Kinetic factors in the bicycle model of oxygen evolution by Photosystem II

Flash-induced oxygen evolution and many related processes in thylakoids of oxygenic organisms are modulated with period four by the S-state transitions associated with the oxygen evolving system of Photosystem II (PS II). To analyze these phenomena, we have interpreted the S-state model on the basis of the charge accumulating activities on both sides of PS II-4 charges on the donor side and 2 charges on the acceptor side. This results in the recognition of two parallel reaction center cycles V and W of PS II function (V.P. Shinkarev and C.A. Wraight (1993) Proc Natl Acad Sci USA 90: 1834-1838). The description of damping of the period four oscillations is here extended to include kinetic sources of misses in both cycles. Such misses arise in reaction centers (RCs) in which back reaction between P(+) and QA (-) occurs before the electron transfer equilibria on the donor and acceptor sides of the RC are reached. These are in addition to misses which are determined by reaction centers (RCs) that are inactive at the time of the flash due to the presence of either P(+) or QA (-) according to the electron transfer equilibria on the donor and acceptor sides of the RC. Using known or estimated values of the equilibrium and rate constants for donor and acceptor side reactions of the RC, this provides a natural and quantitatively reasonable description of the flash number dependence of oxygen evolution and other period four modulated processes of PS II. The estimated miss factors are different for both cycles V and W and are dependent on flash number and pH. Estimates based on existing data show that miss factors of the first type (kinetic) are dominant at low pH, while those of the second type (equilibrium) are dominant at high pH.