Abstract
In this work, we applied Stark fluorescence spectroscopy to an iron-stressed cyanobacterial membrane to reveal key insights about the electronic structures and excited state dynamics of the two important pigment-protein complexes, IsiA and PSII, both of which prevail simultaneously within the membrane during iron deficiency and whose fluorescence spectra are highly overlapped and hence often hardly resolved by conventional fluorescence spectroscopy. Thanks to the ability of Stark fluorescence spectroscopy, the fluorescence signatures of the two complexes could be plausibly recognized and disentangled. The systematic analysis of the SF spectra, carried out by employing standard Liptay formalism with a realistic spectral deconvolution protocol, revealed that the IsiA in an intact membrane retains almost identical excited state electronic structures and dynamics as compared to the isolated IsiA we reported in our earlier study. Moreover, the analysis uncovered that the excited state of the PSII subunit of the intact membrane possesses a significantly large CT character. The observed notably large magnitude of the excited state CT character may signify the supplementary role of PSII in regulative energy dissipation during iron deficiency.
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Acknowledgements
The authors thankfully acknowledge the contribution of Jos Thieme for his technical assistance. Md. W., A. M. A. and R. v. G. were supported by the VU University Amsterdam, the Laserlab-Europe Consortium and the advanced investigator grant (267333, PHOTPROT) from the European Research Council. Md. W. and R. v. G. were supported further by the TOP grant (700.58.305) from the Foundation of Chemical Sciences part of NWO.
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Md. W., A. M. A., and R. v. G. designed experiment. S.D prepared IsiA membrane. A. M. A, S. D., and Md. W. prepared Stark samples. Md. W. and A. M. A. carried out Stark experiments. A. M. A. and Md. W. performed Stark data analysis. A. M. A., S. D., R. v. G., and Md. W. wrote the manuscript.
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Ara, A.M., D’Haene, S., van Grondelle, R. et al. Unveiling large charge transfer character of PSII in an iron-deficient cyanobacterial membrane: A Stark fluorescence spectroscopy study. Photosynth Res (2024). https://doi.org/10.1007/s11120-024-01099-1
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DOI: https://doi.org/10.1007/s11120-024-01099-1