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Critical parameters for the analysis of anionic oligosaccharides by desorption electrospray ionization mass spectrometry
Author(s) -
Przybylski Cédric,
Gonnet Florence,
Buchmann William,
Daniel Régis
Publication year - 2012
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.3052
Subject(s) - chemistry , mass spectrometry , chromatography , orbitrap , electrospray ionization , sulfation , electrospray , tandem mass spectrometry , detection limit , hyaluronic acid , desorption electrospray ionization , chemical ionization , ionization , organic chemistry , biochemistry , ion , biology , genetics
Sulfated oligosaccharides derived from glycosaminoglycans (GAGs) are fragile compounds, highly polar and anionic. We report here on the rare but successful application of desorption electrospray ionization (DESI) — LTQ‐Orbitrap mass spectrometry (MS) to the high‐resolution analysis of anionic and sulfated oligosaccharides derived from the GAGs hyaluronic acid and heparin. For that purpose, key parameters affecting DESI performance, comprising the geometric parameters of the DESI source, the probed surface and the spraying conditions, applied spray voltage, flow rates and solvent composition were investigated. Under suitable conditions, the DESI technique allows the preservation of the structural integrity of such fragile compounds. DESI enabled the sensitive detection of anionic hyaluronic acid and heparin oligosaccharides with a limit of detection (LOD) down to 5 fmol (≈10 pg) for the hyaluronic acid decasaccharide. Detection of hyaluronic acid oligosaccharides in urine sample was also successfully achieved with LOD values inferior to the ng range. Multistage tandem mass spectrometry (MS n ) through the combination of the DESI source with a hybrid linear ion trap‐orbitrap mass spectrometer allowed the discrimination of isomeric sulfated oligosaccharides and the sequence determination of a hyaluronic acid decasaccharide. These results open promising ways in glycomic and glycobiology fields where structure–activity relationships of bioactive carbohydrates are currently questioned. Copyright © 2012 John Wiley & Sons, Ltd.