关键词: 磁性纳米粒子, 硼亲和, 金属有机骨架, 气相色谱-质谱, 农药残留, 茶叶

Abstract:

Tea is one of the most popular beverages worldwide, and its quality is often affected by the excessive pesticide residues during production. During the detection of pesticide residues in tea by chromatography-mass spectrometry and other methods, a strong matrix effect attributed to tea polyphenols and pigments is observed, which seriously impacts the analysis results. In this study, Fe₃O₄ magnetic nanoparticles and boric acid-functionalized metal organic framework (BA-MOF) materials were combined to prepare a highly efficient adsorbent Fe₃O₄@BA-MOF for capturing tea polyphenols and pigments. An effective analysis method for pesticide residues in tea samples in combination with gas chromatography-mass spectrometry was established. The introduction of boronic acid ligands into the metal organic framework, as the recognition site of cis-diols, enhanced the polyphenol capture ability. Adsorption of the pigment in the matrix was achieved through π-π interactions between the MOF ligand and the pigment. This new material has significant advantages such as rapid magnetic separation, large surface area, and abundant functional sites.
Fe₃O₄@BA-MOF was prepared by employing simple conditions and characterized by Fouriertransform infrared spectroscopy, scanning electron microscopy, and X-ray diffractometry to identify its functional groups and morphology. After investigating the adsorption effect of different doses of Fe₃O₄@BA-MOF adsorbents (5, 10, 30, 50, and 80 mg) on tea polyphenols, 50 mg of the adsorbent was added to the tea matrix and shaken thoroughly. The tea polyphenol content in the matrix solution was determined using an ultraviolet spectrophotometer. The polyphenols were reduced by 74.58% within 5 min. The effect of solution pH (2.0, 4.0, 6.0, and 7.0) on the adsorption efficiency was investigated, and pH 7.0 was chosen as the optimal condition. By adjusting the pH of the solution, Fe₃O₄@BA-MOF could be recycled, and it maintained the excellent adsorption performance after four cycles of use. The introduction of Fe₃O₄ magnetic nanoparticles led to rapid magnetic response characteristics during sample pretreatment and improved the pretreatment efficiency. In the actual application of tea pesticide detection, after Fe₃O₄@BA-MOF pretreatment, the average recovery rates of the ten pesticides were in the range of 75.8%-138.6%, and the RSD was in the range of 0.5%-18.7% (n=3).
The Fe₃O₄@BA-MOF nanocomposite prepared by introducing the boric acid ligand into the MOF structure and incorporating Fe₃O₄ magnetic nanoparticles could specifically adsorb the tea polyphenol matrix. When applied to the detection of pesticide residues in tea, it purifies the matrix and improves the detection efficiency, thus being suitable for the detection and analysis of pesticides in tea.

Key words: magnetic nanoparticles, boron affinity, metal organic framework (MOF), gas chromatography-mass spectrometry (GC-MS), pesticide residues, tea