No description available.

In this thesis, we study arylsilane oxidation from both a synthetic and a mechanistic perspective. Building upon previous work within our group, we demonstrate in an early chapter that arylhydrosilanes are surprisingly reactive to oxidation. This disproves the previous assumptions of the Tamao oxidation and provides new insights into the mechanism of the reaction. Furthermore, we find that the best substrates for oxidation are arylmethoxysilanes, and we describe rapid and efficient syntheses for these compounds. A further chapter addresses applications of arylsilane oxidation to natural product synthesis, protecting group chemistry and cycloadditions. By collecting concentration profiles of the oxidation of various arylsilanes, we reveal a rapid equilibration between arylmethoxysilanes and arylsilanols. By comparison, phenol formation (especially from silanol) is often slow. The rate of oxidation turns out to be highly sensitive to both the concentration of the oxidising agent and the substituents of the aromatic ring. In the final chapter we discuss in detail the consequences of these observations for the mechanism of arylsilane oxidation.

published_or_final_version / Biological Sciences / Doctoral / Doctor of Philosophy

Different sample preparation methodologies were evaluated for the determination of pollutants in different matrices. The methods investigated were chosen on the merits of decreased sample preparation time and low toxic solvent consumption with the aim to provide viable alternatives to more laborious methods, such as, Soxhlet extraction. Techniques were developed to extract and quantify organic pollutants from contaminated soils and water. The results from shake flask extraction of aged phenolic contaminated soils were used in attempt to relate sorption to both the soil, and pollutant properties. This was to help gain an understanding of the transport and fate of phenols in different environmental situations. The partitioning (sorption/desorption) of radiolabelled phenols between aqueous solution and soil was investigated using a modified shake flask technique. This provides additional information which can be related to soil characteristics, hence pertaining to the fate mechanisms involved for phenols in the environment. The results from these investigations suggest that more than one factor contributes to the sorption of phenols in soils.

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Thesis (doctoral)--University of Helsinki, 2007. / Includes bibliographical references. Also available on the World Wide Web.

Thesis (M.S.)--Duquesne University, 2007. / Title from document title page. Abstract included in electronic submission form. Includes bibliographical references (p. 101-104) and index.

Stuttgart, Univ., Diss., 2002.

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No description available.