Unique binding site for Mn2+ ion responsible for reducing an oxidized YZ tyrosine in manganese-depleted photosystem II membranes

Biochemistry. 1999 Jul 6;38(27):8778-85. doi: 10.1021/bi982949s.

Abstract

Binding of Mn2+ to manganese-depleted photosystem II and electron donation from the bound Mn2+ to an oxidized YZ tyrosine were studied under the same equilibrium conditions. Mn2+ associated with the depleted membranes in a nonsaturating manner when added alone, but only one Mn2+ ion per photosystem II (PS II) was bound to the membranes in the presence of other divalent cations including Ca2+ and Mg2+. Mn2+-dependent electron donation to photosystem II studied by monitoring the decay kinetics of chlorophyll fluorescence and the electron paramagnetic resonance (EPR) signal of an oxidized YZ tyrosine (YZ+) after a single-turnover flash indicated that the binding of only one Mn2+ ion to the manganese-depleted PS II is sufficient for the complete reduction of YZ+ induced by flash excitation. The results indicate that the manganese-depleted membranes have only one unique binding site, which has higher affinity and higher specificity for Mn2+ compared with Mg2+ and Ca2+, and that Mn2+ bound to this unique site can deliver an electron to YZ+ with high efficiency. The dissociation constant for Mn2+ of this site largely depended on pH, suggesting that a single amino acid residue with a pKa value around neutral pH is implicated in the binding of Mn2+. The results are discussed in relation to the photoactivation mechanism that forms the active manganese cluster.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Binding Sites
  • Chlorophyll / chemistry
  • Chlorophyll / metabolism
  • Chlorophyll A
  • Chloroplasts / chemistry
  • Chloroplasts / metabolism
  • Free Radicals / chemistry
  • Free Radicals / metabolism
  • Intracellular Membranes / chemistry
  • Intracellular Membranes / metabolism*
  • Kinetics
  • Light-Harvesting Protein Complexes
  • Manganese / chemistry
  • Manganese / metabolism*
  • Oxidation-Reduction
  • Photolysis
  • Photosynthetic Reaction Center Complex Proteins / chemistry
  • Photosynthetic Reaction Center Complex Proteins / metabolism*
  • Photosystem II Protein Complex
  • Spectrometry, Fluorescence
  • Spinacia oleracea
  • Tyrosine / analogs & derivatives*
  • Tyrosine / chemistry
  • Tyrosine / metabolism

Substances

  • Free Radicals
  • Light-Harvesting Protein Complexes
  • Photosynthetic Reaction Center Complex Proteins
  • Photosystem II Protein Complex
  • tyrosyl radical YZ
  • Chlorophyll
  • Tyrosine
  • Manganese
  • Chlorophyll A