Charge recombination and thermoluminescence in photosystem II

In the recombination process of Photosystem II (S(2)Q(A)(-) --> /S(1)Q(A)) the limiting step is the electron transfer from the reduced primary acceptor pheophytin Ph- to the oxidized primary donor P+ and the rate depends on the equilibrium constant between states S(2)PPhQ(A)(-) and S1P+Ph- Q(A): Accordingly, mutations that affect the midpoint potential of Ph or of P result in a modified recombination rate. A strong correlation is observed between the effects on the recombination rate and on thermoluminescence (TL, the light emission from S-2 Q(A)(-) during a warming ramp): a slower recombination corresponds to a large enhancement and higher temperature of the TL peak. The current theory of TL does not account for these effects, because it is based on the assumption that the rate-limiting step coincides with the radiative process. When implementing the known fact that the radiative pathway represents a minor leak, the modified TL theory readily accounts qualitatively for the observed behavior. However, the peak temperature is still lower than predicted from the temperature-dependence of recombination. We argue that this reflects the heterogeneity of the recombination process combined with the enhanced sensitivity of TL to slower components. The recombination kinetics are accurately fitted as a sum of two exponentials and we show that this is not due to a progressive stabilization of the charge-separated state, but to a pre-existing conformational heterogeneity.