【作者】 储晓刚；

【导师】 姚惠源；

【作者基本信息】 江南大学 ， 粮油、油脂与植物蛋白， 2007， 博士

【摘要】 本研究论文是国家“十五”食品安全重大专项课题“农兽药残留系统检测方法和快速筛选检测方法的建立”（2001BA804A11）和“农药残留检测技术研究”（2001BA804A17）课题研究的一部分。在充分调研和查新的基础上,课题针对除草剂残留检测技术的空白,在国内外残留限量（除草剂限量）规定的不断的严格和增加的情况下展开研究。论文综述了18类已使用的除草剂的创制和应用历史、近年的发展趋势和推广情况,介绍了除草剂的理化性质和毒理学研究进展。综述了除草剂的最大残留限量的变化,特别是近年大幅度的变化情况,如日本的“肯定列表制度”所涉及的大豆用除草剂最大残留限量的情况,由于限量的变化和除草剂残留检测技术的缺乏而对我国大豆消费和进出口所产生的影响。据国内外大豆除草剂残留分析方法的现状,技术上的缺陷和依据现代仪器分析技术的进步所带来的分析方法技术指标的大幅度提高,系统研究了能够满足最大残留限量标准的除草剂残留的检测方法。研究分别建立了二硝基苯胺类、苯氧羧酸类、磺酰脲类、三嗪类、酰胺类等多类常用除草剂残留检测方法,以适用于不同的检测目的。二硝基苯按类除草剂属于脂溶性化学物质,易溶于有机溶剂,另外分子中带有电负性原子,因此选择气相色谱/电子铺获检测器建立检测方法,方法灵敏度高、选择性好,同时建立了气相色谱/质谱确证检测参数。苯氧羧酸类除草剂由于是有机酸类除草剂,水溶性好,应用三氟化硼-乙醚/甲醇溶液衍生化的方式,使得苯氧羧酸类除草剂形成甲酯化产物,应用气相色谱/质谱建立了定性定量检测方法,方法的灵敏度达到了0.005 mg/kg。磺酰脲类除草剂在磷酸缓冲溶液/乙腈梯度洗脱下,完成分离和液相色谱定量检测。三嗪类除草剂经过方法学实验,以乙腈/水梯度洗脱,在228 nm波长下液相色谱/二极管矩阵检测器检测,各组分均获得良好的分离。根据酰胺类除草剂的性质,在优化提取分离条件下,以乙腈/水为流动相,在210nm波长下测定,获得很好的检测下限和分离度。研究还建立了基于1.7μm小颗粒最新技术的超高效分析条件,UPLC^TM比传统HPLC具有更高的分离柱效。可以在很高的线速度、流速和反压下进行高效的分离工作,采用UPLC/MS/MS技术对14类除草剂共计111种在农业上广泛使用的除草剂进行了提取净化和分离条件实验研究,方法的最高灵敏度达到0.1mg/kg。论文首次应用液相色谱/飞行时间质谱研究并建立了大豆中未知除草剂残留筛查检测方法。飞行时间质谱可以给出疑似除草剂残留的所检出化合物的精确分子量,据此完成未知靶标除草剂残留的筛查确证。该方法的建立解决了全未知样品的筛查检测技术关键,为国家植物源性农产品质量监控和抽查提供技术手段。更多还原

【Abstract】 The study was based on the 10th five-year plan Food Safety Key Project "Establishment of systematic determination and rapid screening methods of pesticides and veterinary drugs residues"（2001BA804All） and "Study on pesticides residues determination technology" （2001BA804A17）.The study was aimed at filling the blank of herbicides residues determination technology and meeting the international requirement of more and more stringent MRLs.Our paper summarized the development and application history,trend in recent years and generalization of 18 kinds widely used pesticides.The physical and chemical properties and toxicological research were also introduced.This chapter also reviewed the change of pesticides MRLs values,especially the huge change in recent years.For example,the MRLs of the pesticides used in soybeans involved in Japan "positive list" were reviewed.The influence of the MRLs change and lack of determination technology on the soybean consumption and export was also analyzed.The chapter emphasized on the situation of analytical methods of pesticides residues in soybean in China and abroad.In addition,the prohibited pesticides regulated in developed countries and some limitation standards on soybean in our country were also analyzed in the chapter.The toxicology and analytical methods of pesticides metabolites arisen recently in foreign countries were also reviewed.The establishment of systematic determination technology was put forward to meet the requirement of pesticides MRLs.According to the pesticides classification,the determination methods of dinitroaniline, phenoxycarboxylic acids,sulfonyluerea,amides,triazines residues were demonstrated to meet the different requirements.Dinitroaniline herbicides were soluble in organic solvent and there were electronegative atoms in molecules,therefore,GC/ECD method which showed great sensitivity and selectivity was chosen and the parameters of GC-MS for confirmative determination was established.Phenoxycarboxylic acids herbicides belong to organic acid herbicides and were easily dissolved in water.To get the formate products,boron trifluoride-ether-methanol was used for derivation.Then the GC-MS method was established for both qualitative and quantitative analysis and the sensitivity of method was up to 0.005 mg/kg.The baseline separation and HPLC quantitative determination of sulfonyluerea herbicides were achieved using phosphate buffer/acetonitrile gradient elution and the method was reliable.In this part,the satisfactory detection limits and resolution were obtained under the optimal extraction conditions.Acetonitrile/ water were used as mobile phase and the wavelength was set at 210 nm.The mixture of triazine herbicides were well separated using HPLC/DAD method,the experimental conditions were acetonitrile/water gradient elution and 228 nm.The ultra performance analytical method based on 1.7μm particles was established. Compared with HPLC,UPLC^TM has higher column efficiency and the separation could be achieved under higher flow rate and back pressure.UPLC/MS/MS method was used for the determination of 14 different kinds herbicides commonly used in agriculture,totally 111 compounds were extracted,purified and separated,the excellent results were obtained.The sensitivity of the method was up to 0.1 mg/kg.HPLC-TOF-MS method was used for the screening and determination of unknown herbicides residues in soybean for the first time.TOF-MS could provide the accurate molecular weight for the suspicious herbicide residues,therefore,the screening and confirmation of the unknown targeted herbicide residues could be achieved.The establishment of the method solved the key problem of the screening technology of totally unknown samples and provided the technical support for the national farm produce residues monitoring and spot test.更多还原