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Current state of the primary charge separation mechanism in photosystem I of cyanobacteria

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Abstract

This review analyzes new data on the mechanism of ultrafast reactions of primary charge separation in photosystem I (PS I) of cyanobacteria obtained in the last decade by methods of femtosecond absorption spectroscopy. Cyanobacterial PS I from many species harbours 96 chlorophyll a (Chl a) molecules, including six specialized Chls denoted Chl1A/Chl1B (dimer P700, or PAPB), Chl2A/Chl2B, and Chl3A/Chl3B arranged in two branches, which participate in electron transfer reactions. The current data indicate that the primary charge separation occurs in a symmetric exciplex, where the special pair P700 is electronically coupled to the symmetrically located monomers Chl2A and Chl2B, which can be considered together as a symmetric exciplex Chl2APAPBChl2B with the mixed excited (Chl2APAPBChl2B)* and two charge-transfer states P700+Chl2A and P700+Chl2B. The redistribution of electrons between the branches in favor of the A-branch occurs after reduction of the Chl2A and Chl2B monomers. The formation of charge-transfer states and the symmetry breaking mechanisms were clarified by measuring the electrochromic Stark shift of β-carotene and the absorption dynamics of PS I complexes with the genetically altered Chl2B or Chl2A monomers. The review gives a brief description of the main methods for analyzing data obtained using femtosecond absorption spectroscopy. The energy levels of excited and charge-transfer intermediates arising in the cyanobacterial PS I are critically analyzed.

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Acknowledgments

This work was supported by Lomonosov Moscow State University Program of Development. Optical measurements were performed using core research facilities of FRCCP RAS (no. 1440743, 506694).

Funding

This work was supported by the Russian Science Foundation Grant RSF 22–24-00705.

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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by Fedor E. Gostev, Ivan V. Shelaev, Mahir D. Mamedov, Arseniy V. Aybush, Alexey Yu. Semenov, Vladimir A. Shuvalov and Victor A. Nadtochenko. The first draft of the manuscript was written by Dmitry A. Cherepanov and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Victor A. Nadtochenko.

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Cherepanov, D.A., Semenov, A.Y., Mamedov, M.D. et al. Current state of the primary charge separation mechanism in photosystem I of cyanobacteria. Biophys Rev 14, 805–820 (2022). https://doi.org/10.1007/s12551-022-00983-1

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  • DOI: https://doi.org/10.1007/s12551-022-00983-1

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