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

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [3];  [3];  [4];  [3];  [5];  [6];  [7];  [7];  [7];  [3];  [3];  [2]
  1. Department of Chemistry, University of California, Davis CA 95616 USA
  2. Department of Chemistry, University of California, Davis CA 95616 USA; 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
+ Show Author Affiliations

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Biotechnology and Biological Sciences Research Council (BBSRC); National Institutes of Health (NIH); USDOE Office of Science (SC)
DOE Contract Number:
AC02-06CH11357
OSTI ID:
1393198
Journal Information:
Angewandte Chemie (International Edition), Vol. 55, Issue 47; ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English

References (35)

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Hydride bridge in [NiFe]-hydrogenase observed by nuclear resonance vibrational spectroscopy journal August 2015

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