K. Gibasiewicz et al., Modulation of primary radical pair kinetics and energetics in photosystem II by the redox state of the quinone electron acceptor Q(A), BIOPHYS J, 80(4), 2001, pp. 1617-1630
Time-resolved photovoltage measurements on destacked photosystem II membran
es from spinach with the primary quinone electron acceptor Q(A) either sing
ly or doubly reduced have been performed to monitor the time evolution of t
he primary radical pair P680(+)Pheo(-). The maximum transient concentration
of the primary radical pair is about five times larger and its decay is ab
out seven times slower with doubly reduced compared with singly reduced Q(A
). The possible biological significance of these differences is discussed.
On the basis of a simple reversible reaction scheme, the measured apparent
rate constants and relative amplitudes allow determination of sets of molec
ular rate constants and energetic parameters for primary reactions in the r
eaction centers with doubly reduced Q(A) as well as with oxidized or singly
reduced Q(A). The standard free energy difference DeltaG degrees between t
he charge-separated slate P680(+)Pheo(-) and the equilibrated excited state
(Chl(N)P680)* was found to be similar when Q(A) was oxidized or doubly red
uced before the flash (similar to -50 meV). In contrast, single reduction o
f Q(A) led to a large change in DeltaG degrees (similar to-+40 meV), demons
trating the importance of electrostatic interaction between the charge on Q
(A) and the primary radical pair, and providing direct evidence that the do
ubly reduced Q(A) is an electrically neutral species, i.e., is doubly proto
nated. A comparison of the molecular rate constants shows that the rate of
charge recombination is much more sensitive to the change in DeltaG degrees
than the rate of primary charge separation.