| dc.contributor.author | Pearson, Jason K. | en_US |
| dc.date.accessioned | 2014-10-21T12:33:54Z | |
| dc.date.available | 2007 | |
| dc.date.issued | 2007 | en_US |
| dc.identifier.other | AAINR31491 | en_US |
| dc.identifier.uri | http://hdl.handle.net/10222/54953 | |
| dc.description | This thesis describes the application of high-level ab initio molecular orbital calculations on the properties of selenium-containing antioxidants as well as the bond dissociation energies of bonds having first and/or second-row atoms. | en_US |
| dc.description | An evaluation of Hartree-Fock and density functional theory for the prediction of geometries and bond dissociation energies of organoselenium compounds is carried out for the purpose of identifying valid computational schemes appropriate for the quantum chemical treatment of reactions of biological interest. | en_US |
| dc.description | The organoselenium antioxidant ebselen as well as models and derivatives of ebselen are the focus of much of the remaining chapters of the thesis. Specifically, the direct oxidation of models of ebselen, ebselen selenol, and ebselen diselenide by hydrogen peroxide are investigated. The results are used to propose reactive intermediates in the catalytic cycle of ebselen and determine mechanistic details regarding the redox reaction. The reduction of hydrogen peroxide by the full ebselen, ebselen selenolate, and ebselen diselenide molecules is also carried out which allows for a more complete understanding of the redox activity of these compounds. The energetics of these reactions are decomposed to their atomic origins with the use of the quantum theory of atoms in molecules and an atomic origin of the catalytic activity of ebselen is demonstrated. | en_US |
| dc.description | Substituent effects on the antioxidant activity of ebselen are examined by investigating the mechanism and energetics of the reduction of hydrogen peroxide by several substituted ebselen derivatives and the effect of solvation is incorporated. The results suggest a clear method of improving the antioxidant ability of the ebselen structure. | en_US |
| dc.description | Finally, the atomic contributions to bond dissociation energies involving selected first and second-row atoms are investigated for the purpose of determining which atoms dominate the energy profile of such reactions. | en_US |
| dc.description | Thesis (Ph.D.)--Dalhousie University (Canada), 2007. | en_US |
| dc.language | eng | en_US |
| dc.publisher | Dalhousie University | en_US |
| dc.publisher | | en_US |
| dc.subject | Chemistry, Inorganic. | en_US |
| dc.title | Theoretical studies of selenium-dependent reaction mechanisms. | en_US |
| dc.type | text | en_US |
| dc.contributor.degree | Ph.D. | en_US |
