Distribution of the cationic state over the chlorophyll pair of the photosystem II reaction center

Keisuke Saito, Toyokazu Ishida, Miwa Sugiura, Keisuke Kawakami, Yasufumi Umena, Nobuo Kamiya, Jian Ren Shen, Hiroshi Ishikita

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

The reaction center chlorophylls a (Chla) of photosystem II (PSII) are composed of six Chla molecules including the special pair Chla P D1/P D2 harbored by the D1/D2 heterodimer. They serve as the ultimate electron abstractors for water oxidation in the oxygen-evolving Mn 4CaO 5 cluster. Using the PSII crystal structure analyzed at 1.9 Å resolution, the redox potentials of P D1/P D2 for one-electron oxidation (E m) were calculated by considering all PSII subunits and the protonation pattern of all titratable residues. The E m(Chla) values were calculated to be 1015-1132 mV for P D1 and 1141-1201 mV for P D2, depending on the protonation state of the Mn 4CaO 5 cluster. The results showed that E m(P D1) was lower than E m(P D2), favoring localization of the charge of the cationic state more on P D1. The P D1 •+/P D2 •+ charge ratio determined by the large-scale QM/MM calculations with the explicit PSII protein environment yielded a P D1 •+/P D2 •+ ratio of ∼80/∼20, which was found to be due to the asymmetry in electrostatic characters of several conserved D1/D2 residue pairs that cause the E m(P D1)/E m(P D2) difference, e.g., D1-Asn181/D2-Arg180, D1-Asn298/D2-Arg294, D1-Asp61/D2-His61, D1-Glu189/D2-Phe188, and D1-Asp170/D2-Phe169. The larger P D1 •+ population than P D2 •+ appears to be an inevitable fate of the intact PSII that possesses water oxidation activity.

Original languageEnglish
Pages (from-to)14379-14388
Number of pages10
JournalJournal of the American Chemical Society
Volume133
Issue number36
DOIs
Publication statusPublished - Sep 14 2011

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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