Electronic Structure of the Mn4OxCa Cluster in the S0 and S2 States of the Oxygen-Evolving Complex of Photosystem II Based on Pulse 55Mn-ENDOR and EPR Spectroscopy. Kulik, L. V., Epel, B., Lubitz, W., & Messinger, J. Journal of the American Chemical Society, 129(44):13421–13435, November, 2007. Publisher: American Chemical Society![Electronic Structure of the Mn4OxCa Cluster in the S0 and S2 States of the Oxygen-Evolving Complex of Photosystem II Based on Pulse 55Mn-ENDOR and EPR Spectroscopy [link]](https://bibbase.org/img/filetypes/link.svg "link")
Paper doi abstract bibtex The heart of the oxygen-evolving complex (OEC) of photosystem II is a Mn4OxCa cluster that cycles through five different oxidation states (S0 to S4) during the light-driven water-splitting reaction cycle. In this study we interpret the recently obtained 55Mn hyperfine coupling constants of the S0 and S2 states of the OEC [Kulik et al. J. Am. Chem. Soc. 2005, 127, 2392−2393] on the basis of Y-shaped spin-coupling schemes with up to four nonzero exchange coupling constants, J. This analysis rules out the presence of one or more Mn(II) ions in S0 in methanol (3%) containing samples and thereby establishes that the oxidation states of the manganese ions in S0 and S2 are, at 4 K, Mn4(III, III, III, IV) and Mn4(III, IV, IV, IV), respectively. By applying a “structure filter” that is based on the recently reported single-crystal EXAFS data on the Mn4OxCa cluster [Yano et al. Science 2006, 314, 821−825] we (i) show that this new structural model is fully consistent with EPR and 55Mn-ENDOR data, (ii) assign the Mn oxidation states to the individual Mn ions, and (iii) propose that the known shortening of one 2.85 Å Mn−Mn distance in S0 to 2.75 Å in S1 [Robblee et al. J. Am. Chem. Soc. 2002, 124, 7459−7471] corresponds to a deprotonation of a μ-hydroxo bridge between MnA and MnB, i.e., between the outer Mn and its neighboring Mn of the μ3-oxo bridged moiety of the cluster. We summarize our results in a molecular model for the S0 → S1 and S1 → S2 transitions.
@article{kulik_electronic_2007,
title = {Electronic {Structure} of the {Mn4OxCa} {Cluster} in the {S0} and {S2} {States} of the {Oxygen}-{Evolving} {Complex} of {Photosystem} {II} {Based} on {Pulse} {55Mn}-{ENDOR} and {EPR} {Spectroscopy}},
volume = {129},
issn = {0002-7863},
url = {https://doi.org/10.1021/ja071487f},
doi = {10.1021/ja071487f},
abstract = {The heart of the oxygen-evolving complex (OEC) of photosystem II is a Mn4OxCa cluster that cycles through five different oxidation states (S0 to S4) during the light-driven water-splitting reaction cycle. In this study we interpret the recently obtained 55Mn hyperfine coupling constants of the S0 and S2 states of the OEC [Kulik et al. J. Am. Chem. Soc. 2005, 127, 2392−2393] on the basis of Y-shaped spin-coupling schemes with up to four nonzero exchange coupling constants, J. This analysis rules out the presence of one or more Mn(II) ions in S0 in methanol (3\%) containing samples and thereby establishes that the oxidation states of the manganese ions in S0 and S2 are, at 4 K, Mn4(III, III, III, IV) and Mn4(III, IV, IV, IV), respectively. By applying a “structure filter” that is based on the recently reported single-crystal EXAFS data on the Mn4OxCa cluster [Yano et al. Science 2006, 314, 821−825] we (i) show that this new structural model is fully consistent with EPR and 55Mn-ENDOR data, (ii) assign the Mn oxidation states to the individual Mn ions, and (iii) propose that the known shortening of one 2.85 Å Mn−Mn distance in S0 to 2.75 Å in S1 [Robblee et al. J. Am. Chem. Soc. 2002, 124, 7459−7471] corresponds to a deprotonation of a μ-hydroxo bridge between MnA and MnB, i.e., between the outer Mn and its neighboring Mn of the μ3-oxo bridged moiety of the cluster. We summarize our results in a molecular model for the S0 → S1 and S1 → S2 transitions.},
number = {44},
urldate = {2024-12-12},
journal = {Journal of the American Chemical Society},
author = {Kulik, Leonid V. and Epel, Boris and Lubitz, Wolfgang and Messinger, Johannes},
month = nov,
year = {2007},
note = {Publisher: American Chemical Society},
pages = {13421--13435},
}
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Soc. 2005, 127, 2392−2393] on the basis of Y-shaped spin-coupling schemes with up to four nonzero exchange coupling constants, J. This analysis rules out the presence of one or more Mn(II) ions in S0 in methanol (3%) containing samples and thereby establishes that the oxidation states of the manganese ions in S0 and S2 are, at 4 K, Mn4(III, III, III, IV) and Mn4(III, IV, IV, IV), respectively. By applying a “structure filter” that is based on the recently reported single-crystal EXAFS data on the Mn4OxCa cluster [Yano et al. Science 2006, 314, 821−825] we (i) show that this new structural model is fully consistent with EPR and 55Mn-ENDOR data, (ii) assign the Mn oxidation states to the individual Mn ions, and (iii) propose that the known shortening of one 2.85 Å Mn−Mn distance in S0 to 2.75 Å in S1 [Robblee et al. J. Am. Chem. Soc. 2002, 124, 7459−7471] corresponds to a deprotonation of a μ-hydroxo bridge between MnA and MnB, i.e., between the outer Mn and its neighboring Mn of the μ3-oxo bridged moiety of the cluster. 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