Deep eutectic solvents (DES) have emerged in the past few years as a new class of solvents with promising applications in several fields. In the present work, the application of DES (formed by binary mixtures of cholinium chloride and carboxylic acids or urea) as phase forming components of aqueous biphasic systems (ABS) is inves tigated. The mechanisms associated with the phases demixing of ABS composed of DES, as well as the DES stability in aqueous solutions, are investigated to address the critical question whether DES based ABS are in fact ternary or quaternary mixtures. It is shown that the DES integrity is destroyed in ABS by the disruption of the hydrogen bonding interactions of the complex (a result of the isolated components preferential solvation by water), and as confirmed by a nonstoichiometric partition of the DES components between the coexisting phases. As a result, there are no "real" DES based ABS; instead, there is the formation of ABS composed of four components, where the carboxylic acid used as the hydrogen bond donor species seems to act as an additive. Finally, it is shown that these ABS have an outstanding potential to be used in extraction processes, as it is here demonstrated with the complete separation of two dyes. However, the volatile nature of short chain carboxylic acids and the nonstoichiometric partition of the DES components in ABS make the development of recovery and recycling steps more difficult to accomplish. The formation of DES results from the formation of strong hydrogen bonds between the two starting materials, namely, a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA). The formation of ion−HBD complexes leads to a lower entropic difference of the phase transition and to the further depression of the freezing temperature.5−7 The first reported DES (composed of [N 111(2OH) ]Cl and urea) 1 remains the most widely investigated. However, DES can be formed by mixing other substituted tetralkylammonium or phosphonium salts with a HBD, such as amines, carboxylic acids, and carbohydrates, among others. 8−10Many DES share some of the unique characteristics of ionic liquids (ILs), namely, a low volatility, high conductivity, wide liquid temperature range, and high solvation ability for a large number of compounds.3,4 DES are also able to overcome some of the disadvantages related to ILs. They are easier to prepare, by a simple mixture of the starting materials at moderate temperatures, without requiring a reaction step. Furthermore, the addition of an agent able to disrupt hydrogen bonding interactions can lead to the recovery of at least one of the initial compounds. 3,4,11,12 The starting materials are usually cheaper, toxicologically well characterized, and often derived from renewable resources, which results in low cost and more environmentally friendly products. 3,4,11,12 As in ILs, innumer ous combinations of the starting materials can be attempted, and therefore, DES may also be classified as "designer solvents". Since DES have fewer restrictions ...

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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.

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Immunoglobulins G (IgG) could become widespread biopharmaceuticals if cost-efficient processes for their extraction and purification are available. In this work, aqueous biphasic systems (ABS) composed of polyethylene glycols and a buffered salt, and with ionic liquids (ILs) as adjuvants, have been studied as alternative extraction and purification platforms of IgG from a rabbit serum source. Eleven ILs were investigated to provide insights on the chemical features which maximize the IgG partitioning. It is shown that in polymer-salt systems pure IgG preferentially partitions to the polymer-rich phase; yet, the complete extraction was never attained. Remarkably, after the addition of 5wt% of adequate ILs to polymer-salt ABS, the complete extraction of pure IgG in a single-step was accomplished. The best systems and conditions were then applied to the extraction and purification of IgG directly from rabbit serum samples. The complete extraction of IgG in a single-step was maintained while its purity in the polymer-rich phase was enhanced by ca. 37% as compared to the IL-free ABS. The antibody stability was also evaluated revealing that appropriate ILs are able to maintain the IgG stability and can be used as phase-forming components of ABS when envisaging the purification of high-cost biopharmaceuticals.

Chlorophylls and their derivatives are currently used in a wide range of applications. To replace the volatile organic solvents commonly applied for their extraction from biomass, aqueous solutions of non-ionic surfactants are studied herein in the extraction of chlorophylls from spinach leaves. Aqueous solutions of several surfactants were screened, demonstrating that their hydrophilic-lipophilic balance (HLB) plays the pivotal role on the extraction performance, with the best results obtained for surfactants with a HLB ranging between 10 and 13. A response surface methodology (RSM) was then used to optimize operational conditions (surfactant concentration, solid-liquid ratio and temperature), leading to a maximum extraction yield of chlorophylls of 0.94 mg/g. After the extraction step, the chlorophylls-rich extract was concentrated by heating above the surfactant-water cloud point, leading to the separation into two-phases, and to a concentration factor of 9 and a recovery of 97% of chlorophylls in the surfactant-rich phase. The antioxidant activity of the extracts was finally appraised, showing that the antioxidant activity of the aqueous chlorophylls-rich extracts is higher than that obtained with volatile organic solvents. The obtained results show the potential of aqueous solutions of non-ionic surfactants to extract highly hydrophobic compounds from biomass and their possible direct use in cosmetic and nutraceutical applications, without requiring an additional recovery or purification step.

Thermoreversible aqueous biphasic systems (ABS) composed of ammonium-based zwitterions (ZIs) and polymers are here disclosed to act as integrated bioreaction-separation processes. The biocatalytic reaction involving laccase occurs in homogeneous media, after which small changes in temperature induce the formation of two phases and the complete separation of the enzyme from the products in a single-step. These systems also allow the recover and reuse of the enzyme, along with the ZI-rich phase, contributing towards the development of sustainable biocatalytic processes.