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Metalloradical EPR Signals from the YZ·S-State Intermediates in Photosystem II

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Abstract

The redox-active tyrosine residue (YZ) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced YZ· in magnetic interaction with the CaMn4-cluster in the particular S-state, YZ·SX intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient YZ· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) YZ in the lower S-states was oxidized by P680+ formed via charge separation, while (ii) YZ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the YZ·SX intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the CaMn4-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the YZ oxidation. The apparent pK as found for decreased split signal induction were interpreted in the fate of the phenol proton.

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The Swedish Research Council, the Swedish Energy Agency and the Knut and Alice Wallenberg Foundation are acknowledged for financial support.

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  1. Molecular Biomimetics, Department of Photochemistry and Molecular Science, Ångström Laboratory, Uppsala University, P.O. Box 523, 751 20, Uppsala, Sweden

    Kajsa G. V. Havelius, Johannes Sjöholm, Felix M. Ho, Fikret Mamedov & Stenbjörn Styring

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  1. Kajsa G. V. Havelius
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Havelius, K.G.V., Sjöholm, J., Ho, F.M. et al. Metalloradical EPR Signals from the YZ·S-State Intermediates in Photosystem II. Appl Magn Reson 37, 151–176 (2010). https://doi.org/10.1007/s00723-009-0045-z

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