Techn. Hochsch., Diss., 2005--Aachen.

Thesis (Ph. D.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains ix, 115 p. : ill., map. Includes abstract. Includes bibliographical references.

Thesis (M.S.)--Springfield College, 2004. / Includes bibliographical references.

Thesis (M.S.)--Dept. of Exercise and Sport Science, University of Utah, 2006. / Includes bibliographical references (leaves [65]-69).

Thesis (Ph.D.)--University of Nebraska-Lincoln, 2007. / Title from title screen (site viewed July 09, 2007). PDF text: viii, 392 p. UMI publication number: AAT 3252438. Also available in microfilm and microfiche formats.

Thesis (M.S.)--University of Utah, 2006. / Includes bibliographical references (leaves [65]-69). Also available online (PDF file) by a subscription to the set or by purchasing the individual file.

abstract: Cellular redox phenomena are essential for the life of organisms. Described here is a summary of the synthesis of a number of redox-cycling therapeutic agents. The work centers on the synthesis of antitumor antibiotic bleomycin congeners. In addition, the synthesis of pyridinol analogues of alpha-tocopherol is also described. The bleomycins (BLMs) are a group of glycopeptide antibiotics that have been used clinically to treat several types of cancers. The antitumor activity of BLM is thought to be related to its degradation of DNA, and possibly RNA. Previous studies have indicated that the methylvalerate subunit of bleomycin plays an important role in facilitating DNA cleavage by bleomycin and deglycobleomycin. A series of methylvalerate analogues have been synthesized and incorporated into deglycobleomycin congeners by the use of solid-phase synthesis. All of the deglycobleomycin analogues were found to effect the relaxation of plasmid DNA. Those analogues having aromatic C4-substituents exhibited cleavage efficiency comparable to that of deglycoBLM A5. Some, but not all, of the deglycoBLM analogues were also capable of mediating sequence-selective DNA cleavage. The second project focused on the synthesis of bicyclic pyridinol analogues of alpha-tocopherol. Bicyclic pyridinol antioxidants have recently been reported to suppress the autoxidation of methyl linoleate more effectively than alpha-tocopherol. However, the complexity of the synthetic routes has hampered their further development as therapeutic agents. Described herein is a concise synthesis of two bicyclic pridinol antioxidants and a facile approach to their derivatives with simple alkyl chains attached to the antioxidant core. These analogues were shown to retain biological activity and exhibit tocopherol-like behaviour. / Dissertation/Thesis / Ph.D. Chemistry 2011

The process of fatigue during 30 s of high-intensity exercise results in rapid and substantial mechanical, electrical and biochemical changes in muscle fibres. This thesis describes a series of experiments, performed upon a friction-loaded cycle ergometer, which investigated whether the magnitude of the mechanical and biochemical changes is affected by changes in average pedalling rate. The ability to generate peak power in a subsequent sprint of 6 s duration was used to assess the magnitude of the mechanical changes. Changes in the concentrations of blood and muscle metabolites pre- and post-exercise permitted some of the biochemical changes to be measured.

Many behavioral interventions have attempted to increase sports performance. These interventions include: goal setting and feedback, behavioral coaching, and acoustical guidance. The use of technological devices in all areas of life continues to steadily increase. Therefore, behavioral interventions should also adapt to meet these changes in technology. One such intervention is in-vivo audio feedback in which participants receive live feedback about their current performance while practicing the skill. In-vivo audio feedback has not yet been rigorously evaluated as a means of improving sports performance. This study used a multiple baseline across participants design to evaluate the effects of in-vivo audio feedback on cycling performance. Results from this study suggest that in-vivo audio feedback was an effective method for improving cycling performance for individuals wishing to increase their average cycling speed.

Subsurface contamination is common at nuclear sites and it is likely that radioactive wastes will be managed in the long-term via burial in a deep Geological Disposal Facility (GDF). The migration of radionuclides in the geosphere from such sites is a major societal concern. In particular, long-lived, redox-active radionuclides (in the case of this thesis: 99Tc and Np) can migrate over large distances due to their high solubility under oxic conditions. Bioremediation has been proposed as a mechanism to limit the migration of 99Tc and Np in the environment. Here, an electron donor is supplied to the subsurface and soluble Tc(VII) and Np(V) are reduced to poorly soluble Tc(IV) and Np(IV), respectively. Reduction occurs via direct microbial action (termed bioreduction) or through radionuclide reaction with the by-products of microbial metabolism (primarily Fe(II)). Given the ubiquity of microorganisms and Fe in the geosphere, similar reactions can be expected in the deep subsurface surrounding a GDF. Once reduced, the long-term stability of the Tc(IV) and Np(IV) phases will significantly impact migration rates. Oxidative dissolution of Tc(IV)- and Np(IV)-bearing solids has been demonstrated in the literature and can be pervasive, thus questioning the efficacy of bioreduction. However, these studies have been conducted over short time-scales and during a single period of oxidation. Given the long half-life of 99Tc and Np and the ephemeral nature of redox conditions in the subsurface, there is a need to better understand 99Tc and Np biogeochemistry during longer time-scales and across multiple redox cycles. In this thesis, microcosm experiments have been used to address this knowledge gap. Sediment and groundwater used in the microcosms were representative of the Sellafield Ltd. nuclear site. For Tc, three successive redox cycles (reduction followed by oxidation with O2) over 2 years, gradually reduced the extent of Tc remobilisation during oxidation, and molecular scale characterisation of solids revealed that sediment associated Tc was always present as Tc(IV). Further, over time sequential extractions and EXAFS revealed an increased significance of Tc-Fe bonding in the sediment at the expense of TcO2. Despite this, a small but significant fraction of Tc(IV) was also found to be stable in solution during the experiments and XAS and TEM analysis suggested this was Tc(IV) associated with magnetite colloids. In other experiments completed with higher concentrations of bioavailable Fe (added as ferrihydrite to sediments, and in pure culture experiments with Geobacter sulfurreducens), the significance of Tc-Fe bonding was again highlighted, and potential Tc(IV) incorporation into biogenic magnetite was also documented. In experiments with Np, virtually all of the Np(V) added to oxic groundwater was removed to the sediment commensurate with microbially mediated Fe(III) reduction. Further, in systems with elevated bioavailable Fe, Np removal from solution was more extensive. Taken together, the data for Tc and Np reveals critical links between redox-active radionuclides and Fe cycling in sediments over periods of years and across multiple redox cycles. Furthermore, these processes help to predict the long-term fate of radioactive contamination at the Sellafield Ltd. nuclear site and have implications for contaminated land worldwide.