Photochemical tyrosine oxidation with a hydrogen-bonded proton acceptor by bidirectional proton-coupled electron transfer

Autor:	Daniel G. Nocera, Arturo A. Pizano, Jay L. Yang
Přispěvatelé:	Massachusetts Institute of Technology. Department of Chemistry, Pizano, Arturo Alejandro, Yang, Jay L., Nocera, Daniel G.
Rok vydání:	2012
Předmět:	Quenching Electron transfer chemistry Hydrogen Yield (chemistry) chemistry.chemical_element General Chemistry Tyrosine Rhenium Proton-coupled electron transfer Photochemistry Small molecule Article
Zdroj:	PMC
ISSN:	2041-6539 2041-6520
Popis:	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. National Institutes of Health (U.S.) (GM47274)
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::714298e9f02a1940dc1767a1aac468b5 https://doi.org/10.1039/c2sc20113e Zobrazit plný text záznamu