During the past decade, ionic-liquid-based Aqueous Biphasic Systems (ABS) have been the focus of a significant amount of research. Based on a compilation and analysis of the data hitherto reported, this critical review provides a judicious assessment of the available literature on the subject. We evaluate the quality of the data and establish the main drawbacks found in the literature. We discuss the main issues which govern the phase behaviour of ionic-liquid-based ABS, and we highlight future challenges to the field. In particular, the effect of the ionic liquid structure and the various types of salting-out agents (inorganic or organic salts, amino acids and carbohydrates) on the phase equilibria of ABS is discussed, as well as the influence of secondary parameters such as temperature and pH. More recent approaches using ionic liquids as additives or as replacements for common salts in polymer-based ABS are also presented and discussed to emphasize the expanding number of aqueous two-phase systems that can actually be obtained. Finally, we address two of the main applications of ionic liquid-based ABS: extraction of biomolecules and other added-value compounds, and their use as alternative approaches for removing and recovering ionic liquids from aqueous media.

5In the past decade, ionic liquids (ILs) have been the focus of intensive research regarding their use as potential and alternative solvents in many chemical applications. Targeting their effectiveness, recent investigations have attempted to establish polarity scales capable of ranking ILs according to their chemical behaviours. However, some major drawbacks have been found since polarity scales are only report relative behaviours because they depend on the set of probe dyes used, and they are sensitive to 10 measurement conditions such as purity levels of the ILs and procedures employed.. Due to all these difficulties it is of crucial importance to find alternative and/or predictive methods and to evaluate them as a priori approaches able to provide the chemical properties of ILs. Furthermore, the large number of ILs available makes their experimental characterization, usually achieved by a trial and error methodology, burdensome. In this context, we firstly evaluated COSMO-RS, Conductor-Like Screening

Hydrotropes are compounds able to enhance the solubility of hydrophobic substances in aqueous media and therefore are widely used in the formulation of drugs, cleaning and personal care products. In this work, it is shown that ionic liquids are a new class of powerful catanionic hydrotropes where both the cation and the anion synergistically contribute to increase the solubility of biomolecules in water. The effects of the ionic liquid chemical structures, their concentration and the temperature on the solubility of two model biomolecules, vanillin and gallic acid were evaluated and compared with the performance of conventional hydrotropes. The solubility of these two biomolecules was studied in the entire composition range, from pure water to pure ionic liquids, and an increase in the solubility of up to 40-fold was observed, confirming the potential of ionic liquids to act as hydrotropes. Using dynamic light scattering, NMR and molecular dynamics simulations, it was possible to infer that the enhanced solubility of the biomolecule in the IL aqueous solutions is related to the formation of ionic-liquid-biomolecules aggregates. Finally, it was demonstrated that hydrotropy induced by ionic liquids can be used to recover solutes from aqueous media by precipitation, simply by using water as an anti-solvent. The results reported here have a significant impact on the understanding of the role of ionic liquid aqueous solutions in the extraction of value-added compounds from biomass as well as in the design of novel processes for their recovery from aqueous media.

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Aqueous biphasic systems (ABS) provide an alternative and efficient approach for the extraction, recovery and purification of biomolecules through their partitioning between two liquid aqueous phases. In this work, the ability of hydrophilic phosphonium-based ionic liquids (ILs) to form ABS with aqueous K3PO4 solutions was evaluated for the first time. Ternary phase diagrams, and respective tie-lines and tie-lines length, formed by distinct phosphonium-based ILs, water, and K3PO4 at 298 K, were measured and are reported. The studied phosphonium-based ILs have shown to be more effective in promoting ABS compared to the imidazolium-based counterparts with similar anions. Moreover, the extractive capability of such systems was assessed for distinct biomolecules (including amino acids, food colourants and alkaloids). Densities and viscosities of both aqueous phases, at the mass fraction compositions used for the biomolecules extraction, were also determined. The evaluated IL-based ABS have been shown to be prospective extraction media, particularly for hydrophobic biomolecules, with several advantages over conventional polymer-inorganic salt ABS.

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In this work, the ability of Na(2)SO(4) and ionic liquids to induce the formation of acidic aqueous two-phase systems (ATPS) is investigated. Ternary phase diagrams, tie lines, and tie-line lengths for several systems were determined and reported at 298 K and atmospheric pressure. It is here shown that among the ionic liquids studied only those containing long alkyl side chains at the ions and/or anions with low hydrogen bond basicity are capable of undergoing liquid-liquid demixing in the presence of Na(2)SO(4) aqueous solutions. The results obtained indicate that, besides the salting-out ability of the inorganic salt, the pH of the aqueous solution plays a crucial role toward the formation of ionic-liquid-based ATPS. In acidic media the range of ionic liquids that are able to undergo ATPS formation is substantially reduced when compared to alkaline aqueous salt solutions. The use of inorganic salts and ionic liquids to promote acidic ATPS is envisaged as particularly valuable in the extraction of compounds that exhibit low acid dissociation constants.

a b s t r a c tTo explore proper extractive solvents and to design an optimized separation process it is highly imperative to understand the molecular-based phenomena governing the solutes partitioning. Moreover, the development of new techniques for the biomolecules separation and purification, while maintaining their functional characteristics unchanged, is still ongoing. Therefore, in this work, the partition coefficients of vanillin, a compound with well-known organoleptic properties, were determined using improved ionicliquid-based aqueous two-phase systems (ATPS). Three main parameters were evaluated through the vanillin partitioning process: the ionic liquid (IL) cation and anion structure, the temperature of equilibrium and the available concentration of vanillin in the global system. In all systems and conditions tested, vanillin preferentially migrates for the IL-rich phase. In addition, the three studied parameters largely influence the vanillin partitioning. In an attempt to elucidate the thermodynamics of the partitioning process, the standard molar thermodynamic functions of transfer of vanillin were also determined based on the temperature dependence data. These data indicate that the partition of vanillin results from an interplay between enthalpic and entropic contributions where both the IL anion and more complex cations play an essential role. Moreover, viscosities and densities of both aqueous phases were experimentally measured at the mass fraction compositions for which the partition coefficients were determined. The results gathered in this work indicate that IL-based ATPS can be further employed in the extraction and purification of vanillin from different matrices, as confirmed by the large partition coefficients obtained and improved low viscosity systems.