Efficient transfer of DNP-enhanced 1 H magnetization to half-integer quadrupolar nuclei in solids at moderate spinning rate

Abstract

We show herein how the proton magnetization enhanced by dynamic nuclear polarization (DNP) can be efficiently transferred at moderate magic-angle spinning (MAS) frequencies to half-integer quadrupolar nuclei, S ≥ 3/2, using the Dipolar-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer (D-RINEPT) technique, in which a symmetry-based $\mathrm{SR}{4}_1^2$ recoupling scheme built from adiabatic inversion ¹ H pulses reintroduces the ¹ H-S dipolar couplings, while suppressing the ¹ H-¹ H ones. The use of adiabatic pulses also improves the robustness to offsets and radiofrequency (rf)-field inhomogeneity. Furthermore, the efficiency of the polarization transfer is further improved by using ¹ H composite pulses and continuous-wave irradiations between the recoupling blocks, as well as by manipulating the S satellite transitions during the first recoupling block. Furthermore, in the case of large ¹ H-S dipolar couplings, the D-RINEPT variant with two pulses on the quadrupolar channel results in an improved transfer efficiency. We compare here the performances of this new adiabatic scheme with those of its parent version with single π pulses, as well as with those of PRESTO and CPMAS transfers. This comparison is performed using simulations as well as DNP-enhanced ²⁷ Al, ⁹⁵ Mo, and ¹⁷ O NMR experiments on isotopically unmodified γ-alumina, hydrated titania-supported MoO₃ , Mg(OH)₂ , and l-histidine·HCl·H₂ O. The introduced RINEPT method outperforms the existing methods, both in terms of efficiency and robustness to rf-field inhomogeneity and offset.

Keywords: DNP; adiabatic pulse; half-integer quadrupolar nuclei; solid-state NMR.