Journal
CURRENT OPINION IN CHEMICAL BIOLOGY
Volume 16, Issue 1-2, Pages 3-10Publisher
ELSEVIER SCI LTD
DOI: 10.1016/j.cbpa.2012.02.011
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Funding
- Berlin Cluster of Excellence on Unifying Concepts in Catalysis (UniCat)
- European Union
- Deutsche Forschungsgemeinschaft
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Photosynthetic water oxidation chemistry at the unique manganese-calcium complex of photosystem II (PSII) is of fundamental importance and serves as a paragon in the development of efficient synthetic catalysts. A recent crystal structure of PSII shows the atoms of the water-oxidizing complex; its Mn4CaO5 core resembles inorganic manganese-calcium oxides. Merging of crystallographic and spectroscopic information reverses radiation-induced modifications at the Mn-complex in silico and facilitates discussion of the O-O bond chemistry. Coordinated proton movements are promoted by a water network connecting the Mn4CaO5 core with the oxidant, a tyrosine radical and one possibly mobile chloride ion. A basic reaction-cycle model predicts an alternating proton and electron removal from the catalytic site, which facilitates energetically efficient water oxidation.
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