Microchimica Acta

, 187:12 | Cite as

Fluorometric determination of fipronil by integrating the advantages of molecularly imprinted silica and carbon quantum dots

  • Chunhui Yang
  • Lihong Wang
  • Zhen Zhang
  • Yujie Chen
  • Qiliang DengEmail author
  • Shuo WangEmail author
Original Paper


A fluorometric method is described for the determination of fipronil, a frequently-used insecticide. It exploits the blue fluorescence of carbon quantum dots (CQDs) and the selectivity of molecularly imprinted silica (MIS). The MIS was prepared via the sol-gel method by using fipronil as the template, 3-aminopropyltriethoxysilane as functional monomer, and tetraethoxysilane as cross-linker in the presence of CQDs. The blue fluorescence of the CQD@MIS, with excitation/emission peaks at 340/422 nm, is quenched by fipronil. The assay works in the 0. 70 pM to 47 μM fipronil concentration range, and the limit of detection is 19 pM. The method was successfully applied to the quantitation of fipronil in spiked eggs, milk, and tap water. Recoveries between 83.8 and 114.0% were achieved. The corresponding relative standard deviations (RSD) are less than 6.67%.

Graphical abstract

Schematic representation of a high sensitivite and selectivite fluorescence nanoprobe constructed by combining the excellent fluorescence property of carbon quantum dots and the predicted selectivity of molecularly imprinted silica. It was applied to analyze fipronil in egg, milk and tap water, respectively.


Food safety Fluorescence quenching Milk Analysis Egg Analysis Insecticide 



The authors are grateful for the financial support provided by the Ministry of Science and Technology of China (Project No.2016YFD0401101) and the National Natural Science Foundation of China (Project No.21375094).

Supplementary material

604_2019_4005_MOESM1_ESM.doc (23.9 mb)
ESM 1 (DOC 24473 kb)


  1. 1.
    Tu Q, Hickey ME, Yang T, Gao S, Zhang Q, Qu Y, Du X, Wang J, He L (2019) A simple and rapid method for detecting the pesticide fipronil on egg shells and in liquid eggs by Raman microscopy. Food Control 96:16–21. CrossRefGoogle Scholar
  2. 2.
    Li X, Li H, Ma W, Guo Z, Li X, Song S, Tang H, Li X, Zhang Q (2019) Development of precise GC-EI-MS method to determine the residual fipronil and its metabolites in chicken egg. Food Chem 281:85–90. CrossRefPubMedGoogle Scholar
  3. 3.
    Qu H, Ma R, Wang F, Gao J, Wang P, Zhou Z, Liu D (2018) The effect of biochar on the mitigation of the chiral insecticide fipronil and its metabolites burden on loach (Misgurnus.anguillicaudatus). J Hazard Mater 360:214–222. CrossRefPubMedGoogle Scholar
  4. 4.
    Ratra GS, Kamita SG, Casida JE (2001) Role of human GABA(A) receptor beta3 subunit in insecticide toxicity. Toxicol Appl Pharmacol 172(3):233–240. CrossRefPubMedGoogle Scholar
  5. 5.
    Caboni P, Sammelson RE, Casida JE (2003) Phenylpyrazole insecticide photochemistry, metabolism, and GABAergic action: Ethiprole compared with fipronil. J Agric Food Chem 51(24):7055–7061. CrossRefPubMedGoogle Scholar
  6. 6.
    Buxbaum JD, Silverman JM, Smith CJ, Greenberg DA, Kilifarski M, Reichert J, Cook EH, Fang Y, Song CY, Vitale R (2002) Association between a GABRB3 polymorphism and autism. Mol Psychiatry 7(3):311–316. CrossRefPubMedGoogle Scholar
  7. 7.
    Vasylieva N, Ahn KC, Barnych B, Gee SJ, Hammock BD (2015) Development of an immunoassay for the detection of the Phenylpyrazole insecticide Fipronil. Environ Sci Technol 49(16):10038–10047. CrossRefPubMedPubMedCentralGoogle Scholar
  8. 8.
    Vılchez JL, Prieto A, Araujo L, Navalon A (2001) Determination of fipronil by solid-phase microextraction and gas chromatography–mass spectrometry. J Chromatogr A 919(1):215–221. CrossRefPubMedGoogle Scholar
  9. 9.
    Peng XT, Li YN, Xia H, Peng LJ, Feng YQ (2016) Rapid and sensitive detection of fipronil and its metabolites in edible oils by solid-phase extraction based on humic acid bonded silica combined with gas chromatography with electron capture detection. J Sep Sci 39(11):2196–2203. CrossRefPubMedGoogle Scholar
  10. 10.
    Li X, Chen J, He X, Wang Z, Wu D, Zheng X, Zheng L, Wang B (2019) Simultaneous determination of neonicotinoids and fipronil and its metabolites in environmental water from coastal bay using disk-based solid-phase extraction and high-performance liquid chromatography-tandem mass spectrometry. Chemosphere 234:224–231. CrossRefPubMedGoogle Scholar
  11. 11.
    Ma J, Lu X, Xia Y, Yan F (2015) Determination of pyrazole and pyrrole pesticides in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with high-performance liquid chromatography. J Chromatogr Sci 53(2):380–384. CrossRefPubMedGoogle Scholar
  12. 12.
    Wang K, Vasylieva N, Wan D, Eads DA, Yang J, Tretten T, Barnych B, Li J, Li QX, Gee SJ, Hammock BD, Xu T (2018) Quantitative detection of Fipronil and Fipronil-Sulfone in sera of black-tailed prairie dogs and rats after Oral exposure to Fipronil by camel single-domain antibody-based immunoassays. Anal Chem. 91(2):1532-1540. CrossRefGoogle Scholar
  13. 13.
    Yin J, Chen X, Chen Z (2019) Quenched electrochemiluminescence sensor of ZnO@g-C3N4 modified glassy carbon electrode for fipronil determination. Microchem J 145:295–300. CrossRefGoogle Scholar
  14. 14.
    Hong KL, Sooter LJ (2017) In vitro selection of a single-stranded DNA molecular recognition element against the pesticide Fipronil and sensitive detection in river water. Int J Mol Sci 19(1):85. CrossRefGoogle Scholar
  15. 15.
    Yang SL, Lu JN, Zhang SJ, Zhang CX, Wang QL (2018) 2D europium coordination polymer as a regenerable fluorescence probe for efficiently detecting fipronil. Analyst 143(20):4901–4906. CrossRefPubMedGoogle Scholar
  16. 16.
    Ensafi AA, Hghighat Sefat S, Kazemifard N, Rezaei B, Moradi F (2017) A novel one-step and green synthesis of highly fluorescent carbon dots from saffron for cell imaging and sensing of prilocaine. Sensors Actuators B Chem 253:451–460. CrossRefGoogle Scholar
  17. 17.
    Rao H, Liu W, Lu Z, Wang Y, Ge H, Zou P, Wang X, He H, Zeng X, Wang Y (2016) Silica-coated carbon dots conjugated to CdTe quantum dots: a ratiometric fluorescent probe for copper(II). Microchim Acta 183(2):581–588. CrossRefGoogle Scholar
  18. 18.
    Ayankojo AG, Reut J, Opik A, Furchner A, Syritski V (2018) Hybrid molecularly imprinted polymer for amoxicillin detection. Biosens Bioelectron 118:102–107. CrossRefPubMedGoogle Scholar
  19. 19.
    Liu H, Wu D, Zhou K, Wang J, Sun B (2016) Development and applications of molecularly imprinted polymers based on hydrophobic CdSe/ZnS quantum dots for optosensing of N(epsilon)-carboxymethyllysine in foods. Food Chem 211:34–40. CrossRefPubMedGoogle Scholar
  20. 20.
    Ye T, Yin W, Zhu N, Yuan M, Cao H, Yu J, Gou Z, Wang X, Zhu H, Reyihanguli A, Xu F (2018) Colorimetric detection of pyrethroid metabolite by using surface molecularly imprinted polymer. Sensors Actuators B Chem 254:417–423. CrossRefGoogle Scholar
  21. 21.
    Li H, Zhao L, Xu Y, Zhou T, Liu H, Huang N, Ding J, Li Y, Ding L (2018). Single-hole hollow molecularly imprinted polymer embedded carbon dot for fast detection of tetracycline in honey. Talanta 185: 542–549. CrossRefGoogle Scholar
  22. 22.
    Feng L, Tan L, Li H, Xu Z, Shen G, Tang Y (2015) Selective fluorescent sensing of alpha-amanitin in serum using carbon quantum dots-embedded specificity determinant imprinted polymers. Biosens Bioelectron 69:265–271. CrossRefPubMedGoogle Scholar
  23. 23.
    Xu L, Fang G, Pan M, Wang X, Wang S (2016). One-pot synthesis of carbon dots-embedded molecularly imprinted polymer for specific recognition of sterigmatocystin in grains. Biosens Bioelectron 77:950–956. CrossRefGoogle Scholar
  24. 24.
    Xu S, Lu H (2016) Mesoporous structured MIPs@CDs fluorescence sensor for highly sensitive detection of TNT. Biosens Bioelectron 85:950–956. CrossRefPubMedGoogle Scholar
  25. 25.
    Wang Y, Yang Y, Liu W, Ding F, Zhao Q, Zou P, Wang X, Rao H (2018) Colorimetric and fluorometric determination of uric acid based on the use of nitrogen-doped carbon quantum dots and silver triangular nanoprisms. Microchim Acta 185(6):281. CrossRefGoogle Scholar
  26. 26.
    Fu JW, Xu Q, Chen JF, Chen ZM, Huang XB, Tang XZ (2010) Controlled fabrication of uniform hollow core porous shell carbon spheres by the pyrolysis of core/shell polystyrene/cross-linked polyphosphazene composites. Chem Commun 46(35):6563–6565. CrossRefGoogle Scholar
  27. 27.
    Fan H, Wang J, Meng Q, Jin Z (2019) Monodisperse hollow-shell structured molecularly imprinted polymers for photocontrolled extraction alpha-cyclodextrin from complex samples. Food Chem 281:1–7. CrossRefPubMedGoogle Scholar
  28. 28.
    Ren X, Chen L (2015) Quantum dots coated with molecularly imprinted polymer as fluorescence probe for detection of cyphenothrin. Biosens Bioelectron 64:182–188. CrossRefPubMedGoogle Scholar

Copyright information

© Springer-Verlag GmbH Austria, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Chemical Engineering and Materials ScienceTianjin University of Science and TechnologyTianjinChina
  2. 2.Tianjin Key Laboratory of Food Science and Health, School of MedicineNankai UniversityTianjinChina

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