气相色谱-质谱联用法实验教学设计的探索与实践

阐述如何有效地设计气相色谱-质谱联用法实验教学系统,包括教学内容的设计原则、有效实施以及教学效果评价;介绍了几个适用于本科生和研究生教学的气相色谱-质谱联用分析实验。国家基础科学人才培养基金(No.J1210014

Solid-phase microextraction combined with gas chromatography - mass apectrometry: fundamental studies and applications in environmental and clinical toxicological analyses

自从1989年Pawliszyn研究小组提出“固相微萃取”的概念后，该技术作为一种样品前处理技术得到了快速的发展。其装置的核心部分是涂渍有各种固定液或吸附材料的纤维。固相微萃取全过程包括待测物在纤维与样品（空气、水等）之间的分配或吸附以及将纤维上富集的待测物解吸到分析仪器分离检测。该技术的使用无须使用有机溶剂，装置简单，价格低廉，萃取效率高，选择性好，可以与许多其他的分析方法联用。本论文的工作主要基于气相色谱-质谱分析系统，进行各种纤维吸附材料的基础研究。选择合适的纤维萃取待测物，可以获得好的固/液分配系数，从而极大提高方法的灵敏度。 研究的目的主要有：（1）为某些固相微萃取理论的论证提供...Solid-phase microextraction (SPME) is a sample preparation technique which has been rapidly developing since the basic concept of SPME was first described by Belardi and Pawliszyn in 1989. It consists of two processes: partitioning of analytes between the stationary phase immobilized on a fiber and the matrix (air, water, etc.), and followed by sequent desorption of the concentrated analytes into ...学位：理学博士院系专业：化学化工学院化学系_无机化学学号：B19962500

非平衡体系中固相微萃取技术的定量分析研究——快速监测水中痕量的有机污染物(多环芳烃)

采用固相微萃取技术，以100μM膜厚的聚二甲基硅氧烷纤维萃取水中10种多环芳烃，在60MIn采样时间内纤维上的吸附量与采样的时间近乎成正比，分配体系达到平衡前可以定量地测定水中的待测物.该方法的线性范围在0.1~100μg/l，检出限在0.01~0.03μg/l，15μg/l的回收率在80%~100%，相对标准偏差在20%以

The preparation of SPME coating using manganese oxide nanorod and its applications in the analysis of acrylamide in food samples

采用水热法合成氧化锰纳米棒,并以物理涂渍的方法固定于不锈钢丝上,制备获得氧化锰纳米棒固相萃取(SPME)涂层.该涂层对丙烯酰胺具有较好的富集能力,且具有较强的机械强度.实验通过优化萃取时间、萃取温度、解吸温度、解吸时间以及离子强度等影响萃取效率的实验条件,建立了利用该SPME与气相色谱-电子捕获检测器分析法,进行了薯片和饼干中丙烯酰胺含量的检测.结果显示,氧化锰纳米棒纤维涂层对于上述两种具有复杂基质样品中的丙烯酰胺具有较好的萃取能力,实验测得的薯片和饼干中丙烯酰胺的含量分别为2.43和1.31 mg g~(-1).Novel manganese oxide nanorods were synthesized using hydro-thermal method and applied as a coating material for solid phase microextraction(SPME). The extraction efficiency of acrylamide using the coating was investigated. Extraction conditions including extraction time, extraction temperature, desorption temperature, desorption time and ionic strength in the SPME of acrylamide were optimized. Under the optimized conditions, the SPME-GC-ECD method was successfully applied in the determination of acrylamide in potato chip and cookies samples. The detection results reveal the excellent extraction ability towards acrylamide in the two complex matrix samples. The obtained contents of acrylamide for the selected samples were found to be 2.43 and 1.31 mg g~(-1).厦门市科技局高校创新项目(编号:3502Z20143025);; 福建省科技重大专项(编号:2011YZ0001-1)资助项

Application of Sol-gel Technology in Solid-phase Microextraction(SPME)

固相微萃取技术的萃取效率及应用范围主要取决于其涂层的选择。传统的固相微萃取涂层热稳定性、使用寿命都不理想,溶胶凝胶技术的引入不但增加了涂层的种类,而且增加了使用寿命,提高了其使用温度及抗溶剂冲洗能力,大大拓宽了固相微萃取技术的应用范围。Stationary phase is the key to determine the extraction efficiency and the range of application of SPME. The traditional coatings of SPME are unstable at high temperature. The sol-gel technology can overcome the typical drawbacks of SPME coating, increase its anti-solution ability and thermal stability and broaden its application scope.国家"863"资助项目(编号:2002AA639390

Determination of polycyclic aromatic hydrocarbons(PAHs) in tea using solid phase microextraction coupled gas chromatography mass spectrometry

本文优化了萃取条件,建立了顶空-固相微萃取(HS-SPME)、气相色谱-质谱测定茶叶中4种多环芳烃的方法.茶叶中多环芳烃含量和对应的信号强度在0.3~150mg kg~(-1)范围内呈良好的线性关系,检出限为0.1~0.2mg kg~(-1),回收率在72.6%~102.4%之间;茶汤中含量和对应的信号强度在0.01~10mg kg~(-1)范围内呈良好的线性关系,检出限为0.005~0.01mg kg~(-1),回收率为76.4%~103.6%.In this study, GC-MS coupled head-space solid-phase microextraction(HS-SPME) was applied to detect 4 kinds of PAHs in tea and in tea infusion. After the optimization of the experimental consideration, the linear ranges for the PAH4 signal intensity and their concentrations are found to be 0.3–150 and 0.01–10 mg kg~(-1). The detection limit is 0.1–0.2 and 0.005–0.01 mg kg~(-1), with recovery of 72.6%–102.4% and 76.4%–103.6%, respectively

顶空薄膜微萃取-表面增强拉曼光谱法快速检测枸杞子中的二氧化硫残留量

目的:结合顶空薄膜微萃取技术具有的本底基质干扰小、萃取效率高的优点和表面增强拉曼光谱技术具有的检测快速、灵敏的特点,拟实现枸杞子中二氧化硫残（SO2）留量的快速分析。方法:在1个1...福建省自然科学基金(No.2015J01058);; 国家基础科学人才培养基金(NFFTBS-J1310024

Applications of multi-micro-volume pressure-assisted derivatization reaction device for analysis of polar heterocyclic aromatic amines by gas chromatography-mass spectrometry

设计并制作了耐压多样品微量衍生反应装置。在该装置中采用n-(叔丁基二甲基硅烷基)-n-甲基三氟乙酰胺(MTbSTfA,含1%叔丁基二甲基氯硅烷)硅烷化试剂高温衍生极性杂环胺,衍生产物可以直接在气相色谱-质谱联用仪上分析。使用该装置,既可以在比试剂沸点高的温度下实现衍生反应,也可以实现多个微量样品的同时衍生。着重考察了衍生化过程中反应瓶的顶空体积、试剂蒸发面积、温度、时间等实验条件的影响。结果表明,在90℃衍生时,与普通衍生装置相比,使用耐压衍生装置可以有效地减小挥发损失,显著增大衍生产量;在150℃衍生时,由于试剂挥发损失严重导致普通衍生装置无法使用,而采用耐压衍生装置却可以实现定量衍生,但通过加温加压方式来加快衍生反应速率的效果并不十分明显。A multi-micro-volume pressure-assisted derivatization reaction device has been designed and made for the silylation derivatization of polar heterocyclic aromatic amines by N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide(MTBSTFA) with 1% catalyst tert-butyldimethylchlorosilane(TBDMCS) at a high temperature.The tert-butyldimethylsilyl derivatives then could be automatically analyzed by gas chromatography-mass spectrometry.Using the pressure-assisted device,the silylation reaction may occur at a temperature higher than the boiling points of the reagents,and several micro-volume samples can be simultaneously pretreated in the same device to shorten the sample-preparation time and to improve the repeatability.The derivatization conditions including the headspace volume of the vial,the evaporative surface area of the reagent,derivatization temperature and time have been discussed for the use of the pressure-assisted device.The experimental results proved that the device is an effective way for the simultaneous derivatization of several micro-volume samples at a high temperature.Compared with a common device,the derivative amounts were obviously increased when using the pressure-assisted device at 90 ℃.Quantitative derivatization can be achieved even at 150 ℃ while there was no common device could be applied at such a high temperature due to the heavy losses of reagents by evaporation.However,no obviously higher reaction speed has been observed in such a circumstance with a higher temperature and a higher pressure using the pressure-assisted device.国家自然科学基金项目(21105084); 福建省自然科学基金项目(2009J01042); 福建省科技重大专项专题项目(2011YZ0001-1

Octadecyltrimethoxysilane functionalized ZnO nanorods as a novel coating for solid-phase microextraction with strong hydrophobic surface

National Natural Scientific Foundation of China [21105123, 21105084]; Science and Technology Projects of Fujian Province [2011Y0007]; Shandong Young Scientist Awards [BS2012CL037]In this paper, we have, for the first time, proposed an approach by combining self-assembled monolayers (SAMs) and nanomaterials (NMs) for the preparation of novel solid-phase microextraction (SPME) coatings. The self-assembly of octadecyltrimethoxysilane (OTMS) on the surface of ZnO nanorods (ZNRs) was selected as a model system to demonstrate the feasibility of this approach. The functionalization of OTMS on the surface of ZNRs was characterized and confirmed using scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The OTMS-ZNRs coated fiber exhibited stronger hydrophobicity after functionalization, and its extraction efficiency for non-polar benzene homologues was increased by a factor of 1.5-3.6 when compared to a ZNRs fiber with almost identical thickness and facade. In contrast, the extraction efficiency of the OTMS-ZNRs coated fiber for polar aldehydes was 1.6-4.0-fold lower than that of the ZNRs coated fiber, further indicating its enhanced surface hydrophobicity. The OTMS-ZNRs coated fiber revealed a much higher capacity upon increasing the OTMS layer thickness to 5 mm, leading to a factor of 12.0-13.4 and 1.8-2.5 increase in extraction efficiency for the benzene homologues relative to a ZNRs coated fiber and a commercial PDMS fiber, respectively. The developed HS-SPME-GC method using the OTMS-ZNRs coated fiber was successfully applied to the determination of the benzene homologues in limnetic water samples with recovery ranging from 83 to 113% and relative standard deviations (RSDs) of less than 8%