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Triplet state spectra and dynamics of geometric isomers of carotenoids

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Abstract

The observation of preferential binding of cis-carotenoids in purple bacterial photosynthetic reaction centers versus trans-isomers in antenna pigment protein complexes has led to the hypothesis that the natural selection of stereoisomers has physiological significance. In order to test this hypothesis, we have undertaken a systematic series of investigations comparing the optical spectroscopic properties and excited state dynamics of cis and trans isomers of carotenoids. The present work compares the triplet state spectra, lifetimes, and energy transfer rates of all-trans-spheroidene and 13,14-locked-cis-spheroidene, the latter of which is incapable of isomerizing to the all-trans configuration, and therefore provides a unique opportunity to examine the triplet state properties of a structurally stable cis molecule. The data reveal only small differences in spectra, decay dynamics, and transfer times and suggest there is little intrinsic advantage in either triplet energy transfer or triplet state decay arising from the inherently different isomeric forms of cis compared to trans carotenoids.

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Abbreviations

HPLC:

high performance liquid chromatography

TPP:

tetraphenylporphyrin

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Acknowledgements

The authors thank Christian Brückner for supplying the TPP for these experiments. This work has been supported in the laboratory of HAF by grants from the National Institutes of Health (GM-30353) and the University of Connecticut Research Foundation, and to JL from the Netherlands Foundation of Chemical Research (SON), which is financed by the Netherlands Organization for the Advancement of Pure Research (NWO).

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Authors and Affiliations

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

    Zeus D. Pendon & Harry A. Frank

  2. Gorlaeus Laboratories, Leiden University, 2300 RA, Leiden, The Netherlands

    Ineke der Hoef & Johan Lugtenburg

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  1. Zeus D. Pendon
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  2. Ineke der Hoef
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  3. Johan Lugtenburg
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  4. Harry A. Frank
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Correspondence to Harry A. Frank.

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Pendon, Z.D., der Hoef, I., Lugtenburg, J. et al. Triplet state spectra and dynamics of geometric isomers of carotenoids. Photosynth Res 88, 51–61 (2006). https://doi.org/10.1007/s11120-005-9026-8

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