Analytical and Bioanalytical Chemistry

, Volume 405, Issue 24, pp 7597–7613 | Cite as

Bioanalytical separation and preconcentration using ionic liquids

  • Leticia B. Escudero
  • Alexander Castro Grijalba
  • Estefanía M. Martinis
  • Rodolfo G. WuilloudEmail author


Ionic liquids (ILs) are novel solvents that display a number of unique properties, such as negligible vapor pressure, thermal stability (even at high temperatures), favorable viscosity, and miscibility with water and organic solvents. These properties make them attractive alternatives to environmentally unfriendly solvents that produce volatile organic compounds. In this article, a critical review of state-of-the-art developments in the use of ILs for the separation and preconcentration of bioanalytes in biological samples is presented. Special attention is paid to the determination of various organic and inorganic analytes—including contaminants (e.g., pesticides, nicotine, opioids, gold, arsenic, lead, etc.) and functional biomolecules (e.g., testosterone, vitamin B12, hemoglobin)—in urine, blood, saliva, hair, and nail samples. A brief introduction to modern microextraction techniques based on ILs, such as dispersive liquid–liquid microextraction (DLLME) and single-drop microextraction (SDME), is provided. A comparison of IL-based methods in terms of their limits of detection and environmental compatibilities is also made. Finally, critical issues and challenges that have arisen from the use of ILs in separation and preconcentration techniques are also discussed.


The roles and applications of ionic liquids in biological analysis


Ionic liquids Microextraction Separation Preconcentration Biological samples 


Extraction techniques


Aqueous two-phase system


Cold vapor ionic-liquid-assisted headspace single-drop microextraction


Cold vapor generation

cycle-flow SDME

Cycle-flow single-drop microextraction


Directly immersed in a stirred solution single drop microextraction


Dispersive liquid–liquid microextraction


Dynamic liquid-phase microextraction


Flow-injection atomic fluorescence spectrometry


Hollow-fiber liquid-phase microextraction


Headspace single-drop microextraction


Liquid–liquid extraction


Liquid–liquid microextraction


Liquid-phase microextraction


Microwave-assisted dispersive liquid–liquid microextraction


Stir-bar sorptive extraction


Single-drop microextraction


Sodium dodecyl sulfate polyacrylamide gel electrophoresis


Sequential injection dispersive liquid–liquid microextraction


Solid-phase extraction


Solid-phase microextraction


Temperature-assisted dispersive liquid–liquid microextraction


Ultrasound-assisted dispersive liquid–liquid microextraction

Detection technique


Capillary electrophoresis–diode array detector


Cold-vapor atomic absorption spectrometry


Electrothermal atomic absorption spectrometry


Electrothermal vaporization–inductively coupled plasma–mass spectrometry


Flame atomic absorption spectrometry


Gas chromatography


Gas chromatography–mass spectrometry


High-performance liquid chromatography


Matrix-assisted laser desorption/ionization

Ionic liquids


1-Butyl-3-methylimidazolium tetrafluoroborate


1-Hexyl-3-methylimidazolium tetrafluoroborate

[C4mim] [CF3SO3]-

1-Butyl-3-methylimidazolium trifluoromethanesulfonate

[C2mim] [(CF3SO3)2 N]

1-Ethyl-3-methylimidazolium bis[(trifluoromethylsulfonyl)]imide

[C8mim] [(CF3SO3)2 N]

1-Octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide


1-Butyl-3-methylimidazolium chloride


1-Hexyl-3-methylimidazolium chloride


1-Butyl-3-methyl imidazolium hydroxide


1-Butyl-3-methylimidazolium hexafluorophosphate


1-Hexyl-3-methylimidazolium hexafluorophosphate


1-Octyl-3-methylimidazolium hexafluorophosphate


1-Butyl-3-methylpyridinium bromide


1-Butyl-3-methylpyrrolidinium bromide


1-Butyl-3-trimethylsilylimidazolium hexafluorophosphate


Trihexyl(tetradecyl)phosphonium chloride

[EC2mim] [(CF3SO2)2 N]

1-Ethoxyethyl-3-methylimidazolium bis[(trifluoromethylsulfonyl)]imide


N-methylimidazolium chloride


1-Methyl-3-octylimidazolium tetrafluoroborate


N,N-bis[2-methylbutyl]imidazolium hexafluorophosphate

(PY BS)3PW12O40

Keggin-based ionic liquid



This work was supported by Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Agencia Nacional de Promoción Científica y Tecnológica (FONCYT) (PICT-BID), and Universidad Nacional de Cuyo (Argentina).


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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Leticia B. Escudero
    • 1
    • 2
  • Alexander Castro Grijalba
    • 1
    • 2
  • Estefanía M. Martinis
    • 1
    • 2
  • Rodolfo G. Wuilloud
    • 1
    • 2
    Email author
  1. 1.Laboratory of Analytical Chemistry for Research and Development (QUIANID), Instituto de Ciencias BásicasUniversidad Nacional de CuyoMendozaArgentina
  2. 2.Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET)Ciudad Autónoma de Buenos AiresArgentina

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