Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for the period 2005–2006

Abstract

This review is the fourth update of the original review, published in 1999, on the application of MALDI mass spectrometry to the analysis of carbohydrates and glycoconjugates and brings coverage of the literature to the end of 2006. The review covers fundamental studies, fragmentation of carbohydrate ions, method developments, and applications of the technique to the analysis of different types of carbohydrate. Specific compound classes that are covered include carbohydrate polymers from plants, N- and O-linked glycans from glycoproteins, glycated proteins, glycolipids from bacteria, glycosides, and various other natural products. There is a short section on the use of MALDI-TOF mass spectrometry for the study of enzymes involved in glycan processing, a section on industrial processes, particularly the development of biopharmaceuticals and a section on the use of MALDI-MS to monitor products of chemical synthesis of carbohydrates. Large carbohydrate-protein complexes and glycodendrimers are highlighted in this final section.

Sensitive and Structure-Informative <i>N</i>-Glycosylation Analysis by MALDI-MS; Ionization, Fragmentation, and Derivatization

“…Various solid and liquid matrices have been reported for enhancing the ion yield of glycans. [9][10][11][12][13][14][15] Another way to improve ionization eciency is to perform derivatization (i.e., labeling). e chemical labeling of the reducing end of glycans was originally developed for HPLC analysis with UV or uorescent detectors.…”

“…us, MALDI-MS enjoys widespread use in a variety of applications for the analysis of glycans and glycopeptides. [9][10][11][12][13][14][15] However, the mass spectrometric analysis of glycosylation still remains a challenging task due to the low ionization e ciency, labile nature and complicated branched structures involving various linkage isomers. In general, released glycans show lower ionization e ciency than other biopolymers, such as peptides.…”

Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation

“…Upon closer examination, the use of MALDI can be found in a rather wide variety of applications, including glycans analysis [1] and, more generally, for investigations of all types of large biomolecules [2]. The small sample quantity required to perform an analysis has earned the MALDI technique renown as an exceptionally sensitive tool that is more tolerant of the presence of salts than other mass spectrometric ionization techniques (e.g., electrospray ionization).…”

“…The negative ion mode has been less frequently employed, with the exception of its application toward specific compound classes, such as DNA [8] , sugars [1], and lipids [9].…”

MALDI-MS/MS with Traveling Wave Ion Mobility for the Structural Analysis ofN-Linked Glycans

“…Their analysis has received much attention over the past three decades and involves techniques such as HPLC, exoglycosidase sequencing, and mass spectrometry [2][3][4][5][6][7][8][9][10][11][12][13]. The introduction of fast-atom bombardment (FAB) mass spectrometry in the 1980s catalysed much work on the positive ion mass spectrometry of permethylated glycans [14][15][16][17][18] but FAB has now largely been replaced by ionization using matrixassisted laser desorption/ionization (MALDI) [3,19] and electrospray ionization (ESI) mass spectrometry [20], which enable both derivatized and underivatized glycans to be examined. Nevertheless, positive ionization remains the most popular mode, and permethylation is still widely used for purposes such as increasing ion yields and providing linkage information by fragmentation [21].…”