"Internal residue loss": rearrangements occurring during the fragmentation of carbohydrates derivatized at the reducing terminus.

Journal article

Rearrangement reactions involving migration of fucose and, occasionally, other residues have been found in the CID spectra of [M + H]+ and [M + 2H]2+ ions, but not [M + Na]+ ions, generated from several O-linked carbohydrates and milk sugars derivatized at their reducing termini with aromatic amines such as 2-aminobenzamide. Such rearrangements, which are similar to those reported by other investigators from several underivatized carbohydrates and glycosides, cause an apparent loss of sugar residues from within a carbohydrate chain and can produce ambiguous results during spectral interpretation. A mechanism, involving initial protonation of the amine nitrogen atom of the derivative, is proposed to account for the formation of the observed ions.

Authors: Harvey, D; Mattu, T; Wormald, M; Royle, L; Dwek, R

• Publication status: Published
• Journal: Analytical chemistry
• Volume: 74
• Issue: 4
• Pages: 734-740
• Publication date: 2002-02-01
• DOI: 10.1021/ac0109321
• EISSN: 1520-6882
• ISSN: 0003-2700
• Language: English
• Keywords: Amines; Animals; Molecular Sequence Data; Models, Molecular; Oxidation-Reduction; Carbohydrate Sequence; Fucose; Carbohydrates; Spectrometry, Mass, Electrospray Ionization; Milk