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Stepwise Transition of the Tetra-Manganese Complex of Photosystem II to a Binuclear Mn₂(µ-O)₂ Complex in Response to a Temperature Jump: A Time-Resolved Structural Investigation Employing X-Ray Absorption Spectroscopy

Pavel Pospíil^*,, MichaelHaumann ^*, Jens Dittmer, V. Armando Solé and Holger Dau^*

^* Freie Universität Berlin, FB Physik, D-14195 Berlin, Germany; Philipps-Universität Marburg, FB Biologie, D-35032 Marburg, Germany; and ESRF, 38043 Grenoble Cedex, France

Correspondence: Address reprint requests to Prof. Holger Dau, FU Berlin, FB Physik, Arnimallee 14, D-14195 Berlin, Germany. Tel.: +49-(0)30-8385-3581; Fax: +49-(0)30-8385-6299; E-mail: holger.dau{at}physik.fu-berlin.de.

In oxygenic photosynthesis, water is oxidized at a protein-cofactor complex comprising four Mn atoms and, presumably, one calcium. Using multilayers of Photosystem II membrane particles, we investigated the time course of the disassembly of the Mn complex initiated by a temperature jump from 25°C to 47°C and terminated by rapid cooling after distinct heating periods. We monitored polarographically the oxygen-evolution activity, the amount of the Y_D^ox radical and of released Mn²⁺ by EPR spectroscopy, and the structure of the Mn complex by x-ray absorption spectroscopy (XAS, EXAFS). Using a novel approach to analyze time-resolved EXAFS data, we identify three distinct phases of the disassembly process: (1) Loss of the oxygen-evolution activity and reduction of Y_D^ox occur simultaneously (k₁ = 1.0 min^-1). EXAFS spectra reveal the concomitant loss of an absorber-backscatterer interaction between heavy atoms separated by 3.3 Å, possibly related to Ca release. (2) Subsequently, two Mn(III) or Mn(IV) ions seemingly separated by 2.7 Å in the native complex are reduced to Mn(II) and released (k₂ = 0.18 min^-1). The x-ray absorption spectroscopy data is highly suggestive that the two unreleased Mn ions form a di-µ-oxo bridged Mn(III)₂ complex. (3) Finally, the tightly-bound Mn₂(µ-O)₂ unit is slowly reduced and released (k₃ = 0.014 min^-1).

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