Study and Application of Analytical Method for Pesticide Residue in Food by Gas Chromatography-Mass Spectrometry and Gas Chromatography-Tandem Mass Spectrometry

食品的质量与安全是决定人类生存质量的重要因素之一。食品中的农药残留是影响食品安全的突出问题，已引起世界各国政府和组织的密切关注。随着世界各国对食品中农药残留限量标准的要求越来越低，迫切需要开展简单、快速和有效的分析方法。 本学位论文致力于有机氯、有机磷、拟除虫菊酯类农药残留分析的方法研究，优化了气相色谱-质谱(GC-MS)和气相色谱-串联质谱(GC-MS/MS)分析条件，初步建立了食品中多农药残留的GC-MS与GC-MS/MS分析方法，论文内容分为以下四章。 第1章简要阐述了有机氯、有机磷、氨基甲酸酯和拟除虫菊酯类农药的发展简史、对人体健康的影响及其毒理学简要原理；综述了食品中多农药残留分...The quality and safety of food is crucial to human’s life.However, the presence of pesticide residue in food has become one of the serious problems that has greatly attracted government and organization’s concerns. As the maximum residue levels of pesticides adopted by the legislation in the world become more and more strict, it is very important to develop simple, fast and efficient analytical me...学位：理学硕士院系专业：化学化工学院化学系_分析化学学号：20042502

牛奶中32种农药的气相色谱-离子阱串联质谱法测定

建立了牛奶中有机氯、有机磷和拟除虫菊酯3类32种农药残留的气相色谱-离子阱串联质谱(GC-IT-MS/MS)分析方法。针对目标物灵敏度不同选择电子轰击电离源或化学电离源,系统地优化了串联质谱的分析条件,并分析了产生这些影响的机理。在优化条件下,32种农药在25(10)～500(200)μg/L范围内线性关系良好,相关系数均大于0. 994;倍硫磷和毒死蜱的方法检出限(MDL)分别为1. 7μg/kg和2. 8μg/kg,其它30种农药的MDL为0. 026～1. 2μg/kg;当样品的加标浓度水平为50、200μg/kg(有机氯类农药的加标浓度为20、100μg/kg)时,32种目标物的平均加标回收率为71. 5%～116%,相对标准偏差为1. 9%～14%。将方法应用于实际样品的检测,其抗干扰能力强,能减少分析结果的假阳性。国家自然科学基金青年基金资助项目(51603175

气相色谱-质谱联用同时测定蔬菜中16种邻苯二甲酸酯残留

研究了蔬菜中16种邻苯二甲酸酯(PAEs)环境激素残留的气相色谱-电子轰击离子源质谱(GC-EI/MS)分析方法。优化了样品的前处理条件,以苯甲酸苄酯(BB)为内标物,采用GC-EI/MS的选择离子检测方式(SIM)进行定性和定量分析。当蔬菜样品的加标浓度水平分别为100和200μg/kg时,加标回收率为70.9%~123.0%,相对标准偏差为1.6%~15%。除邻苯二甲酸二甲氧基已酯(DMEP)外,其它15种PAEs的方法检测限(MDL)均为0.11~2.77μg/kg。在50.0~800.0μg/kg浓度范围内16种PAEs都呈现良好的线性关系,r为0.99623~0.99998。方法已用于5种蔬菜中16种痕量PAEs残留的分析

基质固相分散-气相色谱-离子阱串联质谱法分析牛奶中有机磷农药

将改进的基质固相分散法与GC-MS/MS分析方法结合应用于牛奶中13种有机磷农药残留的同时分析。优化各样品前处理参数后,样品与分散剂中性氧化铝研磨后,采用乙腈超声提取。过滤浓缩后以灭线磷为内标物,采用GC-MS/MS进行定性与定量分析。从样品前处理到分析约需1 h,当样品的加标水平为50、200μg/kg时,平均加标回收率为70.4%~117.6%,相对标准偏差为0.8%~19%;除倍硫磷和毒死蜱的检测限分别为5.60和9.35μg/kg外,其它11种有机磷农药的检测限均在0.37~3.77μg/kg之间;线性范围为25~500μg/kg,相关系数均大于0.9949

Determination of 19 Organophosphorous Pesticides Residues in Milk Drink and Milk Powder by Gas Chromatography-Negative Chemical Ionization-Mass Spectrometry

将气相色谱-负离子化学源质谱法(GC-NCIMS)应用于牛奶饮品和奶粉中19种有机磷农药残留的同时分析。牛奶饮品和奶粉经乙腈提取剂超声提取、Florisil硅藻土和中性氧化铝双净化剂同时净化及正己烷-乙酸乙酯(体积比1∶1)混合洗脱剂洗脱后,以三苯基磷酸酯为内标物,采用GC-NCI MS的选择离子监测方式(SIM)定性与定量分析。当牛奶饮品和奶粉的加标浓度水平为20、100、500μg/kg时,平均加标回收率为64.5%~129%,相对标准偏差为2%~20%;除喹硫磷的方法检出限(MDL)为2.4μg/kg外,其余18种有机磷农药的MDL均小于1.0μg/kg;线性范围为10~500μg/kg,相关系数均大于0.9988,此分析方法成功地应用于牛奶饮品和奶粉中多种痕量有机磷农药残留的分析。A rapid method was developed for the determination of 19 organophosphorous pesticides residues in commercial milk drink and milk powder.Under optimized conditions,the pesticides were extracted from milk drink or milk powder with acetonitrile in an ultrasonic bath and cleaned up on a Florisil and neutral alumina column,and were determined by gas chromatography with negative chemical ionization mass spectrometric detection in the selected ion monitoring mode with triphenyl phosphate as internal standard.The recoveries for all the pesticides studied ranged from 64.5% to 129% with a relative standard deviation range of 2%-20%.The detection limit of the method was less than 1.0 μg/kg for most of the pesticides except for the quinolphos.The linear ranges of the calibration curves ranged from 10 μg/kg to 500 μg/kg with correlation coefficients of 0.998 8.The proposed method was successfully applied to the analysis of these compounds in milk drink and milk powder

Multiresidue Determination of Organophosphorus Pesticide Residues in Vegetables and Fruit by Gas Chromatography-Negative Ion Chemical Ionization-Mass Spectrometry

将气相色谱-负离子化学电离质谱法(GC-NC I-M S)应用于蔬菜水果中9种有机磷农药残留的分析测定,初步解析了这些农药的NC I-M S特征阴离子结构和断裂机理,并初步探讨了GC-NC I-M S分析蔬菜水果中有机磷农药残留时基体效应的影响。采用空白样品基体匹配校准曲线法(M C)进行定量分析,有效地降低了基体效应的影响。蔬菜水果样品用乙酸乙酯超声提取,以乙硫磷为内标物,采用GC-NC I-M S的选择离子监测方式(S IM)进行定性和定量分析。9种有机磷农药的方法检测限为0.12~1.0μg/kg。在方法的检测限与1 000μg/kg范围内,线性相关系数都大于0.999 3。当空白蔬菜水果(西红柿)样品的加标水平为100,400,800μg/kg时,平均加标回收率为78%~126%,相对标准偏差为0.58%~14.7%。An analytical method of gas chromatography coupled with negative ion chemical ionization-mass spectrometry for simultaneous determination of nine organophosphorus pesticide residues in vegetables and fruit has been developed,and the negative ions structure and partition mechanism of the nine organophosphorus pesticides were interpreted.Meanwhile,the matrix effect for sample analysis was discussed,and matrix-matched calibration for quantification was introduced to reduce the matrix effect in this method.Pesticides were extracted from sample with ethyl acetate in an ultrasonic bath,then determined by gas chromatography-mass spectrometry operated in negative chemical ionization mode and quantified in selective ion monitoring mode,and ethion was used as an internal standard.The detection limits of the method were 0.12-1.0 μg/kg for the nine organophosphorus pesticides,and the relative coefficients were higher than(0.9993).A blank sample(tomato) was spiked at 100,400,800 μg/kg for each pesticide,and the recoveries were determined to be from 78% to 126% with relative standard deviations from 0.58% to 14.7% for the pesticides

Determination of Multiple Pesticide Residues in Honey Using Gas Chromatography-Mass Spectrometry

开展了蜂蜜中23种农药残留的气相色谱-电子轰击离子源质谱(GC-E I/M S)分析方法的研究,并对其中3种农药的E I/M S碎片离子的断裂机理与结构进行了初步解析。探讨了蜂蜜试样前处理条件的优化与选择。将蜂蜜试样用乙酸乙酯提取剂超声提取、F lo ris il硅藻土色谱柱净化和正己烷-乙酸乙酯(体积比为7∶3)混合洗脱剂洗脱后,以PCB103为内标物,采用选择离子监测(S IM)方式下的GC-E I/M S分析。当试样的加标浓度为50,100和200μg/kg时,加标回收率为82%~120%,相对标准偏差小于11.0%。23种农药的检测限都小于10.0μg/kg,线性范围为10~500μg/kg,相关系数都大于0.995。此分析方法已成功地应用于蜂蜜中23种痕量农药残留的分析。An analytical method was developed for the simultaneous determination of 23 pesticide residues in various commercial honeys.Meanwhile,the characteristic ions and fragmentation mechanism of three pesticides in the process of electron ionization mass spectrometry(EI/MS) were evaluated.After the optimization of different parameters such as the extraction solvent,pesticides were extracted from honey with ethyl acetate in an ultrasonic bath,cleaned up on a Florisil column by an elution of mixture of hexane and ethyl acetate(7∶ 3,v/v), and analyzed by gas chromatography-electron ionization mass spectrometry(GCEI/MS) in the selected ion monitoring mode(SIM) with PCB103 as internal standard.Recovery studies were performed at 50,100 and 200 μg/kg fortification levels for each pesticide,and the recoveries ranged from 82% to 120% with relative standard deviations between 1.8% and 11.0% for different pesticides.The limit of detection was less than 10.0 μg/kg for all the pesticides.The developed method was linear in the range of 10-500 μg/kg,with correlation coefficients larger than 0.995.Finally,the developed analytical method has been successfully applied to the determination of pesticide residues in several honey samples

Determination of Five Polybrominated Diphenyl Ether Residues in Deep-Sea Fish Oil Using Gas Chromatography-Negative Chemical Ionization/Mass Spectrometry

建立了气相色谱-负离子化学电离质谱法(GC-NCI/MS)同时分析深海鱼油食品中5种多溴联苯醚残留的分析方法。深海鱼油食品用正己烷超声提取、中性与酸性硅胶色谱柱净化和正己烷洗脱后,以PCB103为内标物,采用GC-NCI/MS的选择离子监测方式(SIM)分析;同时探讨了5种多溴联苯醚的NCI/MS特征离子的断裂机理。当空白深海鱼油食品的加标浓度为20.0和100.0μg/kg时,加标回收率为88.6%-111.3%,相对标准偏差为3.8%-13.5%,方法的检测限为0.77-1.34μg/kg,线性范围为1.0-500.0μg/kg,相关系数均大于0.999 2。此方法已成功地应用于深海鱼油食品中5种痕量多溴联苯醚残留的同时分析。Polybrominated diphenyl ethers(PBDEs) are a kind of brominated flame retardants(BFRs),which refer to compounds used in some plastics to impede or even suppress the combustion process.As the emission or disposal of plastics,PBDE residues have been found in both environment and biota.In this work,an analytical method was developed for the simultaneous determination of 5 PBDE residues in deep-sea fish oil.PBDEs were extracted from deep-sea fish oil with n-hexane,cleaned up on a silical gel column,and determined by using gas chromatography-negative chemical ionization/mass spectrometry(GC-NCI/MS) in the selected ion-monitoring(SIM) mode,with PCB103 as the internal standard.Meanwhile,the characteristic ion and fragmentation mechanism of some PBDEs in NCI/MS were evaluated.Recovery studies were performed at 20.0 and 100.0 μg/kg fortification levels for each PBDE,and the recoveries ranged from 88.6% to 111.3% with relative standard deviations between 3.8% and 13.5% for different PBDEs.The limits of detection(LOD) were from 0.77 to 1.34 μg/kg for different PBDEs.The developed method was linear over the range assayed,1.0-500.0 μg/kg,with correlation coefficients larger than 0.999 2.The developed method has also been successfully applied to the determination of PBDEs in several deep-sea fish oil samples and the three most abundant PBDEs(PBDE-47,PBDE-99 and PBDE-100) were found

Simultaneous determination of 14 phthalate ester residues in animal innards by gas chromatography-mass spectrometry with electron impact ionization

开展了动物内脏中14种酞酸酯类(PAEs)环境激素残留的气相色谱-电子轰击离子源质谱(GC-EI/MS)分析方法的研究,优化与选择了动物内脏样品的前处理条件。动物内脏样品经正己烷-二氯甲烷(体积比为1∶1)混合提取剂超声提取、Florisil硅土固相萃取柱净化与乙酸乙酯-正己烷(体积比为2∶3)混合洗脱剂洗脱和浓缩后,以邻苯二甲酸二苯基酯(DPhP)为内标物,采用GC-EI/MS的选择离子检测方式(SIM)进行定性和定量分析。当猪肝样品的加标浓度水平为100,200,400μg/kg时,加标回收率为60%~110%,相对标准偏差为0.8%~10.3%。除邻苯二甲酸二甲氧基乙酯(DMEP)与邻苯二甲酸二(2-乙氧基乙基)酯(DEEP)的方法检出限(MDL)分别为3.30μg/kg与2.25μg/kg外,其余12种PAEs的MDL均不大于1.74μg/kg;线性范围为50.0~800.0μg/kg,相关系数均大于0.9994。该分析方法已成功地应用于6种动物内脏中14种痕量PAEs残留的分析。An analytical multiresidue method was developed for the simultaneous determination of 14 phthalate esters (PAEs) in animal innards by gas chromatography-mass spectrometry with electron impact ionization (GC-EI/MS). After the optimization of different parameters such as the extraction solvent, PAEs were extracted from animal innards with hexane-dichloromethane (1∶1, v/v) in an ultrasonic bath and cleaned up on a Florisil column, then were determined by GC-EI/MS in selected ion monitoring mode with diphenyl phthalate (DPhP) as internal standard. The recovery studies were performed at 100, 200 and 400 μg/kg levels for each PAE, and the recoveries ranged from 60%-110% with the relative standard deviations between 0.8% and 10.3% for different PAEs. The detection limit of the method was less than 1.74 μg/kg for most of PAEs except dimethoxyethyl phthalate (DMEP) and di(2-ethoxyethyl) phthalate (DEEP). The method was linear over the range of 50.0-800.0 μg/kg with the correlation coefficients larger than 0.999 4. The method has been successfully applied to the determination of 14 PAEs in six animal innards.国家基础科学人才培养基金(J0630429)项目资

类泛素蛋白及其中文命名

泛素家族包括泛素及类泛素蛋白,约20种成员蛋白.近年来,泛素家族领域取得了迅猛发展,并已与生物学及医学研究的各个领域相互交叉.泛素家族介导的蛋白质降解和细胞自噬机制的发现分别于2004和2016年获得诺贝尔奖.但是,类泛素蛋白并没有统一规范的中文译名. 2018年4月9日在苏州召开的《泛素家族介导的蛋白质降解和细胞自噬》专著的编委会上,部分作者讨论了类泛素蛋白的中文命名问题,并在随后的\"泛素家族、自噬与疾病\"(Ubiquitinfamily,autophagy anddiseases)苏州会议上提出了类泛素蛋白中文翻译草案,此草案在参加该会议的国内学者及海外华人学者间取得了高度共识.冷泉港亚洲\"泛素家族、自噬与疾病\"苏州会议是由美国冷泉港实验室主办、两年一度、面向全球的英文会议.该会议在海内外华人学者中具有广泛影响,因此,参会华人学者的意见具有一定的代表性.本文介绍了10个类别的类泛素蛋白的中文命名,系统总结了它们的结构特点,并比较了参与各种类泛素化修饰的酶和它们的生物学功能.文章由45名从事该领域研究的专家合作撰写,其中包括中国工程院院士1名,相关学者4名,长江学者3名,国家杰出青年科学基金获得者18名和美国知名高校华人教授4名.他们绝大多数是参加编写即将由科学出版社出版的专著《泛素家族介导的蛋白质降解和细胞自噬》的专家