Study and Application of Analytical Method for Pesticide Residues in Tobacco, Vegetables and Fruits by GC-EI/MS

化学农药在防治农作物病虫害的同时也给人类与环境带来了负面影响，食品的质量 与安全是决定人类生存质量的重要因素之一。农药残留问题是目前影响食品安全的首要 问题，一直被世界各国政府和组织所关注，随着世界各国对食品中农药残留种类的要求 越来越多、最高农药残留限量标准的要求越来越低，研究与建立行之有效的农药残留分 析方法，以保证食品的质量与安全和促进农产品的出口贸易十分必要。 本学位论文致力于食品中有机氯类、有机磷类和拟除虫菊酯类农药的农药残留分析 方法研究，优化了气相色谱-电子轰击电离源/质谱联用法(GC-EI/MS)的分析条件，探讨 了水果保鲜剂中农药组分对水果中农药残留的影响，初步...Pesticide is a double-edged sword, it protects agriculture products from destroyed by plant diseases and insect pests and provides benefits in increasing crop production while it has a negative impact or even a threat to human and environment as well. The quality and safety of food is crucial to human’s life while the pesticide residue is one of the most important problems which attract much att...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：2052006115192

Determination of 29 pesticide residues in tobacco by gas chromatography-electron impact ionization mass spectrometry

开展了卷烟和烟叶中有机氯、有机磷和拟除虫菊酯3类29种农药残留的气相色谱-电子轰击离子源质谱(gC-EI/MS)的分析方法研究。优化与选择了卷烟和烟叶样品的前处理条件,样品经正己烷-丙酮(体积比为1∶1)混合提取剂超声提取、flOrISIl硅土和中性氧化铝双净化剂固相萃取柱净化、二氯甲烷-正己烷(体积比为95∶5)混合洗脱剂洗脱和浓缩后,以磷酸三苯酯(TPP)为内标物,采用gC-EI/MS的选择离子监测方式(SIM)进行定性和定量分析。当样品的加标水平为20,50,100μg/kg时,加标回收率为70%--110%,相对标准偏差在2%--8%之间;除了甲氰菊酯、氯菊酯和溴氰菊酯的方法检出限(lOd)分别为1.85,1.74与2.54μg/kg外,其余的26种农药的lOd均小于0.8μg/kg;线性范围为5.0--500.0μg/kg,相关系数都大于等于0.999 4。此分析方法已成功地应用于卷烟和烟叶样品中3类29种痕量农药残留的分析。A method was developed for rapid determination of 29 pesticide residues in tobacco based on gas chromatography coupled with electron impact ionization mass spectrometric detection(GC-EI/MS).After the optimization of different parameters,such as the extraction solvent,elution solvent,purificant,pesticides were extracted from tobacco with hexane-acetone(1∶1,v/v) in an ultrasonic bath,cleaned-up on a column,packed with Florisil and neutral alumina,eluted with dichloromethane-hexane(95∶5,v/v),and then determined by GC-EI/MS in the selected ion monitoring mode(SIM) with triphenyl phosphate(TPP) as internal standard.The recoveries were performed at 20,50 and 100 μg/kg fortification levels for each pesticide,and the recoveries ranged from 70% to 110% with the relative standard deviations between 2% and 8%.The detection limits were less than 0.8 μg/kg for 26 pesticides except for the fenpropathrin,deltamethrin and permethrin.The method was linear over the range of 5.0-500.0 μg/kg with the correlation coefficients between 0.9994 to 0.9999.The method was successfully applied to the analysis of these pesticides in tobacco.国家基础科学人才培养基金项目(J0630429

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

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

Determination of polybrominated diphenyl ethers and polybrominated biphenyls in sediment from Xiamen sea by gas chromatography-mass spectrometry-negative chemical ionization and gas chromatography-electron capture detector

将气相色谱-负离子化学源-质谱法(gC-nCI/MS)和气相色谱-电子捕获检测法(gC-ECd)应用于分析沉积物中6种多溴联苯醚(PbdES)和5种多溴联苯(PbbS)残留。沉积物样品以V(正己烷)∶V(丙酮)=1∶1作为提取剂,采用索式提取法,提取液经酸性硅胶和中性硅胶层析柱净化和正己烷洗脱后,以PCb-103为内标物和gC-nCI-MS的选择离子监测方式(SIM)进行定性与定量分析,PbdE-209则采用gC-ECd法分析。平均加标回收率为93.3%--110.8%,相对标准偏差为1.2%--8.6%,方法检测限均小于0.20μg/kg(PbdE-209的方法检测限是7.74μg/kg),相关系数都大于0.9990。所分析沉积物样品中均含有微量的PbdE-99、Pbb-49和PbdE-209。Soxhlet extraction was developed for the determination of six polybrominated diphenyl ethers and five polybrominated biphenyls in sediment.Hexane/actone(1∶1, V/V) was used as the extraction solvent and hexane as elution solvent,after the extraction was cleaned by the cartridge filling with acidic and neutral silica gel,the analysis of samples was accomplished by using gas chromatography with negative chemical ionization mass spectrometric detection(GC-NCI/MS) in the selected ion monitoring mode(SIM) and gas chromatography-electron capture detector,and with PCB-103 as internal standard(IS).The average recoveries of the spiked-samples ranged from 93.3% to 110.8% with relative standard deviations between 1.2% and 8.6%,the detection limit(MDL) was smaller than 0.20 μg/kg (the MDL was 7.74 μg/kg for PBDE-209),and the correlation coefficients were larger than 0.9990.PBDE-99、 PBB-49 and PBDE-209 were detected in all sediments

Analysis of Nine Polybrominated Diphenyl Ethers Residue in Marine Samples by Gas Chromatography-Negative Chemical Ionization/Mass Spectrometry

建立了海产品中九种多溴联苯醚(PBDEs)残留的气相色谱-负化学离子源/质谱(GC-NCI/MS)分析方法。采用正己烷提取剂超声提取、Florisil硅藻土净化柱净化和正己烷洗脱剂洗脱的样品前处理方法,以PCB-103作为内标物,以GC-NCI/MS的选择离子监测方式(SIM)对海产品中九种PBDEs残留进行了定性与定量分析。分析方法的线性相关系数均≥0.9988,九种PBDEs两种添加浓度水平时的平均加标回收率为88.1%~97.3%,相对标准偏差为2.0%~6.6%,方法检出限均小于0.106 ng/g。线性范围除PBDE-183为0.60~300.0 ng/g外,其余八种PBDEs为0.50~250.0 ng/g。同时分析了紫菜、海带、鲜海带、鱼干和花蛤干等海产品,在这些海产品干货中都检出了较多种的PBDEs残留。In this paper,gas chromatography coupled with negative chemical ionization mass spectrometric(GC-NCI/MS) was described to detect the residue of nine polybrominated diphenyl ethers in marine samples.Samples was extracted by hexane and cleaned up on a Florisil column,then were determined by GC-NCI/MS in the selected ion monitoring mode and with PCB-103 as the internal standard.The recovery studies were performed at 10.0 and 25.0 ng/g fortification levels for eight PBDEs(12.0 and 30.0 ng/g for PBDE-183),and the recoveries ranged from 88.1%~97.3% with a relative standard deviation between 2.0%~6.6%.The developed method was linear over the range of 0.50~250.0 μg/L(for PBDE-183: 0.60~300.0 μg/L) with correlation coefficient in the range of 0.9988~0.9999,and the detection limits are lower than 0.106 ng/g.The method was successfully applied to the determination of nine polybrominated diphenyl ethers residue in five marine samples.国家基础科学人才培养基金(No.J0630429

Determination of nine polybrominated diphenyl ethers residues in animal liver by gas chromatography-negative chemical ionization/mass spectrometry

建立了动物肝脏中9种PBDEs残留量的气相色谱-负化学离子源/质谱(GC-NCI/MS)的分析方法。动物肝脏样品经V(正己烷)∶V(丙酮)=1∶1超声辅助提取,中性与酸性硅胶层析柱净化和V(正已烷)∶V(CH2Cl2)=1∶1洗脱和浓缩后,以PCB-103为内标物,采用GC-NCI/MS的选择离子监测方式(SIM)对其中的9种PBDEs残留量进行了定性与定量分析。当动物肝脏空白样品的加标质量浓度为5.0、20.0μg/kg(PBDE-183为6.0、24.0μg/kg)时,9种PBDEs的平均加标回收率为75.1%~88.2%,相对标准偏差为3.3%~7.9%,方法检出限均小于0.07μg/kg;线性范围除PBDE-183为0.12~600.0μg/kg外,其余8种PBDEs为0.1~500.0μg/kg,相关系数都大于0.9993。所建立的分析方法已用于5种动物肝脏的8个样品中9种PBDEs残留量的分析。An analytical method for the determination of nine polybrominated diphenyl ethers(PBDEs) residue in animal liver is described based on gas chromatography coupled with negative chemical ionization mass spectrometry(GC-NCI/MS).In this paper,hexane/acetone(1/1,V/V) and hexane/dichloromethane(1/1,V/V) were used as the extraction and elution solvents.After the extraction was cleaned by silica and acid silica,the analysis of nine PBDEs in samples was accomplished using GC-NCI/MS in the selected ion monitoring mode(SIM) with PCB-103 as the internal standard(IS).This method performs well: the average recoveries of spiked samples range from 75.1% to 88.2% with relative standard deviations between 3.3% and 7.9%,method detection limit is lower than 0.07 μg/kg,the range of linearity is from 0.1 to 500.0 μg/kg for the other eight PBDEs except 0.12 to 600.0 μg/kg for PBDE-183,with correlation coefficients larger than 0.9993.The method has been applied successfully to the determination of nine polybrominated diphenyl ethers residues in eight samples of five animal livers.国家基础科学人才培养基金(J0630429)项目资

中华医学会精神病学分会 会议论文集

&lt;正&gt;目的精神分裂症患者存在认知缺陷症状,尤其是社会认知和情绪管理方面。以前研究发现精神分裂症患者在进行情绪任务时腹内侧前额叶(ventral medial prefrontal cortex,vMPFC)的激活异常,表明了vMPFC在情绪信息处理过程中的重要作用。目前为止,vMPFC和其他脑区的关系尚不清楚。本研究应用静息态磁共振脑成像技术研究精神分裂症患者vMPFC和其他脑区的功能连接,探索精&nbsp;</p

缓步行走3km对血压心率的影响及其辅助降压的β内啡肽机制

目的比较正常血压年轻人低、中、高强度运动前后血压、心率的变化,观察缓步行走对高血压患者血压、心率的影响,探讨真实世界研究中低代谢当量(MET,<3 METs)的温和运动之辅助降压作用及其神经内分泌机制。方法本试验分两部分:第一部分共入选正常血压年轻人32名,分别进行低强度[缓步行走3km,耗时(49±4)min]、中等强度[快步行走3km,耗时(32±2)min]和高强度(健身房综合锻炼1h)运动,其中32人全部参加缓步行走,自我评估体力可耐受中等强度运动的24人参加快步行走,平素有健身房锻炼习惯的9人参加高强度运动,于运动前、运动后即刻,5及10min分别测静息血压、心率,并计算简易心肌耗氧量(收缩压×心率),检测尿常规、白蛋白、尿β内啡肽;第二部分共入选20～86岁高血压患者30例及年龄相似的正常血压对照24人,均进行缓步行走3km,步行前后测静息血压、心率、尿白蛋白、尿β内啡肽及生长激素。结果 (1)正常血压年轻人一次性缓步行走3km可显著降低运动后10min内的静息血压、心率与简易心肌耗氧量[运动后10min比运动前:收缩压(108±8)比(115±8)mm Hg,心率(70±11)比(76±12)次/min,简易心肌耗氧量(7225±1189)比(8690±1633)mm Hg·次/min,均P<0.01],而快步行走显著增加运动后即刻静息收缩压、心率与心肌耗氧量[运动后即刻比运动前:收缩压(115±11)比(110±10)mm Hg,心率(89±18)比(73±10)次/min,简易心肌耗氧量(9151±2374)比(7230±1368)mm Hg·次/min,均P<0.01];高强度运动1h显著增加运动后10min内的静息心率(P<0.01)及心肌耗氧(P<0.05),增加血尿和(或)尿白蛋白阳性率(P<0.05)。(2)高血压患者缓步行走3km可显著降低步行后10min内的静息收缩压、舒张压、心率与简易心肌耗氧量[运动后10min比运动前:收缩压(125±11)比(133±9)mm Hg,心率(73±10)比(78±12)次/min,简易心肌耗氧量(8469±2075)比(9523±2216)mm Hg·次/min,均P<0.01];缓步行走过程中立位心率及心肌耗氧量变化不显著。(3)缓步行走3km可显著增加正常血压人群及高血压患者运动开始后1h尿β内啡肽排出量(P<0.05),而尿生长激素及白蛋白排出量无显著变化。结论真实世界研究中高血压患者缓步行走3km,可在不显著增加心血管负荷的情况下,降低运动后短期内的静息血压及心率,其辅助降压机制可能部分与运动增加β内啡肽释放有关。国家自然科学基金资助项目(31171099,30971154