A modification of γ-encoded RN symmetry pulses for increasing the scaling factor and more accurate measurements of the strong heteronuclear dipolar couplings

Abstract

Symmetry based γ-encoded RN_n^ν elements are broadly used in magic-angle spinning solid-state NMR experiments to achieve selective recoupling of the heteronuclear dipolar interactions. The recoupled dipolar couplings in such experiments are scaled by a factor, K_sc, which theoretically depends on the chosen symmetry numbers N, n, and ν. However, the maximum theoretical value of K_sc for γ-encoded RN_n^ν pulses is limited to ~0.25, resulting in long RN_n^ν experiment times. Also, the dependence of K_sc on the experimental parameters can result in systematic errors in the experimental determination of the dipolar couplings, especially at low and moderate MAS rates. In this manuscript, we investigate the use of MODifiEd RN_n^ν symmetry (MODERN_n^ν(ϕ_M)) pulses that increase the dipolar scaling factor by at least 1.45 fold compared to γ-encoded RN_n^ν. The second advantage of MODERN_n^ν(ϕ_M) pulses with respect to traditional RN_n^ν pulses is the reduced influence of experimental parameters on K_sc, which allows for more accurate measurement of short-range distances. The robustness of MODERN_n^ν(ϕ_M) is compared with γ-encoded R14₂³ symmetry pulses. The enhanced performance is demonstrated on two uniformly-¹³C-enriched samples, N-acetyl valine and the microcrystalline protein GB1, at a 31.111 kHz MAS rate.

Keywords: Constant scaling factor; Heteronuclear dipolar recoupling; Magic angle spinning NMR; Symmetry rules.