Invited Talk 21st International Conference on Biological Inorganic Chemistry 2025

Redox Partner and Substrate Mediated Allosteric Control in Cytochromes P450 (125119)

Thomas Poulos 1 , Jessica A Gable 2 , Alec H Follmer 2 3
  1. Departments of Molecular Biology and Biochemistry, Chemistry and Pharmaceutical Sciences, University of California, Irvine, California
  2. Department of Chemistry, University of California, Davis, California
  3. Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA

A majority of P450 structures with substrate bound leave open two fundamental questions: how do substrates access and products exit the active site, given that most of the structures show a tightly closed active site, and how are protons delivered to the iron-linked dioxygen intermediate required for heterolytic cleavage of the oxygen O-O bond? These two questions highlight the requirement that P450s must undergo significant conformational dynamics to facilitate catalysis. Not too surprisingly, most detailed understanding of conformational dynamics derives from work on P450cam. A combination of crystallographic and computational studies have shown that P450cam fluctuates between three major conformational states, which are controlled by redox partner binding and an allosteric substrate-binding site far from the active site. This complexity prompts the question: Are these intricate dynamics unique to P450cam? While the structural details of substrate- and redox partner- mediated conformational dynamics are increasingly clear, the reason for this complexity remains elusive. Addressing these questions necessitates tackling an even greater challenge: understanding the biological basis/requirements and evolutionary drivers for such sophisticated control for a seemingly simple oxidation reaction.