@article{9c62bca069e3495a83e09ab31b0206b2,
title = "Tuning Catalytic Bias of Hydrogen Gas Producing Hydrogenases",
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.",
author = "Artz, {Jacob H.} and Zadvornyy, {Oleg A.} and Mulder, {David W.} and Keable, {Stephen M.} and Cohen, {Aina E.} and Ratzloff, {Michael W.} and Williams, {S. Garrett} and Bojana Ginovska and Neeraj Kumar and Jinhu Song and McPhillips, {Scott E.} and Davidson, {Catherine M.} and Lyubimov, {Artem Y.} and Natasha Pence and Schut, {Gerrit J.} and Jones, {Anne K.} and Soltis, {S. Michael} and Adams, {Michael W.W.} and Simone Raugei and King, {Paul W.} and Peters, {John W.}",
note = "Funding Information: This work is supported as part of the Biological and Electron Transfer and Catalysis (BETCy) EFRC, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science (DE-SC0012518). This work was authored in part by Alliance for Sustainable Energy, LLC, the manager and operator of the National Renewable Energy Laboratory for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Use of the Linac Coherent Light Source (LCLS) and use of the Stanford Synchrotron Radiation Lightsource (SSRL), SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. The SSRL Structural Molecular Biology Program is supported by the U.S. Department of Energy Office of Biological and Environmental Research and by the National Institutes of Health (NIH), National Institute of General Medical Sciences (including P41GM103393). The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes. B.G., N.K., and S.R. were supported by the Center for Molecular Electrocatalysis (CME), an Energy Frontier Research Center funded by the U.S. DOE, Office of Science, Office of Basic Energy Sciences (BES), and the U.S. DOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Bio-Sciences (DE-AC05-76RL01830). Pacific Northwest National Laboratory is operated by Battelle for the U.S. DOE. Computational resources were provided by the National Energy Research Computing Center (NERSC) at the Lawrence Berkeley National Laboratory and W. R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy{\textquoteright}s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",
year = "2020",
month = jan,
day = "22",
doi = "10.1021/jacs.9b08756",
language = "English (US)",
volume = "142",
pages = "1227--1235",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "3",
}