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Hyperfine Interaction Tensors of 13C Nuclei for Ring Carbons of Ubisemiquinone-10 Hydrogen Bonded in Alcohol Solvents

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Abstract

The anion radicals of ubiquinones-10 13C chemically labeled at the C5 or C6 ring positions in alcohol have been studied by 1D and 2D ESEEM to define the hyperfine interaction tensors with the 13C nuclei. Analysis of the cross-peak line shapes and simulations of the spectra allowed us to conclude that the hyperfine tensors are characterized by an anisotropic component T ~6 MHz and an isotropic coupling a ~−3 MHz with support from DFT calculations. However, these values were found to be inconsistent with the shift of the sum combination harmonic in the four-pulse ESEEM spectra. Simulations resolve this apparent discrepancy by showing that the shift of the sum combination to lower frequency and its broadening can be accounted for by a distribution of the hyperfine couplings. A spread of the methoxy group conformations, as supported by previous experimental observations, is suggested as the mechanism influencing the distribution of the hyperfine couplings for the ring carbons.

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Acknowledgments

This research was supported by the DE-FG02-08ER15960 Grant from Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Sciences, US Department of Energy and NIH Grant GM062954 (S.A.D.), and NCRR/NIH Grant S10-RR15878 and S10-RR025438 for pulsed EPR instrumentation. A.T.T. gratefully acknowledges support as a NIH trainee of the Molecular Biophysics Training Program (5T32-GM008276). P.J.O’M. acknowledges the use of computer resources granted by the EPSRC UK national service for computational chemistry software (NSCCS). Part of this work was supported by the Netherlands Organization for Scientific Research (NOW). R.I.S. thanks NOW for sponsoring her stay at Leiden University and the group of Prof. J. Lugtenburg for its hospitality.

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Authors and Affiliations

  1. V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Russian Academy of Sciences, Novosibirsk, 630090, Russian Federation

    Rimma I. Samoilova

  2. Center for Biophysics and Computational Biology, University of Illinois at Urbana-Champaign, Urbana, IL, 61801, USA

    Alexander T. Taguchi

  3. Department of Veterinary Clinical Medicine, University of Illinois at Urbana-Champaign, Urbana, IL, 61801, USA

    Sergei A. Dikanov

  4. School of Chemistry, The University of Manchester, Manchester, M13 9PL, UK

    Patrick J. O’Malley

  5. Leiden Institute of Chemistry, Gorlaeus Laboratory, Leiden University, P. O. Box 9502, 2300 RA, Leiden, Netherlands

    Johan Lugtenburg

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  1. Rimma I. Samoilova
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  2. Alexander T. Taguchi
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  3. Patrick J. O’Malley
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  4. Sergei A. Dikanov
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  5. Johan Lugtenburg
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Corresponding authors

Correspondence to Patrick J. O’Malley, Sergei A. Dikanov or Johan Lugtenburg.

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723_2014_574_MOESM1_ESM.docx

Figure S1-structure and IUPAC numbering of ubiquinone-10; Figures S2–S3 experimental 1D and 2D ESEEM spectra; Figures S4–S7 comparison of calculated and experimental spectra (DOCX 1287 kb)

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Samoilova, R.I., Taguchi, A.T., O’Malley, P.J. et al. Hyperfine Interaction Tensors of 13C Nuclei for Ring Carbons of Ubisemiquinone-10 Hydrogen Bonded in Alcohol Solvents. Appl Magn Reson 45, 941–953 (2014). https://doi.org/10.1007/s00723-014-0574-y

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  • DOI: https://doi.org/10.1007/s00723-014-0574-y

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