两种叶菜中5种典型手性农药对映体的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法研究
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摘要
基于手性固定相/超高效液相色谱-串联质谱技术建立了同时拆分2种叶菜类蔬菜(菜心、油麦菜)中5种典型手性农药(多效唑、腈菌唑、甲霜灵、三唑酮和唑菌酮)对映体的分析方法。样品用乙腈提取,N-丙基乙二胺(PSA)粉和石墨化碳黑(GCB)粉净化,经手性色谱柱CHIRALCEL OD-RH拆分后,超高效液相色谱-串联质谱(UPLC-MS/MS)检测。结果表明,5种手性农药在0.005~1.0 mg·L-1范围内均呈良好线性关系;在0.01、0.1、0.5 mg·kg-1加标水平下的平均回收率为68.8%~104%,相对标准偏差(n=6)为1.0%~13.7%。该方法准确、简单、可靠,可以满足叶菜类蔬菜中多种手性农药残留的检测要求,并为这5种手性农药对映体在蔬菜中的残留及消解规律研究提供技术支持。
A method based on ultra performance liquid chromatography-tandem mass spectrometry with chiral stationary phase was developed for the simultaneous analysis of five chiral pesticide residues( paclobutrazo,myclobutanil,metalaxyl,triazolone and famoxadone) in leafy vegetables,including Chinese flowering cabbage and leaf lettuce. The sample was extracted with acetonitrile,then purified with primary secondary amine and graphitized carbon black. The upper clear liquid was filtered after centrifugation. After separated with a CHIRRALCEL OD-RH chiral column,the extract was detected using UPLC-MS/MS. Results indicated that the calibration curves of the five chiral pesticides showed good linear relationships in the concentration range of 0. 005-1. 0 mg·L-1. The recoveries at three spiked levels of 0. 01,0. 1,0. 5 mg·kg-1 were in the range of 68. 8%-104%with relative standard deviations of 1. 0%-13. 7%. This method is rapid,convenient and reliable,and could meet the requirements for residue analysis,and could provide a technical support for the investigation on five chiral pesticides residues in vegetables and their digestion regularity.
A method based on ultra performance liquid chromatography-tandem mass spectrometry with chiral stationary phase was developed for the simultaneous analysis of five chiral pesticide residues( paclobutrazo,myclobutanil,metalaxyl,triazolone and famoxadone) in leafy vegetables,including Chinese flowering cabbage and leaf lettuce. The sample was extracted with acetonitrile,then purified with primary secondary amine and graphitized carbon black. The upper clear liquid was filtered after centrifugation. After separated with a CHIRRALCEL OD-RH chiral column,the extract was detected using UPLC-MS/MS. Results indicated that the calibration curves of the five chiral pesticides showed good linear relationships in the concentration range of 0. 005-1. 0 mg·L-1. The recoveries at three spiked levels of 0. 01,0. 1,0. 5 mg·kg-1 were in the range of 68. 8%-104%with relative standard deviations of 1. 0%-13. 7%. This method is rapid,convenient and reliable,and could meet the requirements for residue analysis,and could provide a technical support for the investigation on five chiral pesticides residues in vegetables and their digestion regularity.
引文
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[21]GB/T23200.46-2016.National Food Safety Standards—Determination of Pyrimethanil,Mepanipyrim,Myclobutanil and Azoxystrobin Residues in Foods Gas Chromatography-Mass Spectrometry.National Standards of the People's Republic of China(食品安全国家标准食品中嘧霉胺、嘧菌胺、腈菌唑、嘧菌酯残留量的测定气相色谱-质谱法.中华人民共和国国家标准).
[22]GB/T20769-2008.Determination of 450 Pesticides and Related Chemicals Residues in Fruits and Vegetables-LC-MS/MS Method.National Standards of the People's Republic of China(水果和蔬菜中450种农药及相关化学品残留量的测定液相色谱-串联质谱法.中华人民共和国国家标准).
[23]GB/T23200.8-2016.National Food Safety Standards—Determination of 500 Pesticides and Related Chemicals Residues in Fruits and Vegetables Gas Chromatography-Mass Spectrometry.National Standards of the People's Republic of China(食品安全国家标准水果和蔬菜中500种农药及相关化学品残留量的测定气相色谱-质谱法.中华人民共和国国家标准).
[24]De M A S,Caboni P,Cabras P,Luigi G V,Alves A.Anal.Chim.Acta,2006,573/574(1):291.
[25]GB/T2763-2016.National Food Safety Standard—Maximum Residue Limits for Pesticides in Food.National Standards of the People's Republic of China(食品安全国家标准食品中农药最大残留限量.中华人民共和国国家标准).
[26]Wang M Y.Study on Stereoselective Degradation of Chiral Pesticide Metalaxyl.Nanjing:Nanjing Agricultural University(王美云.手性农药甲霜灵的立体选择性降解研究.南京:南京农业大学),2014.
[27]Sun M J.Study on the Environmental Behavior of Four Chiral Triazole Pesticides Enatiomers.Beijing:China Agricultural University(孙明婧.四种三唑类手性农药的环境行为研究.北京:中国农业大学),2014.
[28]Song S L,Li C J,Ma X D,Rao Z,Wei Q.Chin J.Anal.Chem.(宋淑玲,李重九,马晓东,饶竹,韦倩.分析化学),2008,36(11):1526-1530.
[2]Liu W P,Xu C,Zhou S S.Environ.Chem.(刘维屏,徐超,周珊珊.环境化学),2006,25(3):247-251.
[3]Zhang Q,Wang C,Zhang X F,Jin D Q,Huang C J,Zhao M R.Environ.Monit.,2012,14:465-472.
[4]Ye J,Zhao M R,Liu J,Liu W P.Environ.Pollut.,2010,158(7):2371-2383.
[5]Dong F S,Chen X,Xu J,Liu X G,Chen Z L,Li Y B,Zhang H J,Zheng Y Q.Chirality,2013,25(12):904-909.
[6]Gao Y X,Wang H L,Qin F,Xu P,Lv X T,Li J Z,Guo B Y.Chirality,2014,26(2):88.
[7]Deng Z B,Hu J Y.Agrochemicals(邓朱波,胡继业.农药),2011,50(5):371-373.
[8]Wang P,Jiang S R,Liu D H,Wang P,Zhou Z Q.Biochem.Biop.Methods,2005,62(3):219-230.
[9]Lan S S,Lin T,Lin X,Yang F,Sha L J,Liu H C.Chin.J.Pestici.Sci.(兰珊珊,林涛,林昕,杨芳,沙凌杰,刘宏程.农药学学报),2016,18(5):612-618.
[10]Su S F,Xue X,Wang J,Wang Y L,Zhang H,Hu M.Chem.Res.Appl.(宿书芳,薛霞,王骏,王艳丽,张卉,胡梅.化学研究与应用),2014,26(3):460-463.
[11]Zheng X H,Pan Y B,LüD Z,Xie D F,Feng X P.Chin.J.Tropic.Agric.(郑雪虹,潘永波,吕岱竹,谢德芳,冯信平.热带农业科学),2013,33(9):50-54.
[12]Lou Z Y,Tang F B,Luo F J,Liu G M,Chen Z M.Agrochemicals(楼正云,汤富彬,罗逢健,刘光明,陈宗懋.农药),2008,47(3):205-207.
[13]Xu H,Li Z,Zhao H,Wu M,Hu X Q.Agrochemicals(徐浩,李振,赵华,吴珉,胡秀卿.农药),2006,45(3):184-185.
[14]Liu C Y,Wan K,Huang J X,Wang Y C,Wang F H.Ecotoxicol.Environ.Saf.Sci.,2011,84:112-116.
[15]Cheng C,Huang L,Diao J,Zhou Z Q.Chirality,2013,25(12):858.
[16]Li R,Chu D K,Zhang P J,Gao Y Q,Huang S Y.J.Instrum.Anal.(李蓉,储大可,张朋杰,高永清,黄思允.分析测试学报),2015,34(5):502-511.
[17]Liang L,Li W P,Liu W.Pestic.Sci.Admin.(梁林,李文平,刘伟.农药科学与管理),2017,38(3):34-37.
[18]Tian Q,Ren L P,LüC G,Zhou Z Q.Chin.Anal.Chem.(田芹,任丽萍,吕春光,周志强.分析化学),2010,38(5):688-692.
[19]Bai X H,Han X Q,Zhao L,Lei X Y.J.Tianshui Normal Univ.(白小华,韩小茜,赵丽,雷新有.天水师范学院学报),2007,27(2):47-48.
[20]Zhang X Z,Zhao Y C,Luo F J,Chen Z M,Cui X Y,Zhou L,Lou Z Y.J.Instrum.Anal.(张新忠,赵悦臣,罗逢健,陈宗懋,崔新仪,周利,楼正云.分析测试学报),2016,35(11):1376-1383.
[21]GB/T23200.46-2016.National Food Safety Standards—Determination of Pyrimethanil,Mepanipyrim,Myclobutanil and Azoxystrobin Residues in Foods Gas Chromatography-Mass Spectrometry.National Standards of the People's Republic of China(食品安全国家标准食品中嘧霉胺、嘧菌胺、腈菌唑、嘧菌酯残留量的测定气相色谱-质谱法.中华人民共和国国家标准).
[22]GB/T20769-2008.Determination of 450 Pesticides and Related Chemicals Residues in Fruits and Vegetables-LC-MS/MS Method.National Standards of the People's Republic of China(水果和蔬菜中450种农药及相关化学品残留量的测定液相色谱-串联质谱法.中华人民共和国国家标准).
[23]GB/T23200.8-2016.National Food Safety Standards—Determination of 500 Pesticides and Related Chemicals Residues in Fruits and Vegetables Gas Chromatography-Mass Spectrometry.National Standards of the People's Republic of China(食品安全国家标准水果和蔬菜中500种农药及相关化学品残留量的测定气相色谱-质谱法.中华人民共和国国家标准).
[24]De M A S,Caboni P,Cabras P,Luigi G V,Alves A.Anal.Chim.Acta,2006,573/574(1):291.
[25]GB/T2763-2016.National Food Safety Standard—Maximum Residue Limits for Pesticides in Food.National Standards of the People's Republic of China(食品安全国家标准食品中农药最大残留限量.中华人民共和国国家标准).
[26]Wang M Y.Study on Stereoselective Degradation of Chiral Pesticide Metalaxyl.Nanjing:Nanjing Agricultural University(王美云.手性农药甲霜灵的立体选择性降解研究.南京:南京农业大学),2014.
[27]Sun M J.Study on the Environmental Behavior of Four Chiral Triazole Pesticides Enatiomers.Beijing:China Agricultural University(孙明婧.四种三唑类手性农药的环境行为研究.北京:中国农业大学),2014.
[28]Song S L,Li C J,Ma X D,Rao Z,Wei Q.Chin J.Anal.Chem.(宋淑玲,李重九,马晓东,饶竹,韦倩.分析化学),2008,36(11):1526-1530.