Unusual Local Molecular Motions in the Solid State Detected by Dynamic Nuclear Polarization Enhanced NMR Spectroscopy

Polyethylene glycol (PEG) and three related surfactants were studied by dynamic nuclear polarization (DNP) enhanced solid state NMR spectroscopy and differential scanning calorimetry (DSC). DNP enhanced solid state NMR surprisingly reveals the presence of local molecular motions that are normally understood to be inactive at temperatures ∼100 K. This surprising phenomenon could be explained by the experimentally necessary rapid freezing of the studied samples. Specifically, DSC shows that PEG 200 forms a glass upon freezing and that the three PEG-related surfactants are at least partially in a glass state or some other thermodynamic nonequilibrium state when rapidly frozen to the temperatures of the DNP enhanced solid state NMR experiments. This effect of preserving local molar motions by rapid freezing also holds true for solutions of organic solutes in the PEG 200 solvent matrix.