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

Autor: Toa ZSD; Department of Chemistry, Princeton University, Washington Road, Princeton, NJ 08540, United States., Dean JC; Department of Physical Science, Southern Utah University, 351 West University Boulevard, Cedar City, UT 84720, United States., Scholes GD; Department of Chemistry, Princeton University, Washington Road, Princeton, NJ 08540, United States. Electronic address: gscholes@princeton.edu.
Jazyk: angličtina
Zdroj: Journal of photochemistry and photobiology. B, Biology [J Photochem Photobiol B] 2019 Jan; Vol. 190, pp. 110-117. Date of Electronic Publication: 2018 Nov 19.
DOI: 10.1016/j.jphotobiol.2018.11.007
Abstrakt: 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. 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.
(Copyright © 2018 Elsevier B.V. All rights reserved.)
Databáze: MEDLINE
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