In the third issue of the then new journal Green Chemistry (2001, 3, 156-164), we published our first paper describing the physical properties of a few hydrophilic and hydrophobic ionic liquids (ILs) representing one of the first such studies to be published. To help celebrate the 15 th anniversary of the Journal, we revisit the 'design' aspect of ILs by reviewing the growing area of what most are calling 'ionic liquid mixtures'. In 2001, designing IL properties meant essentially independent variation or synthesis of the cations and anions and determining what physical or chemical properties these liquid salts possessed. Recently, however, the mixing of ILs has been proposed and investigated as a way to add increased scope to the accessible properties of IL media. In this review, we question whether the same thinking and approach used for organic solvent mixtures should be applied to ILs simply because of the way they were made. Unlike organic solvent mixtures, IL compositions of varied ions, do not retain their individual nature, need not be made by simple mixing of two-ion salts, and preferential interactions of a given cation for a given anion are possible in these 3-ion, 4-ion, or higher order liquids. When two ILs are mixed together, one can't identify which ion is from which IL, and the chemistry is simply not based on the identity of the individual ILs, but on the ions comprising them and the interactions of each individual ion, independently of the counterion. Thus, we ask if it would not be better to consider these as unique ion combinations whose solvent properties are derived from the specific choice and abundance of each ion in the system. Through this review of the available literature, we support the concept of Double Salt Ionic Liquids (DSILs) and discuss the interactions involved in these systems, by examining their physicochemical properties and the novel applications they offer.

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The relative ability of cholinium-([Ch](+))-based salts, including ionic liquids (ILs), to form biocompatible aqueous biphasic systems (ABS) with polyethylene glycols (PEGs) was deeply scrutinized in this work. Aqueous solutions of low molecular weight PEG polymers (400, 600, and 1000 g mol(-1)) and [Ch](+) salts of chloride, acetate, bicarbonate, glycolate, lactate, dihydrogenphosphate, dihydrogencitrate, and bitartrate can undergo liquid-liquid demixing at certain concentrations of the phase-forming components and at several temperatures. Cholinium butanoate and propanoate were also studied; however, these long alkyl side chain ILs are not able to promote an immiscibility region with PEG aqueous solutions. The ternary liquid-liquid phase diagrams, binary water activities, PEG-salt and salt-H2O solubility data, and binary and ternary excess enthalpies estimated by COSMO-RS (COnductor-like Screening MOdel for Realistic Solvation) were used to obtain new insights into the molecular-level mechanisms responsible for phase separation. Instead of the expected and commonly reported salting-out phenomenon induced by the [Ch](+) salts over the polymer, the formation of PEG-[Ch](+) salt ABS was revealed to be an end result of a more intricate molecular scenario. The multifaceted approach employed here reveals that the ability to promote an ABS is quite different for the higher melting salts vs. the lower melting or liquid ILs. In the latter systems, the ABS formation seems to be controlled by the interplay of the relative strengths of the ion-ion, ion-water, ion-PEG, and water-PEG interactions, with a significant contribution from specific hydrogen-bonding between the IL anion and the PEG hydroxyl groups.

New polyethylene glycol (PEG)/ionic liquid aqueous biphasic systems (ABS) are presented. Distinct pairs of PEG polymers and ionic liquids can induce phase separation in aqueous media when dissolved at appropriate concentrations. Phase diagrams have been determined for a large array of systems at 298, 308 and 323 K. A comparison of the binodal curves allowed the analysis of the tunable structural features of the ionic liquid (i.e., anionic nature, cationic core, cationic alkyl side chain length and functionalisation, and number of alkyl substituents in the cation) and the influence of the molecular weight of the PEG polymer on the ability of these solutes to induce an ABS. It was observed that contrary to typical ABS based on ionic liquids and inorganic salts, in which the phase behaviour is dominated by the formation of the hydration complexes of the ions, the interactions between the PEG polymers and ionic liquids control the phase demixing in the polymer-type ABS studied herein. It is shown that both the ionic liquids and PEG polymers can act as the salting-out species; that is, it is an occurrence that is dependent on the structural features of the ionic liquid. For the first time, PEG/ionic liquid ABS are reported and insight into the major interactions that govern the polymer/ionic liquid phase behaviour in aqueous media are provided. The use of two different nonvolatile and tunable species (i.e., ionic liquids and PEG polymers) to form ABS allows the polarities of the phases to be tailored. Hence, the development of environmentally friendly separation processes that make use of these novel systems is envisaged.

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This work reveals, for the first time, that polymer-ionic-liquid-based aqueous biphasic systems (ABS) exhibit a much wider hydrophilic-hydrophobic range than conventional systems reported to date. Three probe dyes were used to demonstrate that either the polymer-rich or the ionic-liquid-rich layer can serve as the most hydrophobic phase. It was found that the phase polarities can be easily tuned by the choice of an appropriate ionic liquid.

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a b s t r a c tThe partitioning of Clavulanic Acid (CA) in a novel inexpensive and stable aqueous two-phase system (ATPS) composed by poly(ethylene glycol) (PEG) and sodium polyacrylate (NaPA) has been studied. The aqueous two-phase systems are formed by mixing both polymers with a salt (NaCl or Na 2 SO 4 ) and an aqueous solution of CA. The stability of CA on the presence of both polymers was investigated and it was observed that these polymers do not degrade the biomolecule. The effect of PEG-molecular size, polymer concentrations on the commercial CA partitioning has been studied, at 25°C. The data showed that commercial CA was preferentially partitioned for the PEG-rich phase with a partition coefficient (K CA ) between 1 and 12 in the PEG/NaPA aqueous two phase systems supplemented with NaCl and Na 2 SO 4 . The partition to the PEG phase was increased in the systems with high polymer concentrations. Furthermore, Na 2 SO 4 caused higher CA preference for the PEG-phase than NaCl. The systems having a composition with 10 wt.% of PEG4000, 20 wt.% of NaPA8000 and 6 wt.% of Na 2 SO 4 were selected as the optimal ones in terms of recovery of CA from fermented broth of Streptomyces clavuligerus. The partitioning results (K CA = 9.15 ± 1.06) are competitive with commercial extraction methods of CA (K CA = 11.91 ± 2.08) which emphasizes that the system PEG/NaPA/Na 2 SO 4 can be used as a new process to CA purification/concentration from fermented broth.