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J Magn Reson. 2015 Sep;258:86-95. doi: 10.1016/j.jmr.2015.06.008. Epub 2015 Jul 7.

Comparison of various NMR methods for the indirect detection of nitrogen-14 nuclei via protons in solids.

Author information

1
UCCS, CNRS UMR 8181, Univ. Lille, Villeneuve d'Ascq 59652, France; Physics Department & Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China.
2
UCCS, CNRS UMR 8181, Univ. Lille, Villeneuve d'Ascq 59652, France.
3
Institute for Frontier Materials, Deakin University, Waurn Ponds Campus, Geelong, Victoria 3220, Australia.
4
UCCS, CNRS UMR 8181, Univ. Lille, Villeneuve d'Ascq 59652, France. Electronic address: olivier.lafon@univ-lille1.fr.
5
Physics Department & Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China.
6
UCCS, CNRS UMR 8181, Univ. Lille, Villeneuve d'Ascq 59652, France; Physics Department & Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062, China. Electronic address: jean-paul.amoureux@univ-lille1.fr.

Abstract

We present an experimental comparison of several through-space Hetero-nuclear Multiple-Quantum Correlation experiments, which allow the indirect observation of homo-nuclear single- (SQ) or double-quantum (DQ) (14)N coherences via spy (1)H nuclei. These (1)H-{(14)N} D-HMQC sequences differ not only by the order of (14)N coherences evolving during the indirect evolution, t1, but also by the radio-frequency (rf) scheme used to excite and reconvert these coherences under Magic-Angle Spinning (MAS). Here, the SQ coherences are created by the application of center-band frequency-selective pulses, i.e. long and low-power rectangular pulses at the (14)N Larmor frequency, ν0((14)N), whereas the DQ coherences are excited and reconverted using rf irradiation either at ν0((14)N) or at the (14)N overtone frequency, 2ν0((14)N). The overtone excitation is achieved either by constant frequency rectangular pulses or by frequency-swept pulses, specifically Wide-band, Uniform-Rate, and Smooth-Truncation (WURST) pulse shapes. The present article compares the performances of four different (1)H-{(14)N} D-HMQC sequences, including those with (14)N rectangular pulses at ν0((14)N) for the indirect detection of homo-nuclear (i) (14)N SQ or (ii) DQ coherences, as well as their overtone variants using (iii) rectangular or (iv) WURST pulses. The compared properties include: (i) the sensitivity, (ii) the spectral resolution in the (14)N dimension, (iii) the rf requirements (power and pulse length), as well as the robustness to (iv) rf offset and (v) MAS frequency instabilities. Such experimental comparisons are carried out for γ-glycine and l-histidine.HCl monohydrate, which contain (14)N sites subject to moderate quadrupole interactions. We demonstrate that the optimum choice of the (1)H-{(14)N} D-HMQC method depends on the experimental goal. When the sensitivity and/or the robustness to offset are the major concerns, the D-HMQC sequence allowing the indirect detection of (14)N SQ coherences should be employed. Conversely, when the highest resolution and/or adjusted indirect spectral width are needed, overtone experiments are the method of choice. The overtone scheme using WURST pulses results in broader excitation bandwidths than that using rectangular pulses, at the expense of reduced sensitivity. Numerically exact simulations also show that the sensitivity of the overtone (1)H-{(14)N} D-HMQC experiment increases for larger quadrupole interactions.

KEYWORDS:

(14)N isotope; Indirect detection; Overtone; Solid-state NMR; Through-space HETCOR

PMID:
26232366
DOI:
10.1016/j.jmr.2015.06.008

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