Structural Characterization of Carbohydrates by Fourier Transform Tandem Mass Spectrometry

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.

Fragmentation study of major spirosolane‐type glycoalkaloids by collision‐induced dissociation linear ion trap and infrared multiphoton dissociation Fourier transform ion cyclotron resonance mass spectrometry

“…The nomenclature used in this paper for oligosaccharide fragmentation is based on that described by Domon and Costello . Oligosaccharides show two types of common bond cleavages in MS/MS: glycosidic cleavages (B‐, C‐, Y‐, Z‐type) that break a bond between monosaccharides, and cross‐ring cleavages (A‐ and X‐type) that involve the breaking across carbohydrate rings . Glycosidic cleavages provide information regarding monosaccharide composition while cross‐ring cleavages are particularly helpful in determining linkage type …”

Oligosaccharide Analysis by Mass Spectrometry: A Review of Recent Developments

“…Alkali adducted methylated oligosaccharides produce both glycosidic and cross-ring fragments by MS/MS, yielding fine structural details. 4–10 …”

“…Singly charged ions are also formed as adducts with alkali or alkaline earth metals, and these kind of ions have been found to generate useful fragment ions during tandem mass spectrometry analysis. 4 MALDI imparts more internal energy into the analyte than does ESI, and can cause in-source fragmentation of labile groups such as sulfates, phosphates, or sialic acids.…”

Collisional Activation Dissociation Mass Spectrometry Studies of Oligosaccharides Conjugated with Na+-Encapsulated Dibenzo-18-Crown-6 Ether

“…10 To acquire this information, a variety of tandem mass spectrometry methods are being used in glycan analysis: collision activation dissociation (CAD), infrared multiphoton dissociation (IRMPD), ultraviolet photodissociation (UV-PD), and electron-aided fragmentation methods. 8,9,11 Among those, CAD is the most widely used method. In the CAD of protonated glycans, glycosidic bond cleavage is a prevalent process, which reveals the sequence of glycans through the laddering approach.…”