Recent studies have shown that only quinones with a 2-methoxy group can act simultaneously as the primary (Q) and secondary (Q) electron acceptors in photosynthetic reaction centers from purple bacteria such as . C HYSCORE measurements of the 2-methoxy group in the semiquinone states, SQ and SQ, were compared with DFT calculations of the C hyperfine couplings as a function of the 2-methoxy dihedral angle. X-ray structure comparisons support 2-methoxy dihedral angle assignments corresponding to a redox potential gap (Δ) between Q and Q of 175-193 mV. A model having a methyl group substituted for the 2-methoxy group exhibits no electron affinity difference. This is consistent with the failure of a 2-methyl ubiquinone analogue to function as Q in mutant reaction centers with a Δ of ∼160-195 mV. The conclusion reached is that the 2-methoxy group is the principal determinant of electron transfer from Q to Q in type II photosynthetic reaction centers with ubiquinone serving as both acceptor quinones.
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| http://dx.doi.org/10.1021/jz500967d | DOI Listing |
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