Comment on mr-2021-29

Abstract

Half-integer spin quadrupolar nuclei are the only magnetic isotopes for the majority of the chemical elements.Therefore, the transfer of polarization from protons to these isotopes under magic-angle spinning (MAS) can provide precious insights into the interatomic proximities in hydrogen-containing solids, including organic, hybrid, nanostructured and biological solids. Furthermore, this transfer has recently been combined with dynamic nuclear polarization (DNP) in order to enhance the NMR signal of half-integer quadrupolar isotope. Nevertheless, the cross-polarization transfer lacks of robustness in the case of quadrupolar nuclei and we have recently introduced as an alternative technique a through-space refocused insensitive nuclei enhancement by polarization transfer (D-RINEPT) scheme combining hetero-nuclear dipolar recoupling built from adiabatic pulses and continuous wave decoupling. This technique has been demonstrated at 9.4 T with moderate MAS frequencies, νR  10-15 kHz, in order to transfer the DNP-enhanced 1 H polarization to quadrupolar nuclei. Nevertheless, polarization transfers from protons to quadrupolar nuclei are also required at higher MAS frequencies in order to improve the resolution of 1 H spectra. We investigate how this transfer can be achieved at νR  20 and 60 kHz. We demonstrate that the D-RINEPT sequence using adiabatic pulses still produces efficient and robust transfer but requires large rf-fields, which may not be compatible with the specifications of commonly employed MAS NMR probes. As an alternative, we introduce robust and efficient variants of D-RINEPT and PRESTO (phase-shifted recoupling effects a smooth transfer of order) sequences using symmetry-based recoupling schemes built from single and composite π-pulses. Their performances are compared using the