Formation of tyrosine radicals in photosystem II under far-red illumination

Photosystem II (PS II) contains two redox-active tyrosine residues on the donor side at symmetrical positions to the primary donor, P₆₈₀. Tyr_Z, part of the water-oxidizing complex, is a preferential fast electron donor while Tyr_D is a slow auxiliary donor to P₆₈₀ ⁺. We used PS II membranes from spinach which were depleted of the water oxidation complex (Mn-depleted PS II) to study electron donation from both tyrosines by time-resolved EPR spectroscopy under visible and far-red continuous light and laser flash illumination. Our results show that under both illumination regimes, oxidation of Tyr_D occurs via equilibrium with Tyr_Z ^? at pH 4.7 and 6.3. At pH 8.5 direct Tyr_D oxidation by P₆₈₀ ⁺ occurs in the majority of the PS II centers. Under continuous far-red light illumination these reactions were less effective but still possible. Different photochemical steps were considered to explain the far-red light-induced electron donation from tyrosines and localization of the primary electron hole (P₆₈₀ ⁺) on the Chl_D1 in Mn-depleted PS II after the far-red light-induced charge separation at room temperature is suggested.