Population transfer HMQC for half-integer quadrupolar nuclei

This work presents a detailed analysis of a recently proposed nuclear magnetic resonance method [Wang et al., Chem. Commun. 49(59), 6653-6655 (2013)] for accelerating heteronuclear coherence transfers involving half-integer spin quadrupolar nuclei by manipulating their satellite transitions. This method, called Population Transfer Heteronuclear Multiple Quantum Correlation (PT-HMQC), is investigated in details by combining theoretical analyses, numerical simulations, and experimental investigations. We find that compared to instant inversion or instant saturation, continuous saturation is the most practical strategy to accelerate coherence transfers on half-integer quadrupolar nuclei. We further demonstrate that this strategy is efficient to enhance the sensitivity of J-mediated heteronuclear correlation experiments between two half-integer quadrupolar isotopes (e.g., Al-27-O-17). In this case, the build-up is strongly affected by relaxation for small T-2' and J coupling values, and shortening the mixing time makes a huge signal enhancement. Moreover, this concept of population transfer can also be applied to dipolar-mediated HMQC experiments. Indeed, on the AlPO4-14 sample, one still observes experimentally a 2-fold shortening of the optimum mixing time albeit with no significant signal gain in the P-31-{Al-27} experiments. (C) 2015 AIP Publishing LLC.