Analytical and Bioanalytical Chemistry

, Volume 407, Issue 16, pp 4615–4627 | Cite as

Automated direct-immersion solid-phase microextraction using crosslinked polymeric ionic liquid sorbent coatings for the determination of water pollutants by gas chromatography

  • María Cordero-Vaca
  • María J. Trujillo-Rodríguez
  • Cheng Zhang
  • Verónica Pino
  • Jared L. Anderson
  • Ana M. Afonso
Research Paper


Four different crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were evaluated in an automated direct-immersion solid-phase microextraction method (automated DI-SPME) in combination with gas chromatography (GC). The crosslinked PIL coatings were based on vinyl-alkylimidazolium- (ViCnIm-) or vinylbenzyl-alkylimidazolium- (ViBzCnIm-) IL monomers, and di-(vinylimidazolium)dodecane ((ViIm)2C12-) or di-(vinylbenzylimidazolium)dodecane ((ViBzIm)2C12-) dicationic IL crosslinkers. In addition, a PIL-based hybrid coating containing multi-walled carbon nanotubes (MWCNTs) was also studied. The studied PIL coatings were covalently attached to derivatized nitinol wires and mounted onto the Supelco assembly to ensure automation when acting as SPME coatings. Their behavior was evaluated in the determination of a group of water pollutants, after proper optimization. A comparison was carried out with three common commercial SPME fibers. It was observed that those PILs containing a benzyl group in their structures, either in the IL monomer and crosslinker (PIL–1–1) or only in the crosslinker (PIL–0–1), were the most efficient sorbents for the selected analytes. The validation of the overall automated DI-SPME-GC-flame ionization detector (FID) method gave limits of detection down to 135 μg · L−1 for p-cresol when using the PIL–1–1 and down to 270 μg · L−1 when using the PIL–0–1; despite their coating thickness: ~2 and ~5 μm, respectively. Average relative recoveries with waters were of 85 ± 14 % and 87 ± 15 % for PIL–1–1 and PIL–0–1, respectively. Precision values as relative standard deviation were always lower than 4.9 and 7.6 % (spiked level between 10 and 750 μg · L−1, as intra-day precision).

Graphical Abstract

Automated DI–SPME–GC–FID using crosslinked–PILs sorbent coatings for the determination of waterpollutants


Ionic liquids Polymeric ionic liquids Multi-walled carbon nanotubes Solid-phase microextraction Coatings Gas chromatography 



V.P. thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for the Ramón y Cajal contract with the University of La Laguna (ULL). V.P. also acknowledges MINECO for the Project Ref. MAT2013-43101-R and funding from Fundación CajaCanarias project ref. SPDs-AGUA05. M.J.T.-R. thanks Fundación CajaCanarias for her PhD research fellowship with ULL. J.L.A. acknowledges funding from the Chemical Measurement and Imaging Program at the National Science Foundation (Grant number CHE-1413199). Authors declare no conflict of interest.

Supplementary material

216_2015_8658_MOESM1_ESM.pdf (1.3 mb)
ESM 1 (PDF 1.34 mb)


  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.
    Mehdinia A, Aziz-Zanjani MO (2013) Advances for sensitive, rapid and selective extraction in different configurations of solid-phase microextraction. Trends Anal Chem 51:13–22CrossRefGoogle Scholar
  3. 3.
    Chary NS, Fernandez–Alba AR (2012) Determination of volatile organic compounds in drinking and environmental waters. Trends Anal Chem 32:60–75CrossRefGoogle Scholar
  4. 4.
    Musteata FM, Pawliszyn J (2007) Bioanalytical applications of solid-phase microextraction. Trends Anal Chem 26:36–45CrossRefGoogle Scholar
  5. 5.
    Xu J, Zheng J, Tian J, Zhu F, Zeng F, Su C, Ouyang G (2013) New materials in solid-phase microextraction. Trends Anal Chem 47:68–83CrossRefGoogle Scholar
  6. 6.
    Martín-Esteban A (2013) Molecularly-imprinted polymers as a versatile, highly selective tool in sample preparation. Trends Anal Chem 45:169–181CrossRefGoogle Scholar
  7. 7.
    Gholivand MB, Abolghasemi MM, Fattahpour P (2011) A hexagonally ordered nanoporous silica-based fiber coating for SPME of polycyclic aromatic hydrocarbons from water followed by GC–MS. Chromatographia 74:807–815CrossRefGoogle Scholar
  8. 8.
    Yang Y, Li Y, Lia H, Wang X, Du X (2014) Electrodeposition of gold nanoparticles onto an etched stainless steelwire followed by a self-assembled monolayer of octanedithiol as afiber coating for selective solid-phase microextraction. J Chromatogr A 1372:25–33CrossRefGoogle Scholar
  9. 9.
    Mehdinia A, Bashour F, Roohi F, Jabbari A (2012) A strategy to enhance the thermal stability of a nanostructured polypyrrole-based coating for solid phase microextraction. Microchim Acta 177:301–308CrossRefGoogle Scholar
  10. 10.
    Zhang S-L, Du Z, Li G-K (2011) Layer-by-layer fabrication of chemical–bonded graphene coating for solid-phase microextraction. Anal Chem 83:7531–7541CrossRefGoogle Scholar
  11. 11.
    Li Q, Ma X, Yuan D, Chen J (2010) Evaluation of the solid-phase microextraction fiber coated with single walled carbon nanotubes for the determination of benzene, toluene, ethylbenzene, xylenes in aqueous samples. J Chromatogr A 1217:2191–2196CrossRefGoogle Scholar
  12. 12.
    Chen X-F, Zang H, Wang X, Cheng J-G, Zhao R-S, Cheng C-G, Lu X-Q (2012) Metal–organic framework MIL-53(Al) as a solid-phase microextraction adsorbent for the determination of 16 polycyclic aromatic hydrocarbons in water samples by gas chromatography–tandem mass spectrometry. Analyst 137:5411–5419CrossRefGoogle Scholar
  13. 13.
    Yu H, Ho TD, Anderson JL (2013) Ionic liquid and polymeric ionic liquid coatings in solid-phase microextraction. Trends Anal Chem 45:219–232CrossRefGoogle Scholar
  14. 14.
    Ho TD, Zhang C, Hantao LW, Anderson JL (2012) Ionic liquids in analytical chemistry: fundamentals, advances, and perspectives. Anal Chem 86:262–285CrossRefGoogle Scholar
  15. 15.
    Yuan J, Mecerreyes D, Antonietti M (2013) Poly(ionic liquid)s: an update. Prog Polym Sci 38:1009–1036CrossRefGoogle Scholar
  16. 16.
    Zhao F, Meng Y, Anderson JL (2008) Polymeric ionic liquids as selective coatings for the extraction of esters using solid-phase microextraction. J Chromatogr A 1208:1–9CrossRefGoogle Scholar
  17. 17.
    Meng Y, Anderson JL (2010) Tuning the selectivity of polymeric ionic liquid sorbent coatings for the extraction of polycyclic aromatic hydrocarbons using solid-phase microextraction. J Chromatogr A 1217:6143–6152CrossRefGoogle Scholar
  18. 18.
    López–Darias J, Pino V, Anderson JL, Graham CM, Afonso AM (2010) Determination of water pollutants by direct-immersion solid-phase microextraction using polymeric ionic liquid coatings. J Chromatogr A 1217:1236–1243CrossRefGoogle Scholar
  19. 19.
    Xu L, Jia J, Feng J, Liu J, Jiang S (2013) Polymeric ionic liquid modified stainless steel wire as a novel fiber for solid-phase microextraction. J Sep Sci 36:369–375CrossRefGoogle Scholar
  20. 20.
    Ho TD, Yu H, Cole WTS, Anderson JL (2012) Ultraviolet photoinitiated on-fiber copolymerization of ionic liquid sorbent coatings for headspace and direct immersion solid-phase microextraction. Anal Chem 84:9520–9528Google Scholar
  21. 21.
    Jia J, Liang X, Wang L, Guo Y, Liu X, Jiang S (2013) Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds. J Chromatogr A 1320:1–9CrossRefGoogle Scholar
  22. 22.
    Trujillo–Rodríguez MJ, Yu H, Cole WTS, Ho TD, Pino V, Anderson JL, Afonso AM (2014) Polymeric ionic liquid coatings versus commercial solid-phase microextraction coatings for the determination of volatile compounds in cheeses. Talanta 121:153–162CrossRefGoogle Scholar
  23. 23.
    Ho TD, Cole WTS, Augusto F, Anderson JL (2013) Insight into the extraction mechanism of polymeric ionic liquid sorbent coatings in solid-phase microextraction. J Chromatogr A 1298:146–151CrossRefGoogle Scholar
  24. 24.
    Pang L, Liu J-F (2012) Development of a solid-phase microextraction fiber by chemical binding of polymeric ionic liquid on a silica coated stainless steel wire. J Chromatogr A 1230:8–14CrossRefGoogle Scholar
  25. 25.
    Zheng J, Li S, Wang Y, Li L, Su C, Liu H, Zhu F, Jiang R, Ouyang G (2014) In situ growth of IRMOF-3 combined with ionic liquids to prepare solid-phase microextraction fibers. Anal Chim Acta 829:22–27CrossRefGoogle Scholar
  26. 26.
    Gao Z, Li W, Liu B, Liang F, He H, Yang S, Sun C (2011) Nano-structured polyaniline-ionic liquid composite film coated steel wire for headspace solid–phase microextraction of organochlorine pesticides in water. J Chromatogr A 1218:6285–6291CrossRefGoogle Scholar
  27. 27.
    Zhao F, Wang M, Ma Y, Zeng B (2011) Electrochemical preparation of polyaniline-ionic liquid based solid phase microextraction fiber and its application in the determination of benzene derivatives. J Chromatogr A 1218:387–391CrossRefGoogle Scholar
  28. 28.
    Feng J, Sun M, Li L, Wang X, Duan H, Luo C (2014) Multiwalled carbon nanotubes-doped polymeric ionic liquids coating for multiple headspace solid-phase microextraction. Talanta 123:18–24CrossRefGoogle Scholar
  29. 29.
    Zhang C, Anderson JL (2014) Polymeric ionic liquid bucky gels as sorbent coatings for solid-phase microextraction. J Chromatogr A 1344:15–22CrossRefGoogle Scholar
  30. 30.
    Shearrow AM, Harris GA, Fang L, Sekhar PK, Nguyen LT, Turner EB, Bhansali S, Malik A (2009) Ionic liquid-mediated sol–gel coatings for capillary microextraction. J Chromatogr A 1216:5449–5458CrossRefGoogle Scholar
  31. 31.
    Ho TD, Toledo BR, Hantao LW, Anderson JL (2014) Chemical immobilization of crosslinked polymeric ionic liquids on nitinol wires produces highly robust sorbent coatings for solid-phase microextraction. Anal Chim Acta 843:18–26CrossRefGoogle Scholar
  32. 32.
    Joshi MD, Ho TD, Cole WTS, Anderson JL (2014) Determination of polychlorinated biphenyls in ocean water and bovine milk using crosslinked polymeric ionic liquid sorbent coatings by solid-phase microextraction. Talanta 118:172–179CrossRefGoogle Scholar
  33. 33.
    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

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • María Cordero-Vaca
    • 1
  • María J. Trujillo-Rodríguez
    • 1
  • Cheng Zhang
    • 2
  • Verónica Pino
    • 1
  • Jared L. Anderson
    • 2
  • Ana M. Afonso
    • 1
  1. 1.Departamento de Química (Área de Química Analítica)Universidad de La Laguna (ULL)La Laguna (Tenerife)Spain
  2. 2.Department of Chemistry and BiochemistryThe University of ToledoToledoUSA

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