Physical Sciences and Mathematics Commons^™

Mechanistic Studies Of Atypical Reactions And Uncommon Substrates Native To Bacterial Cytochrome P450 Enzymes OletJe And Nikq, Courtney Elizabeth Wise

Theses and Dissertations

Cytochrome P450 (CYP) enzymes typically perform hydroxylation chemistry on small molecule substrates using atmospheric oxygen and electrons from redox partner proteins. This reactivity is dependent on a thiolate-ligated heme cofactor that also allows for spectroscopic detection of ligation, oxidation, and environmental changes to the iron metal. The onset of the genomics era has resulted in the discovery of CYPs that deviate from this paradigm in terms of reaction performed, cosubstrate requirements, and substrate-scope. This work focuses on two of these unusual P450s – OleT and NikQ. OleT performs an unconventional H2O2-dependent decarboxylation reaction on a standard small molecule fatty acid …