Genetically introduced hydrogen bond interactions reveal an asymmetric charge distribution on the radical cation of the special-pair chlorophyll P680

Ryo Nagao, Motoki Yamaguchi, Shin Nakamura, Hanayo Ueoka-Nakanishi, Takumi Noguchi

Research output: Contribution to journalArticle

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Abstract

The special-pair chlorophyll (Chl) P680 in photosystem II has an extremely high redox potential (Em) to enable water oxidation in photosynthesis. Significant positive-charge localization on one of the Chl constituents, PD1 or PD2, in P680+ has been proposed to contribute to this high Em. To identify the Chl molecule on which the charge is mainly localized, we genetically introduced a hydrogen bond to the 131-keto C=O group of PD1 and PD2 by changing the nearby D1-Val-157 and D2-Val-156 residues to His, respectively. Successful hydrogen bond formation at PD1 and PD2 in the obtained D1-V157H and D2-V156H mutants, respectively, was monitored by detecting 131-keto C=O vibrations in Fourier transfer infrared (FTIR) difference spectra upon oxidation of P680 and the symmetrically located redox-active tyrosines YZ and YD, and they were simulated by quantum-chemical calculations. Analysis of the P680+/P680 FTIR difference spectra of D1-V157H and D2-V156H showed that upon P680+ formation, the 131-keto C=O frequency upshifts by a much larger extent in PD1 (23 cm-1) than in PD2 (<9 cm-1). In addition, thermoluminescence measurements revealed that the D1-V157H mutation increased the Em of P680 to a larger extent than did the D2-V156H mutation. These results, together with the previous results for the mutants of the His ligands of PD1 and PD2, lead to a definite conclusion that a charge is mainly localized to PD1 in P680+.

Original languageEnglish
Pages (from-to)7474-7486
Number of pages13
JournalJournal of Biological Chemistry
Volume292
Issue number18
DOIs
Publication statusPublished - May 5 2017
Externally publishedYes

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Charge distribution
Chlorophyll
Cations
Hydrogen
Hydrogen bonds
Oxidation-Reduction
Infrared radiation
Oxidation
Mutation
Thermoluminescence
Photosystem II Protein Complex
Photosynthesis
Vibration
Tyrosine
Ligands
Molecules
Water

ASJC Scopus subject areas

  • Biochemistry
  • Molecular Biology
  • Cell Biology

Cite this

Genetically introduced hydrogen bond interactions reveal an asymmetric charge distribution on the radical cation of the special-pair chlorophyll P680. / Nagao, Ryo; Yamaguchi, Motoki; Nakamura, Shin; Ueoka-Nakanishi, Hanayo; Noguchi, Takumi.

In: Journal of Biological Chemistry, Vol. 292, No. 18, 05.05.2017, p. 7474-7486.

Research output: Contribution to journalArticle

Nagao, Ryo ; Yamaguchi, Motoki ; Nakamura, Shin ; Ueoka-Nakanishi, Hanayo ; Noguchi, Takumi. / Genetically introduced hydrogen bond interactions reveal an asymmetric charge distribution on the radical cation of the special-pair chlorophyll P680. In: Journal of Biological Chemistry. 2017 ; Vol. 292, No. 18. pp. 7474-7486.
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