Selective 1H–1H recoupling via symmetry sequences in fully protonated samples at fast magic angle spinning

Abstract

Proton-detected solid-state NMR at fast Magic Angle Spinning (MAS) is becoming the norm to characterize molecules. Routinely 1H–1H and 1H-X dipolar couplings are used to characterize the structure and dynamics of molecules. Selective proton recoupling techniques are emerging as a method for structural characterization via estimation of qualitative and quantitative distances. In the present study, we demonstrate through numerical simulations and experiments that the well-characterized CNvn sequences can also be tailored for selective recoupling of proton spins by employing C elements of the type (β)Φ(4β)Φ+π(3β)Φ. Herein, several CNvn sequences were examined through numerical simulations and experiments. C614 recoupling sequence with a modified POST-element ((β)Φ(4β)Φ+π(3β)Φ) shows selective polarization transfer efficiencies on the order of 40–50% between various proton spin pairs in fully protonated samples at rf amplitudes ranging from 0.3 to 0.8 times the MAS frequency. These selective recoupling sequences have been labeled as frequency-selective-CNvn sequences. The extent of selectivity, polarization transfer efficiency and the feasibility of experimentally measuring proton-proton distances in fully protonated samples are explored here. The development of efficient and robust selective 1H–1H recoupling experiments is required to structurally characterize molecules without artificial isotope enrichment or the need for diffracting crystals.