By Alison Jayne Shumate, PhD.

A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University.

Virginia Commonwealth University, 2023

Major Director: Dr. Fred M. Hawkridge, Professor, Department of Chemistry


The temperature dependence of the formal potential and the rate constant of the heterogeneous electron transfer reaction of myoglobin has been investigated using cyclic voltammetry. Evidence for the non-spontaneous disassociation of the heme from the protein followed by the spontaneous complete unfolding and denaturation of the protein is indicated by a radical change in the reaction center entropy (D S_rc) at 37° C. Furthermore, from 5-37° C, the cyclic voltammograms display trends consistent with the gradual increase in the reversibility of the reaction. From 37-50° C, the cyclic voltammograms show switch to more irreversible reactions. The electrochemistry of myoglobin will be analyzed and discussed in context with analogous experimental studies which have been performed on ferricyanide and cytochrome c. 

dissertation

acknowledgements