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Primary light-energy conversion in tetrameric chlorophyll structure of photosystem II and bacterial reaction centers: II. Femto- and picosecond charge separation in PSII D1/D2/Cyt b559 complex

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Abstract

In Part I of the article, a review of recent data on electron-transfer reactions in photosystem II (PSII) and bacterial reaction center (RC) has been presented. In Part II, transient absorption difference spectroscopy with 20-fs resolution was applied to study the primary charge separation in PSII RC (DI/DII/Cyt b 559 complex) excited at 700 nm at 278 K. It was shown that the initial electron-transfer reaction occurs within 0.9 ps with the formation of the charge-separated state P680+ChlD1 −, which relaxed within 14 ps as indicated by reversible bleaching of 670-nm band that was tentatively assigned to the ChlD1 absorption. The subsequent electron transfer from ChlD1 − within 14 ps was accompanied by a development of the radical anion band of PheoD1 at 445 nm, attributable to the formation of the secondary radical pair P680+PheoD1 −. The key point of this model is that the most blue Q y transition of ChlD1 in RC is allowing an effective stabilization of separated charges. Although an alternative mechanism of charge separation with ChlD1* as a primary electron donor and PheoD1 as a primary acceptor can not be ruled out, it is less consistent with the kinetics and spectra of absorbance changes induced in the PSII RC preparation by femtosecond excitation at 700 nm.

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Abbreviations

BA :

Bacteriochlorophyll, primary electron acceptor in BRC

BRC:

Bacterial reaction center

D1/D2/Cytb559:

PSII RC

CD:

Circular dichroism

Chl:

Chlorophyll a

ChlD1 :

Chl located in D1 protein subunit

ET:

Electron transfer

HOMO:

Highest occupied molecular orbital

LUMO:

Lowest unoccupied molecular orbital

Pheo:

Pheophytin a

PheoD1 :

Pheo located in D1 protein subunit

PSII:

Photosystem II

QA :

Primary plastoquinone electron acceptor

RC:

Reaction center

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Acknowledgments

We thank Prof. VV Klimov for preparations of PSII RC and for discussion, and MM Leonova for assistance in manuscript preparation. This work was supported by MCB and “Femtosecond optics and new optical materials”grants from the Russian Academy of Sciences, by the State contract 02.512.11.2085, by the President of RF grant SS-4525.2008.4 and by RFFI grants.

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Authors and Affiliations

  1. NN Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117991, Moscow, Russia

    I. V. Shelaev, F. E. Gostev, V. A. Nadtochenko & O. M. Sarkisov

  2. Institute of Basic Biological Problems, Russian Academy of Sciences, Pushchino, Moscow Region, 142290, Russia

    A. Ya. Shkuropatov, A. A. Zabelin & V. A. Shuvalov

  3. AN Belosersky Institute of Physical–Chemical Biology, Moscow State University, 119992, Moscow, Russia

    M. D. Mamedov & A. Yu. Semenov

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  1. I. V. Shelaev
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  2. F. E. Gostev
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  3. V. A. Nadtochenko
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  4. A. Ya. Shkuropatov
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  5. A. A. Zabelin
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  6. M. D. Mamedov
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  7. A. Yu. Semenov
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  8. O. M. Sarkisov
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  9. V. A. Shuvalov
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Correspondence to V. A. Shuvalov.

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Shelaev, I.V., Gostev, F.E., Nadtochenko, V.A. et al. Primary light-energy conversion in tetrameric chlorophyll structure of photosystem II and bacterial reaction centers: II. Femto- and picosecond charge separation in PSII D1/D2/Cyt b559 complex. Photosynth Res 98, 95–103 (2008). https://doi.org/10.1007/s11120-008-9371-5

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