It is now 25 years since we commenced the study of the negative‐ion fragmentations of peptides and we have recently concluded this research with investigations of the negative‐ion chemistry of most post‐translational functional groups. Our first negative‐ion peptide review (Bowie, Brinkworth, & Dua, 2002) dealt with the characteristic backbone fragmentations and side‐chain cleavages from (M–H)⁻ ions of underivatized peptides, while the second (Bilusich & Bowie, 2009) included negative‐ion backbone cleavages for Ser and Cys and some initial data on some post‐translational groups including disulfides. This third and final review provides a brief summary of the major backbone and side chain cleavages outlined before (Bowie, Brinkworth, & Dua, 2002) and describes the quantum mechanical hydrogen tunneling associated with some proton transfers in enolate anion/enolate systems. The review then describes, in more depth, the negative‐ion cleavages of the post‐translational groups Kyn, isoAsp, pyroglu, disulfides, phosphates, and sulfates. Particular emphasis is devoted to disulfides (both intra‐ and intermolecular) and phosphates because of the extensive and spectacular anion chemistry shown by these groups. © 2016 Wiley Periodicals, Inc. Mass Spec Rev

中文翻译：

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肽的（MH）-阴离子的负离子裂解。第3部分。翻译后修改

自从我们开始研究肽的负离子片段化以来已有25年了，最近我们对大多数翻译后官能团的负离子化学进行了研究，从而结束了这项研究。我们的第一个负离子肽综述（Bowie，Brinkworth和Dua，2002年）涉及（MH）的特征性骨架断裂和侧链裂解^-离子化未衍生肽，第二个离子（Bilusich＆Bowie，2009）包括Ser和Cys的负离子主链裂解以及一些翻译后基团（包括二硫化物）的一些初始数据。第三篇也是最后一篇综述简要概述了之前概述的主要骨架和侧链断裂（Bowie，Brinkworth和Dua，2002年），并描述了与烯醇阴离子/烯醇体系中某些质子转移相关的量子力学氢隧穿。然后，该综述更深入地描述了翻译后基团Kyn，isoAsp，pyrglu，二硫化物，磷酸盐和硫酸盐的负离子裂解。由于二硫化物（分子内和分子间）和磷酸根的广泛和引人入胜的阴离子化学性质，它们尤其受到关注。©2016 Wiley Periodicals，Inc.