Electrogenic reactions in Mn-depleted photosystem II core particles in the presence of synthetic binuclear Mn complexes

An electrometrical technique was used to investigate electron transfer between synthetic binuclear manganese (Mn) complexes, designated M − 2 and M − 3, and the redox-active neutral tyrosine radical (Y_Z ^•) in proteoliposomes containing Mn-depleted photosystem II (PS II) core particles in response to single laser flashes. In the absence of Mn-containing compounds, the observed flash-induced membrane potential (ΔΨ) decay was mainly due to charge recombination between the reduced primary quinone acceptor Q_A ⁻ and the oxidized Y_Z ^•. More significant slowing down of the ΔΨ decay in the presence of lower concentrations of M − 2 and M − 3 associated with electron donation from Mn in the Mn-binding site to Y_Z ^• indicates that these synthetic compounds are more effective electron donors than MnCl₂. The exponential fitting of the kinetics of additional electrogenic components of ΔΨ rise in the presence of Mn-containing compounds revealed the following relative amplitudes (A) and lifetimes (τ): for MnCl₂ - A∼ 3.5, τ∼150 μs, for M − 2 - A∼5%, τ∼1.4 ms, and for M − 3 - A∼5.5%, τ∼150 μs. This suggests that the efficiency of the manganese complexes in electron donation depends on the chemical nature of ligands. The experiments with EDTA-treated samples indicated that the ligands for M − 2 and M − 3 are required for their tight binding with the PS II reaction center. The obtained results demonstrate the importance of understanding the molecular mechanism(s) of flash-induced electrogenic reduction of the tyrosine radical Y_Z ^• by synthetic Mn complexes capable of splitting water into oxygen and reducing equivalents.