Solid-state NMR indirect detection of nuclei experiencing large anisotropic interactions using spinning sideband-selective pulses

Under Magic-Angle Spinning (MAS), a long radio-frequency (rf) pulse applied on resonance achieves the selective excitation of the center-band of a wide NMR spectrum. We show herein that these rf pulses can be applied on the indirect channel of Hetero-nuclear Multiple-Quantum Correlation (HMQC) sequences, which facilitate the indirect detection via spin-1/2 isotopes of nuclei exhibiting wide spectra. Numerical simulations show that this indirect excitation method is applicable to spin-1/2 nuclei experiencing a large chemical shift anisotropy, as well as to spin-1 isotopes subject to a large quadrupole interaction, such as ¹⁴N. The performances of the long pulses are analyzed by the numerical simulations of scalar-mediated HMQC (J-HMQC) experiments indirectly detecting spin-1/2 or spin-1 nuclei, as well as by dipolar-mediated HMQC (D-HMQC) experiments achieving indirect detection of ¹⁴N nuclei via ¹H in crystalline γ-glycine and N-acetyl-valine samples at a MAS frequency of 60 kHz. We show on these solids that for the acquisition of D-HMQC spectra between ¹H and ¹⁴N nuclei, the efficiency of selective moderate excitation with long-pulses at the ¹⁴N Larmor frequency, ν₀(¹⁴N), is comparable to those with strong excitation pulses at ν₀(¹⁴N) or 2ν₀(¹⁴N) frequencies, given the rf field delivered by common solid-state NMR probes. Furthermore, the D-HMQC experiments also demonstrate that the use of long pulses does not produce significant spectral distortions along the ¹⁴N dimension. In summary, the use of center-band selective weak pulses is advantageous for HMQC experiments achieving the indirect detection of wide spectra since it (i) requires a moderate rf field, (ii) can be easily optimized, (iii) displays a high robustness to CSAs, offsets, rf-field inhomogeneities, and fluctuations in MAS frequency, and (iv) is little dependent on the quadrupolar coupling constant.