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Carbon-carbon bonds are ubiquitous in synthetic chemistry and constitute the skeletal backbone of a significant number of compounds. Utilizing transition metal mediated catalysis, a wide array of fused and spirocyclic ring systems containing diverse functionalization were accessed. These investigations provide unique ways to prepare carbon frameworks that are otherwise nontrivial to construct using classical approaches. The derivatives were rapidly accessed through optimized methods. / text

Thesis (Ph. D.)--University of Wisconsin--Madison, 1940. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 423-435).

Thesis (M.A.)--University of Wisconsin--Madison, 1937. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 80-82).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1940. / Typescript. Vita. Title from title screen (viewed May 9, 2006). Includes bibliographical references (leaves 423-435). Online version of the print original.

This thesis describes continuing development of new programming language C Plus conceived in earlier Bachelor’s Thesis oriented on enhancing C language with high level constructs with no additional cost. During development, several important languages were compared and C Plus along with its grammar were expanded, advantages of additions were discussed and compared with solutions in other languages. Described enhancements were implemented in the compiler.

Cytochrome c was immobilized to several supports to study the effects of immobilization on the molecule and to serve as a model for the in vivo system. Immobilization was accomplished by covalent attachment of cytochrome c to the support surface, either Sepharose 6MB or glassy carbon. The effect of the coupling conditions on the covalent attachment reaction was studied with Sepharose 6MB. The reactive groups were monitored colorimetrically and were highly susceptible to hydrolysis. Correction for hydrolysis indicated that the covalent attachment reaction was first order with respect to reacted groups. Coupling conditions most affecting the amount of attached cytochrome c were the initial cytochrome c concentration, temperature, and pH. A detailed study of the resulting immobilized cytochrome c was conducted based on its three characteristic properties: spectra, oxidation reduction potential, and biological activity. The spectral properties demonstrated that no major conformational changes had occurred upon immobilization since the spectra were essentially the same. The redox potentials for most samples of immobilized cytochrome c loaded with different amounts of protein were found to be 20-25 mV lower than native cytochrome c (+ 270 mV). Two samples, the heaviest loaded, were approximately equal to the native protein suggesting that they may be least affected by immobilization. The biological activity measurements provide an indication of the ability of the molecule to function properly. The Michaelis constant (K(m)) for cytochrome oxidase and reductase with immobilized cytochromes c were significantly higher (20-400X) than the K(m) for soluble cytochrome c. The higher K(m)s reflect that about 1% of the immobilized cytochrome c is availble for reaction in agreement with distribution and exclusion studies. Correction of the immobilized cytochrome c K(m)s for available protein results in values similar to the soluble cytochrome c K(m). Immobilization of cytochrome c to glassy carbon was performed by two procedures employing a carbodiimide or 4-vinylpyridine as the coupling reagents. The former resulted in electrodes with higher specific activities and lower protein loadings than the latter. In both cases up to 60% of the immobilized protein was held by adsorption on the surface. Protein coverages were approximately 10⁻⁸ to 10⁻⁹ moles/cm² which corresponds to 100-800 layers.

Texte remanié de: Doct-diss.--Philos.--London, 1977. / Bibliogr. p. 377-383. Index.

Texte remanié de: Diss.--Sprach- und Literaturwissenschaften--Erlangen, 1978. / Bibliogr. p. V-IX.

Hepatitis C virus (HCV) infection is a major global health burden affecting 1-2% of the world’s population. The majority of infected individuals will develop chronic infection and are at risk of cirrhosis and hepatocellular carcinoma. There is currently no preventative vaccine available for HCV. In the developed world, the highest HCV incidence and prevalence rate is amongst intravenous drug users (IDU). The duration, frequency of IDU, and sharing of drug injecting equipment contribute to particularly high rates of HCV infection in this population. Individuals at high risk of recurrent exposure to HCV infection from long term IDU have been recruited in Plymouth, UK, from 2003 onwards and if they remain negative for HCV infection are termed exposed uninfected (EU). Understanding the factors that prevent HCV infection in this cohort could give valuable insight into the mechanisms of natural resistance to HCV infection. The EU cohort was previously shown to have characteristics attributable to the activation of both the adaptive and the innate arms of the immune system with no known dominant, immune or non- immune, mechanism of HCV protection. The aim of this thesis was to attempt and identify this mechanism and for that purpose a comparative transcriptional profile study was initially performed between 3 groups: EU, individuals who spontaneously cleared HCV infection (SR) and patients with chronic HCV infection (CHCV). Of the differentially regulated genes, the association with resistance to HCV was strongest for Interleukin-27 (IL-27) which was significantly upregulated in EU compared to the 2 other groups and C X C motif chemokine 7 (CXCL7) which was significantly upregulated in EU relative to the CHCV group. The CD28 mediated T-helper cell signalling pathway was significantly upregulated in SR relative to the 2 other groups. We attempted to corroborate the above findings and we demonstrated that IL-27 is overexpressed in EU, compared to SR and CHCV. The possible role of IL-27 in natural protection from HCV infection remains to be elucidated and requires further study.