Abstract
A set of Mn K-edge XANES spectra due to the redox states S0−S3 of the OEC were determined by constructing a highly-sensitive X-ray detection system for use with physiologically native PS II membranes capable of cycling under a series of saturating laser-flashes. The spectra showed almost parallel upshifts with relatively high K-edge half-height energies given by 6550.9±0.2 eV, 6551.7±0.2 eV, 6552.5±0.2 eV and 6553.6±0.2 eV for the S0, S1, S2 and S3 states, respectively. The successive difference spectra between S0 and S1, S1 and S2, and S2 and S3 states were found to exhibit a similar peak around 6552–6553 eV, indicating that one Mn(III) ion or its direct ligand is univalently oxidized upon each individual S-state transition from S0 to S3. The present data, together with other observations of EPR and pre-edge XANES spectroscopy, suggest that the oxidation state of the Mn cluster undergoes a periodic change; S0: Mn(III,III,III,IV) → S1: Mn(III,IV,III,IV) → S2: Mn(III,IV,IV,IV) → S3: Mn(IV,IV,IV,IV) or Mn(III,IV,IV,IV)·L+ with L being a direct ligand of a Mn(III) ion.
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Abbreviations
- Chl:
-
chlorophyll
- D:
-
tyrosine 160 on the D2 protein, an accessory electron donor in PS II
- D+ :
-
the oxidized form of D
- EDTA:
-
ethylene-diaminetetraacetic acid
- EPR:
-
electron paramagnetic resonance
- EXAFS:
-
extended X-ray absorption fine structure
- HL:
-
py-2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol
- Mes:
-
2-(N-morpholino)ethanesulfonic acid
- N4:
-
py-tris(2-pyridylmethyl)amine
- OEC:
-
oxygen evolving complex
- P680:
-
primary electron donor of PS II
- PS II:
-
Photosystem II
- Q400 :
-
a high spin Fe3+ of the iron-quinone acceptor complex in PS II
- SSD:
-
solid state detector
- XAFS:
-
X-ray absorption fine structure
- XANES:
-
X-ray absorption near edge structure
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Kusunoki, M., Ono, T., Noguchi, T. et al. Manganese K-edge X-ray absorption spectra of the cyclic S-states in the photosynthetic oxygen-evolving system. Photosynth Res 38, 331–339 (1993). https://doi.org/10.1007/BF00046758
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DOI: https://doi.org/10.1007/BF00046758