Mimicking the photosynthetic triplet energy-transfer relay

John Devens Gust, Thomas A Moore, Ana L Moore, Alexander A. Krasnovsky, Paul A. Lidell, David Nicodem, Janice M. DeGraziano, Pamela Kerrigan, Lewis R. Making, Peter J. Pessiki

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Abstract

In the reaction of photosynthetic organisms, chlorophyll triplet states are sometimes formed by recombination of charge-separated intermediates. These triplets are for singlet oxygen formation. Carotenoid can provide photoprotection from singlet oxygen generation by rapidly quenching chlorophyll triplet via triplet-triplet energy transfer. Because in bacteria the reaction center carotenoid is not located adjacent to the bacteriochlorophyll special pair, which is the origin of the charge separation, it has been postulated that quenching may occur via a triplet relay involving an intermediate chlorophyll monomer. We now report the synthesis and spectroscopic study of a covalently linked carotenoid (C)-porphyrin (P)-pyropheophorbide (Ppd) triad molecule which this triplet relay. The pyropheophorbide singlet-state C-P-1Ppd (generated by direct excitation or energy transfer from the attached porphyrin) undergoes intersystem crossing to the triplet C-P-3Ppd. In oxygen-free solutions, this triplet decays to 3C-P-Ppd through a triplet-transfer relay involving an intermediate C-3P-Ppd species. In solutions, quenching of C-P-3Ppd by the carotenoid with oxygen sensitization and thus provides a degree of photoprotection. In a similar triad containing a zinc porphyrin moiety, triplet transfer is slow due to the of the C-3PZn-Ppd intermediate, photoprotection via the relay is nonexistent. The triplet relay to function at low temperatures in both the natural and biomimetic cases due to the endergonicity of the first step.

Original languageEnglish
Pages (from-to)5684-5691
Number of pages8
JournalJournal of the American Chemical Society
Volume115
Issue number13
Publication statusPublished - 1993

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ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Gust, J. D., Moore, T. A., Moore, A. L., Krasnovsky, A. A., Lidell, P. A., Nicodem, D., DeGraziano, J. M., Kerrigan, P., Making, L. R., & Pessiki, P. J. (1993). Mimicking the photosynthetic triplet energy-transfer relay. Journal of the American Chemical Society, 115(13), 5684-5691.