Characterization of Iron Dinitrosyl Species Formed in the Reaction of Nitric Oxide with a Biological Rieske Center
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Tinberg et al JACS.pdf
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Author(s)
Wang, Hongxin
Yoda, Yoshitaka
Cramer, Stephen P.
Tinberg, Christine E.
Tonzetich, Zachary J.
Do, Loi Hung
Lippard, Stephen J.
Date Issued
December 2010
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Tinberg, Christine E. et al. “Characterization of Iron Dinitrosyl Species Formed in the Reaction of Nitric Oxide with a Biological Rieske Center.” Journal of the American Chemical Society 132 (2010): 18168-18176. Web. 15 Dec. 2011. © 2011 American Chemical Society
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Author's final manuscript
Abstract
Reactions of nitric oxide with cysteine-ligated iron−sulfur cluster proteins typically result in disassembly of the iron−sulfur core and formation of dinitrosyl iron complexes (DNICs). Here we report the first evidence that DNICs also form in the reaction of NO with Rieske-type [2Fe-2S] clusters. Upon treatment of a Rieske protein, component C of toluene/o-xylene monooxygenase from Pseudomonas sp. OX1, with an excess of NO(g) or NO-generators S-nitroso-N-acetyl-d,l-pencillamine and diethylamine NONOate, the absorbance bands of the [2Fe-2S] cluster are extinguished and replaced by a new feature that slowly grows in at 367 nm. Analysis of the reaction products by electron paramagnetic resonance, Mössbauer, and nuclear resonance vibrational spectroscopy reveals that the primary product of the reaction is a thiolate-bridged diiron tetranitrosyl species, [Fe[subscript 2](μ-SCys)[subscript 2](NO)[subscript 4]], having a Roussin’s red ester (RRE) formula, and that mononuclear DNICs account for only a minor fraction of nitrosylated iron. Reduction of this RRE reaction product with sodium dithionite produces the one-electron-reduced RRE, having absorptions at 640 and 960 nm. These results demonstrate that NO reacts readily with a Rieske center in a protein and suggest that dinuclear RRE species, not mononuclear DNICs, may be the primary iron dinitrosyl species responsible for the pathological and physiological effects of nitric oxide in such systems in biology.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja106290p
