Proton-coupled electron transfer of tyrosine oxidation: Buffer dependence and parallel mechanisms

Tania Irebo, Steven Y. Reece, Martin Sjödin, Daniel G. Nocera*, Leif Hammarstrom

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

184 Citations (Scopus)


The proton-coupled electron transfer (PCET) from tyrosine covalently linked to a metal complex has been studied. The reaction was induced by laser flash excitation of the metal complex, and PCET was bidirectional, with electron transfer to the excited or flash-quenched oxidized metal complex and proton transfer to water or added buffers in the solution. We found a competition between three different PCET mechanisms: (1) A concerted PCET with water as the proton acceptor, which indeed shows a pH-dependence as earlier reported (Sjödin, M.; Styring, S.; Åkermark, B.; Sun, L.; Hammarström, L. J. Am. Chem. Soc. 2000, 122, 3932); (2) a stepwise electron transfer-proton transfer (ETPT) that is pH-independent; (3) a buffer-assisted concerted PCET. The relative importance of reaction 2 increases with oxidant strength, while that of reaction 1 increases with pH. At higher buffer concentrations reaction 3 becomes important, and the rate follows the expected first-order dependence on the concentration of the buffer base. Most importantly, the pH-dependence of reaction 1, with a slope of 0.4-0.5 in a plot of logk vs pH, is independent of buffer and cannot be explained by reaction schemes with simple first-order dependencies on [OH-], [H3O+], or buffer species.

Original languageEnglish
Pages (from-to)15462-15464
Number of pages3
JournalJournal of the American Chemical Society
Issue number50
Publication statusPublished - 2007 Dec 19
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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