Orientation of calcium in the Mn4Ca cluster of the oxygen-evolving complex determined using polarized strontium EXAFS of photosystem II membranes

Biochemistry. 2004 Oct 26;43(42):13271-82. doi: 10.1021/bi036308v.

Abstract

The oxygen-evolving complex of photosystem II (PS II) in green plants and algae contains a cluster of four Mn atoms in the active site, which catalyzes the photoinduced oxidation of water to dioxygen. Along with Mn, calcium and chloride ions are necessary cofactors for proper functioning of the complex. The current study using polarized Sr EXAFS on oriented Sr-reactivated samples shows that Fourier peak II, which fits best to Mn at 3.5 A rather than lighter atoms (C, N, O, or Cl), is dichroic, with a larger magnitude at 10 degrees (angle between the PS II membrane normal and the X-ray electric field vector) and a smaller magnitude at 80 degrees . Analysis of the dichroism of the Sr EXAFS yields a lower and upper limit of 0 degrees and 23 degrees for the average angle between the Sr-Mn vectors and the membrane normal and an isotropic coordination number (number of Mn neighbors to Sr) of 1 or 2 for these layered PS II samples. The results confirm the contention that Ca (Sr) is proximal to the Mn cluster and lead to refined working models of the heteronuclear Mn(4)Ca cluster of the oxygen-evolving complex in PS II.

Publication types

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

MeSH terms

  • Calcium / chemistry*
  • Calcium / metabolism
  • Catalytic Domain
  • Electron Spin Resonance Spectroscopy
  • Fourier Analysis
  • Free Radicals / chemistry
  • Free Radicals / metabolism
  • Manganese / chemistry*
  • Manganese / metabolism
  • Models, Chemical
  • Models, Molecular
  • Normal Distribution
  • Oxygen / chemistry
  • Oxygen / metabolism*
  • Photosystem II Protein Complex / chemistry*
  • Photosystem II Protein Complex / metabolism
  • Spectrum Analysis / methods
  • Spectrum Analysis / statistics & numerical data
  • Spinacia oleracea
  • Strontium / chemistry
  • Tyrosine / analogs & derivatives*
  • Tyrosine / chemistry
  • Tyrosine / metabolism
  • X-Rays

Substances

  • Free Radicals
  • Photosystem II Protein Complex
  • tyrosyl radical Y(D)
  • Tyrosine
  • Manganese
  • Oxygen
  • Calcium
  • Strontium