Abstract
The paper reports on the absorption dynamics of chlorophyll a in a symmetric tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP. It was measured by a broadband femtosecond laser pump-probe spectroscopy within the range from 400 to 750 nm and with a time resolution of 20 fs-200 ps. When BoWSCP was excited in the region of the Soret band at a wavelength of 430 nm, nonradiative intramolecular conversion S3→S1 was observed with a characteristic time of 83 ± 9 fs. When the complex was excited in the region of the Qy band at 670 nm, relaxation transition between two excitonic states of the chlorophyll dimer was observed in the range of 105 ± 10 fs. Absorption spectra of the excited singlet states S1 and S3 of chlorophyll a were obtained. The delocalization of the excited state between exciton-coupled Chl molecules in BoWSCP tetramer changed in time and depended on the excitation energy. When BoWSCP is excited in the Soret band region, an ultrafast photochemical reaction is observed. This could result from the reduction of tryptophan in the vicinity of chlorophyll.
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Abbreviations
- BoWSCP:
-
water-soluble chlorophyll-binding protein (WSCP) from Brassica oleracea var. botrytis
- Chl:
-
chlorophyll
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Acknowledgments
The authors thank A. L. Dobryakov for assistance in developing the coherent artifact approximation method and setting the femtosecond device. In this paper the equipment (the femtosecond device) provided by the Center for Collective Use of N. N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences “Analysis of Chemical and Biological Systems and Natural Materials: Mass Spectral Microscopy and Femtosecond Laser Microscopy and Spectroscopy” (registration number: 506694). The expression vector pET-24b with the embedded BoWSCP gene was kindly provided by Prof. Dr. Harald Paulsen (Institute of Molecular Physiology, Johannes Gutenberg University Mainz, Germany)
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This research was funded by the Russian Science Foundation (grant no. 21-74-20155).
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D.A.Ch. analysis of spectral measurement results; K.V.N., Yu.N.O., and Yu.V.M. production, recovery, and biochemical characterization of BoWSCP preparations; F.E.G., I.V.Sh., and A.V.A. development of a mathematical apparatus, methods and performing femtosecond measurements; M.S.K. and V.A.N. concept development. All authors made a considerable contribution to the manuscript.
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Cherepanov, D.A., Neverov, K.V., Obukhov, Y.N. et al. Femtosecond Dynamics of Excited States of Chlorophyll Tetramer in Water-Soluble Chlorophyll-Binding Protein BoWSCP. Biochemistry Moscow 88, 1580–1595 (2023). https://doi.org/10.1134/S0006297923100139
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DOI: https://doi.org/10.1134/S0006297923100139