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      Mechanisms ruling the partition of solutes in ionic-liquid-based aqueous biphasic systems – the multiple effects of ionic liquids

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          Abstract

          In the past decade it has been demonstrated the remarkable potential of ionic-liquid-based aqueous biphasic systems (IL-based ABS) to extract and purify a large range of valued-added biocompounds. However, the transposal of lab-experiments to an industrial scale has been precluded by a poor understanding of the molecular-level mechanisms ruling the separation or partition of target compounds between the coexisting phases. To overcome this limitation we carried out a systematic evaluation of specific interactions, induced by ILs and several salts used as phase-forming components, and their impact on the partition of several solutes in IL-based ABS. To this end, the physicochemical characterization of ABS composed of imidazolium-based ILs, three salts (Na 2SO 4, K 2CO 3 and K 3C 6H 5O 7) and water was performed. The ability of the coexisting phases to participate in different solute-solvent interactions (where “solvent” corresponds to each ABS phase), were estimated based on the Gibbs free energy of transfer of a methylene group between the phases in equilibrium, Δ G( CH 2), and on the Kamlet-Taft parameters – dipolarity/polarizability (π*), hydrogen-bonding donor acidity ( α) and hydrogen-bonding acceptor basicity ( β) – of the coexisting phases. Relationships between the partition coefficients, the phases properties expressed as Kamlet-Taft parameters and COSMO-RS descriptors were established, highlighting the ability of ILs to establish specific interactions with given solutes. The assembled results clearly support the idea that the partition of solutes in IL-based ABS is due to multiple effects resulting from both global solute-solvent and specific solute-IL interactions. Solute-IL specific interactions are often dominant in IL-based ABS, explaining the higher partition coefficients, extraction efficiencies and selectivities observed with these systems when compared to more traditional ones majorly composed of polymers.

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          Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena

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            Ionic liquids: solvent properties and organic reactivity

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              COSMO-RS: a novel and efficient method for the a priori prediction of thermophysical data of liquids

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                Author and article information

                Journal
                100888160
                32386
                Phys Chem Chem Phys
                Phys Chem Chem Phys
                Physical chemistry chemical physics : PCCP
                1463-9076
                1463-9084
                24 September 2018
                28 March 2018
                28 September 2018
                : 20
                : 13
                : 8411-8422
                Affiliations
                CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
                Author notes
                Article
                PMC6161819 PMC6161819 6161819 ems79727
                10.1039/c8cp00383a
                6161819
                29542784
                2f44689b-d4bc-49ca-b9fb-e9ca67d1520f
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