Hydrogen atom loss in electron-capture dissociation: a Fourier transform-ion cyclotron resonance study with single isotopomeric ubiquitin ions

Hydrogen atom loss in electron-capture dissociation: a Fourier transform-ion cyclotron resonance study with single isotopomeric ubiquitin ions
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DOI:
10.1255/ejms.487
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发表时间:
2002-01-01
影响因子:
1.3
通讯作者:
McLafferty, FW
McLafferty, FW
中科院分区:
化学4区
文献类型:
--
作者:
Breuker, K;Oh, HB;McLafferty, FW

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在电子捕获解离 (ECD) 中,捕获在傅里叶变换离子回旋共振 (FT-ICR) 单元中的多质子化蛋白质离子在质子化位点捕获低能电子。在主要反应途径中,产生的氢原子攻击主链羰基氧,形成高价物质,该物质立即解离成互补的 c、z(.) 离子对。对于较大的蛋白质,还原的奇电子离子 (M + nH)((n-1)+.) 是主要产物,如此处使用同位素分离的前体所示。此外,氢原子可以在不进一步反应的情况下丢失,产生[M + (n - 1)H]((n-1)+)偶数电子离子。电荷态对这些离子产率的巨大影响表明 9+ 至 11+ 电荷态具有新颖的电荷溶剂化二级结构。
In electron-capture dissociation (ECD), a multiply-protonated protein ion, trapped in a Fourier transform-ion cyclotron resonance (FT-ICR) cell, captures a low-energy electron at a protonated site. In a major reaction pathway, the resulting hydrogen atom attacks a backbone carbonyl oxygen to form a hypervalent species that immediately dissociates into a complementary c, z(.) ion pair. For larger proteins, the reduced odd-electron ion (M + nH)((n-1)+.) is a major product, as shown here using isotopically isolated precursors. In addition, a hydrogen atom can be lost without further reaction, yielding the [M + (n - 1)H]((n-1)+) even-electron ions. The large effect of charge state on the yield of these ions suggests that the 9+ to 11+ charge states have novel charge-solvated secondary structures.