Analytical and Bioanalytical Chemistry

, Volume 387, Issue 3, pp 1007–1016 | Cite as

Selective solid-phase extraction of tebuconazole in biological and environmental samples using molecularly imprinted polymers

  • Mai-ling Hu
  • Ming Jiang
  • Peng Wang
  • Su-rong Mei
  • Yan-fei Lin
  • Xiao-zhong Hu
  • Yun Shi
  • Bin LuEmail author
  • Kang Dai
Original Paper


Molecularly imprinted polymers (MIPs) were prepared by precipitation polymerization using tebuconazole (TBZ) as a template. Frontal chromatography and selectivity experiments were used to determine the binding capabilities and binding specificities of different MIPs. The polymer that had the highest binding selectivity and capability was used as the solid-phase extraction (SPE) sorbent for the direct extraction of TBZ from different biological and environmental samples (cabbage, pannage, shrimp, orange juice and tap water). The extraction protocol was optimized and the optimum conditions were: conditioning with 5 mL methanol:acetic acid (9:1), 5 mL methanol and 5 mL water respectively, loading with 5 mL aqueous samples, washing with 1.2 mL acetonitrile (ACN):phosphate buffer (5:5, pH3), and eluting with 3 mL methanol. The MIPs were able to selectively recognize, effectively trap and preconcentrate TBZ over a concentration range of 0.5–15 μmol/L. The intraday and interday RSDs were less than 9.7% and 8.6%, respectively. The limit of quantification was 0.1 μmol/L. Under optimum conditions, the MISPE recoveries of spiked cabbage, pannage, shrimp, orange juice and tap water were 62.3%, 75.8%, 71.6%, 89% and 93.9%, respectively. MISPE gave better HPLC separation efficiencies and higher recoveries than C18 SPE and strong cation exchange (SCX) SPE.


HPLC analysis of spiked pannage after MISPE (A) and after C18 SPE (B). HQ (1), E3 (2), p-NP (3), FTF (4), TBZ (5), PNZ (6), HXZ (7)


Molecularly imprinted polymers Frontal chromatography Solid-phase extraction Tebuconazole Biological and environmental samples 



This work was supported by the National Natural Science Foundation of China (Grant No. 20307004 and NO. 20477013), and the Entry-Exit Inspection and Quarantine Bureau of PRC (NO 2005G0082).

Supplementary material

216_2006_1004_MOESM1_ESM.doc (206 kb)
Fig. S1 Scanning electron micrographs of the particles prepared: a the length of the bar is 1 μm; b the length of the bar is 5 μm (DOC 210 kb)


  1. 1.
    Stehmann C, Waard de MA (1996) Crop Prot 15:39–47CrossRefGoogle Scholar
  2. 2.
    Sanagi MM, See HH, Ibrahim WAW, Naim AA (2004) J Chromatogr A 1059:95–101CrossRefGoogle Scholar
  3. 3.
    US EPA (1999) Federal Register: Rules and Regulations 64:1132–1138Google Scholar
  4. 4.
    Paoli MD, Tacchedo M, Damiato V, Fabbro D Bruno R (1997) J Chromatogr A 765:127–131CrossRefGoogle Scholar
  5. 5.
    Colume A, Cardenas S, Gallego M, Valcarcel M (2000) J Chromatogr A 882:193–203CrossRefGoogle Scholar
  6. 6.
    Blasco C, Pico Y, Manes J, Font G (2002) J Chromatogr A 947:227–235CrossRefGoogle Scholar
  7. 7.
    Blasco C, Pico Y, Font G (2002) J AOAC Int 3:704–710Google Scholar
  8. 8.
    Rodriguez R, Manes J, Pico Y (2003) Anal Chem 75:452–459CrossRefGoogle Scholar
  9. 9.
    Zhu XL, Yang J, Su QD, Cai JB, Gao Y (2005) J Chromatogr A 1092:161–169CrossRefGoogle Scholar
  10. 10.
    Osemwengie LI, Steinberg S (2001) J Chromatogr A 932:107–118CrossRefGoogle Scholar
  11. 11.
    Xu F, Liang XM, Lin BC, Su F, Schramm KW, Kettrup A (1999) Chemosphere 39:2239–2248CrossRefGoogle Scholar
  12. 12.
    Miyauchi T, Mori M, Ito K (2005) J Chromatogr A 1063:137–141CrossRefGoogle Scholar
  13. 13.
    Redondo MJ, Ruiz MJ, Boluda R, Font G (1996) J Chromatogr A 719:69–76CrossRefGoogle Scholar
  14. 14.
    Delaunay N, Pichon V, Hennion MC (2000) J Chromatogr B 745:15–37CrossRefGoogle Scholar
  15. 15.
    Rashid BA, Aherne GW, Katmeh MF, Wasowski PK, Stevenson D (1998) J Chromatogr A 797:245–250CrossRefGoogle Scholar
  16. 16.
    Hennion MC, Pichon V (2003) J Chromatogr A 1000:29–52CrossRefGoogle Scholar
  17. 17.
    Sellergren B (1994) Anal Chem 66:1578–1582CrossRefGoogle Scholar
  18. 18.
    Baggiani C, Trotta F, Giraudi G, Giovannoli C, Vanni A (1999) Anal Commun 36:263–269CrossRefGoogle Scholar
  19. 19.
    Turiel E, Martin-Esteban A, Fernandez P, Perez-Conde C, Camara C (2001) Anal Chem 73:5133–5141CrossRefGoogle Scholar
  20. 20.
    Mena ML, Martinez-Ruiz P, Reviejo AJ, Pingarron JM (2002) Anal Chim Acta 451:297–304CrossRefGoogle Scholar
  21. 21.
    Matsui J, Okada M, Tsuruoka M, Takeuchi T (1997) Anal Commun 34:85–87CrossRefGoogle Scholar
  22. 22.
    Zhu QZ, Degelmann P, Niessner R, Knopp D (2002) Environ Sci Technol 36:5411–5420CrossRefGoogle Scholar
  23. 23.
    Ye L, Cormack PAG, Mosbac K (1999) Anal Commun 36:35–38CrossRefGoogle Scholar
  24. 24.
    Jiang M, Zhang JH, Mei SR, Shi Y, Zou LJ, Zhu YX, Dai K, Lu B (2006) J Chromatogr A 1110:27–34CrossRefGoogle Scholar
  25. 25.
    Theodoridis G, Zacharis CK, Tzanavaras PD, Themelis DG, Economou A (2004) J Chromatogr A 1030:69–76CrossRefGoogle Scholar
  26. 26.
    Kasai K, Oda Y, Nishikata M, Ishii S (1986) J Chromatogr 376:33–42CrossRefGoogle Scholar
  27. 27.
    Cheong SH, McNiven S, Rachkov A, Levi R, Yano K, Karube I (1997) Macromolecules 30:1317–1322CrossRefGoogle Scholar
  28. 28.
    Tamayo FG, Casillas JL, Martin-Esteban A (2005) Anal Bioanal Chem 381:1234–1240CrossRefGoogle Scholar
  29. 29.
    (1997) Method for the determination of triadimentol residues in cereals for export (SN0644)Google Scholar
  30. 30.
    Zhang JH, Jiang M, Zou LJ, Shi D, Mei SR, Zhu YX, Shi Y, Dai K, Lu B (2006) Anal Bioanal Chem 785:780–786CrossRefGoogle Scholar
  31. 31.
    Wang J, Cormack PAG, Sherrington DC, Khoshdel E (2003) Angew Chem Int Ed 42:5336–5338CrossRefGoogle Scholar
  32. 32.
    Tamayo FG, Casillas JL, Martin-Esteban A (2005) J Chromatogr A 1069:173–181CrossRefGoogle Scholar
  33. 33.
    Olof R, Lars IA, Mosbach K (1993) J Org Chem 58:7562–7564CrossRefGoogle Scholar
  34. 34.
    Barcelo D, Hennion MC (1995) Anal Chim Acta 318:1–41CrossRefGoogle Scholar
  35. 35.
    Hennion MC, Coquart V (1993) J Chromatogr 642:211–219CrossRefGoogle Scholar
  36. 36.
    Zander A, Findlay P, Renner T, Sellergren B (1998) Anal Chem 70:3304–3314CrossRefGoogle Scholar
  37. 37.
    Theodoridis G, Manesiotis P (2002) J Chromatogr A 948:163–169CrossRefGoogle Scholar
  38. 38.
    Andersson LI (2000) Analyst 125:1515–1517CrossRefGoogle Scholar
  39. 39.
    Chapuis F, Pichon V, Lanza F, Sellergren B, Hennion MC (2003) J Chromatogr A 999:23–33CrossRefGoogle Scholar
  40. 40.
    Karlsson JG, Andersson LI, Nicholls IA (2001) Anal Chim Acta 435:57–64CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • Mai-ling Hu
    • 1
  • Ming Jiang
    • 1
  • Peng Wang
    • 2
  • Su-rong Mei
    • 1
  • Yan-fei Lin
    • 2
  • Xiao-zhong Hu
    • 2
  • Yun Shi
    • 1
  • Bin Lu
    • 1
    Email author
  • Kang Dai
    • 1
  1. 1.Key Laboratory of Environment & Health of Ministry of Education, Institute of Environmental Medicine, School of Public Health, Tongji Medical CollegeHuazhong University of Science and TechnologyHubeiPeople’s Republic of China
  2. 2.Hubei Entry-Exit Inspection and Quarantine Bureau of PRCHubeiChina

Personalised recommendations