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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >On the Mechanism of Electron-Capture-Induced Dissociation of Peptide Dications from ~(15)N-Labeling and Crown-Ether Complexation
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On the Mechanism of Electron-Capture-Induced Dissociation of Peptide Dications from ~(15)N-Labeling and Crown-Ether Complexation

机译：电子捕获诱导肽阳离子从〜（15）N-标记和冠醚络合解离的机理

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摘要

~(15)N-labeling of di-and tripeptides reveals that electron capture to doubly protonated peptides results almost exclusively in ammonia loss from the N-terminal end,which clearly shows that a significant fraction of electron capture occurs at this end.In accordance with this finding,the competing channel of N-C_(alpha)bond breakage leads to z~(+·)ions and neutral c fragments after electron capture to small dications.In larger peptides that live long enough for internal proton exchanges to occur,c~+ions are also formed and in some cases in dominant yield.Attachment of one or two crown ethers to ammonium groups is likely to reduce the probability of proton transfer,which enhances the formation of z~(+·)relative to c~+.The total yield of z~(+·)and c~+is,however,more or less unchanged,which indicates that proton transfer or hydrogen transfer from a NH3 group to the amide group is not required for the N-C_(alpha)bond breakage.
机译：〜和（15）N标记的二肽和三肽表明，电子捕获到双质子化肽几乎完全导致N端氨气损失，这清​​楚地表明在此端发生了很大一部分电子捕获。有了这个发现，N-C_α键断裂的竞争通道在电子捕获成小的指示后导致z〜（+·）离子和中性c片段。在寿命长到足以发生内部质子交换的较大的肽中，也形成c〜+离子，在某些情况下占主导地位。将一或两个冠醚连接到铵基上可能会降低质子转移的可能性，从而增加相对于c〜的z〜（+·）的形成。 +。但是，z〜（+·）和c〜+的总收率几乎没有变化，这表明N-C_（不需要质子转移或氢从NH3基团转移至酰胺基团alpha）键断裂。

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