Dynamics of Glyceline and Interactions of Constituents: A Multitechnique NMR Study

The dynamics of the organic components of the deep eutectic solvent (DES) glyceline are analyzed using an array of complementary nuclear magnetic resonance (NMR) methods. Fast-field cycling H-1 relaxometry, pulsed field gradient diffusion, nuclear overhauser effect spectroscopy (NOESY), C-13 NMR relaxation, and pressure-dependent NMR experiments are deployed to sample a range of frequencies and modes of motion of the glycerol and choline components of the DES. Generally, translational and rotational diffusion of glycerol are more rapid than those of choline while short-range rotational motions observed from C-13 relaxation indicate slow local motion of glycerol at low choline chloride (ChCl) content. The rates of glycerol and choline local motions become more similar at higher ChCl. This result taken together with pressure-dependent NMR studies show that the addition of ChCl makes it easier to disrupt glycerol packing. Finally, a relatively slow hydroxyl H-exchange process between glycerol and choline protons is deduced from the data. Consistent with this, NOESY results indicate relatively little direct H-bonding between glycerol and choline. These results suggest that the glycerol H-bonding network is disrupted as choline is added, but primarily in regions where there is intimate mixing of the two components. Thus, the local dynamics of most of the glycerol resembles that of pure glycerol until substantial choline chloride is present.

Automated summary

The dynamics of the organic components of the deep eutectic solvent glycerol are analyzed using various nuclear magnetic resonance (NMR) methods. The study reveals that rotational and translational diffusion of glycerol is faster than that of choline, and the addition of choline chloride disrupts the glycerol's hydrogen bonding network. The data also suggests a relatively slow hydroxyl H-exchange process between glycerol and choline.