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Structural characterization of the GM1 ganglioside by infrared multiphoton dissociation, electron capture dissociation, and electron detachment dissociation electrospray ionization FT-ICR MS/MS

Journal article
Authors Melinda A McFarland
Alan G Marshall
Christopher L Hendrickson
Carol L Nilsson
Pam Fredman
Jan-Eric Månsson
Published in J Am Soc Mass Spectrom
Volume 16
Issue 5
Pages 752-62
ISSN 1044-0305 (Print)
Publication year 2005
Published at Institute of Clinical Neurosciences, Section of Experimental Neuroscience
Pages 752-62
Language en
Keywords Animals, Cattle, G(M1) Ganglioside/*analysis/*chemistry/radiation effects, Infrared Rays, Molecular Structure, Spectrometry, Mass, Electrospray Ionization/*methods, Spectroscopy, Fourier Transform Infrared/*methods
Subject categories Neurochemistry, Clinical chemistry


Gangliosides play important biological roles and structural characterization of both the carbohydrate and the lipid moieties is important. The FT-ICR MS/MS techniques of electron capture dissociation (ECD), electron detachment dissociation (EDD), and infrared multiphoton dissociation (IRMPD) provide extensive fragmentation of the protonated and deprotonated GM1 ganglioside. ECD provides extensive structural information, including identification of both halves of the ceramide and cleavage of the acetyl moiety of the N-acetylated sugars. IRMPD provides similar glycan fragmentation but no cleavage of the acetyl moiety. Cleavage between the fatty acid and the long-chain base of the ceramide moiety is seen in negative-ion IRMPD but not in positive-ion IRMPD of GM1. Furthermore, this extent of fragmentation requires a range of laser powers, whereas all information is available from a single ECD experiment. However, stepwise fragmentation by IRMPD may be used to map the relative labilities for a series of cleavages. EDD provides the alternative of electron-induced fragmentation for negative ions with extensive fragmentation, but suffers from low efficiency as well as complication of data analysis by frequent loss of hydrogen atoms. We also show that analysis of MS/MS data for glycolipids is greatly simplified by classification of product ion masses to specific regions of the ganglioside based solely on mass defect graphical analysis.

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