Flash induced XANES spectroscopy for the Ca-depleted Mn-cluster in the photosynthetic O2-evolving enzyme

Flash-induced changes of the Mn K-edge absorption spectra have been studied in the oxygen-evolving complex depleted of Ca. The Mn K-edge energy for the Ca-depleted S1-state was lower by 1.5 eV than that for the normal S1-state. The K-edge energy upshifted by 1 eV after one flash, indicative of an oxidation of Mn. After two flashes, the K-edge was elevated as well by 0.4 eV, and then reached a steady-state high level after continuous illumination where the K-edge energy was higher by 0.9 eV than that after one flash. The results indicate that the Mn-cluster and/or its direct ligand could be oxidized up to two electrons but further events are blocked.