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Formation of cyclic acylphosphoramidates in mass spectra of N ‐monoalkyloxyphosphoryl amino acids using electrospray ionization tandem mass spectrometry
Author(s) -
Gao Xiang,
Ni Feng,
Bao Jian,
Liu Yan,
Zhang Zhen,
Xu Pengxiang,
Zhao Yufen
Publication year - 2010
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1768
Subject(s) - chemistry , fragmentation (computing) , electrospray ionization , tandem mass spectrometry , mass spectrum , mass spectrometry , amino acid , electrospray , medicinal chemistry , stereochemistry , chromatography , biochemistry , computer science , operating system
The fragmentation reactions of N ‐monoalkyloxyphosphoryl amino acids ( N ‐MAP‐AAs) were studied by electrospray ionization tandem mass spectrometry (ESI‐MS). The sodiated cyclic acylphosphoramidates (CAPAs) were formed through a characteristic pentacoordinate phosphate participated rearrangement reaction in the positive‐ion ESI‐MS/MS and HR‐MS/MS of N ‐MAP‐AAs, in which the fragmentation patterns were clearly different from those observed in the corresponding ESI‐MS/MS of N ‐dialkyloxyphosphoryl amino acids/peptides and N ‐phosphono amino acids. The formation of CAPAs depended on the chemical structures of N ‐terminal phosphoryl groups, such as alkyloxy group, negative charge and alkali metal ion. A possible integrated rearrangement mechanism for both P ‐ N to P ‐ O phosphoryl group migration and formation of CAPAs was proposed. The fragmentation patterns of CAPAs as novel intermediates in gas phase were also investigated. In addition, it was found that the formation of α‐amino acid CAPAs was more favorable than β‐ or γ‐CAPAs in gas phase, which was consistent with previous solution‐phase experiments. Copyright © 2010 John Wiley & Sons, Ltd.