三七药材禁用农药残留的检测研究  

Determination of prohibited pesticide residues in traditional Chinese medicines Notoginseng Radix et Rhizoma

作　　者：冯红 李金柱 肖践丽 王晓东 陆文亮 万会花 陈士林 FENG Hong;LI Jin-zhu;XIAO Jian-li;WANG Xiao-dong;LU Wen-liang;WANG Hui-hua;CHEN Shi-lin(Tianjin University of Traditional Chinese Medicine,Tianjin 301617,China;Wenshan Notoginseng Digital Materia Medica Testing Center Co.,Ltd.,Wenshan 660399,China;Hebei Traditional Hebal Medicine Quality Control Research Center Co.,Ltd.,Baoding 071000,China;Institute of Chinese Materia Medica,China Academy of Chinese Medical Sciences,Beijing 100700,China)

机构地区：[1]天津中医药大学研究生院,天津301617 [2]文山三七数字本草检验中心有限公司,文山660399 [3]河北省中药材质量检验检测研究中心有限公司,保定071000 [4]中国中医科学院中药研究所,北京100700

出　　处：《药物分析杂志》2022年第11期1980-1988,共9页Chinese Journal of Pharmaceutical Analysis

摘　　要：目的:建立中药材三七中33种禁用农药残留的检测方法。方法:以乙腈为溶剂,高速匀浆提取。检测方法:气相色谱-串联质谱(GC-MS/MS)法,采用DB17MS弹性石英毛细管柱(30 m×0.25 mm×0.25μm),电子轰击离子源(EI);超高效液相色谱-串联质谱(UPLC-MS/MS)法,采用十八烷基硅烷键合硅胶柱Hypersil GOLD aQC18(150 mm×2.1 mm,3μm),以0.1%甲酸水溶液(含5 mmol·L^(-1)甲酸铵)和0.1%甲酸乙腈溶液(含5 mmol·L^(-1)甲酸铵)(95∶5)为流动相,梯度洗脱,电喷雾离子源(ESI),正离子模式下多反应监测(MRM)。结果:GC-MS/MS法检测的禁用农药质量浓度在20~600 ng·mL^(-1)范围内线性关系良好,相关系数在0.9903以上,回收率在85.0%~127.6%,精密度RSD(n=6)在1.3%~25.0%;UPLC-MS/MS法检测的禁用农药质量浓度在20~600 ng·mL^(-1)范围内线性关系良好,相关系数在0.9911以上,回收率在76.2%~123.7%,精密度RSD(n=6)在1.0%~13.0%。基于GC-MS/MS和UPLC-MS/MS分析方法,60批样品中共检出12种农药,其中特丁硫磷检出率最高为10.8%;农药残留超出限量范围的有特丁硫磷、苯线磷、氯唑磷、地虫硫磷、杀虫脒,其中杀虫脒超出限量值的3倍。结论:本方法能快速有效地检测中药材三七中的农药多残留,为其他药用植物中的农残检测提供借鉴,为三七规范化种植提供依据。Objective:To establish a method for the determination of 33 prohibited pesticide residues in traditional Chinese medicines Notoginseng Radix et Rhizoma.Methods:The analytes were extracted with acetonitrile by high speed homogenizer.The detection method of GC-MS/MS with DB17 MS capillary column(30 m×0.25 mm×0.25μm)and electron impact source(EI)and UPLC-MS/MS with Hypersil GOLD aQC18column(150 mm×2.1 mm,3μm)were performed by gradient elution using a mobile phase consisting of 0.1%formic acid(containing 5 mmol·L^(-1)ammonium formate)and acetonitrile-0.1%formic acid solution(containing 5 mmol·L^(-1)ammonium formate)(95∶5).A multiple reaction monitoring(MRM)applied in positive ion mode electrospray ion(ESI)source.Results:The banned pesticides detected by GC-MS/MS showed good linearity in the range of 20 to 600 ng·mL^(-1),the correlation coefficients werehigher than 0.9903,the recoveries were 85.0%-127.6%,the RSDs for precision tests were 1.3%-25.0%(RSD,n=6);the banned pesticides detected by UPLC-MS/MS showed good linearity in the range of 20 to 600 ng·mL^(-1),the correlation coefficients were higher than 0.9911,the recoveries were 76.2%-123.7%,the RSDs for precision tests were 1.0%-13.0%(RSD,n=6).Base on GC-MS/MS and UPLC-MS/MS methods,the detection rate of terbufos was 10.8%which was the highest rate in 12 detected pesticides of 60 batches samples.The pesticide residues exceeding the limit range included terbufos,fenamiphos,isazafos,chlordimeform and fonofos,among which fonofos exceeded the limit value by 3 times.Conclusions:The method can be used for rapid and effective detection of pesticide residues in Notoginseng Radix et Rhizoma,which can provide reference for the detection of pesticide residues in other medicinal plants and provide basis for the standardized cultivation of Notoginseng Radix et Rhizoma.

关 键 词：中药材 三七 禁用农药残留 快速样品处理法 超高效液相色谱-串联质谱法 气相色谱-串联质谱法 

分 类 号：R917[医药卫生—药物分析学]