有机磷和氨基甲酸酯农药质谱断裂规律及其酶抑制效应和残留分析方法研究
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摘要
烟草作为特殊的食品,其吸食安全性问题受到人们越来越广泛的关注。其中,烟草中的农药残留危害着广大烟民的健康,有机磷和氨基甲酸酯类农药在我国农业生产中有着广泛的使用。因此,对有机磷和氨基甲酸酯类农药的结构和性质做深入的研究,并对烟草中此类农药多残留体系进行进一步的探索,有助于为烟草吸食安全提供理论参考,为烟草安全性评价提供数据支持。
本论文运用质谱技术,研究了有机磷和氨基甲酸酯类农药的电喷雾质谱断裂规律及其对乙酰胆碱酯酶活性的抑制率大小,并建立了烟草中这两类农药残留的气相色谱质谱分析方法。研究内容主要包括：
第一章,综述了有机磷和氨基甲酸酯类农药的结构和致毒机理,总结了质谱常用的离子源和质量检测器类型,并概述了质谱技术用于有机磷和氨基甲酸酯类农药研究的现状。
第二章,研究了14种有机磷和10种氨基甲酸酯农药在电喷雾离子阱质谱中的断裂规律,推导其断裂路径。对监测模式和毛细管温度进行了优化,结果显示,大部分被测农药分子在正离子模式下容易电离,被测的氨基甲酸酯类农药在此质谱条件下容易丢失质荷比为57的碎片离子,有机磷农药容易丢失烷基。
第三章,建立了一种检测有机磷和氨基甲酸酯类农药对乙酰胆碱酯酶活性抑制作用的液相色谱-串接质谱(LC-MS/MS)新方法。本方法在恒温体系中,加入乙酰胆碱和乙酰胆碱酯酶以及不同农药,恒温反应20mmin后,定量检测乙酰胆碱,计算各种农药对乙酰胆碱酯酶的抑制率,该方法灵敏度高,检测限低。相同浓度下,用此方法检测了34种有机磷和氨基甲酸酯农药对乙酰胆碱酯酶的抑制率大小,结果在1%到71%之间。总结出氨基甲酸酯类农药的抑制作用普遍大于有机磷,伯胺类氨基甲酸酯农药的抑制率大于仲胺的规律,并推测了所测农药的抑制率大小与其结构的关系。
第四章,采用优化的QuEChERS前处理方法,气相色谱质谱分析了烟草中31种有机磷和氨基甲酸酯类农药残留。解决了实际样品检测过程中出现的杂峰过多的问题。在白肋烟和烤烟基质中,31种农药在0.25mg/kg,0.50mg/kg和1.0mg/kg三个加标水平下的回收率在60%～116%之间,相对标准偏差为2%～20%,可为烟草中多农药残留分析体系的建立提供参考。
Tobacco, as a kind of special food, has been paid more and more attention by people for safety. And the pesticides in tobacco can do harm for the health of smokers. So, it is important to investigate the structures, the properties and the multi-analytical method system of pesticedes, especially for organophosphorous and carbamate pesticides which have been used widely in China these years. In this thesis, the production of fragment ions of organophosphorous and carbamate pesticides in electrospray ionization ion source-ion trap mass spectrum, the inhibiton activity of35kinds of organophosphorous and carbamate pesticides on cholinesterase and the multi-residue analysis method of organophosphorous and carbamate pesticides in tobacco are disscussed.
This thesis includes four parts:
In chapter one, the toxication mechanisms and structures of organophosphorous and carbamate pesticides were reviewed. And the types of ion sources and detectors of mass spectra used widely in pesticide analysis were summarized. The researches of organophosphorus and carbamate pesticides using mass spectrum in these years were also reviewed.
In chapter two, the production of fragment ions of organophosphorous and carbamate pesticides in electrospray ionization ion source-ion trap mass spectrum were detected. And the fragment passways were also deduced by the loss of mass.
In chapter three, a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was established for the determination of the inhibition activity of35kinds of organophosphorous and carbamate pesticides on Cholinesterase. hi this method, acetylcholines cholinesterase and pesticides were added into the reaction system of37'C and after20min, the concentration of acetylcholine was determined by HPLC-MS/MS. The result suggested that the inhibition activity of35kinds of pesticides on cholinesterase were between1%and71%.And the relationship between the structure of inhibitor and the Inhibition Activity on AChE were also discussed.
In chapter four, a gas chromatography-mass spectrometry method was created to determine the residues of organophosphorous and carbamate pesticides in tobacco. The result showed that the recoveries of the thirty-one pesticides ranged from60%to116%with the standard's levels at0.25mg/kg,0.50mg/kg and l.Omg/kg, and the relative standard deviation(RSD) ranged from2%to20%.This method can provide guidance for the standard multi-residue analysis method.
本论文运用质谱技术,研究了有机磷和氨基甲酸酯类农药的电喷雾质谱断裂规律及其对乙酰胆碱酯酶活性的抑制率大小,并建立了烟草中这两类农药残留的气相色谱质谱分析方法。研究内容主要包括：
第一章,综述了有机磷和氨基甲酸酯类农药的结构和致毒机理,总结了质谱常用的离子源和质量检测器类型,并概述了质谱技术用于有机磷和氨基甲酸酯类农药研究的现状。
第二章,研究了14种有机磷和10种氨基甲酸酯农药在电喷雾离子阱质谱中的断裂规律,推导其断裂路径。对监测模式和毛细管温度进行了优化,结果显示,大部分被测农药分子在正离子模式下容易电离,被测的氨基甲酸酯类农药在此质谱条件下容易丢失质荷比为57的碎片离子,有机磷农药容易丢失烷基。
第三章,建立了一种检测有机磷和氨基甲酸酯类农药对乙酰胆碱酯酶活性抑制作用的液相色谱-串接质谱(LC-MS/MS)新方法。本方法在恒温体系中,加入乙酰胆碱和乙酰胆碱酯酶以及不同农药,恒温反应20mmin后,定量检测乙酰胆碱,计算各种农药对乙酰胆碱酯酶的抑制率,该方法灵敏度高,检测限低。相同浓度下,用此方法检测了34种有机磷和氨基甲酸酯农药对乙酰胆碱酯酶的抑制率大小,结果在1%到71%之间。总结出氨基甲酸酯类农药的抑制作用普遍大于有机磷,伯胺类氨基甲酸酯农药的抑制率大于仲胺的规律,并推测了所测农药的抑制率大小与其结构的关系。
第四章,采用优化的QuEChERS前处理方法,气相色谱质谱分析了烟草中31种有机磷和氨基甲酸酯类农药残留。解决了实际样品检测过程中出现的杂峰过多的问题。在白肋烟和烤烟基质中,31种农药在0.25mg/kg,0.50mg/kg和1.0mg/kg三个加标水平下的回收率在60%～116%之间,相对标准偏差为2%～20%,可为烟草中多农药残留分析体系的建立提供参考。
Tobacco, as a kind of special food, has been paid more and more attention by people for safety. And the pesticides in tobacco can do harm for the health of smokers. So, it is important to investigate the structures, the properties and the multi-analytical method system of pesticedes, especially for organophosphorous and carbamate pesticides which have been used widely in China these years. In this thesis, the production of fragment ions of organophosphorous and carbamate pesticides in electrospray ionization ion source-ion trap mass spectrum, the inhibiton activity of35kinds of organophosphorous and carbamate pesticides on cholinesterase and the multi-residue analysis method of organophosphorous and carbamate pesticides in tobacco are disscussed.
This thesis includes four parts:
In chapter one, the toxication mechanisms and structures of organophosphorous and carbamate pesticides were reviewed. And the types of ion sources and detectors of mass spectra used widely in pesticide analysis were summarized. The researches of organophosphorus and carbamate pesticides using mass spectrum in these years were also reviewed.
In chapter two, the production of fragment ions of organophosphorous and carbamate pesticides in electrospray ionization ion source-ion trap mass spectrum were detected. And the fragment passways were also deduced by the loss of mass.
In chapter three, a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was established for the determination of the inhibition activity of35kinds of organophosphorous and carbamate pesticides on Cholinesterase. hi this method, acetylcholines cholinesterase and pesticides were added into the reaction system of37'C and after20min, the concentration of acetylcholine was determined by HPLC-MS/MS. The result suggested that the inhibition activity of35kinds of pesticides on cholinesterase were between1%and71%.And the relationship between the structure of inhibitor and the Inhibition Activity on AChE were also discussed.
In chapter four, a gas chromatography-mass spectrometry method was created to determine the residues of organophosphorous and carbamate pesticides in tobacco. The result showed that the recoveries of the thirty-one pesticides ranged from60%to116%with the standard's levels at0.25mg/kg,0.50mg/kg and l.Omg/kg, and the relative standard deviation(RSD) ranged from2%to20%.This method can provide guidance for the standard multi-residue analysis method.
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