[FeFe]‐Hydrogenase: Defined Lysate‐Free Maturation Reveals a Key Role for Lipoyl‐H‐Protein in DTMA Ligand Biosynthesis
Abstract
Abstract Maturation of [FeFe]‐hydrogenase (HydA) involves synthesis of a CO, CN − , and dithiomethylamine (DTMA)‐coordinated 2Fe subcluster that is inserted into HydA to make the active hydrogenase. This process requires three maturation enzymes: the radical S‐adenosyl‐ l ‐methionine (SAM) enzymes HydE and HydG, and the GTPase HydF. In vitro maturation with purified maturation enzymes has been possible only when clarified cell lysate was added, with the lysate presumably providing essential components for DTMA synthesis and delivery. Here we report maturation of [FeFe]‐hydrogenase using a fully defined system that includes components of the glycine cleavage system (GCS), but no cell lysate. Our results reveal for the first time an essential role for the aminomethyl‐lipoyl‐H‐protein of the GCS in hydrogenase maturation and the synthesis of the DTMA ligand of the H‐cluster. In addition, we show that ammonia is the source of the bridgehead nitrogen of DTMA.
- Authors:
-
[1];
[1];
[1];
[2];
[1];
[4];
[2];
[1];
[1]
- Department of Chemistry &, Biochemistry Montana State University Bozeman MT 59717 USA
- Department of Chemistry Northwestern University Evanston IL 60208 USA
- Department of Chemistry The Pennsylvania State University University Park PA 16802 USA
- Department of Chemistry The Pennsylvania State University University Park PA 16802 USA, Howard Hughes Medical Institute Chevy Chase MD 20815 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1862893
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 134 Journal Issue: 22; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Pagnier, Adrien, Balci, Batuhan, Shepard, Eric M., Yang, Hao, Warui, Douglas M., Impano, Stella, Booker, Squire J., Hoffman, Brian M., Broderick, William E., and Broderick, Joan B. [FeFe]‐Hydrogenase: Defined Lysate‐Free Maturation Reveals a Key Role for Lipoyl‐H‐Protein in DTMA Ligand Biosynthesis. Germany: N. p., 2022.
Web. doi:10.1002/ange.202203413.
Pagnier, Adrien, Balci, Batuhan, Shepard, Eric M., Yang, Hao, Warui, Douglas M., Impano, Stella, Booker, Squire J., Hoffman, Brian M., Broderick, William E., & Broderick, Joan B. [FeFe]‐Hydrogenase: Defined Lysate‐Free Maturation Reveals a Key Role for Lipoyl‐H‐Protein in DTMA Ligand Biosynthesis. Germany. https://doi.org/10.1002/ange.202203413
Pagnier, Adrien, Balci, Batuhan, Shepard, Eric M., Yang, Hao, Warui, Douglas M., Impano, Stella, Booker, Squire J., Hoffman, Brian M., Broderick, William E., and Broderick, Joan B. Mon .
"[FeFe]‐Hydrogenase: Defined Lysate‐Free Maturation Reveals a Key Role for Lipoyl‐H‐Protein in DTMA Ligand Biosynthesis". Germany. https://doi.org/10.1002/ange.202203413.
@article{osti_1862893,
title = {[FeFe]‐Hydrogenase: Defined Lysate‐Free Maturation Reveals a Key Role for Lipoyl‐H‐Protein in DTMA Ligand Biosynthesis},
author = {Pagnier, Adrien and Balci, Batuhan and Shepard, Eric M. and Yang, Hao and Warui, Douglas M. and Impano, Stella and Booker, Squire J. and Hoffman, Brian M. and Broderick, William E. and Broderick, Joan B.},
abstractNote = {Abstract Maturation of [FeFe]‐hydrogenase (HydA) involves synthesis of a CO, CN − , and dithiomethylamine (DTMA)‐coordinated 2Fe subcluster that is inserted into HydA to make the active hydrogenase. This process requires three maturation enzymes: the radical S‐adenosyl‐ l ‐methionine (SAM) enzymes HydE and HydG, and the GTPase HydF. In vitro maturation with purified maturation enzymes has been possible only when clarified cell lysate was added, with the lysate presumably providing essential components for DTMA synthesis and delivery. Here we report maturation of [FeFe]‐hydrogenase using a fully defined system that includes components of the glycine cleavage system (GCS), but no cell lysate. Our results reveal for the first time an essential role for the aminomethyl‐lipoyl‐H‐protein of the GCS in hydrogenase maturation and the synthesis of the DTMA ligand of the H‐cluster. In addition, we show that ammonia is the source of the bridgehead nitrogen of DTMA.},
doi = {10.1002/ange.202203413},
journal = {Angewandte Chemie},
number = 22,
volume = 134,
place = {Germany},
year = {Mon Apr 11 00:00:00 EDT 2022},
month = {Mon Apr 11 00:00:00 EDT 2022}
}
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