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Nitroxide Spin Labels—Magnetic Parameters and Hydrogen-Bond Formation: A High-Field EPR and EDNMR Study

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Abstract

In this work, we report on a detailed high-field EPR investigation of magnetic parameters of deuterated nitroxide radicals dissolved in deuterated frozen solvents of polar or unpolar, protic or aprotic character including ortho-terphenyl, methanol, propanol, glycerol, aniline, phenol, and water. The analysis of the high-resolution W-band (95 GHz) pulsed ELDOR-detected NMR (EDNMR) and 244 GHz cw EPR spectra yielded precise electron Zeeman, gxx, 14N hyperfine, Azz, and 14N quadrupole, Pzz, tensor components, which are most sensitive probes for the microenvironment of dissolved nitroxide radicals. Remarkable changes in the solvation networks were found in the various matrices. The solvent-dependent magnetic parameters of the nitroxide are discussed on the basis of previous semi-empirical and DFT quantum chemical calculations in an attempt to adequately model the nitroxide–matrix interactions. The obtained results demonstrate that the principal values of all the magnetic interaction parameters primarily depend on the nitroxide hydrogen-bond situation and the type of hydrogen-bond donor group of the solvent. The solvent bulk polarity, as described by the static dielectric constant, is of minor importance.

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Acknowledgements

We thank Yuri Grishin (Institute of Chemical Kinetics and Combustion, Novosibirsk, Russia) for enduring technical support and Herbert Zimmermann (Max-Planck Institute for Medical Research, Heidelberg) for providing the deuterated nitroxide radical. We thank Gudrun Klihm (Max Planck Institute for Chemical Energy Conversion, Mülheim) for technical assistance with the 244 GHz EPR spectrometer. This work was supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft and the Max-Planck-Gesellschaft. K.M. and M.P. acknowledge sustaining support by the Freie Universität Berlin.

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Authors and Affiliations

  1. Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany

    Anna Nalepa, Klaus Möbius, Wolfgang Lubitz & Anton Savitsky

  2. Department of Physics, Free University Berlin, Arnimallee 14, 14195, Berlin, Germany

    Klaus Möbius & Martin Plato

  3. Faculty of Physics, Technical University Dortmund, Otto-Hahn-Str. 4a, 44227, Dortmund, Germany

    Anton Savitsky

Authors
  1. Anna Nalepa
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  2. Klaus Möbius
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  3. Martin Plato
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  4. Wolfgang Lubitz
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  5. Anton Savitsky
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Correspondence to Anton Savitsky.

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Dedicated to Jack H. Freed (Cornell University, N. Y., USA) on the occasion of his 80th birthday.

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Nalepa, A., Möbius, K., Plato, M. et al. Nitroxide Spin Labels—Magnetic Parameters and Hydrogen-Bond Formation: A High-Field EPR and EDNMR Study. Appl Magn Reson 50, 1–16 (2019). https://doi.org/10.1007/s00723-018-1073-3

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  • DOI: https://doi.org/10.1007/s00723-018-1073-3

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