Proton-coupled electron transfer in a model for tyrosine oxidation in photosystem II

J Am Chem Soc. 2003 Aug 27;125(34):10429-36. doi: 10.1021/ja035588z.

Abstract

Theoretical calculations of a model for tyrosine oxidation in photosystem II are presented. In this model system, an electron is transferred to ruthenium from tyrosine, which is concurrently deprotonated. This investigation is motivated by experimental measurements of the dependence of the rates on pH and temperature (Sjödin et al. J. Am. Chem. Soc. 2000, 122, 3932). The mechanism is proton-coupled electron transfer (PCET) at pH < 10 when the tyrosine is initially protonated and is single electron transfer (ET) for pH > 10 when the tyrosine is initially deprotonated. The PCET rate increases monotonically with pH, whereas the single ET rate is independent of pH and is 2 orders of magnitude faster than the PCET rate. The calculations reproduce these experimentally observed trends. The pH dependence for the PCET reaction arises from the decrease in the reaction free energies with pH. The calculations indicate that the larger rate for single ET arises from a combination of factors, including the smaller solvent reorganization energy for ET and the averaging of the coupling for PCET over the reactant and product hydrogen vibrational wave functions (i.e., a vibrational overlap factor in the PCET rate expression). The temperature dependence of the rates, the solvent reorganization energies, and the deuterium kinetic isotope effects determined from the calculations are also consistent with the experimental results.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Hydrogen-Ion Concentration
  • Kinetics
  • Models, Chemical
  • Models, Molecular
  • Oxidation-Reduction
  • Photosystem II Protein Complex / chemistry*
  • Photosystem II Protein Complex / metabolism*
  • Temperature
  • Thermodynamics
  • Tyrosine / chemistry*
  • Tyrosine / metabolism*

Substances

  • Photosystem II Protein Complex
  • Tyrosine