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Picosecond Photoreduction of Inducible Nitric Oxide Synthase by Rhenium(I)−Diimine Wires

Belliston-Bittner, Wendy and Dunn, Alexander R. and Nguyen, Yen Hoang Le and Stuehr, Dennis J. and Winkler, Jay R. and Gray, Harry B. (2005) Picosecond Photoreduction of Inducible Nitric Oxide Synthase by Rhenium(I)−Diimine Wires. Journal of the American Chemical Society, 127 (45). pp. 15907-15915. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170516-102144501

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Abstract

In a continuing effort to unravel mechanistic questions associated with metalloenzymes, we are developing methods for rapid delivery of electrons to deeply buried active sites. Herein, we report picosecond reduction of the heme active site of inducible nitric oxide synthase bound to a series of rhenium−diimine electron-tunneling wires, [Re(CO)_3LL‘]^+, where L is 4,7-dimethylphenanthroline and L‘ is a perfluorinated biphenyl bridge connecting a rhenium-ligated imidazole or aminopropylimidazole to a distal imidazole (F_8bp-im (1) and C_3-F_8bp-im (2)) or F (F_9bp (3) and C_3-F_9bp (4)). All four wires bind tightly (K_d in the micromolar to nanomolar range) to the tetrahydrobiopterin-free oxidase domain of inducible nitric oxide synthase (iNOSoxy). The two fluorine-terminated wires displace water from the active site, and the two imidazole-terminated wires ligate the heme iron. Upon 355-nm excitation of iNOSoxy conjugates with 1 and 2, the active site Fe(III) is reduced to Fe(II) within 300 ps, almost 10 orders of magnitude faster than the naturally occurring reduction.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0543088DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja0543088PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja0543088PublisherSupporting Information
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2005 American Chemical Society. Received 29 June 2005. Published online 19 October 2005. Published in print 1 November 2005. This research was supported by NIH (DK19038; GM070868), the Parsons Foundation (W.B.-B.), the Fannie and John Hertz Foundation (A.R.D.), the Ellison Medical Foundation (Senior Scholar Award in Aging to H.B.G.), and the Arnold and Mabel Beckman Foundation.
Funders:
Funding AgencyGrant Number
NIHDK19038
NIHGM070868
Ralph M. Parsons FoundationUNSPECIFIED
Fannie and John Hertz FoundationUNSPECIFIED
Ellison Medical FoundationUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
Issue or Number:45
Record Number:CaltechAUTHORS:20170516-102144501
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170516-102144501
Official Citation:Picosecond Photoreduction of Inducible Nitric Oxide Synthase by Rhenium(I)−Diimine Wires Wendy Belliston-Bittner, Alexander R. Dunn, Yen Hoang Le Nguyen, Dennis J. Stuehr, Jay R. Winkler, and Harry B. Gray Journal of the American Chemical Society 2005 127 (45), 15907-15915 DOI: 10.1021/ja0543088
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77495
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:16 May 2017 17:35
Last Modified:22 Nov 2019 09:58

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