Freeze-drying of aqueous solutions of deep eutectic solvents: a suitable approach to deep eutectic suspensions of self-assembled structures.

This work describes how the preparation of deep eutectic solvents (DES) in its pure state can be accomplished through a simple approach based on the freeze-drying of aqueous solutions of the individual counterparts of DES. DES in its pure state obtained via freeze-drying are studied by (1)H NMR, which reveals the formation of halide ion-hydrogen-bond-donor supramolecular complexes (characteristic of DES), and by cryo-etch-SEM, which provides insight about the capability of aqueous solutions of DES to be segregated in DES and ice upon freezing. The paper also explores the suitability of the freeze-drying approach to incorporate organic self-assemblies (in particular, liposomes of ca. 200 nm) in DES with full preservation of their self-assembled structure. This is not a trivial issue given that amphiphilic molecules tend to be readily dissolved (hence, disassembled) in DES. The strategy proposed in this work is based on the freeze-drying of aqueous solutions containing the individual counterparts of DES and the preformed liposomes (also known as large unilamellar vesicles or LUV). The simplicity of the method should also make it suitable for the incorporation of different self-assembled structures (such other types of vesicles and micelles) in DES in its pure state.