Date of Award
2014
Publication Type
Doctoral Thesis
Degree Name
Ph.D.
Department
Chemistry and Biochemistry
Keywords
Computational Chemistry, DFT, Enzymology, QM/MM, Quantum Mechanics, Sulfur Chemistry
Supervisor
Gauld, James
Rights
info:eu-repo/semantics/openAccess
Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 4.0 International License.
Abstract
In biochemistry, sulfur-containing biomolecules enrich the chemical diversity in cells. This occurs via their participation in several reactions including disulfide formation, metal-binding and redox catalysis. Since sulfur occurs in various oxidation states, it exhibits interesting chemistry and reactivity. In this Dissertation computational modeling techniques have been used to investigate several aspects of sulfur's unique chemistry. Particularly, previously proposed mechanisms for sulfenic acids formation and reduction/overoxidation pathways have been examined In detail. A holistic picture of sulfur/sulfenic acid chemistry in biochemistry has been portrayed. For instance, the importance of non-covalent interaction in stabilizing the unstable sulfenic acid intermediates has been highlighted. Furthermore, the mechanism of Thiol activation in several active sites as well as the factors affecting thiolate stabilization has been determined in several enzymes. The role of protein dynamics and possible effects on catalysis has been emphasized. Moreover, a novel antioxidant pathway has been proposed. Computationally, the effect of choosing starting structure for modelling was also stressed.
Recommended Citation
Dokainish, Hisham Mohammed Mohammed, "Computational Insights into Sulfur Redox Chemistry in Enzymology" (2014). Electronic Theses and Dissertations. 5206.
https://scholar.uwindsor.ca/etd/5206