Analytical and Bioanalytical Chemistry

, Volume 409, Issue 17, pp 4157–4166 | Cite as

Molecularly imprinted polymers based stir bar sorptive extraction for determination of cefaclor and cefalexin in environmental water

  • Jun Peng
  • Donghao Liu
  • Tian Shi
  • Huairu Tian
  • Xuanhong Hui
  • Hua HeEmail author
Research Paper


Although stir bar sportive extraction was thought to be a highly efficiency and simple pretreatment approach, its wide application was limited by low selectivity, short service life, and relatively high cost. In order to improve the performance of the stir bar, molecular imprinted polymers and magnetic carbon nanotubes were combined in the present study. In addition, two monomers were utilized to intensify the selectivity of molecularly imprinted polymers. Fourier transform infrared spectroscopy, scanning electron microscopy, and selectivity experiments showed that the molecularly imprinted polymeric stir bar was successfully prepared. Then micro-extraction based on the obtained stir bar was coupled with HPLC for determination of trace cefaclor and cefalexin in environmental water. This approach had the advantages of stir bar sportive extraction, high selectivity of molecular imprinted polymers, and high sorption efficiency of carbon nanotubes. To utilize this pretreatment approach, pH, extraction time, stirring speed, elution solvent, and elution time were optimized. The LOD and LOQ of cefaclor were found to be 3.5 ng · mL–1 and 12.0 ng · mL–1, respectively; the LOD and LOQ of cefalexin were found to be 3.0 ng · mL–1 and 10.0 ng · mL–1, respectively. The recoveries of cefaclor and cefalexin were 86.5 ~ 98.6%. The within-run precision and between-run precision were acceptable (relative standard deviation <7%). Even when utilized in more than 14 cycles, the performance of the stir bar did not decrease dramatically. This demonstrated that the molecularly imprinted polymeric stir bar based micro-extraction was a convenient, efficient, low-cost, and a specific method for enrichment of cefaclor and cefalexin in environmental samples.


Molecularly imprinted polymers Magnetic carbon nanotubes Cephalosporins Environmental water Stir bar sorption microextraction 



This work was financially supported by the Chinese College Students Innovation Project for the R&D of Novel Drugs (J1310032), Jiangsu Province Environmental Protection Scientific Research Subject and Science and Technology Project-Nanotechnology Special(ZX201441) of Suzhou Municipal Science and Technology Bureau.

Compliance with Ethical Standards

No conflict of interest exists in the submission of this manuscript, and the manuscript is approved by all authors for publication. The authors have declared no conflict of interest.

Supplementary material

216_2017_365_MOESM1_ESM.pdf (118 kb)
ESM 1 (PDF 118 kb)


  1. 1.
    DeMuri GP, Wald ER. Clinical practice. Acute bacterial sinusitis in children. New Engl J Med. 2012;367:1128–34.CrossRefGoogle Scholar
  2. 2.
    Tomić Z, Tomas A, Vukmirović S, Mikov M, Horvat O, Tomić N, et al. Do we bury antibacterials when launching? Cefaclor example. J Pharmaceut Sci. 2016;105(3):1295–300.CrossRefGoogle Scholar
  3. 3.
    Pan H, Luo H, Chen S, Thein WB. Pharmacopoeial quality of antimicrobial drugs in southern China. Lancet Global Health. 2016;4:e300–2.CrossRefGoogle Scholar
  4. 4.
    Laxminarayan R, Matsoso P, Pant S, Brower C, Røttingen JA, Klugman K, et al. Access to effective antimicrobials: a worldwide challenge. Lancet. 2016;387:168–75.CrossRefGoogle Scholar
  5. 5.
    Centner TJ. Efforts to slacken antibiotic resistance: labeling meat products from animals raised without antibiotics in the United States. Sci Total Environ. 2016;563(564):1088–94.CrossRefGoogle Scholar
  6. 6.
    Yang GCC, Wang C-L, Chiu Y-H. Occurrence and distribution of phthalate esters and pharmaceuticals in Taiwan river sediments. J Soil Sediment. 2014;15(1):198–210.CrossRefGoogle Scholar
  7. 7.
    Wang J, Wang S. Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: a review. J Environ Manage. 2016;182:620–40.CrossRefGoogle Scholar
  8. 8.
    Wang L, Li Y-Q. Simultaneous determination of 10 antibiotic residues in milk by UPLC. Chromatographia. 2009;70(1/2):253–8.CrossRefGoogle Scholar
  9. 9.
    Gago-Ferrero P, Borova V, Dasenaki ME, Tauhomaidis Nu S. Simultaneous determination of 148 pharmaceuticals and illicit drugs in sewage sludge based on ultrasound-assisted extraction and liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem. 2015;407:4287–97.CrossRefGoogle Scholar
  10. 10.
    Dasenaki ME, Thomaidis NS. Multi-analyte method for the determination of pharmaceuticals in wastewater samples using solid-phase extraction and liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem. 2015;407:4229–45.CrossRefGoogle Scholar
  11. 11.
    Rageh AH, Klein K-F, Pyell U. Off-line and on-line enrichment of α-aminocephalosporins for their analysis in surface water samples using CZE coupled to LIF. Chromatographia. 2016;79(3/4):225–41.CrossRefGoogle Scholar
  12. 12.
    Liu W, Zhang Z, Liu Z. Determination of beta-lactam antibiotics in milk using micro-flow chemiluminescence system with on-line solid phase extraction. Anal Chim Acta. 2007;592(2):187–92.CrossRefGoogle Scholar
  13. 13.
    Barceló D, Petrovic M. Challenges and achievements of LC-MS in environmental analysis: 25 years on. TrAC-Trend Anal Chem. 2007;26:2–11.CrossRefGoogle Scholar
  14. 14.
    Bejrowska A, Kudłak B, Owczarek K, Szczepańska N, Namieśnik J, Mazerska Z. New generation of analytical tests based on the assessment of enzymatic and nuclear receptor activity changes induced by environmental pollutants. TrAC-Trend Anal Chem. 2015;74:109–19.CrossRefGoogle Scholar
  15. 15.
    Dimpe KM, Nomngongo PN. Current sample preparation methodologies for analysis of emerging pollutants in different environmental matrices. TrAC-Trend Anal Chem. 2016;82:199–207.CrossRefGoogle Scholar
  16. 16.
    Backe WJ, Field JA. Is SPE necessary for environmental analysis? A quantitative comparison of matrix effects from large-volume injection and solid-phase extraction based methods. Environ Sci Technol. 2012;46:6750–8.CrossRefGoogle Scholar
  17. 17.
    Tlili I, Caria G, Ouddane B, Ghorbel-Abid I, Ternane R, Trabelsi-Ayadi M, et al. Simultaneous detection of antibiotics and other drug residues in the dissolved and particulate phases of water by an off-line SPE combined with on-line SPE-LC-MS/MS: method development and application. Sci Total Environ. 2016;563(564):424–33.CrossRefGoogle Scholar
  18. 18.
    Sun C, Tan H, Zhang Y, Zhang H. Phenolics and abscisic acid identified in acacia honey comparing different SPE cartridges coupled with HPLC-PDA. J Food Compos Anal. 2016;53:91–101.CrossRefGoogle Scholar
  19. 19.
    Kawaguchi M, Takatsu A, Ito R, Nakazawa H. Applications of stir bar sorptive extraction to food analysis. TrAC-Trend Anal Chem. 2013;45:280–93.CrossRefGoogle Scholar
  20. 20.
    Hu C, Chen B, He M, Hu B. Amino modified multi-walled carbon nanotubes/polydimethylsiloxane coated stir bar sorptive extraction coupled to high performance liquid chromatography-ultraviolet detection for the determination of phenols in environmental samples. J Chromatogr A. 2013;1300:165–72.CrossRefGoogle Scholar
  21. 21.
    Lei Y, Xu G, Wei F, Yang J, Hu Q. Preparation of a stir bar coated with molecularly imprinted polymer and its application in analysis of dopamine in urine. J Pharmaceut Biomed Anal. 2014;94:118–24.CrossRefGoogle Scholar
  22. 22.
    Peng J, Xiao D, He H, Zhao H, Wang C, Shi T, et al. Molecularly imprinted polymeric stir bar: preparation and application for the determination of naftopidil in plasma and urine samples. J Sep Sci. 2016;39:383–90.CrossRefGoogle Scholar
  23. 23.
    Díaz-Bao M, Regal P, Barreiro R, Fente CA, Cepeda A. A facile method for the fabrication of magnetic molecularly imprinted stir bars: a practical example with aflatoxins in baby foods. J Chromatogr A. 2016;1471:51–9.CrossRefGoogle Scholar
  24. 24.
    Díaz-Álvarez M, Turiel E, Martín-Esteban A. Molecularly imprinted polymer monolith containing magnetic nanoparticles for the stir bar sorptive extraction of triazines from environmental soil samples. J Chromatogr A. 2016;1469:1–7.CrossRefGoogle Scholar
  25. 25.
    Bole AL, Manesiotis P. Advanced materials for the recognition and capture of whole cells and microorganisms. Adv Mater. 2016;28:5349–66.CrossRefGoogle Scholar
  26. 26.
    Li X-S, Zhu G-T, Luo Y-B, Yuan B-F, Feng Y-Q. Synthesis and applications of functionalized magnetic materials in sample preparation. TrAC-Trend Anal Chem. 2013;45:233–47.CrossRefGoogle Scholar
  27. 27.
    Wang H, Wang R, Han Y. Preparation of molecular imprinted microspheres based on inorganic-organic co-functional monomer for miniaturized solid-phase extraction of fluoroquinolones in milk. J Chromatogr B. 2014;949:24–9.Google Scholar
  28. 28.
    Wang P, Chen S, Zhu X, Xie J. Daidzein-imprinted membranes using co-functional monomers. J Chromatogr A. 2009;1216:7639–44.CrossRefGoogle Scholar
  29. 29.
    Ribeiro AR, Schmidt TC. Determination of acid dissociation constants (pKa) of cephalosporin antibiotics: Computational and experimental approaches. Chemosphere. 2017;169:524–33.CrossRefGoogle Scholar
  30. 30.
    Egawa H, Maeda S, Yonemochi E, Oguchi T, Yamamoto K, Nakai Y. Solubility parameter and dissolution behavior of cefalexin powders with different crystallinity. Chem Pharm Bull. 1992;40:819–20.CrossRefGoogle Scholar
  31. 31.
    Olsson GD, Karlsson BC, Shoravi S, Wiklander JG, Nicholls IA. Mechanisms underlying molecularly imprinted polymer molecular memory and the role of crosslinker: resolving debate on the nature of template recognition in phenylalanine anilide imprinted polymers. J Mol Recognit. 2012;25:69–73.CrossRefGoogle Scholar
  32. 32.
    Lv T, Yan H, Cao J, Liang S. Hydrophilic molecularly imprinted resorcinol–formaldehyde–melamine resin prepared in water with excellent molecular recognition in aqueous matrices. Anal Chem. 2015;87:11084–91.CrossRefGoogle Scholar
  33. 33.
    Yin Y, Pan J, Cao J, Ma Y, Pan G, Wu R, et al. Rationally designed hybrid molecularly imprinted polymer foam for highly efficient λ-cyhalothrin recognition and uptake via twice imprinting strategy. Chem Eng J. 2016;286:485–96.CrossRefGoogle Scholar
  34. 34.
    Liu S, Pan J, Zhu H, Pan G, Qiu F, Meng M, et al. Graphene oxide-based molecularly imprinted polymers with double recognition abilities: the combination of covalent boronic acid and traditional non-covalent monomers. Chem Eng J. 2016;290:220–31.CrossRefGoogle Scholar
  35. 35.
    Barrow SJ, Kasera S, Rowland MJ, Del Barrio J, Scherman OA. Cucurbituril-based molecular recognition. Chem Rev. 2015;115:12320–406.CrossRefGoogle Scholar
  36. 36.
    Taverniers I, De Loose M, Van Bockstaele E. Trends in quality in the analytical laboratory. II. Analytical method validation and quality assurance. TrAC-Trend Anal Chem. 2004;23:535–52.CrossRefGoogle Scholar
  37. 37.
    Lara FJ, del Olmo-Iruela M, Cruces-Blanco C, Quesada-Molina C, García-Campaña AM. Advances in the determination of β-lactam antibiotics by liquid chromatography. TrAC-Trend Anal Chem. 2012;38:52–66.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Jun Peng
    • 1
    • 3
  • Donghao Liu
    • 1
  • Tian Shi
    • 1
  • Huairu Tian
    • 1
  • Xuanhong Hui
    • 1
  • Hua He
    • 1
    • 2
    • 3
    Email author
  1. 1.Department of Analytical ChemistryChina Pharmaceutical UniversityNanjingChina
  2. 2.Key Laboratory of Drug Quality Control and Pharmacovigilance, Ministry of EducationChina Pharmaceutical UniversityNanjingChina
  3. 3.Key Laboratory of Biomedical Functional MaterialsChina Pharmaceutical UniversityNanjingChina

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