7EC- and 522EC-. In Sake wine, the urea degrading strains K7EC- and 522EC- reduced EC by 87% and 84% respectively, while the urea importing strains K7D3 and 522D3 were significantly less capable of reducing EC (15% and 12% respectively). In Chardonnay and Sake wine, engineered strains that constitutively co-expressed DUR1,2 and DUR3 did not reduce EC more effectively than strains in which either gene was expressed solely. Uptake of 14C-urea under non-inducing conditions was enhanced in urea importing strains; parental strains failed to incorporate any 14C-urea thus confirming the functionality of the urea permease derived from the integrated DUR3 cassette.