Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9 th Sulfur”
Abstract
Abstract Nitrogenases catalyze the reduction of N 2 to NH 4 + at its cofactor site. Designated the M‐cluster, this [MoFe 7 S 9 C( R ‐homocitrate)] cofactor is synthesized via the transformation of a [Fe 4 S 4 ] cluster pair into an [Fe 8 S 9 C] precursor (designated the L‐cluster) prior to insertion of Mo and homocitrate. We report the characterization of an eight‐iron cofactor precursor (designated the L*‐cluster), which is proposed to have the composition [Fe 8 S 8 C] and lack the “9 th sulfur” in the belt region of the L‐cluster. Our X‐ray absorption and electron spin echo envelope modulation (ESEEM) analyses strongly suggest that the L*‐cluster represents a structural homologue to the l ‐cluster except for the missing belt sulfur. The absence of a belt sulfur from the L*‐cluster may prove beneficial for labeling the catalytically important belt region, which could in turn facilitate investigations into the reaction mechanism of nitrogenases.
- Authors:
-
[5]
- Department of Molecular Biology &, Biochemistry University of California, Irvine Irvine CA 92697-3900 USA
- Department of Chemistry University of California, Davis Davis CA 95616 USA
- Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory Stanford University Menlo Park CA 94025 USA
- Stanford Synchrotron Radiation Lightsource SLAC National Accelerator Laboratory Stanford University Menlo Park CA 94025 USA, Department of Chemistry Stanford University Stanford CA 94305 USA
- Department of Molecular Biology &, Biochemistry University of California, Irvine Irvine CA 92697-3900 USA, Department Chemistry University of California, Irvine Irvine CA 92697-2025 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1560340
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 131 Journal Issue: 41; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Jasniewski, Andrew J., Wilcoxen, Jarett, Tanifuji, Kazuki, Hedman, Britt, Hodgson, Keith O., Britt, R. David, Hu, Yilin, and Ribbe, Markus W. Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9 th Sulfur”. Germany: N. p., 2019.
Web. doi:10.1002/ange.201907593.
Jasniewski, Andrew J., Wilcoxen, Jarett, Tanifuji, Kazuki, Hedman, Britt, Hodgson, Keith O., Britt, R. David, Hu, Yilin, & Ribbe, Markus W. Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9 th Sulfur”. Germany. https://doi.org/10.1002/ange.201907593
Jasniewski, Andrew J., Wilcoxen, Jarett, Tanifuji, Kazuki, Hedman, Britt, Hodgson, Keith O., Britt, R. David, Hu, Yilin, and Ribbe, Markus W. Thu .
"Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9 th Sulfur”". Germany. https://doi.org/10.1002/ange.201907593.
@article{osti_1560340,
title = {Spectroscopic Characterization of an Eight‐Iron Nitrogenase Cofactor Precursor that Lacks the “9 th Sulfur”},
author = {Jasniewski, Andrew J. and Wilcoxen, Jarett and Tanifuji, Kazuki and Hedman, Britt and Hodgson, Keith O. and Britt, R. David and Hu, Yilin and Ribbe, Markus W.},
abstractNote = {Abstract Nitrogenases catalyze the reduction of N 2 to NH 4 + at its cofactor site. Designated the M‐cluster, this [MoFe 7 S 9 C( R ‐homocitrate)] cofactor is synthesized via the transformation of a [Fe 4 S 4 ] cluster pair into an [Fe 8 S 9 C] precursor (designated the L‐cluster) prior to insertion of Mo and homocitrate. We report the characterization of an eight‐iron cofactor precursor (designated the L*‐cluster), which is proposed to have the composition [Fe 8 S 8 C] and lack the “9 th sulfur” in the belt region of the L‐cluster. Our X‐ray absorption and electron spin echo envelope modulation (ESEEM) analyses strongly suggest that the L*‐cluster represents a structural homologue to the l ‐cluster except for the missing belt sulfur. The absence of a belt sulfur from the L*‐cluster may prove beneficial for labeling the catalytically important belt region, which could in turn facilitate investigations into the reaction mechanism of nitrogenases.},
doi = {10.1002/ange.201907593},
journal = {Angewandte Chemie},
number = 41,
volume = 131,
place = {Germany},
year = {Thu Sep 05 00:00:00 EDT 2019},
month = {Thu Sep 05 00:00:00 EDT 2019}
}
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