高效液相色谱-串联质谱法测定中草药中多种新烟碱类农药的残留量
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摘要
目的建立液相色谱-串联质谱分析法同时测定中草药夏枯草、野菊花、金银花、苏银花中噻虫嗪、氯噻啉、吡虫啉、啶虫脒、噻虫胺、噻虫啉6种新烟碱类农药残留量。方法样品中的6种新烟碱类杀虫剂经乙腈提取,QuEChERS方法净化后,液相色谱-串联质谱法分离和测定,外标法定量。结果方法检出限为0.1～4.8μg/kg,在方法的检测限与200 ng/mL测定范围内有良好的线性关系(r>0.9990),在所添加5个水平浓度下,方法的回收率在70.4%～108.3%,相对标准偏差在1.0%～8.8%。结论该方法准确、简单、快速,适用于中草药中多种新烟碱类农药的同时检测。
Objective To establish a method for simultaneous determination of 6 neonicotinoid insecticides residues(thiamethoxam, imidaclothiz, imidacloprid, acetamiprid, clothianidin and thiacloprid) in Chinese herbal medicine of selfheal, wild chrysanthemum, honeysuckle, and honeysuckle bud by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods Totally 6 neonicotinoid insecticides in the sample were extracted by acetonitrile, purified by QuEChERS method, separated and determined by liquid chromatography-tandem mass spectrometry, and quantified by external standard method. Results The limits of detection of the method were 0.1-4.8 g/kg, and there were good linear relationships between the limits of detection of the method and the determination range of 200 ng/mL(r>0.9990). The recoveries of the method were 70.4%-108.3%and the relative standard deviations were 1.0%-8.8% at the addition of 5 levels of concentration. Conclusions The method is accurate, simple and rapid, which is suitable for simultaneous detection of several neonicotinoid pesticides in Chinese herbal medicine.
Objective To establish a method for simultaneous determination of 6 neonicotinoid insecticides residues(thiamethoxam, imidaclothiz, imidacloprid, acetamiprid, clothianidin and thiacloprid) in Chinese herbal medicine of selfheal, wild chrysanthemum, honeysuckle, and honeysuckle bud by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods Totally 6 neonicotinoid insecticides in the sample were extracted by acetonitrile, purified by QuEChERS method, separated and determined by liquid chromatography-tandem mass spectrometry, and quantified by external standard method. Results The limits of detection of the method were 0.1-4.8 g/kg, and there were good linear relationships between the limits of detection of the method and the determination range of 200 ng/mL(r>0.9990). The recoveries of the method were 70.4%-108.3%and the relative standard deviations were 1.0%-8.8% at the addition of 5 levels of concentration. Conclusions The method is accurate, simple and rapid, which is suitable for simultaneous detection of several neonicotinoid pesticides in Chinese herbal medicine.
引文
[1]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.Lyu CG,Wang S,He XH,et al.Status and further development of regulation for pesticide registration for chinese medicinal materials[J].China J Chin Mater Med,2018,43(19):3984-3988.
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[8]黄超群,黄雪,吴娟,等.多壁碳纳米管分散固相萃取-液相色谱-串联质谱法测定茶叶中5种烟碱类农药的残留量[J].理化检验-化学分册,2018,54(5):584-590.Huang CQ,Huang X,Wu J,et al.Determination of residues of five nicotine pesticides in tea by multiwalled carbon nanotubes dispersive solid phase extraction-liquid chromatography-tandem mass spectrometry[J].Phys Test Chem Anal Part B,2018,54(5):584-590.
[9]Lu Z,Fang N,Zhang ZB,et al.Simultaneous determination of five neonicotinoid insecticides in edible fungi using ultrahigh-performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS)[J].Food Anal Methods,2018,11(4):1086-1094.
[10]Watanabe E,Iwafune T,Baba K,et al.Organic solvent-saving sample preparation for systematic residue analysis of neonicotinoid insecticides in agricultural products using liquid chromatography-diode array detection[J].Food Anal Methods,2016,9(1):245-254.
[11]Kruve A,Künnapas A,Herodes K,et al.Matrix ffects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry[J].JChromatogr A,2008,1187:58-66.
[12]曾广丰,王志元,陈文锐,等.QuEChERS前处理技术与LC-Q-TOF-MS法测定蔬菜中7种烟碱类农药残留[J].检验检疫学刊,2015,15(4):5-8.ZENG GF,Wang ZY,Chen WR,et al.Determination of seven kinds of nicotinoid insecticides in vegetables by LC-Q-TOF-MS with QuEChERS[J].J Inspect Quarant,2015,15(4):5-8.
[13]谢文,钱艳,侯建波,等.棉花中7种烟碱类农药残留的液相色谱-串联质谱法测定[J].纺织学报,2014,35(9):100-107.Xie W,Qian Y,Hou JB,et al.Determination of seven neonicotinoid pesticide residues in cotton samples by high performance liquid chromatography tandem mass spectrometry[J].J Text Res,2014,35(9):100-107.
[14]吕岱竹,罗金辉,王明月,等.超高压液相色谱-串联质谱法测定含硫蔬菜中烟碱类农药残留[J].农药,2011,50(5):359-361.Lu DZ,Luo JH,Wang MY,et al.Determination of nicotinoid pesticides resdues in vegetable with sulfur matrix by ultra-performance liquid chromatography-electrospray tandem mass spectrometry[J].Agrochemicals,2011,50(5):359-361.
[15]GB/T 27404-2008实验室质量控制规范食品理化检测[S].GB/T 27404-2008 Criterion on quality control of laboratories-Chemical testing of food[S].
[16]CAC/GL 40-1993 Guidelines on good laboratory practice in pesticide residue analysis[S].
[2]谭和平,李怀平,王顾希.我国中药材卫生质量标准与检测技术研究[J].中国测试,2016,42(1):1-6.Tan HP,Li HP,Wang GX.Research of hygienic quality standards and detection technology of traditional Chinese medicine[J].China Measure Test,2016,42(1):1-6.
[3]李慧君,张文生,吴洁珊,等.中药材农药残留研究现状[J].中国中药杂志,2019,44(1):48-52.Li HJ,Zhang WS,Wu JS,et al.Research progress of pesticide residues in traditional chinese medicines[J].China J Chin Mater Med,2019,44(1):48-52.
[4]《中国药典》四部[M].北京:中国医药科技出版社出版,2015.Chinese Pharmacopoeia,volume IV[M].Beijing:Published by China Medical Science and Technology Press,2015.
[5]Lu Z,Fang N,Zhang ZB,et al.Simultaneous determination of five neonicotinoid insecticides in edible fungi using ultrahigh-performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS)[J].Food Anal Methods,2018,11(4):1086-1094.
[6]乔琳.新烟碱类杀虫剂在金银药种植与加工过程中的降解及安全性评价[D].合肥:安微农业大学,2014.Qian L.New neonicotinoid insecticides in honeysuckle planting and processing in the process of biodegradation and safety evaluation[D].Hefei:Anhui Agricultural University,2014.
[7]段丽村,徐芳,夏清海,等.QuEChERS-高效液相色谱法测定云南省食用花卉中4种烟碱农药残留[J].现代预防医学,2016,43(20):3780-3784.Duàn LC,Xu F,Xia QH,et al.Determination of 4 neonicotinoid pesticides residues in edible flowers in Yunnan by QuEChERS-HPLC[J].Mod Prev Med,2016,43(20):3780-3784.
[8]黄超群,黄雪,吴娟,等.多壁碳纳米管分散固相萃取-液相色谱-串联质谱法测定茶叶中5种烟碱类农药的残留量[J].理化检验-化学分册,2018,54(5):584-590.Huang CQ,Huang X,Wu J,et al.Determination of residues of five nicotine pesticides in tea by multiwalled carbon nanotubes dispersive solid phase extraction-liquid chromatography-tandem mass spectrometry[J].Phys Test Chem Anal Part B,2018,54(5):584-590.
[9]Lu Z,Fang N,Zhang ZB,et al.Simultaneous determination of five neonicotinoid insecticides in edible fungi using ultrahigh-performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS)[J].Food Anal Methods,2018,11(4):1086-1094.
[10]Watanabe E,Iwafune T,Baba K,et al.Organic solvent-saving sample preparation for systematic residue analysis of neonicotinoid insecticides in agricultural products using liquid chromatography-diode array detection[J].Food Anal Methods,2016,9(1):245-254.
[11]Kruve A,Künnapas A,Herodes K,et al.Matrix ffects in pesticide multi-residue analysis by liquid chromatography-mass spectrometry[J].JChromatogr A,2008,1187:58-66.
[12]曾广丰,王志元,陈文锐,等.QuEChERS前处理技术与LC-Q-TOF-MS法测定蔬菜中7种烟碱类农药残留[J].检验检疫学刊,2015,15(4):5-8.ZENG GF,Wang ZY,Chen WR,et al.Determination of seven kinds of nicotinoid insecticides in vegetables by LC-Q-TOF-MS with QuEChERS[J].J Inspect Quarant,2015,15(4):5-8.
[13]谢文,钱艳,侯建波,等.棉花中7种烟碱类农药残留的液相色谱-串联质谱法测定[J].纺织学报,2014,35(9):100-107.Xie W,Qian Y,Hou JB,et al.Determination of seven neonicotinoid pesticide residues in cotton samples by high performance liquid chromatography tandem mass spectrometry[J].J Text Res,2014,35(9):100-107.
[14]吕岱竹,罗金辉,王明月,等.超高压液相色谱-串联质谱法测定含硫蔬菜中烟碱类农药残留[J].农药,2011,50(5):359-361.Lu DZ,Luo JH,Wang MY,et al.Determination of nicotinoid pesticides resdues in vegetable with sulfur matrix by ultra-performance liquid chromatography-electrospray tandem mass spectrometry[J].Agrochemicals,2011,50(5):359-361.
[15]GB/T 27404-2008实验室质量控制规范食品理化检测[S].GB/T 27404-2008 Criterion on quality control of laboratories-Chemical testing of food[S].
[16]CAC/GL 40-1993 Guidelines on good laboratory practice in pesticide residue analysis[S].