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Fluorine-functionalized zirconium-based metal-organic framework immobilized thin film microextraction array for high-throughput analysis of glyphosate residues
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Sainan LI1, Xiaoju YIN1, Jiawei LIU1, *, Yang YANG2, *, Quan BAI1
Chinese Journal of Chromatography | 2026, 44(10) : 1233 - 1242
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Chinese Journal of Chromatography | 2026, 44(10): 1233-1242
• Articles •
Fluorine-functionalized zirconium-based metal-organic framework immobilized thin film microextraction array for high-throughput analysis of glyphosate residues
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Sainan LI1, Xiaoju YIN1, Jiawei LIU1, *, Yang YANG2, *, Quan BAI1
Affiliations
  • 1Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Key Laboratory of Modern Separation Science in Shaanxi Province, College of Chemistry & Materials Science, Northwest University, Xi’an 710127, China
  • 2State Key Laboratory of Chemistry for NBC Hazards Protection, Beijing 102205, China
Published: 2026-10-08 doi: 10.3724/SP.J.1123.2026.01034
Outline
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The development of high-throughput sample pretreatment methods is essential for the rapid screening and accurate analysis of contaminants in food and environmental matrices. In this study, we established a novel high-throughput sample pretreatment approach for glyphosate using a 96-blade thin-film microextraction (TFME) device. The blade surface was coated with a functionalized metal-organic framework (MOF) as the extractive phase. Specifically, a fluorinated zirconium-based MOF (UiO-66-F4) was synthesized via a hydrothermal method. Various characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and nitrogen adsorption-desorption isotherms, were employed to confirm the successful synthesis of UiO-66-F4 crystals. The results demonstrated that the synthesized crystals possessed a high specific surface area (559.5 m2/g) and an irregularly stacked porous structure. The prepared UiO-66-F4 was subsequently homogenized with a polyacrylonitrile (PAN) solution to form a slurry. This slurry was solidified onto 96 stainless-steel blades using an improved laboratory-developed spraying technique. As a result, an array of 96 UiO-66-F4/PAN extraction coatings was obtained. Each coating in the array was fabricated with uniform dimensions of 2 cm in length, 0.2 cm in width, and approximately 100 μm in thickness. The relative standard deviations (RSDs, n=8) for the length, width, and thickness of the coatings measured were 0.29%, 0.48%, and 4.64%, respectively. The UiO-66-F4 adsorbent offers multiple interaction forces with glyphosate, including metal coordination, hydrogen bonding, and electrostatic interactions. Therefore, the adsorption of glyphosate onto UiO-66-F4 occurred rapidly, reaching equilibrium within 5 min. The pseudo-second-order kinetic model provides a superior fit for the adsorption kinetics behavior of glyphosate on the surface of UiO-66-F4, suggesting that the adsorption process is predominantly controlled by chemisorption. Furthermore, the glyphosate adsorption isotherms indicate that its adsorption behavior closely conforms to the Langmuir isotherm model (R2>0.97). This finding suggests that glyphosate is adsorbed as a monolayer on the adsorbent surface, giving rise to a maximum adsorption capacity of 239.4 mg/g. The developed TFME method efficiently enriches glyphosate from aqueous solutions at pH 5–7 within 30 min and allows for analyte desorption using an aqueous solution containing 5% (V/V) triethylamine. The UiO-66-F4/PAN coatings displayed high repeatability and reproducibility, as evidenced by the RSD values below 2.3% (n=5). In addition, the coatings exhibited remarkable robustness, maintaining a recovery of 98.2% after nine consecutive TFME processing cycles. Furthermore, coupling this TFME method with ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) enabled high-throughput analysis of glyphosate. The method demonstrated excellent linearity over a range of 0.5–500 ng/mL (R2=0.999 9). The limits of detection (LOD) and quantification (LOQ) were 0.12 ng/mL and 0.5 ng/mL, respectively. Intra-day (n=3) and inter-day (n=5) precisions, expressed as RSDs, were 3.6% and 1.6%, respectively. The method was successfully applied to real-world environmental water and fruit samples, detecting glyphosate residues of (1.7±0.7) ng/g in orange peel and (1.2±0.5) ng/mL in irrigation river water. Spiked recoveries in real samples ranged from 88.1% to 107.1%, with precisions (RSDs, n=3) below 8.1%. This method is accurate, reliable, and reproducible, enabling parallel processing of 96 samples, which are well-suited for rapid screening and precise quantification of glyphosate contamination in large-scale sample analyses.

metal-organic frameworks (MOFs)  /  array-type thin-film microextraction  /  glyphosate  /  high-throughput analysis
李赛楠, 殷小菊, 刘家玮, 杨旸, 白泉. 氟功能化锆基金属有机框架负载薄膜微萃取阵列用于草甘膦残留的高通量分析. 色谱, 2026 , 44 (10) : 1233 -1242 . DOI: 10.3724/SP.J.1123.2026.01034
Sainan LI, Xiaoju YIN, Jiawei LIU, Yang YANG, Quan BAI. Fluorine-functionalized zirconium-based metal-organic framework immobilized thin film microextraction array for high-throughput analysis of glyphosate residues[J]. Chinese Journal of Chromatography, 2026 , 44 (10) : 1233 -1242 . DOI: 10.3724/SP.J.1123.2026.01034
  • National Natural Science Foundation of China (Nos. 22474108, 22174108).
Year 2026 volume 44 Issue 10
28
9
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Article Info
doi: 10.3724/SP.J.1123.2026.01034
  • Receive Date:2026-01-30
  • Online Date:2026-10-29
  • Published:2026-10-08
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  • Received:2026-01-30
Funding
National Natural Science Foundation of China (Nos. 22474108, 22174108).
Affiliations
    1Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Key Laboratory of Modern Separation Science in Shaanxi Province, College of Chemistry & Materials Science, Northwest University, Xi’an 710127, China
    2State Key Laboratory of Chemistry for NBC Hazards Protection, Beijing 102205, China
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表12种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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