液相色谱-串联质谱法测定蜂产品中吡虫啉及其3种代谢物
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摘要
建立了蜂蜜和蜂花粉中吡虫啉及其代谢物吡虫啉烯烃、吡虫啉脲、6-氯烟酸的液相色谱-串联质谱(LC-MS/MS)检测方法。在Qu ECh ERS方法基础上,针对目标物化学性质和样品杂质情况,对提取溶液的p H值、提取次数、净化材料等参数进行了优化。最终以5%甲酸-乙腈溶液提取两次,无水Mg SO_4、NaCl盐析分层,提取液经增强型脂类去除材料(EMR)净化,以LC-MS/MS进行测定,基质外标法进行定量分析。结果表明,蜂蜜和蜂花粉中吡虫啉、吡虫啉烯烃、吡虫啉脲、6-氯烟酸的平均加标回收率为86.0%~111.5%,相对标准偏差在1.7%~9.6%之间,检出限分别为0.20、3.50、0.40和14.00μg/kg,定量限分别为0.60、11.64、1.20和45.00μg/kg。本方法分析速度快、灵敏度高、重现性好,适用于蜂蜜和蜂花粉中吡虫啉及其3种代谢物的快速测定。
A method was developed for the determination of imidacloprid and its metabolites imidacloprid olefin,imidacloprid urea and 6-chloronicotinic acid in honey and bee pollen by liquid chromatography tandem mass spectrometry( LC-MS/MS). On the basis of typical Qu ECh ERS method,the p H and times of extraction solvent,sorbents were optimized to ensure the extraction efficiency and the purification of extraction. Finally,the method was developed as follows: matrix was extracted with 5% formic acid-acetonitrile twice,and the extraction was cleaned with enhanced matrix removal-lipid( EMR),detected with LC-MS/MS and quantified with external matrix standards. The results indicated that the average spiked recoveries of imidacloprid,imidacloprid olefin,imidacloprid urea and 6-chloronicotinic acid in honey and pollen samples were 86. 0%-111.5% with relative standard deviations( RSDs) of 1. 7%-9. 6%,the LODs were 0. 20,3. 50,0. 40 and14.00 μg/kg,and the LOQs were 0.60,11.64,1.20 and 45.00 μg/kg. The method was rapid and simple with high sensitivity and good reproducibility,and suitable for the determination of imidacloprid and its three metabolites residues in honey and bee pollen.
A method was developed for the determination of imidacloprid and its metabolites imidacloprid olefin,imidacloprid urea and 6-chloronicotinic acid in honey and bee pollen by liquid chromatography tandem mass spectrometry( LC-MS/MS). On the basis of typical Qu ECh ERS method,the p H and times of extraction solvent,sorbents were optimized to ensure the extraction efficiency and the purification of extraction. Finally,the method was developed as follows: matrix was extracted with 5% formic acid-acetonitrile twice,and the extraction was cleaned with enhanced matrix removal-lipid( EMR),detected with LC-MS/MS and quantified with external matrix standards. The results indicated that the average spiked recoveries of imidacloprid,imidacloprid olefin,imidacloprid urea and 6-chloronicotinic acid in honey and pollen samples were 86. 0%-111.5% with relative standard deviations( RSDs) of 1. 7%-9. 6%,the LODs were 0. 20,3. 50,0. 40 and14.00 μg/kg,and the LOQs were 0.60,11.64,1.20 and 45.00 μg/kg. The method was rapid and simple with high sensitivity and good reproducibility,and suitable for the determination of imidacloprid and its three metabolites residues in honey and bee pollen.
引文
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2 WANG Xiao-Hui,WAN Xiao-Chun,HOU Ru-Yan.Journal of Tea Science,2012,32(3):203-209王孝辉,宛晓春,侯如燕.茶叶科学,2012,32(3):203-209
3 ZHAO YI-Nan,GAO Jing-Lin,WANG Yu-Jie,LIU Jun-Feng,ZHAO Dong-Xiang.Agrochemicals,2014,53(3):206-209赵怡楠,高景林,王玉洁,刘俊峰,赵冬香.农药,2014,53(3):206-209
4 Decourtye A,Armengaud C,Renou M,Devillers J,Cluzeau S,Gauthier M,Pham-Delegue M H.Pestic.Biochem.Physiol.,2004,78(2):83-92
5 ZHANG Heng-Min,ZHAO Ping,YAN Qiu-Xu,LI Xin.Agrochemicals,2012,51(12):858-862张恒敏,赵平,严秋旭,李新.农药,2012,51(12):858-862
6 Cresswell J E.Ecotoxicology,2011,20(1):149-157
7 Whitehorn P R,O'Connor S,Wackers F L,Goulson D.Science,2012,336(6079):351-352
8 LIN Zhe-Guang,MENG Fei,ZHENG Huo-Qing,ZHOU Ting,HU Fu-Liang.Acta Entomol.Sin.,2014,57(5):607-615蔺哲广,孟飞,郑火青,周婷,胡福良.昆虫学报,2014,57(5):607-615
9 Suchail S,Guez D,Belzunces L P.Environ.Toxicol.Chem.,2001,20(11):2482-2486
10 LAN Shan-Shan,LIU Hong-Cheng,LI Qi-Wan,SHAO Jin-Liang,YANG Fang.J.Anal.Sci.,2011,27(2):171-174兰珊珊,刘宏程,黎其万,邵金良,杨芳.分析科学学报,2011,27(2):171-174
11 YANG Dong-Dong,CONG Lu-Jing,TIAN Ming-Ming,WANG Ming-Hua.Chinese J.Anal.Chem.,2014,42(6):872-877杨东冬,丛路静,田明明,王鸣华.分析化学,2014,42(6):872-877
12 Fidente P,Seccia S,Vanni F,Morrica P.J.Chromatogr.A,2005,1094(1-2):175-178
13 Martel A C,Lair C.Inter.J.Environ.Anal.Chem.,2011,91(10):978-988
14 Kamel A.J.Agric.Food Chem.,2010,58(10):5926-5931
15 Garcia M D G,Galera M M,Valverde R S,Galanti A,Girotti S.J.Chromatogr.A,2007,1147(1):17-23
16 Anastassiades M,Lehotay S J,Stajnbaher D,Schenck F J.J.AOAC Int.,2003,86(2):412-431
17 Wiesta L,Bulete A,Giroud B,Fratta C,Amic S,Lambert O,Pouliquen H,Arnaudguilhem C.J.Chromatogr.A,2011,1218(34):5743-5756
18 Li Y,Kelley R A,Anderson T D,Lydy M J.Talanta,2015,140:81-87
19 Han L J,Matarrita J,Sapozhnikova Y,Lehotay S J.J.Chromatogr.A,2016,1449:17-29
20 SONG Shu-Ling,LI Chong-Jiu,MA Xiao-Dong,RAO Zhu,WEI Qian.Chinese J.Anal.Chem.,2008,36(11):1526-1530宋淑玲,李重九,马晓东,饶竹,韦倩.分析化学,2008,36(11):1526-1530
21 Nardic D,Bonellif.Rapid.Commun.Mass Spectrom.,2006,20(18):2709-2716