Efficient heteronuclear dipolar decoupling in solid-state NMR using frequency-swept SPINAL sequences

Abstract

Aiming to improve heteronuclear spin decoupling efficiency in NMR spectroscopy of solids and liquid crystals, we have modified the original Small Phase Incremental ALteration (SPINAL) sequence by incorporating a frequency sweep into it. For the resulting sequence, termed SW(f)-SPINAL, the decoupling performance of a large number of sweep variants was explored by both numerical simulations and NMR experiments. It is found that introducing a frequency sweep generally increases both the 'on-resonance' decoupling performance and the robustness towards parameter offsets compared to the original SPINAL sequence. This validates the concept of extending the range of efficient decoupling by introducing frequency sweeps, which was recently suggested in the context of the frequency-swept SW(f)-TPPM method. The sequence found to be best performing among the SW(f)-SPINAL variants consists of fully swept 16 pulse pairs and is designated SW(f)(lin)(32)-SPINAL-32. Its good decoupling performance for rigid spin systems is confirmed by numerical simulations and also experimentally, by evaluating the CH(2) resonance of a powder sample of l-tyrosine under MAS. For moderate MAS frequencies, the new sequence matches the decoupling achieved with SW(f)-TPPM, and outperforms all other tested sequences, including TPPM and SPINAL-64. SW(f)(lin)(32)-SPINAL-32 also shows excellent decoupling characteristics for liquid crystalline systems, as exemplified by experiments on the 5CB liquid crystal.