电喷雾萃取电离-串联质谱中N,N-二乙基苯胺类化合物的特征碎裂反应
Characteristic Fragmentation Behavior of N,N-Diethylaniline Compounds by Extractive Electrospray Ionization Tandem Mass Spectrometry
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摘要: 掌握串联质谱中的裂解反应是深刻理解质谱裂解规律，从而对复杂基体中相关化合物进行快速、精准结构解析的关键。本文以电喷雾萃取电离-串联质谱（EESI-MS/MS）为手段，研究N,N-二乙基苯胺类化合物的串联质谱行为，考察不同的取代基模式对裂解反应的影响，揭示裂解反应机理，总结该类化合物发生裂解反应的特征和基本规律。研究结果不仅丰富了气相离子化学的研究内容，还从根本上降低了检测的假阳性率，为实际样品中相关化合物的结构分析鉴定提供了科学依据。
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关键词:
- 电喷雾萃取电离串联质谱（EESI-MS/MS） /
- N,N-二乙基苯胺 /
- 裂解机理
Abstract: Electrospray ionization mass spectrometry (ESI-MS) is commonly used nowadays in the structural analysis of a large variety of compounds. Successful structure elucidation based on tandem mass spectrometry (MS/MS) data is dependent on correct interpretation of the fragmentation pathways. However, MS/MS based structural elucidation has been challenging due to the widespread rearrangement reactions in the fragmentation process. Thus, mastering the migration reaction mechanism in MS/MS is a key to deeply understand the fragmentation behavior and to clarify the structure elucidation of related compounds in complex matrices. In this work, the fragmentation reactions of protonated N,N-diethylaniline compounds were researched by EESI-MS. The intramolecular reactions included proton transfer, electron transfer, and hydride transfer reaction were occurred in the gas phase dissociation of protonated N,N-diethylaniline compounds, which were explored by extractive electrospray ionization tandem mass spectrometry (EESI-MS/MS). Upon collisional activation, protonaed N,N-diethylaniline underwent dissociation reaction via cleavage of the bond to give reactive ion-neutral complex (INC) intermediate. INC was found to be ubiquitous in gas-phase ion reactions. To support the proposed mechanism, deuterium-labeled experiments and the effects of different substituents on the fragmentation reaction were prepared and evaluated. The typical characteristics and basic rules of fragmentation reaction of these compounds were summarized. The implementation of this project not only enriches the research content of gas-phase ion chemistry, but also fundamentally reduces the false positive rate of detection, providing a scientific basis for structural analysis and identification of related compounds in actual samples. -
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