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Confining deep eutectic solvents in nanopores: insight into thermodynamics and chemical activity

We have established the detailed phase diagram of the prototypical deep eutectic solvent ethaline (ethylene glycol / choline chloride 2:1) as a function of the hydration level, in the bulk state and confined in the nanochannels of mesostructured porous silica matrices MCM-41 and SBA-15, with pore radii $R_P$ = 1.8 nm and 4.15 nm. For neat and moderately hydrated DESs, freezing was avoided and glassforming solutions were formed in all cases. For mass fraction of water above a threshold value $W_g'\approx30\%$, crystallization occurred and led to the formation of a maximally-freeze concentrated DES solution. In this case, extremely deep melting depressions were attained in the confined states, due to the combination of confinement and cryoscopic effects. These phenomena were analyzed quantitatively, based on an extended version of the classical Gibbs-Thomson and Raoult thermodynamic approaches. In this framework, the predicted values of the water chemical activity in the confined systems were shown to systematically deviate from those of the bulk counterparts. The origin of this striking observation is discussed with respect to thermodynamic anomalies of water in the 'no-man's land' and to the probable existence of specific nanostructures in DES solutions when manipulated in nanochannels or at interfaces with solids.