液相色谱-串联质谱法测定豇豆及其栽培土壤中吡唑萘菌胺及其代谢物和嘧菌酯
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摘要
目的建立用于豇豆及土壤中吡唑萘菌胺及其代谢物和嘧菌酯残留量检测的液相色谱-串联质谱方法。方法采用水和乙腈提取匀浆后豇豆和土壤样品,经N-丙基乙二胺和无水硫酸镁净化,使用甲醇(A)和0.05%甲酸水(B)作为流动相进行梯度洗脱,质谱(ESI+)采用多反应监测(multiple reaction monitoring,MRM)对吡唑萘菌胺及其代谢物和嘧菌酯的定量离子和定性离子进行扫描,结合目标物标准曲线进行定量分析。结果经过3个水平的添加回收率实验,建立方法的平均回收率在74%~101%之间,相对标准偏差0.9%~9.2%(n=5)。吡唑萘菌胺顺式异构体(SYN 534969)、吡唑萘菌胺反式异构体(SYN 534968)、吡唑萘菌胺代谢物一(SYN545364)、吡唑萘菌胺代谢物二(SYN 545449)和嘧菌酯的仪器检出限分别为0.1、0.1、0.1、0.8和0.03 mg/kg,加标回收实验得出吡唑萘菌胺代谢物二(SYN 545449)在豇豆和土壤中的最低检出浓度均为0.05 mg/kg,吡唑萘菌胺顺式异构体、反式异构体、吡唑萘菌胺代谢物一(SYN 545364)及嘧菌酯的最低检出浓度均为0.005 mg/kg。结论该方法简单、快速、准确,灵敏度高,适用于豇豆及土壤中吡唑萘菌胺及其代谢物和嘧菌酯残留量检测。
Objective To establish a method for simultaneous determination of azoxystrobin and isopyrazam residues and its degradation products in cowpea and soil by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods Cowpea and soil samples after homogenate were extracted by acetonitrile and water, purified by PSA and dehydrated by magnesium sulfate anhydrous, gradient elution using methanol(A) and 0.05% formic acid water(B) as the mobile phase. Quantitative and qualitative ions of pyrazole naphthylamine and its metabolites and cyprolactone were scanned and quantitatively analyzed in combination with the standard curve of the target substance. Results The average recoveries of the method were between 74%-101% for 3 spiked levels, and the relative standard deviations were 0.9%-9.2%(n=5). Instrument limits of detection(LODs) of cis-isomer and trans-isomer of isopyrazam, SYN 545364, SYN 545449 and azoxystrobin were 0.1, 0.1, 0.1, 0.8 and 0.03 μg/kg, respectively. The results of recoveries showed that the lowest detectable concentrations in cowpea and soil were 0.05 mg/kg for SYN 545449, and 0.005 mg/kg for cis-isomer and trans-isomer of isopyrazam, SYN 545364 and azoxystrobin. Conclusion The method is simple, rapid, accurate, and had the advantages of high sensitivity. It is suitsble for the detection of azoxystrobin and isopyrazam residues and its degradation products in cowpea and soil.
Objective To establish a method for simultaneous determination of azoxystrobin and isopyrazam residues and its degradation products in cowpea and soil by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS). Methods Cowpea and soil samples after homogenate were extracted by acetonitrile and water, purified by PSA and dehydrated by magnesium sulfate anhydrous, gradient elution using methanol(A) and 0.05% formic acid water(B) as the mobile phase. Quantitative and qualitative ions of pyrazole naphthylamine and its metabolites and cyprolactone were scanned and quantitatively analyzed in combination with the standard curve of the target substance. Results The average recoveries of the method were between 74%-101% for 3 spiked levels, and the relative standard deviations were 0.9%-9.2%(n=5). Instrument limits of detection(LODs) of cis-isomer and trans-isomer of isopyrazam, SYN 545364, SYN 545449 and azoxystrobin were 0.1, 0.1, 0.1, 0.8 and 0.03 μg/kg, respectively. The results of recoveries showed that the lowest detectable concentrations in cowpea and soil were 0.05 mg/kg for SYN 545449, and 0.005 mg/kg for cis-isomer and trans-isomer of isopyrazam, SYN 545364 and azoxystrobin. Conclusion The method is simple, rapid, accurate, and had the advantages of high sensitivity. It is suitsble for the detection of azoxystrobin and isopyrazam residues and its degradation products in cowpea and soil.
引文
[1]Dubos T,Pasquali M,Pogoda F,et al.Differences between the succinate dehydrogenase sequences of isopyrazam sensitive Zymoseptoria tritici and insensitive Fusarium graminearum strains[J].Pest Biochem Phys,2013,105(1):28-35.
[2]李良孔,袁善奎,潘洪玉,等.琥珀酸脱氢酶抑制剂类(SDHIs)杀菌剂及其抗性研究进展[J].农药,2011,50(3):165-169.Li LK,Yuan SK,Pan HY,et al.Progress in research on SDHIs fungicides and its resistance[J].Agrochemicals,2011,50(3):165-169.
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[6]杨欢,孙伟华,曹赵云,等.改良QuEChERS方法快速测定果蔬中8种新型琥珀酸脱氢酶抑制剂类杀菌剂[J].色谱,2016,34(11):1070-1076.Yang H,Sun WH,Cao ZY,et al.Determination of eight novel succinate dehydrogenase inhibitor fungicides in vegetables and fruits by modified Qu ECh ERS[J].Chin J Chromatogr,2016,34(11):1070-1076.
[7]陈祥准,夏碧琪,黄芙珍,等.液相色谱-串联质谱法同时测定葡萄酒中6种吡唑类杀菌剂[J].分析测试学报,2015,34(11):1311-1314.Chen XZ,Xia BQ,Huang FZ,et al.Simultaneous determination of six pyrazole fungicides in grape wine by liquid chromatography-tandem mass spectrometry[J].J Instrum Anal,2015,34(11):1311-1314.
[8]郑振山,陈勇达,张少军,等.气相色谱法测定黄瓜中吡唑萘菌胺及其代谢物[J].食品安全质量检测学报,2016,7(2):540-544.Zheng ZS,Chen YD,Zhang SJ,et al.Determination of isopyrazam residues and its degradation products in cucumber by gas chromatography[J].J Food Saf Qual,2016,7(2):540-544.
[9]智沈伟,赵尔成,李兴海,等.气相色谱-串联质谱法测定西瓜和黄瓜中吡唑萘菌胺及其代谢物残留[J].农药学学报,2018,(2):217-222.Zhi SW,Zhao EC,Li XH,et al.Determination of isopyrazam and its metabolites residues in watermelon and cucumber by gas chromatography-tandem mass spectrometry[J].Chin J Pest Sci,2018,(2):217-222.
[10]范丽丽,王娟,吴加伦.气相色谱法测定铁皮石斛、浙贝母和人参中嘧菌酯残留[J].分析科学学报,2017,33(2):222-226.Fan LL,Wang J,Wu JL.Determination of azoxystrobin residues in dendrobium of ficinale,fritiliariae thunbergii and panax ginseng by gas chromatography[J].J Anal Sci,2017,33(2):222-226.
[11]薄海波,毕阳,陈立仁.气相色谱法测定甜瓜和苹果中嘧菌酯残留[J].分析化学,2005,33(5):695-698.Bi HB,Bi Y,Chen LR.Determination of azoxystrobin residues in muskmelon and apple by gas chromatography[J].Chin J Anal Chem,2005,33(5):695-698.
[12]侯雪,韩梅,邱世婷,等.改进的QuEChERS气相色谱-串联质谱法测定草莓中21种杀菌剂残留[J].农药学学报,2017,19(1):46-52.Hou X,Han M,Qiu ST,et al.Residues of 21 fungicides in Fragaria ananassa by modified QuEChERS and gas chromatography-tandem mass spectrometry[J].Chin J Pest Sci,2017,19(1):46-52.
[13]石峰,赵科华,车军,等.高效液相色谱法分析砂糖桔中嘧菌酯残留[J].河北农业科学,2010,14(2):161-163.Shi F,Zhao KH,Che J,et al.Determination of residues azoxystrobin in citrus sha tang ju by HPLC[J].Hebei J Agric Sci,2010,14(2):161-163.
[14]张育乐,黄超群,朱晓雨,等.固相萃取-液相色谱-串联质谱法测定中药材中7种甲氧基丙烯酸酯类杀菌剂的残留量[J].色谱,2013,31(3):264-269.Zhang YL,Huang CQ,Zhu XY,et al.Determination of seven strobilurin fungicide residues in Chinese herbs by liquid chromatography-tandem mass spectrometry coupled with solid phase extraction[J].Chin JChromatogr,2013,31(3):264-269.
[15]徐永,梁赤周,虞淼,等.嘧菌酯在枇杷中残留及消解动态[J].农药科学与管理,2017,38(11):28-34.Xu Y,Liang CZ,Yu M,et al.Residue and degradation dynamics of azoxysstrobin in loquat[J].Pest Sci Admin,2017,38(11):28-34.
[16]Lehotay SJ,Son KA,Kwon H,et al.Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables[J].J Chromatogr A,2010,1217(16):2548-2560.
[2]李良孔,袁善奎,潘洪玉,等.琥珀酸脱氢酶抑制剂类(SDHIs)杀菌剂及其抗性研究进展[J].农药,2011,50(3):165-169.Li LK,Yuan SK,Pan HY,et al.Progress in research on SDHIs fungicides and its resistance[J].Agrochemicals,2011,50(3):165-169.
[3]申瑞平,宋莹莹,王秋红,等.两种新型琥珀酸脱氢酶抑制剂的抑菌活性比较[J].农药科学与管理,2014,35(8):52-57.Shen RP,Song YY,Wang QH,et al.Compare of fungistasis of two new succinate dehydrogenase inhibitor[J],Pest Sci Admin,2014,35(8):52-57.
[4]张红芬,佘世超,史建华,等.吡唑萘菌胺顺反异构体分离测定[J].现代农药,2015,(4):30-31.Zhang HF,She SC,Shi JH,et al.Determination of cis-and trans-isomers of isopyrazam[J].Mod Agrochem,2015,14(4):30-31.
[5]Furzer GS,Veldhuis L,Hall JC.Development and comparison of three diagnostic immunoassay formats for the detection of azoxystrobin[J].J Agric Food Chem,2006,54(3):688-693.
[6]杨欢,孙伟华,曹赵云,等.改良QuEChERS方法快速测定果蔬中8种新型琥珀酸脱氢酶抑制剂类杀菌剂[J].色谱,2016,34(11):1070-1076.Yang H,Sun WH,Cao ZY,et al.Determination of eight novel succinate dehydrogenase inhibitor fungicides in vegetables and fruits by modified Qu ECh ERS[J].Chin J Chromatogr,2016,34(11):1070-1076.
[7]陈祥准,夏碧琪,黄芙珍,等.液相色谱-串联质谱法同时测定葡萄酒中6种吡唑类杀菌剂[J].分析测试学报,2015,34(11):1311-1314.Chen XZ,Xia BQ,Huang FZ,et al.Simultaneous determination of six pyrazole fungicides in grape wine by liquid chromatography-tandem mass spectrometry[J].J Instrum Anal,2015,34(11):1311-1314.
[8]郑振山,陈勇达,张少军,等.气相色谱法测定黄瓜中吡唑萘菌胺及其代谢物[J].食品安全质量检测学报,2016,7(2):540-544.Zheng ZS,Chen YD,Zhang SJ,et al.Determination of isopyrazam residues and its degradation products in cucumber by gas chromatography[J].J Food Saf Qual,2016,7(2):540-544.
[9]智沈伟,赵尔成,李兴海,等.气相色谱-串联质谱法测定西瓜和黄瓜中吡唑萘菌胺及其代谢物残留[J].农药学学报,2018,(2):217-222.Zhi SW,Zhao EC,Li XH,et al.Determination of isopyrazam and its metabolites residues in watermelon and cucumber by gas chromatography-tandem mass spectrometry[J].Chin J Pest Sci,2018,(2):217-222.
[10]范丽丽,王娟,吴加伦.气相色谱法测定铁皮石斛、浙贝母和人参中嘧菌酯残留[J].分析科学学报,2017,33(2):222-226.Fan LL,Wang J,Wu JL.Determination of azoxystrobin residues in dendrobium of ficinale,fritiliariae thunbergii and panax ginseng by gas chromatography[J].J Anal Sci,2017,33(2):222-226.
[11]薄海波,毕阳,陈立仁.气相色谱法测定甜瓜和苹果中嘧菌酯残留[J].分析化学,2005,33(5):695-698.Bi HB,Bi Y,Chen LR.Determination of azoxystrobin residues in muskmelon and apple by gas chromatography[J].Chin J Anal Chem,2005,33(5):695-698.
[12]侯雪,韩梅,邱世婷,等.改进的QuEChERS气相色谱-串联质谱法测定草莓中21种杀菌剂残留[J].农药学学报,2017,19(1):46-52.Hou X,Han M,Qiu ST,et al.Residues of 21 fungicides in Fragaria ananassa by modified QuEChERS and gas chromatography-tandem mass spectrometry[J].Chin J Pest Sci,2017,19(1):46-52.
[13]石峰,赵科华,车军,等.高效液相色谱法分析砂糖桔中嘧菌酯残留[J].河北农业科学,2010,14(2):161-163.Shi F,Zhao KH,Che J,et al.Determination of residues azoxystrobin in citrus sha tang ju by HPLC[J].Hebei J Agric Sci,2010,14(2):161-163.
[14]张育乐,黄超群,朱晓雨,等.固相萃取-液相色谱-串联质谱法测定中药材中7种甲氧基丙烯酸酯类杀菌剂的残留量[J].色谱,2013,31(3):264-269.Zhang YL,Huang CQ,Zhu XY,et al.Determination of seven strobilurin fungicide residues in Chinese herbs by liquid chromatography-tandem mass spectrometry coupled with solid phase extraction[J].Chin JChromatogr,2013,31(3):264-269.
[15]徐永,梁赤周,虞淼,等.嘧菌酯在枇杷中残留及消解动态[J].农药科学与管理,2017,38(11):28-34.Xu Y,Liang CZ,Yu M,et al.Residue and degradation dynamics of azoxysstrobin in loquat[J].Pest Sci Admin,2017,38(11):28-34.
[16]Lehotay SJ,Son KA,Kwon H,et al.Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables[J].J Chromatogr A,2010,1217(16):2548-2560.