激光后电离技术对高电离能元素的信号增强

固体样品的元素分析一直是分析化学重点关注的对象。激光作为一种固体直接采样和电离技术,常与飞行时间质谱联用,用于固体样品的元素分析。然而,对于高电离能元素的检测往往需要较大的激光功率密度,导致其离子的动能分散较大,严重影响谱图分辨率。本研究使用激光解吸/激光后电离质谱法（解吸激光波长515 nm,后电离激光波长266 nm）对固体样品中的Pd、Sb、Cd、Au等高电离能元素进行分析。一方面,采用较弱的解吸激光能量解决了强激光解吸电离所带来的动能分散问题,显著提高了谱图分辨率;另一方面,利用较强的后电离激光电离原来被“浪费”掉的绝大部分中性原子,提高原子利用率和仪器灵敏度。该方法无需任何样品前处理、分析时间短、操作简单,适用于固体中高电离能元素的快速检测。     

离子—分子反应及其在质谱分析中的应用

利用离子—分子反应 ,不仅可以提供分子离子峰 ,而且可以提高检测的灵敏度 ,了解分子的结构特征。本文根据离子—分子反应的机理 ,介绍了金属离子的亲和力的测定方法和金属离子在化合物上的加合位点 ,并阐述了离子—分子反应在化学电离质谱 ( CI-MS)、碱金属离子化学电离质谱 ( ACI-MS)、电喷雾电离质谱 ( ESI-MS)、快原子轰击质谱 ( FAB-MS)、以及基质辅助激光解吸电离质谱 ( MALDI-MS)中的应用     

光致二溴甲烷离子化学电离质谱分析VOCs

以真空紫外（VUV）灯作为电离源的单光子电离质谱（SPI-MS）分析方法是一种快速分析复杂样品中挥发性有机物（VOCs）的技术,但SPI-MS灵敏度受限于VUV灯较低的光通量及部分VOCs较小的电离截面。本工作自行研制了一种基于VUV Kr灯的新型光致二溴甲烷正离子化学电离源,并将该电离源与飞行时间质谱（TOF MS）联用进行VOCs分析。该电离源以体积分数1000 μL/L的二溴甲烷为试剂气体,利用VUV光电离产生稳定且充足的二溴甲烷正离子,二溴甲烷正离子与样品分子通过电荷转移发生化学电离,大大提高了样品的电离效率。与SPI源相比,该电离源不仅对电离能在10.0 eV附近的VOCs信号强度提升100倍以上（如对2-丙醇、乙酸乙酯和3-氯丙烯分别提高了103、118和126倍）,而且保持着与SPI一致的软电离特性。该电离源10 s内对复杂样品EPA TO-14、TO-15/17校准标气中的42种化合物的最低检测限达到0.06 μg/m³,并且因其具有较好的稳定性,在VOCs的实时在线监测方面有着广泛的应用。     

基质辅助激光解吸电离质谱用于生物组织的质谱成像应用进展

基质辅助激光解吸电离质谱(MALDI MS)用于分析组织切片已成为质谱学的一个新领域。质谱成像技术通过直接对组织切片表面的质谱扫描,可以快速直观地分析组织中的分子,如蛋白质、多肽、药物分子、代谢产物等及其空间分布信息。本工作综述了组织切片的质谱成像原理,方法学和相关应用。     

电喷雾电离质谱及其在蛋白质化学研究中的应用

本文介绍了电喷雾电离质谱并综述其在蛋白质化学研究中的应用.由于电喷雾电离质谱可产生多电荷峰,因此扩大了检测的分子质量范围,同时灵敏度较高,另外它可与HPLC及高效毛细管电泳分离技术联用,扩大了质谱在蛋白质化学研究中的应用.     

真空紫外光电离质谱及其在大气化学中的应用研究

大气环境污染成因复杂，往往涉及一系列复杂的化学反应过程，且包含众多的挥发性有机物气体分子、自由基和气溶胶颗粒物等，在线检测是大气化学领域的难点和热点问题。真空紫外光电离质谱技术使分子吸收单个光子能量后，在其电离能阈值附近“软”电离，可以获得分子离子质量信息，具有质谱图简洁、碎片离子少和易于解析等特点，能够从分子层面上在线测量大气化学反应过程中关键的化学成分，揭示复杂的大气化学反应机理，在大气化学领域具有较好的应用前景。本文介绍了基于真空紫外激光、同步辐射光源、自由电子激光和真空紫外放电灯等多种光源的真空紫外光电离质谱技术，阐述了近年来该技术在大气挥发性有机物、自由基以及气溶胶颗粒物化学成分检测方面的进展，并展望真空紫外光电离质谱技术的发展方向。     

在线纯化技术应用于MALDI-TOFMS测定溶菌酶的分子量

在用基质辅助激光解吸电离飞行时间质谱(MALDI-TOFMS)测定蛋白质分子量的过程中,一些盐和蛋白质变性剂经常大大抑制样品信号,产生一些难以解析的离子峰,因此测试前应尽可能去除样品中的添加剂。为此,本研究建立了MALDI—TOFMS测试中在线纯化蛋白质样品的新方法。采用硝酸纤维素膜作为固相载体,将标准蛋白质溶菌酶制成含6 mol/L盐酸胍变性剂、2％SDS表面活性剂的100 mmol/L Tris—HCL溶液进行质谱测定。结果表明:新方法简单、快速,可明显增强离子峰的强度,提高测定蛋白质分子量的灵敏度。     

化学电离质谱学

本文从六个方面总结了1966—1982年间化学电离质谱学的状况:(1)仪器发展概况;(2)基本理论;(3)反应试剂;(4)离子分子反应类型;(5)各类有机化合物的化学电离质谱;(6)分析应用。     

铀材料分析中的无机与同位素质谱法研究进展

综述了近年来中国工程物理研究院材料研究所应用无机与同位素质谱法进行铀材料分析的相关研究工作。在痕量铀同位素测量方面,发展了一种以氧化石墨烯作为电离增强剂的热电离质谱制样技术,显著增强了电离效率。在铀材料中杂质元素分析方面,开发了基于微流控芯片与电感耦合等离子体质谱联用的在线分离、分析方法,提高了分析的自动化程度。在金属铀中杂质元素的辉光放电质谱直接测定方面,基于相对灵敏度因子影响因素的研究基础,获得了一套普适性的相对灵敏度因子,实现了缺乏基体匹配标准物质时的准确测定。利用飞行时间-二次离子质谱法研究了铀及铀合金的偏析行为、夹杂物的表征、氢化/氧化腐蚀行为,为铀材料研究提供了表征手段。最后,对无机与同位素质谱法用于铀材料分析的发展前景进行了展望。     

混杂样品各组分顺次电离装置的研制与应用

本工作研发了能与质谱联用的混杂样品顺次电离装置,用于在分子层次获取样品中不同组分的分子结构、丰度以及空间分布等信息。本装置设计了包括试剂选择与混配、形貌显微分析、微量样品电解与电离等多个模块。在微型反应池内,不同溶剂选择性地溶出样品中物理化学性质各异的组分,在时序触发与智能控制模块的调控下实现混杂样品的顺次电离与质谱分析。利用该装置实现了对合金、矿石、生物样品中有机及无机组分的顺次检测,获得了丰富的组分信息,在材料、能源、地球、生命等科学领域具有良好的应用前景。     

（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯异构体的GC/MS研究

为了研究钯催化的2,4-二甲氧基苯甲酸与烯丙基丙二酸二乙酯的脱羧Heck反应的产物结构,建立了（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯同分异构体的分离与鉴定的气相色谱-离子阱质谱方法。首先通过脱羧Heck反应制得（2,4-二甲氧基苯基）烯丙基丙二酸二乙酯异构体混合物,然后利用GC/MS联用技术对混合物进行分析,得到各组分的EI和CI全扫描模式质谱信息。通过对照各组分的分子离子峰确定互为异构体的组分,再对异构体组分采用MS/MS模式获取各自的裂解碎片。通过分析异构体的不同的裂解碎片,讨论质谱裂解方式,从而确定异构体的结构。该方法省时、经济、高效,可为此类化合物的分析与鉴别提供参考。     

A Dual Ionization Source with Laser Desorption Sample Introduction in a Time-of-Flight Mass Spectrometer

Abstract

A new mass spectrometric detection system has been developed for the analysis of non-volatile chemical species such as biochemicals. This system involves the use of a novel dual ionization source, consisting of laser-induced electron ionization (EI) and multiphoton ionization (MPI), to provide versatile ionization for a wide range of chemicals in a time-of-flight mass spectrometer. Laser desorption is incorporated into the system for sample vaporization.

The experimental design of this system is described. It is demonstrated that two ionization modes can be interchanged very readily by simply adjusting the position and focus of the laser beam. EI and MPI mass spectra of a number of amino acids and small peptides are shown to illustrate the detection capability of the system. For chemicals amenable to both ionization methods, EI and MPI can provide sensitive detection with different fragmentation patterns. Thus, the operation in a dual ionization mode provides enhanced structural information. In addition, laser-induced EI is shown to be a more general ionization method while MPI provides selective ionization with controlled fragmentation. The combination of these unique properties is demonstrated in the study of laser desorption process of an organic salt.     

Direct-EI in LC-MS: towards a universal detector for small-molecule applications

This review article will give an up-to-date and exhaustive overview on the efficient use of electron ionization (EI) to couple liquid chromatography and mass spectrometry (LC-MS) with an innovative interface called Direct-EI. EI is based on the gas-phase ionization of the analytes, and it is suitable for many applications in a wide range of LC-amenable compounds. In addition, thanks to its operating principles, it prevents unwelcome matrix effects (ME). In fact, although atmospheric pressure ionization (API) methodologies have boosted the use of LC-MS, the related analytical methods are sometime affected by inaccurate quantitative results, due to unavoidable and unpredictable ME. In addition, API's soft ionization spectra always demand for costly and complex tandem mass spectrometry (MS/MS) instruments, which are essential to acquire an "information-rich" spectrum and to obtain accurate quantitative information. In EI a one-stage analyzer is sufficient for a qualitative investigation and MS/MS detection is only used to improve sensitivity and to cut chemical noise. The technology illustrated here provides a robust and straightforward access to classical, well-characterized EI data for a variety of LC applications, and readily interpretable spectra for a wide range of areas of research. The Direct-EI interface can represent the basis for a forthcoming universal LC-MS detector for small molecules.     

Secondary ion counting for surface-sensitive chemical analysis of organic compounds using time-of-flight secondary ion mass spectroscopy with cluster ion impact ionization

We report suitable secondary ion (SI) counting for surface-sensitive chemical analysis of organic compounds using time-of-flight (TOF) SI mass spectroscopy, based on considerably higher emission yields of SIs induced by cluster ion impact ionization. A SI counting system for a TOF SI mass spectrometer was developed using a fast digital storage oscilloscope, which allows us to perform various types of analysis as all the signal pulses constituting TOF SI mass spectra can be recorded digitally in the system. Effects of the SI counting strategy on SI mass spectra were investigated for C(8) and C(60) cluster ion impacts on an organically contaminated silicon wafer and on polytetrafluoroethylene targets by comparing TOF SI mass spectra obtained from the same recorded signals with different SI counting procedures. Our results show that the use of a counting system, which can cope with high SI yields, is necessary for quantitative analysis of SI mass spectra obtained under high SI yield per impact conditions, including the case of cluster ion impacts on organic compounds.     

几种含硒二茂铁衍生物的质谱分析

本文报导了几种含硒二茂铁衍生物的ＥＩ－ＭＳ，讨论了这些化合物结构的特征信息，并通过磁场／静电场（Ｂ／Ｅ）的联动扫描技术，研究了这类化合物的质谱断裂规律。     

Modification of an AEI/GEC MS9 High-Resolution Mass Spectrometer for Electron Impact/Chemical Ionization Studies

ABSTRACT

A double-focusing MS9 mass spectrometer has been modified to permit operation in both chemical ionization (CI) and electron impact (EI) modes. The modifications consist mainly of a closed ion chamber, a high capacity pumping system, a reactant gas inlet system, a new solid sample probe, and a source pressure measuring device. Changes have also been made in the electronic system and a new ion source power supply has been incorporated. The new ion source can be operated in the CI mode at pressures up to 1 Torr while the pressure in the analyzer is better than 10^?7 Torr. The new set-up has the ability to analyze solid, liquid, and gas samples in both CI and EI mode. It has also the ability to do GC/MS without a Separator.

The sensitivity in the CI mode is comparable to the sensitivity in the EI mode, and the maximum resolution obtained with the CI/EI source is similar to that obtained with the original EI source.     

五味子中木脂素类化合物的电喷雾质谱分析

lignan constituents in Schisandra Chinensis (Turcz.) Baill. were investigated using electrospray ionization multi-stage tandem mass spectrometry (ESI-MSⁿ). Four compounds in Schisandra chinensis (Turcz.) Baill. were observed in the positive mode. The experimental results demonstrate that the ESI-MSⁿ can provide the information of the relative molecular mass and chemical structure of the compounds.     

高效液相色谱-质谱联用法分析龙胆中的环稀醚萜类成分

A rapid method was developed to analyze the extract of the Gentiana scabra Bge. by using high performance liquid chromatograghy-electrospray ionization multi-stage tandem mass spectrometry (HPLC-ESI-MSⁿ). 5 compounds in Gentiana scabra Bge. are identified in the positive and negative mode. The research results demonstrate that the HPLC-ESI-MSⁿ can quickly identified the components in Gentiana scabra Bge. . It also can provide the information of the relative molecular mass and chemical structure of the compounds in the extract of the Gentiana scabra Bge. .     

Mass spectrometry in the characterization of reactive metal alkoxides

Metal alkoxides are metal‐organic compounds characterized by the presence of M?O?C bonds (M = metal). Their chemistry seems to be, in principle, relatively simple but the number of possible reactant species arising as a consequence of their behavior is very remarkable. The physico‐chemical properties of metal alkoxides are determined by many different parameters, the most important ones being the electronegativity of the metal, the ramification of the ligand, and the acidity of the corresponding alcohol. Their reactivity makes them suitable and versatile candidates for many applications, including homogeneous catalysis, synthesis of new ceramic materials through the sol‐gel process and, recently, also for Cultural Heritage. Metal alkoxides are characterized by a strong tendency to give clusters and/or oligomers through oxo‐bridges. Mass spectrometry has been successfully employed for the characterization of metal alkoxides in the gas‐phase. Electron ionization (EI) allowed the assessment of the molecular weight and of the most relevant decomposition pathways giving information on the relative bond strength of differently substituted molecules. On the other hand, information on the reactivity in solution of these molecules have been obtained by electrospray ionization (ESI)‐matrix assisted laser desorption ionization (MALDI) experiments performed on their reaction products. These data were relevant to investigate the sol‐gel process. In this review, these aspects are described and the results obtained are critically evaluated. © 2016 Wiley Periodicals, Inc. Mass Spec Rev     

多氯代多环芳烃的质谱裂解规律

为揭示多氯代多环芳香化合物的质谱裂解规律,对10种标准多氯代多环芳香化合物（PCAHs）进行电子轰击质谱（EI-MS）和大气压化学电离质谱（APCI-MS）分析。发现在EI-MS中,所有C—Cl键均易断裂,得到失去一个或多个氯原子的碎片峰,这些碎片峰呈现偶强（失去偶数个氯原子）奇弱（失去奇数个氯原子）的分布规律,而且大多数PCAHs的分子离子峰为基峰。在APCI-MS中,完全由六元芳香环构成的全氯代芳香烃不出现分子离子峰,而其他的PCAHs则均出现分子离子峰和加合峰。