H. Dau et al., The tetra-manganese complex of photosystem II during its redox cycle - X-ray absorption results and mechanistic implications, BBA-BIOENER, 1503(1-2), 2001, pp. 24-39
Using X-ray absorption spectroscopy (XAS), relevant information on structur
e and oxidation state of the water-oxidizing Mn complex of photosystem II h
as been obtained for all four semi-stable intermediate states of its cataly
tic cycle. We summarize our recent XAS results and discuss their mechanisti
c implications. The following aspects are covered: (a) information content
of X-ray spectra (pre-edge feature, edge position, extended X-ray absorptio
n fine-structure (EXAFS), dichroism in the EXAFS of partially oriented samp
les); (b) S-1-state structure; (c) X-ray edge results on oxidation state ch
anges; (d) EXAFS results on structural changes during the S-state cycle; (e
) a structural model for the Mn complex in its S-3-state; (f) XAS-based wor
king model for the S-2-S-3 transition; (g) XAS-based working model for the
S-0-S-1 transition; (h) potential role of hydrogen atom abstraction by the
Mn complex. Finally, we present a specific hypothesis on the mechanism of d
ioxygen formation during the S-3-(S-4)-S-0 transition. According to this hy
pothesis, water oxidation is facilitated by manganese reduction that is cou
pled to proton transfer from a substrate water to bridging oxides. (C) 2001
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