大气气溶胶质谱研究进展

文中较为详细地介绍了大气气溶胶粒子质谱研究的发展概况,从离线的质谱测量技术到实时在线的测量技术,特别是目前应用较为广泛的激光电离气溶胶飞行时间质谱技术——一种可以同时测量气溶胶粒子的大小和化学成分的方法的原理和应用。     

大气气溶胶飞行时间激光质谱仪实时数据采集处理系统

自行研制了一台大气气溶胶飞行时间激光质谱仪(ATOFLMS),它可以实时地对气溶胶单粒子进行物理和化学特性分析,是大气气溶胶研究和测量的一个有力工具.该仪器在运行过程中将产生海量的实验数据,对这些数据的实时、自动处理、提取有价值的信息是整机系统的关键之一.我们基于面向对象的技术为它开发了配套计算机软件MS-ACS,该软件能够自动地实现气溶胶单粒子的粒径和化学成分信息的实时采集、分析和存储功能.     

若干芳香族化合物气溶胶单粒子的在线测量

通过在自行研制的气溶胶飞行时间激光质谱仪上对苯酚、苯胺、1,3-二氯苯、硝基苯气溶胶单粒子的质谱特征进行了激光解吸附电离飞行时间质谱(laser desorption/ionization time-of-flight mass spectra,LDI-TOFMS)研究,分别得到了它们的质谱图,分析了它们特征谱的形成机理.发现这几种芳香族化合物气溶胶单粒子的LDI-TOFMS谱都是容易优先失去一个电子形成母体离子峰M ,其官能团也极易脱落,这为我们进行有机分子在气溶胶状态下的激光质谱特征研究以及单颗粒大气气溶胶化学组成的鉴别提供了基本信息.     

提高激光电离飞行时间质谱分辨率的分析研究

本文从理论上分析了影响激光电离飞行时间质谱仪分辨率的因素，提出了改善其分辨率的关键是：压缩质谱仪电离源内电离激光束的时间和空间分布，即采用激光锁模技术和表面电离方式等以获得高的分辨本领。     

源后脉冲聚焦技术应用于气溶胶激光飞行时间质谱仪

采用源后脉冲聚焦(PSPF)技术,极大地改善了气溶胶激光飞行时间质谱仪(ALTOFMS)系统的分辨率,在可聚焦的质量数范围内分辨率提高到原来的5.7倍.细致研究PSPF技术中的两个关键参数(脉冲电压延时和幅值),得到最佳的脉冲电压延时和幅值范围.采用多项式标定质量数,标定时的理沦相对误差为10-4～10-5.PSPF.ALTOFMS现已应用于在线实时检测空气气溶胶粒子.     

用气溶胶飞行时间质谱仪测量气溶胶粒子折射率

利用自行研制的气溶胶飞行时间质谱仪（aerosol time-of-flight mass spectrometer, ATOFMS）对气溶胶粒子的折射率进行测量。首先利用ATOFMS对气溶胶粒子的粒径和光散射强度进行测量,然后由Mie散射理论结合ATOFMS光散射区域的几何结构,推算出光电倍增管（PMT）接收的理论光通量与气溶胶粒子的大小和折射率之间的函数关系。通过比较实验测量的气溶胶粒子光散射平均强度与Mie散射理论值,对粒子的折射率进行反演。与实际样品数据参数对比的结果表明该方法是可行的。     

气溶胶单粒子的检测效率与基质辅助激光解吸电离研究

利用基质辅助激光解吸电离(MALDI)技术,在自行研制的气溶胶飞行时间质谱仪(ATOFMS)上实时探测单个生物气溶胶粒子的粒径和化学成分。采用双束激光空气动力学方法进行气溶胶粒子粒径的测量,并用266 nm的Nd∶YAG激光器对粒子进行激光解吸电离。以2,5-二羟基苯甲酸(DHB)和芥子酸为基质,对多肽生物样品进行了实验研究。质谱峰中质子化的分析物阳离子是在气相时,和基质通过质子转移反应形成的;而分析物碱金属加和物阳离子是在气相离子分子反应中,通过气相阳离子转移反应形成的。气溶胶粒子的检测效率为0.01%左右,命中率为10%左右。实验结果表明,该仪器可以满足大气中气溶胶单粒子的实时在线检测。     

飞行时间质谱峰形分析

报道了在用脉冲355 nm的YAG激光对水/甲醇二元团簇的多光子电离飞行时间质谱研究中,发现在电离激光相对于脉冲分子束的不同延时或是同一延时下不同的激光能量下,测得的离子谱峰除强度变化外,峰值发生漂移.离子峰值漂移的大小与信号强度密切相关.信号强度越大,离子的飞行时间越短,峰值漂移越大.分析认为:这种峰值漂移不是因为新质量数谱峰的出现,而是离子在穿越质谱仪的离子引出区和加速区极板时发生部分离子吸附,引起极板间电压的起伏造成的.离子信号越强,意味着极板对离子吸附的量越大,导致离子峰值的漂移越大.离子在电场起伏下的数值模拟结果与实验中观测到的离子峰值漂移规律一致.     

激光解吸电离飞行时间质谱计的谱峰定标

研制了一套飞行时间质谱计（TOF）,能够同时或分别在电子碰撞电离（EBI）和激光解吸电离（LDI）两种机制下工作。利用EBI模式下得到的真空残气质谱图,对LDI模式下得到的TOF质谱峰进行了定标。通过在作为LDI靶材的金属基底表面添加碱金属卤化物的实验,证实了这种定标方法的可行性。     

用基质辅助激光解吸电离法分析罗丹明系列染料

在飞行时间质谱仪上安装了一个新设计的固体样品快速进样装置,并改进了离子源结构,使用波长为248nm的KrF准分子激光器,以2,5二羟基苯甲酸为基质,对几种罗丹明染料进行了基质辅助激光解吸电离研究,得到了各种样品的质谱图并进行了分析。同时研究了入射激光强度和不同浓度样品对质谱信号的重复性和分辨率的影响。结果表明,只要样品和基质能够同时溶于同一种溶剂,只需一台单一波长激光器就能对众多的物质成分进行分析和检测。     

Trace Analysis and Reaction Monitoring by Nanophotonic Ionization Mass Spectrometry from Elevated Bowtie and Silicon Nanopost Arrays

Silicon nanopost arrays (NAPA) are used in trace analysis by mass spectrometry (MS) because they enable highly efficient ion production from small molecules and thin tissue sections by UV laser desorption ionization (LDI). Such nanophotonic ionization of adsorbates relies on localized interactions between a nanostructured substrate and laser radiation. In LDI from NAPA, only the component of the oscillating electric field vector that is parallel with the posts couples the laser energy into the nanostructure. Enhancements in control over adsorbate ionization and fragmentation are expected if the surface‐parallel component can also interact with the nanostructure. Here, an alternative nanophotonic ionization platform is introduced for LDI‐MS, the elevated bowtie (EBT) array by adding triangular chromium features on top of silicon post pairs to form bowties. Compared to NAPA, the threshold fluence for ionization from EBT is lower, and at low laser fluences the ionization efficiency is increased by a factor of ≈17. The EBT platform with optimized apex angle exhibits a higher survival yield for molecular ions produced from biomolecules and xenobiotics and allows more control over fragmentation by adjusting the fluence. These unique nanophotonic ionization attributes are utilized for trace analysis and reaction monitoring in complex biological samples.     

Laser-Induced Surface Reconstruction of Nanoporous Au-Modified TiO2 Nanowires for In Situ Performance Enhancement in Desorption and Ionization Mass Spectrometry

The physicochemical properties of nanostructured substrates significantly impact laser desorption/ionization mass spectrometry (LDI-MS) performance. Fundamental understanding of the substrate properties can provide insights into the design and development of an efficient LDI matrix. Herein, a hybrid matrix of nanoporous Au-modified TiO₂ nanowires (npAu-TNW) is developed to achieve enhanced LDI-MS performance. Its origin is investigated based on hybrid matrix properties including photo–thermal conversion and electronic band structure. Notably, further improvement is obtained in the npAu-TNW than in the pristine TNW and non-porous Au nanoisland-modified TNW (Au-TNW) hybrid, which is attributed to the laser-induced surface restructuring/melting phenomenon. Noticeable surface restructuring/melting occurs in the npAu by laser exposure through efficient photo–thermal conversion of the highly porous npAu. At this instant of npAu structural changes, internal energy transfer from the npAu to the adsorbed analyte is promoted, which facilitates desorption. Moreover, strain is developed in situ in the TNW adjacent to the restructuring npAu, which distorts the TNW lattice. The strain development reduces recombination rates of charge carriers by introducing shallow trap levels in the bandgap, which enhances the ionization process. Ultimately, the high LDI-MS performance based on the npAu-TNW hybrid matrix is demonstrated by analyzing neurotransmitter.     

对苯二酚的快速测量

对苯二酚在大气中经常以"对苯二酚粉尘"的形式存在,为了达到快速检测环境中的对苯二酚的目的,我们首先对固体对苯二酚进行了离线分析,指出了对苯二酚的特征离子峰是母体离子峰(m/z=110);然后用激光气溶胶飞行时间质谱仪对气溶胶态的对苯二酚进行了激光解吸附/电离质谱研究;并且发现杂质NaCl的加入对气溶胶态对苯二酚分子离子峰没有产生影响.     

Silicon‐Based Laser Desorption Ionization Mass Spectrometry for the Analysis of Biomolecules: A Progress Report

Matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) is widely used in the biomedical field for the label‐free analysis of molecules such as drugs, lipids, peptides, proteins, and biological tissues for molecular imaging. However, organic matrices used in traditional MALDI‐MS applications introduce excessive interferences in the low m/z range. For this reason, nanostructured materials—and in particular silicon‐based LDI strategies—have become a promising alternative, since they provide a much weaker background. Herein, the recent developments in fabrication, functionalization, and practical applications of silicon‐based LDI‐MS methods are reviewed. Also the basic requirements of silicon‐based substrates for optimal LDI analysis by providing an overview of the LDI mechanisms that use silicon‐based substrates instead of organic matrices are reported. Finally, the considerable potential of silicon‐based substrates is discussed, giving suggestions for topics for future research.     

262～272 nm波段氯苯的激光质谱研究

在自行研制的具有恒温加热进样系统的激光质谱仪上获得了262～272 nm波段气相氯苯的(1 1)共振增强多光子电离/飞行时间质谱(REMPI-TOFMS).研究表明,该波长范围内获得的光激发谱的光谱结构是氯苯第一激发态1B2(S1)振动能级的反映,对其中14条谱线进行了尝试性指认.分析了氯苯在266 nm波长处不同激光能量下的光电离质谱特点,讨论了造成77C4H5 质谱的非对称增宽的原因.实验研究了266 nm波长处氯苯分子离子信号强度与样品浓度之间的关系,估算出氯苯的探测限为ng/L量级.