Off-resonance NOVEL

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2017
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Jain, Sheetal K.
Griffin, Robert G.
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The Journal of Chemical Physics. 2017, 147(16), 164201. ISSN 0021-9606. eISSN 1089-7690. Available under: doi: 10.1063/1.5000528
Zusammenfassung

Dynamic nuclear polarization (DNP) is theoretically able to enhance the signal in nuclear magnetic resonance (NMR) experiments by a factor γen, where γ’s are the gyromagnetic ratios of an electron and a nuclear spin. However, DNP enhancements currently achieved in high-field, high-resolution biomolecular magic-angle spinning NMR are well below this limit because the continuous-wave DNP mechanisms employed in these experiments scale as ω−n0 where n ~ 1–2. In pulsed DNP methods, such as nuclear orientation via electron spin-locking (NOVEL), the DNP efficiency is independent of the strength of the main magnetic field. Hence, these methods represent a viable alternative approach for enhancing nuclear signals. At 0.35 T, the NOVEL scheme was demonstrated to be efficient in samples doped with stable radicals, generating 1H NMR enhancements of ~430. However, an impediment in the implementation of NOVEL at high fields is the requirement of sufficient microwave power to fulfill the on-resonance matching condition, ω0I = ω1S, where ω0I and ω1S are the nuclear Larmor and electron Rabi frequencies, respectively. Here, we exploit a generalized matching condition, which states that the effective Rabi frequency, ωeff1S, matches ω0I. By using this generalized off-resonance matching condition, we generate 1H NMR signal enhancement factors of 266 (~70% of the on-resonance NOVEL enhancement) with ω1S/2π = 5 MHz. We investigate experimentally the conditions for optimal transfer of polarization from electrons to 1H both for the NOVEL mechanism and the solid-effect mechanism and provide a unified theoretical description for these two historically distinct forms of DNP.

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Fachgebiet (DDC)
540 Chemie
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pulsed DNP, NOVEL, MAS NMR, trityl radicals
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ISO 690JAIN, Sheetal K., Guinevere MATHIES, Robert G. GRIFFIN, 2017. Off-resonance NOVEL. In: The Journal of Chemical Physics. 2017, 147(16), 164201. ISSN 0021-9606. eISSN 1089-7690. Available under: doi: 10.1063/1.5000528
BibTex
@article{Jain2017-10-28Offre-40823,
  year={2017},
  doi={10.1063/1.5000528},
  title={Off-resonance NOVEL},
  number={16},
  volume={147},
  issn={0021-9606},
  journal={The Journal of Chemical Physics},
  author={Jain, Sheetal K. and Mathies, Guinevere and Griffin, Robert G.},
  note={Article Number: 164201}
}
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