Reconstitution of the water-oxidizing complex in manganese-depleted photosystem II preparations using synthetic Mn complexes: A fluorine-19 NMR study of the reconstitution process

Reconstitution of Mn-depleted photosystem II (PSII) particles was examined with synthetic trinuclear Mn complexes of newly developed tripod ligands. Rates of the electron transfer and oxygen evolution were up to 74-86 and 52-56% of those measured in native PSII. These values are higher than those for the PSII reconstituted by MnCl₂. The role of the tripod ligands during the reconstitution process was examined by ¹⁹F NMR. Due to the high NMR sensitivity of the ¹⁹F nucleus and the low abundance of fluorine atoms in natural PSII, it was possible to selectively observe the fluorine atoms on the tripod ligand. It was shown that the tripod ligands were released from the Mn complex after the reconstitution. We propose that the primary step in the reconstitution process is the prebinding of the Mn complex to the hydrophobic part of the PSII particle.