Calcium, conformational selection, and redox-active tyrosine YZ in the photosynthetic oxygen-evolving cluster.

ABSTRACT: In Photosystem II (PSII), YZ (Tyr161D1) participates in radical transfer between the chlorophyll donor and the Mn₄CaO₅ cluster. Under flashing illumination, the metal cluster cycles among five S_n states, and oxygen is evolved from water. The essential YZ is transiently oxidized and reduced on each flash in a proton-coupled electron transfer (PCET) reaction. Calcium is required for function. Of reconstituted divalent ions, only strontium restores oxygen evolution. YZ is predicted to hydrogen bond to calcium-bound water and to His190D1 in PSII structures. Here, we report a vibrational spectroscopic study of YZ radical and singlet in the presence of the metal cluster. The S₂ state is trapped by illumination at 190 K; flash illumination then generate

SUBMITTER: Guo Z 

PROVIDER: S-EPMC5984522 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature