Choline Acetate/Water Mixtures: Physicochemical Properties and Structural Organization

In the quest for greener alternatives to conventional organic solvents, Deep Eutectic Solvents (DESs) have gained significant attention due to their sustainability, biodegradability, and tunability. The use of water as an active and genuine component has recently led to the emergence of water-based DESs (wb-DESs). Here, a careful experimental characterization was performed on choline acetate (ChAc)/water mixtures across a range of water:ChAc molar ratios (n = 2–6). Differential Scanning Calorimetry (DSC) revealed glass transitions between 150 and 180 K, with no first-order transitions, leading to a classification of these mixtures as Low Transition-Temperature Mixtures (LTTMs). Physicochemical measurements, including density, viscosity, electrical conductivity, and refractive index, were conducted over a broad temperature range. NMR analyses provided insights into dynamics and solvation environments, with 1 H T1 slow relaxation times reaching their lowest value at n = 2, consistent with the formation of a strong hydrogen-bonding network. The n = 2 mixture was further investigated using Small and Wide-Angle X-ray Scattering (S-WAXS) and ab initio molecular dynamics (AIMD). These studies, jointly with 1 H NMR choline diffusion coefficient, directly challenge previous claims of the existence of aggregation phenomena in wb-DES. The simulation revealed a well-organized solvation structure, where acetate and water synergistically stabilize the choline cation through a cooperative hydrogen-bonding network. These findings highlight the impact and significance of an integrated physicochemical study in guiding the rational development of new sustainable systems, such as wb-DESs.