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.

Ionic-liquid-based aqueous biphasic systems (ABS) have been the focus of a significant amount of research in the last decade. However, only (moderately) toxic and poorly biodegradable ionic liquids have been explored hitherto. Focusing on the development of more benign and sustainable approaches, a novel class of ABS using cholinium-based ionic liquids is proposed. For the first time, it is shown that a large assortment of cholinium-based ionic liquids is capable of undergoing liquid–liquid demixing in the presence of aqueous solutions with strong salting-out species. In order to assess the applicability of these systems for separation purposes, the partitioning of two antibiotics and/or their hydrochloride forms was also investigated. Cholinium-based ABS are shown to be improved routes for the extraction of pharmaceuticals, achieving complete extractions in a single-step by way of the proper tailoring of the phase forming components and their concentrations in the aqueous media.

Novel ionic liquids containing ampicillin as an active pharmaceutical ingredient anion were prepared with good yields by using a new, efficient synthetic procedure based on the neutralization of a moderately basic ammonia solution of ampicillin with different organic cation hydroxides. The relevant physical and thermal properties of these novel ionic liquids based on ampicillin were also evaluated.