In:
Rapid Communications in Mass Spectrometry, Wiley, Vol. 16, No. 8 ( 2002-04-30), p. 790-796
Abstract:
The negative‐ions of N ‐phosphoryl amino acids were studied by electrospray ionization tandem mass spectrometry (ESI‐MS/MS). The negative‐ion ESI‐MS/MS of N ‐phosphoryl amino acids showed characteristic fragmentation patterns different from those observed in the corresponding positive‐ion ESI‐MS/MS and negative‐ion fast‐atom bombardment mass spectra. For negative‐ion ESI‐MS/MS, a unique fragmentation from the N‐terminal of N ‐phosphoryl amino acids or peptides containing a free β‐OH or CO 2 H group was observed to yield the characteristic fragment ion (RO) 2 P(O)O − . The ease of the rearrangement depended on the position of the hydroxyl group in amino acids or peptides, and the N → O rearrangement mechanism was proposed to involve the participation of the hydroxyl group. From previous solution‐phase experiments and theoretical calculations, it was found that the β‐OH group was more active than γ‐OH, and the corresponding difference in negative‐ion ESI‐MS/MS was consistent with those previous findings. Copyright © 2002 John Wiley & Sons, Ltd.
Type of Medium:
Online Resource
ISSN:
0951-4198
,
1097-0231
Language:
English
Publisher:
Wiley
Publication Date:
2002
detail.hit.zdb_id:
2002158-6
detail.hit.zdb_id:
58731-X
SSG:
11