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 journalArticlepeer-review

49 Scopus citations

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
StatePublished - Jan 22 2020

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint

Dive into the research topics of 'Tuning Catalytic Bias of Hydrogen Gas Producing Hydrogenases'. Together they form a unique fingerprint.
  • 1.0 Angstrom crystal structure of [FeFe]-hydrogenase

    Artz, J. H. (Contributor), Zadvornyy, O. A. (Contributor), Mulder, D. W. (Contributor), Keable, S. M. (Contributor), Cohen, A. E. (Contributor), Ratzloff, M. W. (Contributor), Williams, S. G. (Contributor), Ginovska, B. (Contributor), Kumar, N. (Contributor), Song, J. (Contributor), McPhillips, S. E. (Contributor), Davidson, C. M. (Contributor), Lyubimov, A. Y. (Contributor), Pence, N. (Contributor), Schut, G. J. (Contributor), Jones, A. (Contributor), Soltis, S. M. (Contributor), Adams, M. W. W. (Contributor), Raugei, S. (Contributor), King, P. W. (Contributor) & Peters, J. W. (Contributor), Protein Data Bank (PDB), Dec 25 2019

    Dataset

  • Crystal structure of [FeFe]-hydrogenase I (CpI) solved with single pulse free electron laser data

    Artz, J. H. (Contributor), Zadvornyy, O. A. (Contributor), Mulder, D. W. (Contributor), Keable, S. M. (Contributor), Cohen, A. E. (Contributor), Ratzloff, M. W. (Contributor), Williams, S. G. (Contributor), Ginovska, B. (Contributor), Kumar, N. (Contributor), Song, J. (Contributor), McPhillips, S. E. (Contributor), Davidson, C. M. (Contributor), Lyubimov, A. Y. (Contributor), Pence, N. (Contributor), Schut, G. J. (Contributor), Jones, A. (Contributor), Soltis, S. M. (Contributor), Adams, M. W. W. (Contributor), Raugei, S. (Contributor), King, P. W. (Contributor) & Peters, J. W. (Contributor), Protein Data Bank (PDB), Dec 11 2019

    Dataset

  • Crystal structure of [FeFe]-hydrogenase in the presence of 7 mM Sodium dithionite

    Artz, J. H. (Contributor), Zadvornyy, O. A. (Contributor), Mulder, D. W. (Contributor), Keable, S. M. (Contributor), Cohen, A. E. (Contributor), Ratzloff, M. W. (Contributor), Williams, S. G. (Contributor), Ginovska, B. (Contributor), Kumar, N. (Contributor), Song, J. (Contributor), McPhillips, S. E. (Contributor), Davidson, C. M. (Contributor), Lyubimov, A. Y. (Contributor), Pence, N. (Contributor), Schut, G. J. (Contributor), Jones, A. (Contributor), Soltis, S. M. (Contributor), Adams, M. W. W. (Contributor), Raugei, S. (Contributor), King, P. W. (Contributor) & Peters, J. W. (Contributor), Protein Data Bank (PDB), Dec 25 2019

    Dataset

Cite this