Structural evidence for a dynamic metallocofactor during N 2 reduction by Mo-nitrogenase
Abstract
The enzyme nitrogenase uses a suite of complex metallocofactors to reduce dinitrogen (N 2 ) to ammonia. Mechanistic details of this reaction remain sparse. We report a 1.83-angstrom crystal structure of the nitrogenase molybdenum-iron (MoFe) protein captured under physiological N 2 turnover conditions. This structure reveals asymmetric displacements of the cofactor belt sulfurs (S2B or S3A and S5A) with distinct dinitrogen species in the two αβ dimers of the protein. The sulfur-displaced sites are distinct in the ability of protein ligands to donate protons to the bound dinitrogen species, as well as the elongation of either the Mo–O5 (carboxyl) or Mo–O7 (hydroxyl) distance that switches the Mo-homocitrate ligation from bidentate to monodentate. These results highlight the dynamic nature of the cofactor during catalysis and provide evidence for participation of all belt-sulfur sites in this process.
- Authors:
-
[1];
[1];
[1];
[2];
[1]
- Department of Molecular Biology and Biochemistry, University of California, Irvine, Irvine, CA 92697-3900, USA.
- Department of Molecular Biology and Biochemistry, University of California, Irvine, Irvine, CA 92697-3900, USA., Department of Chemistry, University of California, Irvine, Irvine, CA 92697-2025, USA.
- Publication Date:
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1633847
- Grant/Contract Number:
- SC0016510
- Resource Type:
- Published Article
- Journal Name:
- Science
- Additional Journal Information:
- Journal Name: Science Journal Volume: 368 Journal Issue: 6497; Journal ID: ISSN 0036-8075
- Publisher:
- American Association for the Advancement of Science (AAAS)
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Kang, Wonchull, Lee, Chi Chung, Jasniewski, Andrew J., Ribbe, Markus W., and Hu, Yilin. Structural evidence for a dynamic metallocofactor during N 2 reduction by Mo-nitrogenase. United States: N. p., 2020.
Web. doi:10.1126/science.aaz6748.
Kang, Wonchull, Lee, Chi Chung, Jasniewski, Andrew J., Ribbe, Markus W., & Hu, Yilin. Structural evidence for a dynamic metallocofactor during N 2 reduction by Mo-nitrogenase. United States. https://doi.org/10.1126/science.aaz6748
Kang, Wonchull, Lee, Chi Chung, Jasniewski, Andrew J., Ribbe, Markus W., and Hu, Yilin. Thu .
"Structural evidence for a dynamic metallocofactor during N 2 reduction by Mo-nitrogenase". United States. https://doi.org/10.1126/science.aaz6748.
@article{osti_1633847,
title = {Structural evidence for a dynamic metallocofactor during N 2 reduction by Mo-nitrogenase},
author = {Kang, Wonchull and Lee, Chi Chung and Jasniewski, Andrew J. and Ribbe, Markus W. and Hu, Yilin},
abstractNote = {The enzyme nitrogenase uses a suite of complex metallocofactors to reduce dinitrogen (N 2 ) to ammonia. Mechanistic details of this reaction remain sparse. We report a 1.83-angstrom crystal structure of the nitrogenase molybdenum-iron (MoFe) protein captured under physiological N 2 turnover conditions. This structure reveals asymmetric displacements of the cofactor belt sulfurs (S2B or S3A and S5A) with distinct dinitrogen species in the two αβ dimers of the protein. The sulfur-displaced sites are distinct in the ability of protein ligands to donate protons to the bound dinitrogen species, as well as the elongation of either the Mo–O5 (carboxyl) or Mo–O7 (hydroxyl) distance that switches the Mo-homocitrate ligation from bidentate to monodentate. These results highlight the dynamic nature of the cofactor during catalysis and provide evidence for participation of all belt-sulfur sites in this process.},
doi = {10.1126/science.aaz6748},
journal = {Science},
number = 6497,
volume = 368,
place = {United States},
year = {Thu Jun 18 00:00:00 EDT 2020},
month = {Thu Jun 18 00:00:00 EDT 2020}
}
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