双电离源(辉光放电/激光溅射电离)四极杆质谱仪的研制

本研究将辉光电离源与激光溅射电离源巧妙地结合在同一台仪器中,使固体样品在离子源腔体中既能辉光电离,也能激光电离;并且使用同一质量分析器,两种离子源的结果可以相互比对,进而得到更为准确的分析结果.此仪器主要由真空系统、离子源、离子传输系统、四极杆质量分析器及检测与数据采集系统等组成.实验中分别用两种离子源测试了标准样品SRM 1262b,并获得了半定量结果.结果表明,仪器具有定性能力强,分析速度快,检测灵敏度高等优点,对固体样品元素分析的检出限可达μg/g量级.实验表明,激光溅射电离质谱的性能优于辉光放电质谱.     

大气采样辉光放电质谱仪的设计与应用

针对某些弱极性类物质难以通过大气压离子源直接电离的问题,提出基于大气采样辉光放电电离方式实现弱极性物质在大气压下直接进样、电离和质谱分析的方法.通过在大气压接口-四极质谱仪的第一级真空中的离子透镜上施加交流高压产生放电,简化了辉光放电离子源的设计,能直接离子化大气压接口吸人的物质,离子在离子透镜的传输下进入四极杆质量分析器实现质谱分析.实验表明,本方法能电离电喷雾电离离子源和大气压化学电离离子源未能电离的弱极性物质——艾试剂,并且负离子工作模式比正离子工作模式的信号至少强40倍.     

一种新型二次离子质谱的一次离子源及其离子光学系统

本研究设计了一种新型用于二次离子质谱的一次离子源及其离子光学系统.通过此一次离子源,大气压下产生的一次离子可以被加速、聚焦并传输到位于真空条件下的样品表面并电离样品得到可供质谱仪分析的二次离子.通过理论模拟结合实验系统研究了此一次离子源的主要组成部分——离子光学系统的原理、结构和性能.以电喷雾电离源为例,成功地将大气压...     

VG 354质谱计离子源电离带低温测量设备及其应用

设计了一种用于VG 354 型热电离质谱计电离带低温测量装置(DWZZ).它由热电偶温度计及连接件组装而成,能即时测定电离带的表面温度.测定的离子源中电离带的低温段温度与加热电流的关系可用关系式y=-ax3+bx2-cx+d表示,温度测定的误差＜±2℃.此装置已用于石墨非还原热离子发射特性和石墨存在下M2BO+2、M2X+离子的发射机理的研究.     

大气压光电离技术及其应用研究进展

大气压光电离离子源(APPI)是一种新兴的用于液质联用的软电离离子源,它是利用光化学作用将气相中样品电离的离子化技术,该技术促进了质谱技术对弱极性化合物的分析检测。介绍了液相色谱–质谱/质谱联用技术中大气压光电离的基本原理、应用优点,综述了其在定性、定量分析检测中的应用。     

在线实时直接分析离子源的研制

本文介绍了自制的常温常压下在线实时直接分析(Direct analysis in real-time,DART)离子源的原理及结构。在国内首次成功研制DART离子源,利用其对空气中挥发的丙酮和香烟侧流烟气进行电离,通过自制高分辨率垂直引入飞行时间质谱仪(Orthogonal-injection time-of-flight mass spectrometer,O-TOF-MS)进行分析和检测,得到丙酮分子峰及团簇峰和香烟烟气中尼古丁等大部分有害成分。实验结果表明,自制DART离子源能有效地对样品进行电离,使质谱仪器的质量半峰宽分辨率优于半高宽(Full width at half maximum,FWHM)6881,达到自制DART离子源的设计及实验分析要求。     

在线实时直接分析离子源的研制

本文介绍了自制的常温常压下在线实时直接分析(Direct analysis in real-time,DART)离子源的原理及结构。在国内首次成功研制DART离子源,利用其对空气中挥发的丙酮和香烟侧流烟气进行电离,通过自制高分辨率垂直引入飞行时间质谱仪(Orthogonal-injection time-of-flight mass spectrometer,O-TOF-MS)进行分析和检测,得到丙酮分子峰及团簇峰和香烟烟气中尼古丁等大部分有害成分。实验结果表明,自制DART离子源能有效地对样品进行电离,使质谱仪器的质量半峰宽分辨率优于半高宽(Full width at half maximum,FWHM)6881,达到自制DART离子源的设计及实验分析要求。     

改善液体辅助表面解吸常压化学电离质谱成像空间分辨率的研究

液体辅助表面解吸常压化学电离源(LA-DAPCI)通过电晕放电产生的初级离子和高密度带电液滴,能够对样品表面的中性待测物进行解吸电离,该离子源具有较高的离子化效率,适合复杂基体样品的质谱成像研究.为了满足质谱成像对空间分辨率的要求,本实验通过优化离子源结构、萃取剂组成、萃取剂流量、载气流速、离子源的几何位置参数等实验条件,有效提高了LA-DAPCI源的空间分辨率(从(441±14) μm提高到(58±7)μm).应用LA-DAPCI-MS/MS方法对罗丹明6G进行测定,检测限为0.01 ng/cm2,实验结果令人满意,为其应用于复杂基体样品的质谱成像研究提供科学依据.     

常压热解离化学电离源的研制及表征

自行研制了常压热解离化学电离源(TDCI),与商品化LTQ XL质谱仪成功联用,进一步考察了TDCI的性能,并对其应用领域进行了初步探索.TDCI-MS/MS谱图表明,离子液体可在现有实验条件下产生特征离子碎片;升高TDCI源偏置电压和温度,可以提高离子液体的信号强度.基于优化后的实验参数,常压热解离化学电离质谱方法(...     

常压下能量与电荷在分子间的传递机制

离子源是质谱仪的心脏,制备待测物的离子是质谱分析的首要前提.如何有效地电离含有复杂基体的实际样品中的痕量待测物分子是制约实际样品直接质谱分析的重要瓶颈.本文提出了用电子云模型帮助理解能量与电荷传递和中性分子电离过程的关系,从分子的基本物性参数、能量耦合方式等角度讨论了能量与电荷在不同相态、组成和维度的复杂基体样品分子间传递的过程,着重阐述了能荷传递过程中分子的电子云变化规律及其对分子电离的影响,并简要讨论了这些影响在质谱分析中的应用.     

气相色谱法测定大气中氪和氙

设计了一套测定气体的可调压进样装置,提出了气相色谱法-脉冲放电氦离子化检测器测定大气中氪和氙的含量。通过采用低温分离、柱程序升温及高效吸气柱消除了样品中基体气体对氪、氙测定的干扰。氪和氙的检出限(3S/N)分别为11 pg和24 pg。     

Liquid chromatography/atmospheric pressure photoionization tandem mass spectrometry for analysis of Dechloranes

Liquid chromatography/atmospheric pressure photoionization tandem mass spectrometry (LC/APPI-MS/MS) was investigated as an instrumental method for the analysis of the halogenated norbornene flame retardants, Mirex, Dechloranes 602, 603, 604, and Dechlorane Plus (DP). The LC separation was optimized by screening a variety of stationary and mobile phases, resulting in a short LC separation time of 5 min. Different atmospheric pressure ionization approaches were examined including electrospray ionization, atmospheric pressure chemical ionization, and APPI, each with and without post-column addition. APPI without post-column addition was chosen for providing the best ionization response. The optimized LC/APPI-MS/MS approach resulted in instrument detection limits ranging between 25 and 50 pg. Good linearity was also achieved (up to 25.0 ng/μL; R >0.999). The method was applied to extracts of environmental samples including surface water, fish and sediments for screening purposes, and the results agreed well with those obtained by gas chromatography/mass spectrometry.     

Atmospheric pressure gas chromatography-tandem mass spectrometry analysis of fourteen emerging polycyclic aromatic sulfur heterocycles in PM_(2.5)

Research on pollution characteristics and toxicities of emerging polycyclic aromatic sulfur heterocycles(PASHs) in PM_(2.5) has not been reported due to the lack of analytical method with the needed performance.In the present study,a novel method for the determination of 14 PASHs in PM_(2.5) was developed using atmospheric pressure gas chro matography-tandem mass spectrometry(APGC-MS/MS).Atmospheric pressure chemical ionization was operated with multiple reaction monitoring in positive ionization mode.High sensitivity(method detection limit 1.673 pg/m~3),acceptable re coveries(67.6%-120.8%) and precisions(RSD of 2.2%-15.4%) were obtained.The method was successfully applied for analyzing PASHs in 10 PM_(2.5) samples collected from Taiyuan,a typical industrial city in China,in 2016,The total concentrations were from 929 pg/m~3 to 14,593 pg/m~3.The determined levels indicated that further investigations on environmental fate and toxicities of PM_(2.5)-bound PASHs may be needed.     

Gold and silver nanoparticles‐based laser desorption/ionization mass spectrometry method for detection and quantification of carboxylic acids

A comparison of ionization efficiency for gold and silver nanoparticles used as an active media of matrix‐less laser desorption/ionization (LDI) mass spectrometry (MS) methods was made for carboxylic acids including fatty acids. The matrix‐assisted laser desorption/ionization (MALDI)‐type targets containing monoisotopic cationic ¹⁰⁹Ag nanoparticles (¹⁰⁹AgNPs) and Au nanoparticles (AuNPs) were used for rapid MS measurements of 10 carboxylic acids of different chemical properties. Carboxylic acids were directly quantified in experiments with 10 000‐fold concentration change conditions ranging from 1 mg/ml to 100 ng/ml which equates to 1 μg to 100 pg of carboxylic acids per measurement spot.     

High performance liquid chromatography/ion-trap mass spectrometry for separation and simultaneous determination of ethynylestradiol, gestodene, levonorgestrel, cyproterone acetate and desogestrel

A fast and highly sensitive high performance liquid chromatographic/ion-trap mass spectrometric method (LC/MS) has been developed for simultaneous determination of ethynylestradiol (EE2), gestodene (GES), levonorgestrel (LNG), cyproterone acetate (CPA) and desogestrel (DES). Among three types of sorbents tested (C8, C18 and phenyl) from two suppliers, the best separation was achieved on reverse phase Zorbax SB-Phenyl column using aqueous methanol as a mobile phase. A linear gradient profile from 70 up to 100% (v/v) in 7th min, kept constant at 100% up to 10th min and followed by a negative gradient to 70% of methanol up to 12th min was used for elution. Applicability of electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) and influence of the mobile phase composition, its flow rate, capillary/vaporizer temperature of API source and in-source fragmentor voltage ionization are discussed. The on-column limits of quantification (10 S/N) were 300 pg of EE2, 14 pg of GES and LNG, 4 pg of CPA and 960 pg of DES per injection (1 μL) using APCI with data collection in selected ion monitoring (SIM) mode. The analytical performance of the method was evaluated using the determination of EE2, GES, LNG, CPA and DES in contraceptives and river water samples.     

Determination of phenylalkylamine compounds using surface-assisted desorption/ionization from amorphous silicon

A new method has been developed for the mass spectrometric determination of phenylalkylamines based on surface-assisted laser desorption/ionization (SALDI). Films of amorphous α-Si, obtained by radiofrequency sputtering have been tested as ion emitters. The high efficiency of the ionization method combined with gas chromatography and the time-of-flight mass spectrometry has been demonstrated. The main analytical parameters have been determined for 12 phenylalkylamines. The detection limit for the studied compounds has been found to vary in the range 5–150 pg/mL.     

Determination of 24,25-dihydroxyvitamin D(3) in human plasma using liquid chromatography-mass spectrometry after derivatization with a Cookson-type reagent

A practical LC-MS method for determination of (24R)-24,25-dihydroxyvitamin D(3) [24,25(OH)(2)D(3)] in human plasma has been developed using derivatization with a Cookson-type reagent, 4-[4-(6-methoxy-2-benzoxazolyl)phenyl]-1,2,4-triazoline-3,5-dione (MBOTAD). The derivatization with MBOTAD significantly improved the ionization efficiency of the analyte with a detection limit of 18 fmol [equivalent to 7.5 pg of 24,25(OH)(2)D(3)] per injection. The method employed protein precipitation with acetonitrile, purification with OASIS HLB cartridge and silica gel column, derivatization with MBOTAD and atmospheric pressure chemical ionization MS detection. The mass spectrometer was operated in the positive-ion mode of mass chromatography and [26,26,26,27,27,27-(2)H(6)]-24,25(OH)(2)D(3) was used as an internal standard. The intra- and inter-assay coefficients of variation were below 3.4 and 2.5%, respectively, and the analytical recovery of 24,25(OH)(2)D(3) was quantitative. Assay linearity was obtained in the range of 0.05-1.2 ng per tube and the limit of quantitation was 0.23 ng/mL for a 0.3 mL plasma aliquot. The developed method was applied to plasma samples obtained from volunteers and gave satisfactory results.     

Liquid chromatography/tandem mass spectrometry for analysis of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) and 1,2,5,6-tetrabromocyclooctane (TBCO)

Although the two flame retardants 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) and 1,2,5,6-tetrabromocyclooctane (TBCO) have been widely used, a selective instrumental method of analysis for these compounds has not been developed to date. In this study, we demonstrate the feasibility to utilize liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the separation and analysis of α- and β-TBCO and α-, β-, γ-, and δ-TBECH. Acetone was initially used in a tetrahedron solvent system for LC optimization. A simple isocratic elution allowed near-baseline separation of these compounds. Different ionization approaches and mechanisms were investigated. The mass spectrometric transition of [M + O(2)](-) => Br(-) (459.8 => 78.9) was a selective detection method for the target analytes. Good instrument detection limits (5 pg for γ-/δ-TBECH, 125 pg for α-/β-TBECH, and 30 pg for α-/β-TBCO with 2.0 μL injection) were obtained. Excellent linearity up to 50 ng/μL (R(2) >0.999) was also achieved. This method has been applied to environmental samples (surface water) for screening purposes with recoveries ranging from 76-92% (CV%: 5-8%). This method shows significant improvement over previous methods.     

Study of Gaseous Sample Ionization by Excited Particles Formed in Glow Discharge Using High-Resolution Orthogonal Acceleration Time-of-Flight Mass Spectrometer

The experimental results of a mass spectral analysis of volatile organic compounds in a gaseous sample, obtained using an original design of an ion source based on the Penning ionization of a gas sample by excited metastable inert gas atoms, are presented. Using ANSYS software, a gas-dynamic simulation of reagent gas flow from discharge zone to ionization region was carried out to analyze the effect of gas flow profile on the transport of metastable atoms and ionization efficiency. The n-octane and toluene samples diluted with helium at 100 ppb mole concentrations were used for our experiments. The resulting mass spectra of n-octane and toluene samples containe far more intensive molecular ions in comparison to n-octane and toluene electron ionization mass spectra from the NIST database. The sensitivity of 5 ions per 1 pg and 130 ions per 1 pg was achieved for n-octane and toluene molecular ions using the developed ion source combined with our mass spectrometer. The corresponding detection limits are 2.3 pg s^–1 for n-octane molecular ions and 0.08 pg s^–1 for toluene molecular ions. The detection limit for the reported ion source was considered theoretically.     

Simultaneous determination of hexabromocyclododecanes and tris (2,3-dibromopropyl) isocyanurate using LC-APCI-MS/MS

Hexabromocyclododecanes (HBCDs) and tris (2,3-dibromopropyl) isocyanurate (TBC) are both brominated flame retardants, and have been used throughout the world with subsequent concern for potential environment pollution. Here we describe the development of a method for the simultaneous determination of TBC and HBCD diastereoisomers in environmental matrices by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The method recovery ranged from 81% to 93% and limits of detections (LODs) on column were 4.3 pg, 0.5 pg, 0.4 pg, 0.3 pg for TBC, α-HBCD, β-HBCD, and γ-HBCD, respectively, which showed high sensitivity compared to previous published methods. Compared to electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) was found to be a more sensitive, effective ionization mode for determination of HBCDs. This novel method was further validated by analyzing TBC and HBCDs in biotic and abiotic samples. The concentration ranges of TBC, α, β, γ-HBCD in sediment samples were 136.1-5884.6 ng/g, 9.0-1079.6 ng/g, 1.0-1161.7 ng/g, and 65.4-3964.2 ng/g, respectively. The concentration range for TBC, α-HBCD, β-HBCD, and γ-HBCD in common carp samples were 51.1-1899 ng/g, 21.6-1338 ng/g, <LOD-10.9 ng/g, and 1.4-101 ng/g, respectively.