Reconstruction of the water-oxidizing complex in manganese-depleted Photosystem II using synthetic manganese complexes

The efficiency of a trinuclear and two binuclear manganese complexes in reconstituting electron transport and O2 evolution activity in Mn-depleted Photosystem II preparations is analyzed. The trinuclear Mn-complex is more efficient than two binuclear Mn-complexes in restoring oxygen evolution, but it is less effective as an electron donor than binuclear Mn-complexes. It is inferred from our results that recovery of electron transport and O2 evolution with polynuclear Mn-complexes is affected with different factors. Moreover, the trinuclear Mn-complex is extremely sensitive to the addition of CaCl2. It is suggested that there is an interaction between Ca2+ and carboxyl within the trinuclear Mn-complex during photoactivation and this interaction benefits the ligation of Mn atom to the apo-WOC and form an active WOC. Binuclear Mn(III)Mn(III) complex shows slightly higher efficiency than binuclear Mn(III)Mn(IV) complex in restoration of O2 evolution activity. The efficiency of three Mn-complexes in the reconstitution of WOC is in an order: trinuclear Mn3(III) > binuclear Mn(III)Mn(III) > binuclear Mn(III)Mn(IV).