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首页> 外文期刊>Journal of mass spectrometry: JMS >From the mobile proton to wandering hydride ion: Mechanistic aspects of gas-phase ion chemistry
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From the mobile proton to wandering hydride ion: Mechanistic aspects of gas-phase ion chemistry

机译：从移动质子到徘徊的氢化物离子：气相离子化学的机理方面

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摘要

Structural characterization of molecular species by mass spectrometry supposes the knowledge of the type of ions generated and the mechanism by which they dissociate. In this context, a need for a rationalization of electrospray ionization(+)(-) mass spectra of small molecules has been recently expressed. Similarly, at the other end of the mass scale, efforts are currently made to interpret the major fragmentation processes of protonated and deprotonated peptides and their reduced forms produced in electron capture or electron transfer experiments. Most fragmentation processes of molecular and pseudo-molecular ions produced in the ion source of a mass spectrometer may be described by a combination of several key mechanistic steps: simple bond dissociation, formation of ion-neutral complex intermediates, hydrogen atom, hydride ion or proton migrations and nucleophilic attack. Selected crucial aspects of these elementary reactions, occurring inside positively charged ions, will be recalled and illustrated by examples taken in recent mass spectrometry literature. Emphasis will be given on the protonation process and its consequence in terms of structure and energetic.
机译：通过质谱对分子种类进行结构表征，需要了解所生成离子的类型及其离解的机理。在这种情况下，最近已经表达出对小分子电喷雾电离（+）（-）质谱的合理化的需求。同样，在质量规模的另一端，目前正在努力解释质子化和去质子化肽的主要裂解过程及其在电子捕获或电子转移实验中产生的还原形式。质谱仪离子源中产生的大多数分子离子和假分子离子的裂解过程可以通过几个关键的机械步骤组合来描述：简单的键解离，离子中性复合中间体的形成，氢原子，氢化物离子或质子迁移和亲核攻击。这些基本反应的选定关键方面发生在带正电的离子中，将通过最近的质谱文献中的示例进行回顾和说明。重点将讨论质子化过程及其在结构和能量方面的后果。

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