On the dynamics of fragment isomerization in collision-induced dissociation of peptides

被引:80
作者
Polfer, Nick C. [1 ]
Bohrer, Brian C. [2 ]
Plasencia, Manolo D. [2 ]
Paizs, Bela [3 ]
Clemmer, David E. [2 ]
机构
[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[2] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
[3] German Res Ctr, D-69120 Heidelberg, Germany
关键词
D O I
10.1021/jp0763937
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
The structures of peptide collision-induced dissociation (CID) product ions are investigated using ion mobility/mass spectrometry techniques combined with theoretical methods. The cross-section results are consistent with a mixture of linear and cyclic structures for both b(4) and a(4) fragment ions. Direct evidence for cyclic structures is essential in rationalizing the appearance of fragments with scrambled (i.e., permutated) primary structures, as the cycle may not open up where it was initially formed. It is demonstrated here that cyclic and linear a(4) structures can interconvert freely as a result of collisional activation, implying that isomerization takes place prior to dissociation.
引用
收藏
页码:1286 / 1293
页数:8
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