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• W2023843667 endingPage "586" @default.
• W2023843667 startingPage "576" @default.
• W2023843667 abstract "The site for water oxidation in Photosystem II (PSII) goes through five sequential oxidation states (S0 to S4) before O2 is evolved. It consists of a Mn4CaO5-cluster close to a redox-active tyrosine residue (YZ). Cl− is also required for enzyme activity. By using EPR spectroscopy it has been shown that both Ca2+/Sr2+ exchange and Cl−/I− exchange perturb the proportions of centers showing high (S = 5/2) and low spin (S = 1/2) forms of the S2-state. The S3-state was also found to be heterogeneous with: i) a S = 3 form that is detectable by EPR and not sensitive to near-infrared light; and ii) a form that is not EPR visible but in which Mn photochemistry occurs resulting in the formation of a (S2YZ)′ split EPR signal upon near-infrared illumination. In Sr/Cl-PSII, the high spin (S = 5/2) form of S2 shows a marked heterogeneity with a g = 4.3 form generated at low temperature that converts to a relaxed form at g = 4.9 at higher temperatures. The high spin g = 4.9 form can then progress to the EPR detectable form of S3 at temperatures as low as 180 K whereas the low spin (S = 1/2) S2-state can only advance to the S3 state at temperatures ≥ 235 K. Both of the two S2 configurations and the two S3 configurations are each shown to be in equilibrium at ≥ 235 K but not at 198 K. Since both S2 configurations are formed at 198 K, they likely arise from two specific populations of S1. The existence of heterogeneous populations in S1, S2 and S3 states may be related to the structural flexibility associated with the positioning of the oxygen O5 within the cluster highlighted in computational approaches and which has been linked to substrate exchange. These data are discussed in the context of recent in silico studies of the electron transfer pathways between the S2-state(s) and the S3-state(s)." @default.
• W2023843667 created "2016-06-24" @default.
• W2023843667 creator A5026174254 @default.
• W2023843667 creator A5026928374 @default.
• W2023843667 creator A5079892264 @default.
• W2023843667 date "2015-06-01" @default.
• W2023843667 modified "2023-10-10" @default.
• W2023843667 title "Electron transfer pathways from the S2-states to the S3-states either after a Ca2+/Sr2+ or a Cl−/I− exchange in Photosystem II from Thermosynechococcus elongatus" @default.
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• W2023843667 doi "https://doi.org/10.1016/j.bbabio.2015.03.006" @default.
• W2023843667 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/25843552" @default.
• W2023843667 hasPublicationYear "2015" @default.
• W2023843667 type Work @default.

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