Thesis (Ph. D.)--University of Wisconsin, 1942. / Typescript (carbon copy). eContent provider-neutral record in process. Description based on print version record. Includes bibliographies.

Tübingen, Univ., Diss., 2003.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1959. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 97-99).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1969. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Würzburg, Univ., Diss., 2002.

University, Diss., 2003--Regensburg.

As metabolic substrates, ketone bodies provide an alternative to glucose in order to pro- long survival during starvation. A low carbohydrate, high fat diet can be used to promote ketogenesis without fasting, but long-term compliance can be difficult. Dietary ketone bod- ies may be an alternative method to induce ketosis, so the aim of the work in this Thesis was to investigate the metabolism of exogenous ketones. In the first experimental Chap- ter, the effects of ketone ester and salt drinks on blood β-hydroxybutyrate (βHB), glucose, lipids, electrolytes and pH were determined in healthy humans at rest. Blood D-βHB levels were higher following ketone ester drinks, but it was found that total βHB levels with ke- tone salts were similar, as over 50% of βHB delivered in the salt was the L-isoform, which was only slowly removed from the blood. Circulating glucose and lipid concentrations fell following both ketone drinks. Blood pH fell following ketone ester consumption, but rose following ketone salt drinks, whilst both compounds raised blood sodium and chloride, and lowered potassium. Work in the second Chapter investigated the repeatability of ketone es- ter metabolism with food, successive drinks or continuous nasogastric (NG) infusion. Peak D-βHB levels were repeatable between- and within- subjects at rest but were lower after a meal, although blood acetoacetate, breath acetone and urine βHB were unaffected by feed- ing. βHB kinetic parameters were not altered by existing hyperketonemia from successive ketone ester drinks and total βHB uptake was identical when isovolumetric amounts of ketone ester were continuously infused through a NG tube. The third Chapter explored side-effects of ketone drinks: ketone ester drinks decreased appetite compared to isocaloric dextrose; which may have been linked to effects of βHB on enteroendocrine cells. Fur- thermore, both ester and salt drinks were found to be unpalatable, and to cause a few, mild gastro-intestinal effects that increased with intake. As exogenous ketones could be a per- formance enhancing supplement in sport, the fourth Chapter used a survey to investigate supplement use by endurance athletes. The results demonstrated widespread supplement use, which was highest at the elite level. In the final Chapter, the effect of glycogen lev- els on the oxidation of βHB was determined in isolated perfused rat hearts. Low cardiac glycogen levels decreased βHB oxidation and levels of the intermediates of glycolysis and the Krebs cycle, whilst increasing muscle amino acid levels, suggesting that low glycogen may have impaired anaplerosis. In conclusion, this work extends current understanding of the novel physiological ketosis that occurs following exogenous ketone consumption.

<p> The reaction of lead tetra-acetate with ketone carbohydrazones and 4-substituted semicarbazones gave a series of 2-(substituted imino)-△^3-1,3,4-oxadiazolines. Spectroscopic and chemical evidence is presented to establish the proposed structure, and the scope of the reaction is described. The thermolysis of the 5,5-diaryl-2-phenylimino-△^3-1,3,4-oxadiazolines was studied in chlorobenzene solution. The results of kinetic experiments (gas evolution and infra-red) are reported, and the mechanism of the decomposition is discussed. A survey of the literature pertaining to related lead tetra-acetate oxidations, and to decomposition of cyclic azo compounds is presented.</p> / Thesis / Doctor of Philosophy (PhD)

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Nesse trabalho avaliamos o potencial enzimático de diferentes linhagens de fungos, visando determinar a presença de mono-oxigenases capazes de oxidar cetonas aromáticas e cíclicas. Todas as linhagens empregadas apresentaram atividade de álcool desidrogenase e Baeyer-Villiger mono-oxigenases. Adicionalmente foram sintetizadas oito moléculas bi-funcionalizadas com grupos sulfeto, seleneto e carbonila (cetona). Os produtos das reações biocatalisadas foram isolados e caracterizados. / In this work, we evaluated the enzymatic potential of different Aspergillus strains, through the biotransformations of two substrates: 2- and 4-methylcyclohexanone (1a e 1b). All the strains employed showed alcohol dehydrogenase and Baeyer-Villiger monooxygenase (CPMO and CHMO) activities. These enzymes can perform ketone biorreduction and oxidation. Using the A. terreus SSP 1498 selected from the screening study, we prepared alcohols and lactones in good enantiosselectivity. In this way, other fungal strains were studied aiming to determine the presence of monooxygenase activity by means of the biotransformation of aromatic ketones. Like the Aspergillus, we observed that all strains used in this study showed alcohol dehydrogenase and Baeyer-Villiger monooxygenase (APMO) activities. We selected 1-phenyl-etanone and its para substituted derivates as substrates. Additionally, we synthesized eight examples of bi-functionalized compounds with sulfide, selenide and ketone groups. These compounds were submitted to the action of enzymatic system of different fungi which were selected from the initial screening. The products from the biotransformation were isolated and characterized.