Abstract

AbstractAn expedient conversion of N‐glycans to the naphthimidazole (NAIM) derivatives is established by the iodine‐promoted oxidative condensation of N‐glycans with 2,3‐naphthalenediamine at room temperature. The NAIM derivatization not only introduces a UV/fluorescence sensitive chromophore but also increases the hydrophobicity of N‐glycans to improve the ionization efficiency in mass spectrometry (MS). Thus, the NAIM derivatives of N‐linked oligosaccharide Man9 and tetra‐antennary N‐glycan NA4 show enhanced sodiated ions in matrix‐assisted laser desorption/ionization time‐of‐flight MS with a detection limit of 50 pmol, whereas the NAIM derivative of sialic acid‐containing tri‐antennary N‐glycan A3 is detected as the protonated ion by linear trap quadrupole Fourier transform MS. Furthermore, the N‐glycans of ovalbumin and fetuin are released and directly converted to the NAIM derivatives for facilitated HPLC and MS analyses. This is the first study of N‐glycan‐NAIM for MS measurement, which is especially valuable in glycan analysis of biological samples containing sensitive subunits.

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