Mechanism of photosynthetic water oxidation: Combining biophysical studies of photosystem II with inorganic model chemistry

John S. Vrettos, Julian Limburg, Gary W Brudvig

Research output: Contribution to journalArticle

237 Citations (Scopus)

Abstract

A mechanism for photosynthetic water oxidation is proposed based on a structural model of the oxygen-evolving complex (OEC) and its placement into the modeled structure of the D1/D2 core of photosystem II. The structural model of the OEC satisfies many of the geometrical constraints imposed by spectroscopic and biophysical results. The model includes the tetranuclear manganese cluster, calcium, chloride, tyrosine Z, H190, D170, H332 and H337 of the D1 polypeptide and is patterned after the reversible O2-binding diferric site in oxyhemerythrin. The mechanism for water oxidation readily follows from the structural model. Concerted proton-coupled electron transfer in the S2→S3 and S3→S4 transitions forms a terminal Mn(V)=O moiety. Nucleophilic attack on this electron-deficient Mn(V)=O by a calcium-bound water molecule results in a Mn(III)-OOH species, similar to the ferric hydroperoxide in oxyhemerythrin. Dioxygen is released in a manner analogous to that in oxyhemerythrin, concomitant with reduction of manganese and protonation of a μ-oxo bridge. Copyright (C) 2001 .

Original languageEnglish
Pages (from-to)229-245
Number of pages17
JournalBiochimica et Biophysica Acta - Bioenergetics
Volume1503
Issue number1-2
DOIs
Publication statusPublished - Jan 5 2001

Keywords

  • Calcium
  • Chloride
  • Manganese
  • Oxygen-evolving complex
  • Photosystem II
  • Tyrosyl radical
  • Water oxidation

ASJC Scopus subject areas

  • Biophysics

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