Ionic liquid matrix for direct UV-MALDI-TOF-MS analysis of dermatan sulfate and chondroitin sulfate oligosaccharides

Polyanionic oligosaccharides such as dermatan sulfate (DS) and chondroitin sulfate (CS) exhibit poor ionization efficiencies and tend to undergo thermal fragmentation through the loss of SO3 under conventional ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) conditions. A new ionic liquid matrix (ILM), a guanidinium salt of alpha-cyano-4-hydroxycinnamic acid, facilitates direct UV-MALDI mass spectrometric (MS) analysis of underivatized DS and CS oligosaccharides up to a decasaccharide in their common form as sodium salts. The resulting mass spectra show very low extent of fragmentation through an SO3 loss. The new ILM is suitable for MALDI-MS analysis of mixtures containing oligosaccharides with different numbers of sulfo groups.