Structural Characterization of Carbohydrates by Fourier Transform Tandem Mass Spectrometry

Wen      Zhou; Kristina      Hakansson

Abstract

Fourier transform tandem mass spectrometry (MS/MS) provides high mass accuracy, high sensitivity, and analytical versatility and has therefore emerged as an indispensable tool for structural elucidation of biomolecules. Glycosylation is one of the most common posttranslational modifications, occurring in ∼50% of proteins. However, due to the structural diversity of carbohydrates, arising from non-template driven biosynthesis, achievement of detailed structural insight is highly challenging. This review briefly discusses carbohydrate sample preparation and ionization methods, and highlights recent developments in alternative high-resolution MS/MS strategies, including infrared multiphoton dissociation (IRMPD), electron capture dissociation (ECD), and electron detachment dissociation (EDD), for carbohydrates with a focus on glycans and proteoglycans from mammalian glycoproteins.

Keywords: Tandem mass spectrometry, Electron capture dissociation (ECD), Electron detachment dissociation (EDD), glycosylation, infrared multiphoton dissociation (IRMPD), oligosaccharides, Electrospray ionization, Dimethyl sulfoxide, Ultraviolet photodissociation, Peptide-N-glycosidase F, Nuclear magnetic resonance, Negative electron transfer dissociation