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.

The potential use of ionic liquids (ILs) as adjuvants in typical polymer-salt aqueous systems for the separation and purification of vital biomolecules is investigated. An innovative study involving the addition of various imidazolium-based ILs to conventional PEG/inorganic salt aqueous biphasic systems (ABS), aiming at controlling their phase behaviour and extraction capability for L-tryptophan, is carried out here. For this purpose, phase diagrams and respective tie-lines for PEG 600/Na₂SO₄ ABS with the addition of small quantities of IL were established. In addition, the partition coefficients of L-tryptophan were determined in those systems. The results obtained indicate that the addition of small amounts of IL to the typical PEG/inorganic salt aqueous systems could largely control the extraction efficiency for L-tryptophan, and that efficiency depends on the IL employed. Salting-in inducing ILs enhance the partition coefficient of L-tryptophan for the PEG-rich phase while salting-out inducing ILs decrease the partitioning of the amino acid. These results are an interesting advance in biotechnological separation processes regarding the extraction of biomolecules that could be used instead of the common approach of PEG functionalization.