Double echo symmetry-based REDOR and RESPDOR pulse sequences for proton detected measurements of heteronuclear dipolar coupling constants

Abstract

1H{X} symmetry-based rotational echo double resonance pulse sequences (S-REDOR) and symmetry-based rotational echo saturation pulse double resonance (S-RESPDOR) solid-state NMR experiments have found widespread application for 1H detected measurements of difference NMR spectra, dipolar coupling constants, and internuclear distances under conditions of fast magic angle spinning (MAS). In these experiments the supercycled R412 (SR412) symmetry-based recoupling pulse sequence is typically applied to the 1H spins to reintroduce heteronuclear dipolar couplings. However, the timing of SR412 and other symmetry-based pulse sequences must be precisely synchronized with the rotation of the sample, otherwise, the evolution of 1H CSA and other interactions will not be properly refocused. For this reason, significant distortions are often observed in experimental dipolar dephasing difference curves obtained with S-REDOR or S-RESPDOR pulse sequences. Here we introduce a family of double echo (DE) S-REDOR/S-RESPDOR pulse sequences that function in an analogous manner to the recently introduced t1-noise eliminated (TONE) family of dipolar heteronuclear multiple quantum coherence (D-HMQC) pulse sequences. Through numerical simulations and experiments the DE S-REDOR/S-RESPDOR sequences are shown to provide dephasing difference curves similar to those obtained with S-REDOR/S-RESPDOR. However, the DE sequences are more robust to the deviations of the MAS frequency from the ideal value that occurs during typical solid-state NMR experiments. The DE sequences are shown to provide more reliable 1H detected dipolar dephasing difference curves for nuclei such as 15N (with isotopic labelling), 183W and 35Cl. The double echo sequences are therefore recommended to be used in place of conventional S-REDOR/S-RESPDOR sequences for measurement of weak dipolar coupling constants and long-range distances.