质谱动力学方法原理及应用

Theory and Application of Mass Spectrometric Kinetic Method

质谱动力学方法(Kinetic Method,简称KM法)是一种基于经质量选择的簇离子竞争解离反应速率的不同对热力学数据进行测定的方法,由于采用串联质谱技术,分析样品无需纯化,具有简便、快速、灵敏等优点。目前该方法已应用于气相酸碱度和质子亲合势的测定、电子亲和能的测定、电离能的测定、多电荷生物分子气相碱度的测定、金属离子与生物分子亲和力的测定、异裂离解能的测定、离子结构的检测及对手性化合物对映体过量的测定等。本工作在介绍质谱动力学方法原理的同时,列举了其应用实例,详细地对质谱动力学方法进行了综合述评。

The mass spectrometric kinetic method based on the competitive dissociations of mass-selected cluster ions has been increasingly applied to thermochemical determination mainly due to its simplicity, speediness and sensitivity. Because the kinetic method employs tandem mass spectrometry, the compounds of interest need not be available in pure form. The kinetic method has been used to estimate gas-phase acidity and basicity and proton af- finity, electron affinity, ionization energy, gas-phase basicities of multiply-charged biomolecules, metal ion affinities, heterolytic bond dissociation energies, chiral recognition and quantification. In this paper the theory of kinetic method is introduced in detail and its applications are enumerated.