Skip to main content
Log in

An amino-functionalized zirconium-based metal-organic framework of type UiO-66-NH2 covered with a molecularly imprinted polymer as a sorbent for the extraction of aflatoxins AFB1, AFB2, AFG1 and AFG2 from grain

  • Original Paper
  • Published:
Microchimica Acta Aims and scope Submit manuscript

Abstract

A surface imprinted polymer of type UiO-66-NH2@MIP was prepared by combining molecular imprinted polymers (MIPs) and an amino-functionalized zirconium-based metal-organic framework. Quercetin is used as the virtual template, UiO-66-NH2 acts as the carrier to which the monomer acrylamide can be copolymerized. The material was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. It was used as a sorbent in a solid-phase extraction column. The extraction conditions were optimized. The adsorption capacities for aflatoxins AFB1, AFB2, AFG1 and AFG2 by this SPE and by the commercial SPE were compared. The method was successfully applied to quantify the aflatoxins in grain. Figures of merit include (a) good linearity (range from 0.20–45 μg·kg−1) with R2 (range from 0.9986–0.9994), (b) low detection limits (90–130 ng·kg−1), (c) acceptable reproducibility (1.0–5.9%; for n = 6), and (d) relatively satisfactory recovery rates (74.3–98.6%). The new sorbent has good selectivity and reusability.

UiO-66-NH2@MIPs were synthesized with modified UIO-66-NH2 as core and quercetin as pseudo template. A cartridge was prepared with the polymers as the sorbent, and its performance was compared with different commercial SPE cartridges.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

References

  1. Li R, Wang X, Zhou T, Yang D, Wang Q, Zhou Y (2014) Occurrence of four mycotoxins in grains and oil products in Yangtze Delta region of China and their food safety risks. Food Control 35(1):117–122. https://doi.org/10.1016/j.foodcont.2013.06.042

    Article  CAS  Google Scholar 

  2. Giray B, Girgin G, Engin AB, Aydın S, Sahin G (2007) Aflatoxin levels in wheat samples consumed in some regions of Turkey. Food Control 18(1):23–29. https://doi.org/10.1016/j.foodcont.2005.08.002

    Article  CAS  Google Scholar 

  3. Ding X, Li P, Bai Y, Zhou H (2012) Aflatoxin B1 in post-harvest peanuts and dietary risk in China. Food Control 23(1):143–148. https://doi.org/10.1016/j.foodcont.2011.06.026

    Article  CAS  Google Scholar 

  4. Li P, Zhang Q, Zhang W (2009) Immunoassays for aflatoxins. TrAC Trends Anal Chem 28(9):1115–1126. https://doi.org/10.1016/j.trac.2009.07.003

    Article  CAS  Google Scholar 

  5. Andrade PD, da Silva JLG, Caldas ED (2013) Simultaneous analysis of aflatoxins B1, B2, G1, G2, M1 and ochratoxin a in breast milk by high-performance liquid chromatography/fluorescence after liquid–liquid extraction with low temperature purification (LLE–LTP). J Chromatogr A 1304:61–68. https://doi.org/10.1016/j.chroma.2013.06.049

    Article  CAS  PubMed  Google Scholar 

  6. Blesa J, Soriano JM, Molto JC, Marin R, Manes J (2003) Determination of aflatoxins in peanuts by matrix solid-phase dispersion and liquid chromatography. J Chromatogr A 1011(1–2):49–54. https://doi.org/10.1016/S0021-9673(03)01102-6

    Article  CAS  PubMed  Google Scholar 

  7. Quinto M, Spadaccino G, Palermo C, Centonze D (2009) Determination of aflatoxins in grains flours by solid-phase microextraction coupled with liquid chromatography and post-column photochemical derivatization-fluorescence detection. J Chromatogr A 1216(49):8636–8641. https://doi.org/10.1016/j.chroma.2009.10.031

    Article  CAS  PubMed  Google Scholar 

  8. Zhang L, Dou X, Kong W, Liu C, Han X, Yang M (2017) Assessment of critical points and development of a practical strategy to extend the applicable scope of immunoaffinity column cleanup for aflatoxin detection in medicinal herbs. J Chromatogr A 1483:56–63. https://doi.org/10.1016/j.chroma.2016.12.079

    Article  CAS  PubMed  Google Scholar 

  9. Liu S, Qiu F, Kong W, Wei J, Xiao X, Yang M (2013) Development and validation of an accurate and rapid LC-ESI-MS/MS method for the simultaneous quantification of aflatoxin B1, B2, G1 and G2 in lotus seeds. Food Control 29(1):156–161. https://doi.org/10.1016/j.foodcont.2012.05.069

    Article  CAS  Google Scholar 

  10. Sun S, Yao K, Zhao S, Zheng P, Wang S, Zeng Y, Liang D, Ke Y, Jiang H (2018) Determination of aflatoxin and zearalenone analogs in edible and medicinal herbs using a group-specific immunoaffinity column coupled to ultra-high-performance liquid chromatography with tandem mass spectrometry. J Chromatogr B Anal Technol Biomed Life Sci 1092:228–236. https://doi.org/10.1016/j.jchromb.2018.06.012

    Article  CAS  Google Scholar 

  11. Zuo HG, Zhu JX, Shi L, Zhan CR, Guo P, Wang Y, Zhang YM, Liu JP (2018) Development of a novel Immunoaffinity column for the determination of Deoxynivalenol and its acetylated derivatives in Grainss. Food Anal Methods 11(8):2252–2260. https://doi.org/10.1007/s12161-018-1211-4

    Article  Google Scholar 

  12. Xie J, Peng T, He J-L, Shao Y, Fan C-L, Chen Y, Jiang W-X, Chen M, Wang Q, Pei X-Y, Ding S-Y, Jiang H-Y (2015) Preparation and characterization of an immunoaffinity column for the selective extraction of aflatoxin B1 in 13 kinds of foodstuffs. J Chromatogr B 998-999:50–56. https://doi.org/10.1016/j.jchromb.2015.06.022

    Article  CAS  Google Scholar 

  13. Hennion MC (1999) Solid-phase extraction: method development, sorbents, and coupling with liquid chromatography. J Chromatogr A 856(1–2):3–54

    Article  CAS  PubMed  Google Scholar 

  14. Mashhadizadeh MH, Amoli-Diva M, Pourghazi K (2013) Magnetic nanoparticles solid phase extraction for determination of ochratoxin a in grainss using high-performance liquid chromatography with fluorescence detection. J Chromatogr A 1320(20):17–26. https://doi.org/10.1016/j.chroma.2013.10.062

    Article  CAS  PubMed  Google Scholar 

  15. Speltini A, Scalabrini A, Maraschi F, Sturini M, Profumo A (2017) Newest applications of molecularly imprinted polymers for extraction of contaminants from environmental and food matrices: a review. Anal Chim Acta 974:1–26. https://doi.org/10.1016/j.aca.2017.04.042

    Article  CAS  PubMed  Google Scholar 

  16. Kryscio DR, Peppas NA (2012) Critical review and perspective of macromolecularly imprinted polymers. Acta Biomater 8(2):461–473. https://doi.org/10.1016/j.actbio.2011.11.005

    Article  CAS  PubMed  Google Scholar 

  17. Chen W, Xue M, Xue F, Mu X, Xu Z, Meng Z, Zhu G, Shea KJ (2015) Molecularly imprinted hollow spheres for the solid phase extraction of estrogens. Talanta 140:68–72. https://doi.org/10.1016/j.talanta.2015.02.048

    Article  CAS  PubMed  Google Scholar 

  18. He C, Long Y, Pan J, Li K, Liu F (2007) Application of molecularly imprinted polymers to solid-phase extraction of analytes from real samples. J Biochem Biophys Methods 70(2):133–150. https://doi.org/10.1016/j.jbbm.2006.07.005

    Article  CAS  PubMed  Google Scholar 

  19. Wu C, He J, Chen N, Li Y, Yuan L, Zhao D, He L, Gu K, Zhang S (2018) Synthesis of cobalt-based magnetic nanoporous carbon core-shell molecularly imprinted polymers for the solid-phase extraction of phthalate plasticizers in edible oil. Anal Bioanal Chem 410(26):6943–6954. https://doi.org/10.1007/s00216-018-1299-9

    Article  CAS  PubMed  Google Scholar 

  20. Kuppler RJ, Timmons DJ, Fang QR, Li JR, Makal TA, Young MD, Yuan DQ, Zhao D, Zhuang WJ, Zhou HC (2009) Potential applications of metal-organic frameworks. Coord Chem Rev 253(23–24):3042–3066. https://doi.org/10.1016/j.ccr.2009.05.019

    Article  CAS  Google Scholar 

  21. Chen X, Ding N, Zang H, Yeung H, Zhao R-S, Cheng C, Liu J, Chan TWD (2013) Fe3O4@MOF core–shell magnetic microspheres for magnetic solid-phase extraction of polychlorinated biphenyls from environmental water samples. J Chromatogr A 1304:241–245. https://doi.org/10.1016/j.chroma.2013.06.053

    Article  CAS  PubMed  Google Scholar 

  22. Zhang X-F, Feng Y, Wang Z, Jia M, Yao J (2018) Fabrication of cellulose nanofibrils/UiO-66-NH2 composite membrane for CO2/N2 separation. J Membr Sci 568:10–16. https://doi.org/10.1016/j.memsci.2018.09.055

    Article  CAS  Google Scholar 

  23. Zhang W, Yan Z, Gao J, Tong P, Liu W, Zhang L (2015) Metal-organic framework UiO-66 modified magnetite@silica core-shell magnetic microspheres for magnetic solid-phase extraction of domoic acid from shellfish samples. J Chromatogr A 1400(31):10–18. https://doi.org/10.1016/j.chroma.2015.04.061

    Article  CAS  PubMed  Google Scholar 

  24. Chen X, Ding N, Zang H, Yeung H, Zhao RS, Cheng C, Liu J, Chan TW (2013) Fe(3)O(4)@MOF core-shell magnetic microspheres for magnetic solid-phase extraction of polychlorinated biphenyls from environmental water samples. J Chromatogr A 1304(16):241–245. https://doi.org/10.1016/j.chroma.2013.06.053

    Article  CAS  PubMed  Google Scholar 

  25. Li W, Wang R, Chen Z (2018) Zr-based metal-organic framework-modified cotton for solid phase micro-extraction of non-steroidal anti-inflammatory drugs. J Chromatogr A 1576:19–25. https://doi.org/10.1016/j.chroma.2018.09.032

    Article  CAS  PubMed  Google Scholar 

  26. Lian L, Zhang X, Hao J, Lv J, Wang X, Zhu B, Lou D (2018) Magnetic solid-phase extraction of fluoroquinolones from water samples using titanium-based metal-organic framework functionalized magnetic microspheres. J Chromatogr A 1579:1–8. https://doi.org/10.1016/j.chroma.2018.10.019

    Article  CAS  PubMed  Google Scholar 

  27. National Food Safety Standard Determination of Zearalenone in Foods, 5009.96, National Standards of the People’s Republic of China (2016)

Download references

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant numbers 21575034, 51502079, 21475119, 21775140), the Fundamental Research Funds for the Henan Provincial Colleges and Universities in Henan University of Technology (grant numbers 2017RCJH10).

Author information

Authors and Affiliations

Authors

Contributions

These authors contributed equally.

Corresponding author

Correspondence to Juan He.

Ethics declarations

Conflict of interest

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

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOCX 760 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liang, Y., He, J., Huang, Z. et al. An amino-functionalized zirconium-based metal-organic framework of type UiO-66-NH2 covered with a molecularly imprinted polymer as a sorbent for the extraction of aflatoxins AFB1, AFB2, AFG1 and AFG2 from grain. Microchim Acta 187, 32 (2020). https://doi.org/10.1007/s00604-019-3959-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00604-019-3959-7

Keywords

Navigation