Analytical and Bioanalytical Chemistry

, Volume 410, Issue 2, pp 509–519 | Cite as

β-Cyclodextrin molecularly imprinted solid-phase microextraction coatings for selective recognition of polychlorophenols in water samples

Research Paper
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Abstract

A series of β-cyclodextrin derivatives were designed and synthesized. The derivatives were investigated as functional monomers in molecularly imprinted polymeric solid-phase microextraction (MIP-SPME) fiber coatings. The coatings, with a layer thickness of 250 μm, were immobilized onto stainless steel using a capillary tube as a mold. This study employed a simple, easy, and reproducible method to prepare uniform coatings for polychlorophenols extraction. The combination of molecular inclusion effects and the molecular imprinting sites was expected to enhance the molecular recognition ability for polychlorophenols. Compared with non-imprinted polymer coatings and MIP coatings with methacrylic acid as the functional monomer, the β-cyclodextrin MIP-SPME coatings exhibited significantly higher extraction amounts and excellent selectivity to the template of triclosan. The MIP-SPME coatings exhibited a favorable synergistic extraction capacity resulting from the β-cyclodextrin cavity and molecularly imprinted binding sites. The method of β-cyclodextrin MIP-SPME coupled with high performance liquid chromatography (HPLC) for triclosan and polychlorophenols analysis in real water samples was developed. The limit of quantification was 1 μg/L for the three polychlorophenols. The recovery for three analytes ranged from 83.71% to 109.98%, with the relative standard deviation (RSD) of 2.83% to 12.19%. The β-cyclodextrin MIP-SPME fiber coatings could be used for at least 100 cycles.

Graphical Abstract

Synergistic effects in β-cyclodextrin MIP-SPME

Keywords

Molecularly imprinted polymer Solid-phase microextraction β-Cyclodextrin Synergistic effects Polychlorophenols 

Notes

Acknowledgements

This work is supported by the National Natural Science Foundation of China (21565018).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

216_2017_746_MOESM1_ESM.pdf (647 kb)
ESM 1 (PDF 646 kb)

References

  1. 1.
    Arthur CL, Pawliszyn J. Solid-phase microextraction with thermal-desorption using fused-silica optical fibers. Anal Chem. 1990;62(19):2145–8.CrossRefGoogle Scholar
  2. 2.
    Martín-Esteban A. Molecularly-imprinted polymers as a versatile, highly selective tool in sample preparation. Trends Anal Chem. 2013;45:169–81.CrossRefGoogle Scholar
  3. 3.
    Hu YL, Pan JL, Zhang KG, Lian HX, Li GK. Novel application of molecularly-imprinted polymers in sample preparation. Trends Anal Chem. 2013;43:37–52.CrossRefGoogle Scholar
  4. 4.
    Koster EHM, Crescenzi C, Hoedt WD, Ensing K, de Jong GJ. Fibers coated with molecularly imprinted polymers for solid-phase microextraction. Anal Chem. 2001;73:3140–5.CrossRefGoogle Scholar
  5. 5.
    Mullett WM, Martin P, Pawliszyn J. In-tube moleculary imprinted polymer solid-phase microextraction for the selective determination of propranolol. Anal Chem. 2001;73:2383–9.CrossRefGoogle Scholar
  6. 6.
    Tamayo FG, Turiel E, Martínesteban A. Molecularly imprinted polymers for solid-phase extraction and solid-phase microextraction: recent developments and future trends. J Chromatogr A. 2007;1152(1/2):32.CrossRefGoogle Scholar
  7. 7.
    Turiel E, Tadeo JL, Martínesteban A. Molecularly imprinted polymeric fibers for solid-phase microextraction. Anal Chem. 2009;32(19):3278–84.Google Scholar
  8. 8.
    Liu RM, Feng F, Chen GL, Liu ZM, Xu ZG. Barbell-shaped stir bar sorptive extraction using dummy template molecularly imprinted polymer coatings for analysis of bisphenol A in water. Anal Bioanal Chem. 2016;408:5329–35.CrossRefGoogle Scholar
  9. 9.
    Sun XL, Wang JC, Li Y, Jin J, Zhang BQ, Shah SM, et al. Highly selective dummy molecularly imprinted polymer as a solid-phase extraction sorbent for five bisphenols in tap and river water. J Chromatogr A. 2014;1343:33–41.CrossRefGoogle Scholar
  10. 10.
    Surikumaran H, Mohamad S, Sarih NM, Raoov M. β-Cyclodextrin based molecularly imprinted solid phase extraction for class selective extraction of priority phenols in water. Sep Sci Technol. 2015;50:2342–51.Google Scholar
  11. 11.
    Che XM, Yan KG, Xiao XH, Li GK. Analysis of forchlorfenuron and thidiazuron in fruits and vegetables by surface-enhanced Raman spectroscopy after selective solid-phase extraction with modified β-cyclodextrin. J Sep Sci. 2016;39(12):2340–6.CrossRefGoogle Scholar
  12. 12.
    Egawa Y, Shimura Y, Nowatari Y, Aiba D, Juni K. Preparation of molecularly imprinted cyclodextrin microspheres. Int J Pharm. 2005;293:165–70.CrossRefGoogle Scholar
  13. 13.
    Zhang W, Qin L, He XW, Li WY, Zhang YK. Novel surface modified molecularly imprinted polymer using acryloyl-β-cyclodextrin and acrylamide as monomers for selective recognition of lysozyme in aqueous solution. J Chromatogr A. 2009;1216:4560–7.CrossRefGoogle Scholar
  14. 14.
    Zhang Y, Li YW, Hu YL, Li GK, Chen YQ. Preparation of magnetic indole-3-acetic acid imprinted polymer beads with 4-vinylpyridine and β-cyclodextrin as binary monomer via microwave heating initiated polymerization and their application to trace analysis of auxins in plant tissues. J Chromatogr A. 2010;217(47):7337–44.CrossRefGoogle Scholar
  15. 15.
    Sedghi R, Heidari B, Yassari M. Novel molecularly imprinted polymer based on β-cyclodextrin@graphene oxide: synthesis and application for selective diphenylamine determination. J Colloid Interface Sci. 2017;503:47–56.CrossRefGoogle Scholar
  16. 16.
    Yang C, Nie J, Li Z, Zhen Y, Xu G, Li H, et al. A molecularly imprinted polymer synthesized using β-cyclodextrin as the monomer for the efficient recognition of forchlorfenuron in fruits. Anal Bioanal Chem. 2017;409(21):5065.CrossRefGoogle Scholar
  17. 17.
    Asanuma H, Akiyama T, Kajiya K, Hishiya T, Komiyama M. Molecular imprinting of cyclodextrin in water for the recognition of nanometer-scaled guests. Anal Chim Acta. 2001;435:25–33.CrossRefGoogle Scholar
  18. 18.
    Li SH, Wu XJ, Zhang Q, Li PP. Synergetic dual recognition and separation of the fungicide carbendazim by using magnetic nanoparticles carrying a molecularly imprinted polymer and immobilized β-cyclodextrin. Microchim Acta. 2016;183:1433–9.CrossRefGoogle Scholar
  19. 19.
    Liu XY, Fang HX, Yu LP. Molecularly imprinted photonic polymer based on β-cyclodextrin for amino acid sensing. Talanta. 2013;116:283–9.CrossRefGoogle Scholar
  20. 20.
    Guo MJ, Hu X, Fan Z, Liu J, Wang XC, Wang Y, et al. Molecularly imprinted photonic polymer based on p-cyclodextrin for amino acid sensing. Talanta. 2013;105:409–16.CrossRefGoogle Scholar
  21. 21.
    Cheng Y, Dong XC. Preparation of molecularly imprinted fluorescent chemosensor using quinoline modified vinyl-β-cyclodextrin and acrylamide as monomers for selective recognition of spermidine. Anal Methods. 2016;8:5838–42.CrossRefGoogle Scholar
  22. 22.
    Matsui T, Osawa T, Shirasaka K, Katayama M, Hishiya T, Asanuma H, et al. Improved method of molecular imprinting of cyclodextrin on silica-gel surface for the preparation of stable stationary HPLC phase. J Incl Phenom Macrocycl. 2006;56:39–44.CrossRefGoogle Scholar
  23. 23.
    Qin L, He XW, Li WY, Zhang YK. Molecularly imprinted polymer prepared with bonded beta-cyclodextrin and acrylamide on functionalized silica gel for selective recognition of tryptophan in aqueous media. J Chromatogr A. 2008;1187:94–102.CrossRefGoogle Scholar
  24. 24.
    Hishiya T, Shibata M, Kakazu M, Hiroyuki Asanuma A, Komiyama M. Molecularly imprinted cyclodextrins as selective receptors for steroids. 1. Macromolecules. 1999;7:2265–9.CrossRefGoogle Scholar
  25. 25.
    Kawamura A, Kiguchi T, Nishihata T, Uragami T, Miyata T. Target molecule-responsive hydrogels designed via molecular imprinting using bisphenol A as a template. Chem Commun. 2014;50:11101–3.CrossRefGoogle Scholar
  26. 26.
    Yang Z, Shi D, Chen M, Liu S. Free-standing molecularly imprinted photonic hydrogels based on β-cyclodextrin for the visual detection of l-tryptophan. Anal Methods. 2015;7(19):8352–9.CrossRefGoogle Scholar
  27. 27.
    Michalowicz J, Duda W. Phenols sources and toxicity. Pol J Environ Stud. 2007;16:347–62.Google Scholar
  28. 28.
    Ribeiro A, Neves MH, Almeida MF, Alves A, Santos L. Direct determination of chlorophenols in land-fill leachates by solid-phase microextraction gas chromatography-mass spectrometry. J Chromatogr A. 2002;975:267–74.CrossRefGoogle Scholar
  29. 29.
    Surikumaran H, Mohamad S, Sarih NM. Molecular imprinted polymer of methacrylic acid functionalized β-cyclodextrin for selective removal of 2,4-dichlorophenol. Int J Mol Sci. 2014;15:6111–36.CrossRefGoogle Scholar
  30. 30.
    Qiu XZ, Liang Y, Guo HS, Wang XB, Lin CX. Determination of phenolic compounds in environmental water by HPLC combination with on-line solid-phase extraction using molecularly imprinted polymers. J Nanosci Nanotechnol. 2015;15:9578–84.CrossRefGoogle Scholar
  31. 31.
    EC Drinking Water Guideline, 98/83/CE, November (1998) European Union, BrusselsGoogle Scholar
  32. 32.
    Federal Register, EPA method 604, Phenols, Part VIII, 40 CFR Part 136, Washington (1984) US Environmental Protection Agency (EPA)Google Scholar
  33. 33.
    Yueh MF, Taniguchi K, Chen SJ, Evans RM, Hammock BD, Karin M, et al. The commonly used antimicrobial additive triclosan is a liver tumor promoter. Proc Natl Acad Sci U S A. 2014;111:17200–5.CrossRefGoogle Scholar
  34. 34.
    Louch D, Motlagh S, Pawliszyn J. Dynamics of organic compound extraction from water using liquid-coated fused silica fibers. Anal Chem. 1992;64:1187–99.CrossRefGoogle Scholar
  35. 35.
    Saraullo A, Martos PA, Pawliszyn J. Water analysis by solid phase microextraction based on physical chemical properties of the coating. Anal Chem. 1997;69:1992–8.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2017

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of ScienceKunming University of Science and TechnologyKunmingChina

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