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Time-Dependent Hydrogen Bond Network Formation in Glycerol-Based Deep Eutectic Solvents
Authors:Katarzyna Dziubinska-Kühn  Marion Pupier  Prof Dr Jörg Matysik  Dr Jasmine Viger-Gravel  Dr Beatrice Karg  Dr Magdalena Kowalska
Institution:1. CERN, Esplanade des Particules 1, 1211 Geneva, Switzerland

Institute of Analytical Chemistry, University of Leipzig, D-, 04103 Leipzig, Germany;2. Department of Organic Chemistry, University of Geneva, 1211 Geneva, Switzerland;3. Institute of Analytical Chemistry, University of Leipzig, D-, 04103 Leipzig, Germany;4. CERN, Esplanade des Particules 1, 1211 Geneva, Switzerland

Abstract:Over the last few years, Deep Eutectic Solvents have gained popularity as a novel class of green solvents, due to their feasible synthesis and overall low production costs. The properties of glycerol (Gly)-based Deep Eutectic Solvents are frequently associated with the formation of an extended hydrogen bond network. In this study, two-dimensional Nuclear Magnetic Resonance (NMR) spectroscopy is employed to analyse the effect of glycerol oversaturation of the hydrogen bond acceptor, choline chloride (ChCl) on the structural arrangement of glyceline (molar ratio 1 : 2 ChCl:Gly), selected to represent Gly-based Deep Eutectic Solvents. The rearrangement of glycerol molecules, additionally trapping water molecules inside of isolated clusters, is revealed during a time-resolved analysis, performed in the presence of various fractions of water added to solvent. 200 % oversaturated Deep Eutectic Solvent (1 : 4 ChCl:Gly) is found to be a suitable cryoprotectant candidate, based on the revealed glycerol-water interactions.
Keywords:deep eutectic solvents  NMR spectroscopy  structural analysis  solute structure  kinetics
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