Electron Acceptor-Donor Iron Sites in the Iron-Sulfur Cluster of Photosynthetic Electron-Transfer Pathways

In photosystem I, two electron-transfer pathways via quinones (A_1A and A_1B) are merged at the iron-sulfur Fe₄S₄ cluster F_X into a single pathway toward the other two Fe₄S₄ clusters F_A and F_B. Using a quantum mechanical/molecular mechanical approach, we identify the redox-active Fe sites in the clusters. In F_A and F_B, the Fe site, which does not belong to the CxxCxxCxxxCP motif, serves as an electron acceptor/donor. F_X has two independent electron acceptor Fe sites for A- and B-branch electron transfers, depending on the Asp-B575 protonation state, which causes the A_1A-to-F_X electron transfer to be uphill and the A_1B-to-F_X electron transfer to be downhill. The two asymmetric electron-transfer pathways from A₁ to F_X and the separation of the electron acceptor and donor Fe sites are likely associated with the specific role of F_X in merging the two electron transfer pathways into the single pathway.