超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法非靶向筛查苹果中苯脲类农药  

Non-targeted Screening of Phenylurea Pesticides in Apples by Ultrahigh Performance Liquid Chromatography-Quadrupole/Electrostatic Field Orbitrap High Resolution Mass Spectrometry

作　　者：岳宁 李晓慧 李敏洁[1] 王琦 邵华[1] 郑鹭飞[1] 王静[1] 金芬[1] YUE Ning;LI Xiao-hui;LI Min-jie;WANG Qi;SHAO Hua;ZHENG Lu-fei;WANG Jing;JIN Fen(Institute of Quality Standard and Testing Technology for Agro-products,Chinese Academy of Agricultural Science,Beijing 100081,China)

机构地区：[1]中国农业科学院农业质量标准与检测技术研究所,北京100081

出　　处：《分析测试学报》2022年第6期805-811,共7页Journal of Instrumental Analysis

基　　金：国家重点研发计划(2018YFC1602403)。

摘　　要：建立了超高效液相色谱-四极杆/静电场轨道阱高分辨质谱(UPLC-Q/Orbitrap HRMS)非靶向筛查苹果中苯脲类农药的方法。样品采用QuEChERS法提取净化,Acquity BEH C_(18)色谱柱(100 mm×2.1 mm,1.7μm)分离,以甲醇和含0.1%甲酸的水溶液为流动相进行梯度洗脱,在电喷雾正离子模式下采用四极杆/静电场轨道阱高分辨质谱进行检测。将13种苯脲类除草剂和9种苯甲酰脲类杀虫剂按化学结构分为4类。首先通过对4类22种典型苯脲类农药标准品的准分子离子和二级质谱碎片进行分析,总结苯脲类农药的质谱裂解规律如下:绿麦隆等9种苯脲类除草剂的主要特征离子碎片为m/z 72.04459,可通过特征丢失中性分子二甲胺(m/z 45.05803)产生特征离子碎片;绿谷隆等4种苯脲类除草剂可通过特征丢失中性分子甲醇[CH_(3)OH]或卤化氢[HR_(1)](R=Cl,Br,F)产生离子碎片;除虫脲等7种含氟苯甲酰脲杀虫剂的主要特征离子碎片为m/z 158.04047、141.01500,也可发生特征中性丢失2,6-氟苯甲酰胺结构[C_(8)H_(3)F_(2)O_(2)NH_(2)](m/z 183.01321);杀铃脲等2种含氯苯甲酰脲类杀虫剂的主要特征离子碎片为m/z 156.02025、138.99376、113.01528。利用该方法对北京12份市售苹果进行非靶向筛查,在1份样品中筛查出绿麦隆。该方法可为快速筛查农产品中相似结构特征的苯脲类化合物提供参考。An ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry(UPLC-Q/Orbitrap HRMS)was established for the non-targeted screening of phenylurea herbicides and benzoylurea insecticides in apples.Apple samples were extracted with acetonitrile,then purified by QuEChERS method.The purified solution was separated on an Acquity BEH C_(18)column(100 mm×2.1 mm,1.7μm)using a gradient mobile phase consisting of water(containing 0.1%formic acid)and methanol,then analyzed by HRMS with electrospray ion source under positive ion mode.The 13 phenylurea herbicides and 9 benzoylurea insecticides were divided into four groups based on their structural differences.The secondary mass fragments of four typical standards in the four groups of phenylurea herbicides and benzoylurea insecticides were analyzed,and then,the regularities of the characteristic fragment ions and neutral loss fragments produced by collision induced dissociation of the phenylurea herbicides and benzoylurea insecticides were summarized.The main characteristic fragment ions of 9 herbicides such as chlorotoluron are m/z 72.04459,and fragments can also be produced by neutral loss of dimethylamine(m/z 45.05803).Four herbicides such as monolinuron lose neutral methanol[CH_(3)OH]m/z 23.02559 or hydrogen halide[HR_(1)](R=Cl,Br,F)to produce fragment ions.The main characteristic fragment ions of seven fluorine atom substituted benzoylurea insecticides such as diflubenzuron are m/z 158.04047 and m/z 141.01500,and the neutral loss of 2,6-fluorobenzamide structure[C_(8)H_(3)F_(2)O_(2)NH_(2)](m/z 183.01321)can produce characteristic fragment ions.The main characteristic fragment ions of triflumuron and chlorobenzuron,which were chlorine atom substituted benzoylurea insecticides,are m/z 156.02025,m/z 138.99376 and m/z 113.01528.A total of 12 apple samples collected from local supermarket in Beijing were screened by this non-targeted method.Chlorotoluron was identified and confirmed in one apple sample,which demonst

关 键 词：苯脲类除草剂 苯甲酰脲类杀虫剂 静电场轨道阱高分辨质谱 裂解规律 非靶向筛查 

分 类 号：O657.63[理学—分析化学] TS207.3[理学—化学]