The Effects of Trivalent Lanthanide Cationization on the Electron Transfer Dissociation of Acidic Fibrinopeptide B and its Analogs.
The Effects of Trivalent Lanthanide Cationization on the Electron Transfer Dissociation of Acidic Fibrinopeptide B and its Analogs.
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DOI：
10.1007/s13361-016-1428-7
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发表时间：
2016-09
影响因子：
3.2
通讯作者：
Cassady CJ
中科院分区：
文献类型：
--
作者：
Commodore JJ;Cassady CJ
对酸性纤维蛋白肽 B 和具有三价镧系元素盐的两种肽类似物的混合物进行电喷雾电离 (ESI)，生成 [M + Met + H]4+、[M + Met]3+ 和 [M + Met − H]2+，其中 M = 肽，Met = 金属（放射性钷除外）。这些离子经历广泛且高效的电子转移解离 (ETD)，形成金属化和非金属化的 c 离子和 z 离子。所有金属加合产物离子均含有至少两个酸性位点，这表明镧系元素阳离子连接在一个或多个酸性残基的侧链上。这三种肽经历相似的断裂。 [M + Met + H]4+ 上的 ETD 导致每个残基裂解；金属离子和额外质子的存在对于促进序列信息碎片非常有效。 [M + Met]3+ 的主链解离也很广泛，尽管裂解并不总是发生在相邻的谷氨酸残基之间。对于 [M + Met − H]2+，形成的产物离子范围更有限。除铕 (Eu) 外，所有镧系金属肽复合物均表现出类似的碎裂。 [M + Eu − H]2+ 和 [M + Eu]3+ 上的 ETD 产生有限量的肽主链裂解；然而，[M + Eu + H]4+ 会在每个残基处广泛解离并裂解。除了 Eu(III) 的结果外，ESI 形成的金属化肽离子、ETD 裂解效率和产物离子形成不受镧系元素阳离子的影响。与三价镧系金属离子的加合是通过 ETD 对酸性肽进行序列分析的有前途的工具。
Electrospray ionization (ESI) on mixtures of acidic fibrinopeptide B and two peptide analogs with trivalent lanthanide salts generates [M + Met + H]4+, [M + Met]3+, and [M + Met − H]2+, where M = peptide and Met = metal (except radioactive promethium). These ions undergo extensive and highly efficient electron transfer dissociation (ETD) to form metallated and non-metallated c- and z-ions. All metal adducted product ions contain at least two acidic sites, which suggests attachment of the lanthanide cation at the side chains of one or more acidic residues. The three peptides undergo similar fragmentation. ETD on [M + Met + H]4+ leads to cleavage at every residue; the presence of both a metal ion and an extra proton is very effective in promoting sequence-informative fragmentation. Backbone dissociation of [M + Met]3+ is also extensive, although cleavage does not always occur between adjacent glutamic acid residues. For [M + Met − H]2+, a more limited range of product ions form. All lanthanide metal peptide complexes display similar fragmentation except for europium (Eu). ETD on [M + Eu − H]2+ and [M + Eu]3+ yields a limited amount of peptide backbone cleavage; however, [M + Eu + H]4+ dissociates extensively with cleavage at every residue. With the exception of the results for Eu(III), metallated-peptide ion formation by ESI, ETD fragmentation efficiencies, and product ion formation are unaffected by the identity of the lanthanide cation. Adduction with trivalent lanthanide metal ions is a promising tool for sequence analysis of acidic peptides by ETD.