Schäfer M, Budzikiewicz H
Mass Spectrometry Facilities, Institute of Organic Chemistry, University at Cologne Greinstr. 4, D-50939 Cologne, Germany.
J Mass Spectrom. 2001 Sep;36(9):1062-8. doi: 10.1002/jms.209.
In this mass spectrometry (MS) study of doubly charged porphyrin salts, fast atom bombardment (FAB) and matrix-assisted laser desorption/ionization (MALDI) MS techniques are utilized to examine several unique ionic species. The predominant transformation of preformed doubly charged ions in the desorption/ionization mechanism of FAB and MALDI is the result of deprotonation reactions to form singly charged ions of the type M(2+) - H(+) and of one-electron reductions to form radical cations M(2+) + e(-). The dependence of this phenomenon and the formation of a number of additional ionic species on the different matrices and the FAB-matrix additive benzoquinone is examined. The significant analogous behavior of doubly charged porphyrins in FAB- and MALDI-MS leads to the conclusion that one-electron reductions are of distinct relevance in the desorption/ionization mechanism of MALDI.
在这项关于双电荷卟啉盐的质谱（MS）研究中，采用快原子轰击（FAB）和基质辅助激光解吸/电离（MALDI）MS技术来检测几种独特的离子物种。在FAB和MALDI的解吸/电离机制中，预先形成的双电荷离子的主要转变是去质子化反应形成M(2+) - H(+)型单电荷离子以及单电子还原形成自由基阳离子M(2+) + e(-)的结果。研究了这种现象以及许多其他离子物种的形成对不同基质和FAB - 基质添加剂苯醌的依赖性。双电荷卟啉在FAB - 和MALDI - MS中的显著类似行为得出结论，单电子还原在MALDI的解吸/电离机制中具有明显的相关性。
