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Molecular interactions of the quinone electron acceptors QA, QB, and QC in photosystem II as studied by the fragment molecular orbital method

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Abstract

Molecular interactions of the three plastoquinone electron acceptors, QA, QB, and QC, in photosystem II (PSII) were studied by fragment molecular orbital (FMO) calculations. Calculations at the FMO-MP2/6-31G level using PSII models deduced from the X-ray structure of the PSII complexes from Thermosynechococcus elongatus provided the binding energies of QA, QB, and QC as −56.1, −37.9, and −30.1 kcal/mol, respectively. The interaction energies with surrounding fragments showed that the contributions of lipids and cofactors were 0, 24 and 45 % of the total interaction energies for QA, QB, and QC, respectively. These results are consistent with the fact that QA is strongly bound to the PSII protein, whereas QB functions as a substrate and is exchangeable with other quinones and herbicides, and the presence of QC is highly dependent on PSII preparations. It was further shown that the isoprenoid tail is more responsible for the binding than the head group in all the three quinones, and that dispersion forces rather than electrostatic interactions mainly contribute to the stabilization. The relevance of the stability and molecular interactions of QA, QB, and QC to their physiological functions is discussed.

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Abbreviations

FMO:

Fragment molecular orbital

PQ:

Plastoquinone

PSII:

Photosystem II

P680:

Special pair chlorophylls in PSII

Pheo:

Redox-active pheophytin in PSII

Car:

β-Carotene

Chl:

Chlorophyll

Cyt:

Cytochrome

DGDG:

Digalactosyl-diacylglycerol

SQDG:

Sulfoquinovosyl-diacylglycerol

MGDG:

Monogalactosyl-diacylglycerol

PG:

Phosphatidyl-glycerol

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Acknowledgments

This study was supported by the Grants-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology (21370063, 23657099, and 24000018 to T.N.).

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Authors and Affiliations

  1. AdvanceSoft Corporation, Akasaka, Tokyo, 107-0052, Japan

    Koji Hasegawa

  2. Division of Material Science, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8602, Japan

    Takumi Noguchi

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  1. Koji Hasegawa
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  2. Takumi Noguchi
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Correspondence to Koji Hasegawa or Takumi Noguchi.

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Hasegawa, K., Noguchi, T. Molecular interactions of the quinone electron acceptors QA, QB, and QC in photosystem II as studied by the fragment molecular orbital method. Photosynth Res 120, 113–123 (2014). https://doi.org/10.1007/s11120-012-9787-9

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