title: Charge separation is virtually irreversible in photosystem II core complexes with oxidized primary quinone acceptor.
abstract: X-ray structures of the Photosystem II (PSII) core revealed relatively large interpigment distances between the CP43 and CP47 antenna complexes and the reaction center (RC) with respect to the interpigment distances in a single unit. This finding questions the possibility of fast energy equilibration among the antenna and the RC, which has been the basic explanation for the measured PSII fluorescence kinetics for more than two decades. In this study, we present time-resolved fluorescence measurements obtained with a streak-camera setup on PSII core complexes from Thermosynechococcus elongatus at room temperature (RT) and at 77 K. Kinetic modeling of the RT data obtained with oxidized quinone acceptor Q(A), reveals that the kinetics are best described by fast primary charge separation at a time scale of 1.5 ps and slow energy transfer from the antenna into the RC, which results in an energy equilibration time between the antenna and the RC of about 44 ps. This model is consistent with structure-based computations. Primary radical pair formation was found to be a virtually irreversible process. Energy equilibration within the CP43 and CP47 complexes is shown to occur at a time scale of 8 ps. Kinetic modeling of the 77 K data reveals similar energy transfer time scales in the antenna units and among the antenna and the RC as at RT, respectively, 7 and 37 ps. We conclude that the energy transfer from the CP43/CP47 antenna to the RC is the dominant factor in the total charge separation kinetics in intact PSII cores.
authors.affiliation: Department of Physics and Astronomy, Faculty of Sciences, VU University Amsterdam, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.
authors.forename: C D
authors.initials: CD
authors.lastname: van der Weij-de Wit
authors.forename: J P
authors.initials: JP
authors.lastname: Dekker
authors.forename: R
authors.initials: R
authors.lastname: van Grondelle
authors.forename: I H M
authors.initials: IH
authors.lastname: van Stokkum
mesh_terms: D000458:Cyanobacteria / Q000737:chemistry; D010084:Oxidation-Reduction; D045332:Photosystem II Protein Complex / Q000737:chemistry / Q000378:metabolism*; D011809:Quinones / Q000737:chemistry / Q000302:isolation & purification / Q000378:metabolism*
chemical_list: D045332:Photosystem II Protein Complex; D011809:Quinones