Effect of bicarbonate on the water-oxidizing complex of photosystem II in the super-reduced S-states.

It is shown that the hydrazine-induced transition of the water-oxidizing complex (WOC) to super-reduced S-states depends on the presence of bicarbonate in the medium so that after a 20 min treatment of isolated spinach thylakoids with 3 mM NH(2)NH(2) at 20 degrees C in the CO(2)/HCO(3)(-)-depleted buffer the S-state populations are: 42% of S(-3), 42% of S(-2), 16% of S(-1) and even formal S(-4) state is reached, while in the presence of 2 mM NaHCO(3), the same treatment produces 30% of S(-3), 38% of S(-2), and 32% of S(-1) and there is no indication of the S(-4) state. Bicarbonate requirement for the oxygen-evolving activity, very low in untreated thylakoids, considerably increases upon the transition of the WOC to the super-reduced S-states, and the requirement becomes low again when the WOC returns back to the normal S-states using pre-illumination. The results are discussed as a possible indication of ligation of bicarbonate to manganese ions within the WOC.