Study and Application of GC-NCI-MS Analytical Method on Organophosphorus Pesticides Residue in Vegetables and Fruits

摘要社会的进步使得人们越来越多地关注自身健康，科学技术的发展也使得人们对食品安全性问题有了更多的了解。食品安全不仅影响消费者的健康，而且影响国际食品贸易的发展，甚至影响社会的稳定，因此食品安全问题已成为全世界普遍关心的热点问题。本学位论文致力于食品中有机磷农药(organophosphoruspesticides,OPs)残留的分析方法研究与应用，全部内容分为三章。第一章简单介绍了OPs的发展简史及其毒理学原理。综述了食品中OPs残留分析研究进展，重点阐述了波谱分析检测技术、色谱分析检测技术、酶抑制分析检测技术和免疫分析检测技术在食品中OPs残留检测中的应用。最后，阐述了本学位论文的选题设想和...ABSTRACT People pay more attention to their own health because of the progress of the society, at the same time, people know more about the food security problem because of the development of science and technology. The food security not only affects the healthy of the consumer, but also affects progress of the international food trade, even affects the stabilization of the society. So the...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：20022501

基于FBG传感技术的复合材料加筋板低速冲击损伤监测

针对碳纤维增强树脂基复合材料低速冲击损伤的实时监测,本文设计将布拉格光纤光栅(FBG)传感器埋植在复合材料加筋板结构的三角填充区,在线监测复合材料T型加筋板冲击损伤过程。分别将FBG传感器埋植于复合材料层合板内部和复合材料T型加筋板的三角填充区,对比FBG传感器的埋入对复合材料层合板与复合材料T型加筋板对力学性能的影响,结果表明内埋FBG传感器的复合材料层合板试样的拉伸强度比未埋植传感器的层合板试样降低了约5%,但在FBG传感器的破坏应变范围内,FBG传感器可以准确、实时地监测复合材料的应变信号。将FBG传感器埋入复合材料T型加筋板的三角填充区,内埋FBG传感器的加筋板样件压缩破坏载荷与未埋植的样件基本一致。通过对比加筋板蒙皮上冲击位置、冲击能量对FBG传感器测得的冲击过程持续时间和最大应变值的影响,表明冲击过程持续时间随着冲击能量增加而延长,最大应变值随着冲击距离的增加呈下降趋势,而最大应变值随着冲击能量的增加呈上升趋势。利用FBG传感器测得的应变信号可初步实现对复合材料T型加筋板蒙皮冲击损伤位置及冲击能量的实时监测。国家重点研发计划(2016YFD0700603);;航空科学基金(2016ZF68011);;江苏省重点研发计划(BE2015007);;福建省科技创新平台建设计划(2014H2006

Multiresidue Determination of Organophosphorus Pesticides in Fruits and Vegetables by Gas Chromatography-Negative Chemical Ionization-Mass Spectrometry

建立同时分析果蔬中多种有机磷农药残留。果蔬样品经乙酸乙酯提取剂提取与flOrISIl硅藻土层析柱净化后,以乙硫磷为内标物,采用气相色谱-负化学离子化-质谱法同时的选择离子监测方式对多种有机磷农药残留进行定性与定量分析。结果表明:此方法快速、简便、灵敏度高和选择性好;9种有机磷农药残留的检测限为0.12~1.21μg/kg,平均回收率为76.5%~112%,相对标准偏差为1.45%~11.0%。A gas chromatography-negative chemical ionization-mass spectrometry(GC-NCI-MS) method was established to simultaneously determine 9 organophosphorus pesticide residues in fruits and vegetables.Samples were extracted with ethyl acetate and cleaned up on a Florisil column before GC-NCI-MS analysis in a selective ion-monitoring(SIM) mode.The internal standard used was ethion.The presented method was rapid,simple,sensitive and selective.The detection limits of this method for 9 organophosphorus pesticides were in the range of 0.12-1.21 μg/kg.The average recovery rates of 9 organophosphorus pesticides varied from 76.5% to 112% with a relative standard deviation of 1.45%-11.0%.江西省自然科学基金项目(2009GQH0018);江西省教育厅科学技术研究项目(GJJ09580

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

长汀县赢坪史前遗址发掘简报

2012年福建博物院对赢坪两处遗址进行了抢救性考古发掘,获得了一批包括石器、陶器、铜器、石范等内涵丰富的文化遗物,这批遗物可进一步了解闽西地区的史前文化发展序列及文化面貌,并且对于多地区文化间的交流研究也有一定的作用

Multiresidue Determination of Pyrethroid Pesticides in Fruits and Vegetables by Gas Chromatography-negative Chemical Ionization-mass Spectrometry

用气相色谱-负化学离子化质谱法(GC-NC I-MS)同时分析了水果蔬菜中7种拟除虫菊酯农药残留.试样用正己烷和丙酮混合提取剂提取与F lorisil硅藻土层析柱净化后,以δ-六六六为内标物,采用GC-NC I-MS的选择离子监测方式(SIM)对7种农药残留进行定性与定量分析.结果表明,此方法快速、简便、灵敏度高和选择性好;7种拟除虫菊酯农药残留的检测限为0.05~1.00μg.kg-1,平均回收率为74.6%~109%,相对标准偏差为9.9%~30%.GC-NCI-MS was applied to the simultaneous determination of seven pyrethoid pesticides (bifenthrin, fenpropathrin,cyhalothrin,permethrin,cypermethrin,fenvalerate and deltamethrin) in fruits and vegetables.The pesticide residues were extracted with hexane-acetone (11,by vol.) in an ultrasonic bath and cleaned up on a Florisil column to remove the co-extractives,then they were determined by Gas Chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS) in selected ion monitoring mode with δ-BHC as internal standard.Parameters of NCI were optimized with the result that the ion source temperature was set as 200℃ and the reagent gas pressure as 3.00×10~(-3) Pa.The detection limit of the method was in the range from 0.05 to 1.00 μg·kg~(-1) and the average recoveries of the seven pyrethroid pesticides varied between 74.6% and 108.5% with relative standard deviation ranging from 9.9% to 30.4%.The method showed excellent sensitivity and selectivity for pyrethroid pesticides.The analytical results of samples were as follow: fenpropathrin was 33.0 μg·kg~(-1) in celery;cypermethrin was 9.3 μg·kg~(-1) in pear,93.4 μg·kg~(-1) in tomato and 0.43 μg·kg~(-1) in celery;fenvalerate was 4.35 μg·kg~(-1) in tomato and 0.61 μg·kg~(-1) in celery

Multiresidue determination of pyrethroid pesticides in fruit juices by matrix solid-phase dispersion and gas chromatography-negative chemical ionization-mass spectrometry

建立了基质固相分散法(MSPD)和气相色谱-负化学离子源-质谱法(GC-NCI-MS)应用于果汁中10种拟除虫菊酯农药残留量的快速分析方法,并对这些农药NCI-MS的阴离子结构与断裂机理进行初步探讨。采用以中性氧化铝为吸附剂、Florisil硅藻土为净化剂和乙酸乙酯为洗脱剂的MSPD样品前处理方法,以PCB103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。当样品的加标浓度水平为50、250μg/kg时,平均加标回收率为86.7%~114.8%,相对标准偏差为1.9%~14.1%;除氯菊酯农药的方法检出限(MDL)为14.7μg/kg外,其余农药的MDL大都小于1.0μg/kg;线性范围为10~500μg/kg,相关系数都大于0.997,在所分析的大部分果汁中至少分析出两种以上的拟除虫菊酯农药残留。A rapid method based on matrix solid-phase dispersion was developed for the determination of ten pyrethroid pesticides in commercial juices.Meanwhile,negative ion structure and fracture mechanism of these pesticides of negative chemical ionization mass spectrometry were evaluated.The group of pesticides was added to juice and blended with neutral alumina,the mixture was packed into disposable filtration column,this column was tandem with florisil as cleaning and was eluted with ethyl acetate.The analysis of samples was accomplished using gas chromatography with negative chemical ionization mass spectrometric detection(GC-NCIMS) in the selected ion monitoring mode(SIM),and with PCB103 as internal standard.Recovery studies were performed at 50 and 250 μg/kg fortification levels for each pesticide,and the average recoveries ranged from 86.7 to 114.8% with a relative standard deviation between 1.9% and 14.1% for the different pesticides. The detection limit of the method was less than 1.0 μg/kg for most of pesticides except for the permethrin.The developed method was linear over the range assayed,10～500μg/kg,with correlation coefficients >0.997.The proposed method was applied to the analysis of these compounds in commercial juice samples.At least two pesticides was found in most of the samples

不同剂量C离子注入Si单晶中Si_(1-x)C_x合金的形成及其特征

室温下在单晶Si中注入(0.6-1.5)%的C原子，利用高温退火固相外延了Si_(1-x)C_x合金，研究了不同注入剂量下Si_(1-x)C_x合金的形成及其特征，如果注入C原子的浓度小于0.6%，在850-950℃退火过程中，C原子容易与注入产生的损伤缺陷结合，难于形成Si_(1-x)C_x合金相。随注入C原子含量的增加，C原子几乎全部进入晶格位置形成Si_(1-x)C_x合金，但如果注入C原子的浓度达到1.5%，只有部分C原子参与形成Si_(1-x)C_x合金。升高退火温度，Si_(1-x)C_x合金相基本消失