Asynchronising five-fold symmetry sequence for better homonuclear polarisation transfer in magic-angle-spinning solid-state NMR

Recoupling, decoupling, and multidimensional correlation experiments in magic-angle-spinning (MAS) solid-state NMR can be designed by exploiting the symmetry of internal spin interactions. One such scheme, namely, ${C5}_2^1$, and its supercycled version ${SPC5}_2^1$, notated as a five-fold symmetry sequence, is widely used for double-quantum dipole-dipole recoupling. Such schemes are generally rotor synchronised by design. We demonstrate an asynchronous implementation of the ${SPC5}_2^1$ sequence leading to higher double-quantum homonuclear polarisation transfer efficiency compared to the normal synchronous implementation. Rotor-synchronisation is broken in two different ways: lengthening the duration of one of the pulses, denoted as pulse-width variation (PWV), and mismatching the MAS frequency denoted as MAS variation (MASV). The application of this asynchronous sequence is shown on three different samples, namely, U–¹³C-alanine and 1,4-¹³C-labelled ammonium phthalate which include ¹³C_α-¹³C_β, ¹³C_α-¹³C_o, and ¹³C_o–¹³C_o spin systems, and adenosine 5′- triphosphate disodium salt trihydrate (ATP⋅3H₂O). We show that the asynchronous version performs better for spin pairs with small dipole-dipole couplings and large chemical-shift anisotropies, for example, ¹³C_o–¹³C_o. Simulations and experiments are shown to corroborate the results.