Designing the ammonium cation to achieve a higher hydrophilicity of bistriflimide-based ionic liquids.

In this work, we have found complete water miscibility for a priori, water immiscible (highly hydrophobic) ionic liquids by chemical manipulation of the quaternary ammonium cation grafted with hydroxyethyl moieties. Specifically, we were able to obtain bistriflimide-based ionic liquids completely miscible with water, even below room temperature. The underlying reason is the full integration of the OH groups of the cation in the continuous H-bonded network of water.

Viscosity minima in binary mixtures of ionic liquids + molecular solvents.

The viscosity (η) of four binary mixtures (ionic liquids plus molecular solvents, ILs+MSs) was measured in the 283.15 < T/K < 363.15 temperature range. Different IL/MS combinations were selected in such a way that the corresponding η(T) functions exhibit crossover temperatures at which both pure components present identical viscosity values. Consequently, most of the obtained mixture isotherms, η(x), exhibit clear viscosity minima in the studied T-x range. The results are interpreted using auxiliary molecular dynamics (MD) simulation data in order to correlate the observed η(T,x) trends with the interactions in each mixture, including the balance between electrostatic forces and hydrogen bonding.

Shifts in the temperature of maximum density (TMD) of ionic liquid aqueous solutions.

This work investigates for the first time shifts in the temperature of maximum density (TMD) of water caused by ionic liquid solutes. A vast amount of high-precision volumetric data--more than 6000 equilibrated (static) high-precision density determination corresponding to ∼90 distinct ionic liquid aqueous solutions of 28 different types of ionic liquid--allowed us to analyze the TMD shifts for different homologous series or similar sets of ionic solutes and explain the overall effects in terms of hydrophobic, electrostatic and hydrogen-bonding contributions. The differences between the observed TMD shifts in the -2 < t/°C < 4 range and salting-in or salting-out effects produced by the same type of ions in aqueous solutions at higher temperatures are discussed taking into account the different types of possible solute-water interactions that can modify the structure of the aqueous phase. The results also reveal different insights concerning the nature of the ions that constitute typical ionic liquids and are consistent with previous results that established hydrophobic and hydrophilic scales for ionic liquid ions based on their specific interactions with water and other probe molecules.

Interactions of fluorinated gases with ionic liquids: solubility of CF4, C2F6, and C3F8 in trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)amide.

The interactions between ionic liquids and totally fluorinated alkanes are investigated by associating gas solubility measurements with molecular simulation calculations. Experimental values for the solubility of perfluoromethane, perfluoroethane, and perfluoropropane in one ionic liquidtrihexyltetradecylphophonium bis(trifluoromethylsulfonyl)amide [P 6,6,6,14][Ntf 2]are reported between 303 and 343 K and close to atmospheric pressure. All mole fraction solubilities decrease with increasing temperature. From the variation of Henry's law constants with temperature, the thermodynamic functions of solvation were calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations, is always better than +/-3%. By the analysis of the differences between the solute-solvent radial distribution functions of perfluoromethane and perfluoropropane obtained by molecular simulation, it was possible to explain why solubility increases with the size of the perfluoroalkane. The trend of solubility is explained on the basis of the location of the solute with respect to the solvent ions as well as on the differences in the solute-solvent energies of interaction.

Fluorination effects on the thermodynamic, thermophysical and surface properties of ionic liquids.

This paper reports the thermal, thermodynamic, thermophysical and surface properties of eight ionic liquids with fluorinated alkyl side chain lengths equal or greater than four carbon atoms. Melting and decomposition temperatures were determined together with experimental densities, surface tensions, refractive indices, dynamic viscosities and ionic conductivities in a temperature interval ranging from 293.15 to 353.15 K. The surface properties of these fluorinated ionic liquids were discussed and several thermodynamic functions, as well as critical temperatures, were estimated. Coefficients of isobaric thermal expansion, molecular volumes and free volume effects were calculated from experimental values of density and refractive index and compared with previous data. Finally, Walden plots were used to evaluate the ionicity of the investigated ionic liquids.

Ionic liquids in pharmaceutical applications.

In the past several years, ionic liquids (ILs) have been at the cutting edge of the most promising science and technology. ILs not only have found applications in classical areas of knowledge but also are important candidates to solve classical problems within several societal challenges, such as clean and efficient energy, through the development of a broad swath of energy technologies, such as advanced batteries, dye-sensitized solar cells, double-layer capacitors, actuators, fuel cells, thermo-cells, and water splitting, essentially related to highly efficient carbon capture and storage technologies and resource efficiency to date. This review focuses on the application of IL methodologies to solve critical pharmaceutical problems, in particular, the low solubility and thus bioavailability of pharmaceutical compounds and the presence of polymorphs, which severely hamper the efficacy of important commercially available drugs. The development of strategies to use ILs as carriers of pharmaceutical active compounds is an extremely promising and wide avenue. Further, the synthesis of liquid salts through the discerning combination of cations and anions with several distinct pharmaceutical roles provides answers to some of today's pharmaceutical industrial challenges.

Characteristics of aggregation in aqueous solutions of dialkylpyrrolidinium bromides.

Three pyrrolidinium-based ionic liquids-N-dodecyl-N-methylpyrrolidinium bromide, N-butyl-N-octylpyrrolidinium bromide, and N-butyl-N-dodecylpyrrolodinium bromide-were synthesized and characterized by their decomposition temperatures (T(d)) measured by thermogravimetric analysis, and by their melting point (T(m)), glass transition (T(g)) and crystallization temperatures (T(cryst)) determined by differential scanning calorimetry. Their self-aggregation properties in aqueous solution were studied and their behavior is compared with that of analogous conventional cationic surfactants, namely tetra-alkylammonium bromide salts. The critical micellar concentration, cmcs were obtained by isothermal titration calorimetry (ITC); which were further validated by measurements of interfacial tension, fluorescence and NMR spectroscopy. Enthalpies of micellization were measured at three different temperatures using ITC. The Taylor dispersion method and DOSY NMR were used to determine diffusion coefficients of the ionic liquid surfactants in aqueous solution at 298.15K. Several correlations between structural features of the surfactant species, such as the number and size of their alkyl chains, and the thermodynamic quantities of micellization-expressed by experimental values of cmc, counter-ion binding fraction, Δ(mic)G°, Δ(mic)°, and Δ(mic)S°-are established. We could interpret the different contributions of the two alkyl side chains to the aggregation properties in terms of the balance of interactions in homogeneous and micellar phases, contributing to understanding the aggregation behavior of ionic liquids in water and the parallel between these systems and traditional ionic surfactants.