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Angew Chem Int Ed Engl. 2016 Nov 14;55(47):14575-14579. doi: 10.1002/anie.201607033. Epub 2016 Oct 25.

Nitrosylation of Nitric-Oxide-Sensing Regulatory Proteins Containing [4Fe-4S] Clusters Gives Rise to Multiple Iron-Nitrosyl Complexes.

Author information

1
Department of Chemistry, University of California, Davis, CA, 95616, USA.
2
Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
3
Centre for Molecular and Structural Biochemistry, School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, UK.
4
School of Biological Sciences, University of East Anglia, Norwich, NR4 7TJ, UK.
5
University of Tennessee Space Institute, Tullahome, TN, 37388-9700, USA.
6
Research and Utilization Division, SPring-8/JASRI, 1-1-1 Kouto, Sayo, Hyogo, 679-5198, Japan.
7
Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439, USA.

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)7 S3 ]. In the latter case, the absence of 32 S/34 S 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.

KEYWORDS:

gene regulation; iron-sulfur clusters; nitric oxide; nuclear vibrational resonance spectroscopy; synchrotron radiation

PMID:
27778474
PMCID:
PMC5204455
DOI:
10.1002/anie.201607033
[Indexed for MEDLINE]
Free PMC Article

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