Positive-ion ESI mass spectrometry of regioisomeric nonreducing oligosaccharide fatty acid monoesters: In-source fragmentation of sodium adducts

Structural characterization and differentiation of a novel group of regioisomeric monolaurate esters of the nonreducing trisaccharides raffinose and melezitose, and the nonreducing tetrasaccharide stachyose has been obtained using positive electrospray ionization (ESI) mass spectrometry with in-sour...

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Bibliographic Details
Authors: Pérez-Victoria, Ignacio, Zafra, Alberto, Morales, Juan Carlos
Format: article
Publication Date:2008
Country:España
Institution:Consejo Superior de Investigaciones Científicas (CSIC)
Repository:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/377057
Online Access:http://hdl.handle.net/10261/377057
Access Level:Open access
Keyword:Oligosaccharide fatty acid monoesters
Electrospray mass spectrometry
In-source fragmentation
Sodium adducts
Nonreducing oligosaccharides
Description
Summary:Structural characterization and differentiation of a novel group of regioisomeric monolaurate esters of the nonreducing trisaccharides raffinose and melezitose, and the nonreducing tetrasaccharide stachyose has been obtained using positive electrospray ionization (ESI) mass spectrometry with in-source fragmentation. The surfactant nature and high polarity of these compounds make them appropriate analytes for being studied by conventional ESI-MS. The position of the acyl chain in each particular regioisomer has been used as a reporter group that allows unambiguous rationalization of the fragmentation routes of the corresponding natriated molecular ions [M + Na]+. In all cases, the main fragment ions were produced through cleavage of the glycosidic bond involving two anomeric carbons, the C-1′ and C-2″ of the α-D-Glcp-(1–2)-β-D-Fruf bond, and it was observed that sodium cation retention occurred on the heavier mass fragment of the two formed fragments, (e.g. di- or trisaccharide type vs monosaccharide type). Our results may help to better understand the fragmentation behavior of nonreducing oligosaccharides (as sodium adducts) in positive ESI mass spectrometry.