Microchimica Acta

, 185:19 | Cite as

Magnetic mesoporous polymelamine-formaldehyde resin as an adsorbent for endocrine disrupting chemicals

  • Yuhong Song
  • Ruiyang Ma
  • Caina Jiao
  • Lin Hao
  • Chun Wang
  • Qiuhua Wu
  • Zhi Wang
Original Paper


A magnetic mesoporous poly(melamine-formaldehyde) composite (Fe3O4-mPMF) was prepared via grafting poly(melamine-formaldehyde) onto the surface of amino-functionalized magnetite (Fe3O4) nanoparticles. The material was characterized by scanning electron micrography, transmission electron microscopy, X-ray diffraction, Fourier transform-infrared spectroscopy, nitrogen adsorption-desorption isotherms, and thermogravimetric analysis. It has a large surface area, a typical mesoporous structure, and a high thermal stability. It was employed as a magnetic sorbent for the solid phase extraction of the following endocrine disrupting chemicals (EDCs): Bisphenol A, 4-tert-butylphenol, 4-tert-octylphenol and nonylphenol. The EDCs were then quantified by HPLC. Under the optimized conditions, the response to the EDCs is linear in the range of 0.5–100 ng·mL−1, and the limits of detection are 0.02–0.1 ng·mL−1. The high adsorption capability of the Fe3O4-mPMF is mainly attributed to multiple interactions including π-stacking, hydrogen bonding, and hydrophobic interactions. The method was applied to the extraction of EDCs from spiked river water and bottled juice samples. The results demonstrated that the Fe3O4-mPMF is an efficient adsorbent for the extraction of organic compounds with large conjugated π-system, plenty of hydrogen-bonding sites, and strong hydrophobicity.

Graphical abstract

A magnetic mesoporous polymelamine-formaldehyde composite (Fe3O4-mPMF) was prepared and employed as a magnetic sorbent for the solid phase extraction of endocrine disrupting chemicals from river water and bottled juice samples prior to high-performance liquid chromatographic analysis.


High-performance liquid chromatography Magnetic solid phase extraction Adsorption mechanism Fourier transform infrared spectra Powder X-ray diffraction Transmission electron microscopy X-ray photoelectron spectroscopy Magnetic adsorbent River water Bottled juice 



Financial supports from the National Natural Science Foundation of China (31471643, 31571925, 31671930), the Hebei “Double First Class Discipline” Construction Foundation for the Discipline of Food Science and Engineering of Hebei Agricultural University (2016SPGCA18), the Natural Science Foundation of Hebei Province (B2016204136, B2016204146, B2017204025), the Scientific and Technological Research Foundation of the Department of Education of Hebei Province (ZD2016085) and the Natural Science Foundation of Hebei Agricultural University (LG201607) are gratefully acknowledged.

Compliance with ethical standards

The author(s) declare that they have no competing interests.

Supplementary material

604_2017_2593_MOESM1_ESM.docx (1.1 mb)
ESM 1 (DOCX 1096 kb)


  1. 1.
    Colborn T, vom Saal FS, Soto AM (1993) Developmental effects of endocrine-disrupting chemicals in wildlife and humans. Environ Health Perspect 101(5):378–383CrossRefGoogle Scholar
  2. 2.
    Vandenberg LN, Colborn T, Hayes TB, Heindel JJ, Jacobs DR, Lee DH, Shioda T, Soto AM, vom Saal FS, Welshons WV, Zoeller RT, Myers JP (2012) Hormones and endocrine-disrupting chemicals: low-dose effects and nonmonotonic dose responses. Endocr Rev 33(3):378–455Google Scholar
  3. 3.
    Vos JG, Dybing E, Greim HA, Ladefoged O, Lambré C, Tarazona JV, Brandt I, Vethaak AD (2000) Health effects of endocrine-disrupting chemicals on wildlife, with special reference to the European situation. Crit Rev Toxicol 30(1):71–133CrossRefGoogle Scholar
  4. 4.
    Mclachlan JA (2001) Environmental signaling: what embryos and evolution teach us about endocrine disrupting chemicals. Endocr Rev 22(3):319–341CrossRefGoogle Scholar
  5. 5.
    Johnson AC, Sumpter JP (2001) Removal of endocrine-disrupting chemicals in activated sludge treatment works. Environ Sci Technol 35(24):4697–4703CrossRefGoogle Scholar
  6. 6.
    Esplugas S, Bila DM, Krause LGT, Dezotti M (2007) Ozonation and advanced oxidation technologies to remove endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) in water effluents. J Hazard Mater 149(3):631–642CrossRefGoogle Scholar
  7. 7.
    Ridgway K, Lalljie SPD, Smith RM (2007) Sample preparation techniques for the determination of trace residues and contaminants in foods. J Chromatogr A 1153(2):36–53CrossRefGoogle Scholar
  8. 8.
    Chen Y, Guo Z, Wang X, Qiu C (2008) Sample preparation. J Chromatogr A 1184(1–2):191–219CrossRefGoogle Scholar
  9. 9.
    Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. J AOAC Int 86(2):412–431Google Scholar
  10. 10.
    Basheer C, Lee HK (2004) Analysis of endocrine disrupting alkylphenols, chlorophenols and bisphenol-A using hollow fiber-protected liquid-phase microextraction coupled with injection port-derivatization gas chromatography–mass spectrometry. J Chromatogr A 1057(1–2):163–169CrossRefGoogle Scholar
  11. 11.
    Kataoka H, Lord HL, Pawliszyn J (2000) Applications of solid-phase microextraction in food analysis. RSC 880:36–62Google Scholar
  12. 12.
    Zhao Q, Wei F, Luo YB, Ding J, Xiao N, Feng YQ (2011) Rapid magnetic solid-phase extraction based on magnetic multiwalled carbon nanotubes for the determination of polycyclic aromatic hydrocarbons in edible oils. J Agric Food Chem 59(24):12794–12800Google Scholar
  13. 13.
    Chen B, Heng S, Peng H, Hu B, Yu X, Zhang Z, Pang D, Yue X, Zhu Y (2010) Magnetic solid phase microextraction on a microchip combined with electrothermal vaporization-inductively coupled plasma mass spectrometry for determination of Cd, Hg and Pb in cells. J Anal At Spectrom 25(12):1931–1938CrossRefGoogle Scholar
  14. 14.
    Gao Q, Luo D, Ding J, Feng YQ (2010) Rapid magnetic solid-phase extraction based on magnetite/silica/poly(methacrylic acid-co-ethylene glycol dimethacrylate) composite microspheres for the determination of sulfonamide in milk samples. J Chromatogr A 1217(35):5602–5609CrossRefGoogle Scholar
  15. 15.
    Shultz AM, Farha OK, Hupp JT, Nguyen ST (2011) Synthesis of catalytically active porous organic polymers from metalloporphyrin building blocks. Chem Sci 2(4):686–689CrossRefGoogle Scholar
  16. 16.
    Song WC, Xu XK, Chen Q, Zhuang ZZ, Bu XH (2013) Nitrogen-rich diaminotriazine-based porous organic polymers for small gas storage and selective uptake. Polym Chem 4(17):4690–4696CrossRefGoogle Scholar
  17. 17.
    Kaur P, Hupp JT, Nguyen ST (2011) Porous organic polymers in catalysis: opportunities and challenges. ACS Catal 1(7):819–835CrossRefGoogle Scholar
  18. 18.
    Schwarz D, Weber J (2017) Synthesis of mesoporous poly(melamine-formaldehyde) particles by inverse emulsion polymerization. J Colloid Interface Sci 498:335–342CrossRefGoogle Scholar
  19. 19.
    Tan MX, Zhang Y, Ying JY (2013) Mesoporous poly(melamine-formaldehyde) solid sorbent for carbon dioxide capture. ChemSusChem 6(7):1186–1190CrossRefGoogle Scholar
  20. 20.
    Zhang X, Chen F (2016) Facile synthesis of mesoporous poly(melamine–formaldehyde) solid adsorbent in ethylene glycol. Chem Lett 45(4):412–414CrossRefGoogle Scholar
  21. 21.
    Tan MX, Sum YN, Ying JY, Zhang Y (2013) A mesoporous poly-melamine-formaldehyde polymer as a solid sorbent for toxic metal removal. Energy Environ Sci 6(11):3254CrossRefGoogle Scholar
  22. 22.
    Li Y, Yang CX, Yan XP (2017) Controllable preparation of core-shell magnetic covalent-organic framework nanospheres for efficient adsorption and removal of bisphenols in aqueous solution. Chem Commun 53(16):2511–2514CrossRefGoogle Scholar
  23. 23.
    Xiong S, Wang M, Cai D, Li Y, Gu N, Wu Z (2013) Electrochemical detection of Pb(II) by glassy carbon electrode modified with amine-functionalized magnetite nanoparticles. Anal Lett 46(6):912–922CrossRefGoogle Scholar
  24. 24.
    Das M, Dhak P, Gupta S, Mishra D, Maiti TK, Basak A, Pramanik P (2010) Highly biocompatible and water-dispersible, amine functionalized magnetite nanoparticles, prepared by a low temperature, air-assisted polyol process: a new platform for bio-separation and diagnostics. Nanotechnology 21(12):125103CrossRefGoogle Scholar
  25. 25.
    McCullum C, Tchounwou P, Ding LS, Liao X, Liu YM (2014) Extraction of aflatoxins from liquid foodstuff samples with polydopamine-coated superparamagnetic nanoparticles for HPLC-MS/MS analysis. J Agric Food Chem 62(19):4261–4267CrossRefGoogle Scholar
  26. 26.
    Wang L, Bao J, Wang L, Zhang F, Li Y (2006) One-pot synthesis and bioapplication of amine-functionalized magnetite nanoparticles and hollow nanospheres. Chemistry 12(24):6341–6347CrossRefGoogle Scholar
  27. 27.
    He S, Zeng T, Wang S, Niu H, Cai Y (2017) Facile synthesis of magnetic covalent organic framework with three-dimensional bouquet-like structure for enhanced extraction of organic targets. ACS Appl Mater Interfaces 9(3):2959–2965CrossRefGoogle Scholar
  28. 28.
    Tan MX, Yin NS, Ying JY, Zhang Y (2013) A mesoporous poly-melamine-formaldehyde polymer as a solid sorbent for toxic metal removal. Energy Environ Sci 6(11):3254–3259CrossRefGoogle Scholar
  29. 29.
    Li J, Li Q, Li LS, Xu L (2017) Removal of perfluorooctanoic acid from water with economical mesoporous melamine-formaldehyde resin microsphere. Chem Eng J 320:501–509CrossRefGoogle Scholar
  30. 30.
    Xue SW, Li J, Xu L (2017) Preparation of magnetic melamine-formaldehyde resin and its application to extract nonsteroidal anti-inflammatory drugs. Anal Bioanal Chem 409(12):3103–3113CrossRefGoogle Scholar
  31. 31.
    Pei M, Zhang Z, Huang X, Wu Y (2017) Fabrication of a polymeric ionic liquid-based adsorbent for multiple monolithic fiber solid-phase microextraction of endocrine disrupting chemicals in complicated samples. Talanta 165:152–160CrossRefGoogle Scholar
  32. 32.
    Wang J, Hao L, Wang C, Wu Q, Wang Z (2017) Nanoporous carbon as the solid-phase extraction adsorbent for the extraction of endocrine disrupting chemicals from juice samples. Food Anal Methods 10(8):2710–2717CrossRefGoogle Scholar
  33. 33.
    Li F, Cai C, Cheng J, Zhou H, Ding K, Zhang L (2015) Extraction of endocrine disrupting phenols with iron-ferric oxide core-shell nanowires on graphene oxide nanosheets, followed by their determination by HPLC. Microchim Acta 182(15–16):2503–2511CrossRefGoogle Scholar
  34. 34.
    Liu L, Feng T, Wang C, Wu Q, Wang Z (2014) Magnetic three-dimensional graphene nanoparticles for the preconcentration of endocrine-disrupting phenols. Microchim Acta 181(11–12):1249–1255CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of Chemistry, College of ScienceHebei Agricultural UniversityBaodingChina
  2. 2.College of Landscape and TravelHebei Agricultural UniversityBaodingChina

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