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Amino-functional magnetic covalent organic framework as an effective adsorbent for the determination of neonicotinoids in food samples

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Abstract

Recently, covalent organic frameworks have gained popularity in sample pretreatment. However, the application of covalent organic frameworks in the enrichment of hydrophilic compounds remains a challenge. Thus, a functionalized magnetic covalent organic framework equipped with amino groups was constructed using a bottom-up functionalization strategy. Considering the advantages of this novel adsorbent such as high porosity, large adsorption capacity, and hydrophilic surface, a sensitive magnetic solid-phase extraction coupled with high-performance liquid chromatography-tandem mass spectrometry method was established for the effective determination of neonicotinoids. This method exhibited good linearities with correlation coefficients ranging from 0.9983 to 0.9995, low detection limits in the range 0.003–0.009 ng g−1 and 0.001–0.013 ng mL−1, and limits of quantification in the range 0.010–0.031 ng g−1 and 0.004–0.044 ng mL−1. Furthermore, satisfactory repeatability with relative standard deviations ≤ 6.7% and spiked recoveries between 82.3 and 99.8% were obtained. This work not only provided a promising adsorbent for the sensitive determination of trace-level neonicotinoids but also represented a unique insight for effective enrichment of super hydrophilic hazards.

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Data availability

The data and materials generated during and/or analyzed during the current study are available from the corresponding authors on reasonable request.

Abbreviations

COFs:

Covalent organic frameworks

POPs:

Porous organic polymers

Fe3O4@TFPA-DAB-NH2 :

A functionalized magnetic covalent organic framework equipped with amino groups

Fe3O4@TFPA-BD:

A magnetic covalent organic framework without amino groups

HPLC:

High-performance liquid chromatography

MS/MS:

Triple quadrupole tandem mass spectrometry

UV:

Ultraviolet

FLD:

Fluorescence

DAD:

Diode array detection

LLE:

Liquid-liquid extraction

DSPE:

Dispersive solid-phase extraction

MSPE:

Magnetic solid-phase extraction

HPLC-MS/MS:

High-performance liquid chromatography-tandem mass spectrometry

MSPE-HPLC-MS/MS:

High-performance liquid chromatography-tandem mass spectrometry based on magnetic solid-phase extraction

NEOs:

Neonicotinoids

FPNs:

Fipronils

AFs:

Aflatoxins

SUs:

Sulfonylurea insecticides

ICL:

Imidacloprid

CTN:

Clothianidin

TCL:

Thiacloprid

ACT:

Acetamiprid

DAB:

3,3′-Diaminobenzidine

TFPA:

Tris(4-formylphenyl) amine

BD:

Benzidine

FeCl3·6H2O:

Iron trichloride hexahydrate

CH3COONa:

Sodium acetate anhydrous

EG:

Ethylene glycol

THF:

Tetrahydrofuran

HAC:

Acetic acid

FA:

Formic acid

AC:

Acetone

MA:

Methanol

EA:

Ethanol

ACN:

Acetonitrile

SEM:

Scanning electron microscopy

TEM:

Transmission electron microscope

FTIR:

Fourier transform infrared

XPS:

X-ray photoelectron spectroscopy

BET:

Brunauer-Emmett-Teller

BJH:

Barrett-Joyner-Halenda

TGA:

Thermogravimetric analysis

DTG:

Derivative thermogravimetry

XRD:

X-ray diffraction

R 2 :

Determination coefficient in adsorption isothermal and kinetic experiment

r:

Correlation coefficient

LODs:

Detection limits

LOQs:

Limits of quantification

RSDs:

Relative standard deviations

ME:

Matrix effect

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Acknowledgements

The authors extend their gratitude to Shiyanjia Lab (www.shiyanjia.com) for providing invaluable assistance with all the characterization analysis.

Funding

The study was supported by the National Key Project of Research and Development Plan (2022YFF1100900).

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Author notes

  1. Xinyue Zhang and Minli Yang contributed equally to the work.

Authors and Affiliations

  1. Institute of Food Safety, Chinese Academy of Inspection and Quarantine, Beijing, 100176, China

    Xinyue Zhang, Minli Yang, Feng Zhang & Xiujuan Wang

  2. School of Pharmacy, East China University of Science and Technology, Shanghai, 200237, China

    Xinyue Zhang & Feifang Zhang

  3. Key Laboratory of Food Quality and Safety for State Market Regulation, Beijing, 100176, China

    Xinyue Zhang, Minli Yang, Feng Zhang & Xiujuan Wang

Authors
  1. Xinyue Zhang
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  2. Minli Yang
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Contributions

Xinyue Zhang: conceptualization, methodology, formal analysis, investigation, visualization, writing—original draft, writing—review and editing. Minli Yang: conceptualization, investigation, writing—review and editing. Feng Zhang: supervision, funding acquisition. Xiujuan Wang: investigation, writing—review and editing. Feifang Zhang: supervision, writing—review and editing

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Correspondence to Feng Zhang or Feifang Zhang.

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Zhang, X., Yang, M., Zhang, F. et al. Amino-functional magnetic covalent organic framework as an effective adsorbent for the determination of neonicotinoids in food samples. Microchim Acta 191, 220 (2024). https://doi.org/10.1007/s00604-024-06277-5

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