摘 要

本论文由问题鸡蛋入手，经过方法比对，采用液相色谱-串联质谱方法测定鸡蛋中的氟虫腈及其代谢物。经过条件优化后，用乙腈提取，PSA粉末、C₁₈粉末和无水硫酸镁净化，DIONEX Acclaim RSLC 120，，C₁₈，2.2μm，3.0×100mm色谱柱分离，质谱条件选用ESI负离子模式。在SRM模式下，使用液相色谱-串联质谱分析方法进行分析。检测结果在0.00～20.00ng/mL的浓度范围内线性关系良好，线性相关系数均大0.9993，检出限(S/N=3)和定量限(S/N=10)分别0.30~1.00μg/kg和1.00~5.00μg/kg范围内，在4.00、20.00、40.00μg/kg三个添加水平下，平均回收率在72.9%~101.1%内，相对标准偏差为1.4%～2.0%。此方法操作简便、检出限低,可满足鸡蛋中氟虫腈及其代谢物的检测要求。

关键词：液相色谱-质谱联用；氟虫腈及其代谢物；鸡蛋

Determination of fipronil and its metabolites in eggs by LC-MS

Abstract

In this paper, dealing with the problem egg.To better determine fipronil and its metabolites in eggs , after the comparison of the methods, this paper use the liquid chromatography-tandem mass spectrometry method.then,purified by PSA powder, C₁₈ powder and anhydrous magnesium sulfate, and separated by DIONEX Acclaim RSLC 120 C₁₈, 2.2 μ m, 3.0 × 100mm chromatographic column, and ESI negative ion mode was used for mass spectrometry with SRM mode, the analysis was carried out by liquid chromatography-tandem mass spectrometry (LC-MS). The linear relationship was good in the concentration range of 0.00~20.00ng/mL, and the linear correlation coefficients were more than 0.9993. The detection limit (S/N=3) and quantitative limit (S/N=10) were Separate between 0.30 ~ 1.00 μ g / kg and 1.00 ~ 5.00 μ g / kg,. At the levels of 4.00、20.00、40.00 μ g / kg, the average recovery was in the range of 72.9% to 101.1%. The relative standard deviation is 1.4% to 2.0%. This method meets the requirements of detection, rapid and accurate, and can be used for the determination of fipronil and its metabolites in eggs.

Key words: liquid chromatography-mass spectrometry; fipronil and its metabolites; egg

目 录

摘 要 Ⅰ

Abstract Ⅱ

第一章 文 献 综 述.............................................................................................................1

1.1“毒鸡蛋”事件起由...................................................................................................1

1.2氟虫腈..........................................................................................................................1

1.2.1氟虫腈概述.......................................................................................................1

1.2.2氟虫腈在生物体内的作用机理及危害...........................................................2

1.2.3氟虫腈体内代谢及毒性和安全性...................................................................3

1.3氟虫腈的常用检测方法..............................................................................................4

1.3.1气相色谱法（GC）.........................................................................................4

1.3.2高效液相色谱法（HPLC）..............................................................................5

1.3.3气相色谱-质谱联用法（GC-MS/MS）...........................................................5

1.3.4液相色谱-质谱联用法（LC-MS/MS）...........................................................5

1.4研究目的及意义.......................................................................................................6

第二章 材料与方法................................................................................................................7

2.1实验材料...................................................................................................................7

2.1.1试剂..............................................................................................................7

2.1.2溶液配制......................................................................................................8

2.1.3材料..............................................................................................................8

2.1.4试样制备......................................................................................................8

2.2实验仪器.................................................................................................................9

2.3 实验方法................................................................................................................9

2.3.1实验方法选择..............................................................................................9

2.3.2液相色谱条件和质谱离子条件的优化....................................................10

2.3.3基质混合标准工作曲线的优化................................................................10

2.3.4提取溶剂的优化........................................................................................10

2.3.5净化方法方优化........................................................................................10

2.3.6加标回收率的测定....................................................................................10

2.3.7精密度的测定............................................................................................10

2.3.8检出限和定量限的测定............................................................................11

2.3.9相对标准不确定度的测定........................................................................11

第三章 结果与讨论..............................................................................................................12

3.1液相色谱条件和质谱离子条件的优化结果.........................................................12

3.2 基质混合标准工作曲线的优化............................................................................14

3.3提取溶剂的优化.....................................................................................................15

3.4提取溶剂用量的优化.............................................................................................16

3.5净化方法的优化.....................................................................................................16

3.6方法验证.................................................................................................................16