A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis

Rudi Berera, Christian Herrero, Ivo H.M. Van Stokkum, Mikas Vengris, Gerdenis Kodis, Rodrigo E. Palacios, Herbert Van Amerongen, Rienk Van Grondelle, Devens Gust, Thomas A. Moore, Ana L. Moore, John T.M. Kennis

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109 Citations (Scopus)

Abstract

Under excess illumination, plant photosystem II dissipates excess energy through the quenching of chlorophyll fluorescence, a process known as nonphotochemical quenching. Activation of non-photochemical quenching has been linked to the conversion of a carotenoid with a conjugation length of nine double bonds (violaxanthin) into an 11-double-bond carotenoid (zeaxanthin). It has been suggested that the increase in the conjugation length turns the carotenoid from a nonquencher into a quencher of chlorophyll singlet excited states, but unequivocal evidence is lacking. Here, we present a transient absorption spectroscopic study on a model system made up of a zinc phthalocyanine (Pc) molecule covalently linked to carotenoids with 9, 10, or 11 conjugated carbon-carbon double bonds. We show that a carotenoid can act as an acceptor of Pc excitation energy, thereby shortening its singlet excited-state lifetime. The conjugation length of the carotenoid is critical to the quenching process. Remarkably, the addition of only one double bond can turn the carotenoid from a nonquencher into a very strong quencher. By studying the solvent polarity dependence of the quenching using target analysis of the time-resolved data, we show that the quenching proceeds through energy transfer from the excited Pc to the optically forbidden S1 state of the carotenoid, coupled to an intramolecular charge-transfer state. The mechanism for excess energy dissipation in photosystem II is discussed in view of the insights obtained on this simple model system.

Original languageEnglish
Pages (from-to)5343-5348
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume103
Issue number14
DOIs
Publication statusPublished - Apr 4 2006

Keywords

  • Artificial photosynthesis
  • Carotenoid
  • Nonphotochemical quenching
  • Photoprotection
  • Xanthophyll cycle

ASJC Scopus subject areas

  • General

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    Berera, R., Herrero, C., Van Stokkum, I. H. M., Vengris, M., Kodis, G., Palacios, R. E., Van Amerongen, H., Van Grondelle, R., Gust, D., Moore, T. A., Moore, A. L., & Kennis, J. T. M. (2006). A simple artificial light-harvesting dyad as a model for excess energy dissipation in oxygenic photosynthesis. Proceedings of the National Academy of Sciences of the United States of America, 103(14), 5343-5348. https://doi.org/10.1073/pnas.0508530103