Proton-coupled electron transfer dynamics in the catalytic mechanism of a [NiFe]-hydrogenase

Journal of the American Chemical Society
Brandon L GreeneR Brian Dyer

Abstract

The movement of protons and electrons is common to the synthesis of all chemical fuels such as H2. Hydrogenases, which catalyze the reversible reduction of protons, necessitate transport and reactivity between protons and electrons, but a detailed mechanism has thus far been elusive. Here, we use a phototriggered chemical potential jump method to rapidly initiate the proton reduction activity of a [NiFe] hydrogenase. Coupling the photochemical initiation approach to nanosecond transient infrared and visible absorbance spectroscopy afforded direct observation of interfacial electron transfer and active site chemistry. Tuning of intramolecular proton transport by pH and isotopic substitution revealed distinct concerted and stepwise proton-coupled electron transfer mechanisms in catalysis. The observed heterogeneity in the two sequential proton-associated reduction processes suggests a highly engineered protein environment modulating catalysis and implicates three new reaction intermediates; Nia-I, Nia-D, and Nia-SR(-). The results establish an elementary mechanistic understanding of catalysis in a [NiFe] hydrogenase with implications in enzymatic proton-coupled electron transfer and biomimetic catalyst design.

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Citations

Oct 1, 2015·Inorganic Chemistry·Geoffrey M ChambersWolfgang Lubitz
Oct 6, 2015·Journal of the American Chemical Society·Patrick KwanAnne K Jones
Nov 7, 2015·Archaea : an International Microbiological Journal·Chang-Hao WuMichael W W Adams
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Sep 13, 2016·Journal of the American Chemical Society·Brandon L GreeneR Brian Dyer
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Oct 31, 2017·Accounts of Chemical Research·Brandon L GreeneR Brian Dyer

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