Atmospheric Pressure Photoionization with Halogen Anion Attachment for Mass Spectrometric Analysis of Hydrocarbons and Hydrocarbon-Based Polymers.

IF 3.1 2区 化学 Q2 BIOCHEMICAL RESEARCH METHODS
Essi Rytkönen, Juha Rouvinen, Janne Jänis, Marko Mäkinen
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Abstract

Aliphatic hydrocarbons and hydrocarbon-based synthetic polymers are of interest in many fields, but their characterization by mass spectrometric methods is generally limited due to their poor ionizability. Recently, atmospheric pressure photoionization (APPI), combined with halogen anion attachment in negative-ion mode, has drawn attention as a potential method for ionizing various polymers without extensive fragmentation or other unwanted side reactions. In this work, the applicability of halogen anion attachment with APPI was studied using several synthetic polymers, including polyethylene, polypropylene, polyisoprene, and polystyrene, as well as simple n-alkanes of various chain lengths. For hydrocarbon-based polymers, the method produced clear distributions of intact polymer adduct ions when different halogen anions were used. It was found that increasing the halogen anion size decreased ionization efficiency, particularly in the absence of π-bonds in the polymer structure. Testing with simple n-alkanes showed that only molecules containing fifty or more carbon atoms formed detectable halogen adducts, possibly due to the low gas-phase stabilities of the lighter n-alkane adduct ions. In conclusion, halogen anion attachment with negative-ion APPI appears to be a highly promising method for polymer analysis, providing structural data and clean polymer mass spectra with minimal fragmentation, which can be useful for the identification of unknown samples.

用于碳氢化合物和碳氢化合物基聚合物质谱分析的常压光离子化与卤素阴离子附着。
脂肪族碳氢化合物和以碳氢化合物为基础的合成聚合物在许多领域都备受关注,但由于其电离性差,使用质谱方法对其进行表征通常受到限制。最近,在负离子模式下结合卤素阴离子附着的常压光离子化(APPI)作为一种潜在的方法引起了人们的关注,这种方法可以在不产生大量碎片或其他不必要的副反应的情况下电离各种聚合物。在这项研究中,我们使用几种合成聚合物(包括聚乙烯、聚丙烯、聚异戊二烯和聚苯乙烯以及不同链长的简单正构烷烃)研究了卤素阴离子附着与 APPI 的适用性。对于烃基聚合物,当使用不同的卤素阴离子时,该方法可产生清晰的完整聚合物加成离子分布。研究发现,增加卤素阴离子的大小会降低电离效率,尤其是在聚合物结构中没有 π 键的情况下。使用简单的正构烷烃进行的测试表明,只有含有 50 个或更多碳原子的分子才会形成可检测到的卤素加成物,这可能是由于较轻的正构烷烃加成离子的气相稳定性较低。总之,使用负离子 APPI 进行卤素阴离子附着似乎是一种非常有前途的聚合物分析方法,它可以提供结构数据和干净的聚合物质谱,碎片极少,有助于鉴定未知样品。
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来源期刊
CiteScore
5.50
自引率
9.40%
发文量
257
审稿时长
1 months
期刊介绍: The Journal of the American Society for Mass Spectrometry presents research papers covering all aspects of mass spectrometry, incorporating coverage of fields of scientific inquiry in which mass spectrometry can play a role. Comprehensive in scope, the journal publishes papers on both fundamentals and applications of mass spectrometry. Fundamental subjects include instrumentation principles, design, and demonstration, structures and chemical properties of gas-phase ions, studies of thermodynamic properties, ion spectroscopy, chemical kinetics, mechanisms of ionization, theories of ion fragmentation, cluster ions, and potential energy surfaces. In addition to full papers, the journal offers Communications, Application Notes, and Accounts and Perspectives
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