Advertisement

Microchimica Acta

, 185:373 | Cite as

Computer-aided design of magnetic dummy molecularly imprinted polymers for solid-phase extraction of ten phthalates from food prior to their determination by GC-MS/MS

  • Chunxia Lu
  • Zonggui Tang
  • XiaoXu Gao
  • Xiaomei Ma
  • Changbin Liu
Original Paper
  • 36 Downloads

Abstract

Magnetic dummy molecularly imprinted polymers (MDMIPs) were prepared by combining the surface imprinting technique with computer simulation for selective recognition of phthalate esters (PAEs). A computational study based on the density functional theory was performed to evaluate the template–monomer geometry and interaction energy in the prepolymerization mixture. The MDMIPs were characterized by transmission electron microscopy, scanning electron microscopy, vibrating sample magnetometry, X-ray diffraction, and Fourier transform infrared spectroscopy. They exhibited (a) high saturation magnetization of 53.14 emu g−1 (leading to fast separation), and (b) large adsorption capacity, fast binding kinetics, and high selectivity for PAEs. Subsequently, a molecularly imprinted solid-phase extraction procedure followed by GC-MS was established for selective extraction and determination of 10 PAEs in food samples. Under the optimal experimental conditions, the response (peak area) was linear in the 0.5–100 ng mL−1 concentration range. The limits of detection ranged from 0.15 to 1.64 ng g−1. The method was applied to the determination of PAEs in spiked real samples. The recoveries for 10 PAEs from various foods were in the range of 73.7%–98.1%, with relative standard deviations of 1.7%–10.2%.

Graphical abstract

Magnetic dummy molecularly imprinted polymers (MDMIPs) were prepared and successfully were applied as a special sorbent for the selective recognition and fast enrichment of 10 PAEs from different complex matrix.

Keywords

Phthalate esters Molecular simulation Quantum chemical calculations Dummy template Molecularly imprinted polymers Surface imprinting Magnetic solid-phase extraction Adsorbent Food analysis Gas chromatography-tandem mass spectrometry 

Notes

Acknowledgements

This study was financially supported by the Doctoral Scientific Fund Project of the Xinjiang Production and Construction Corps (2014BB007); National Natural Science Foundation of China (21567027).

Compliance with ethical standards

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

Supplementary material

604_2018_2892_MOESM1_ESM.doc (9.4 mb)
ESM 1 (DOC 9588 kb)

References

  1. 1.
    Bach C, Dauchy X, Chagnon MC, Etienne S (2012) Chemical compounds and toxicological assessments of drinking water stored in polyethylene terephthalate (PET) bottles: a source of controversy reviewed. Water Res 46:571–583CrossRefGoogle Scholar
  2. 2.
    Ma TT, Christie P, Luo YM, Teng Y (2013) Phthalate esters contamination in soil and plants on agricultural land near an electronic waste recycling site. Environ Geochem Hlth 35:465–476CrossRefGoogle Scholar
  3. 3.
    Cao XL (2010) Phthalate esters in foods: sources, occurrence, and analytical methods. Compr Rev Food Sci F 9:21–43CrossRefGoogle Scholar
  4. 4.
    Högberg J, Hanberg A, Berglund M, Skerfving S, Remberger M, Calafat AM, Filipsson AF, Jansson B, Johansson N, Appelgren M, Hakansson H (2008) Phthalate diesters and their metabolites in human breast milk, blood or serum, and urine as biomarkers of exposure in vulnerable populations. Environ Health Perspect 116:334–339CrossRefGoogle Scholar
  5. 5.
    Blystone CR, Kissling GE, Bishop JB, Chapin RE, Wolfe GW, Foster PMD (2010) Determination of the di-(2-ethylhexyl) phthalate NOAEL for reproductive development in the rat: importance of the retention of extra animals to adulthood. Toxicol Sci 116:640–646CrossRefGoogle Scholar
  6. 6.
    Foster PM (2006) Disruption of reproductive development in male rat offspring following in utero exposure to phthalate esters. Int J Androl 29:140–147CrossRefGoogle Scholar
  7. 7.
    Benson R (2009) Hazard to the developing male reproductive system from cumulative exposure to phthalate esters-dibutyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, diethylhexyl phthalate, dipentyl phthalate, and diisononyl phthalate. Regul Toxicol Pharmacol 53(2):90–101CrossRefGoogle Scholar
  8. 8.
    Wu W, Hu J, Wang JQ, Chen XR, Na Y, Tao J, Zhou YK (2015) Analysis of phthalate esters in soils near an electronics manufacturing facility and from a non-industrialized area by gas purge microsyringe extraction and gas chromatography. Sci Total Environ 508:445–451CrossRefGoogle Scholar
  9. 9.
    Li XY, Yang YC, Cui X, Li SF, Zhu XL, Tang SK (2015) Determination of phthalate esters in textiles by solid phase extraction and gas chromatography–mass spectrometry. Anal Lett 48:2544–2552CrossRefGoogle Scholar
  10. 10.
    Lian Y, Qiu X, Yang Y (2014) Vortex-assisted liquid–liquid microextraction combined with HPLC for the simultaneous determination of five phthalate esters in liquor samples. Food Anal Methods 7:636–644CrossRefGoogle Scholar
  11. 11.
    Li XJ, Xiong WM, Lin H, Zhuo LY, Lv SY, Tang X, Chen MS, Zou ZX, Lin ZY, Qiu B, Chen GN (2013) Analysis of 16 phthalic acid esters in food simulants from plastic food contact materials by LC-ESI-MS/MS. J Sep Sci 36:477–484CrossRefGoogle Scholar
  12. 12.
    Russo MV, Notardonato I, Avino P, Cinelli G (2014) Determination of phthalate esters at trace levels in light alcoholic drinks and soft drinks by XAD-2 adsorbent and gas chromatography coupled with ion trap-mass spectrometry detection. Anal Methods-UK 6:7030–7037CrossRefGoogle Scholar
  13. 13.
    Heffernan AL, Thompson K, Eaglesham G, Vijayasarathy S, Mueller JF, Sly PD, Gomez MJ (2016) Rapid, automated online SPE-LC-QTRAP-MS/MS method for the simultaneous analysis of 14 phthalate metabolites and 5 bisphenol analogues in human urine. Talanta 151:224–233CrossRefGoogle Scholar
  14. 14.
    Guo PQ, Xu XY, Xian L, Ge YH, Luo ZM, Du W, Jing WH, Zeng AG, Chang C, Fu Q (2016) Development of molecularly imprinted column-on line-two dimensional liquid chromatography for rapidly and selectively monitoring estradiol in cosmetics. Talanta 161:830–837CrossRefGoogle Scholar
  15. 15.
    Wulff G (2013) Forty years of molecular imprinting in synthetic polymers: origin, features and perspectives. Microchim Acta 180(15–16):1359–1370CrossRefGoogle Scholar
  16. 16.
    Chen NN, He J, Wu CJ, Li YY, Suo A, Wei HL, He LJ, Zhang SS (2017) Synthesis of molecularly imprinted polymers by atom transfer radical polymerization for the solid-phase extraction of phthalate esters in edible oil. J Sep Sci 40:1327–1333CrossRefGoogle Scholar
  17. 17.
    Shaikh H, Memon N, Khan H, Bhanger MI, Nizamani SM (2010) 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 1247:125–133CrossRefGoogle Scholar
  18. 18.
    Kang YF, Duan WP, Li Y, Kang JX, Xie J (2012) Molecularly imprinted polymers of allyl-β-cyclodextrin and methacrylic acid for the solid-phase extraction of phthalate. Carbohydr Polym 88:459–464CrossRefGoogle Scholar
  19. 19.
    Nicholls IA, Andersson HS, Golker K, Henschel H, Karlsson BCG, Olsson GD, Rosengren AM, Shoravi S, Suriyanarayanan S, Wiklander JG, Wikman S (2011) Rational design of biomimetic molecularly imprinted materials: theoretical and computational strategies for guiding nanoscale structured polymer development. Anal Bioanal Chem 400:1771–1786CrossRefGoogle Scholar
  20. 20.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Gaussian, Inc., Wallingford CTGoogle Scholar
  21. 21.
    Reed AE, Weinstock RB, Weinhold F (1985) Natural population analysis. J Chem Phys 83:735–746CrossRefGoogle Scholar
  22. 22.
    Cossi M, Rega N, Scalmani G, Barone V (2003) Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model. J Comput Chem 24:669–681CrossRefGoogle Scholar
  23. 23.
    Zhang ZH, Luo LJ, Cai R, Chen HJ (2013) A sensitive and selective molecularly imprinted sensor combined with magnetic molecularly imprinted solid phase extraction for determination of dibutyl phthalate. Biosens Bioelectron 49:367–373CrossRefGoogle Scholar
  24. 24.
    National Standard of the People’s Republic of China, GB/T 21911–2008Google Scholar
  25. 25.
    Xu M, Liu MH, Sun MR, Chen K, Cao XJ, Hu YM (2016) Magnetic solid-phase extraction of phthalate esters (PAEs) in apparel textile by core-shell structured Fe3O4@silica@triblock-copolymer magnetic microspheres. Talanta 150:125–134CrossRefGoogle Scholar
  26. 26.
    Hu JH, Feng T, Li WL, Zhai H, Liu Y, Wang LY, Hu CL, Xie MX (2014) Surface molecularly imprinted polymers with synthetic dummy template for simultaneously selective recognition of nine phthalate esters. J Chromatogr A 1330:6–13CrossRefGoogle Scholar
  27. 27.
    Yang R, Liu YX, Yan XY, Liu SM (2016) Simultaneous extraction and determination of phthalate esters in aqueous solution by yolk-shell magnetic mesoporous carbon-molecularly imprinted composites based on solid-phase extraction coupled with gas chromatography-mass spectrometry. Talanta 161:114–121CrossRefGoogle Scholar
  28. 28.
    Zhou ZP, Li T, Xu WZ, Huang WH, Wang NW, Yang WM (2017) Synthesis and characterization of fluorescence molecularly imprinted polymers as sensor for highly sensitive detection of dibutyl phthalate from tap water samples. Sensor Actuat B-Chem 240:1114–1122CrossRefGoogle Scholar
  29. 29.
    Du JJ, Gao RX, Mu H (2016) A novel molecularly imprinted polymer based on carbon nanotubes for selective determination of dioctyl phthalate from beverage samples coupled with GC/MS. Food Anal Methods 9:2026–2035CrossRefGoogle Scholar
  30. 30.
    Li XJ, Wang XJ, Li LL, Duan HM, Luo CN (2015) Electrochemical sensor based on magnetic graphene oxide@gold nanoparticles-molecular imprinted polymers for determination of dibutyl phthalate. Talanta 131:354–360CrossRefGoogle Scholar
  31. 31.
    Qiu HM, Fan LL, Li XJ, Li LL, Sun M, Luo CN (2013) A microflow chemiluminescence sensor for indirect determination of dibutyl phthalate by hydrolyzing based on biological recognition materials. J Pharmaceut Biomed 75:123–129CrossRefGoogle Scholar
  32. 32.
    He J, Lv RH, Cheng J, Li YX, Xue JF, Lu K, Wang FC (2010) Preparation and characterization of molecularly imprinted microspheres for dibutyl phthalate recognition in aqueous environment. J Sep Sci 33:3409–3414CrossRefGoogle Scholar
  33. 33.
    Barciela-Alonso MC, Otero-Lavandeira N, Bermejo-Barrera P (2017) Solid phase extraction using molecular imprinted polymers for phthalate determination in water and wine samples by HPLC-ESI-MS. Microchem J 132:233–237CrossRefGoogle Scholar
  34. 34.
    Jiao C, Ma R, Li M, Hao L, Wang C, Wu Q, Wang Z (2017) Magnetic cobalt-nitrogen-doped carbon microspheres for the preconcentration of phthalate esters from beverage and milk samples. Microchim Acta 184(8):2551–2559CrossRefGoogle Scholar
  35. 35.
    Yamini Y, Faraji M, Adeli M (2015) Magnetic silica nanomaterials for solid-phase extraction combined with dispersive liquid-liquid microextraction of ultra-trace quantities of plasticizers. Microchim Acta 182(7–8):1491–1499CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Life Science and Technology InstituteYangtze Normal UniversityChongqingPeople’s Republic of China
  2. 2.Analysis and Testing CenterXinjiang Academy of Agriculture and Reclamation ScienceShiheziPeople’s Republic of China
  3. 3.Key Laboratories of Sheep Breeding and ReproduceXinjiang Academy of Agriculture and Reclamation ScienceShiheziPeople’s Republic of China

Personalised recommendations