Pre-Steady-State Kinetics of Catalytic Intermediates of an [FeFe]-Hydrogenase

[FeFe]-hydrogenases catalyze the reversible production of hydrogen gas from protons and electrons, but the mechanism of catalysis is still the subject of debate. In this report, we describe a pre-steady-state photoreduction methodology for correlating putative intermediates to the reactivity of an [...

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Published inACS catalysis Vol. 7; no. 3; pp. 2145 - 2150
Main Authors Greene, Brandon L, Schut, Gerrit J, Adams, Michael W. W, Dyer, R. Brian
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 03.03.2017
American Chemical Society (ACS)
Subjects
08 HYDROGEN
09 BIOMASS FUELS
BASIC BIOLOGICAL SCIENCES
bio-inspired
biofuels (including algae and biomass)
hydrogen and fuel cells
solar (fuels)
electron bifurcation
time-resolved infrared spectroscopy
kinetics
[FeFe]-hydrogenase
enzymology
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Abstract [FeFe]-hydrogenases catalyze the reversible production of hydrogen gas from protons and electrons, but the mechanism of catalysis is still the subject of debate. In this report, we describe a pre-steady-state photoreduction methodology for correlating putative intermediates to the reactivity of an [FeFe]-hydrogenase from Thermotoga maritima. In this method, MV+ is rapidly formed photochemically by pulsed laser excitation and the intermolecular ET and active site dynamics are followed by nanosecond time-resolved visible and infrared spectroscopy, respectively. The results kinetically validate the Hox, Hred, and Hsred intermediates, strongly supporting a vast body of literature on their involvement in proton reduction.
AbstractList [FeFe]-hydrogenases catalyze the reversible production of hydrogen gas from protons and electrons, but the mechanism of catalysis is still the subject of debate. In this report, we describe a pre-steady-state photoreduction methodology for correlating putative intermediates to the reactivity of an [FeFe]-hydrogenase from Thermotoga maritima. In this method, MV+ is rapidly formed photochemically by pulsed laser excitation and the intermolecular ET and active site dynamics are followed by nanosecond time-resolved visible and infrared spectroscopy, respectively. The results kinetically validate the Hox, Hred, and Hsred intermediates, strongly supporting a vast body of literature on their involvement in proton reduction.
Author Greene, Brandon L
Adams, Michael W. W
Dyer, R. Brian
Schut, Gerrit J
AuthorAffiliation Department of Chemistry
Emory University
Department of Biochemistry and Molecular Biology
University of Georgia
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  givenname: Gerrit J
  surname: Schut
  fullname: Schut, Gerrit J
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  givenname: Michael W. W
  surname: Adams
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  givenname: R. Brian
  orcidid: 0000-0002-0090-7580
  surname: Dyer
  fullname: Dyer, R. Brian
  email: briandyer@emory.edu
  organization: Emory University
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Keywords electron bifurcation
time-resolved infrared spectroscopy
kinetics
[FeFe]-hydrogenase
enzymology
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Snippet [FeFe]-hydrogenases catalyze the reversible production of hydrogen gas from protons and electrons, but the mechanism of catalysis is still the subject of...
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SubjectTerms 08 HYDROGEN
09 BIOMASS FUELS
BASIC BIOLOGICAL SCIENCES
bio-inspired
biofuels (including algae and biomass)
hydrogen and fuel cells
solar (fuels)
Title Pre-Steady-State Kinetics of Catalytic Intermediates of an [FeFe]-Hydrogenase
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