Microsoft Word 张 云-二校 出2860

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1 7 7 Vol. 7 No Journal of Food Safety and Quality Jul., 张 云 1*, 黄传辉 2, 陈泽宇 1 (1., ; 2., ) 摘要 : 目的 3 -(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS) 方法 -, (gel permeation chromatography, GPC), UPLC Syncronic C 18, 5 mmol/l ;, 结果 mg/kg, 0.01~0.2 mg/l, r>0.9988, mg/kg 3, 72.6%~90.8%; RSD 2.9%~9.9% 结论,, 关键词 : ; ; ; - Determination of anthranilic diamide pesticides in vegetable oil by ultra performance liquid chromatography-tandem mass spectrometry ZHANG Yun 1*, HUANG Chuan-Hui 2, CHEN Ze-Yu 1 (1. Sanming Entry-Exit Inspection and Quarantine Bureau, Sanming , China; 2. Sanming food and drug evaluation and adverse reaction monitoring center, Sanming , China) ABSTRACT: Objective To establish a method for simultaneous determination of 3 kinds of anthranilic diamide pesticide residues including cyantraniliprole, chlorantraniliprole and flubendiamide in vegetable oil by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Method Vegetable oil was extracted with cyclohexane and ethyl acetate solution, purified by gel permeation chromatography system (GPC), and separated by the Syncronic C 18 column with acetonitrile and 5 mmol/l ammonium acetate solution as mobile phase for gradient elution. Mass spectrometry used electro spray ionization in positive mode (ESI+) and multiple reaction monitoring (MRM) mode for detection with external standard method for quantification. Results The limits of detection of 3 kinds of anthranilic diamide pesticides could achieve 0.01 mg/kg, and they had good linear relationships in the range of 0.01~0.2 mg/l with correlation coefficients larger than The recoveries spiked at 基金项目 : (2015IK034) Fund: Supported by the General Administration of Quality Supervision, Inspection and Quarantine Science and Technology Project (2015IK034) * 通讯作者 :,,, @qq.com *Corresponding author: ZHANG Yun, Engineers, Master, Sanming Entry-Exit Inspection and Quarantine Bureau, Qianlong Village 30#, Donqian Road, Meilie District, Sanming , Fujian, China @qq.com

2 7, : levels of 0.01, 0.02 and 0.1 mg/kg were between 72.6%~90.8% with the relatively standard deviations (RSDs) of 2.9%~9.9%. Conclusion The method is quick, simple and sensitive, its purifying effect is good, which can significantly shorten the detection time and be applied on the rapid analysis of anthranilic diamide pesticides in vegetable oil. KEY WORDS: vegetable oil; anthranilic diamide; gel permeation chromatography; ultra performance liquid chromatography-tandem mass spectrometry 1 引言 [1],,,,, [2] (yantraniliprole) (flubendiamide) (chloranteraniliprole) 3 Dupont [3], [4,5],,,,, [6], [7,8] [9-12], - (ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS) 3 (gel permeation chromatography, GPC) UPLC-MS/MS, 3 2 材料与方法 2.1 仪器与试剂 AB SCIEX 3500 ( AB SCIEX ), Autoclean ( LabTech ), AE240 ( ), SPT-24A ( ), KQ-500DE ( ), Direct8 ( Millipore ) (, ); (, 97%, Tedia ); ( 99%, ) : GB/T 6682, 97%, Dr.Ehrenstorfer 2.2 实验方法 样品前处理 2.0 g( 0.1 g) 10 ml, -(1:1, V:V) 10 ml 2 ml,, 9~15 min, 50, 1 ml, 0.22 μm, 仪器条件 (1) : S-X 3 Bio-Beads( 38~75 μm, 22 g); : -(1:1, V:V); ; : 5 ml/min; : 0~9 min, 9~16 min (2) - : Thermo syncronic C 18 (50 mm 2.1 mm, 1.7 µm), ; : 10 µl; : 30 ; : 0.3 ml/min; 1: (electronic spray ion+, ESI+); : (multiple reaction monitoring, MRM); ; 3 2 表 1 Table 1 超高效液相色谱梯度洗脱程序 Gradient elution program of UPLC min 5 mmol/l -(%) (%)

3 Table 2 表 2 氰虫酰胺 氟虫酰胺 氯虫苯甲酰胺的质谱条件 Mass spectrometry parameters of cyantraniliprole, chloranteraniliprole and flubendiamide m/z ev ev ev 474.9/285.9* / /273.9* / /452.9* / : * 标准溶液的配制 100 mg/l, -18,, mg/l 定量测定,, 3 结果与讨论 3.1 净化条件的选择 : (1) - [13],, ; (2) [14-16],, GPC,,, [17], GPC, 6 min, 1 min, min 1, 15, 50,, UPLC-MS/MS, 6~8 min 16~20min, 9~16 min 3.2 质谱条件的优化,, 1 mg/l, Q ,, ; Q1, [+H] [+NH 4 ], , Q3, [+H],, m/z: 474.9/ / / / / /273.9, m/z: 474.9/285.9, 483.9/ / ~3 3.3 方法的线性范围和检出限, mg/l 2.2.2, Y X, r , 0.01~0.2 mg/l ( S/N 10 limit of quantization, LOQ S/N 3 limit of detection, LOD),, 方法的准确度和精密度, mg/kg, 2.2, 6, 实际样品测定 10

4 7, : ,, 0.09 mg/kg, 4~5, 3, Fig. 1 1 Extract ion chromatogram of cyantraniliprole Fig. 2 2 Extract ion chromatogram of chlorantraniliprole

5 Fig. 3 3 Extract ion chromatogram of flubendiamide Table 3 表 3 邻氨基苯甲二酰胺类农药的线性回归方程 相关系数 检出限和定量限 Linear regression equations, correlation coefficients, LODs and LOQs of anthranilic diamide pesticides (mg/l) r LOD(μg/kg) LOQ(mg/kg) 0.01~0.2 Y= X ~0.2 Y = X ~0.2 Y = X Table 4 表 4 植物油样品中邻氨基苯甲二酰胺类农药的回收率和精密度 (n=6) Recoveries and precisions of anthranilic diamide pesticides in vegetable oil (n=6) (mg/kg) (%) (%) (%)

6 7, : Fig. 4 1-; 2- ; Chromatogram of 3 kinds of anthranilic diamide pesticides standard Fig. 5 5 Chromatogram of actual vegetable oil sample 4 结论 GPC UPLC-MS/MS mg/kg; 0.01~0.2 mg/l,

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