Abstract
The Mn4Ca oxygen-evolving complex (OEC) in Photosystem II (PSII) is assembled in situ from free Mn2+, Ca2+, and water. In an early light-driven step, Mn2+ in a protein high-affinity site is oxidized to Mn3+. Using dual-mode electron paramagnetic resonance spectroscopy, we observed that Mn3+ accumulation increases as chloride concentration increases in spinach PSII membranes depleted of all extrinsic subunits. At physiologically relevant pH values, this effect requires the presence of calcium. When combined with pH studies, we conclude that the first Mn2+ oxidation event in OEC assembly requires a deprotonation that is facilitated by chloride.
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Acknowledgements
The experimental work was funded the U.S. Department of Energy, Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences, Photosynthetic Systems through Grant DE-SC0020119. B.P.R. was supported by the Herman Frasch Fund for Chemical Research through Grant 822-HF17. Instrumentation support was provided by the Louisiana Board of Regents Support Fund. We thank M. Rita Riggio for technical support.
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Russell, B.P., Vinyard, D.J. Chloride facilitates Mn(III) formation during photoassembly of the Photosystem II oxygen-evolving complex. Photosynth Res 152, 283–288 (2022). https://doi.org/10.1007/s11120-021-00886-4
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DOI: https://doi.org/10.1007/s11120-021-00886-4
Keywords
- Photosystem II
- Oxygen-evolving complex
- Assembly
- Electron paramagnetic resonance spectroscopy