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

Alexander T. Taguchi; Aidas J. Mattis; Patrick J. O'Malley; Sergei A. Dikanov; Colin A. Wraight

doi:10.1021/bi4011896

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

Alexander T. Taguchi, Aidas J. Mattis, Patrick J. O'Malley, Sergei A. Dikanov, Colin A. Wraight

Research output: Contribution to journal › Article › peer-review

Abstract

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. 13C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQA and SQB, were compared with quantum mechanics calculations of the 13C 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 Q B 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. © 2013 American Chemical Society.

Original language	English
Pages (from-to)	7164-7166
Number of pages	2
Journal	Biochemistry
Volume	52
Issue number	41
DOIs	https://doi.org/10.1021/bi4011896
Publication status	Published - 15 Oct 2013

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Taguchi, A. T., Mattis, A. J., O'Malley, P. J., Dikanov, S. A., & Wraight, C. A. (2013). 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. Biochemistry, 52(41), 7164-7166. https://doi.org/10.1021/bi4011896

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title = "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",

abstract = "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. 13C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQA and SQB, were compared with quantum mechanics calculations of the 13C 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 Q B 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. {\textcopyright} 2013 American Chemical Society.",

author = "Taguchi, {Alexander T.} and Mattis, {Aidas J.} and O'Malley, {Patrick J.} and Dikanov, {Sergei A.} and Wraight, {Colin A.}",

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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. / Taguchi, Alexander T.; Mattis, Aidas J.; O'Malley, Patrick J. et al.
In: Biochemistry, Vol. 52, No. 41, 15.10.2013, p. 7164-7166.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

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N2 - 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. 13C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQA and SQB, were compared with quantum mechanics calculations of the 13C 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 Q B 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. © 2013 American Chemical Society.

AB - 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. 13C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQA and SQB, were compared with quantum mechanics calculations of the 13C 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 Q B 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. © 2013 American Chemical Society.

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