Ion Mobility Spectrometry: Principles and Applications

Abstract

General principles are reviewed for ion mobility spectrometry including new methods for ion separation through field dependent mobilities in strong electric fields with high frequency asymmetric waveform. Additionally, recent advances in the instrumentation for the characterization of ion mobilities in air at ambient pressure are described and critically reviewed. Advances in instrumentation, understanding of principles of measurements by IMS, and the development of hyphenated technologies have resulted in an increase in the number of applications in recent years.     

Mass Spectrometric Determination of Transuranium Elements

Abstract

Mass spectrometric techniques are playing a predominant role for the determination of transuranium elements in bulk samples as well as in microparticles. Their applications to liquid and solid samples for the determination of the isotopic composition as well as for the concentration measurements are discussed. The new developments for the characterization of microparticles stemming from different release scenarios of radioactivity are considered. Inductively coupled plasma mass spectrometry and its hyphenation with other techniques for resolving isobaric interferences are presented. The application of glow discharge and laser ablation directly to solid samples is highlighted. Finally, the exploitation of secondary ion mass spectrometry, accelerator mass spectrometry, resonance ionization mass spectrometry, and thermal ionization mass spectrometry for the determination of the isotopic composition of uranium and plutonium in microparticles is illustrated.     

一种新颖的在线监测仪器--离子流动光谱仪

离子流动光谱仪（IMS）体积小，重量轻，耗能少，价格便宜，灵敏度高，适用范围广，能用于在线分析，是一种前景广阔的监测仪器。但有关的报道在国内却很少，本文介绍了它的基本原理、仪器构造、特点，局限性以及与色谱和质谱的连用，向小型化发展的方向。从德国光谱化学与应用光谱学研究所在此方面所作的工作讨论了离子流动光谱仪在爆炸物监控、化学武器鉴定、毒品稽查以及在线工业分析和环境监测中的应用。     

Comparison of Mid-IR with NIR in Polymer Analysis

Abstract

Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) represents a powerful technique for analyzing biological samples due to the ultrahigh resolving power, high mass accuracy, and multiple-stage tandem mass spectrometry (MSⁿ). With the advent of electrospray ionization (ESI), determinations of binding stoichiometry and binding sites for protein complexes are available. This review summarizes the recent FT-ICR MS applications in characterization of protein complexes, such as protein-peptide complexes, protein-protein complexes, and protein-nucleic acid complexes. Especially, combined with ECD and SWIFT techniques, FT-ICR MS has unique ion manipulation capabilities and plays a critical role in the analysis of protein complexes.     

Dielectric Barrier Discharge in Analytical Spectrometry

Abstract

Dielectric barrier discharge is a nonequilibrium plasma, and its industrial application has been on a large scale. Similarly, its prominent features of high dissociation ability at low working temperature and low power consumption, simple and adjustable configuration, ambient working conditions, and long lifetime are favorable for developing a wide array of analytical devices as well. This review addresses the basics of dielectric barrier discharge and emphasizes their analytical applications in analytical atomic spectrometry, chemiluminescence, gas chromatographic detectors, ion source for mass spectrometry, and ion mobility spectrometry with 103 references.     

New physical methods of organic compound identification using a surface ionization drift spectrometer

A new material for an ion thermoemitter is developed that provides efficient selective ionization of nitrogen-, sulfur-, phosphorus-, and arsenic-based organics and stability of ionization parameters. A new design of a drift spectrometer that allows for drift spectrometry analysis of unneutralized ion beams is suggested. It is shown that a drift spectrometer of such a design makes it possible to simultaneously determine a number of physicochemical characteristics of organic molecules (such as a complete set of drift mobility parameters for ions, activation energy of organic molecule ionization, and activation energy of organic molecule desorption from the test sample carrier), which is equivalent to significant improvement of the instrument’s effective resolution.     

同分异构体挥发性有机物的放电离子淌度谱研究

离子淌度谱利用大气压下不同离子在电场中的运动速度不同来达到分离离子的目的。离子在电场中的运动速度不仅与离子的质量有关,也与离子的结构有关,因此离子淌度谱可以有效地用来区分同分异构体。文章报道了用自行研制的放电离子源离子淌度谱仪对碳骨架异构、官能团类别异构和官能团位置异构的三类同分异构体进行了实验研究,得到了九种挥发性有机物的离子淌度谱,测量了各离子的约化迁移率,与前人使用神经网络理论得到的计算值相一致。实验表明这些同分异构体有机物能够在高分辨的离子淌度谱中实现分离,而且对本实验所研究的九种同分异构体有机物而言,迁移率大小符合规律：醇类<酮类<芳香类,直链<分支<环状,对位<间位<邻位。实验中使用指数稀释法对样品进行了定量分析,利用该方法得到的检测限达到ng·L-1量级。其中对官能团类别异构的同分异构体以及丁醇同分异构体的放电离子淌度谱研究均为首次报道。     

Mass Spectrometry,Review of the Basics: Electrospray,MALDI, and Commonly Used Mass Analyzers

Abstract

Mass spectrometry (MS) has progressed to become a powerful analytical tool for both quantitative and qualitative applications. The first mass spectrometer was constructed in 1912 and since then it has developed from only analyzing small inorganic molecules to biological macromolecules, practically with no mass limitations. Proteomics research, in particular, increasingly depends on MS technologies. The ability of mass spectrometry analyzing proteins and other biological extracts is due to the advances gained through the development of soft ionization techniques such as electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) that can transform biomolecules into ions. ESI can efficiently be interfaced with separation techniques enhancing its role in the life and health sciences. MALDI, however, has the advantage of producing singly charges ions of peptides and proteins, minimizing spectral complexity. Regardless of the ionization source, the sensitivity of a mass spectrometer is related to the mass analyzer where ion separation occurs. Both quadrupole and time of flight (ToF) mass analyzers are commonly used and they can be configured together as QToF tandem mass spectrometric instruments. Tandem mass spectrometry (MS/MS), as the name indicates, is the result of performing two or more sequential separations of ions usually coupling two or more mass analyzers. Coupling a quadrupole and time of flight resulted in the production of high-resolution mass spectrometers (i.e., Q-ToF). This article will historically introduce mass spectrometry and summarizes the advantages and disadvantages of ESI and MALDI along with quadrupole and ToF mass analyzers, including the technical marriage between the two analyzers. This article is educational in nature and intended for graduate students and senior biochemistry students as well as chemists and biochemists who are not familiar with mass spectrometry and would like to learn the basics; it is not intended for mass spectrometry experts.     

酮类有机物放电离子淌度谱研究

离子淌度谱是一种快速检测痕量挥发性有机物的高灵敏方法。在放电离子源离子淌度谱装置上,研究了八种酮类有机物的离子淌度谱。实验测量了各种离子的约化迁移率,其中丙酮、正丁酮、1-甲基-2-吡咯烷酮、环己酮、苯乙酮的实验结果与前人63Ni放射源离子淌度谱相一致,而甲基异丙基酮、4-甲基-2-戊酮、环戊酮单体和二聚体离子的约化迁移率则是首次报道。实验测量的约化迁移率与离子质量线性相关,获得的对酮类有机物检测灵敏度在ng·L-1量级。     

Characterization of Conifers and Their Products by Optical Atomic Spectrometry

Abstract

Conifers are primarily evergreen trees that are widely distributed; admired for their beauty; used as biomonitors for elements; processed for lumber, paper, fuel, and other products; and employed for food and medicinal products. Optical atomic spectrometry includes the widely used elemental analysis techniques of atomic absorption, atomic emission, and atomic fluorescence. This review considers applications of optical atomic spectrometry for conifers and their products. The goal is to assemble these diverse applications to assist analytical chemists and associated scientists in the development of methodology. The conclusion summarizes these studies and forecasts future developments.     

Fast Atom BombardmenUMass Spectrometry (FABMS) and Its Industrial Applications

Abstract

“Soft ionization” techniques which permit direct desorptton of gasphase analyte ions without the need for vaporization have greatly expanded the potential applications of mass spectrometry (MS). By using such techniques as field desorption (FD), desorption chemical ionization (DCI), and fast atom bombardment (FAB), thermally labile and higher molecular weight compounds are now amenable to MS exambation without significant thermal degradation. This ability to ionize higher molecular weight species has been paralleled by high field, inhomogeneous magnet development, allowing magnetic sector mass spectrometers to reach 10,000ν at full accelerating voltage. These advancements in ionization techniques and instrument design now permit useful MS data for organic compounds of several thousand molecular weight to be produced on a near routine basis in many laboratories.     

Trace Analysis Using Position-Sensitive Detection in Magnetic Sector Mass Spectrometry

Abstract

A position-sensitive ion detection system for trace analysis with magnetic sector mass spectrometers is described in detail, with particular application to high temperature mass spectrometry. The detection system consists of two stacked microchannel plates (Chevron assembly) backed by a resistive anode encoder and associated electronics. The range of masses simultaneously detectable is m to 1.2m. For electron impact ionization of silver at an electron energy of 10.5 eV, the sensitivity is 1.6 × 10^?7 Pa, and the mass resolution is 260 at mass 80 (valley 10% of the peak height definition). Additional applications for the detection system are discussed.     

A brief review on mass/optical spectrometry for imaging analysis of biological samples

Imaging analysis, especially bioimaging analysis, has been a hot research topic in recent years. There are numerous imaging analysis techniques for diverse applications of a wide spectrum of samples, with their unique advantages and disadvantages, and there are several related reviews published yearly. Among them, imaging mass spectrometry (IMS) is a relatively novel analytical technique for studying the distribution of molecular or ionic species at the level of tissue, cell, or subcellular, with its main feature of combining mass spectra for molecular identification and image visualization for quick and convenient analysis. The IMS does not require chemical labeling or complex sample preparation. This review, therefore, mainly focuses on the popular emerging IMS technique, including related ionization techniques in connection with their IMS applications, and some unique optical imaging techniques such as chemiluminescence imaging and dual-modal bioimaging for biological sample analysis, with 105 related recent references.     

Microplasma Technology and Its Applications in Analytical Chemistry

Abstract

This review article describes some existing microplasma sources and their applications in analytical chemistry. These microplasmas mainly include direct current glow discharge (DC), microhollow-cathode discharge (MHCD) or microstructure electrode (MSE), dielectric barrier discharge (DBD), capacitively coupled microplasmas (CCμPs), miniature inductively coupled plasmas (mICPs), and microwave-induced plasmas (MIPs). The historical development and recent advances in these microplasma techniques are presented. Fundamental properties of the microplasmas, the unique features of the reduced size and volume, as well as the advantageous device structures for chemical analysis are discussed in detail, with the emphasis toward detection of gaseous samples. The analytical figures of merit obtained using these microplasmas as molecular/elemental-selective detectors for emission spectrometry and as ionization sources for mass spectrometry are also given in this review article.     

Determination of Trace Elements in Vegetable Oils and Biodiesel by Atomic Spectrometric Techniques—A Review

Abstract

The determination of trace elements in edible oils and biodiesel using atomic spectrometric methods is reviewed. Problems related to sample pretreatment for appropriate sample introduction and calibration are addressed as well as the strategies to overcome them. Recent trends aimed at simplifying sample manipulation are presented. The applications and scope of atomic absorption spectrometry (AAS), flame optical emission spectrometry (F-OES), inductively coupled plasma–optical emission spectrometry (ICP-OES), and inductively coupled plasma–mass spectrometry (ICP-MS) techniques for the determination of trace metals in edible oils and biodiesel are discussed, as well as some current instrumental new developments.     

离子迁移谱检测技术及其应用

离子迁移谱技术是最近几十年发展起来的对微量化学物质进行检测的一种方法．目前它在探测各种化学物质，尤其是毒品和爆炸物方面获得了广泛的应用．文章主要对离子迁移谱仪的原理和检测方法、核心部件——迁移管的构造、其中的化学反应过程以及仪器的应用等几个方面作了介绍．     

Thermal Ionization and Inductively Coupled Plasma Mass Spectrometry: Potential for Application to Studies on the Biokinetics of Molybdenum in Humans

Abstract

The use of stable isotopes as tracers in biokinetic investigations provides a means to obtain important metabolic data directly in humans without exposing the subjects to undue risks. In this work, three types of mass spectrometers are compared with regard to the determination of the abundances of stable isotopes of molybdenum in natural and enriched aqueous samples. The data show a good response of thermal ionization mass spectrometry (TIMS) and of high-resolution inductively coupled plasma mass spectrometry (ICPMS) to the isotopic enrichment of the samples, whereas conventional quadrupole ICPMS shows an unsatisfactory reproducibility of the results. Moreover, only TIMS can achieve an accuracy of better than 1% for the obtained isotopic ratios. Although a tedious procedure for the preparation of the biological samples is required and less sensitivity is achieved as compared to ICPMS, TIMS still seems to be method of choice for the accurate assessment of isotope ratios as required in multitracer studies on human biokinetics of trace metals.     

Mass Spectrometry,Review of the Basics: Ionization

Abstract: Mass spectrometry (MS) has become an integral tool in life sciences. The first step in MS analysis is ion formation (ionization). Many ionization methods currently exist; electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) are the most commonly used. ESI relies on the formation of charged droplets releasing ions from the surface (ion evaporation model) or via complete solvent evaporation (charge residual model). MALDI ionization, however, is facilitated via laser energy and the use of a matrix. Despite wide use, ESI cannot efficiently ionize nonpolar compounds. Atmospheric pressure chemical ionization (APCI) and atmospheric pressure photo ionization (APPI) are better suited for such tasks. APPI requires photon energy and a dopant, whereas APCI is similar to chemical ionization. In 2004, ambient MS was introduced in which ionization occurs at the sample in its native form. Desorption electrospray ionization (DESI) and direct analysis in real time (DART) are the most widely used methods. In this mini-review, we provide an overview of the main ionization methods and the mechanisms of ion formation. This article is educational and intended for students/researchers who are not very familiar with MS and would like to learn the basics; it is not for MS experts.     

Thermal Lens Spectrometric Detection in Flow Injection Analysis and Separation Techniques

Abstract

Recent applications of thermal lens spectrometry in liquid chromatography (HPLC, ion chromatography), capillary electrophoresis, and flow injection analysis are reviewed. Possible effects of performing TLS measurements in flows are discussed initially for different TLS configurations. The emphasis is given to the analysis of real samples, and the performances of various detection schemes in combination with chromatographic techniques and FIA are discussed particularly in terms of sensitivity, sample throughput, and eventual interferences from complex matrices. Coaxial TLS detection with continuous wave excitation is most suitable for detection in HPLC, ion chromatography, and FIA using long‐path length cells, when large volume samples are available. On the other hand, transverse or crossed beam TLS was found most suitable for detection in CE where it provides low absolute LODs, which are lowered even further by thermal lens microscopy on microchips, where the capability of detecting a single molecule in the detection volume was demonstrated.     

基于时频谱特征的白酒品质分类方法研究

为了建立快速、准确的白酒品质鉴别方法,利用机器学习方法对不同品质的白酒建模。为了提取不同品质白酒的特征,使用离子迁移谱对不同品质白酒进行分析,构建了基于白酒离子迁移谱信号的特征向量,并对不同品质的白酒进行了识别与分类。白酒样本的离子迁移谱信号通过利用美国Excellims公司GA2100型电喷雾-离子迁移谱仪（ESI-IMS）采集获得,每一个离子迁移谱信号是强度随时间变化的时间序列信号;提取了原始数据离子迁移谱的时域特征谱峰。为了获得更全面的特征,对离子迁移谱数据进行了傅里叶变换并提取频域内的特征谱峰。同时为了表述信号变化的特征,计算了离子迁移谱的谱熵和过零率,构建N×9维的特征向量矩阵;使用主成分分析(PCA)和线性判别分析(LDA)分别对上述获得的特征进行了特征降维,其中使用PCA对特征向量矩阵降维后的前三维特征对整体特征的累计贡献率达到了95%,而使用LDA对特征向量矩阵降维后的前两维特征对整体特征的累计贡献率就达到了95%。因此,选择了LDA作为特征降维方法;最后,利用机器学习中的非线性分类器支持向量机(SVM)对白酒离子迁移谱数据进行分类研究。实验结果表明,在真酒和添加酒精的白酒二分类中,SVM方法正确分类率达到100%;而在真酒和分别添加10%,20%,30%,40%和50%酒精浓度的五种假酒的六分类中,SVM方法正确分类率达到99.7%。比较了逻辑回归(LRM)分类、模糊C均值分类(FCM)和K近邻分类(KNN)对白酒样本离子迁移谱分类实验结果。研究表明,对于离子迁移谱非常接近的真酒和添加酒精的白酒,基于频谱特征向量的SVM方法能够准确的区分开来,为白酒的品质鉴别提供了一种新的检测方法。