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Excitation relaxation dynamics of carotenoids constituting the diadinoxanthin cycle

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Abstract

Carotenoids (Cars) exhibit two functions in photosynthesis, light-harvesting and photoprotective functions, which are performed through the excited states of Cars. Therefore, increasing our knowledge on excitation relaxation dynamics of Cars is important for understanding of the functions of Cars. In light-harvesting complexes, there exist Cars functioning by converting the π-conjugation number in response to light conditions. It is well known that some microalgae have a mechanism controlling the conjugation number of Cars, called as the diadinoxanthin cycle; diadinoxanthin (10 conjugations) is accumulated under low light, whereas diatoxanthin (11 conjugations) appears under high light. However, the excitation relaxation dynamics of these two Cars have not been clarified. In the present study, we investigated excitation relaxation dynamics of diadinoxanthin and diatoxanthin in relation to their functions, by the ultrafast fluorescence spectroscopy. After an excitation to the S2 state, the intramolecular vibrational redistribution occurs, followed by the internal conversion to the S1 state. The S2 lifetimes were analyzed to be 175 fs, 155 fs, and 140 fs in diethyl ether, ethanol, and acetone, respectively, for diadinoxanthin, and 155 fs, 135 fs, and 125 fs in diethyl ether, ethanol, and acetone, respectively for diatoxanthin. By converting diadinoxanthin to diatoxanthin, the absorption spectra shift to longer wavelengths by 5–7 nm, and lifetimes of S2 and S1 states decrease by 11–13% and 52%, respectively. Differences in levels and lifetimes of excited states between diadinoxanthin and diatoxanthin are small; therefore, it is suggested that changes in the energy level of chlorophyll a are necessary to efficiently control the functions of the diadinoxanthin cycle.

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Acknowledgements

This work was supported by the Grants-in-Aid for Scientific Research from Japan Society for the Promotion of Science JP17H06433 (to J.-R. S.) and JP16H06553 (to S. A.).

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Authors and Affiliations

  1. Graduate School of Science, Kobe University, Kobe, 657-8501, Japan

    Kohei Kagatani & Seiji Akimoto

  2. Research Institute for Interdisciplinary Science and Graduate School of Natural Science and Technology, Okayama University, Okayama, 700-8530, Japan

    Ryo Nagao & Jian-Ren Shen

  3. Comprehensive Education and Research Center, Kobe Pharmaceutical University, Kobe, 658-8558, Japan

    Yumiko Yamano

  4. Faculty of Life Sciences, Tokyo University of Agriculture, Tokyo, 156-8502, Japan

    Shinichi Takaichi

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  1. Kohei Kagatani
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Correspondence to Seiji Akimoto.

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Kagatani, K., Nagao, R., Shen, JR. et al. Excitation relaxation dynamics of carotenoids constituting the diadinoxanthin cycle. Photosynth Res 154, 13–19 (2022). https://doi.org/10.1007/s11120-022-00944-5

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