Indirect detection of broad spectra in solid-state NMR using interleaved DANTE trains

We analyze the performances and the optimization of ¹H-{I} HMQC experiments using basic and interleaved DANTE schemes for the indirect detection of nuclei I = 1/2 or 1 exhibiting wide lines dominated by chemical shift anisotropy (CSA) or quadrupole interaction, respectively. These sequences are first described using average Hamiltonian theory. Then, we analyze using numerical simulations (i) the optimal lengths of the DANTE train and the individual pulses, (ii) the robustness of these experiments to offset, and (iii) the optimal choice of the defocusing and refocusing times for both ¹H-{I} J- and D-HMQC sequences for ¹⁹⁵Pt (I = 1/2) and ¹⁴N (I = 1) nuclei subject to large CSA and quadrupole interaction, respectively. These simulations are compared to ¹H-{¹⁴N} D-HMQC experiments on γ-glycine and L-histidine.HCl at B₀ = 18.8 T and MAS frequency of 62.5 kHz. The present study shows that (i) the optimal defocusing and refocusing times do not depend on the chosen DANTE scheme, (ii) the DANTE trains must be applied with the highest rf-field compatible with the probe specifications and the stability of the sample, (iii) the excitation bandwidth along the indirect dimension of HMQC sequence using DANTE trains is inversely proportional to their length, (iv) interleaved DANTE trains increase the excitation bandwidth of these sequences, and (v) dephasing under residual ¹H–¹H and ¹H-I dipolar couplings, as well as ¹⁴N second-order quadrupole interaction, during the length of the DANTE scheme attenuate the transfer efficiency.