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Only quinones with a 2-methoxy group can act simultaneously as the primary (QA) and secondary (QB) electron acceptors in photosynthetic reaction centers from Rhodobacter sphaeroides. (13)C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQA and SQB, were compared with quantum mechanics calculations of the (13)C couplings as a function of the dihedral angle. X-ray structures support dihedral angle assignments corresponding to a redox potential gap (ΔEm) between QA and QB of ~180 mV. This is consistent with the failure of a ubiquinone analogue lacking the 2-methoxy to function as QB in mutant reaction centers with a ΔEm of ≈160-195 mV.

biochemistry

Tuning Cofactor Redox Potentials: The 2-Methoxy Dihedral Angle Generates a Redox Potential Difference of &gt;160 mV between the Primary (Q<sub>A</sub>) and Secondary (Q<sub>B</sub>) Quinones of the Bacterial Photosynthetic Reaction Center

Tuning Cofactor Redox Potentials: The 2-Methoxy Dihedral Angle Generates a Redox Potential Difference of >160 mV between the Primary (QA) and Secondary (QB) Quinones of the Bacterial Photosynthetic Reaction Center

Tuning Cofactor Redox Potentials: The 2-Methoxy Dihedral Angle Generates a Redox Potential Difference of >160 mV between the Primary (Q_A) and Secondary (Q_B) Quinones of the Bacterial Photosynthetic Reaction Center