INEPT and CP transfer efficiencies of dynamic systems in MAS solid-state NMR

Hartmann–Hahn cross polarization and INEPT polarization transfer are the most popular sequences to increase the polarization of low-γ nuclei in magic-angle spinning solid-state NMR. It is well known that the two methods preferentially lead to polarization transfer in different parts of molecules. Cross polarization works best in rigid segments of the molecule while INEPT-based polarization transfer is efficient in highly mobile segments where (nearly) isotropic motion averages out the dipolar couplings. However, there have only been few attempts to define the time scales of motion that are compatible with cross polarization or INEPT transfer in a more quantitative way. We have used simple isotropic jump models in combination with simulations based on the stochastic Liouville equation to elucidate the time scales of motion that allow either cross polarization or INEPT-based polarization transfer. We investigate which motional time scales interfere with one or both polarization-transfer schemes. We have modeled isolated I-S two-spin systems, strongly-coupled I2S three-spin systems and more loosely coupled I–I-S three-spin systems as well as I3S groups. Such fragments can be used as models for typical environments in fully deuterated and back-exchanged molecules (I-S), for fully protonated molecules (I2S and I3S) or situations in between (I–I-S).