The Mobile Proton Hypothesis in Fragmentation of Protonated Peptides: A Perspective
The Mobile Proton Hypothesis in Fragmentation of Protonated Peptides: A Perspective
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DOI：
10.1016/j.jasms.2010.04.017
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发表时间：
2010-08-01
影响因子：
3.2
通讯作者：
Somogyi, Arpad
中科院分区：
文献类型：
--
作者：
Boyd, Robert;Somogyi, Arpad
美国质谱学会的杰出贡献奖“-表彰在基础或应用质谱方面的专注的，独特的成就或贡献，与表彰终身成就的奖项相反-对质谱的基本理解和/或实践产生重大影响的贡献。”这个被称为移动质子模型的假设显然既满足基本标准，又满足实际标准。很高兴应邀为这期特刊撰写一篇简短的介绍文章，以纪念该模型的主要发起者和支持者、2009年这一享有盛誉的奖项的获得者Vicki Wysocki和Simon Gaskell。两篇优秀的综述涵盖了截至2005年的相关文献[1,2]。这篇短文的目的是试图从一个更广阔的角度来看待移动质子模型。质谱法在分子结构测定中的应用依赖于对碎片离子谱的解释，然而，使用一套规则是多年扩展经典物理有机化学概念的经验的结果。大多数的碎片化规律都是根据用电子电离法得到的正离子质谱的经验得出的。关于这些解释性规则的最著名的指南可能是McLafferty和Turecek b[3]合著的书。这些“经典”规则的基本主题是，一个活化离子分解成两个或更多碎片的电子重排是由分解离子分子结构中特定位置上的电荷定位（和/或自由基离子的不成对电子自旋）触发的。的确，这些规则几乎完全是经验性的，但它们在实践中的持续成功表明，它们在某种意义上必须与现实现象相对应。化学电离的引入，以及后来强大的快速原子轰击（FAB）[4]、电喷雾（ESI）[5]和MALDI[6]电离技术的出现，将分子自由基阳离子的断裂规律扩展到由内合形成的偶电子分子
The Distinguished Contribution Award of the American Society for Mass Spectrometry“—recognizes a focused, singular achievement in or contribution to fundamental or applied mass spectrometry, in contrast to awards that recognize lifetime achievement—a contribution that has had a significant impact on the fundamental understanding and/or practice of mass spectrometry.” The hypothesis that has come to be known as the mobile proton model clearly satisfies both the fundamental and practical criteria. It is a pleasure to have been asked to contribute a brief introductory article to this special issue that honors Vicki Wysocki and Simon Gaskell, the principal originators and proponents of the model and the 2009 recipients of this prestigious award. Two excellent reviews cover the relevant literature up to about 2005 [1, 2]. The purpose of this short article is to attempt to view the mobile proton model relative to a wider perspective.Application of mass spectrometry to determination of molecular structure relies on interpretation of fragment ion spectra, however obtained, using a set of rules that are the result of years of experience in extending concepts of classical physical-organic chemistry. Most of the fragmentation rules were derived from experience with positive ion mass spectra obtained using electron ionization. Probably the best-known guide to these interpretative rules is the book authored by McLafferty and Turecek [3]. The underlying theme of these “classical” rules is that the electron rearrangements involved in decomposition of an activated ion into two or more fragments are triggered by localization of charge (and/or unpaired electron spin in the case of radical ions) on specific sites within the molecular structure of the decomposing ion. It is true that these rules are almost entirely empirical, but their continuing practical success indicates that they must correspond to real phenomena in some sense. The introduction of chemical ionization, and later the powerful fast atom bombardment (FAB)[4], electrospray (ESI)[5], and MALDI [6] ionization techniques led to extension of the rules for fragmentations of molecular radical cations to even-electron molecular species formed by adduction of