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Probing the heme-thiolate oxygenase domain of inducible nitric oxide synthase with Ru(II) and Re(I) electron tunneling wires

Whited, Charlotte A. and Belliston-Bittner, Wendy and Dunn, Alexander R. and Winkler, Jay R. and Gray, Harry B. (2008) Probing the heme-thiolate oxygenase domain of inducible nitric oxide synthase with Ru(II) and Re(I) electron tunneling wires. Journal of Porphyrins and Phthalocyanines, 12 (9). pp. 971-978. ISSN 1088-4246. PMCID PMC2744429. https://resolver.caltech.edu/CaltechAUTHORS:WHIjpp08

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Abstract

Nitric oxide synthase (NOS) catalyzes the production of nitric oxide from L-arginine and dioxygen at a thiolate-ligated heme active site. Although many of the reaction intermediates are as yet unidentified, it is well established that the catalytic cycle begins with substrate binding and rate-limiting electron transfer to the heme. Here, we show that Ru(II)-diimine and Re(I)-diimine electron tunneling wires trigger nanosecond photoreduction of the active-site heme in the enzyme. Very rapid generation of a reduced thiolate-ligated heme opens the way for direct observation of short-lived intermediates in the NOS reaction cycle.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1142/S1088424608000352DOIArticle
http://www.worldscientific.com/doi/abs/10.1142/S1088424608000352PublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2744429PubMed CentralArticle
ORCID:
AuthorORCID
Dunn, Alexander R.0000-0001-6096-4600
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2008 Society of Porphyrins & Phthalocyanines. Received 19 September 2008. Accepted 28 September 2008. Our work is supported by the NIH (DK 19038 and GM070868 to HBG; GM068461 to JRW); the Ellison Medical Foundation (Senior Scholar Award in Aging to HBG); an NSF graduate fellowship (CAW); the Fannie and John Hertz Foundation (ARO); the Parsons Foundation (WBB); and the Arnold and Mabel Beckman Foundation.
Funders:
Funding AgencyGrant Number
NIHDK 19038
NIHGM070868
NIHGM068461
NSFUNSPECIFIED
Fannie and John Hertz FoundationUNSPECIFIED
Ralph M. Parsons FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Subject Keywords:rhenium(I)-diimine wires; photoinduced oxidation; tetrahydrobiopterin; cytochrome-P450; mechanism; pterin; chemistry; ligands; probes
Issue or Number:9
PubMed Central ID:PMC2744429
Record Number:CaltechAUTHORS:WHIjpp08
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:WHIjpp08
Official Citation:Probing the heme-thiolate oxygenase domain of inducible nitric oxide synthase with Ru(II) and Re(I) electron tunneling wires Charlotte A. Whited, Wendy Belliston-Bittner, Alexander R. Dunn, Jay R. Winkler, and Harry B. Gray Journal of Porphyrins and Phthalocyanines 2008 12:09, 971-978
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:13376
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 Apr 2009 17:19
Last Modified:18 Feb 2021 23:42

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