凝胶色谱结合GC-MS/MS法测定树脂类中药中禁用农药残留  

Determination of Forbidden Pesticide Residues in Resinous ChineseMedicine by Gel Permeation Chromatography Combined with Gas Chromatography TandemMass Spectrometry

作　　者：陈树东 林晓佳 梁金钊 陈筠桦 胡文军 CHEN Shudong;LIN Xiaojia;LIANG Jinzhao;CHEN Junhua;HU Wenjun(Guangdong Institute of Traditional Chinese Medicine,Guangzhou 510640,China;Guangzhou Inspection Testing and Certification Group Co.,Ltd.,Guangzhou 511447,China)

机构地区：[1]广东省中药研究所,广东广州510640 [2]广州检测认证集团有限公司,广东广州511447

出　　处：《特产研究》2024年第6期125-131,共7页Special Wild Economic Animal and Plant Research

基　　金：广东省药品监督管理局重点实验室项目(2022ZDB13);广东省中药生产企业的中药材中药饮片中33种禁用农药污染残留情况研究项目(粤药监〔2024〕1089号);药食同源儿童健康食品创新团队项目(云科函〔2022〕16号)。

摘　　要：本研究采用凝胶渗透色谱(GPC)净化技术,建立了气相色谱-串联质谱法(GC-MS/MS)同时检测树脂类中药材中24种农药残留的方法。通过对比不同前处理方式的净化效果,选择以乙腈提取树脂类药材中农药成分,以乙酸乙酯-环己烷(1:1,v/v)复溶,采用BIO-Beads SX3(25 mm×300 mm)凝胶净化柱进行净化,分离去除树脂类、色素等大部分杂质后,选用VF-5ms (30m×0.25 mm×0.25μm)色谱柱分离,结合电子轰击电离源(EI)和多反应监测(MRM)模式检测,采用内标法进行定量分析。结果表明,24种禁用农药在一定浓度范围内具有较好的线性关系,相关系数(r)均大于0.99,检测限为0.001~0.005 mg/kg。典型的样品基质在不同浓度的加标水平下的平均加标回收率为66.7%~117.5%,相对标准偏差(RSD)为2.3%~12.5%。研究采用凝胶渗透色谱技术作为树脂类药材基质的净化方式,克服了分散固相萃取和固相萃取法净化容量不足的缺陷,解决了树脂类基质杂质对质谱系统的污染和干扰问题,提高了定性和定量的准确性,具有可操作性强、灵敏度高、重复性好等特点,可以满足树脂类药材中禁用农药的高通量检测要求,可作为特殊基质药材中禁用农药检测方法的有效补充。A gas chromatography tandemmass spectrometry(GC-MS/MS)was established for the determination of 24 forbidden pesticide residues in resinous Chinese medicine,based on gel permeation chromatography(GPC)cleanup.By comparing the purification effects of different pre-treatment methods,acetonitrile was selected to extract pesticide compounds fromresinous Chinese medicine.After concentration,the extracted solution was redissolved in ethyl acetate-cyclohexane solution(1:1,V/V).BIO-Beads SX3(25 mm×300 mm)gel purification columns were used to purify the samples through gel permeation chromatography to separate and remove most impurities such as resins and pigments.The purified solution separated on a VF-5ms(30 m×0.25 mm×0.25μm)capillary column,finally detected with electron bombardment ionization source(EI)in selected ion monitoring(SIM)mode and quantified by internal standard method.The results showed that the 24 prohibited pesticides had a good linear relationship in a certain concentration range,the correlation coefficients(r)was greater than 0.99,the detection limit was 0.001~0.005 mg/kg.For typical olibanumsample matrices,the average recoveries at three spiked levels ranged from66.7%~117.5%,with relative standard deviations(RSD)of 2.3%~12.5%.In this study,gel permeation chromatography technology was used as the purification method of resinous medicine,which overcame the defects of insufficient purification capacity of dispersed solid phase extraction and solid phase extraction,solved the pollution and interference problems of resinous medicine impurities on the mass spectrometry system,improved the qualitative and quantitative accuracy,and has the characteristics of strong operability,high sensitivity and good repeatability.It can meet the high throughput detection requirements of prohibited pesticides in resinous medicine,and form an effective supplement of detection methods of prohibited pesticides in special matrix medicinal materials.

关 键 词：凝胶色谱 气相色谱串联质谱法 树脂类中药 农药残留 

分 类 号：R284.1[医药卫生—中药学]