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Article | Open Access

Facile synthesis of magnetic covalent organic framework nanocomposites for the enrichment and quantification of trace organophosphorus pesticides in fruit juice

Quanbin Fua,b,c, Xin Suna, Lu Liub, Hailong Jiangb(), Geoffrey I. N. Waterhoused(), Shiyun Aia,c(), Rusong Zhaob
College of Food Science and Engineering, Shandong Agricultural University, Tai’an 271018, China
Qilu University of Technology (Shandong Academy of Sciences), Shandong Analysis and Test Center, Key Laboratory for Applied Technology of Sophisticated Analytical Instruments of Shandong Province, Jinan 250014, China
College of Chemistry and Material Science, Shandong Agricultural University, Tai’an 271018, China
School of Chemical Sciences, The University of Auckland, Auckland 1142, New Zealand

Peer review under responsibility of Tsinghua University Press.

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Highlights

• Covalent organic framework-coated magnetic nanoparticles (M-COF) were synthesized at room temperature.

• M-COF showed excellent performance for the magnetic solid-phase extraction (MSPE) of OPPs.

• MSPE-GC/MS allowed OPPs quantification in spiked fruit juices with high recoveries.

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Abstract

Organophosphorus pesticides (OPPs) in foods pose a serious threat to human health, motivating the development of novel analytical methods for their rapid detection and quantification. A magnetic covalent organic framework (M-COF) adsorbent for the magnetic solid-phase extraction (MSPE) of OPPs from foods was reported. M-COF was synthesized by the Schiff base condensation reaction of 1,3,5-tris(4-aminophenyl)benzene and 4,4-biphenyldicarboxaldehyde on the surface of amino-functionalized magnetic nanoparticles. Density functional theory (DFT) calculations showed that adsorption of OPPs onto the surface of M-COF involved hydrophobic effects, van der Waals interactions, π-π interactions, halogen-N bonding, and hydrogen bonding. Combined with gas chromatography-mass spectrometry (GC-MS) technology, the MSPE method features low limits of detection for OPPs (0.002–0.015 μg/L), good reproducibility (1.45%–6.14%), wide linear detection range (0.01–1 μg/L, R ≥ 0.9935), and satisfactory recoveries (87.3%–110.4%). The method was successfully applied for the trace analysis of OPPs in spiked fruit juices.

Keywords

Covalent organic frameworkGas chromatography-mass spectrometryMagnetic solid-phase extractionOrganophosphorus pesticidesFruit juice

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Food Science and Human Wellness
Volume 14 Issue 3,
March 2025
Article number: 9250072
DOI: 10.26599/FSHW.2024.9250072
Cite this article:
Fu Q, Sun X, Liu L, et al. Facile synthesis of magnetic covalent organic framework nanocomposites for the enrichment and quantification of trace organophosphorus pesticides in fruit juice. Food Science and Human Wellness, 2025, 14(3): 9250072. https://doi.org/10.26599/FSHW.2024.9250072
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Linearity, sensitivity, and precision validation results for the detection of OPPs by the MSPE method.

Analyte Linear range(µg/L) Regression equation R2 LOD(µg/L) LOQ(µg/L) Repeatability (%)
Intra-day (n = 6) Inter-day (n = 3)
Terbufos 0.01–1 Y = 2390.52X + 9.26 0.9973 0.002 0.007 4.39 4.75
Chlorpyrifos 0.05–1 Y = 1449.05X + 44.22 0.9949 0.010 0.033 2.17 5.37
Parathion 0.05–1 Y = 298.88X – 0.42 0.9935 0.015 0.050 3.42 6.14
Bromophos 0.02–1 Y = 1448.27X + 4.98 0.9954 0.008 0.027 1.45 5.32
Bromophos ethyl 0.05–1 Y = 789.23X + 6.46 0.9962 0.012 0.040 3.52 4.20

Comparison of the performances of different magnetic adsorbents for the detection of OPPs.

Analytical method Material Sample type Linear range (µg/L) LOD (µg/L) Recovery (%) Reference
MSPE-GC-MS MNPs/MWCNTs Tea 0.08–2.0 0.006–0.024 72.5–109.1 [4]
MSPE-LC-UV Fe3O4@TiO2/CTAB water 0.1–15 0.026–0.030 88.5–96.7 [5]
MSPE-GC-FPD Fe3O4@COF@Zr4+ Vegetable 2–250 0.7–3.0 87.0–121.0 [6]
MSPE-LC-MS Fe3O4/MoS2 water 0.5–200 0.02–0.4 89.1–102.3 [7]
MSPE-GC-FID BeW12O40-ILSCCFNPS Water and fruit juice 0.08–300 0.02–0.06 70.0–89.2 [12]
MSPE-GC-FID KHA/Fe3O4 Water and fruit juice 0.1–200 0.03–0.1 89.0–99.7 [13]
MSPE-GC-MS Fe3O4@C18 water 0.01–0.6 0.001–0.008 70.2–110.2 [37]
MSPE-GC-MS M-COFs fruit juice 0.01–1 0.002–0.015 87.3–110.4 This work

Spiked recoveries of OPPs in fruit juice samples using the MSPE method.

Sample Spiked (μg/L) Terbufos Chlorpyrifos Parathion bromophos Bromophos ethyl
Note: aNot detected. bMean ± standard deviation (n = 3).
Mango juice 0 NDa ND ND ND ND
0.2 91.6 ± 1.9b 89.1 ± 0.8 92.2 ± 1.8 98.4 ± 1.9 101.5 ± 2.9
0.5 95.9 ± 2.6 103.2 ± 2.7 95.7 ± 1.6 87.3 ± 1.8 94.2 ± 1.9
1 110.4 ± 2.6 91.4 ± 1.3 97.7 ± 1.4 98.8 ± 2.4 99.4 ± 3.1
Apple juice 0 ND ND ND ND ND
0.2 95.5 ± 1.3 90.2 ± 1.4 96.4 ± 3.3 95.5 ± 1.0 99.6 ± 2.1
0.5 94.1 ± 2.3 87.7 ± 1.6 95.2 ± 1.5 96.1 ± 2.3 98.2 ± 1.0
1 92.7 ± 2.7 97.4 ± 1.8 91.6 ± 4.1 89.9 ± 0.7 95.4 ± 2.1
Pineapple juice 0 ND ND ND ND ND
0.2 93.3 ± 0.8 93.4 ± 4.1 100.8 ± 3.4 96.6 ± 5.3 91.5 ± 7.4
0.5 89.8 ± 3.8 94.3 ± 5.4 87.9 ± 3.8 89.5 ± 2.3 88.8 ± 2.4
1 95 ± 2.7 94.7 ± 3.2 89.0 ± 6.5 90.7 ± 2.1 96.6 ± 2.3
Orange juice 0 ND ND ND ND ND
0.2 94.9 ± 1.2 91.9 ± 1.2 86.6 ± 2.6 90.6 ± 6.4 94.0 ± 2.2
0.5 93.3 ± 1.3 92.3 ± 3.2 87.3 ± 4.7 88.2 ± 5.9 95.3 ± 1.7
1 92.1 ± 1.9 88.2 ± 2.8 93.0 ± 3.5 89.0 ± 1.8 93.9 ± 1.7