Site-Specific Oxidation State Assignments of the Iron Atoms in the [4Fe:4S] 2+/1+/0 States of the Nitrogenase Fe-Protein
Abstract
The nitrogenase iron protein (Fe-protein) contains an unusual [4Fe:4S] iron-sulphur cluster that is stable in three oxidation states: 2 + , 1 + , and 0. Here, we use spatially resolved anomalous dispersion (SpReAD) refinement to determine oxidation assignments for the individual irons for each state. Additionally, we report the 1.13-c resolution structure for the ADP bound Fe-protein, the highest resolution Fe-protein structure presently determined. In the dithionitereduced [4Fe:4S]1+ state, our analysis identifies a solvent exposed, delocalized Fe2.5+ pair and a buried Fe2+ pair. We propose that ATP binding by the Fe-protein promotes an internal redox rearrangement such that the solvent-exposed Fe pair becomes reduced, thereby facilitating electron transfer to the nitrogenase molybdenum iron-protein. In the [4Fe:4S]0 and [4Fe:4S]2+ states, the SpReAD analysis supports oxidation states assignments for all irons in these clusters of Fe2+ and valence delocalized Fe2.5+ , respectively.
- Authors:
-
[1];
[2];
[2]
- California Institute of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
- California Institute of Technology (CalTech), Pasadena, CA (United States). Howard Hughes Medical Institute; California Institute of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1623488
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 12; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; iron-sulphur cluster; multiple-wavelength anomalous diffraction; nitrogenase; x-ray crystallography
Citation Formats
Wenke, Belinda B., Spatzal, Thomas, and Rees, Douglas C. Site-Specific Oxidation State Assignments of the Iron Atoms in the [4Fe:4S] 2+/1+/0 States of the Nitrogenase Fe-Protein. United States: N. p., 2019.
Web. doi:10.1002/anie.201813966.
Wenke, Belinda B., Spatzal, Thomas, & Rees, Douglas C. Site-Specific Oxidation State Assignments of the Iron Atoms in the [4Fe:4S] 2+/1+/0 States of the Nitrogenase Fe-Protein. United States. https://doi.org/10.1002/anie.201813966
Wenke, Belinda B., Spatzal, Thomas, and Rees, Douglas C. Mon .
"Site-Specific Oxidation State Assignments of the Iron Atoms in the [4Fe:4S] 2+/1+/0 States of the Nitrogenase Fe-Protein". United States. https://doi.org/10.1002/anie.201813966. https://www.osti.gov/servlets/purl/1623488.
@article{osti_1623488,
title = {Site-Specific Oxidation State Assignments of the Iron Atoms in the [4Fe:4S] 2+/1+/0 States of the Nitrogenase Fe-Protein},
author = {Wenke, Belinda B. and Spatzal, Thomas and Rees, Douglas C.},
abstractNote = {The nitrogenase iron protein (Fe-protein) contains an unusual [4Fe:4S] iron-sulphur cluster that is stable in three oxidation states: 2 + , 1 + , and 0. Here, we use spatially resolved anomalous dispersion (SpReAD) refinement to determine oxidation assignments for the individual irons for each state. Additionally, we report the 1.13-c resolution structure for the ADP bound Fe-protein, the highest resolution Fe-protein structure presently determined. In the dithionitereduced [4Fe:4S]1+ state, our analysis identifies a solvent exposed, delocalized Fe2.5+ pair and a buried Fe2+ pair. We propose that ATP binding by the Fe-protein promotes an internal redox rearrangement such that the solvent-exposed Fe pair becomes reduced, thereby facilitating electron transfer to the nitrogenase molybdenum iron-protein. In the [4Fe:4S]0 and [4Fe:4S]2+ states, the SpReAD analysis supports oxidation states assignments for all irons in these clusters of Fe2+ and valence delocalized Fe2.5+ , respectively.},
doi = {10.1002/anie.201813966},
journal = {Angewandte Chemie (International Edition)},
number = 12,
volume = 58,
place = {United States},
year = {Mon Mar 18 00:00:00 EDT 2019},
month = {Mon Mar 18 00:00:00 EDT 2019}
}
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Figure 1: (Left) Electron density for the MgADP molecule and [4Fe:4S] cluster from the dithionite-reduced, ADP-bound structure at 1.13 Å-resolution. The cluster bridges the dimer interface and 2$F$o-$F$c map is contoured at 1$σ$. (Right) The Fe labelling scheme used in this work is indicated.
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