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Triplet state spectra and dynamics of peridinin analogs having different extents of π-electron conjugation

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Abstract

The Peridinin-Chlorophyll a-Protein (PCP) complex has both an exceptionally efficient light-harvesting ability and a highly effective protective capacity against photodynamic reactions involving singlet oxygen. These functions can be attributed to presence of a substantial amount of the highly-substituted and complex carotenoid, peridinin, in the protein and the facts that the low-lying singlet states of peridinin are higher in energy than those of chlorophyll (Chl) a, but the lowest-lying triplet state of peridinin is below that of Chl a. Thus, singlet energy can be transferred from peridinin to Chl a, but the Chl a triplet state is quenched before it can sensitize the formation of singlet oxygen. The present investigation takes advantage of Chl a as an effective triplet state donor to peridinin and explores the triplet state spectra and dynamics of a systematic series of peridinin analogs having different numbers of conjugated carbon–carbon double bonds. The carotenoids investigated are peridinin, which has a C37 carbon skeleton and eight conjugated carbon–carbon double bonds, and three synthetic analogs: C33-peridinin, having two less double bonds than peridinin, C35-peridinin which has one less double bond than peridinin, and C39-peridinin which has one more double bond than peridinin. In this study, the behavior of the triplet state spectra and kinetics exhibited by these molecules has been investigated in polar and nonpolar solvents and reveals a substantial effect of both π-electron conjugated chain length and solvent environment on the spectral lineshapes. However, only a small dependence of these factors is observed on the kinetics of triplet energy transfer from Chl a and on carotenoid triplet state deactivation to the ground state.

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Abbreviations

HPLC:

High performance liquid chromatography

PCP:

Peridinin-Chlorophyll a-Protein

Chl a :

Chlorophyll a

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Acknowledgments

We thank Dr. Tomáš Polívka for useful discussions and suggestions. We also thank Dr. Thomas Netscher of DSM Nutritional Products, Ltd., for the donation of (−)-actinol. This research was supported by a grant from the National Science Foundation (MCB-0913022), and the University of Connecticut Research Foundation. Support for SD was provided by a grant from the National Science Foundation Research Experience for Undergraduates (NSF-REU) Program (CHE-0754580). This study was also supported by a Grant-in-Aid for Science Research on Priority Areas 16073222 from the Ministry of Education, Culture, Sports, Science and Technology, and also Matching Fund Subsidy for a Private University, Japan.

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Authors and Affiliations

  1. Department of Chemistry, University of Connecticut, 55 North Eagleville Road, Storrs, CT, 06269-3060, USA

    Shanti Kaligotla, Sara Doyle, Dariusz M. Niedzwiedzki & Harry A. Frank

  2. Department of Chemistry, Kwansei Gakuin University, Hyogo, 669-1337, Japan

    Shinji Hasegawa, Takayuki Kajikawa & Shigeo Katsumura

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  1. Shanti Kaligotla
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  2. Sara Doyle
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  3. Dariusz M. Niedzwiedzki
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  4. Shinji Hasegawa
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  6. Shigeo Katsumura
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  7. Harry A. Frank
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Correspondence to Harry A. Frank.

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Kaligotla, S., Doyle, S., Niedzwiedzki, D.M. et al. Triplet state spectra and dynamics of peridinin analogs having different extents of π-electron conjugation. Photosynth Res 103, 167–174 (2010). https://doi.org/10.1007/s11120-010-9535-y

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