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Tunneling in PSII.

Christopher C Moser1, Christopher C Page, P Leslie Dutton

  • 1Department of Biochemistry and Biophysics, University of Pennsylvania, Philadelphia, PA 19104-6059, USA. moserc@mail.med.upenn.edu

Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology
|November 25, 2005
PubMed
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Electron transfer in Photosystem II (PSII) is primarily limited by electron tunneling, not bond changes. Simulations suggest rapid charge recombination between pheophytin and chlorophyll may occur.

Area of Science:

  • Biophysics
  • Photosynthesis research
  • Electron transfer mechanisms

Background:

  • High-resolution structures of Photosystem II (PSII) and known redox potentials of cofactors are available.
  • Estimating electron tunneling rates requires reliable reorganization energies, which are lacking for PSII compared to other systems.

Purpose of the Study:

  • To compare theoretical electron tunneling rates with experimental data in PSII.
  • To identify electron transfer reactions governed by simple tunneling versus those involving complex rearrangements or bond changes.

Main Methods:

  • Utilizing available high-resolution PSII structures and cofactor redox midpoint potentials.
  • Comparing calculated electron tunneling rates with experimental observations.
  • Employing tunneling simulations to assess charge recombination pathways.

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Main Results:

  • Most electron transfers in PSII, excluding the oxygen evolving center, appear to be electron-tunneling limited at room temperature.
  • Uncertainty in tunneling rate estimates is significant due to a lack of reorganization energies.

Conclusions:

  • Electron tunneling is the predominant mechanism for electron transfer in PSII at room temperature.
  • Charge recombination from Q(A)(-) may be influenced by a fast electron transfer between pheophytin and chlorophyll cation.