Comparison of collision-induced dissociation and electron-induced dissociation of singly protonated aromatic amino acids, cystine and related simple peptides using a hybrid linear ion trap-FT-ICR mass spectrometer
Comparison of collision-induced dissociation and electron-induced dissociation of singly protonated aromatic amino acids, cystine and related simple peptides using a hybrid linear ion trap-FT-ICR mass spectrometer
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DOI：
10.1007/s00216-007-1535-1
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发表时间：
2007-11-01
影响因子：
4.3
通讯作者：
O'Hair, Richard A. J.
中科院分区：
文献类型：
--
作者：
Lioe, Hadi;O'Hair, Richard A. J.
用市售的混合线性离子阱-傅里叶变换离子回旋共振（FT-ICR）质谱仪研究了单质子化芳香族氨基酸、其简单肽以及分子间二硫键的简单模型的气相裂解反应。低能量碰撞诱导解离（CID）的线性离子阱内的反应进行了比较与电子诱导解离（EID）的FT-ICR细胞内的反应。在低能量CID（通过振动激发发生）和EID之间观察到显著差异。例如，在CID条件下，芳香族氨基酸主要通过NH3和（H2O+CO）的竞争性损失而片段化，而在EID条件下，侧链苄基阳离子是主要片段离子。EID在切割含有分子间二硫键的肽模型的S-S和S-C键方面也表现出上级。涉及作为电子能量的函数的碎片化的系统研究表明，与通常观察到的电子捕获解离碎片化的低电子能量（小于0.2 eV）相比，EID的碎片化效率发生在高电子能量（大于10 eV）。最后，由于在EID条件下观察到的碎片离子的类型之间的相似性和以前报道的紫外光解离实验和电子电离质谱，我们建议，EID的结果通过电子激发和振动激发的碎片。EID可用于分析基质辅助激光解吸电离形成的单电荷分子离子。
The gas-phase fragmentation reactions of singly protonated aromatic amino acids, their simple peptides as well as simple models for intermolecular disulfide bonds have been examined using a commercially available hybrid linear ion trap-Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Low-energy collision-induced dissociation (CID) reactions within the linear ion trap are compared with electron-induced dissociation (EID) reactions within the FT-ICR cell. Dramatic differences are observed between low-energy CID (which occurs via vibrational excitation) and EID. For example, the aromatic amino acids mainly fragment via competitive losses of NH3 and (H2O+CO) under CID conditions, while side-chain benzyl cations are major fragment ions under EID conditions. EID also appears to be superior in cleaving the S-S and S-C bonds of models of peptides containing an intermolecular disulfide bond. Systematic studies involving fragmentation as a function of electron energy reveal that the fragmentation efficiency for EID occurs at high electron energy (more than 10 eV) compared with the low-electron energy (less than 0.2 eV) typically observed for electron capture dissociation fragmentation. Finally, owing to similarities between the types of fragment ions observed under EID conditions and those previously reported in ultraviolet photodissociation experiments and the electron-ionization mass spectra, we propose that EID results in fragmentation via electronic excitation and vibrational excitation. EID may find applications in analyzing singly charged molecular ions formed by matrix-assisted laser desorption ionization.