原位电离与小型质谱在公共安全领域的应用

质谱作为一种具有高准确度、高灵敏度、高选择性的检测仪器,在公共安全领域有着重要的应用前景。公共安全领域的需求主要涉及毒品、毒物、爆炸物等化学物质的现场快速检测,因其影响广泛,检测结果需非常准确。作为实验室分析仪器,质谱的准确性和速度能满足公共安全的应用需求,但作为现场快速检测的仪器仍需要一定改进。现场快速检测一方面要求检测仪器的小型化,另一方面要求样品前处理的简单化,以使整个检测流程可以无需专业人员来完成。对于检测仪器的小型化,小型质谱的开发在近20年得到了充分发展;对于样品前处理的简单化,研究者发明了原位电离技术,使得基质复杂的被分析物无需前处理即可进行质谱检测。该文首先介绍了原位电离技术的发展及其在公共安全领域的应用,特别是对解吸附电喷雾电离、实时直接分析电离、激光烧蚀电喷雾电离、纸喷雾电离与纸毛细管喷雾电离等典型原位电离技术的原理、性能及在公共安全领域的应用进行了详细介绍,并讨论了几种原位电离现场定量方法。然后,对原位电离小型质谱的发展进行了综述,从最初的小型化离子阱,到仅能检测可挥发有机物的小型质谱,再到可检测非挥发性物质的常规大气压电离源小型质谱,最后发展成为有原位电离源的小型质谱,历经20年的发展使得原位电离小型质谱得以出现和提升。并列举了原位电离小型质谱在毒品现场检测与吸毒人员排查、爆炸物现场侦察、食品安全之农用化学品检测、药物质量检查等公共安全领域的应用。最后,对原位电离小型质谱的发展进行了展望,指出原位电离与小型质谱相结合是小型质谱发展的必然趋势,未来需使用更加智能化的原位电离小型质谱,结合云数据平台,实现更方便广泛的应用。     

敞开式离子化质谱在贸易产品化学风险物质筛查中的应用及前景

敞开式离子化质谱是一种新兴的质谱快检技术,具有分析速度快、操作流程简单、特异性强等特点。该技术无需对样品做复杂预处理,尤其在与便携式质谱仪联用时,可用于大量样品的现场、快速、准确筛查,在贸易产品化学风险物质的筛查中展现出广泛的应用前景。该文主要综述敞开式离子化质谱近年来在贸易产品化学风险物质筛查方面的研究进展,并对其未来的发展前景进行了展望。     

实时直接分析质谱新技术及其应用

由于不需要复杂的样品前处理过程,并具有实时、原位分析等特点,常压敞开式离子化技术成为近年来质谱研究的热点之一.实时直接分析(direct analysis in real time,DART)是近年来出现的一种常压敞开式离子化新技术,在食品安全、环境监测、爆炸物检测以及生物医药等诸多研究领域均有广泛的应用.本文简单介绍了常压敞开式离子化方法的发展,DART的基本原理和研究现状.进而介绍了我国质谱研究人员在基于DART的质谱仪器改进、联用技术以及生物药物等检测分析方面取得的新进展和新成果.     

等离子体常压解吸离子源质谱

近年来,常压开源质谱解吸/离子化(ambient desorption/ionization mass spectrometry)技术的开发促进了质谱分析的蓬勃发展.作为常压开源质谱技术的一大重要分支,基于等离子体的常压质谱解吸/离子化技术因无需样品预处理、无溶剂化过程、高灵敏度、高通量、能实时在线检测样品等优点,受到了学术界及仪器制造、化学和生物分析等相关产业界的广泛关注.本文从离子源的种类、原理及应用等角度对目前我国在开源质谱领域中自主研发的基于等离子体的常压离子源的研究进展进行了总结,并对此类等离子体常压离子源的发展进行了展望,重点涉及微波等离子体源、常压微辉光放电等离子体源和解吸电晕束离子源.     

Recent advances of ambient ionization mass spectrometry imaging in clinical research

The structural information and spatial distribution of molecules in biological tissues are closely related to the potential molecular mechanisms of disease origin, transfer, and classification. Ambient ionization mass spectrometry imaging is an effective tool that provides molecular images while describing in situ information of biomolecules in complex samples, in which ionization occurs at atmospheric pressure with the samples being analyzed in the native state. Ambient ionization mass spectrometry imaging can directly analyze tissue samples at a fairly high resolution to obtain molecules in situ information on the tissue surface to identify pathological features associated with a disease, resulting in the wide applications in pharmacy, food science, botanical research, and especially clinical research. Herein, novel ambient ionization techniques, such as techniques based on spray and solid‐liquid extraction, techniques based on plasma desorption, techniques based on laser desorption ablation, and techniques based on acoustic desorption were introduced, and the data processing of ambient ionization mass spectrometry imaging was briefly reviewed. Besides, we also highlight recent applications of this imaging technology in clinical researches and discuss the challenges in this imaging technology and the perspectives on the future of the clinical research.     

介质阻挡放电离子源质谱分析

敞开式离子化质谱可对表面样品进行直接快速分析而受到关注,成为质谱分析的热点研究方向.介质阻挡放电离子源是一种基于等离子体放电机理的敞开式离子源,近年来得到了较快的发展.本文着重介绍该离子源的基本原理、性能特征以及应用进展,并对其发展趋势进行了展望.     

实时直接分析质谱在农药检测中的应用

实时直接分析(Direct analysis in real time,DART)作为一种原位电离技术发展迅猛,其与质谱联用已成为热门的分析技术并广泛应用于法庭科学领域,如食品安全、爆炸物检测、毒物毒品分析和药物分析等方面。目前农药的常规检测方法已非常成熟,但引入原位电离-质谱联用技术可以拓宽检测范围,缩短检测时限。该文从实时直接分析质谱(DART-MS)技术的工作原理、检测条件优化及其在农药检测方面的应用进行综述,并对DART-MS的应用前景进行了展望。     

快速蒸发电离质谱技术及其应用研究进展

近年来,原位电离质谱技术成为质谱分析领域的研究前沿和热点。快速蒸发电离质谱技术源于外科手术中的手术烟雾现象,自2009年报道以来,作为一种新型原位电离质谱技术已被广泛应用于医学、微生物鉴定、食品真伪鉴别、代谢物研究、药用植物成分鉴定等领域。该技术通过电离切割组织或其他生物样品产生的含丰富特定区域生物特征的气溶胶,对其进行原位、在线、实时、快速质谱分析。该文阐述了快速蒸发电离质谱技术的发展历程、电离机制及工作原理,并对其在不同领域的应用研究进展进行了综述,可为相关领域研究人员提供科研思路和技术参考。     

质谱在高通量快速检测技术中的应用研究进展

质谱是现代分析测试技术中同时具备了灵敏度高、特异性好、分析速度快等特性的普适性方法,现已被广泛应用于食品检验、环境监测、药物筛选、临床医学等众多领域的高通量快速检测技术中。该文针对近年来低分辨质谱、高分辨质谱以及原位电离质谱技术在高通量快速检测,特别是小分子化合物的高通量快速检测中的应用研究进展进行了综述,并对质谱技术用于高通量快速检测的发展趋势及应用前景进行了展望,以期为相关领域的科技人员提供理论支持和技术参考。     

Ambient mass spectrometry: bringing MS into the “real world”

Mass spectrometry has recently undergone a second contemporary revolution with the introduction of a new group of desorption/ionization (DI) techniques known collectively as ambient mass spectrometry. Performed in an open atmosphere directly on samples in their natural environments or matrices, or by using auxiliary surfaces, ambient mass spectrometry (MS) has greatly simplified and increased the speed of MS analysis. Since its debut in 2004 there has been explosive growth in the applications and variants of ambient MS, and a very comprehensive set of techniques based on different desorption and ionization mechanisms is now available. Most types of molecules with a large range of masses and polarities can be ionized with great ease and simplicity with the outstanding combination of the speed, selectivity, and sensitivity of MS detection. This review describes and compares the basis of ionization and the concepts of the most promising ambient MS techniques known to date and illustrates, via typical analytical and bioanalytical applications, how ambient MS is helping to bring MS analysis deeper than ever into the “real world” open atmosphere environment—to wherever MS is needed.     

The micro-discharge family (dark, corona, and glow-discharge) for analytical applications realized by dielectric barriers

The similarity principles of electric plasmas, and the current-voltage characteristics of the most prominent kinds of discharges used for analytical applications, are discussed. Most of the discharges can be miniaturized, and some of the analytical applications of different discharges can be realized by use of dielectric barriers for analytical applications, for example element spectrometry, as an ionization source for ion-mobility spectrometry or organic mass spectrometry, and as an electrospray ionization source.     

解吸电喷雾电离技术

本文介绍了一种新近发展起来的质谱离子化方法——解吸电喷雾电离（desorption electrospray ionization, DESI）及其最新研究进展。该方法首次于2004年提出后,由于其具有样品无需前处理就可以在常压条件下从各种载物表面直接分析固相,或凝固相样品等优势而得到了迅速的发展。本文描述了DESI的基本原理、离子源的结构和相关优化的参数,并对该离子化方法中所用的载物表面进行了总结。在实际应用方面,本文综述了DESI技术在常压气相化学反应产物监测,合成高聚物表征,爆炸物和化学战毒剂检测,以及在药品,生物代谢产物和生物组织表面分析方面的应用成果,同时对DESI的基础应用研究方向进行了分析和展望。     

Ambient ionization mass spectrometry: a tutorial

Ambient ionization is a set of mass spectrometric ionization techniques performed under ambient conditions that allows the direct analysis of sample surfaces with little or no sample pretreatment. Using combinations of different types of sample introduction systems and ionization methods, several novel techniques have been developed over the last few years with many applications (e.g., food safety screening; detection of pharmaceuticals and drug abuse; monitoring of environmental pollutants; detection of explosives for antiterrorism and forensics; characterization of biological compounds for proteomics and metabolomics; molecular imaging analysis; and monitoring chemical and biochemical reactions). Electrospray ionization and atmospheric pressure chemical ionization are the two main ionization principles most commonly used in ambient ionization mass spectrometry. This tutorial paper provides a review of the publications related to ambient ionization techniques. We describe and compare the underlying principles of operation, ionization processes, detecting mass ranges, sensitivity, and representative applications of these techniques.     

Direct identification of prohibited substances in cosmetics and foodstuffs using ambient ionization on a miniature mass spectrometry system

Significantly simplified work flows were developed for rapid analysis of various types of cosmetic and foodstuff samples by employing a miniature mass spectrometry system and ambient ionization methods. A desktop Mini 12 ion trap mass spectrometer was coupled with paper spray ionization, extraction spray ionization and slug-flow microextraction for direct analysis of Sudan Reds, parabens, antibiotics, steroids, bisphenol and plasticizer from raw samples with complex matrices. Limits of detection as low as 5 μg/kg were obtained for target analytes. On-line derivatization was also implemented for analysis of steroid in cosmetics. The developed methods provide potential analytical possibility for outside-the-lab screening of cosmetics and foodstuff products for the presence of illegal substances.     

Forensic applications of ambient ionization mass spectrometry

This review highlights and critically assesses forensic applications in the developing field of ambient ionization mass spectrometry. Ambient ionization methods permit the ionization of samples outside the mass spectrometer in the ordinary atmosphere, with minimal sample preparation. Several ambient ionization methods have been created since 2004 and they utilize different mechanisms to create ions for mass-spectrometric analysis. Forensic applications of these techniques—to the analysis of toxic industrial compounds, chemical warfare agents, illicit drugs and formulations, explosives, foodstuff, inks, fingerprints, and skin—are reviewed. The minimal sample pretreatment needed is illustrated with examples of analysis from complex matrices (e.g., food) on various substrates (e.g., paper). The low limits of detection achieved by most of the ambient ionization methods for compounds of forensic interest readily offer qualitative confirmation of chemical identity; in some cases quantitative data are also available. The forensic applications of ambient ionization methods are a growing research field and there are still many types of applications which remain to be explored, particularly those involving on-site analysis. Aspects of ambient ionization currently undergoing rapid development include molecular imaging and increased detection specificity through simultaneous chemical reaction and ionization by addition of appropriate chemical reagents.     

复杂样品质谱分析技术的原理与应用

原位、实时、在线、非破坏、高通量、低耗损的质谱学方法是质谱分析技术发展的重要趋势.在无需样品预处理的条件下对复杂基体样品中痕量待测物直接离子化技术的出现,极大地提高了质谱分析的效率,使实际样品的快速质谱分析成为可能.本文着重综述了能够在无需样品预处理情况下对复杂基体样品离子化的新兴质谱技术及其应用研究,系统阐述了直接离子化技术的基本原理和方法,介绍了几种典型的常压直接离子化技术和装置,对直接离子化质谱分析技术在食品、药品、环境、活体分析、代谢组学、蛋白质组学以及生物组织质谱成像等领域的典型应用进行了述评,讨论了提高复杂样品快速质谱分析选择性的可能方法,并展望了常压直接离子化技术未来发展的可能趋势.     

Direct ionization methods in mass spectrometry: An overview

Within this paper a sub-group of ambient ionization mass spectrometry namely direct ionization mass spectrometry techniques are reviewed. They are characterized by the generation of an electrospray directly from the sample investigated. Prominent representatives include paper spray mass spectrometry, tissue spray mass spectrometry, probe electrospray ionization or thin-layer chromatography mass spectrometry. Applications of all major direct ionization techniques within different fields such as biomedical analysis, analysis of natural products, analysis of technical products and food analysis, just to name a few, are discussed and relevant parameters are listed in five Tables.     

生物质谱

质谱已成为生物和生物化学研究的一个重要的分析工具，特别是在蛋白质组学研究的作用更显突出，它的分析速度、准确性和灵敏度都是传统分析技术所不可比拟的。主要介绍了两种近年来发展最为迅速、应用最为广泛的软离子化质谱技术：即基体辅助激光解吸离子化质谱（MALDI－MS）和电喷了子化质谱（ESI－MS）的原理、技术的最新进展，并简单介绍了它们在蛋白质和多肽分析中的应用。     

嗜酸性氧化亚铁硫杆菌代谢产物的常压化学电离质谱分析

本研究以721矿和745矿嗜酸性氧化亚铁硫杆菌为研究对象,采用常压化学电离质谱直接分析其代谢产物,分别考察了顶空采样( Headspace sampling)、界面采样( Interface sampling)和中性解吸采样( Neutral desorption sampling)3种进样方式对电离效果的影响。在优化条件下,常压化学电离质谱对微生物纯菌种和混合菌种的代谢产物均具有良好的分析能力,可根据获得的代谢产物指纹谱图结合主成分分析( PCA)方法和聚类分析( CA)方法区分2个放射性强弱不同区域共4类嗜酸性微生物样品,并对主要胺类、酯类等代谢成分进行串联质谱鉴定,为耐辐射微生物的相关研究提供了一种可借鉴的分析方法。