Projects per year
Abstract
The reaction of protein-bound iron–sulfur (Fe-S) clusters with nitric oxide (NO) plays key roles in NO-mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe-S clusters has been hampered by a lack of information about the nature of the iron-nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe-4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe2(NO)4(Cys)2]) and Roussin's Black Salt (RBS, [Fe4(NO)7S3]. In the latter case, the absence of 32S/34S shifts in the Fe−S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.
Original language | English |
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Pages (from-to) | 14575–14579 |
Number of pages | 5 |
Journal | Angewandte Chemie-International Edition |
Volume | 55 |
Issue number | 47 |
Early online date | 25 Oct 2016 |
DOIs | |
Publication status | Published - 14 Nov 2016 |
Keywords
- gene regulation
- iron–sulfur clusters
- nitric oxide
- nuclear vibrational resonance spectroscopy
- synchrotron radiation
Profiles
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Nick Le Brun
- School of Chemistry, Pharmacy and Pharmacology - Professor of Biological Chemistry
- Centre for Molecular and Structural Biochemistry - Director
- Chemistry of Life Processes - Member
Person: Research Group Member, Academic, Teaching & Research
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Vasily Oganesyan
- School of Chemistry, Pharmacy and Pharmacology - Reader in Computational Chemistry
- Centre for Molecular and Structural Biochemistry - Member
- Centre for Photonics and Quantum Science - Member
- Chemistry of Life Processes - Member
- Chemistry of Light and Energy - Member
Person: Research Group Member, Research Centre Member, Academic, Teaching & Research
Projects
- 3 Finished
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A new pathway for iron-sulphur cluster repair
Le Brun, N., Crack, J., Thomson, A. & Cull, N.
Biotechnology and Biological Sciences Research Council
30/05/14 → 29/05/17
Project: Research
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Biological roles and mechanisms of nitric oxide reactions with iron-sulfur cluster transcriptional regulators
Le Brun, N., Hutchings, M., Thomson, A. & Cull, N.
Biotechnology and Biological Sciences Research Council
1/07/12 → 30/06/15
Project: Research