The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) 2 (CN)] organometallic precursor

Rao, Guodong; Pattenaude, Scott A.; Alwan, Katherine; Blackburn, Ninian J.; Britt, R. David; Rauchfuss, Thomas B.

doi:10.1073/pnas.1913324116

Title: The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) ₂ (CN)] organometallic precursor

Journal Article · 30 September 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1913324116 · OSTI ID:1567868

^[1]; Pattenaude, Scott A. ^[2]; Alwan, Katherine ^[3];

^[3];

^[1];

^[2]

Department of Chemistry, University of California, Davis, CA 95616,
School of Chemical Sciences, University of Illinois at Urbana–Champaign, Urbana, IL 61801,
Department of Chemical Physiology and Biochemistry, Oregon Health and Science University, Portland, OR 97239

Significance [FeFe]-hydrogenases catalyze H ₂ evolution at extraordinary rates at low overpotential using base metal (not platinum). In the field of renewable energy, the biosynthesis of these enzymes’ active sites, the H-cluster, is of intense interest. Among its many cofactors, the azadithiolate is unique, and its biosynthesis remains enigmatic. Three Fe–S proteins, HydE, HydF, and HydG, are essential for the H-cluster bioassembly. This paper describes an in vitro assembly approach where a synthetic [Fe(cysteine)(CO) ₂ (CN)] complex, “syn-B,” allows HydG-free biosynthesis of the active enzyme. Using isotopic and S/Se labeling, syn-B is shown to contribute Fe(CO) ₂ (CN)S to the biosynthesis. This work sets the stage for further investigation of the H-cluster bioassembly.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1567868

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 116 Journal Issue: 42; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 23 works

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Title: The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) ₂ (CN)] organometallic precursor