Developing qualitative extraction profiles of coffee aromas utilizing polymeric ionic liquid sorbent coatings in headspace solid-phase microextraction gas chromatography–mass spectrometry

  • Jessica López-Darias
  • Jared L. Anderson
  • Verónica Pino
  • Ana M. Afonso
Original Paper


Two solid-phase microextraction (SPME) sorbent coatings based on polymeric ionic liquids (PILs) have been utilized for the analysis of complex coffee aroma samples. The PIL-based SPME coatings examined, namely, poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide) [poly(VBHDIm+ NTf 2 )], with ∼14-μm thickness, and poly(1-vinyl-3-hexylimidazolium chloride) [poly(ViHIm+ Cl)], with ∼8-μm thickness, were employed for the headspace determination of up to 49 analytes from four different coffee beans: two French roast coffees of different brands, Sumatra coffee, and decaffeinated Sumatra coffee. The analysis was conducted using gas chromatography coupled to mass spectrometry. For comparative purposes, the commercial polyacrylate (PA, 85-μm film thickness) SPME coating was utilized under the same extraction conditions. The three SPME coatings tested behaved quite differently as a function of the families of compounds extracted. Thus, the poly(VBHDIm+ NTf 2 ) coating was extremely selective for aldehydes while also exhibiting good extraction efficiencies for acids. The poly-(ViHIm+ Cl) coating exhibited superior performance for aromatic alcohols, and the PA coating worked better for heterocyclic aromatics. Both PIL-based SPME sorbent coatings demonstrated exceptional selectivity and extraction efficiency when dealing with complex coffee aromas in spite of their small film thicknesses.


Solid-phase microextraction Coffee analysis Coffee aroma Gas chromatography Headspace analysis Ionic liquid 



The authors wish to thank Qichao Zhao, Christa Graham, and Yunjing Meng for their assistance and useful discussions. J.L.A. thanks funding from the Analytical and Surface Chemistry Program in the Division of Chemistry and the Separation and Purification Process Program in the Chemical, Environmental, Bioengineering, and Transport Systems Division from the National Science Foundation for a CAREER grant (CHE-0748612). A.M.A. acknowledges funding from the Spanish Ministry of Innovation and Science (MICINN), project ref. CTQ2008-06253/BQU, and from the Canary Agency for Research and Innovation (ACIISI) reinforcement, project ref. SolSubC20081000171. V.P. thanks the MICINN for the Ramón y Cajal contract with the University of La Laguna (ULL). J.L.D. thanks the ACIISI for the contract with the ULL and funding for the stay at The University of Toledo.

Supplementary material

216_2011_5394_MOESM1_ESM.pdf (351 kb)
ESM 1 (PDF 351 kb)


  1. 1.
    Mondello L, Casilli A, Tranchida PQ, Dugo P, Costa R, Festa S, Dugo G (2004) J Sep Sci 27:442–450CrossRefGoogle Scholar
  2. 2.
    Moon J-K, Shibamoto T (2009) J Agric Food Chem 57:5823–5831CrossRefGoogle Scholar
  3. 3.
    Ryan D, Shellie R, Tranchida P, Casilli A, Mondello L, Marriott P (2004) J Chromatogr A 1054:57–65Google Scholar
  4. 4.
    Flament I, Bessiere-Thomas Y (2002) Coffee flavor chemistry. Wiley, Chichester, pp 212–328Google Scholar
  5. 5.
    Tranchida PQ, Purcaro G, Conte L, Dugo P, Dugo G, Mondello L (2009) J Chromatogr A 1216:7301–7306CrossRefGoogle Scholar
  6. 6.
    Ribeiro JS, Teófilo RF, Augusto F, Ferreira MMC (2010) Chemometrics Intell Lab Syst 102:45–52CrossRefGoogle Scholar
  7. 7.
    Pereira J, Pereira J, Câmara JS (2011) Talanta 83:899–906CrossRefGoogle Scholar
  8. 8.
    Pontes M, Marques JC, Câmara JS (2009) Microchem J 93:1–11CrossRefGoogle Scholar
  9. 9.
    Ong BT, Nazimah SAH, Tan CP, Mirhosseini H, Osman A, Mat Hashim D, Rusul G (2008) J Food Compos Anal 21:416–422CrossRefGoogle Scholar
  10. 10.
    Augusto F, Carase E, Silva RGC, Rivellino SR, Batista AD, Martendal E (2010) J Chromatogr A 1217:2533–2542CrossRefGoogle Scholar
  11. 11.
    Turiel E, Martín-Esteban A (2009) J Sep Sci 32:3278–3284CrossRefGoogle Scholar
  12. 12.
    Risticevic S, Niri VH, Vuckovic D, Pawliszyn J (2009) Anal Bioanal Chem 393:781–795CrossRefGoogle Scholar
  13. 13.
    Kumar A, Gaurav, Malik AK, Tewary DK, Singh B (2008) Anal Chim Acta 610:1–14CrossRefGoogle Scholar
  14. 14.
    Ho TD, Canestraro AJ, Anderson JL (2011) Anal Chim Acta 695:18–43CrossRefGoogle Scholar
  15. 15.
    Berthod A, Ruiz-Ángel MJ, Carda-Broch S (2008) J Chromatogr A 1184:6–18CrossRefGoogle Scholar
  16. 16.
    Sun P, Armstrong DW (2010) Anal Chim Acta 661:1–16CrossRefGoogle Scholar
  17. 17.
    Poole CF, Poole SK (2010) J Chromatogr A 1217:2268–2286CrossRefGoogle Scholar
  18. 18.
    Aguilera-Herrador E, Lucena R, Cárdenas S, Valcárcel M (2010) Trends Anal Chem 29:602–616CrossRefGoogle Scholar
  19. 19.
    Zhao Q, Anderson JL (2011) Anal Bioanal Chem 400:1613–1618CrossRefGoogle Scholar
  20. 20.
    Martín-Calero A, Pino V, Afonso AM (2011) Trends Anal Chem doi: 10.1016/j.trac.2011.04.023
  21. 21.
    Zhao F, Meng Y, Anderson JL (2008) J Chromatogr A 1208:1–9CrossRefGoogle Scholar
  22. 22.
    Zhao Q, Wajert JC, Anderson JL (2010) Anal Chem 82:707–713CrossRefGoogle Scholar
  23. 23.
    Meng Y, Pino V, Anderson JL (2009) Anal Chem 81:7107–7112CrossRefGoogle Scholar
  24. 24.
    Meng Y, Pino V, Anderson JL (2011) Anal Chim Acta 687:141–149CrossRefGoogle Scholar
  25. 25.
    López-Darias J, Pino V, Anderson JL, Graham CM, Afonso AM (2010) J Chromatogr A 1217:1236–1243CrossRefGoogle Scholar
  26. 26.
    Meng Y, Anderson JL (2010) J Chromatogr A 121:6143–6152CrossRefGoogle Scholar
  27. 27.
    López-Darias J, Pino V, Meng Y, Anderson JL, Afonso AM (2010) J Chromatogr A 1217:7189–7197CrossRefGoogle Scholar
  28. 28.
    Prosen H, Zupančič-Kralj L (1999) Trends Anal Chem 18:272–282CrossRefGoogle Scholar
  29. 29.
    Bruheim I, Liu X, Pawliszyn J (2003) Anal Chem 75:1002–1010CrossRefGoogle Scholar
  30. 30.
    Wilkes JG, Conte ED, Kim Y, Holcomb M, Sutherland JB, Miller DW (2000) J Chromatogr A 880:3–33CrossRefGoogle Scholar
  31. 31.
    Koziel J, Jia M, Pawliszyn J (2000) Anal Chem 72:5178–5186CrossRefGoogle Scholar
  32. 32.
    Bicchi C, Ruosi MR, Cagliero C, Cordero C, Liberto E, Rubiolo P, Sgorbini B (2011) J Chromatogr A 1218:753–762CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Jessica López-Darias
    • 1
    • 2
  • Jared L. Anderson
    • 1
  • Verónica Pino
    • 2
  • Ana M. Afonso
    • 2
  1. 1.Department of ChemistryThe University of ToledoToledoUSA
  2. 2.Departamento de Química Analítica, Nutrición y BromatologíaUniversidad de La Laguna (ULL)La Laguna (Tenerife)Spain

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