Choline Chloride-Based DES as Solvents/Catalysts/Chemical Donors in Pharmaceutical Synthesis

DES are mixtures of two or more compounds, able to form liquids upon mixing, with lower freezing points when compared to the individual constituents (eutectic mixtures). This attitude is due to the specific hydrogen-bond interactions network between the components of the mixture. A notable characteristic of DES is the possibility to develop tailor-made mixtures by changing the components ratios or a limited water dilution, for special applications, making them attractive for pharmaceutical purposes. In this review, we focused our attention on application of ChCl-based DES in the synthesis of pharmaceutical compounds. In this context, these eutectic mixtures can be used as solvents, solvents/catalysts, or as chemical donors and we explored some representative examples in recent literature of such applications.

Investigation into the hygrothermal behavior of fired clay materials during the freezing of supercooled water using experiments and numerical simulations

In this study, supercooling effects on the hygrothermal behavior of fired clay materials under various experimental conditions, such as water content, cooling rates, and size of specimens were investigated using experimental methods and hygrothermal simulations. We report results of the differential scanning calorimetry (DSC) and temperature distribution changes during a freeze–thaw (FT) experiment using unsaturated specimens. Also, we developed a numerical model of the freezing and thawing processes including the supercooling processes. The DSC results show the freezing of the supercooled water in a fired clay material is considerably faster than that in cement-based materials. It was also found that the dependency of the supercooling effects on the cooling rates seemed to be small. When the water saturation of a material decreases, the rate of the ice saturation increase during the freezing of the supercooled water is decreased while the freezing points of the supercooled water was not changed considerably. The comparison of the results of the FT experiment and hygrothermal simulations show that the combination of the existed hygrothermal model and a modified kinetic equation can reproduce the rapid temperature rise during the freezing of the supercooling water in the FT experiment. Finally, the size effects of specimens on the supercooling phenomenon was discussed based on the experimental and calculation results. The freezing points got higher when a specimen was larger. Due to differences in the ratio of the surface area to the volume, hygrothermal behavior in small specimens and relatively large specimens like that of the DSC and the FT experiment, respectively were markedly different. Water in a relatively large specimen with a small ratio of surface area to volume can achieve the thermodynamic equilibrium in a short period after the freezing starts.

Thermomechanical Formulation of Freezing Point Depression Behavior of Liquid on Solid Surface With Nanostructure

In this study, we investigated the freezing point depression of liquids in nanostructures using a new thermomechanical method. First, we experimentally determined the freezing points of water, cyclohexane, and a certain organic material (Chem.A) in nanoscale structures using DSC measurements. Thereafter, we formulated a new equation by improving the Gibbs–Thomson equation, which is the conventional formula for representing the freezing point depression of a liquid in nanostructures. We introduced a new term in this new equation to represent the increase in the kinetic energy of the liquid molecule as a result of collision between the liquid molecules and nanostructure walls. Subsequently, we evaluated the solid–liquid interface free energy of sublimation materials by fitting the theoretical freezing point derived from the new equation to experimental data. In this study, we succeeded in reproducing the experimental data of freezing point depression using the proposed equation. In particular, the freezing points of cyclohexane and Chem.A in the nanostructure were better fitted by this new equation at 10 nm or more compared with the conventional equation. Our results show that the interaction between the wall of the nanostructure and liquid molecules affects freezing point depression.