Glycerol binding at the narrow channel of photosystem II stabilizes the low-spin S₂ state of the oxygen-evolving complex.

ABSTRACT: The oxygen-evolving complex (OEC) of photosystem II (PSII) cycles through redox intermediate states S_i (i = 0-4) during the photochemical oxidation of water. The S₂ state involves an equilibrium of two isomers including the low-spin S₂ (LS-S₂) state with its characteristic electron paramagnetic resonance (EPR) multiline signal centered at g = 2.0, and a high-spin S₂ (HS-S₂) state with its g = 4.1 EPR signal. The relative intensities of the two EPR signals change under experimental conditions that shift the HS-S₂/LS-S₂ state equilibrium. Here, we analyze the effect of glycerol on the relative stability of the LS-S₂ and HS-S₂ states when bound at the narrow channel of PSII, as reported in an X-ray crystal structure of cyanobacterial PSII. Our quantum mechanics/molecular mechanics (QM/MM) hybrid models of cyanobacterial PSII show that the glycerol molecule perturbs the hydrogen-bond network in the narrow channel, increasing the pK_a of D1-Asp61 and stabilizing the LS-S₂ state relative to the HS-S₂ state. The reported results are consistent with the absence of the HS-S₂ state EPR signal in native cyanobacterial PSII EPR spectra and suggest that the narrow water channel hydrogen-bond network regulates the relative stability of OEC catalytic intermediates during water oxidation.

SUBMITTER: Flesher DA 

PROVIDER: S-EPMC9427693 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature