The Mn
4Ca complex bound to photosystem II (PSII) is the active site of photosynthetic wateroxidation. Its assembly involves binding and light-driven oxidation of manganese, a process denoted asphotoactivation. The disassembly of the Mn complex is a thermally activated process involving distinctintermediates. Starting from intermediate states of the disassembly, which was initiated by a temperaturejump to 47
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C, we photoactivated PSII membrane particles and monitored the activity recovery by O
2polarography and delayed chlorophyll fluorescence measurements. Oxidation state and structural featuresof the formed intermediates of the Mn complex were assayed by X-ray absorption spectroscopy at theMn K-edge. The photoactivation time courses, which exhibit a lag phase characteristic of intermediateformation only when starting with the apo-PSII, suggest that within ~5 min of photoactivation of apo-PSII, a binuclear Mn complex is formed. It is proposed that a Mn
III2(di-
![](/images/entities/mgr.gif)
-oxo) complex is a key intermediateboth in the disassembly and in the assembly reaction paths.