Redox potential of quinones in both electron transfer branches of photosystem I

The redox potentials of the two electron transfer (ET) active quinones in the central part of photosystem I (PSI) were determined by evaluating the electrostatic energies from the solution of the Poisson-Boltzmann equation based on the crystal structure. The calculated redox potentials are -531 mV for A1A and -686 mV for A1B. From these results we conclude the following. (i) Both branches are active with a much faster ET in the B-branch than in the A-branch. (ii) The measured lifetime of 200-290 ns of reduced quinones agrees with the estimate for the A-branch and corroborates with an uphill ET from this quinone to the iron-sulfur cluster as observed in recent kinetic measurements. (iii) The electron paramagnetic resonance spectroscopic data refer to the A-branch quinone where the corresponding ET is uphill in energy. The negative redox potential of A1 in PSI is primarily because of the influence from the negatively charged FX, in contrast to the positive shift on the quinone redox potential in bacterial reaction center and PSII that is attributed to the positively charged non-heme iron atom. The conserved residue Asp-B575 changes its protonation state after quinone reduction. The difference of 155 mV in the quinone redox potentials of the two branches were attributed to the conformation of the backbone with a large contribution from Ser-A692 and Ser-B672 and to the side chain of Asp-B575, whose protonation state couples differently with the formation of the quinone radicals.