Charge-remote fragmentation of odd-electron peptide ions
Charge-remote fragmentation of odd-electron peptide ions
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DOI：
10.1021/ac070777b
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发表时间：
2007-09-01
影响因子：
7.4
通讯作者：
Chu, Ivan K.
中科院分区：
文献类型：
--
作者：
Laskin, Julia;Yang, Zhibo;Chu, Ivan K.
对模型多肽的奇电子M+中心点、[M+H](2+中心点)和[M-2H](-中心点)离子的气相裂解进行了比较，结果表明电荷远程自由基驱动的裂解途径在奇电子多肽离子的解离过程中起着重要作用。我们发现，电荷远程过程是导致前体离子和一些主链断裂的各种侧链损失的原因。这些裂解途径很可能涉及启动后续裂解的自由基位置的氢提取。这些发现通常与我们对奇电子多肽离子通过各种方法产生的碎裂模式的理解有关，这些方法包括捕获低能电子、电子脱离和电子转移。
Comparison between the gas-phase fragmentation of odd-electron M+center dot, [M + H](2+center dot), and [M - 2H](-center dot) ions of model peptides suggests that charge-remote radical-driven fragmentation pathways play an important role in the dissociation of odd-electron peptide ions. We have found that charge-remote processes are responsible for a variety of side-chain losses from the precursor ion and some backbone fragmentation. These fragmentation pathways most likely involve hydrogen abstraction by the radical site that initiates subsequent cleavages. These findings are generally relevant to our understanding of the fragmentation patterns of odd-electron peptide ions produced through various approaches including the capture of low-energy electrons, electron detachment, and electron transfer.