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Temperature dependence of cross-effect dynamic nuclear polarization in rotating solids: advantages of elevated temperatures

Publication: Research - peer-reviewJournal article

DOI

  • Michel-Andreas Geiger
    Michel-Andreas GeigerDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Marcella Orwick-Rydmark
    Marcella Orwick-RydmarkDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Katharina Märker
    Katharina MärkerDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • W Trent Franks
    W Trent FranksDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Dmitry Akhmetzyanov
    Dmitry AkhmetzyanovGoethe-University Frankfurt am Main, Institute of Physical and Theoretical Chemistry and Center for Biomolecular Magnetic Resonance, Max von Laue Str. 7, 60438 Frankfurt am Main, Germany.
  • Daniel Stöppler
    Daniel StöpplerDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Maximilian Zinke
    Maximilian ZinkeDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Edgar Specker
    Edgar SpeckerDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Marc Nazaré
    Marc NazaréDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Anne Diehl
    Anne DiehlDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Barth-Jan van Rossum
    Barth-Jan van RossumDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.
  • Fabien Aussenac
    Fabien AussenacBruker BioSpin S.A.S., 34 rue de l'industire, 67166 Wissembourg, France.
  • Thomas Prisner
    Thomas PrisnerGoethe-University Frankfurt am Main, Institute of Physical and Theoretical Chemistry and Center for Biomolecular Magnetic Resonance, Max von Laue Str. 7, 60438 Frankfurt am Main, Germany.
  • Ümit Akbey
  • Hartmut Oschkinat
    Hartmut OschkinatDepartment for Structural Biology, Leibniz-Institut für Molekulare Pharmakologie, Robert Roessle-Str. 10, 13125 Berlin, Germany. oschkinat@fmp-berlin.de.

Dynamic nuclear polarization exploits electron spin polarization to boost signal-to-noise in magic-angle-spinning (MAS) NMR, creating new opportunities in materials science, structural biology, and metabolomics studies. Since protein NMR spectra recorded under DNP conditions can show improved spectral resolution at 180-200 K compared to 110 K, we investigate the effects of AMUPol and various deuterated TOTAPOL isotopologues on sensitivity and spectral resolution at these temperatures, using proline and reproducibly prepared SH3 domain samples. The TOTAPOL deuteration pattern is optimized for protein DNP MAS NMR, and signal-to-noise per unit time measurements demonstrate the high value of TOTAPOL isotopologues for Protein DNP MAS NMR at 180-200 K. The combined effects of enhancement, depolarization, and proton longitudinal relaxation are surprisingly sample-specific. At 200 K, DNP on SH3 domain standard samples yields a 15-fold increase in signal-to-noise over a sample without radicals. 2D and 3D NCACX/NCOCX spectra were recorded at 200 K within 1 and 13 hours, respectively. Decreasing enhancements with increasing (2)H-content at the CH2 sites of the TEMPO rings in CD3-TOTAPOL highlight the importance of protons in a sphere of 4-6 Å around the nitroxyl group, presumably for polarization pickup from electron spins.

Original languageEnglish
JournalPhysical Chemistry Chemical Physics
Volume18
Pages (from-to)30696-30704
Number of pages9
ISSN1463-9076
DOIs
StatePublished - 28 Oct 2016

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