荔枝与龙眼中噻虫啉、螺虫乙酯及代谢物的高效液相色谱-串联质谱分析
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摘要
采用高效液相色谱-串联三重四极杆质谱结合QuEChERS前处理技术,建立了同时测定荔枝和龙眼中噻虫啉、螺虫乙酯及4种代谢物残留的分析方法。样品采用乙腈作为提取溶剂,经十八烷基键合硅胶(C18)与石墨化碳黑(GCB)吸附剂净化后,由Poroshell-120 EC-C18色谱柱分离,以0. 1%(体积分数)甲酸水溶液-乙腈为流动相等度洗脱,在电喷雾电离(ESI+)和多反应监测模式下进行检测,外标法定量分析。该方法的线性范围为1～500μg/L,相关系数(r~2)均大于0. 990,检出限(LOD)为0. 03～0. 3μg/kg,定量下限(LOQ)为0. 1～1. 5μg/kg。荔枝和龙眼中噻虫啉、螺虫乙酯及4种代谢物在1、10、100μg/kg加标水平下的平均回收率为80. 4%～99. 5%,相对标准偏差(RSD)为1. 4%～6. 4%。该方法操作简单、灵敏度高、准确性好、可靠性强,可满足荔枝和龙眼等水果中噻虫啉、螺虫乙酯及代谢物的快速筛查监测要求。
An analytical method was established for the determination of thiacloprid,spirotetramat and its four metabolites residues in litchi and longan by high performance liquid chromatography-tandem mass spectrometry( HPLC-MS/MS) with Qu EChERS cleanup. The residues in samples were extracted with acetonitrile,dehydrated with anhydrous magnesium sulfate and sodium chloride,then purified with C18 and GCB. The extract was separated on a Poroshell-120 EC-C18 column with0. 1% formic acid-acetonitrile as mobile phase by isocratic elution,detected by HPLC-MS/MS with positive electrospray ion source in multi-reaction monitoring( MRM) mode,and quantified by external standard method. Results showed that there existed good linearities for six analytes in the range of 1-500 μg/L with their correlation coefficients( r~2) more than 0. 990. The limits of detection( LODs) and limits of quantitation( LOQs) were 0. 03-0. 3 μg/kg and 0. 1-1. 5 μg/kg,respectively. The average recoveries for the analytes at spiked levels of 1,10,100 μg/kg were in the range of 80. 4%-99. 5% with relative standard deviations of 1. 4%-6. 4%. The developed method was simple,sensitive,accurate and reliable,and could meet the requirements for rapid screening and monitoring of thiacloprid,spirotetramat and its metabolites in fruits such as litchi and longan.
An analytical method was established for the determination of thiacloprid,spirotetramat and its four metabolites residues in litchi and longan by high performance liquid chromatography-tandem mass spectrometry( HPLC-MS/MS) with Qu EChERS cleanup. The residues in samples were extracted with acetonitrile,dehydrated with anhydrous magnesium sulfate and sodium chloride,then purified with C18 and GCB. The extract was separated on a Poroshell-120 EC-C18 column with0. 1% formic acid-acetonitrile as mobile phase by isocratic elution,detected by HPLC-MS/MS with positive electrospray ion source in multi-reaction monitoring( MRM) mode,and quantified by external standard method. Results showed that there existed good linearities for six analytes in the range of 1-500 μg/L with their correlation coefficients( r~2) more than 0. 990. The limits of detection( LODs) and limits of quantitation( LOQs) were 0. 03-0. 3 μg/kg and 0. 1-1. 5 μg/kg,respectively. The average recoveries for the analytes at spiked levels of 1,10,100 μg/kg were in the range of 80. 4%-99. 5% with relative standard deviations of 1. 4%-6. 4%. The developed method was simple,sensitive,accurate and reliable,and could meet the requirements for rapid screening and monitoring of thiacloprid,spirotetramat and its metabolites in fruits such as litchi and longan.
引文
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[2] Huang F,Zhang R F,Liu H J,Dong L H,Lai T,Zhang M W. J. Food Saf. Qual.(黄菲,张瑞芬,刘慧娟,董丽红,赖婷,张名位.食品安全质量检测学报),2015,6(5):1770-1775.
[3] Sheng K M,Wang H J. Chinese Journal of Experimental Traditional Medical Formula(盛康美,王宏洁.中国实验方剂学杂志),2010,16(5):236-238.
[4] Cai Y Q,Lai Z X,Wu M C,Chen Y T,Li G Q,Gong L F,Zheng W L,Lin X L. Chin. J. Eco-Agric.(蔡英卿,赖钟雄,伍妙聪,陈义挺,李国清,龚丽芬,郑文炉,林秀莲.中国生态农业学报),2007,15(4):86-88.
[5] Zhen Q T,Chen Y L,Wang S Y,Yu Y R,Lu P,Hu D Y,Yang Z H. Biomed. Chromatogr.,2017,32(4):4153-4164.
[6] Hao C Y,Morse D,Zhao X M,Sui L. Rapid Commun. Mass Spectrom.,2015,2225-2232.
[7] He Q,Xu Y B,Wang C H,Tian Z F,Zhu D L. Tobacco Chem.(何庆,徐迎波,王程辉,田振锋,朱栋梁.烟草化学),2011,(12):52-55.
[8] Wang D D,Chen Y,Song N H,Wu W Z,Shi L L. J. Instrum. Anal.(王点点,陈源,宋宁慧,吴文铸,石利利.分析测试学报),2013,32(1):138-142.
[9] Yang D D,Cong L J,Tian M M,Wang M H. Chin. J. Anal. Chem.(杨东冬,丛路静,田明明,王鸣华.分析化学),2014,42(6):872-877.
[10] Zhang Z,Wu Z P,Zhang X Q,Lu J. Food Sci.(张征,武中平,张晓强,卢剑.食品科学),2011,32(24):241-243.
[11] Song N H,Wang D D,Wu W Z,Kong D Y,Li J Y,He J,Shan Z J. Acta Science Circumstantiae(宋宁慧,王点点,吴文铸,孔德洋,李菊颖,何健,单正军.环境科学学报),2014,34(8):2169-2174.
[12] Dong S,Qiao K,Wang H Y,Zhu Y K,Xia X M,Wang K Y. Pest. Manag. Sci.,2014,70:1267-1273.
[13] Kabir M H,Ei-Aty A M A,Rahman M M,Kim S W,Choi J H,Lee Y J,Truong L T B,Lee K B,Kim M R,Shin H C,Shim J H. Biomed. Chromatogr.,2017,31:1-7.
[14] Kooner R,Sahoo S K,Singh B,Battu R S. Quality Aasurance and Safety of Crops&Foods,2010,2(1):36-40.
[15] Saimandir J,Gopal M,Walia S. Pest. Manag. Sci.,2009,65:210-215.
[16] Tian H Z,Du F,Yuan X F,Xu J. Agrochemicals(田宏哲,杜芳,苑馨方,徐静.农药),2015,54(4):289-291.
[17] Guo Q L,Guan X F,Zhao Y,Li R J,Yu J L. Phys. Test. Chem. Anal.:Chem. Anal.(郭庆龙,管旭芳,赵勇,李瑞娟,于建垒.理化检验-化学分册),2017,53(8):885-889.
[18] Shi Y,Zhang X G,Wang X,He Y B,Zheng X P. Food&Machinery(施雅,张小刚,王霞,何亚斌,郑小平.食品与机械),2014,30(5):93-96.
[19] Han B J,Lin B,Huang H Z,He Y,Chen L X. Food Sci. Technol.(韩丙军,林冰,黄海珠,何燕,陈丽霞.食品科技),2017,42(12):297-302.
[20] Cui S H,Li Z Y,Cheng G,Li R J,Wang Y,Zhang X Y,Zhao F. Food Sci.(崔淑华,李正义,程刚,李瑞娟,王宇,张雪琰,赵峰.食品科学),2018,39(8):302-308.
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