Advertisement

Analytical and Bioanalytical Chemistry

, Volume 408, Issue 27, pp 7857–7864 | Cite as

Magnetic molecularly imprinted polymer nanoparticles-based solid-phase extraction coupled with gas chromatography–mass spectrometry for selective determination of trace di-(2-ethylhexyl) phthalate in water samples

  • Chunying Li
  • Xiaoguo MaEmail author
  • Xiaojun Zhang
  • Rui Wang
  • Yuan Chen
  • Zhongyang Li
Research Paper

Abstract

Novel magnetic molecularly imprinted polymer nanoparticles (MMIPs) were synthesized by surface imprinting technology with a sol–gel process, using di(2-ethylhexyl)phthalate (DEHP) as the template. The MMIPs were characterized using Fourier transform–infrared spectroscopy (FT–IR), transmission electron microscopy (TEM), and vibrating sample magnetometry (VSM). The MMIPs displayed good adsorption selectivity for DEHP, with selectivity coefficients of 5.2 and 4.8 with respect to di-n-octyl phthalate and dibutyl phthalate, respectively. The reusability of MMIPs was demonstrated for at least eight repeated cycles without significant loss in adsorption capacity. A novel method for selective preconcentration and determination of trace DEHP in aqueous solutions was developed by using the magnetic DEHP-imprinted nanoparticles as adsorbent for solid-phase extraction (SPE) coupled with gas chromatography–mass spectrometry (GC–MS). The optimum SPE conditions were as follows: adsorbent amount, 50 mg; sample volume, 100 mL; adsorption time, 20 min; eluent, chloroform; and desorption time, 5 min. Results showed that the limit of detection (LOD) and limit of quantification (LOQ) for DEHP were 0.02 and 0.075 μg L−1, respectively. The proposed method was applied to the determination of DEHP in different real water samples, with spiked recovery of 93.3–103.2 % and RSD of 1.2–3.2 %. Therefore, the developed analytical method is rapid, sensitive, and accurate, which provides a new option for the detection of trace DEHP in aqueous samples.

Keywords

Molecularly imprinted polymers Di(2-ethylhexyl) phthalate Surface imprinting Solid-phase extraction Magnetic separation Gas chromatography–mass spectrometry 

Notes

Acknowledgments

The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (No. 41272262), Science and Technology Planning Project of Guangdong Province, China (No. 2016A040403112), and Major projects (natural science) of Education Department of Guangdong Province, China (261555101).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

References

  1. 1.
    Bernard L, Cueff R, Bourdeaux D, Breysse C, Sautou V. Armed study group analysis of plasticizers in poly (vinyl chloride) medical devices for infusion and artificial nutrition: comparison and optimization of the extraction procedures, a pre-migration test step. Anal Bioanal Chem. 2015;407(6):1651–9.CrossRefGoogle Scholar
  2. 2.
    Svechnikova I, Svechnikov K, Söder O. The influence of di-(2-ethylhexyl) phthalate on steroidogenesis by the ovarian granulosa cells of immature female rats. J Endocrinol. 2007;194(3):603–9.CrossRefGoogle Scholar
  3. 3.
    Davis BJ, Weaver R, Gaines LJ, Heindel JJ. Mono-(2-ethylhexyl) phthalate suppresses estradiol production independent of FSH-cAMP stimulation in rat granulosa cells. Toxicol Appl Pharmacol. 1994;128(2):224–8.CrossRefGoogle Scholar
  4. 4.
    Environmental Protection Agency (1984). Fed Reg. 49 43234.Google Scholar
  5. 5.
    Net S, Delmont A, Sempéré R, Paluselli A, Ouddane B. Reliable quantification of phthalates in environmental matrices (air, water, sludge, sediment and soil): a review. Sci Total Environ. 2015;515:162–80.CrossRefGoogle Scholar
  6. 6.
    Zou J, Ma X, Dang Y, Chen Y. Trace determination of cadmium (II) and copper (II) in environmental water samples by solid-phase extraction using a novel ionic liquid-modified composite sorbent combined with flame atomic absorption spectrometry. J Anal At Spectrom. 2014;28(9):1692–7.CrossRefGoogle Scholar
  7. 7.
    Makkliang F, Kanatharana P, Thavarungkul P, Thammakhet C. Development of magnetic micro-solid phase extraction for analysis of phthalate esters in packaged food. Food Chem. 2015;166:275–82.CrossRefGoogle Scholar
  8. 8.
    Cheng J, Ma X, Wu Y. Silica gel chemically modified with ionic liquid as novel sorbent for solid-phase extraction and preconcentration of lead from beer and tea drink samples followed by flame atomic absorption spectrometric determination. Food Anal Methods. 2014;7(5):1083–9.CrossRefGoogle Scholar
  9. 9.
    Shaikh H, Memon N, Khan H, Bhanger MI, Nizamani SM. Preparation and characterization of molecularly imprinted polymer for di (2-ethylhexyl) phthalate: application to sample clean-up prior to gas chromatographic determination. J Chromatogr A. 2012;1247:125–33.CrossRefGoogle Scholar
  10. 10.
    Dolak I. Ion-imprinted polymers for selective recognition of neodymium (III) in environmental samples. Ind Eng Chem Res. 2015;54(9):5328–35.CrossRefGoogle Scholar
  11. 11.
    Haginaka J. Molecularly imprinted polymers as affinity‐based separation media for sample preparation. J Sep Sci. 2009;32(10):1548–65.CrossRefGoogle Scholar
  12. 12.
    Muhammad T, Cui L, Jide W, Piletska EV, Guerreiro AR, Piletsky SA. Rational design and synthesis of water-compatible molecularly imprinted polymers for selective solid phase extraction of amiodarone. Anal Chim Acta. 2012;709:98–104.CrossRefGoogle Scholar
  13. 13.
    Huang BY, Chen YC, Wang GR, Liu CY. Preparation and evaluation of a monolithic molecularly imprinted polymer for the chiral separation of neurotransmitters and their analogues by capillary electrochromatography. J Chromatogr A. 2011;1218:849–55.CrossRefGoogle Scholar
  14. 14.
    Wang R, Ma Y, Lu C, Li T, Du X. Preparation and adsorption property of glutathione magnetic molecularly imprinted polymers. Acta Chim Sinica. 2014;72(5):577–82.CrossRefGoogle Scholar
  15. 15.
    Saad EM, Madbouly A, Ayoub N, El Nashar RM. Preparation and application of molecularly imprinted polymer for isolation of chicoric acid from Chicorium intybus L. medicinal plant. Anal Chim Acta. 2015;877:80–9.CrossRefGoogle Scholar
  16. 16.
    Nezhadali A, Feizy J, Beheshti HR. A molecularly imprinted polymer for the selective extraction and determination of fenvalerate from food samples using high-performance liquid chromatography. Food Anal Methods. 2015;8(5):1225–37.CrossRefGoogle Scholar
  17. 17.
    Gao B, An F, Zhu Y. Novel surface ionic imprinting materials prepared via couple grafting of polymer and ionic imprinting on surfaces of silica gel particles. Polymer. 2007;48(8):2288–97.CrossRefGoogle Scholar
  18. 18.
    Chen L, Xu S, Li J. Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chem Soc Rev. 2011;40(5):2922–42.CrossRefGoogle Scholar
  19. 19.
    Fang G, Feng J, Yan Y, Liu C, Wang S. Highly selective determination of chrysoidine in foods through a surface molecularly imprinted sol–gel polymer solid-phase extraction coupled with HPLC. Food Anal Methods. 2014;7(2):345–51.CrossRefGoogle Scholar
  20. 20.
    Ziaei E, Mehdinia A, Jabbari A. A novel hierarchical nanobiocomposite of graphene oxide–magnetic chitosan grafted with mercapto as a solid phase extraction sorbent for the determination of mercury ions in environmental water samples. Anal Chim Acta. 2014;850:49–56.CrossRefGoogle Scholar
  21. 21.
    Huang SH, Chen DH. Rapid removal of heavy metal cations and anions from aqueous solutions by an amino-functionalized magnetic nano-adsorbent. J Hazard Mater. 2009;163(1):174–9.CrossRefGoogle Scholar
  22. 22.
    Chen Y, Ma X, Huang M, Peng J, Li C. Use of a new magnetic ion–imprinted nanocomposite adsorbent for selective and rapid preconcentration and determination of trace nickel by flame atomic absorption spectrometry. Anal Methods. 2016;8(4):824–9.CrossRefGoogle Scholar
  23. 23.
    Cui C, He M, Chen B, Hu B. Restricted accessed material-copper (II) ion imprinted polymer solid phase extraction combined with inductively coupled plasma-optical emission spectrometry for the determination of free Cu (II) in urine and serum samples. Talanta. 2013;116:1040–6.CrossRefGoogle Scholar
  24. 24.
    Hei L, Feng C, Li Z, Liu L, Gui J. Microporous network polyaniline coated magnetic Fe3O4 nanoparticals supported palladium catalyzed Suzuki and Heck coupling reactions. Chin J Org Chem. 2015;35(8):1673–81.CrossRefGoogle Scholar
  25. 25.
    Jara S, Lysebo C, Greibrokk T, Lundanes E. Determination of phthalates in water samples using polystyrene solid-phase extraction and liquid chromatography quantification. Anal Chim Acta. 2000;407:165–71.CrossRefGoogle Scholar
  26. 26.
    Prapatpong P, Kanchanamayoon W. Solid-phase extraction and gas chromatography. J Appl Sci. 2010;10(17):1987–90.CrossRefGoogle Scholar
  27. 27.
    Xu Q, Yin X, Wu S, Wang, M, Wen Z, Gu Z. Determination of phthalate esters in water samples using Nylon6 nanofibers mat-based solid-phase extraction coupled to liquid chromatography. Microchim Acta. 2010;168(3–4):267–75.CrossRefGoogle Scholar
  28. 28.
    Wang M, Yang X, Bi W. Application of magnetic graphitic carbon nitride nanocomposites for the solid‐phase extraction of phthalate esters in water samples. J Sep Sci. 2015;38(3):445–52.CrossRefGoogle Scholar
  29. 29.
    Jiao Y, Fu S, Ding L, Gong Q, Zhu S, Wang L, et al. Determination of trace leaching phthalate esters in water by magnetic solid phase extraction based on magnetic multi-walled carbon nanotubes followed by GC-MS/MS. Anal Methods. 2012;4(9):2729–34.CrossRefGoogle Scholar
  30. 30.
    Liu HD, Zhao X, Chen YF. Preparation and characterization of nano-magnetic Fe3O4@SiO2 composite. Chin J Chem Res. 2007;18(3):21–3.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Chunying Li
    • 1
  • Xiaoguo Ma
    • 1
    Email author
  • Xiaojun Zhang
    • 1
  • Rui Wang
    • 1
  • Yuan Chen
    • 1
  • Zhongyang Li
    • 1
  1. 1.School of Environmental Science and EngineeringGuangdong University of TechnologyGuangzhouChina

Personalised recommendations