Abstract
Photosystem II catalyzes photosynthetic water oxidation in plants, green algae, and cyanobacteria. The manganese-containing active site cycles through a series of five oxidation states, Sn, where n refers to the number of oxidizing equivalents stored. In this report, reaction-induced Fourier transform infrared and electron paramagnetic resonance spectra of the S1-to-S2 transition are presented. These data suggest that changes in carboxylate ligation to manganese, changes in secondary structure, and/or changes in polarity occur during dark adaptation in the S1 state. These spontaneous structural changes are attributed to a S1′ intermediate, at the same oxidation level as S1, in the process of photosynthetic water oxidation.
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