[40] Tandem mass spectrometry of glycolipids

Costello, Catherine E.; Vath, James E.

doi:10.1016/0076-6879(90)93448-t

Cited by 182 publications

(113 citation statements)

References 26 publications

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“…Asialo GM 1 was also observed to produce an abundant ion at m/z 202.07 from C 2 /Z 3 fragmentation that was absent in spectra of variants containing a 4-linked GalNAc [1,18]. Such product ions were observed in the negative mode for other asialo glyconjugates [19].…”

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confidence: 81%

The influence of sialylation on glycan negative ion dissociation and energetics

Seymour

Costello

Zaia

2006

J. Am. Soc. Mass Spectrom.

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For the analysis of native glycans using tandem mass spectrometry (MS), it is desirable to choose conditions whereby abundances of cross-ring cleavages indicative of branch positions are maximized. Recently, negative ion tandem mass spectrometry has been shown to produce significantly higher abundances of such ions in glycans compared to the positive ion mode. Much of this prior work has concerned fragmentation patterns in asialo glycans. The present work compares the abundances of critical cross-ring cleavage ions using negative mode tandem mass spectrometry for milk oligosaccharides and N-linked glycans. For comparison, product ion formation was studied for deprotonated and nitrated ions formed from asialo glycans and deprotonated ions from sialylated glycans. Breakdown profiles demonstrate clearly that more energy was required to fragment sialylated compounds to the same extent as either their asialo or nitrate adducted counterparts. The extraction of a proton from a ring hydroxyl group during the ionization process may be viewed, qualitatively, as imparting significantly more energy to the ion than would that from a molecule bearing an acidic group, so that acidic glycans are more stable in the gas phase, as the negative charge resides on the carboxyl group. These results have strong practical implications because a major portion of glycans released from mammalian proteins will be sialylated. T he most information-rich tandem mass spectra of oligosaccharides are those in which a combination of abundant glycosidic bond and cross-ring cleavages is observed. Cross-ring cleavages at branching residues and those where linkages are known to vary in the given oligosaccharide or glycoconjugate class provide particularly valuable information. Although abundant A-type and X-type cross-ring cleavages are observed using high-energy collisionalinduced dissociation (CID) [1,2], most modern mass analyzers operate in the low-energy regime. Thus, positive ion CID MS using triple quadrupole, ion trap, quadrupole orthogonal time-of-flight, and FT-ICR analyzers results in low-energy fragmentation in which Band Y-type ions and only those cross-ring cleavage ions that result from particularly facile processes are abundant [3]. Recently, high-energy CID fragmentation, including X-type cross-ring cleavage ions, has been observed for a variety of nonacidic oligosaccharides using matrix-assisted laser desorption/ionization (MALDI) tandem time-of-flight analyzers [4,5]. However, since fragile oligosaccharides, particularly polysialylated [6], and polysulfated molecules [7,8] have been observed to undergo prompt fragmentation in the vacuum MALDI source and metastable decomposition in the analyzer, they are more amenable to electrospray ionization. Negatively charged neutral oligosaccharides undergo fragmentation at very low collision energies [9 -11], and such ions are also more amenable to electrospray ionization than MALDI. Now, there remains no commercial instrument option for producing high-energy CID for fragile molecules. Introdu...

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confidence: 81%

The influence of sialylation on glycan negative ion dissociation and energetics

Seymour

Costello

Zaia

2006

J. Am. Soc. Mass Spectrom.

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“…A combination of the positive-and negative-ion mode plasma desorption mass spectrometry fragmentation patterns was used (32)(33)(34). This method although rarely employed nowadays gives in the high mass region molecularion peaks that are due to the natural heterogeneity of lipid A preparations.…”

Section: Molecular Heterogeneity and Distribution Of The Fatty Acids mentioning

confidence: 99%

Structural characterization of Bordetella parapertussis lipid A

Hamidi¹,

Новиков²,

Karibian³

et al. 2009

Journal of Lipid Research

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Bordetella parapertussis like B. pertussis, is a causal agent of whooping cough but is not a strictly human pathogen. Because its endotoxin, a major structural component of the Gram-negative outer membrane, is an important virulence factor, we have analyzed the structure of its toxic lipid domain, in one rough and two smooth bacterial strains. Chemical analyses and mass spectra obtained before and after recently developed mild-alkali treatments revealed that the lipids A have the common bisphosphorylated b-(1→6)-linked D-glucosamine disaccharide with hydroxytetradecanoic acid in amide linkages. All three strains have two major molecular species: a tetraacyl and a pentaacyl species. The rough strain is richer in a minor hexaacyl species. Acylation at the C-2, C-3, and C-3′ positions was different from that of the B. pertussis lipid A. The C-2 position carries a secondary hexadecanoic acid, the C-3 position is free, and the C-3′ position is substituted with hydroxydecanoic acid (not at C-3 as in B. pertussis), and the rough strain hexaacyl species carries a second secondary hexadecanoic acid. Like the lipid A of B. pertussis, the hydroxytetradecanoic acid at the C-2′ position was substituted by tetradecanoic

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“…Tandem sector mass spectrometric analysis of ceramide with FAB in negative-ion mode was first reported by Costello et al [6], followed by Ann and Adams [7,8]. The structural information obtained from the product-ion spectra was thought to be complimentary to that arising from the [M ϩ Li] ϩ or [M ϩ H] ϩ ions in positive-ion mode [6 -8].…”

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Characterization of ceramides by low energy collisional-activated dissociation tandem mass spectrometry with negative-ion electrospray ionization

Hsu

Turk

2002

J. Am. Soc. Mass Spectrom.

120

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Negative-ion electrospray ionization tandem quadrupole mass spectrometry provides a useful method for the structural characterization of ceramides. Fragment ions referring to the identities of the fatty acid substituent and of the long chain base of the molecules are readily available and the structure of ceramides can be easily determined. A unique fragmentation pathway which leads to formation of the fatty acid carboxylate anions (RCO Ϫ ion species permits an unambiguous identification of the fatty acyl moiety of ceramides. Tandem mass spectrometry methods for characterization of structural isomers of ceramides using product-ion scanning and for identification of specific ceramide subclasses in biological mixtures using neutral loss scanning are also demonstrated. (J Am Soc Mass Spectrom 2002, 13, 558 -570)

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[40] Tandem mass spectrometry of glycolipids

Cited by 182 publications

References 26 publications

The influence of sialylation on glycan negative ion dissociation and energetics

The influence of sialylation on glycan negative ion dissociation and energetics

Structural characterization of Bordetella parapertussis lipid A

Characterization of ceramides by low energy collisional-activated dissociation tandem mass spectrometry with negative-ion electrospray ionization

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