Bimolecular proton-coupled electron transfer from tryptophan with water as the proton acceptor

Ming Tian Zhang, Johan Nilsson, Leif Hammarström

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Proton-coupled electron transfer (PCET) from amino acids with water as the primary proton acceptor is a fundamental model reaction of wide relevance. We have investigated the kinetics and mechanism of PCET from tryptophan derivatives to laser flash-generated [Ru(bpy)3]3+ oxidants in aqueous solutions. The PCET reaction followed either a concerted electron-proton transfer (CEP) mechanism or a step-wise electron transfer-proton transfer (ETPT) mechanism, depending on pH and the identity of the RuIII oxidant. The CEP reaction showed a pH-dependent rate constant, with an increase in log kCEP of 0.3-0.5 per pH unit, and a significant kinetic isotope effect (KIE = 2-4), both in intramolecular and bimolecular model systems. Our results suggest that CEP with water as the proton acceptor is a general feature of amino acid oxidation, and provide further experimental observations towards a detailed understanding of the PCET process in water.

Original languageEnglish
Pages (from-to)7732-7736
Number of pages5
JournalEnergy and Environmental Science
Volume5
Issue number7
DOIs
Publication statusPublished - Jul 2012

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Tryptophan
Protons
electron
Proton transfer
Electrons
Water
water
Oxidants
oxidant
Amino acids
amino acid
Amino Acids
kinetics
Kinetics
Isotopes
Rate constants
aqueous solution
laser
isotope
Derivatives

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Environmental Chemistry
  • Pollution
  • Nuclear Energy and Engineering

Cite this

Bimolecular proton-coupled electron transfer from tryptophan with water as the proton acceptor. / Zhang, Ming Tian; Nilsson, Johan; Hammarström, Leif.

In: Energy and Environmental Science, Vol. 5, No. 7, 07.2012, p. 7732-7736.

Research output: Contribution to journalArticle

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