The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) 2 (CN)] organometallic precursor
Abstract
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.
- Authors:
-
[1];
[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
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1567868
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 42; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Rao, Guodong, Pattenaude, Scott A., Alwan, Katherine, Blackburn, Ninian J., Britt, R. David, and Rauchfuss, Thomas B.. The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) 2 (CN)] organometallic precursor. United States: N. p., 2019.
Web. doi:10.1073/pnas.1913324116.
Rao, Guodong, Pattenaude, Scott A., Alwan, Katherine, Blackburn, Ninian J., Britt, R. David, & Rauchfuss, Thomas B.. The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) 2 (CN)] organometallic precursor. United States. https://doi.org/10.1073/pnas.1913324116
Rao, Guodong, Pattenaude, Scott A., Alwan, Katherine, Blackburn, Ninian J., Britt, R. David, and Rauchfuss, Thomas B.. Mon .
"The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) 2 (CN)] organometallic precursor". United States. https://doi.org/10.1073/pnas.1913324116.
@article{osti_1567868,
title = {The binuclear cluster of [FeFe] hydrogenase is formed with sulfur donated by cysteine of an [Fe(Cys)(CO) 2 (CN)] organometallic precursor},
author = {Rao, Guodong and Pattenaude, Scott A. and Alwan, Katherine and Blackburn, Ninian J. and Britt, R. David and Rauchfuss, Thomas B.},
abstractNote = {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.},
doi = {10.1073/pnas.1913324116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 42,
volume = 116,
place = {United States},
year = {2019},
month = {9}
}
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https://doi.org/10.1073/pnas.1913324116
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