ICP-MS技术及其应用

ICP—MS技术在分析能力上不仅可以覆盖传统的无机元素分析技术如CIPAES、CFAAS等的工作范围,可进行定性、半定量、定量分析,还可以进行同位素比测定,以及与不同的进样技术(如激光熔蚀)及分离技术(如HPLC,HPCE,GC)联用进行元素的形态、分布特性等的分析。ICP—MS已广泛应用于环境、半导体、医学,生物、冶金、地质科学、石油、核材料分析等领域。本文以实例说明ICP—MS技术在各分析领域的应用优点。     

Liquid chromatography-mass spectrometry for the quantitative bioanalysis of anticancer drugs

The monitoring of anticancer drugs in biological fluids and tissues is important during both pre-clinical and clinical development and often in routine clinical use. Traditionally, liquid chromatography (LC) in combination with ultraviolet (UV), fluorescence, or electrochemical detection is employed for this purpose. The successful hyphenation of LC and mass spectrometry (MS), however, has dramatically changed this. MS detection provides better sensitivity and selectivity than UV detection and, in addition, is applicable to a significantly larger group of compounds than fluorescence or electrochemical detection. Therefore, LC-MS has now become the method of first choice for the quantitative bioanalysis of many anticancer agents. There are still, however, a lot of new developments to be expected in this area, such as the introduction of more sensitive and robust mass spectrometers, high-throughput analyses, and further optimization of the coupled LC systems. Many articles have appeared in this field in recent years and are reviewed here. We conclude that LC-MS is an extremely powerful tool for the quantitative analysis of anticancer drugs in biological samples.     

电感耦合等离子体质谱测量硒的研究进展

近年来,准确测量生物、食品、环境、地质等样品中的硒元素含量、同位素组成及其各种形态受到越来越多的关注。随着质谱技术的发展,电感耦合等离子体质谱(ICP-MS)技术成为硒的各种特性量研究和测量的重要手段,使其在生命科学、环境地球化学、生物、营养等研究中有着广泛的应用前景。本文综述了ICP-MS法应用于硒同位素比值,元素总量以及多种形态测量技术方面的最新研究进展。     

ICP-MS相关联用技术在食品元素形态分析中的应用及进展

电感耦合等离子体质谱（ICP-MS）技术凭借其低检出限、多元素同时分析等优点,广泛应用于食品中的元素分析。随着分析技术的发展,以及元素的不同形态在物理、化学、营养、毒理等方面的显著差异,元素形态分析已经引起分析工作者的广泛关注。本工作对近年来ICP-MS技术与各种分离手段联用,在食品中砷、硒及锡等元素形态分析中的应用进行了综述,指出了ICP-MS 相关联用技术应用于食品元素形态分析时存在的问题,并对其未来的发展趋势进行了展望。     

电感耦合等离子体质谱法在临床样品分析中的应用

本文对近年来电感耦合等离子体质谱法（ICP-MS）在临床样品微量元素及形态分析中的应用进行了综述，讨论了应用ICP-MS技术测定临床样品微量元素的三种处理和分析方法（直接稀释法，湿法消解法和微波消解法），列举了部分含量测定的实例。介绍了联用技术高效液相色谱（HPLC）、气相色谱（GC）、超临界流体色谱（SFC）和毛细管电泳（CE）在形态分析中的应用，指出了现存的问题，探讨了可能的解决方案。     

电感耦合等离子体质谱法测定大气气溶胶中金属元素

本文采用微波消解-电感耦合等离子体质谱法对大气气溶胶里的Pb、Cu、V、Cd等4种金属元素进行了同时测定。通过加标回收实验,建立了大气气溶胶中Pb、Cu、V、Cd等4种金属元素的ICP-MS分析方法。经实验,各元素的精密度均小于5%,回收率介于96.0%-108.3%之间。实验结果表明：该方法不仅具有较好的灵敏度和检测精度,而且实现了4种元素的同时测定,大大提高了测定效率。     

DevelopmentofPhotocatalyst-BasedICP-MSCouplingTechniquesforDeterminationofTraceElementsandTheirSpecies

It is well known that the speciation, or chemical form, of metals governs its fate, toxicity, mobility, and bioavailability in environmental and biological systems. To assess these chemical properties and to accurately gauge their impact on human health and the environment, metals need to be characterized at the atomic level. To attain new information about environmental and biological effects of trace elements, new methodologies or modify conventional analytical methods is deemed as vital factor for the progress of bio- and environmental- studies. In view of the limitation on the analytical capability of single instrumental technique, analytical chemists can seldom rely on a single instrumental technique to analyze a sample with complicated matrix and analyte species with a variety of physico-chemical form. It is thus necessary to develop a technique which can fulfill ultratrace analyses of metal species down to the sub-g/L concentration range in complicated samples. Accordingly, the most important features of an analytical tool suitable for meeting the requirement of modern bio-analytical works are shorter temporal resolution, good selectivity and high sensitivity. For ultratrace elements measurements, ICP coupled with Mass Spectrometry (ICP-MS) has been considered as first priority option. Although the analytical sensitivity has been significantly improved by the technical advances in ICP-MS, instrumental limitations, such as difficulties in differentiating elemental species and removing matrix interferences caused by the concomitant salt, still remain in advanced analytical technologies. To satisfy the analytical requirements, the potency of hyphenating analytical separation techniques to mass spectrometers has been recognized. Basically, according to Hirschfeld1, the advantages brought about by coupling techniques are increasing the differentiating and separating power of analytical methods and synergism between methods. However, the design of the analytical system is difficult, owing to the complex composition of the real-world sample, the diversity of physicochemical forms of the element, their lability and low concentrations. For overcoming the abovementioned problems, attempts to couple ICP-MS with various types of chromatography for separation, as well as on-line sample pretreatment techniques for signal enhancement and matrix removal have been made. To expand the analytical capability, in this study, we developed several hyphenated systems by integrating the alternative photo-redox characteristic of nano-TiO₂ into the interfacing device to convert both inorganic and organic metal-containing species to gaseous products that are favor for ICP-MS determination. Based on our experimental results, this presentation will describe the studied hyphenated methods which have been proven feasible for the analyses of trace elements and their chemical species in environmental and biological systems.     

碘的质谱测量方法研究进展

近年来,电感耦合等离子体质谱（ICP-MS）技术的发展着力于应对基质更加复杂的样品和解决测量过程中的干扰问题,同时与进样、分离系统的联用技术也在快速发展,而加速器质谱（AMS）则朝着更加小型化和更高灵敏度的方向发展。ICP-MS测量前需要对样品进行前处理以消解和提取碘,而AMS测量前则还需对样品进一步分离富集和纯化。本文总结了ICP-MS和AMS的发展概况及其在碘测量方面的应用,归纳了ICP-MS和AMS测量含碘样品的前处理方法,综述了国内外总碘、碘同位素及碘形态的质谱测量方法新进展。     

铂基抗癌药物与蛋白质配位键相互作用质谱研究新进展

顺铂及其类似物广泛应用于肿瘤的临床治疗，静脉注射顺铂后，药物通过血液传输进入细胞并最终到达细胞核作用于DNA，这一过程中，大部分的铂与血液及细胞中的蛋白质通过配位键结合，对药物的运输、代谢、累积分布和毒副作用及其生物利用度等起着决定性作用。因此，研究铂类药物与蛋白质的结合行为具有重要意义。质谱作为一种高效的蛋白质分析技术，具有灵敏度高、通量大、耗样量小、精度高等优势，在铂类药物与蛋白质相互作用研究领域发挥着重要作用。本文从Pt(Ⅱ)配合物的配位化学原理出发，阐明铂药发挥抗癌作用的可能机制。同时，着重总结、评述不同类型质谱分析方法探索铂-蛋白质配位相互作用的最新进展，归纳铂类药物在体内可能通过配位键结合的氨基酸侧链和对应的蛋白质。以顺铂为代表的Pt(Ⅱ)金属抗癌药物，最容易结合含有S供体的半胱氨酸、甲硫氨酸和含有咪唑基团的组氨酸等氨基酸侧链。同时，酪氨酸、丝氨酸、苏氨酸、谷氨酸和天冬氨酸等含羟基或羧基侧链的氨基酸也能与Pt(Ⅱ)结合。由于巯基或咪唑侧链可能处于很多蛋白质的重要活性位点或金属结合域，因此，铂类化合物的结合可能直接导致这些蛋白质的活性下降，从而对细胞内的生物过程产生复杂而深远的影响，加强或降低铂类抗癌药物的活性，或产生毒副作用和耐药性。因此，深入研究铂类药物与蛋白质的相互作用，将进一步加深对铂类抗癌药物代谢途径和毒性机制的认识，有助于设计合成更低毒、高效的金属类抗癌药物。     

毛细管电泳-电感耦合等离子体质谱联用技术及其元素形态分析的新进展

元素的形态与它的毒性和生物活性密切相关。近年来,毛细管电泳与电感耦合等离子体质谱联用(CE-ICP-MS)技术成为元素形态分析的有力手段,得到了迅速发展。本工作阐述了CE-ICP-MS联用的各种接口方式,并讨论了几种接口及雾化器装置的优点和不足;综述了近几年采用CE-ICP-MS联用技术对痕量元素形态分析的新进展,对CE-ICP-MS联用技术在元素形态分析上的潜力、限制及发展趋势作了讨论。     

电感耦合等离子体质谱分析方法的重要进展（2005~2016年）

2005~2016这十几年中,电感耦合等离子体质谱（ICP-MS）仪器的性能得到了大幅改善,其灵敏度最高可达10⁶ cps/(1 μg/L, In),稳定性为1%～2%。多接收ICP-MS精密度的提高尤其显著,同位素测量精密度优于0.01%。各类ICP-MS普遍采用高速数据采集技术与数据库技术,使数据处理能力进一步加强。以三重四极杆和高分辨为代表的ICP-MS对基体干扰和多原子离子干扰消除能力进一步加强,绿色节能环保型和智能型ICP-MS也得到了关注。一些电离能较高的贵金属、类金属和非金属元素分析技术得到重视。以激光烧蚀（LA）、高效液相色谱（HPLC）、气相色谱（GC）、离子色谱（IC）、毛细管电泳（CE）、电热蒸发（ETV）和化学气体发生（CVG）为代表的联用技术及形态分析发展快速。单颗粒（SP）和单细胞（SC）等技术与ICP-MS的联用产生了以功能定义的专用ICP-MS,大大扩展了ICP-MS的应用领域。ICP-MS分析技术从传统的无机元素分析发展到有机生物及形态分析,从传统的样品消解后溶液进样分析发展到固体样品在线进样分析,从传统的元素含量分析发展到2D-3D成像分析和高精度同位素分析。ICP-MS在能源、地质、材料、环保、生物医学、食品、国土安全等诸多领域的应用进一步扩展,成熟的ICP-MS分析方法实现了标准化并得到推广和普及。本工作从6个方面总结回顾了2005~2016年间ICP-MS的重要进展,并对其发展前景进行了展望。     

北京冬季大气颗粒物中铅的同位素丰度比的测定和来源研究

本文报道了北京市冬季（1998-1999年）大气颗粒物样品的无机多元素和铅同位素丰度比的测定数据。分别采用HR-ICP-MS和TOF-ICP-MS测定铅同位素丰度比,结果表明ICP-MS的测定精度可适用于大气中铅的来源研究。大气颗粒物样品中一些特征无机元素含量,如Br、Ti、Pb、Zn,与铅的同位素丰度比之间存在相关性。在铅含量高的样品中机动车尾气排放的贡献明显,在铅含量低的样品中土壤扬尘和燃煤飞灰的贡献增加;其中部分样品表现出来自西伯利来地区的长距离传输的特征。样品聚类分组结果结合气象信息可以得到合理解释。应用铅的同位素技术来研究北京市大气颗粒物中的铅的来源是可行的。     

激光溅射电离飞行时间质谱用于矿样分析的研究及技术比较

将自行研制的激光溅射电离飞行时间质谱仪（LAI-TOFMS）用于辉绿岩（GBW07123）、石榴石和硅化木3种矿物样品的直接分析,初步讨论了元素含量和元素相对含量的计算方法,计算过程中选Mn作参考元素,并将LAI-TOFMS与电感耦合等离子体质谱（ICP-MS）、X射线荧光光谱（XRF）在样品分析过程和分析结果方面进行比较。LAI-TOFMS中,元素含量是通过相对灵敏系数（RSC）和Mn的含量计算得到,元素的相对含量与元素的相对原子质量及其质谱峰的强度有关;对于ICP-MS和XRF,元素的相对含量是待测元素和Mn含量的比值。初步研究表明：LAI-TOFMS, ICP-MS和XRF 3种分析方法测得的元素含量和元素相对含量结果相对符合较好。此外,由于具有样品前处理简单、几乎不污染样品、样品消耗量少等优点,LAI-TOFMS能够提高矿物样品的分析检测效率。     

New controlled environment vitrification system for cryo-transmission electron microscopy: design and application to surfactant solutions

A newly designed controlled environment vitrification system for cryo-transmission electron microscopy of vitrified samples (cryo TEM) is presented. It significantly reduces the lag-time from blotting to vitrification by means of an optimized blotting procedure. Furthermore, a modified transfer system allows rapid transfer of the vitrified sample into the microscope and reduces the equilibration time. The practicable throughput of samples is thereby markedly increased. This new equipment is used to determine the overall size of individual polymer-like mixed lecithin–bile salt micelles, which very critically depends on the composition of the sample. The quantitative agreement with the results from independent light scattering experiments on the same sample supports the validity and performance of the presented sample preparation and handling procedures. In addition, these experiments demonstrate that cryo TEM experiments not only provide direct structural information, but furthermore permit a quantitative determination of micellar properties.     

Transmission electron microscopic X-ray quantitative analysis of human dentin at 200 kV accelerating voltage

Qualitative and quantitative x-ray energy dispersive spectroscopy is now used successfully to analyze many features and processes in inorganic samples. When applied to inorganic samples, however, the results are often less satisfactory due to problems of preparation of organic samples, difficulty of measuring x-rays from organic samples, damage of the sample by the electron beam, and other practical problems. In the present study we used a high voltage transmission electron microscope equipped with an energy dispersive x-ray spectrometer to examine accurate quantitative standardless analysis of thin sections of an organic sample, human dentin. Based on our experiments we found the important parameters for quantitative analysis were sample thickness and appropriate choice of model sample. Further, we show that the method of Cliff and Lorimer can be used with biological samples at 200 kV, and we show that quantitative analysis of human dentin can be carried out at 200 kV. Finally, we show that areas of human dentin can be differentiated by their morphological characteristics and x-ray analyses obtained in the transmission electron microscope.     

高纯金属铕及其氧化物中14个稀土杂质的ICP-MS测定

本文针对单同位素元素铥与氧化铕基体的氧化物离子的质量数重叠,在ICP-MS谱法中无法测定的问题,研究了P_(507)萃淋树脂小型柱分离。在试验选择的分离条件下,分离周期(进样-淋洗-洗脱-再生)为2.5h。结合直接测定大部分稀土杂质,最终建立了高纯铕中14个稀土杂质元素的ICP-MS分析方法。方法测定下限(ΣRE)<5μg/g,加标回收率在92～111％范围内,RSD％<10％。方法灵敏、快速、简便,满足4～5N高纯金属铕及其氧化物产品分析的要求。     

电感耦合等离子体质谱（ICP-MS）法测定微量元素时样品制备过程中的质量控制

Sample preparation is a key procedure for determiantion of trace elements in samples by inductively coupled plasma mass spectrometry. This paper gives some experiences on the quality control of sample preparation for determination of trace elements in samples by ICP-MS.     

质谱在金属抗癌药物与蛋白质相互作用研究中的应用

研究细胞毒性金属抗肿瘤药物与蛋白质的相互作用,以及这种相互作用对药物的细胞摄入、转运、代谢和生物利用度的影响,对金属抗癌药物的结构设计和优化,提高药物的抗癌活性,降低毒副作用具有重要意义。基于软电离技术的电喷雾质谱和基质辅助激光解析电离质谱能够在分析检测过程中很好的保留金属抗癌药物与蛋白质的共价(配位)结合,获得药物与蛋白质结合位点的信息。同时,质谱分析还具有灵敏度高,所需样品量少,耗时短以及适用于分析复杂生物样品等优点,已成为研究金属抗癌药物与蛋白质相互作用最强有力的工具,在为药物发现提供大量化学、生物信息的同时,也极大地促进了质谱技术自身的发展。本文将结合我们在金属抗癌药物相互作用组学研究中取得的最新进展,系统地总结、评述Bottom-up和Top-down质谱分析方法在铂、钌类金属抗癌药物与蛋白质相互作用研究中的发展动态,并分析这一前沿交叉领域未来的发展趋势。     

基于液相色谱-质谱联用技术的蛋白质类肿瘤标志物定量方法研究进展

液相色谱-质谱（LC-MS）联用技术因具有高通量、高灵敏度等优点而成为发现、验证生物标志物及对生物标志物进行定量分析的有力工具。近年来,LC-MS在临床应用中,特别是在定量肿瘤生物标志物方面做出了重要贡献。研究人员通过不同的设计原理开发出多种定量方法,逐步实现了对高度复杂样品中蛋白质类肿瘤标志物的准确定量。本文从用于定量蛋白质类肿瘤标志物的样品前处理方法及LC-MS分析中的质谱扫描策略两个方面,对近年来的主要定量方法进行总结。     

HPLC/ICP-MS在环境样品的痕量元素形态分析中的应用

综述了高效液相色谱-电感耦合等离子体质谱联用技术（HPLC/ICP-MS）的最新进展和工作特点，介绍了该技术在环境样品分析中的应用概况、接口类型和应用同位素稀释技术进行元素形态分析等。