Ultrafast excited-state dynamics of Luteins in the major light-harvesting complex LHCII.
Journal
Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology
ISSN: 1474-9092
Titre abrégé: Photochem Photobiol Sci
Pays: England
ID NLM: 101124451
Informations de publication
Date de publication:
27 Dec 2023
27 Dec 2023
Historique:
received:
05
10
2023
accepted:
23
11
2023
medline:
28
12
2023
pubmed:
28
12
2023
entrez:
27
12
2023
Statut:
aheadofprint
Résumé
Carotenoid pigments are known to present a functional versatility when bound to light-harvesting complexes. This versatility originates from a strong correlation between a complex electronic structure and a flexible geometry that is easily tunable by the surrounding protein environment. Here, we investigated how the different L1 and L2 sites of the major trimeric light-harvesting complex (LHCII) of green plants tune the electronic structure of the two embedded luteins, and how this reflects on their ultrafast dynamics upon excitation. By combining molecular dynamics and quantum mechanics/molecular mechanics calculations, we found that the two luteins feature a different conformation around the second dihedral angle in the lumenal side. The s-cis preference of the lutein in site L2 allows for a more planar geometry of the [Formula: see text]-conjugated backbone, which results in an increased degree of delocalization and a reduced excitation energy, explaining the experimentally observed red shift. Despite these remarkable differences, according to surface hopping simulations the two luteins present analogous ultrafast dynamics upon excitation: the bright [Formula: see text] state quickly decays (in [Formula: see text] 50 fs) to the dark intermediate [Formula: see text], eventually ending up in the [Formula: see text] state. Furthermore, by employing two different theoretical approaches (i.e., Förster theory and an excitonic version of surface hopping), we investigated the experimentally debated energy transfer between the two luteins. With both approaches, no evident energy transfer was observed in the ultrafast timescale.
Identifiants
pubmed: 38151602
doi: 10.1007/s43630-023-00518-x
pii: 10.1007/s43630-023-00518-x
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Subventions
Organisme : H2020 European Research Council
ID : ERC-AdG 786714
Informations de copyright
© 2023. The Author(s).
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