MALDI MS in-source decay of glycans using a glutathione-capped iron oxide nanoparticle matrix.

A new matrix-assisted laser desorption ionization (MALDI) mass spectrometry matrix is proposed for molecular mass and structural determination of glycans. This matrix contains an iron oxide nanoparticle (NP) core with gluthathione (GSH) molecules covalently bound to the surface. As demonstrated for the monosaccharide glucose and several larger glycans, the mass spectra exhibit good analyte ion intensities and signal-to-noise ratios, as well as an exceptionally clean background in the low mass-to-charge (m/z) region. In addition, abundant in-source decay (ISD) occurs when the laser power is increased above the ionization threshold; this indicates that the matrix provides strong energy transfer to the sample. For five model glycans, ISD produced extensive glycosidic and cross-ring cleavages in the positive ion mode from singly charged precursor ions with bound sodium ions. Linear, branched, and cyclic glycans were employed, and all were found to undergo abundant fragmentation by ISD. 18O labeling was used t...