Intramolecular hydrogen atom transfer in hydrogen-deficient polypeptide radical cations

被引：52

作者：

Nielsen, ML ^{[1
]}

Budnik, BA ^{[1
]}

Haselmann, KF ^{[1
]}

Olsen, JV ^{[1
]}

Zubarev, RA ^{[1
]}

机构：

[1] Univ So Denmark Odense Univ, Dept Chem, DK-5230 Odense M, Denmark

来源：

CHEMICAL PHYSICS LETTERS | 2000年 / 330卷 / 5-6期

关键词：

D O I：

10.1016/S0009-2614(00)01078-2

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Irradiation of protonated polypeptides NH2-RH+-COOH by >10 eV electrons leads to further ionization and fast intramolecular charge transfer to the free N-terminus. The resulting species may undergo further hydrogen atom rearrangement to form distonic ions N+H3-RH+-COO .. Such transfer is exothermic but can involve an appreciable barrier, e.g., 2.3 +/- 0.5 eV for MH2+ ions of the peptide ACTH 1-10. Radical polypeptide dications can, therefore, be viewed as hydrogen atom wires. Subsequent capture of low energy electrons results in fragmentation. The pattern of this electronic excitation dissociation (EED) is consistent with hydrogen transfer prior to electron capture. (C) 2000 Elsevier Science B.V. All rights reserved.

引用

页码：558 / 562

页数：5

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