Improved resolution for spin-3/2 isotopes in solids via the indirect NMR detection of triple-quantum coherences using the T-HMQC sequence

The indirect NMR detection of quadrupolar nuclei in solids under magic-angle spinning (MAS) is possible with the through-space HMQC (heteronuclear multiple -quantum coherence) scheme incorporating the TRAPDOR (transfer of population in double-resonance) dipolar recoupling. This sequence, called T-HMQC, ex-hibits limited t1-noise. In this contribution, with the help of numerical simulations of spin dynamics, we show that most of the time, the fastest coherence transfer in the T-HMQC scheme is achieved when TRAPDOR recoupling employs the highest radiofrequency (rf) field compatible with the probe specifications. We also demonstrate how the indirect detection of the triple-quantum (3Q) coherences of spin-3/2 quadrupolar nuclei in solids improves the spectral resolution for these isotopes. The sequence is then called T-HMQC3. We demonstrate the gain in resolution provided by this sequence for the indirect proton detection of 35Cl nuclei in L- histidine center dot HCl and L-cysteine center dot HCl, as well as that of 23Na isotope in NaH2PO4. These experiments indicate that the gain in resolution depends on the relative values of the chemical and quadrupolar-induced shifts (QIS) for the different spin-3/2 species. In the case of NaH2PO4, we show that the transfer efficiency of the T-HMQC3 sequence employing an rf-field of 80 kHz with a MAS frequency of 62.5 kHz reaches 75% of that of the t1-noise eliminated (TONE) dipolar-mediated HMQC (D- HMQC) scheme.