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Spectroscopy and Reactivity of a Photogenerated Tryptophan Radical in a Structurally Defined Protein Environment

Miller, Jeremiah E. and Grǎdinaru, Cristian and Crane, Brian R. and Di Bilio, Angel J. and Wehbi, William A. and Un, Sun and Winkler, Jay R. and Gray, Harry B. (2003) Spectroscopy and Reactivity of a Photogenerated Tryptophan Radical in a Structurally Defined Protein Environment. Journal of the American Chemical Society, 125 (47). pp. 14220-14221. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170419-130606164

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Abstract

Near-UV irradiation of structurally characterized [Re(I)(CO)_3(1,10-phenanthroline)(Q107H)](W48F/Y72F/H83Q/Y108W)AzM(II) [Az = Pseudomonas aeruginosa azurin, M = Cu, Zn]/[Co(NH_3)_5Cl]Cl_2 produces a tryptophan radical (W108•) with unprecedented kinetic stability. After rapid formation (k = 2.8 × 10^6 s^(-1)), the radical persists for more than 5 h at room temperature in the folded ReAzM(II) structure. The absorption spectrum of ReAz(W108•)M(II) exhibits maxima at 512 and 536 nm. Oxidation of K_4[Mo(CN)_8] by ReAz(W108•)Zn(II) places the W108•/W108 reduction potential in the protein above 0.8 V vs NHE.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja037203iDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja037203iPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja037203iPublisherSupporting Information
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2003 American Chemical Society. Received 10 July 2003. Published online 1 November 2003. Published in print 1 November 2003. Randy Villahermosa assisted with the transient absorption measurements. J.E.M. thanks the Parsons Foundation for a graduate fellowship. Work at Cornell was supported by NSF (MCB0133546); work at Caltech was supported by NIH (DK19038).
Funders:
Funding AgencyGrant Number
NSFMCB-0133546
NIHDK19038
Issue or Number:47
Record Number:CaltechAUTHORS:20170419-130606164
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170419-130606164
Official Citation:Spectroscopy and Reactivity of a Photogenerated Tryptophan Radical in a Structurally Defined Protein Environment Jeremiah E. Miller, Cristian Grǎdinaru, Brian R. Crane, Angel J. Di Bilio, William A. Wehbi, Sun Un, Jay R. Winkler, and Harry B. Gray Journal of the American Chemical Society 2003 125 (47), 14220-14221 DOI: 10.1021/ja037203i
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76695
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Apr 2017 21:51
Last Modified:22 Nov 2019 09:58

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