Food Analytical Methods

, Volume 12, Issue 1, pp 217–228 | Cite as

Metal Organic Framework-Molecularly Imprinted Polymer as Adsorbent in Matrix Solid Phase Dispersion for Pyrethroids Residue Extraction from Wheat

  • Ting Liang
  • Shangshu Wang
  • Ligang Chen
  • Na Niu


Metal organic frameworks-molecular imprinting polymers (MOFs-MIPs) were applied as dispersants of matrix solid phase dispersion (MSPD) followed by gas chromatography-tandem mass spectrometry (GC-MS/MS) to selectively analyze pyrethroids in wheat. MOFs-MIPs characterized by a series of instrumental techniques and the adsorption properties researched by isothermal, kinetics, thermodynamics, and selective binding experiments. The results revealed that the MOFs-MIPs had a larger adsorption capacity (474.56 mg g−1) and fast adsorption time (20 min). What is more, MOFs-MIPs-MSPD procedure clearly increased extraction efficiency and decreased the consumption of organic solvent. The better recoveries of pyrethroids were reached by optimizing MSPD conditions. Under the excellent conditions, the linearity ranges of pyrethroids in wheat samples were obtained varying from 10 to 1000 ng g−1; the limits of detection were in the range of 1.8–2.8 ng g−1 and the precisions were lower than 6.3%. At the same time, the method was successfully applied for detection of three pyrethroids residue in six kinds of wheat samples and cyhalothrin residue detected in one wheat was 23.96 ng g−1, which is lower than the maximum residue limits allowed by the Ministry of Agriculture of the People’s Republic of China. The developed MOFs-MIPs-MSPD-GC-MS/MS method displayed high selectivity, absorbability, simplicity, rapidity, sensitivity, and excellent practical food control applicability.


Matrix solid phase dispersion Pyrethroids Metal organic framework Gas chromatography-tandem mass spectrometry Molecularly imprinted polymer Wheat 



This study was funded by the Fundamental Research Funds for the Central Universities (No. 2572017EB08), Natural Science Foundation of Heilongjiang Province (JJ2018ZR0081, B20170001), Harbin science and technology innovation talent research special funds (2016RAQXJ151), National Natural Science Foundation of China (NSFC 201401019), Heilongjiang Postdoctoral Fund (LBH-Z16009), and China Postdoctoral Science Foundation (2016M591501, 332017T100218).

Compliance with Ethical Standards

Conflict of Interest

Ting Liang declares that she has no conflict of interest. Shangshu Wang declares that he has no conflict of interest. Ligang Chen declares that he has no conflict of interest. Na Niu declares that she has no conflict of interest.

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

Not applicable.

Supplementary material

12161_2018_1353_MOESM1_ESM.docx (108 kb)
ESM 1 (DOCX 108 kb)


  1. Asfaram A, Ghaedi M, Dashtian K (2017) Ultrasound assisted combined molecularly imprinted polymer for selective extraction of nicotinamide in human urine and milk samples: spectrophotometric determination and optimization study. Ultrason Sonochem 34:640–650. CrossRefGoogle Scholar
  2. Bagheria N, Khataeeb A, Habibia B, Hassanzadeh J (2018) Mimetic Ag nanoparticle/Zn-based MOF nanocomposite (AgNPs@ZnMOF) capped with molecularly imprinted polymer for the selective detection of patulin. Talanta 179:710–718. CrossRefGoogle Scholar
  3. Bottomley P, Baker PG (1984) Multi-residue determination of organochlorine, organophosphorus and synthetic pyrethroid pesticides in grain by gas-liquid and high-performance liquid chromatography. Analyst 109:85–90. CrossRefGoogle Scholar
  4. Chen L, Li B (2012) Determination of imidacloprid in rice by molecularly imprinted-matrix solid-phase dispersion with liquid chromatography tandem mass spectrometry. J Chromatogr B 897:32–36. CrossRefGoogle Scholar
  5. Chen L, Li B (2013) Magnetic molecularly imprinted polymer extraction of chloramphenicol from honey. Food Chem 141:23–28. CrossRefGoogle Scholar
  6. Cheng J, Liu M, Yu Y, Wang X, Zhang H, Ding L, Jin H (2009) Determination of pyrethroids in porcine tissues by matrix solid-phase dispersion extraction and high-performance liquid chromatography. Meat Sci 82:407–412. CrossRefGoogle Scholar
  7. China Food and Drug Administration (2016) National food safety standards-determination of 475 pesticides and related chemicals residues in grains gas chromatography-mass spectrometry. GB/T 23200.9–2016, pp 1–53Google Scholar
  8. Gao L, Han WJ, Li XY, Wang JX, Yan YS, Li CX, Dai JD (2015) Detection of λ-cyhalothrin by a core-shell spherical SiO2-based surface thin fluorescent molecularly imprinted polymer film. Anal Bioanal Chem 407:9177–9184. CrossRefGoogle Scholar
  9. Ge SG, Zhang CC, Yu F, Yan M, Yu JH (2011) Layer-by-layer self-assembly CdTe quantum dots and molecularly imprinted polymers modified chemiluminescence sensor for deltamethrin detection. Sensors Actuators B Chem 156:222–227. CrossRefGoogle Scholar
  10. Hang H, Li C, Pan J, Li L, Dai J, Dai X, Yu P, Feng Y (2013) Selective separation of lambdacyhalothrin by porous/magnetic molecularly imprinted polymers prepared by Pickering emulsion polymerization. J Sep Sci 36:3285–3294. Google Scholar
  11. Ho YS, McKay G (1999) The sorption of lead(II) ions on peat. Water Res 33:578–584. CrossRefGoogle Scholar
  12. Ho Y, Ofomaja A (2006) Pseudo-second-order model for lead ion sorption from aqueous solutions onto palm kernel fiber. J Hazard Mater 129:137–142. CrossRefGoogle Scholar
  13. Hoffmann B, Muench S, Schwaegele F, Neusuess C, Jira W (2017) A sensitive HPLC-MS/MS screening method for the simultaneous detection of lupine, pea, and soy proteins in meat products. Food Control 71:200–209. CrossRefGoogle Scholar
  14. Hong YS, Chen LG (2013) Extraction of quercetin from Herba Lysimachiae by molecularly imprinted-matrix solid phase dispersion. J Chromatogr B 941:38–44. CrossRefGoogle Scholar
  15. Horcajada P, Gref R, Baati T, Allan PK, Maurin G, Couvreur P, Férey G, Morris RE, Serre C (2012) Metal-organic frameworks in biomedicine. Chem Rev 112:1232–1268. CrossRefGoogle Scholar
  16. Ji W, Zhang M, Gao Q, Cui L, Chen L, Wang X (2016) Preparation of hydrophilic molecularly imprinted polymers via bulk polymerization combined with hydrolysis of ester groups for selective recognition of iridoid glycosides. Anal Bioanal Chem 408:5319–5328. CrossRefGoogle Scholar
  17. Lee J, Farha O, Roberts J, Scheidt K, Nguyen S, Hupp J (2009) Metal-organic framework materials as catalysts. Chem Soc Rev 38:1450–1459. CrossRefGoogle Scholar
  18. Li DQ, Zhang X, Kong FF, Qiao XG, Xu ZX (2017a) Molecularly imprinted solid-phase extraction coupled with high-performance liquid chromatography for the determination of trace trichlorfon and monocrotophos residues in fruits. Food Anal Methods 10:1284–1292. CrossRefGoogle Scholar
  19. Li H, Wei X, Xu Y, Lu K, Zhang Y, Yan Y, Li C (2017b) A thin shell and sunny shape molecular imprinted fluorescence sensor in selective detection of trace level pesticides in river. J Alloys Compd 705:524–532. CrossRefGoogle Scholar
  20. Liu CB, Song Z, Pan J, Yan Y, Cao Z, Wei X, Gao L, Wang J, Dai J, Meng M, Yu P (2014) A simple and sensitive surface molecularly imprinted polymers based fluorescence sensor for detection of lambda-cyhalothrin. Talanta 125:14–23. CrossRefGoogle Scholar
  21. Liu HC, Hong YS, Chen LG (2015) Molecularly imprinted polymers coated on carbon nanotubes for matrix solid phase dispersion extraction of camptothecin from Camptotheca acuminate. Anal Methods 7:8100–8108. CrossRefGoogle Scholar
  22. Liu HC, Ren XH, Chen LG (2016) Synthesis and characterization of magnetic metal-organic framework for the adsorptive removal of rhodamine B from aqueous solution. J Ind Eng Chem 34:278–285. CrossRefGoogle Scholar
  23. Liu HL, Mu L, Chen XM, Wang J, Wang S, Sun BG (2017) Core-shell metal-organic frameworks/molecularly imprinted nanoparticles as absorbents for the detection of pyrraline in milk and milk powder. J Agric Food Chem 65:986–992. CrossRefGoogle Scholar
  24. Liu HL, Ni TH, Mu L, Zhang DW, Wang J, Wang S, Sun BG (2018a) Sensitive detection of pyrraline with a molecularly imprinted sensor based on metal-organic frameworks and quantum dots. Sensors Actuators B Chem 256:1038–1044. CrossRefGoogle Scholar
  25. Liu Z, Chen J, Wu Y, Li Y, Zhao J, Na P (2018b) Synthesis of magnetic orderly mesoporous alpha-Fe2O3 nanocluster derived from MIL-100(Fe) for rapid and efficient arsenic (III, V) removal. J Hazard Mater 343:304–314. CrossRefGoogle Scholar
  26. Lozowicka B, Jankowska M, Rutkowska E, Hrynko I, Kaczynski P, Micinski J (2014) The evaluation of a fast and simple pesticide multiresidue method in various herbs by gas chromatography. J Nat Med 68:95–111. CrossRefGoogle Scholar
  27. Ma GF, Chen LG (2014) Development of magnetic molecularly imprinted polymers based on carbon nanotubes-application for trace analysis of pyrethroids in fruit matrices. J Chromatogr A 1329:1–9. CrossRefGoogle Scholar
  28. Ministry of Agriculture of the People’s Republic of China (2016) National food safety standard--maximum residue limits for pesticides in food. GB/T 2763-2016, p 125Google Scholar
  29. Mukdasai S, Thomas C, Srijaranai S (2014) Two-step microextraction combined with high performance liquid chromatographic analysis of pyrethroids in water and vegetable samples. Talanta 120:289–296. CrossRefGoogle Scholar
  30. Palanti S, Predieri G, Vignali F, Feci E, Casoli A, Conti E (2011) Copper complexes grafted to functionalized silica gel as wood preservatives against the brown rot fungus Coniophora puteana. Wood Sci Technol 45:707–718. CrossRefGoogle Scholar
  31. Pan XD, Wu PG, Jiang W, Ma BJ (2015) Determination of chloramphenicol, thiamphenicol, and florfenicol in fish muscle by matrix solid-phase dispersion extraction (MSPD) and ultra-high pressure liquid chromatography tandem mass spectrometry. Food Control 52:34–38. CrossRefGoogle Scholar
  32. Pang G, Fan C, Chao Y, Zhao T (1994) Rapid method for the determination of multiple pyrethroid residues in fruits and vegetables by capillary column gas chromatography. J Chromatogr A 667:348–353. CrossRefGoogle Scholar
  33. Pang G et al (2000) Interlaboratory study of identification and quantitation of multiresidue pyrethroids in agricultural products by gas chromatography-mass spectrometry. J Chromatogr A 882:231–238. CrossRefGoogle Scholar
  34. Qiu H, Gao L, Wang J, Pan J, Yan Y, Zhang X (2017) A precise and efficient detection of seta-cyfluthrin via fluorescent molecularly imprinted polymers with ally fluorescein as functional monomer in agricultural products. Food Chem 217:620–627. CrossRefGoogle Scholar
  35. Ren X, Chen L (2015) Quantum dots coated with molecularly imprinted polymer as fluorescence probe for detection of cyphenothrin. Biosens Bioelectron 64:182–188. CrossRefGoogle Scholar
  36. Riazuddin, Khan M, Iqbal S, Abbas M (2011) Determination of multi-residue insecticides of organochlorine, organophosphorus, and pyrethroids in wheat. Bull Environ Contam Toxicol 87:303–306. CrossRefGoogle Scholar
  37. Uddin R, Iqbal S, Khan M, Parveen Z, Ahmed M, Abbas M (2011) Determination of pesticide residues in rice grain by solvent extraction, column cleanup, and gas chromatography-electron capture detection. Bull Environ Contam Toxicol 86:83–89. CrossRefGoogle Scholar
  38. Wan H, Chen C, Wu Z, Que Y, Feng Y, Wang W, Wang L, Guan G, Liu X (2015) Encapsulation of heteropolyanion-based ionic liquid within the metal-organic framework MIL-100(Fe) for biodiesel production. ChemCatChem 7:441–449. CrossRefGoogle Scholar
  39. Wang T, Tong J, Sun M, Chen L (2011) Fast and selective extraction of chloramphenicol from soil by matrix solid-phase dispersion using molecularly imprinted polymer as dispersant. J Sep Sci 34:1886–1892. CrossRefGoogle Scholar
  40. Wang YP, Sun Y, Gao Y, Xu B, Wu Q, Zhang HQ, Song DQ (2014) Determination of five pyrethroids in tea drinks by dispersive solid phase extraction with polyaniline-coated magnetic particles. Talanta 119:268–275. CrossRefGoogle Scholar
  41. Wang Y, Gao L, Qin DL, Chen LG (2017) Analysis of melamine in milk powder by CNT-MIP with matrix solid phase dispersion and LC-MS/MS. Food Anal Methods 10:1386–1396. CrossRefGoogle Scholar
  42. Wianowska D, Dawidowicz AL (2016) Can matrix solid phase dispersion (MSPD) be more simplified? Application of solventless MSPD sample preparation method for GC-MS and GC-FID analysis of plant essential oil components. Talanta 151:179–182. CrossRefGoogle Scholar
  43. Wu Q, Li MN, Huang Z, Shao YM, Bai L, Zhou LC (2018) Well-defined nanostructured core-shell magnetic surface imprinted polymers (Fe3O4@SiO2@MIPs) for effective extraction of trace tetrabromobisphenol A from water. J Ind Eng Chem 60:268–278. CrossRefGoogle Scholar
  44. Yin Y, Chen Y, Wang X, Liu Y, Liu H, Xie M (2012) Dummy molecularly imprinted polymers on silica particles for selective solid-phase extraction of tetrabromobisphenol A from water samples. J Chromatogr A 1220:7–13. CrossRefGoogle Scholar
  45. Yin YJ, Pan J, Cao J, Ma Y, Pan G, Wu R, Dai X, Meng M, Yan Y (2016) Rationally designed hybrid molecularly imprinted polymer foam for highly efficient λ-cyhalothrin recognition and uptake via twice imprinting strategy. Chem Eng J 286:485–496. CrossRefGoogle Scholar
  46. Yu D, Zeng Y, Qi Y, Zhou T, Shi G (2012) A novel electrochemical sensor for determination of dopamine based on AuNPs@SiO2 core-shell imprinted composite. Biosens Bioelectron 38:270–277. CrossRefGoogle Scholar
  47. Yu X, Li YX, Ng M, Yang HS, Wang SF (2018) Comparative study of pyrethroids residue in fruit peels and fleshes using polystyrene-coated magnetic nanoparticles based clean-up techniques. Food Control 85:300–307. CrossRefGoogle Scholar
  48. Zhao MY, Ma XD, Zhao FJ, Guo HW (2016) Molecularly imprinted polymer silica monolith for the selective extraction of alpha-cypermethrin from soil samples. J Mater Sci 51:3440–3447. CrossRefGoogle Scholar
  49. Zhu WJ, Ma W, Li C, Pan J, Dai X, Gan M, Qu Q, Zhang Y (2014) Magnetic molecularly imprinted microspheres via yeast stabilized Pickering emulsion polymerization for selective recognition of lambda-cyhalothrin. Colloids Surf A 453:27–36. CrossRefGoogle Scholar
  50. Zhu X, Jia C, Zheng Z, Feng X, He Y, Zhao E (2016) Solid-phase extraction combined with dispersive liquid-liquid microextraction for the determination of pyrethroid pesticides in wheat and maize samples. J Sep Sci 39:4621–4628. CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Chemistry, College of ScienceNortheast Forestry UniversityHarbinChina

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