Tuning Catalytic Bias of Hydrogen Gas Producing Hydrogenases

Jacob H. Artz, Oleg A. Zadvornyy, David W. Mulder, Stephen M. Keable, Aina E. Cohen, Michael W. Ratzloff, S. Garrett Williams, Bojana Ginovska, Neeraj Kumar, Jinhu Song, Scott E. McPhillips, Catherine M. Davidson, Artem Y. Lyubimov, Natasha Pence, Gerrit J. Schut, Anne K. Jones, S. Michael Soltis, Michael W.W. Adams, Simone Raugei, Paul W. KingJohn W. Peters

Research output: Contribution to journalArticle

Abstract

Hydrogenases display a wide range of catalytic rates and biases in reversible hydrogen gas oxidation catalysis. The interactions of the iron-sulfur-containing catalytic site with the local protein environment are thought to contribute to differences in catalytic reactivity, but this has not been demonstrated. The microbe Clostridium pasteurianum produces three [FeFe]-hydrogenases that differ in "catalytic bias" by exerting a disproportionate rate acceleration in one direction or the other that spans a remarkable 6 orders of magnitude. The combination of high-resolution structural work, biochemical analyses, and computational modeling indicates that protein secondary interactions directly influence the relative stabilization/destabilization of different oxidation states of the active site metal cluster. This selective stabilization or destabilization of oxidation states can preferentially promote hydrogen oxidation or proton reduction and represents a simple yet elegant model by which a protein catalytic site can confer catalytic bias.

Original languageEnglish (US)
Pages (from-to)1227-1235
Number of pages9
JournalJournal of the American Chemical Society
Volume142
Issue number3
DOIs
Publication statusPublished - Jan 22 2020

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Artz, J. H., Zadvornyy, O. A., Mulder, D. W., Keable, S. M., Cohen, A. E., Ratzloff, M. W., ... Peters, J. W. (2020). Tuning Catalytic Bias of Hydrogen Gas Producing Hydrogenases. Journal of the American Chemical Society, 142(3), 1227-1235. https://doi.org/10.1021/jacs.9b08756