title: Excitation dynamics in the LHCII complex of higher plants: modeling based on the 2.72 Angstrom crystal structure.
abstract: We have modeled steady-state spectra and energy-transfer dynamics in the peripheral plant light-harvesting complex LHCII using new structural data. The dynamics of the chlorophyll (Chl) b-->Chl a transfer and decay of selectively excited "bottleneck" Chl a and b states have been studied by femtosecond pump-probe spectroscopy. We propose an exciton model of the LHCII trimer (with specific site energies) which allows a simultaneous quantitative fit of the absorption, linear-dichroism, steady-state fluorescence spectra, and transient absorption kinetics upon excitation at different wavelengths. In the modeling we use the experimental exciton-phonon spectral density and modified Redfield theory. We have found that fast b-->a transfer is determined by a good connection of the Chls b to strongly coupled Chl a clusters, i.e., a610-a611-a612 trimer and a602-a603 and a613-a614 dimers. Long-lived components of the energy-transfer kinetics are determined by a quick population of red-shifted Chl b605 and blue-shifted Chl a604 followed by a very slow (3 ps for b605 and 12 ps for a604) flow of energy from these monomeric bottleneck sites to the Chl a clusters. The dynamics within the Chl a region is determined by fast (with time constants down to sub-100 fs) exciton relaxation within the a610-a611-a612 trimer, slower 200-300 fs relaxation within the a602-a603 and a613-a614 dimers, even slower 300-800 fs migration between these clusters, and very slow transfer from a604 to the quasi-equilibrated a sites. The final equilibrium is characterized by predominant population of the a610-a611-a612 cluster (mostly the a610 site). The location of this cluster on the outer side of the LHCII trimer probably provides a good connection with the other subunits of PSII.
authors.affiliation: A. N. Belozersky Institute of Physico-Chemical Biology, Moscow State University, Leninskie Gory, 119992 Moscow, Russia.
authors.forename: Vladimir I
authors.initials: VI
authors.lastname: Novoderezhkin
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Palacios
authors.forename: Herbert
authors.initials: H
authors.lastname: van Amerongen
authors.forename: Rienk
authors.initials: R
authors.lastname: van Grondelle
mesh_terms: D003460:Crystallization; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry*; D008958:Models, Molecular; D010944:Plants / Q000737:chemistry*; D011487:Protein Conformation
chemical_list: D045342:Light-Harvesting Protein Complexes