The liquid structure of five different amide-based deep eutectic solvents (DESs) as a function of the chemical structure of the hydrogen bond acceptor (HBA) was investigated by linear Fourier transform infrared (FTIR) and two-dimensional infrared (2DIR) spectroscopies. Linear FTIR spectroscopy shows that the amide band of the DESs is not significantly affected by the chemical structure and symmetry of the HBA cation. However, its excitonic nature does not allow us to draw further conclusions. Analysis of the 13C amide line shapes derived from the 2DIR spectra reveals that the different DESs do not show appreciable differences in the level of disorganization. The vibrational dynamics, derived from the photon echo experiments on the 13C amide, shows that there is a fast component with a time scale of ∼1 ps irrespective of the HBA. The ultrafast dynamics is assigned to hydrogen bond making and breaking between amides. In addition, a slow dynamical component is observed in the time evolution of the photon ech...

Evidence of Molecular Heterogeneities in Amide-Based Deep Eutectic Solvents

Deep eutectic solvents (DES) are a new class of designer solvents with a wide range of possible applications. DESs are typically made from an ionic compound and a hydrogen bond donor, but lately DE...

Molecularly Heterogeneous Structure of a Nonionic Deep Eutectic Solvent Composed of N-Methylacetamide and Lauric Acid.

Deep eutectic solvents (DESs) are one of the most rapidly evolving types of solvents, appearing in a broad range of applications, such as nanotechnology, electrochemistry, biomass transformation, pharmaceuticals, membrane technology, biocomposite development, modern 3D-printing, and many others. The range of their applicability continues to expand, which demands the development of new DESs with improved properties. To do so requires an understanding of the fundamental relationship between the structure and properties of DESs. Computer simulation and machine learning techniques provide a fruitful approach as they can predict and reveal physical mechanisms and readily be linked to experiments. This review is devoted to the computational research of DESs and describes technical features of DES simulations and the corresponding perspectives on various DES applications. The aim is to demonstrate the current frontiers of computational research of DESs and discuss future perspectives. 

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Computer Simulations of Deep Eutectic Solvents: Challenges, Solutions, and Perspectives

A new room-temperature deep eutectic solvent (DES) composed of glucose, urea, and water has been prepared and its relaxation dynamics explored via temperature-dependent time-resolved fluorescence m...

Interaction and Dynamics in a Fully Biodegradable Glucose-Containing Naturally Abundant Deep Eutectic Solvent: Temperature-Dependent Time-Resolved Fluorescence Measurements

Understanding the speciation of metal ions in heterogeneous hydrogen-bonded deep eutectic solvents (DES) has immense importance for their wide range of applications in green technology, environment...

Insight into Speciation and Electrochemistry of Uranyl Ions in Deep Eutectic Solvents.

Solvation of the thiocyanate ion in three different deep eutectic solvents (DES) was investigated by linear FTIR spectroscopy, and Two Dimensional IR spectroscopy. Linear infrared spectroscopy reveals that the thiocyanate ion forms a hydrogen bond through its sulphur atom, while its nitrile end remains free. Photon-echo vibrational spectroscopy shows that the thiocyanate has a frequency–frequency correlation function (FFCF) with two distinct dynamics occurring on the picosecond time scale in all of the studied solvents. The observed dynamics is assigned to in-place and diffusional motions of the components within the thiocyanate solvation shell. Molecular dynamics simulations and ab initio calculations confirm the experimental findings and their molecular interpretation. In addition, theoretical modeling of the thiocyanate nitrile stretch lineshape suggests that alcohol-based DES are more structurally disorganized than the amide-based analogue. However, the organization observed in the different DES is not sufficient to explain physical properties, such as density, indicating that the amount of defects (i.e., hole theory) is not sufficient to fully describe the properties of DES.

Y. Cui

Papers

Solvation dynamics of an ionic probe in choline chloride-based deep eutectic solvents.