title: Absence of Mn-centered oxidation in the S(2) --> S(3) transition: implications for the mechanism of photosynthetic water oxidation.
abstract: A key question for the understanding of photosynthetic water oxidation is whether the four oxidizing equivalents necessary to oxidize water to dioxygen are accumulated on the four Mn ions of the oxygen-evolving complex (OEC), or whether some ligand-centered oxidations take place before the formation and release of dioxygen during the S(3) --> [S(4)] --> S(0) transition. Progress in instrumentation and flash sample preparation allowed us to apply Mn Kbeta X-ray emission spectroscopy (Kbeta XES) to this problem for the first time. The Kbeta XES results, in combination with Mn X-ray absorption near-edge structure (XANES) and electron paramagnetic resonance (EPR) data obtained from the same set of samples, show that the S(2) --> S(3) transition, in contrast to the S(0) --> S(1) and S(1) --> S(2) transitions, does not involve a Mn-centered oxidation. On the basis of new structural data from the S(3)-state, manganese mu-oxo bridge radical formation is proposed for the S(2) --> S(3) transition, and three possible mechanisms for the O-O bond formation are presented.
authors.affiliation: Melvin Calvin Laboratory, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. johannes@struktur.chem.tu-berlin.de
authors.forename: J
authors.initials: J
authors.lastname: Messinger
authors.forename: J H
authors.initials: JH
authors.lastname: Robblee
authors.forename: U
authors.initials: U
authors.lastname: Bergmann
authors.forename: C
authors.initials: C
authors.lastname: Fernandez
authors.forename: P
authors.initials: P
authors.lastname: Glatzel
authors.forename: H
authors.initials: H
authors.lastname: Visser
authors.forename: R M
authors.initials: RM
authors.lastname: Cinco
authors.forename: K L
authors.initials: KL
authors.lastname: McFarlane
authors.forename: E
authors.initials: E
authors.lastname: Bellacchio
authors.forename: S A
authors.initials: SA
authors.lastname: Pizarro
authors.forename: S P
authors.initials: SP
authors.lastname: Cramer
authors.forename: K
authors.initials: K
authors.lastname: Sauer
authors.forename: M P
authors.initials: MP
authors.lastname: Klein
authors.forename: V K
authors.initials: VK
authors.lastname: Yachandra
mesh_terms: D004578:Electron Spin Resonance Spectroscopy; D008345:Manganese / Q000737:chemistry*; D010084:Oxidation-Reduction; D010088:Oxidoreductases / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D010788:Photosynthesis; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry; D045332:Photosystem II Protein Complex; D013052:Spectrometry, X-Ray Emission; D017550:Spectroscopy, Fourier Transform Infrared; D014867:Water / Q000737:chemistry*
chemical_list: D045322:Photosynthetic Reaction Center Complex Proteins; D045332:Photosystem II Protein Complex; D014867:Water; D008345:Manganese; D010088:Oxidoreductases; D010100:Oxygen