Determination of Residues of 35 Prohibited Pesticides in Typhonii Rhizoma by Gas Chromatography-Tandem Mass Spectrometry with QuEChERS
摘 要
在《中华人民共和国药典》(2020年版)四部通则2341新增第五法的基础上,提出了题示方法,并对前处理、色谱、质谱条件进行优化,解决了同分异构体农药在检测过程中易转化、分解的难题。用乙腈和QuEChERS萃取试剂盒提取样品中的35种禁用农药,用农残专用净化管去除杂质,所得样品提取液经氮吹浓缩和乙腈稀释后,加入磷酸三苯酯内标溶液,采用气相色谱-串联质谱法(GC-MS/MS)分析。用DB-17MS毛细管色谱柱在程序升温条件下分离样品溶液中各禁用农药,配有电子轰击离子(EI)源的三重四极杆质谱仪在多反应监测(MRM)模式下检测,基质匹配法联合内标法定量。结果表明:各禁用农药与内标的质量浓度比值均与对应的峰面积比值在一定范围内呈线性关系,相关系数均不小于0.999 8,检出限(3S/N)为0.16~5.00 μg·kg-1;按标准加入法进行回收试验,回收率为61.1%~121%;仪器、方法以及中间精密度试验所得各农药测定值的相对标准偏差分别为1.2%~1.8%(n=6)、2.3%~5.5%(n=6)和2.5%~5.7%(n=12)。方法用于实际样品的分析,6批白附子样品中均未检出35种禁用农药。
Abstract
On the basis of the addition of the fifth method in the fourth part general rule 2341 of Pharmacopoeia of the People's Republic of China (2020 edition), the title method was proposed, and conditions of the pre-treatment, chromatography and mass spectrometry were optimized to solve the problems of easy conversion and decomposition of isomeric pesticides in the detection process. The 35 prohibited pesticides were extracted from the sample using acetonitrile and QuEChERS extraction kit. Impurities were removed using dedicated agricultural residue purification tube. The resulting sample extract was concentrated by nitrogen blowing and diluted with acetonitrile, and then mixed with triphenyl phosphate internal standard solution. The sample solution obtained was analyzed by GC-MS/MS. Prohibited pesticides in the sample solution were separated by DB-17MS capillary column under programmed temperature conditions, detected by triple quadrupole mass spectrometer equipped with EI source in MRM mode, and quantified by matrix matching method combined with internal standard method. It was shown that linear relationships between values of the mass concentration ratio and the peak area ratio of each prohibited pesticide to internal standard were kept in definite ranges, with correlation coefficients not less than 0.999 8 and detection limits (3S/N) ranging from 0.16 μg·kg-1 to 5.00 μg·kg-1. Test for recovery was made by standard addition method, giving results in the range of 61.1%-121%. RSDs of the determined values for each pesticide obtained from tests of the instrument, method and intermediate precision were in the ranges of 1.2%-1.8% (n=6), 2.3%-5.5% (n=6) and 2.5%-5.7% (n=12), respectively. The proposed method was applied to the analysis of actual samples, and the 35 prohibited pesticides were not detected in 6 batches of Typhonii Rhizoma samples.
中图分类号 O657.63 DOI 10.11973/lhjy-hx202308005
所属栏目 工作简报
基金项目 北京市市级项目(11000022T000000455996);北京市改革与发展专项(2021ZL0122)
收稿日期 2022/3/7
修改稿日期
网络出版日期
作者单位点击查看
备注钱冲,高级工程师,硕士,主要从事色谱、质谱分析研究工作
引用该论文: QIAN Chong,MA Bokai,LIU Shanshan,HUANG Wenwen,GOU Xinlei,WANG Wei,GAO Xia,ZHANG Mei. Determination of Residues of 35 Prohibited Pesticides in Typhonii Rhizoma by Gas Chromatography-Tandem Mass Spectrometry with QuEChERS[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2023, 59(8): 896~902
钱冲,马博凯,刘珊珊,黄雯雯,勾新磊,王尉,高峡,张梅. QuEChERS-气相色谱-串联质谱法测定白附子中35种禁用农药的残留量[J]. 理化检验-化学分册, 2023, 59(8): 896~902
共有人对该论文发表了看法,其中:
人认为该论文很差
人认为该论文较差
人认为该论文一般
人认为该论文较好
人认为该论文很好
参考文献
【1】黄金钰,戴忠,马双成.白附子的研究进展[J].中草药, 2015,46(18):2816-2822.
【2】ZHAO Y, ZHAO L, LUO Y, et al. Synergistic effect of radiation and traditional Chinese medicine Rhizoma-Typhonii ethanol extracts depends on P53 expression in treatment of Lewis mouse lung cancer cells[J]. African Journal of Traditional Complementary and Alternative Medicines, 2015,12(1):109-114.
【3】白明,陈静,苗明三.基于数据挖掘的白附子临床外用规律分析[J].中国药师, 2020,23(4):671-675.
【4】孙仟,林林,郭东晓,等.UPLC-MS/MS在中药材农残分析中的应用[J].药学研究, 2020,39(7):420-423.
【5】王莹,魏赫,乔菲,等.气相色谱-串联质谱法快速筛查人参中192种农药残留[J].中国实验方剂学杂志, 2018,24(15):83-92.
【6】康传志,郭兰萍,周涛,等.中药材农残研究现状的探讨[J].中国中药杂志, 2016,41(2):155-159.
【7】孔令军,张娅婷,谷令彪,等.中药材农药残留的研究进展[J].中国实验方剂学杂志, 2015,21(21):231-234.
【8】吕朝耕,王升,何霞红,等.中药材农药使用登记现状、问题及建议[J].中国中药杂志, 2018,43(19):3984-3988.
【9】马雯,薛晓利,秦雪梅,等.中药材农药残留及脱除方法研究进展[J].中草药, 2018,49(3):745-753.
【10】钱冲,胡光辉,张梅,等.气相色谱-三重四极杆质谱法测定人参中22种有机氯农残[J].食品安全质量检测学报, 2020,11(6):1736-1742.
【11】国家药典委员会.中华人民共和国药典:一部[S].北京:中国医药科技出版社, 2020:110-111.
【12】刘虎传,张微,谭莲英,等.硫酸磺化法检测牛奶中19种农残[J].食品与发酵科技, 2015,51(2):97-100.
【13】陈海玲,林麒,王翠玲,等.固相萃取-在线凝胶渗透色谱-气相色谱-串联质谱法测定水中31种有机氯农药[J].理化检验-化学分册, 2021,57(5):450-458.
【14】宁方尧.全自动凝胶渗透色谱法净化-气相色谱-串联质谱法测定茄果类蔬菜中7种有机磷类杀虫剂残留量[J].理化检验-化学分册, 2021,57(5):476-480.
【15】宾婕,王以鑫,胡建林,等.QuEChERS-UPLC-MS/MS法快速测定香茅草中33种农药残留量[J].药物分析杂志, 2021,41(3):466-473.
【16】谭鹏,张海珠,许莉,等.基于QuEChERS-GC-QQQ-MS/MS法同时测定知母中58种农药残留[J].中草药, 2018,49(14):3397-3405.
【17】谭鹏,张海珠,张定堃,等.中药材农药残留快速分析新策略:基于保留指数的八角茴香中12个菊酯类农药GC-QQQ-MS/MS测定方法的建立[J].药物分析杂志, 2019,39(7):1256-1266.
【18】杨秦,张耀海,周杰,等.磁性分散固相萃取-QuEChERS结合气相色谱-串联质谱法检测不同柑橘基质中多种农药残留[J].农药学学报, 2021,23(2):395-404.
【19】孙婷婷,徐彦红,张雪梅,等.QuEChERS-气相色谱-三重四极杆质谱法测定白花蛇舌草中18种有机磷农药[J].理化检验-化学分册, 2021,57(5):463-469.
【2】ZHAO Y, ZHAO L, LUO Y, et al. Synergistic effect of radiation and traditional Chinese medicine Rhizoma-Typhonii ethanol extracts depends on P53 expression in treatment of Lewis mouse lung cancer cells[J]. African Journal of Traditional Complementary and Alternative Medicines, 2015,12(1):109-114.
【3】白明,陈静,苗明三.基于数据挖掘的白附子临床外用规律分析[J].中国药师, 2020,23(4):671-675.
【4】孙仟,林林,郭东晓,等.UPLC-MS/MS在中药材农残分析中的应用[J].药学研究, 2020,39(7):420-423.
【5】王莹,魏赫,乔菲,等.气相色谱-串联质谱法快速筛查人参中192种农药残留[J].中国实验方剂学杂志, 2018,24(15):83-92.
【6】康传志,郭兰萍,周涛,等.中药材农残研究现状的探讨[J].中国中药杂志, 2016,41(2):155-159.
【7】孔令军,张娅婷,谷令彪,等.中药材农药残留的研究进展[J].中国实验方剂学杂志, 2015,21(21):231-234.
【8】吕朝耕,王升,何霞红,等.中药材农药使用登记现状、问题及建议[J].中国中药杂志, 2018,43(19):3984-3988.
【9】马雯,薛晓利,秦雪梅,等.中药材农药残留及脱除方法研究进展[J].中草药, 2018,49(3):745-753.
【10】钱冲,胡光辉,张梅,等.气相色谱-三重四极杆质谱法测定人参中22种有机氯农残[J].食品安全质量检测学报, 2020,11(6):1736-1742.
【11】国家药典委员会.中华人民共和国药典:一部[S].北京:中国医药科技出版社, 2020:110-111.
【12】刘虎传,张微,谭莲英,等.硫酸磺化法检测牛奶中19种农残[J].食品与发酵科技, 2015,51(2):97-100.
【13】陈海玲,林麒,王翠玲,等.固相萃取-在线凝胶渗透色谱-气相色谱-串联质谱法测定水中31种有机氯农药[J].理化检验-化学分册, 2021,57(5):450-458.
【14】宁方尧.全自动凝胶渗透色谱法净化-气相色谱-串联质谱法测定茄果类蔬菜中7种有机磷类杀虫剂残留量[J].理化检验-化学分册, 2021,57(5):476-480.
【15】宾婕,王以鑫,胡建林,等.QuEChERS-UPLC-MS/MS法快速测定香茅草中33种农药残留量[J].药物分析杂志, 2021,41(3):466-473.
【16】谭鹏,张海珠,许莉,等.基于QuEChERS-GC-QQQ-MS/MS法同时测定知母中58种农药残留[J].中草药, 2018,49(14):3397-3405.
【17】谭鹏,张海珠,张定堃,等.中药材农药残留快速分析新策略:基于保留指数的八角茴香中12个菊酯类农药GC-QQQ-MS/MS测定方法的建立[J].药物分析杂志, 2019,39(7):1256-1266.
【18】杨秦,张耀海,周杰,等.磁性分散固相萃取-QuEChERS结合气相色谱-串联质谱法检测不同柑橘基质中多种农药残留[J].农药学学报, 2021,23(2):395-404.
【19】孙婷婷,徐彦红,张雪梅,等.QuEChERS-气相色谱-三重四极杆质谱法测定白花蛇舌草中18种有机磷农药[J].理化检验-化学分册, 2021,57(5):463-469.
相关信息