title: Photochemical Tyrosine Oxidation with a Hydrogen-Bonded Proton Acceptor by Bidirectional Proton-Coupled Electron Transfer.
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.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139-4307; Tel: 61d53 5537.
authors.forename: Arturo A
authors.initials: AA
authors.lastname: Pizano
authors.forename: Jay L
authors.initials: JL
authors.lastname: Yang
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Nocera