Supercritical CO 2 impregnation process applied to polymer samples preparation for dynamic nuclear polarization solid-state NMR.

In this study, supercritical CO (scCO ) was used to impregnate polymers with paramagnetic polarizing agents to prepare samples for dynamic nuclear polarization (DNP) solid-state NMR (ssNMR) experiments. As a proof of concept, we impregnated polystyrene samples with bTbK, which stands for bis-TEMPO-bisketal where TEMPO is 2,2,6,6-tetra-methylpiperindin-1-oxyl. Substantial DNP signal enhancements could be measured on DNP-enhanced H →  C cross-polarization (CP) magic-angle spinning (MAS) spectra recorded at 9.4 T and ~100 K, reaching a maximum value of 8 in the most favorable case, which appeared comparable or even higher than what is typically obtained on similar systems for former sample preparation methods. These results highlight the potential of scCO impregnation as an efficient and possibly versatile methodology to prepare polymer samples for DNP ssNMR investigations.