Combining fast magic angle spinning dynamic nuclear polarization with indirect detection to further enhance the sensitivity of solid-state NMR spectroscopy

Abstract

Dynamic nuclear polarization (DNP) and indirect detection are two commonly applied approaches for enhancing the sensitivity of solid-state NMR spectroscopy. However, their use in tandem has not yet been investigated. With the advent of low-temperature fast magic angle spinning (MAS) probes with 1.3-mm diameter rotors capable of MAS at 40 ​kHz it becomes feasible to combine these two techniques. In this study, we performed DNP-enhanced 2D indirectly detected heteronuclear correlation (idHETCOR) experiments on ¹³C, ¹⁵N, ¹¹³Cd and ⁸⁹Y nuclei in functionalized mesoporous silica, CdS nanoparticles, and Y₂O₃ nanoparticles. The sensitivity of the 2D idHETCOR experiments was compared with those of DNP-enhanced directly-detected 1D cross polarization (CP) and 2D HETCOR experiments performed with a standard 3.2-mm rotor. Due to low CP polarization transfer efficiencies and large proton linewidth, the sensitivity gains achieved by indirect detection alone were lower than in conventional (non-DNP) experiments. Nevertheless, despite the smaller sample volume the 2D idHETCOR experiments showed better absolute sensitivities than 2D HETCOR experiments for nuclei with the lowest gyromagnetic ratios. For ⁸⁹Y, 2D idHETCOR provided 8.2 times better sensitivity than the 1 D⁸⁹Y-detected CP experiment performed with a 3.2-mm rotor.