Evaluation of excitation schemes for indirect detection of 14N via solid-state HMQC NMR experiments

Abstract: It has previously been shown that ${}^{14}$N NMR spectra can be reliably obtained through indirect detection via HMQC experiments. This method exploits the transfer of coherence between single- (SQ) or double-quantum (DQ) ${}^{14}$N coherences, and SQ coherences of a suitable spin-1/2 'spy' nucleus, e.g., ${}^1$H. It must be noted that SQ-SQ methods require a carefully optimized setup to minimize the broadening related to the first-order quadrupole interaction (i.e., an extremely well-adjusted magic angle and a highly stable spinning speed), whereas DQ-SQ ones do not. In this work, the efficiencies of four ${}^{14}$N excitation schemes (DANTE, XiX, Hard Pulse (HP), and Selective Long Pulse (SLP)) are compared using J-HMQC based numerical simulations and either SQ-SQ or DQ-SQ ${}^1$H-{${}^{14}$N} D-HMQC experiments on L-histidine HCl and N-acetyl-L-valine at 18.8 T and 62.5 kHz MAS. The results demonstrate that both DANTE and SLP provide a more efficient 14N excitation profile than XiX and HP. Furthermore, it is shown that the SLP scheme: (i) is efficient over a large range of quadrupole interaction, (ii) is highly robust to offset and rf-pulse length and amplitude, and (iii) is very simple to set up. These factors make SLP ideally suited to widespread, non-specialist use in solid-state NMR analyses of nitrogen-containing materials.