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Manganese K-edge X-ray absorption spectra of the cyclic S-states in the photosynthetic oxygen-evolving system

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  • Structure and Mechanism of Water Oxidizing Complex
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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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Authors and Affiliations

  1. Department of Physics, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, 214, Kawasaki, Kanagawa, Japan

    M. Kusunoki

  2. Solar Energy Research Group, Institute of Physical and Chemical Research (RIKEN), 351-01, Wako, Saitama, Japan

    T. Ono, T. Noguchi & Y. Inoue

  3. Electrotechnical Laboratory, 305, Tsukuba, Ibaraki, Japan

    H. Oyanagi

Authors
  1. M. Kusunoki
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  2. T. Ono
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  3. T. Noguchi
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  4. Y. Inoue
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  5. H. Oyanagi
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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

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