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Title: Revealing structural involvement of chromophores in algal light harvesting complexes using symmetry-adapted perturbation theory

Abstract

The attribution of quantum beats observed in the time-resolved spectroscopy of photosynthetic light-harvesting antennae to nontrivial quantum coherences has sparked a flurry of research activity beginning a decade ago. Even though investigations into the functional aspects of photosynthetic light-harvesting were supported by X-ray crystal structures, the non-covalent interactions between pigments and their local protein environment that drive such function has yet to be comprehensively explored. Using symmetry-adapted perturbation theory (SAPT), we have comprehensively determined the magnitude and compositions of these non-covalent interactions involving light-harvesting chromophores in two quintessential photosynthetic pigment-protein complexes — peridinin chlorophyll-a protein (PCP) from dinoflagellate Amphidinium carterae and phycocyanin 645 (PC645) from cryptophyte Chroomonas mesostigmatica. In PCP, the chlorophylls are dispersion-bound to the peridinins, which in turn are electrostatically anchored to the protein scaffold via their polar terminal rings. This might be an evolutionary design principle in which the relative orientation of the carotenoids towards the aqueous environment determines the arrangement of the other chromophores in carotenoid-based antennas. On the other hand, electrostatics dominate the non-covalent interactions in PC645. As a result, our ab initio simulations also suggest full protonation of the PC645 chromophores in physiological conditions, and that changes to their protonation states result in theirmore » participation as switches between folded and unfolded conformations.« less

Authors:
 [1];  [2];  [1]
+ Show Author Affiliations
  1. Princeton Univ., Princeton, NJ (United States)
  2. Southern Utah Univ., Cedar City, UT (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Bioinspired Light-Escalated Chemistry (BioLEC); Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1502097
Alternate Identifier(s):
OSTI ID: 1636914
Grant/Contract Number:  
SC0019370
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Photochemistry and Photobiology B: Biology
Additional Journal Information:
Journal Volume: 190; Journal Issue: C; Journal ID: ISSN 1011-1344
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES

Citation Formats

Toa, Zi S. Desmond, Dean, Jacob C., and Scholes, Gregory D. Revealing structural involvement of chromophores in algal light harvesting complexes using symmetry-adapted perturbation theory. United States: N. p., 2018. Web. doi:10.1016/j.jphotobiol.2018.11.007.
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Toa, Zi S. Desmond, Dean, Jacob C., & Scholes, Gregory D. Revealing structural involvement of chromophores in algal light harvesting complexes using symmetry-adapted perturbation theory. United States. https://doi.org/10.1016/j.jphotobiol.2018.11.007
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Toa, Zi S. Desmond, Dean, Jacob C., and Scholes, Gregory D. Mon . "Revealing structural involvement of chromophores in algal light harvesting complexes using symmetry-adapted perturbation theory". United States. https://doi.org/10.1016/j.jphotobiol.2018.11.007. https://www.osti.gov/servlets/purl/1502097.
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@article{osti_1502097,
title = {Revealing structural involvement of chromophores in algal light harvesting complexes using symmetry-adapted perturbation theory},
author = {Toa, Zi S. Desmond and Dean, Jacob C. and Scholes, Gregory D.},
abstractNote = {The attribution of quantum beats observed in the time-resolved spectroscopy of photosynthetic light-harvesting antennae to nontrivial quantum coherences has sparked a flurry of research activity beginning a decade ago. Even though investigations into the functional aspects of photosynthetic light-harvesting were supported by X-ray crystal structures, the non-covalent interactions between pigments and their local protein environment that drive such function has yet to be comprehensively explored. Using symmetry-adapted perturbation theory (SAPT), we have comprehensively determined the magnitude and compositions of these non-covalent interactions involving light-harvesting chromophores in two quintessential photosynthetic pigment-protein complexes — peridinin chlorophyll-a protein (PCP) from dinoflagellate Amphidinium carterae and phycocyanin 645 (PC645) from cryptophyte Chroomonas mesostigmatica. In PCP, the chlorophylls are dispersion-bound to the peridinins, which in turn are electrostatically anchored to the protein scaffold via their polar terminal rings. This might be an evolutionary design principle in which the relative orientation of the carotenoids towards the aqueous environment determines the arrangement of the other chromophores in carotenoid-based antennas. On the other hand, electrostatics dominate the non-covalent interactions in PC645. As a result, our ab initio simulations also suggest full protonation of the PC645 chromophores in physiological conditions, and that changes to their protonation states result in their participation as switches between folded and unfolded conformations.},
doi = {10.1016/j.jphotobiol.2018.11.007},
journal = {Journal of Photochemistry and Photobiology B: Biology},
number = C,
volume = 190,
place = {United States},
year = {Mon Nov 19 00:00:00 EST 2018},
month = {Mon Nov 19 00:00:00 EST 2018}
}
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https://doi.org/10.1016/j.jphotobiol.2018.11.007
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