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38349100793
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x symbolizes the number of μ-oxo bridges that varies between the four recent EXAFS models because of the different bridging to Ca (x ≥ 5).
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The HYSCORE measurements were performed at a Bruker ESP-580 X-band pulse EPR spectrometer in a EN4118X cavity equipped with the super XFT bridge and an Oxford-900 liquid helium cryostat with ITC-503 temperature controller. Pellets of dark-adapted PSII membranes (Messinger, J, Robblee, J. H, Yu, W. O, Sauer, K, Yachandra, V. K, Klein, M. P. J. Am. Chem. Soc, 1997, 119, 11349-11350) were washed twice with either H2 16O- or H217O (90% enrichment)-buffer containing 0.4 M sucrose, 25 mM MES-NaOH pH 6.1, 15 mM NaCl, 3 mM MgCl 2, 1 mM EDTA, 0.5 mM PPBQ and 3, methanol. The samples were then concentrated to 20-30 mg chlorophyll/mL in 4 mm X-band EPR tubes by centrifugation. The final enrichment in H217O was ∼75, S2-state samples were prepared by illumination at 200 K. H217O-buffer was prepared by drying aliquots of H 216O-buffer
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17O.
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We did not resolve a nuclear quadrupole-splitting of our 17O-HYSCORE signal. This may have two reasons: (i) the nuclear quadrupole splitting caused by 17O is small because the oxygen is in a symmetric environment, ii) we only observe the m1, 1/2 ↔ +1/2 transition of 17O: the line-width of this transition is affected only in second order by the quadrupole interaction. The signals of the other transitions are too broad
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17O: the line-width of this transition is affected only in second order by the quadrupole interaction. The signals of the other transitions are too broad.
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