QuEChERS-超高效液相色谱-串联质谱法测定蔬菜中9种甲氧基丙烯酸酯类杀菌剂

徐鹏 赵建珍 闫伟伟 陈佳琛 罗慧玉 刘慧

徐鹏,赵建珍,闫伟伟,等. QuEChERS-超高效液相色谱-串联质谱法测定蔬菜中9种甲氧基丙烯酸酯类杀菌剂[J]. 食品工业科技,2021,42(7):1−7. doi:  10.13386/j.issn1002-0306.2020060021
引用本文: 徐鹏,赵建珍,闫伟伟,等. QuEChERS-超高效液相色谱-串联质谱法测定蔬菜中9种甲氧基丙烯酸酯类杀菌剂[J]. 食品工业科技,2021,42(7):1−7. doi:  10.13386/j.issn1002-0306.2020060021
XU Peng, ZHAO Jianzhen, YAN Weiwei, et al. Determination of 9 Strobilurin Fungicides in Vegetables by QuECHERS-Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Science and Technology of Food Industry, 2021, 42(7): 1−7. (in Chinese with English abstract). doi:  10.13386/j.issn1002-0306.2020060021
Citation: XU Peng, ZHAO Jianzhen, YAN Weiwei, et al. Determination of 9 Strobilurin Fungicides in Vegetables by QuECHERS-Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Science and Technology of Food Industry, 2021, 42(7): 1−7. (in Chinese with English abstract). doi:  10.13386/j.issn1002-0306.2020060021

QuEChERS-超高效液相色谱-串联质谱法测定蔬菜中9种甲氧基丙烯酸酯类杀菌剂

doi: 10.13386/j.issn1002-0306.2020060021
详细信息
    作者简介:

    徐鹏(1984−),男,硕士,工程师,研究方向:食品安全与检测,E-mail:413328944@qq.com

    通讯作者:

    陈佳琛(1984−),男,硕士,主管药师,研究方向:食品安全与检测,E-mail:ameng1026.@163.com

Determination of 9 Strobilurin Fungicides in Vegetables by QuECHERS-Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry

  • 摘要: 本文建立了采用QuEChERS方法提取净化,超高效液相色谱-串联质谱法(UPLC/MS/MS)同时测定蔬菜中的9种甲氧基丙烯酸酯(Z-苯氧菌酯、E-苯氧菌酯、嘧菌酯、肟嘧菌胺、醚菌胺、啶氧菌酯、吡唑醚菌酯、肟菌酯、嘧螨酯)杀菌剂残留量的方法。样品经乙腈提取,采用正交试验验优选N-丙基乙二胺(PSA)和C18以及石墨化炭黑(GCB)净化用量。使用0.05%甲酸水和0.05%甲酸乙腈作为流动相梯度洗脱,目标化合物经岛津Shim-PackC18色谱柱(2.1 mm×50 mm,2 μm)分离,在正离子模式下进行测定。结果表明,9种甲氧基丙烯酸酯类杀菌剂在1~100 ng/mL范围内线性关系良好,决定系数在0.9942~0.9995之间,方法检出限(LOD)为0.05~0.3 μg/kg,定量限(LOQ)为0.2~0.9 μg/kg。在2、10和20 μg/kg三个添加水平下,五种蔬菜的回收率在77.26%~111.73%之间,相对标准偏差在0.46%~6.59%之间。该方法准确、快速、便捷、灵敏度高,能够满足蔬菜中9种甲氧基丙烯酸酯类杀菌剂的痕量检测要求。
  • 图  1  9种甲氧基丙烯酸酯类杀菌剂标准物质离子流色谱图

    注:I图为9种物质TIC图;II图为嘧菌酯、肟醚菌胺EIC图;III图为肟菌酯、嘧螨酯EIC图。1:Z-苯氧菌酯;2:E-苯氧菌酯;3:嘧菌酯;4:肟醚菌胺;5:醚菌胺;6:啶氧菌酯;7:吡唑醚菌酯;8:肟菌酯;9:嘧螨酯。

    Figure  1.  Ion current chromatogram of 9 strobilurin fungicides standard solution

    图  2  石墨化炭黑添加量对加标回收率的影响

    Figure  2.  Effect of GCB addition on recovery rate of standard addition

    图  3  PSA添加量对加标回收率的影响

    Figure  3.  Effect of PSA addition on recovery rate of standard addition

    图  4  C18添加量对加标回收率的影响

    Figure  4.  Effect of C18 addition on recovery rate of standard addition

    表  1  9种甲氧基丙烯酸酯类杀菌剂质谱检测参数

    Table  1.   Mass spectrum parameters of 9 strobilurin fungicides

    序号目标物质保留时间Tr(min)母离子(m/z)子离子(m/z)去簇电压DP(V)碰撞能量CE(eV)
    1Z-苯氧菌酯6.84285.1196.3*,167.15522*,49
    2E-苯氧菌酯7.12285.1194.2*,196.29027*,21
    3嘧菌酯7.81404.1329.2*,344.05640*,34
    4肟嘧菌胺7.83392.2116.0*,170.06038*,19
    5醚菌胺8.36327.1116.2*,205.210530*,12
    6啶氧菌酯8.77368.1145.2*,115.211032*,64
    7吡唑醚菌酯9.04388.2163.3*,149.25532*,43
    8肟菌酯9.43409.2186.1*,206.27424*,47
    9嘧螨酯9.44427.2145.2*,205.38832*,12
    注:*定量离子。
    下载: 导出CSV

    表  2  因素与水平表

    Table  2.   Factors and levels table

    水平因素
    A 石墨化炭黑
    添加量(mg)
    B C18添加
    量(mg)
    C PSA添加
    量(mg)
    110150150
    215200200
    325250250
    下载: 导出CSV

    表  3  L9(34)正交试验设计与结果

    Table  3.   L9 (34)Design and results of orthogonal test

    实验序号ABCD(空白)回收率(%)
    Z-苯氧菌酯E-苯氧菌酯嘧菌酯肟醚菌胺醚菌胺啶氧菌酯吡唑醚菌酯肟菌酯嘧螨酯
    1111190.6392.8568.2480.8583.9076.8084.6772.7674.52
    2122293.8791.0782.0984.6389.4488.2393.2191.0778.49
    3133398.0792.6872.4385.0487.1475.6081.4471.9971.05
    4212392.4797.6494.1493.0594.2790.0797.4996.0389.98
    5223194.7791.8282.4478.1384.8176.9091.1081.0879.07
    6231296.5793.5392.9589.0291.3585.9396.9595.1388.86
    7313296.2093.7094.0392.8593.7888.7095.0296.1688.92
    8321394.1092.6181.8282.9785.1371.5773.4480.9278.90
    9332194.3795.8975.2979.4383.0676.9768.9486.8878.20
    Z-苯氧菌酯E-苯氧菌酯嘧菌酯
    k194.1993.1093.7793.2692.2094.7393.0093.5274.2585.4781.0075.32
    k294.6094.2493.5795.5494.3391.8394.8792.7789.8482.1283.8489.69
    k394.8996.3396.3494.8894.0794.0392.7394.3183.7180.2282.9782.79
    R0.703.232.782.292.132.902.131.5415.595.252.8414.37
    肟醚菌胺醚菌胺啶氧菌酯
    k183.5188.9284.2879.4786.8390.6586.7983.9280.2185.1978.1076.89
    k286.7381.9185.7088.8390.1486.4688.9291.5284.3078.9085.0987.62
    k385.0884.5085.3487.0287.3287.1888.5888.8579.0879.5080.4079.08
    R3.227.011.429.363.314.192.137.605.226.296.9910.73
    吡唑醚菌酯肟菌酯嘧螨酯
    k186.4492.3985.0281.5778.6188.3282.9480.2474.6984.4880.7677.26
    k295.1885.9186.5595.0690.7584.3591.3394.1285.9778.8282.2285.42
    k379.1382.4489.1884.1287.9984.6783.0882.9882.0179.3779.6879.98
    R16.059.954.1713.4912.143.978.3913.8811.285.662.548.16
    下载: 导出CSV

    表  4  五种蔬菜基质中目标化合物的基质效应

    Table  4.   Matrix effects of target compounds in five vegetable matrices

    化合物结球甘蓝(%)芹菜(%)土豆(%)菠菜(%)甜椒(%)
    Z-苯氧菌酯3.574.754.7210.329.64
    E-苯氧菌酯3.343.173.559.838.56
    嘧菌酯1.758.520.488.659.28
    肟嘧菌胺2.225.011.596.025.46
    醚菌胺2.324.352.145.486.15
    啶氧菌酯4.226.930.847.698.92
    吡唑醚菌酯1.681.060.641.982.56
    肟菌酯3.334.291.435.967.06
    嘧螨酯2.675.105.177.056.47
    下载: 导出CSV

    表  5  9种化合物线性方程,决定系数(R2),检出限(LOD)和定量限(LOQ)

    Table  5.   Linear equations, coefficient of determination (R2),LODs and LOQs of 9 compounds

    目标物质线性方程决定系数检出限(μg/kg)定量限(μg/kg)
    Z-苯氧菌酯y = 100,219.0501 x + 51,284.81610.99910.150.50
    E-苯氧菌酯y = 53,859.4119 x + 14,999.38300.99950.200.80
    嘧菌酯y = 41,170.2605 x + 120,443.42040.99440.100.40
    肟嘧菌胺y = 187,710.1702 x + 92,889.39030.99900.050.20
    醚菌胺y = 55,222.1053 x + 70,096.54740.99860.200.80
    啶氧菌酯y = 70,299.3601 x + 97,840.97360.99680.200.80
    吡唑醚菌酯y = 90,337.4115 x + 234,830.00230.99690.300.90
    肟菌酯y = 119,296.1178 x + 450,553.40130.99420.080.30
    嘧螨酯y = 70,929.2037 x + 180,603.81670.99700.200.80
    下载: 导出CSV

    表  6  平均回收率和平均相对标准偏差(n=7)

    Table  6.   Average recovery rates and RSDs (n=7)

    目标物质添加水平结球甘蓝芹菜土豆菠菜甜椒
    (μg/kg)平均
    回收率(%)
    相对标准
    偏差(%)
    平均
    回收率(%)
    相对标准
    偏差(%)
    平均
    回收率(%)
    相对标准
    偏差(%)
    平均
    回收率(%)
    相对标准
    偏差(%)
    平均
    回收率(%)
    相对标准
    偏差(%)
    Z-苯氧菌酯289.700.87107.193.8392.053.97105.324.0290.082.01
    1082.041.2586.482.6096.671.1787.562.9386.591.63
    2098.930.7084.511.86108.061.4986.062.0193.521.56
    E-苯氧菌酯284.392.89111.733.6182.801.63106.975.0684.292.05
    1087.630.4691.693.6492.291.3395.213.5990.641.32
    2097.751.2688.191.2593.902.8590.161.6586.241.89
    嘧菌酯278.662.7591.833.3782.611.7596.195.4380.082.56
    1088.042.5093.491.4890.012.9093.642.0586.393.01
    2096.231.9195.201.4782.953.1897.491.8381.231.07
    肟嘧菌胺283.922.4578.814.9585.422.4881.034.3686.563.02
    1096.013.44104.981.9386.192.8993.622.1680.212.08
    2097.932.0883.981.7593.993.2582.361.2679.994.01
    醚菌胺286.613.2691.082.9078.181.8786.563.9679.483.94
    1084.422.3787.642.9588.662.4289.651.5282.163.06
    2096.471.5383.191.9490.411.3883.300.9883.262.95
    啶氧菌酯281.930.8693.613.3978.923.8195.213.8977.263.87
    1089.812.1183.492.4580.901.9486.792.1379.002.65
    2094.693.88100.641.7784.824.7393.121.6381.451.47
    吡唑醚菌酯296.301.7187.002.6686.952.7086.453.6684.262.58
    1091.831.3794.531.7398.051.8396.631.4286.931.69
    2097.811.25101.472.9092.512.9485.492.9690.232.14
    肟菌酯285.232.6587.513.0380.872.8789.296.5985.952.36
    1086.571.6293.111.6291.994.1086.534.2187.493.94
    2097.930.5095.983.8581.111.6686.323.2284.514.86
    嘧螨酯283.281.2988.443.3277.765.4083.215.3283.122.73
    1082.201.6983.682.1084.130.7381.082.9686.980.91
    2094.291.2583.941.5093.732.6579.563.6791.471.82
    下载: 导出CSV
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图(4) / 表(6)
计量
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出版历程
  • 收稿日期:  2020-06-03
  • 网络出版日期:  2021-01-13

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