Optimisation of 1H PMLG homonuclear decoupling at 60 kHz MAS to enable 15N–1H through-bond heteronuclear correlation solid-state NMR spectroscopy

Abstract

The Lee–Goldburg condition for homonuclear decoupling in ¹H magic-angle spinning (MAS) solid-state NMR sets the angle θ, corresponding to arctan of the ratio of the rf nutation frequency, ν₁, to the rf offset, to be the magic angle, θ_m, equal to tan⁻¹(√2) = 54.7°. At 60 kHz MAS, we report enhanced decoupling compared to MAS alone in a ¹H spectrum of ¹⁵N-glycine with at θ = 30° for a ν₁ of ∼100 kHz at a ¹H Larmor frequency, ν₀, of 500 MHz and 1 GHz, corresponding to a high chemical shift scaling factor (λ_CS) of 0.82. At 1 GHz, we also demonstrate enhanced decoupling compared to 60 kHz MAS alone for a lower ν₁ of 51 kHz, i.e., a case where the nutation frequency is less than the MAS frequency, with θ = 18°, λ_CS = 0.92. The ratio of the rotor period to the decoupling cycle time, Ψ = τ_r/τ_c, is in the range 0.53 to 0.61. Windowed decoupling using the optimised parameters for a ν₁ of ∼100 kHz also gives good performance in a ¹H spin-echo experiment, enabling implementation in a ¹H-detected ¹⁵N–¹H cross polarisation (CP)-refocused INEPT heteronuclear correlation NMR experiment. Specifically, initial ¹⁵N transverse magnetisation as generated by ¹H–¹⁵N CP is transferred back to ¹H using a refocused INEPT pulse sequence employing windowed ¹H decoupling. Such an approach ensures the observation of through-bond N–H connectivities. For ¹⁵N-glycine, while the CP-refocused INEPT experiment has a lower sensitivity (∼50%) as compared to a double CP experiment (with a 200 μs ¹⁵N to ¹H CP contact time), there is selectivity for the directly bonded NH₃⁺ moiety, while intensity is observed for the CH₂¹H resonances in the double CP experiment. Two-dimensional ¹⁵N–¹H correlation MAS NMR spectra are presented for the dipeptide β-AspAla and the pharmaceutical cimetidine at 60 kHz MAS, both at natural isotopic abundance. For the dipeptide β-AspAla, different build-up dependence on the first spin-echo duration is observed for the NH and NH₃⁺ moieties demonstrating that the experiment could be used to distinguish resonances for different NH_x groups.