Department of Chemistry, Purdue University, West Lafayette, IN 47907-2084, USA.
J Am Soc Mass Spectrom. 2011 Jan;22(1):3-12. doi: 10.1007/s13361-010-0004-9. Epub 2011 Jan 28.
A range of strategies and tools have been developed to facilitate the determination of primary structures of analyte molecules of interest via tandem mass spectrometry (MS/MS). The two main factors that determine the primary structural information present in an MS/MS spectrum are the type of ion generated from the analyte molecule and the dissociation method. The ion type subjected to dissociation is determined by the ionization method/conditions and ion transformation processes that might take place after initial gas-phase ion formation. Furthermore, the range of analyte-related ion types can be expanded via derivatization reactions prior to mass spectrometry. Dissociation methods include those that simply alter the population of internal states of the mass-selected ion (i.e., activation methods like collision-induced dissociation) as well as processes that rely on the transformation of the ion type prior to dissociation (e.g., electron capture dissociation). A variety of ion interactions have been studied for the purpose of ion dissociation and ion transformation, including ion/neutral, ion/photon, ion/electron, and ion/ion interactions. A wide range of phenomena have been observed, many of which have been explored/developed as means for structural analysis. The techniques arising from these phenomena are discussed within the context of the elements of structural determination in tandem mass spectrometry: ion-type definition and dissociation. Unique aspects of the various ion interactions are emphasized along with any barriers to widespread implementation.
已经开发了一系列策略和工具，以通过串联质谱（MS/MS）来促进对感兴趣的分析物分子的一级结构的确定。决定 MS/MS 谱中存在的一级结构信息的两个主要因素是从分析物分子生成的离子类型和解离方法。要进行解离的离子类型由可能在初始气相离子形成之后发生的电离方法/条件和离子转化过程来决定。此外，还可以通过在质谱之前进行衍生化反应来扩展与分析物相关的离子类型的范围。解离方法包括简单地改变质量选择离子的内部状态的分布的方法（例如，碰撞诱导解离等活化方法），以及依赖于解离前离子类型转化的方法（例如，电子俘获解离）。已经研究了各种离子相互作用，以用于离子解离和离子转化，包括离子/中性、离子/光子、离子/电子和离子/离子相互作用。已经观察到了广泛的现象，其中许多已经被探索/开发为结构分析的手段。在串联质谱中结构确定的要素的上下文中讨论了源于这些现象的技术：离子类型定义和解离。强调了各种离子相互作用的独特方面，以及广泛实施的任何障碍。
