Abstract
During the past 13 years, ionic-liquid-based aqueous biphasic systems (IL-based ABS) have been the focus of remarkable interest and research. They have shown to be promising separation strategies for the most diverse compounds, resulting mainly from their tailoring ability offered by the current large number of IL chemical structures. A significant number of scientific manuscripts on IL-based ABS have been reported up to date, either on their characterization by attempting the determination of their phase diagrams or by exploring their viability on the separation of target compounds. The molecular-based scenario which rules the phase demixing in these systems and the comprehension of the best conditions and systems for improved separation performance have been ascertained. Both IL and other phase-forming components chemical structures, as well as pH and temperature effects, have been deeply evaluated in order to infer on their liquid–liquid demixing aptitude. On the other hand, possible and promising applications of IL-based ABS have been disclosed by investigating their role on the extraction of a wide plethora of biomolecules and compounds, e.g. amino acids, proteins, alkaloids, phenolic acids and antibiotics, amongst others. In fact, IL-based ABS proved to be outstanding separation platforms compared to more traditional polymer-based systems due to their wider hydrophilic–hydrophilic range which allows enhanced and selective extractions. Concentration factors up to 1000-fold and purification factors up to 245 have been reported with IL-based ABS. In this chapter we review and summarize the definition of IL-based ABS; describe the main phase-forming components used for their creation; define the fundamentals behind the formation of two aqueous-rich phases; demonstrate and show examples of their applications at the extraction, purification and concentration levels; evaluate the most promising applications of IL-based ABS; and discuss their future applicability.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Similar content being viewed by others
References
Albertsson PA (1958) Partition of proteins in liquid polymer-polymer two-phase systems. Nature 182:709–711
Albertsson PA (1986) Partitioning of cell particles and macromolecules, 3rd edn. Wiley-Interscience, New York
Zalipsky S (1995) Functionalized poly(ethylene glycols) for preparation of biologically relevant conjugates. Bioconjug Chem 6:150–165
Li J, Kao WJ (2003) Synthesis of polyethylene glycol (PEG) derivatives and PEGylatedpeptide biopolymer conjugates. Biomacromolecules 4:1055–1067
Rosa PAJ, Azevedo AM, Ferreira IF, de Vries J, Korporaal R, Verhoef HJ, Visser TJ, Aires-Barros MR (2007) Affinity partitioning of human antibodies in aqueous two-phase systems. J Chromatogr A 1162:103–113
da Silva NR, Ferreira LA, Madeira PP, Teixeira JA, Uversky VN, Zaslavsky BY (2015) Effect of sodium chloride on solute–solvent interactions in aqueous polyethylene glycol–sodium sulfate two-phase systems. J Chromatogr A 1425:51–61
Gutowski KE, Broker GA, Willauer HD, Huddleston JG, Swatloski RP, Holbrey JD, Rogers RD (2003) Controlling the aqueous miscibility of ionic liquids: aqueous biphasic systems of water-miscible ionic liquids and water-structuring salts for recycle, metathesis, and separations. J Am Chem Soc 125:6632–6633
Freire MG, Cláudio AFM, Araújo JMM, Coutinho JAP, Marrucho IM, Canongia Lopes JN, Rebelo LPN (2012) Aqueous biphasic systems: a boost brought about by using ionic liquids. Chem Soc Rev 41:4966–4995
Plechkova NV, Seddon KR (2008) Applications of ionic liquids in the chemical industry. Chem Soc Rev 37:123–150
Wasserscheid P, Welton T (2002) Ionic liquids in synthesis. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Cláudio AFM, Neves MC, Shimizu K, Canongia Lopes JN, Freire MG, Coutinho JAP (2015) The magic of aqueous solutions of ionic liquids: ionic liquids as a powerful class of catanionic hydrotropes. Green Chem 17:3948–3963
Debeljuh N, Barrow CJ, Henderson L, Byrne N (2011) Structure inducing ionic liquids-enhancement of alpha helicity in the Abeta(1–40) peptide from Alzheimer’s disease. Chem Commun 47:6371–6373
Khimji I, Doan K, Bruggeman K, Huang PJJ, Vajha P, Liu J (2013) Extraction of DNA staining dyes from DNA using hydrophobic ionic liquids. Chem Commun 49:4537–4539
Phama TPT, Choa C-W, Yuna Y-S (2010) Environmental fate and toxicity of ionic liquids: a review. Water Res 44:352–372
Petkovic M, Seddon KR, Rebelo LPN, Pereira CS (2011) Ionic liquids: a pathway to environmental acceptability. Chem Soc Rev 40:1383–1403
Pereira JFB, Rebelo LPN, Rogers RD, Coutinho JAP, Freire MG (2013) Combining ionic liquids and polyethylene glycols to boost the hydrophobic-hydrophilic range of aqueous biphasic systems. Phys Chem Chem Phys 15:19580–19583
Cláudio AFM, Freire MG, Freire CSR, Silvestre AJD, Coutinho JAP (2010) Extraction of vanillin using ionic-liquid-based aqueous two-phase systems. Sep Purif Technol 75:39–47
Quental MV, Passos H, Kurnia KA, Coutinho JAP, Freire MG (2015) Aqueous biphasic systems composed of ionic liquids and acetate-based salts: phase diagrams, densities, and viscosities. J Chem Eng Data 60:1674–1682
Freire MG, Neves CMSS, Carvalho PJ, Gardas RL, Fernandes AM, Marrucho IM, Santos LMNBF, Coutinho JAP (2007) Mutual solubilities of water and hydrophobic ionic liquids. J Phys Chem B 111:13082–13089
Freire MG, Neves CMSS, Marrucho IM, Coutinho JAP, Fernandes AM (2010) Hydrolysis of tetrafluoroborate and hexafluorophosphate counter ions in imidazolium-based ionic liquids. J Phys Chem A 114:3744–3749
Ranke J, Stolte S, Störmann R, Arning J, Jastorff B (2007) Design of sustainable chemical products: the example of ionic liquids. Chem Rev 107:2183–2206
Merchuk JC, Andrews BA, Asenjo JA (1998) Aqueous two-phase systems for protein separation. Studies on phase inversion. J Chromatogr B 711:285–293
Zafarani-Moattar MT, Hamzehzadeh S (2009) Phase diagrams for the aqueous two-phase ternary system containing the ionic liquid 1-butyl-3-methylimidazolium bromide and tri-potassium citrate at T = (278.15, 298.15, and 318.15) K. J Chem Eng Data 54:833–841
Zafarani-Moattar MT, Hamzehzadeh S (2010) Salting-out effect, preferential exclusion, and phase separation in aqueous solutions of chaotropic water-miscible ionic liquids and kosmotropic salts: effects of temperature, anions, and cations. J Chem Eng Data 55:1598–1610
Zafarani-Moattar MT, Hamzehzadeh S (2011) Effect of pH on the phase separation in the ternary aqueous system containing the hydrophilic ionic liquid 1-butyl-3-methylimidazolium bromide and the kosmotropic salt potassium citrate at T = 298.15 K. Fluid Phase Equilib 304:110–120
Chen YH, Wang YG, Cheng QY, Liu XL, Zhang SJ (2009) Carbohydrates-tailored phase tunable systems composed of ionic liquids and water. J Chem Thermodyn 41:1056–1059
Chen YH, Meng YS, Zhang SM, Zhang Y, Liu XW, Yang J (2010) Liquid − liquid equilibria of aqueous biphasic systems composed of 1-butyl-3-methyl imidazolium tetrafluoroborate + sucrose/maltose + water. J Chem Eng Data 55:3612–3616
Han J, Yu C, Wang Y, Xie X, Yan Y, Yin G, Guan W (2010) Liquid–liquid equilibria of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate and sodium citrate/tartrate/acetate aqueous two-phase systems at 298.15 K: experiment and correlation. Fluid Phase Equilib 295:98–103
Han JA, Pan R, Xie XQ, Wang Y, Yan YS, Yin GW, Guan WX (2010) Liquid − liquid equilibria of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate + sodium and ammonium citrate aqueous two-phase systems at (298.15, 308.15, and 323.15) K. J Chem Eng Data 55:3749–3754
Pei YC, Wang JJ, Liu L, Wu K, Zhao Y (2007) Liquid − liquid equilibria of aqueous biphasic systems containing selected imidazolium ionic liquids and salts. J Chem Eng Data 52:2026–2031
Yu C, Han J, Hu S, Yan Y, Li Y (2011) Phase diagrams for aqueous two-phase systems containing the 1-ethyl-3-methylimidazolium tetrafluoroborate/1-propyl-3-methylimidazolium tetrafluoroborate and trisodium phosphate/sodium sulfite/sodium dihydrogen phosphate at 298.15 K: experiment and correlation. J Chem Eng Data 56:3577–3584
Othmer DF, Tobias PE (1942) Liquid-liquid extraction data – toluene and acetaldehyde systems. Ind Eng Chem 34:690–692
Luís A, Dinis TBV, Passos H, Taha M, Freire MG (2015) Good’s buffers as novel phase-forming components of ionic-liquid-based aqueous biphasic systems. Biochem Eng J 101:142–149
Freire MG, Carvalho PJ, Silva AMS, Santos LMNBF, Rebelo LPN, Marrucho IM, Coutinho JAP (2009) Ion specific effects on the mutual solubilities of water and hydrophobic ionic liquids. J Phys Chem 113:202–211
Neves CMSS, Freire MG, Coutinho JAP (2012) Improved recovery of ionic liquids from contaminated aqueous streams using aluminium-based salts. RSC Adv 2:10882–10890
Bridges NJ, Gutowski KE, Rogers RD (2007) Investigation of aqueous biphasic systems formed from solutions of chaotropic salts with kosmotropic salts (salt–salt ABS). Green Chem 9:177–183
Passos H, Ferreira AR, Cláudio AFM, Coutinho JAP, Freire MG (2012) Characterization of aqueous biphasic systems composed of ionic liquids and a citrate-based biodegradable salt. Biochem Eng J 67:68–76
Freire MG, Neves CMSS, Canongia Lopes JN, Marrucho IM, Coutinho JAP, Rebelo LPN (2012) Impact of self-aggregation on the formation of ionic-liquid-based aqueous biphasic systems. J Phys Chem B 116:7660–7668
Cláudio AFM, Ferreira AM, Shahriari S, Freire MG, Coutinho JAP (2011) Critical assessment of the formation of ionic-liquid-based aqueous two-phase systems in acidic media. J Phys Chem B 115:11145–11153
Shahriari S, Neves CMSS, Freire MG, Coutinho JAP (2012) Role of the Hofmeister series in the formation of ionic-liquid-based aqueous biphasic systems. J Phys Chem B 116:7252–7258
Sadeghi R, Golabiazar R, Shekaari H (2010) The salting-out effect and phase separation in aqueous solutions of tri-sodium citrate and 1-butyl-3-methylimidazolium bromide. J Chem Thermodyn 42:441–453
Freire MG, Louros CLS, Rebelo LPN, Coutinho JAP (2011) Aqueous biphasic systems composed of a water-stable ionic liquid + carbohydrates and their applications. Green Chem 13:1536–1545
Wu B, Zhang YM, Wang HP (2008) Phase behavior for ternary systems composed of ionic liquid + saccharides + water. J Phys Chem B 112:6426–6429
Wu B, Zhang YM, Wang HP (2008) Aqueous biphasic systems of hydrophilic ionic liquids + sucrose for separation. J Chem Eng Data 53:983–985
Okuniewski M, Paduszyński K, Domańska U (2016) Effect of cation structure in trifluoromethanesulfonate-based ionic liquids: density, viscosity, and aqueous biphasic systems involving carbohydrates as “salting-out” agents. J Chem Eng Data 61:1296–1304
Zhang M, Zhang YQ, Chen YH, Zhang SJ (2007) Mutual coexistence curve measurement of aqueous biphasic systems composed of [bmim][BF4] and glycine, L-serine, and L-proline, respectively. J Chem Eng Data 52:2488–2490
Domínguez-Pérez M, Tomé LIN, Freire MG, Marrucho IM, Cabeza O, Coutinho JAP (2010) (Extraction of biomolecules using) aqueous biphasic systems formed by ionic liquids and aminoacids. Sep Purif Technol 72:85
Wu CZ, Wang JJ, Pei YC, Wang HY, Li ZY (2010) Salting-out effect of ionic liquids on poly(propylene glycol) (PPG): formation of PPG + ionic liquid aqueous two-phase systems. J Chem Eng Data 55:5004–5008
Zafarani-Moattar MT, Hamzehzadeh S, Nasiri S (2012) A new aqueous biphasic system containing polypropylene glycol and a water-miscible ionic liquid. Biotechnol Prog 28:146–156
Freire MG, Pereira JFB, Francisco M, Rodríguez H, Rebelo LPN, Rogers RD, Coutinho JAP (2012) Insight into the interactions that control the phase behaviour of new aqueous biphasic systems composed of polyethylene glycol polymers and ionic liquids. Chem Eur J 18:1831–1839
Li Z, Liu X, Pei Y, Wang J, He M (2012) Design of environmentally friendly ionic liquid aqueous two-phase systems for the efficient and high activity extraction of proteins. Green Chem 14:2941–2950
Pereira JFB, Kurnia KA, Freire MG, Coutinho JAP, Rogers RD (2015) Controlling the formation of ionic-liquid-based aqueous biphasic systems by changing the hydrogen-bonding ability of polyethylene glycol end groups. ChemPhysChem 16:2219–2225
Visak ZP, Canongia Lopes JN, Rebelo LPN (2007) Ionic liquids in polyethylene glycol aqueous solutions: salting-in and salting-out effects. Monatsh Chem 138:1153–1157
Quental MV, Caban M, Pereira MM, Stepnowski P, Coutinho JAP, Freire MG (2015) Enhanced extraction of proteins using cholinium-based ionic liquids as phase-forming components of aqueous biphasic systems. Biotechnol J 10:1457–1466
Tomé L, Pereira JFB, Rogers RD, Freire MG, Gomes JRB, Coutinho JAP (2014) “Washing-out” ionic liquid from polyethylene glycol to form aqueous biphasic systems. Phys Chem Chem Phys 16:2271–2274
Pereira JFB, Lima ÁS, Freire MG, Coutinho JAP (2010) Ionic liquids as adjuvants for the tailored extraction of biomolecules in aqueous biphasic systems. Green Chem 12:1661–1669
Almeida MR, Passos H, Pereira M, Lima ÁS, Coutinho JAP, Freire MG (2014) Ionic liquids as additives to enhance the extraction of antioxidants in aqueous two-phase systems. Sep Purif Technol 128:1–10
Ventura SPM, Neves CMSS, Freire MG, Marrucho IM, Oliveira J, Coutinho JAP (2009) Evaluation of anion influence on the formation and extraction capacity of ionic-liquid-based aqueous biphasic systems. J Phys Chem B 113:9304–9310
Neves CMSS, Ventura SPM, Freire MG, Marrucho IM, Coutinho JAP (2009) Evaluation of cation influence on the formation and extraction capability of ionic-liquid-based aqueous biphasic systems. J Phys Chem B 113:5194–5199
Ikeda M (2006) Towards bacterial strains overproducing L-tryptophan and other aromatics by metabolic engineering. Appl Microbiol Biotechnol 69:615–626
Lu M, Tjerneld F (1997) Interaction between tryptophan residues and hydrophobically modified dextran: effect on partitioning of peptides and proteins in aqueous two-phase systems. J Chromatogr A 766:99–108
Tomé LIN, Catambas VR, Teles ARR, Freire MG, Marrucho IM, Coutinho JAP (2010) Tryptophan extraction using hydrophobic ionic liquids. Sep Purif Technol 72:167–173
Rosa PAJ, Azevedo AM, Sommerfeld S, Bäcker W, Aires-Barros MR (2011) Aqueous two-phase extraction as a platform in the biomanufacturing industry: economical and environmental sustainability. Biotechnol Adv 29:559–567
Rosa PAJ, Ferreira IF, Azevedo AM, Aires-Barros MR (2010) Aqueous two-phase systems: a viable platform in the manufacturing of biopharmaceuticals. J Chromatogr A 1217:2296–2305
Ruiz-Angel MJ, Pino V, Carda-Broch S, Berthod A (2007) Solvent systems for countercurrent chromatography: an aqueous two phase liquid system based on a room temperature ionic liquid. J Chromatogr A 1:65–73
Pereira MM, Pedro SN, Quental MV, Lima ÁS, Coutinho JAP, Freire MG (2015) Enhanced extraction of bovine serum albumin with aqueous biphasic systems of phosphonium- and ammonium-based ionic liquids. J Biotechnol 206:17–25
Taha M, e Silva FA, Quental MV, Ventura SPM, Freire MG, Coutinho JAP (2014) Good’s buffers as a basis for developing self-buffering and biocompatible ionic liquids for biological research. Green Chem 16:3149–3159
Taha M, Almeida MR, e Silva FA, Domingues P, Ventura SPM, Coutinho JAP, Freire MG (2015) Novel biocompatible and self-buffering ionic liquids for biopharmaceutical applications. Chem Eur J 21:4781–4788
Taha M, Quental MV, Correia I, Freire MG, Coutinho JAP (2015) Extraction and stability of bovine serum albumin (BSA) using cholinium-based Good’s buffers ionic liquids. Process Biochem 50:1158–1166
Dreyer S, Kragl U (2008) Ionic liquids for aqueous two-phase extraction and stabilization of enzymes. Biotechnol Bioeng 99:1416–1424
Ventura SPM, de Barros RLF, de Pinho Barbosa JM, Soares CMF, Lima ÁS, Coutinho JAP (2012) Production and purification of an extracellular lipolytic enzyme using ionic liquid-based aqueous two-phase systems. Green Chem 14:734–740
Souza RL, Ventura SPM, Soares CMF, Coutinho JAP, Lima ÁS (2015) Lipase purification using ionic liquids as adjuvants in aqueous two-phase systems. Green Chem 17:3026–3034
Dutta NN, Borthakur S, Patil GS (1992) Phase transfer catalyzed extraction of phenolic substances from aqueous alkaline stream. Sep Sci Technol 27:1435–1448
Zhang DL, Deng YF, Chen J (2010) Enrichment of aromatic compounds using ionic liquid and ionic liquid-based aqueous biphasic systems. Sep Sci Technol 45:663–669
Ferreira AM, Coutinho JAP, Fernandes AM, Freire MG (2014) Complete removal of textile dyes from aqueous media using ionic-liquid-based aqueous two-phase systems. Sep Purif Technol 128:58–66
Sheikhian L, Akhond M, Absalan G (2014) Partitioning of reactive red–120, 4– (2–pyridylazo) –resorcinol, and methyl orange in ionic liquid–based aqueous biphasic systems. J Environ Chem Eng 2:137–142
de Souza RL, Campos VC, Ventura SPM, Soares CMF, Coutinho JAP, Lima AS (2014) Effect of ionic liquids as adjuvants on PEG–based ABS formation and the extraction of two probe dyes. Fluid Phase Equilib 375:30–36
Passos H, Sousa ACA, Pastorinho MR, Nogueira AJA, Rebelo LPN, Coutinho JAP, Freire MG (2012) Ionic-liquid-based aqueous biphasic systems for improved detection of bisphenol A in human fluids. Anal Methods 4:2664–2667
Dinis TBV, Passos H, Lima DLD, Esteves VI, Coutinho JAP, Freire MG (2015) One-step extraction and concentration of estrogens for an adequate monitoring of wastewater using ionic-liquid-based aqueous biphasic systems. Green Chem 17:2570–2579
Li S, He C, Liu H, Li K, Liu F (2005) Ionic liquid-based aqueous two-phase system, a sample pretreatment procedure prior to high-performance liquid chromatography of opium alkaloids. J Chromatogr B 826:58–62
Freire MG, Neves CMSS, Marrucho IM, Canongia Lopes JN, Rebelo LPN, Coutinho JAP (2010) High-performance extraction of alkaloids using aqueous two-phase systems with ionic liquids. Green Chem 12:1715–1718
Passos H, Trindade MP, Vaz TSM, da Costa LP, Freire MG, Coutinho JAP (2013) The impact of self-aggregation on the extraction of biomolecules in ionic-liquid-based aqueous two-phase systems. Sep Purif Technol 108:174–180
Pereira JFB, Ventura SPM, e Silva FA, Shahriari S, Freire MG, Coutinho JAP (2013) Aqueous biphasic systems composed of ionic liquids and polymers: a platform for the purification of biomolecules. Sep Purif Technol 113:83–89
Cláudio AFM, Marques CFC, Boal-Palheiros I, Freire MG, Coutinho JAP (2014) Development of back-extraction and recyclability routes for ionic-liquid-based aqueous two-phase systems. Green Chem 16:259–268
Santos JH, e Silva FA, Ventura SPM, Coutinho JAP, de Souza RLS, Soares CM, Lima ÁS (2015) Ionic liquid-based aqueous biphasic systems as a versatile tool for the recovery of antioxidant compounds. Biotechnol Prog 31:70–77
Ribeiro BD, Coelho MAZ, Rebelo LPN, Marrucho IM (2013) Ionic liquids as additives for extraction of saponins and polyphenols from mate (Ilex paraguariensis) and tea (Camellia sinensis). Ind Eng Chem Res 52:12146–12153
Akama Y, Ito M, Tanaka S (2000) Selective separation of cadmium from cobalt, copper, iron (III) and zinc by water-based two-phase system of tetrabutylammonium bromide. Talanta 53:645–650
Akama Y, Sali A (2002) Extraction mechanism of Cr(VI) on the aqueous two-phase system of tetrabutylammonium bromide and (NH4)2SO4 mixture. Talanta 57:681–686
Wei XL, Wei ZB, Wang XH, Wang ZN, Sun DZ, Liu J, Zhao HH (2011) Phase behavior of new aqueous two-phase systems: 1-butyl-3-methylimidazolium tetrafluoroborate + anionic surfactants + water. Soft Matter 7:5200–5207
Shahriari S, Tomé LC, Araújo JMM, Rebelo LPN, Coutinho JAP, Marrucho IM, Freire MG (2013) Aqueous biphasic systems: a benign route using cholinium-based ionic liquids. RSC Adv 3:1835–1843
Almeida HFD, Freire MG, Marrucho IM (2016) Improved extraction of fluoroquinolones with recyclable ionic-liquid-based aqueous biphasic systems. Green Chem 18:2717. doi:10.1039/C5GC02464A
Zawadzki M, e Silva FA, Domańska U, Coutinho JAP, Ventura SPM (2016) Recovery of an antidepressant from pharmaceutical wastes using ionic liquid-based aqueous biphasic systems. Green Chem 18:3527–3536. doi:10.1039/C5GC03052H
Passos H, Luís A, Coutinho JAP, Freire MG (2016) Thermoreversible (ionic-liquid-based) aqueous biphasic systems. Sci Rep 6:20276
Acknowledgements
This work was developed within the scope of the project CICECO - Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. The research leading to reported results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement no. 337753.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2016 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Freire, M.G. (2016). Introduction to Ionic-Liquid-Based Aqueous Biphasic Systems (ABS). In: Freire, M. (eds) Ionic-Liquid-Based Aqueous Biphasic Systems. Green Chemistry and Sustainable Technology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-52875-4_1
Download citation
DOI: https://doi.org/10.1007/978-3-662-52875-4_1
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-662-52873-0
Online ISBN: 978-3-662-52875-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)