McCormack A L, Somogyi A, Dongré A R, Wysocki V H
Department of Chemistry, Virginia Commonwealth University, Richmond 23284-2006.
Anal Chem. 1993 Oct 15;65(20):2859-72. doi: 10.1021/ac00068a024.
This paper describes the results of a systematic investigation designed to assess the utility of surface-induced dissociation in the structural analysis of small peptides (500-1800u). A number of different peptides, ranging in mass and amino acid sequence, are fragmented by collision with a surface in a tandem mass spectrometer and the spectra are compared with data obtained by gas-phase collisional activation. The surface-induced dissociation spectra provide ample sequence information for the peptides. Side-chain cleavage ions of type w, which are generally detected upon kiloelectronvolt collisions with gaseous targets but not upon electronvolt collisions with gaseous targets, are detected in the ion-surface collision experiments. A theoretical approach based on MNDO bond order calculations is suggested for the description of peptide fragmentation. This model, supplemented by ab initio calculations, serves as a complement to the experimental work described in the paper and explains (i) the easy cleavage of the amide bond, (ii) charge-remote backbone and side-chain cleavages, and (iii) the influence of intramolecular H-bonding.
本文描述了一项系统研究的结果，该研究旨在评估表面诱导解离在小肽（500 - 1800u）结构分析中的效用。通过串联质谱仪中与表面的碰撞，使多种质量和氨基酸序列各异的不同肽发生碎裂，并将所得光谱与气相碰撞活化获得的数据进行比较。表面诱导解离光谱为肽提供了丰富的序列信息。在离子 - 表面碰撞实验中检测到了w型侧链裂解离子，这种离子通常在与气态靶标发生千电子伏特碰撞时被检测到，而在与气态靶标发生电子伏特碰撞时则不会被检测到。本文提出了一种基于MNDO键级计算的理论方法来描述肽的碎裂。该模型辅以从头算计算，作为本文所述实验工作的补充，解释了（i）酰胺键的易断裂，（ii）电荷远程主链和侧链裂解，以及（iii）分子内氢键的影响。
