Kinetic modeling of electron transfer reactions in photosystem I complexes of various structures with substituted...

The reduction kinetics of the photo-oxidized primary electron donor P₇₀₀ in photosystem I (PS I) complexes from cyanobacteria Synechocystis sp. PCC 6803 were analyzed within the kinetic model, which considers electron transfer (ET) reactions between P₇₀₀, secondary quinone acceptor A₁, iron-sulfur clusters and external electron donor and acceptors - methylviologen (MV), 2,3-dichloro-naphthoquinone (Cl₂NQ) and oxygen. PS I complexes containing various quinones in the A₁-binding site (phylloquinone PhQ, plastoquinone-9 PQ and Cl₂NQ) as well as F _X-core complexes, depleted of terminal iron-sulfur F _A/F _B clusters, were studied. The acceleration of charge recombination in F _X-core complexes by PhQ/PQ substitution indicates that backward ET from the iron-sulfur clusters involves quinone in the A₁-binding site. The kinetic parameters of ET reactions were obtained by global fitting of the P₇₀₀⁺ reduction with the kinetic model. The free energy gap ΔG ₀ between F _X and F _A/F _B clusters was estimated as -130 meV. The driving force of ET from A₁ to F _X was determined as -50 and -220 meV for PhQ in the A and B cofactor branches, respectively. For PQ in A_1A-site, this reaction was found to be endergonic (ΔG ₀ = +75 meV). The interaction of PS I with external acceptors was quantitatively described in terms of Michaelis-Menten kinetics. The second-order rate constants of ET from F _A/F _B, F _X and Cl₂NQ in the A₁-site of PS I to external acceptors were estimated. The side production of superoxide radical in the A₁-site by oxygen reduction via the Mehler reaction might comprise ≥0.3% of the total electron flow in PS I.