Journal of Materials Science

, Volume 53, Issue 7, pp 4897–4912 | Cite as

Preparation and evaluation of superparamagnetic core–shell dummy molecularly imprinted polymer for recognition and extraction of organophosphorus pesticide

Chemical routes to materials
  • 18 Downloads

Abstract

In this paper, we reported a simple and effective strategy to synthesize core–shell dummy template magnetic molecularly imprinted polymers (Fe3O4@DMIPs) using ethyl paraoxon as a template for the recognition and selective extraction of organophosphorus pesticide. Initially, monodisperse Fe3O4 nanoparticles were synthesized directly through a facile one-pot hydrothermal method. Then, the imprinted layer was synthesized directly on the surface of the magnetic core by means of a one-pot sol–gel copolymerization which avoided further modification of the external part of the magnetic core. The structure and morphology of the materials (Fe3O4@DMIPs) were characterized by SEM, TEM, FTIR, XRD, and VSM. It was observed that Fe3O4@DMIPs showed regular morphology, good dispersibility, and superparamagnetism. The synthesis conditions for the formation of Fe3O4@DMIPs were systematically investigated. It was found that the morphology and monodispersity of Fe3O4@DMIPs were highly influenced by the ratio of the mixture solvent of methanol and water and the volume ratio of functional monomer (APTES) and cross-linker (TEOS). The binding performance of the imprinted polymers was investigated through a series of adsorption experiments, which indicated that the Fe3O4@DMIPs had a fast adsorption rate (15 min) and high adsorption capacity (195.7 mg g−1) to methyl parathion and phoxim. Meanwhile, real wine sample tests demonstrated a good extraction effect. This study provides a possibility for the selective extraction of organophosphorus pesticide residue in a complex matrix.

Notes

Acknowledgements

We gratefully acknowledge the Commonwealth Scientific Foundation for Industry of Chinese Inspection and Quarantine (No. 201210071) of the Ministry of National Science and Technology of China.

References

  1. 1.
    Yang YQ, Tu HY, Zhang AD, Du D, Lin YH (2012) Preparation and characterization of Au–ZrO2–SiO2 nanocomposite spheres and their application in enrichment and detection of organophosphorus agents. J Mater Chem 22:4977–4981CrossRefGoogle Scholar
  2. 2.
    Haginaka J, Tabo H, Matsunaga H (2012) Preparation of molecularly imprinted polymers for organophosphates and their application to the recognition of organophosphorus compounds and phosphopeptides. Anal Chim Acta 748:1–8CrossRefGoogle Scholar
  3. 3.
    Yun YH, Shon HK, Yoon SD (2009) Preparation and characterization of molecularly imprinted polymers for the selective separation of 2, 4 dichlorophenoxyacetic acid. J Mater Sci 44:6206–6211.  https://doi.org/10.1007/s10853-009-3863-3 CrossRefGoogle Scholar
  4. 4.
    Zhou MC, Hu F, He H, Shu SH, Wang M (2015) Determination of phosphorothioate pesticides in environmental water by molecularly imprinted matrix solid-phase dispersion coupled with gas chromatography and a nitrogen phosphorus detector. Instrum Sci Technol 43:669–680CrossRefGoogle Scholar
  5. 5.
    Zheng ZZ, Li XY, Dai ZF, Liu SQ, Tang ZY (2011) Detection of mixed organophosphorus pesticides in real samples using quantum dots/bi-enzyme assembly multilayers. J Mater Chem 21:16955–16962CrossRefGoogle Scholar
  6. 6.
    Xin JH, Qiao XG, Ma Y, Xu ZX (2012) Simultaneous separation and determination of eight organophosphorous pesticide residues in vegetables through molecularly imprinted solid-phase extraction coupled to gas chromatography. J Sep Sci 35:3501–3508CrossRefGoogle Scholar
  7. 7.
    Ohno K, Minami T, Matsui Y, Magara Y (2008) Effects of chlorine on organophosphorus pesticides adsorbed on activated carbon: desorption and oxon formation. Water Res 42:1753–1759CrossRefGoogle Scholar
  8. 8.
    Lebel GL, Williams DT, Griffith G, Benoit FM (1979) Isolation and concentration of organophosphorus pesticides from drinking water at the ng/L level, using macroreticular resin. J Assoc Off Anal Chem 62:241–249Google Scholar
  9. 9.
    Moral A, Sicilia MD, Rubio S, Perez-Bendito D (2008) Multifunctional sorbents for the extraction of pesticide multiresidues from natural waters. Anal Chim Acta 608:61–72CrossRefGoogle Scholar
  10. 10.
    Liu XT, Zhang HY, Ma YQ, Wu XL, Meng LX, Guo YL, Yu G, Liu YQ (2013) Graphene-coated silica as a highly efficient sorbent for residual organophosphorus pesticides in water. J Mater Chem A 1:1875–1884CrossRefGoogle Scholar
  11. 11.
    Xu ZF, Deng PH, Li JH, Xu L, Tang SP, Zhang FX (2016) Construction of imprint sites in mesopores of SBA-15 via thiol-ene click reaction. J Mater Sci 51:6295–6308.  https://doi.org/10.1007/s10853-016-9926-3 CrossRefGoogle Scholar
  12. 12.
    Xin JH, Qiao XG, Xu ZX, Zhou J (2013) Molecularly imprinted polymer as sorbent for solid-phase extraction coupling to gas chromatography for the simultaneous determination of trichlorfon and monocrotophos residues in vegetables. Food Anal Methods 6:274–281CrossRefGoogle Scholar
  13. 13.
    Ding SC, Hu XL, Guan P, Zhang N, Li J, Gao XM, Zhang XY, Ding XQ, Du CB (2017) Preparation of surface-imprinted microspheres using ionic liquids as novel cross-linker for recognizing an immunostimulating peptide. J Mater Sci 52:8027–8040.  https://doi.org/10.1007/s10853-017-1005-x CrossRefGoogle Scholar
  14. 14.
    Xu LH, Fang GZ, Pan MF, Wang XF, Wang S (2016) One-pot synthesis of carbon dots-embedded molecularly imprinted polymer for specific recognition of sterigmatocystin in grains. Biosens Bioelectron 77:950–956CrossRefGoogle Scholar
  15. 15.
    Aguilar-García D, Ochoa-Terán A, Paraguay-Delgado F, Elena Díaz-García M, Pina-Luis G (2016) Water-compatible core–shell Ag@SiO2 molecularly imprinted particles for the controlled release of tetracycline. J Mater Sci 51:5651–5663.  https://doi.org/10.1007/s10853-016-9867-x CrossRefGoogle Scholar
  16. 16.
    Chen FF, Chen H, Duan X, Jia JQ, Kong J (2016) Molecularly imprinted polymers synthesized using reduction-cleavable hyperbranched polymers for doxorubicin hydrochloride with enhanced loading properties and controlled release. J Mater Sci 51:9367–9383.  https://doi.org/10.1007/s10853-016-0183-2 CrossRefGoogle Scholar
  17. 17.
    Bui BTS, Haupt K (2010) Molecularly imprinted polymers: synthetic receptors in bioanalysis. Anal Bioanal Chem 398:2481–2492CrossRefGoogle Scholar
  18. 18.
    Maryam A, Mehrorang G, Abbas O (2017) Water compatible molecularly imprinted nanoparticles as a restricted access material for extraction of hippuric acid, a biological indicator of toluene exposure, from human urine. Microchim Acta 184:879–887CrossRefGoogle Scholar
  19. 19.
    Matsui J, Sodeyama T, Saiki Y, Miyazawa T, Yamada T, Tamaki K, Murashima T (2009) Face-to-face porphyrin moieties assembled with spacing for pyrazine recognition in molecularly imprinted polymers. Biosens Bioelectron 25:635–639CrossRefGoogle Scholar
  20. 20.
    Basabe-Desmonts L, Reinhoudt DN, Crego-Calama M (2007) Design of fluorescent materials for chemical sensing. Chem Soc Rev 36:993–1017CrossRefGoogle Scholar
  21. 21.
    Xu ZX, Fang GZ, Wang S (2010) Molecularly imprinted solid phase extraction coupled to high-performance liquid chromatography for determination of trace dichlorvos residues in vegetables. Food Chem 119:845–850CrossRefGoogle Scholar
  22. 22.
    Zhu XL, Yang J, Su QD, Cai JB, Gao Y (2005) Selective solid-phase extraction using molecularly imprinted polymer for the analysis of polar organophosphorus pesticides in water and soil samples. J Chromatogr A 1092:161–169CrossRefGoogle Scholar
  23. 23.
    Meng L, Qiao XG, Song JM, Xu ZX, Xin JH, Zhang YS (2011) Study of an online molecularly imprinted solid phase extraction coupled to chemiluminescence sensor for the determination of trichlorfon in vegetables. J Agric Food Chem 59:12745–12751CrossRefGoogle Scholar
  24. 24.
    Li DQ, Qiao XG, Lu JX, Xu ZX (2016) Synthesis and evaluation of a magnetic molecularly imprinted polymer sorbent for determination of trace trichlorfon residue in vegetables by capillary electrophoresis. Adv Polym Technol.  https://doi.org/10.1002/adv.21745 Google Scholar
  25. 25.
    Wang XL, Tang QH, Wang QQ, Qiao XG, Xu ZX (2014) Study of a molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography for simultaneous determination of trace trichlorfon and monocrotophos residues in vegetables. J Sci Food Agric 94:1409–1415CrossRefGoogle Scholar
  26. 26.
    Wang SM, Zhao P, Li NY, Qiao XG, Xu ZX (2017) Development of a chemiluminescence sensor based on molecular imprinting technology for the determination of trace monocrotophos in vegetables. Adv Polym Technol.  https://doi.org/10.1002/adv.21799 Google Scholar
  27. 27.
    Zhu XL, Cai JB, Yang J, Su QD, Gao Y (2006) Films coated with molecular imprinted polymers for the selective stir bar sorption extraction of monocrotophos. J Chromatogr A 1131:37–44CrossRefGoogle Scholar
  28. 28.
    Xu SF, Li JH, Chen LX (2011) Molecularly imprinted core–shell nanoparticles for determination of trace atrazine by reversible addition-fragmentation chain transfer surface imprinting. J Mater Chem 21:4346–4351CrossRefGoogle Scholar
  29. 29.
    Lu AH, Salabas EL, Schuth F (2007) Magnetic nanoparticles: synthesis, protection, functionalization, and application. Angew Chem Int Ed 46:1222–1244CrossRefGoogle Scholar
  30. 30.
    Xu SY, Guo CJ, Li YX, Yu ZR, Wei CH, Tang YW (2014) Methyl parathion imprinted polymer nanoshell coated on the magnetic nanocore for selective recognition and fast adsorption and separation in soils. J Hazard Mater 264:34–41CrossRefGoogle Scholar
  31. 31.
    Lu CH, Wang Y, Li Y, Yang HH, Chen X, Wang XR (2009) Bifunctional superparamagnetic surface molecularly imprinted polymer core–shell nanoparticles. J Mater Chem 19:1077–1079CrossRefGoogle Scholar
  32. 32.
    Miao SS, Wu MS, Zuo HG, Jiang C, Jin SF, Lu YC, Yang H (2015) Core–shell magnetic molecularly imprinted polymers as sorbent for sulfonylurea herbicide residues. J Agric Food Chem 63:3634–3645CrossRefGoogle Scholar
  33. 33.
    Ma GF, Chen LG (2014) Determination of chlorpyrifos in rice based on magnetic molecularly imprinted polymers coupled with high-performance liquid chromatography. Food Anal Methods 7:377–388CrossRefGoogle Scholar
  34. 34.
    Pan JM, Li LZ, Hang H, Wu RR, Dai XH, Shi WD, Yan YS (2013) Fabrication and evaluation of magnetic/hollow double-shelled imprinted sorbents formed by Pickering emulsion polymerization. Langmuir 29:8170–8178CrossRefGoogle Scholar
  35. 35.
    Liu BH, Han MY, Guan GJ, Wang SH, Liu RY, Zhang ZP (2011) Highly-controllable molecular imprinting at superparamagnetic iron oxide nanoparticles for ultrafast enrichment and separation. J Phys Chem C 115:17320–17327CrossRefGoogle Scholar
  36. 36.
    Zhou MC, Hu NN, Shu SH, Wang M (2015) Molecularly imprinted nanomicrospheres as matrix solid-phase dispersant combined with gas chromatography for determination of four phosphorothioate pesticides in carrot and yacon. J Anal Methods Chem.  https://doi.org/10.1155/2015/385167 Google Scholar
  37. 37.
    Zhang L, Liu XY, Qiu J, Yao X, Zhou PY, Li MQ (2014) Preparation and characterization of broad-spectrum artificial antibody for OPPs based on dummy imprinting technique. Int J Polym Anal Charact 19:510–521CrossRefGoogle Scholar
  38. 38.
    Liu J, Sun ZK, Deng YH, Zou Y, Li CY, Guo XH, Xiong LQ, Gao Y, Li FY, Zhao DY (2009) Highly water-dispersible biocompatible magnetite particles with low cytotoxicity stabilized by citrate groups. Angew Chem Int Ed 48:5989–5993CrossRefGoogle Scholar
  39. 39.
    Liu WJ, Yan XY, Yong GP, Liu SM (2014) One-pot synthesis of yolk–shell mesoporous carbon spheres with high magnetisation. J Mater Chem A 2:9600–9606CrossRefGoogle Scholar
  40. 40.
    Yang S, Zhang X, Zhao WT, Sun LQ, Luo AQ (2016) Preparation and evaluation of Fe3O4 nanoparticles incorporated molecularly imprinted polymers for protein separation. J Mater Sci 51:937–949.  https://doi.org/10.1007/s10853-015-9423-0 CrossRefGoogle Scholar
  41. 41.
    Chang LM, Chen SN, Li X (2012) Synthesis and properties of core–shell magnetic molecular imprinted polymers. Appl Surf Sci 258:6660–6664CrossRefGoogle Scholar
  42. 42.
    Izutsu H, Nair PK, Maeda K, Kiyozumi Y, Mizukami F (1997) Structure and properties of TiO2 SiO2 prepared by sol–gel method in the presence of tartaric acid. Mater Res Bull 32:1303–1311CrossRefGoogle Scholar
  43. 43.
    Yang R, Liu YX, Yan XY, Liu SM, Zheng HS (2016) An effective method for the synthesis of yolk–shell magnetic mesoporous carbon-surface molecularly imprinted microspheres. J Mater Chem A 4:9807–9815CrossRefGoogle Scholar
  44. 44.
    Mangold KM, Schuster J, Weidlich C (2011) Synthesis and properties of magnetite/polypyrrole core–shell nanocomposites and polypyrrole hollow spheres. Electrochim Acta 56:3616–3619CrossRefGoogle Scholar
  45. 45.
    Zhang XB, Tong HW, Liu SM, Yong GP, Guan YF (2013) An improved Stöber method towards uniform and monodisperse Fe3O4@C nanospheres. J Mater Chem A 1:7488–7493CrossRefGoogle Scholar
  46. 46.
    Ma ZY, Guan YP, Liu HZ (2005) Synthesis and characterization of micron-sized monodisperse superparamagnetic polymer particles with amino groups. J Polym Sci A Polym Chem 43:3433–3439CrossRefGoogle Scholar
  47. 47.
    Chang TT, Liu YX, Yan XY, Liu SM, Zheng HS (2016) One-pot synthesis of uniform and monodisperse superparamagnetic molecularly imprinted polymer nanospheres through a sol–gel process for selective recognition of bisphenol A in aqueous media. RSC Adv 6:66297–66306CrossRefGoogle Scholar
  48. 48.
    Stober W, Fink A, Bohn E (1968) Controlled growth of monodisperse silica spheres in the micron size range. J Colloids Interface Sci 26:62–69CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of Science and Technology of ChinaHefeiChina
  2. 2.Technology CenterAnhui Entry-Exit Inspection and Quarantine BureauHefeiChina

Personalised recommendations