Discovery of Combustion-Like in-Source Oxidation of Linear Saturated Hydrocarbons Using GC-APCI-HRMS

IF 1.9 3区 化学 Q3 BIOCHEMICAL RESEARCH METHODS Journal of Mass Spectrometry Pub Date : 2024-09-25 DOI:10.1002/jms.5087
Lindsay P. Brown, Wesley B. Seaton, Joshua B. Powers, Shawn R. Campagna
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Abstract

Atmospheric pressure chemical ionization (APCI) is often used in the analysis of linear saturated hydrocarbons (LSHs) as this ionization technique commonly produces [M − H]+ ions in high abundance. However, APCI (along with other atmospheric pressure sources) is often impacted by in-source oxidation, leading to a variety of ionic products. Identifying these products and understanding their mechanisms of formation is crucial for characterizing complex mixtures with substantial hydrocarbon content, such as those found in the petrochemical industry. In this study, in-source oxidation of LSHs was observed in gas chromatography (GC) coupled to high-resolution mass spectrometry (HRMS) via a custom-built APCI interface. Studies showed that the abundance of these oxidized ions correlated positively with atmospheric water, yet occurred without the inclusion of water-based oxygen as judged by experiments with stable isotope-labeled water. The oxidation of LSHs was further influenced by the reactive species in the ionization atmosphere. Fragmentation data using stable isotope-labeled LSH standards unveiled multiple structurally unique ions with one or more oxidation sites on both primary and secondary carbons. These ionic products bear resemblance to combustion byproducts, suggesting the instrumental configuration fosters plasma-assisted combustion-like processes that encourage the radical-mediated oxidation of LSHs rather than generate [M − H]+. Through these investigative efforts, a mechanism analogous to combustion was proposed for the formation of LSH oxidation products in GC-APCI-HRMS. Data demonstrate that these ions are robustly generated in petrochemical products, allowing for proper characterization of these complex mixtures.

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利用 GC-APCI-HRMS 发现线性饱和碳氢化合物的类似燃烧的源内氧化作用
常压化学电离(APCI)通常用于分析线性饱和碳氢化合物(LSHs),因为这种电离技术通常会产生高丰度的[M - H]+ 离子。然而,APCI(以及其他常压源)经常会受到源内氧化的影响,从而产生各种离子产物。识别这些产物并了解其形成机理对于表征含有大量碳氢化合物的复杂混合物(如石化工业中发现的混合物)至关重要。在本研究中,通过定制的 APCI 接口,在气相色谱 (GC) 与高分辨质谱 (HRMS) 联用系统中观察到了 LSHs 的源内氧化。研究表明,这些氧化离子的丰度与大气中的水呈正相关,但根据稳定同位素标记水的实验判断,发生氧化时并不包含水基氧。LSHs 的氧化还受到电离气氛中活性物种的进一步影响。使用稳定同位素标记的 LSH 标准的碎片数据揭示了多个结构独特的离子,其主碳和次碳上都有一个或多个氧化位点。这些离子产物与燃烧副产物相似,表明仪器配置促进了类似等离子体辅助燃烧的过程,促进了自由基介导的 LSHs 氧化,而不是产生 [M - H]+。通过这些研究工作,我们提出了在 GC-APCI-HRMS 中形成 LSH 氧化产物的类似燃烧的机制。数据表明,这些离子在石油化工产品中生成强劲,可对这些复杂的混合物进行适当的表征。
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来源期刊
Journal of Mass Spectrometry
Journal of Mass Spectrometry 化学-光谱学
CiteScore
5.10
自引率
0.00%
发文量
84
审稿时长
1.5 months
期刊介绍: The Journal of Mass Spectrometry publishes papers on a broad range of topics of interest to scientists working in both fundamental and applied areas involving the study of gaseous ions. The aim of JMS is to serve the scientific community with information provided and arranged to help senior investigators to better stay abreast of new discoveries and studies in their own field, to make them aware of events and developments in associated fields, and to provide students and newcomers the basic tools with which to learn fundamental and applied aspects of mass spectrometry.
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