We have performed a series of broadband multidimensional electronic spectroscopy experiments to probe the electronic and vibrational dynamics of the canthaxanthin chromophore of the Orange Carotenoid Protein (OCP) from Synechocystis sp. PCC 6803 in its photoactivated red state, OCPR. Cross-peaks observed below the diagonal of the two-dimensional electronic spectrum indicate that absorption transitions prepare the bright S2 state of the ketocarotenoid canthaxanthin near to a sequence of conical intersections, allowing passage to the dark S1 state via the Sx intermediate in 50 fs. Rapid damping of excited-state coherent wavepacket motions suggests that the branching coordinates of the conical intersections include out-of-plane deformation and C=C stretching coordinates of the π-conjugated isoprenoid backbone. The unusual proximity of the Franck–Condon S2 state structure to the conical intersections with Sx and S1 suggests that the protein surroundings of canthaxanthin prepare it to function as an excitation energy trap in the OCPR–phycobilisome complex. Numerical simulations using the multimode Brownian oscillator model demonstrate that the ground-state absorption spectrum of OCPR overlaps with the fluorescence emission spectrum of allophycocyanin due to spectral broadening derived especially from the intramolecular motions of the canthaxanthin chromophore in its binding site.
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14 October 2024
Research Article|
October 16 2024
Spectral broadening and vibronic dynamics of the S2 state of canthaxanthin in the orange carotenoid protein
Special Collection:
Time-resolved Vibrational Spectroscopy
Kunwei Yang
;
Kunwei Yang
(Conceptualization, Funding acquisition, Investigation, Methodology, Supervision)
1
Department of Chemistry, Michigan State University
, East Lansing, Michigan 48824, USA
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Nila Mohan T. M.;
Nila Mohan T. M.
a)
(Formal analysis, Investigation, Methodology, Visualization)
1
Department of Chemistry, Michigan State University
, East Lansing, Michigan 48824, USA
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Justin B. Rose;
Justin B. Rose
(Formal analysis, Investigation, Methodology, Software, Visualization)
1
Department of Chemistry, Michigan State University
, East Lansing, Michigan 48824, USA
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Chase H. Leslie
;
Chase H. Leslie
(Data curation, Formal analysis, Investigation, Methodology, Software, Visualization)
1
Department of Chemistry, Michigan State University
, East Lansing, Michigan 48824, USA
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Markus Sutter
;
Markus Sutter
(Formal analysis, Visualization)
2
MSU–DOE Plant Research Laboratory, Michigan State University
, East Lansing, Michigan 48824, USA
3
Environmental Genomics and Systems Biology Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
4
Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
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Cheryl A. Kerfeld
;
Cheryl A. Kerfeld
(Conceptualization, Funding acquisition, Methodology, Project administration, Resources, Writing – original draft, Writing – review & editing)
2
MSU–DOE Plant Research Laboratory, Michigan State University
, East Lansing, Michigan 48824, USA
3
Environmental Genomics and Systems Biology Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
4
Molecular Biophysics and Integrated Bioimaging Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
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Warren F. Beck
Warren F. Beck
b)
(Conceptualization, Investigation, Methodology, Project administration, Supervision, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, Michigan State University
, East Lansing, Michigan 48824, USA
b)Author to whom correspondence should be addressed: beckw@msu.edu
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b)Author to whom correspondence should be addressed: beckw@msu.edu
a)
Present address: Applied Materials, Inc., 3050 Bowers Avenue, Santa Clara, CA 95054, USA.
J. Chem. Phys. 161, 155101 (2024)
Article history
Received:
July 08 2024
Accepted:
September 21 2024
Citation
Kunwei Yang, Nila Mohan T. M., Justin B. Rose, Chase H. Leslie, Markus Sutter, Cheryl A. Kerfeld, Warren F. Beck; Spectral broadening and vibronic dynamics of the S2 state of canthaxanthin in the orange carotenoid protein. J. Chem. Phys. 14 October 2024; 161 (15): 155101. https://doi.org/10.1063/5.0227360
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