Photochemical tyrosine oxidation with a hydrogen-bonded proton acceptor by bidirectional proton-coupled electron transfer
Name
Nocera_Photochemical tyrosine.pdf
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1.42 MB
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2de33c1e24eee120f9c2fc442088e9fa
Author(s)
Yang, Jay L.
Nocera, Daniel G.
Pizano, Arturo Alejandro
Date Issued
May 2012
Journal
Chemical Science
Publisher
Royal Society of Chemistry, The
Citation
Pizano, Arturo A., Jay L. Yang, and Daniel G. Nocera. “Photochemical tyrosine oxidation with a hydrogen-bonded proton acceptor by bidirectional proton-coupled electron transfer.” Chemical Science 3, no. 8 (2012): 2457.
Version
Author's final manuscript
Abstract
Amino acid radical generation and transport are fundamentally important to numerous essential biological processes to which small molecule models lend valuable mechanistic insights. Pyridyl-amino acid-methyl esters are appended to a rhenium(I) tricarbonyl 1,10-phenanthroline core to yield rhenium–amino acid complexes with tyrosine ([Re]–Y–OH) and phenylalanine ([Re]–F). The emission from the [Re] center is more significantly quenched for [Re]–Y–OH upon addition of base. Time-resolved studies establish that excited-state quenching occurs by a combination of static and dynamic mechanisms. The degree of quenching depends on the strength of the base, consistent with a proton-coupled electron transfer (PCET) quenching mechanism. Comparative studies of [Re]–Y–OH and [Re]–F enable a detailed mechanistic analysis of a bidirectional PCET process.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-Noncommercial-Share Alike 3.0
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DOI of Published Version
https://doi.org/10.1039/c2sc20113e
