基于改良QuEChERS-新型超交联聚合物净化的超高效液相-串联四级杆质谱联用法测定5种参类保健食品原料中30种农药残留

俞所银; 梁佳; 俞跃洋

doi:10.13386/j.issn1002-0306.2025040353

基于改良QuEChERS-新型超交联聚合物净化的超高效液相-串联四级杆质谱联用法测定5种参类保健食品原料中30种农药残留

Determination of 30 Pesticide Residues in 5 Kinds of Ginseng Health Food Ingredients by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS)Based on Modified QuEChERS-novel Porous Organic Polymers

摘要

摘要: 为研究参类保健食品原料中农药残留污染现状，建立了改良QuEChERS-新型超交联聚合物（porous organic polymers，POPs）联用净化，超高效液相-串联四级杆质谱测定高丽红参、丹参、玄参、党参和太子参中30种农药残留量分析方法。样品经1%冰乙酸浸润、乙腈提取，QuEChERS（不含石墨化碳黑）净化液经新型超交联聚合物吸附、解吸处理、解吸液浓缩后用1 mL乙腈+水（体积比6+4）定容。滤液经Phenomenx Kinetex C₁₈色谱柱（100 mm×2.1 mm）分离，0.1%甲酸（含5 mmol/L甲酸铵）-乙腈梯度洗脱，电喷雾离子化、正离子扫描和动态多反应监测模式测定，内标法定量。结果表明：化学法自制的10 mg POPs材料对30种农药吸附率可达95%以上，用乙腈+甲苯（体积比3+1）洗脱解吸率达99%、改良QuEChERS-新型超交联聚合物联用净化法使30种农药回收率均提升了5%~40%。30种农药在0.05~100 µg/kg范围内均有较好的线性关系（r>0.990），检出限（limits of detection，LOD，S/N=3）为0.05~5.0 µg/kg。5种参类保健食品原料在低、中、高三水平下的平均回收率为86.4%~113.1%，相对标准偏差（relative standard deviations，RSD，n=6）为0.36%~8.74%，方法定量限（limits of quantification detection，LOQ，S/N=10）为0.10~15.0 µg/kg。本方法回收率高、灵敏度高，能够解决传统QuEChERS前处理对参类保健食品原料中农药回收率低、基质干扰强的问题。

Abstract: In order to study the pesticide residues in ginseng health food ingredients, an analysis method for determination of 30 pesticide residues in Korean Red Ginseng, Salvia miltiorrhiza Bge, Scrophularia radix, Radix Codonopsis, and Pseudostellaria radix was established by combining the modified QuEChERS-novel porous organic polymers (POPs) purification with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were soaked in 1% ice acetic acid and extracted by acetonitrile, then purified by QuEChERS method without graphitized of carbon black. The purificated solutions were adsorbed and desorbed by novel porous organic polymers, concentrated by nitrogen stream and dissolved in 1 mL acetonitrile solution (volume ratio 6+4). The filtrates were separated by the Phenomenx Kinetex C₁₈ (100 mm×2.1 mm) chromatography column, using gradient elution of 0.1% formic acid aqueous solution containing 5 mmol/L ammonium formate-acetonitrile, determined by electrospray ionization, in positive ion switching dynamic multiple reaction monitoring mode, and quantified by the internal standard method. The results showed that the adsorption rate of 10 mg POPs materials self-made by the chemical method for 30 kinds of pesticides could reach more than 95%, and the desorption capacity reached 99% when eluted with acetonitrile-toluene (volume ratio 3+1) solution. The recoveries of 30 kinds of pesticides were increased to 5%~40% by modified QuEChERS-novel porous organic polymers purification. Method validation revealed that all 30 pesticides had good linearities in the range of 0.05~100 µg/kg, with correlation coefficients (r) higher than 0.990, and limits of detection (LOD, S/N=3) were 0.05~5.0 µg/kg. The average recoveries of 5 kinds of ginseng health food ingredients were ranged from 86.4% to 113.1%, with relative standard deviations (RSD, n=6) of 0.36%~8.74% at low, medium and high addition levels. While the limits of quantification (LOQ, S/N=10) were 0.10~15.0 µg/kg. This method has high recovery and high sensitivity, also can solve the issues of low pesticide recovery and strong matrix interference in ginseng health food ingredients by conventional QuEChERS pretreatment.