Analytical and Bioanalytical Chemistry

, Volume 396, Issue 1, pp 511–524

Bonded ionic liquid polymeric material for solid-phase microextraction GC analysis

  • Eranda Wanigasekara
  • Sirantha Perera
  • Jeffrey A. Crank
  • Leonard Sidisky
  • Robert Shirey
  • Alain Berthod
  • Daniel W. Armstrong
Original Paper


Four new ionic liquids (IL) were prepared and bonded onto 5-µm silica particles for use as adsorbent in solid-phase microextraction (SPME). Two ILs contained styrene units that allowed for polymerization and higher carbon content of the bonded silica particles. Two polymeric ILs differing by their anion were used to prepare two SPME fibers that were used in both headspace and immersion extractions and compared to commercial fibers. In both sets of experiments, ethyl acetate was used as an internal standard to take into account adsorbent volume differences between the fibers. The polymeric IL fibers are very efficient in headspace SPME for short-chain alcohols. Immersion SPME also can be used with the IL fibers for short-chain alcohols as well as for polar and basic amines that can be extracted at pH 11 without damage to the IL-bonded silica particles. The sensitivities of the two IL fibers differing by the anion were similar. Their efficacy compares favorably to that of commercial fibers for polar analytes. The mechanical strength and durability of the polymeric IL fibers were excellent.


Chemistry of the polymerized ionic liquid absorbant and its morphology when bonded to the SPME fiber.


Solid-phase microextraction Headspace Immersion Ionic liquid Bonded phase Beverages Gas chromatography 

Supplementary material

216_2009_3254_MOESM1_ESM.pdf (44 kb)
ESM1(PDF 44 kb)


  1. 1.
    Arthur CL, Pawliszyn J (1990) Solid-phase microextraction with thermal desorption using fused silica optical fibers. Anal Chem 62:2145–2148CrossRefGoogle Scholar
  2. 2.
    Pawliszyn J, Pawliszyn B, Pawliszyn M (1997) Solid phase microextraction (SPME). The Chemical Educator. doi:10.1333/s00897970137a Google Scholar
  3. 3.
    Pawliszyn J (1997) Solid phase microextraction theory and practice. Wiley, New York, NY, USAGoogle Scholar
  4. 4.
    Scheppers Wercinsky SA (1999) Solid phase microextraction. A practical guide. CRC Press, Boca Raton, FL, USAGoogle Scholar
  5. 5.
    Hinshaw JV (2003) Solid phase microextraction. LC&GC (Europe) 16:803–807; (North America) 21:1056–1061Google Scholar
  6. 6.
    Majors R (2008) The role of polymers in solid-phase extraction and sample preparation. LC&GC (North America) 26:1074–1090Google Scholar
  7. 7.
    Venkatachalam M. (1999) Properties of Commercial SPME Coatings. In: Pawliszyn J (ed) Applications of SPME. RSC Chromatography Monographs, Ch. 5, pp 57–72Google Scholar
  8. 8.
    Anonymous (1998) SPME: theory and optimization of conditions, Supelco bulletin 923. Supelco, Bellefonte, PA, USAGoogle Scholar
  9. 9.
    Mullett VM, Pawliszyn J (2003) The development of selective and biocompatible coatings for SPME. J Sep Sci 26:251–260CrossRefGoogle Scholar
  10. 10.
    Jiang G, Huang M, Cai Y, Lv J, Zhao J (2006) Progress of SPME coatings and coating techniques. J Chromatogr Sci 44:324–332Google Scholar
  11. 11.
    Dietz C, Sanz J, Cámara C (2006) Recent developments in SPME coatings and related techniques. J Chromatogr A 1103:183–192CrossRefGoogle Scholar
  12. 12.
    Earle MJ, Seddon KR (2000) Ionic liquids: green solvents for the future. Pure Appl Chem 72:1391–1398CrossRefGoogle Scholar
  13. 13.
    Olivier-Bourbigou H, Magna L (2002) Ionic liquids: perspectives for organic and catalytic reactions. J Mol Catal A: Chem 182–183:419–437CrossRefGoogle Scholar
  14. 14.
    Wasserscheid P, Welton T (eds) (2003) Ionic liquids in synthesis. Wiley, Weinheim, GermanyGoogle Scholar
  15. 15.
    Carda-Broch S, Berthod A, Armstrong DW (2003) Solvent properties of the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid. Anal Bioanal Chem 375:191–199Google Scholar
  16. 16.
    Koel M (ed) (2009) Ionic liquids in chemical analysis. CRC, Boca Raton, FL, USAGoogle Scholar
  17. 17.
    Anderson JL, Armstrong DW, Wei GT (2006) Ionic liquids in analytical chemistry. Anal Chem 78:2893–2901Google Scholar
  18. 18.
    Berthod A, Ruiz-Angel MJ, Carda-Broch S (2008) Ionic liquids in separation techniques. J Chromatogr A 1184:6–18CrossRefGoogle Scholar
  19. 19.
    Poole CF, Kollie TO (1993) Interpretation of the influence of temperature on the solvation properties of GC stationary phases using Abraham’s solvation parameter model. Anal Chim Acta 282:1–17CrossRefGoogle Scholar
  20. 20.
    Armstrong DW, He L, Liu YS (1999) Examination of ionic liquids and their interaction with molecules when used as stationary phases in gas chromatography. Anal Chem 71:3873–3876CrossRefGoogle Scholar
  21. 21.
    Anderson JL, Armstrong DW (2003) High stability ionic liquids: a new class of stationary phases for gas chromatography. Anal Chem 75:4851–4858CrossRefGoogle Scholar
  22. 22.
    Anderson JL, Armstrong DW (2005) Immobilized ionic liquids as high selectivity/high temperature/high stability gas chromatography stationary phases. Anal Chem 77:6453–6462CrossRefGoogle Scholar
  23. 23.
    Vidal L, Psillakis E, Domini CE, Grane N, Marken F, Canals A (2007) An ionic liquid for headspace single drop microextraction of chlorobenzenes from water samples. Anal Chim Acta 584:18–195CrossRefGoogle Scholar
  24. 24.
    Aguilera-Herrador E, Lucena R, Cárdenas S, Valcárcel M (2008) Direct coupling of ionic liquids based single drop microextraction and GC/MS. Anal Chem 80:793–800CrossRefGoogle Scholar
  25. 25.
    Hsieh YN, Huang PC, Sun IW, Whang TJ, Hsu CY, Huang HH, Kuei CH (2006) Nafion membrane supported ionic liquid solid phase microextraction for analyzing ultra-trace PAHs in water samples. Anal Chim Acta 557:321–328CrossRefGoogle Scholar
  26. 26.
    Zhao F, Meng Y, Anderson JL (2008) Polymeric ionic liquid as selective coatings for the extraction of esters using solid-phase microextraction. J Chromatogr A 1208:1–9CrossRefGoogle Scholar
  27. 27.
    He Y, Pohl J, Engel R, Rothman L, Thomas M (2009) Preparation of ionic liquid based solid-phase microextraction fiber and its application to forensic determination of methamphetamine and amphetamine in human urine. J Chromatogr A 1216:4824–4830CrossRefGoogle Scholar
  28. 28.
    Huang K, Han X, Zhang X, Armstrong DW (2007) PEG-linked geminal ionic liquids as selective, high-stability GC stationary phase. Anal Bioanal Chem 389:2265–2275CrossRefGoogle Scholar
  29. 29.
    Wu CH, Chen CL, Huang CT, Lee MR, Huang CM (2004) Identification of gasoline soot in suspect arson cases by using headspace solid phase microextraction-GC/MS. Anal Let 37:1373–1384CrossRefGoogle Scholar
  30. 30.
    Anderson JL, Ding J, Welton T, Armstrong DW (2002) Characterizing ionic liquids on the basis of multiple solvation interactions. J Am Chem Soc 124:14247–14254CrossRefGoogle Scholar
  31. 31.
    Berthod A, Ruiz-Angel MJ, Huguet S (2005) Nonmolecular solvents in separation methods: dual nature of room temperature ionic liquids. Anal Chem 77:4071–4080CrossRefGoogle Scholar
  32. 32.
    Sprunger LM, Gibbs J, Proctor A, Acree WE, Abraham MH, Meng Y, Yao C, Anderson JL (2009) Linear free energy relationship correlations for room temperature ionic liquids: revised cation-specific and anion-specific equation coefficients for predictive applications covering a much larger area of chemical space. Ind Eng Chem Res 48:4145–4154CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Eranda Wanigasekara
    • 1
  • Sirantha Perera
    • 1
  • Jeffrey A. Crank
    • 1
  • Leonard Sidisky
    • 2
  • Robert Shirey
    • 2
  • Alain Berthod
    • 3
  • Daniel W. Armstrong
    • 1
  1. 1.Department of ChemistryUniversity of Texas at ArlingtonArlingtonUSA
  2. 2.SupelcoSigma-AldrichBellefonteUSA
  3. 3.CNRSUniversité de LyonVilleurbanneFrance

Personalised recommendations