Liquid structure of a water-based, hydrophobic and natural deep eutectic solvent: The case of thymol-water. A Molecular Dynamics study

The structural organization of the first example of a water-based, type V, hydrophobic, natural deep eutectic solvent (DES) is investigated in this work, exploiting the synergy of X-ray scattering and computational techniques. The stoichiometric mixture of thymol:water (4.8:1) has been recently reported to behave as a DES, with a melting point at-6 degrees C, well below the one foreseen for the ideal liquid mixture. Our study provides an atomistic insight into the structural correlations in this system, highlighting the major role played by hydrogen bonding (HB) correlations in affecting morphology as well as the solid- liquid equilibrium. Thymol engages HB-mediated interactions with both thymol and water molecules: evidences of conventional HB interactions involving the hydroxyl group are found, together with indications of p center dot center dot center dot HAO hydrogen bonding correlations with both thymol and water. Overall, in the mixture, thymol is involved in a larger number of HB interactions than in its neat liquid state. Such a strong interference of water into thymol structural organization strongly hinders the development of HB-mediated thymol hexamers that is the structural leitmotif in crystalline thymol. On the other hand, only 30 % of the present water molecule can engage into correlations with at least another water molecule, thus preventing the formation of an extended HB network among water molecules that would result incompatible with the otherwise hydrophobic environment. Evidences of mesoscopic organization are observed experimentally and confirmed by simulations: these are related to the clustering of thymol hydroxyl groups with water molecules, leading to the formation on polar nano-pools embedded into the apolar matrix. This new solvent extends the range of water based, type V, hydrophobic DES, and represents an additional contribution to the development of sustainable technologies, with appealing properties.(c) 2022 Elsevier B.V. All rights reserved.