The S1 to S2 and S2 to S3 state transitions in plant photosystem II: relevance to the functional and structural heterogeneity of the water oxidizing complex

Photosynth Res. 2024 Apr 25. doi: 10.1007/s11120-024-01096-4. Online ahead of print.

Abstract

In Photosystem II, light-induced water splitting occurs via the S state cycle of the CaMn4O5-cluster. To understand the role of various possible conformations of the CaMn4O5-cluster in this process, the temperature dependence of the S1 → S2 and S2 → S3 state transitions, induced by saturating laser flashes, was studied in spinach photosystem II membrane preparations under different conditions. The S1 → S2 transition temperature dependence was shown to be much dependent on the type of the cryoprotectant and presence of 3.5% methanol, resulting in the variation of transition half-inhibition temperature by 50 K. No similar effect was observed for the S2 → S3 state transition, for which we also show that both the low spin g = 2.0 multiline and high spin g = 4.1 EPR configurations of the S2 state advance with similar efficiency to the S3 state, both showing a transition half-inhibition temperature of 240 K. This was further confirmed by following the appearance of the Split S3 EPR signal. The results are discussed in relevance to the functional and structural heterogeneity of the water oxidizing complex intermediates in photosystem II.

Keywords: Electron paramagnetic resonance; High spin S2 state; Low spin S2 state; Photosystem II; S state transitions; Temperature dependence; Water oxidation.