The structural elucidation of natural products (NPs) remains a challenge due to their structurally diversities and unpredictable functionalities, motifs, and scaffolds. Tandem mass spectrometry (MS/MS) is an effective method that assists the full elucidation of complicated NP structures. Ion activation methods play a key role in determining the fragmentation pathways and the structural information obtained from MS/MS. Electron‐ion reaction‐based dissociation (ExD) methods, including electron capture dissociation (ECD), electron transfer dissociation (ETD), electron‐induced dissociation (EID), and electron detachment dissociation (EDD), can induce the breakage of specific chemical bonds and the generation of distinct fragment ions. This review article provides an overview of the mechanisms, instrumentation, and typical applications related to ExD MS/MS in the structural elucidation of NPs, primarly including lipids, oligosaccharides, glycoconjugates, metabolites, and pharmaceutical drugs. This work aims to reveal the capacity and potential of ExD mass spectrometry in analyzing NPs and consequently helping the NP communities to utilize the modern capabilities of MS/MS in the discovery and evaluation of novel NPs.

中文翻译：

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基于电子离子反应的解离：一种用于阐明天然产物结构的强大离子活化方法

由于天然产物（NPs）的结构多样性以及不可预测的功能性，基序和支架，其结构解析仍然是一个挑战。串联质谱（MS / MS）是一种有效的方法，可帮助您全面阐明复杂的NP结构。离子活化方法在确定片段化途径和从MS / MS获得的结构信息方面起着关键作用。基于电子离子反应的解离（ExD）方法，包括电子俘获解离（ECD），电子转移解离（ETD），电子诱导解离（EID）和电子离解解离（EDD），可导致特定化学物质的断裂键和明显的碎片离子的产生。这篇评论文章概述了各种机制，工具，与ExD MS / MS有关的NP结构解析的典型应用，主要包括脂质，寡糖，糖结合物，代谢物和药物。这项工作旨在揭示ExD质谱分析NP的能力和潜力，从而帮助NP社区利用MS / MS的现代功能来发现和评估新型NP。