Abstract
The detailed structure of catalytic center of water oxidation, Mn4Ca-cluster, in photosystem II (PSII) has been reported recently. However, due to the radiation damage induced by X-ray and the complexity of the Mn4Ca-cluster, the assignment of the μ4-O5 atom coordinated by three Mn and one Ca2+ ions is still lack of essential evidences. In this article, we synthesized one Mn complex containing two μ4-O atoms. It is found that the lengths of all μ4-O-Mn bonds in this Mn complex are in the range of 1.89–2.10 Å, which are significantly shorter than 2.40–2.61 Å distance of μ4-O5-Mn bonds in Mn4Ca-cluster observed in the crystal structure of PSII. In addition, DFT calculations have been carried out on the Mn4Ca-cluster. It is found that the O atom of μ4-O or μ4-OH always trends to deviate from the center position of four metal ions, resulting in unequal bond lengths of four μ4-O-M (M=Mn or Ca), which is obviously different with larger and nearly equal distances between μ4-O and four metal ions observed in the crystal structure. Based on these results, we suggest that the μ4-atom in Mn4Ca-cluster of PSII is unlikely to be a μ4-O, μ4-OH or μ4-OH2, and its assignment is still an open question.
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Wang, Y., Zhang, C., Wang, L. et al. Assignment of the μ4-O5 atom in catalytic center for water oxidation in photosystem II. Chin. Sci. Bull. 58, 3213–3216 (2013). https://doi.org/10.1007/s11434-013-5973-1
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DOI: https://doi.org/10.1007/s11434-013-5973-1