Journal article:
Efficient cross-effect dynamic nuclear polarization without depolarization in high-resolution MAS NMR

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2017
Editors
Mentink-Vigier, Frédéric
Liu, Yangping
Barra, Anne-Laure
Caporini, Marc A.
Lee, Daniel
Hediger, Sabine
Griffin, Robert G.
De Paëpe, Gaël
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Abstract
Dynamic nuclear polarization (DNP) has the potential to enhance the sensitivity of magic-angle spinning (MAS) NMR by many orders of magnitude and therefore to revolutionize atomic resolution structural analysis. Currently, the most widely used approach to DNP for studies of chemical, material, and biological systems involves the cross-effect (CE) mechanism, which relies on biradicals as polarizing agents. However, at high magnetic fields (≥5 T), the best biradicals used for CE MAS-DNP are still far from optimal, primarily because of the nuclear depolarization effects they induce. In the presence of bisnitroxide biradicals, magic-angle rotation results in a reverse CE that can deplete the initial proton Boltzmann polarization by more than a factor of 2. In this paper we show that these depolarization losses can be avoided by using a polarizing agent composed of a narrow-line trityl radical tethered to a broad-line TEMPO. Consequently, we show that a biocompatible trityl-nitroxide biradical, TEMTriPol-1, provides the highest MAS NMR sensitivity at ≥10 T, and its relative efficiency increases with the magnetic field strength. We use numerical simulations to explain the absence of depolarization for TEMTriPol-1 and its high efficiency, paving the way for the next generation of polarizing agents for DNP. We demonstrate the superior sensitivity enhancement using TEMTriPol-1 by recording the first solid-state 2D 13C–13C correlation spectrum at natural isotopic abundance at a magnetic field of 18.8 T.
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540 Chemistry
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Chemical Science ; 8 (2017), 12. - pp. 8150-8163. - ISSN 2041-6520. - eISSN 2041-6539
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Cite This
ISO 690MENTINK-VIGIER, Frédéric, Guinevere MATHIES, Yangping LIU, Anne-Laure BARRA, Marc A. CAPORINI, Daniel LEE, Sabine HEDIGER, Robert G. GRIFFIN, Gaël DE PAËPE, 2017. Efficient cross-effect dynamic nuclear polarization without depolarization in high-resolution MAS NMR. In: Chemical Science. 8(12), pp. 8150-8163. ISSN 2041-6520. eISSN 2041-6539. Available under: doi: 10.1039/c7sc02199b
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@article{MentinkVigier2017Effic-41325,
  year={2017},
  doi={10.1039/c7sc02199b},
  title={Efficient cross-effect dynamic nuclear polarization without depolarization in high-resolution MAS NMR},
  number={12},
  volume={8},
  issn={2041-6520},
  journal={Chemical Science},
  pages={8150--8163},
  author={Mentink-Vigier, Frédéric and Mathies, Guinevere and Liu, Yangping and Barra, Anne-Laure and Caporini, Marc A. and Lee, Daniel and Hediger, Sabine and Griffin, Robert G. and De Paëpe, Gaël}
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