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 (Q_A) and secondary (Q_B) quinones of the bacterial photosynthetic reaction center

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

Veterinary Clinical Medicine

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

Abstract

Only quinones with a 2-methoxy group can act simultaneously as the primary (Q_A) and secondary (Q_B) electron acceptors in photosynthetic reaction centers from Rhodobacter sphaeroides. ¹³C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQ_A and SQ_B, 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 (ΔE_m) between Q_A and Q _B of ∼180 mV. This is consistent with the failure of a ubiquinone analogue lacking the 2-methoxy to function as Q_B in mutant reaction centers with a ΔE_m of ≈160-195 mV.

Original language	English (US)
Pages (from-to)	7164-7166
Number of pages	3
Journal	Biochemistry
Volume	52
Issue number	41
DOIs	https://doi.org/10.1021/bi4011896
State	Published - Oct 15 2013

ASJC Scopus subject areas

Biochemistry

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10.1021/bi4011896

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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 (Q_A) and secondary (Q_B) quinones of the bacterial photosynthetic reaction center. Biochemistry, 52(41), 7164-7166. https://doi.org/10.1021/bi4011896

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. / 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

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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.",

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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T2 - 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

AU - Taguchi, Alexander T.

AU - Mattis, Aidas J.

AU - O'Malley, Patrick J.

AU - Dikanov, Sergei A.

AU - Wraight, Colin A.

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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.

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