Analysis of glycosaminoglycan-derived oligosaccharides using fast-atom-bombardment mass-spectrometry

Linhardt, Robert J.; Wang, Hui M.; Loganathan, Duraikkannu; Lamb, Diane J.; Mallis, Larry M.

doi:10.1016/0008-6215(92)80045-3

Cited by 43 publications

(22 citation statements)

References 16 publications

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“…Mass spectrometric investigation of heparin-derived oligosaccharides poses a serious challenge because they have to be extensively purified and desalted for negative-ion fastatom-bombardment mass spectrometry. This methodology requires large amounts of material (10 nmol/pJ) and still results in partially sodiated anions of monosulfated disaccharides and polysulfated di-to octasaccharides, which contain up to 15 Na+ ions (20)(21)(22). Probably because of these difficulties, little mass spectrometric work concerning this biologically important class of compounds has been reported to date.…”

Section: Resultsmentioning

confidence: 99%

Mass spectrometric molecular-weight determination of highly acidic compounds of biological significance via their complexes with basic polypeptides.

Juhász

Biemann

1994

Proc. Natl. Acad. Sci. U.S.A.

141

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Highly acidic compounds that are difficult to Ionize by matrix-assisted laser desorption onization give excellent spectra when mixed with a basic peptide or protein to form a noncovalent complex. This phenomenon makes it possible to determine the molecular weights of polysulfated, -sulfonated, and -phosphorylated blomolecules such as cysteic acid-containing peptides, oligonucleotides, heparin-derived oligosaccharides, and suramin (a drug containing two trisulfonated naphthalene moieties). Peptides and small proteins rich in arginine were used as the basic components. The extent of complex formation correlates with the number of phosphate and sulfate groups in the acidic component and with the number of arginines in the basic component. Neither the acidic amino acid residue aspartic and glutamic acid nor the basic lysine and histidine contribute to complex formation. For oligonudeotides, histone H4 was found to be the best complexing agent investigated. The analytical utility of the complex formation is demonstrated by the molecular-mass determination of acidic compounds from 500 to 6000 Da at the picomole or sub-picomole level with an accuracy of ± 0.1% or better and by the absence of alkali cation adducts.The development of matrix-assisted laser desorption ionization (MALDI) mass spectrometry permits the determination of the molecular mass of proteins up to the 105-Da range with an accuracy of 0.1-0.01%, requiring only picomoles or subpicomoles of material (1-4). The method is equally applicable to smaller biologically important molecules, such as peptides (5), carbohydrates (6), oligonucleotides (7,8), glycolipids (9), and polar and nonpolar synthetic polymers (10, 11). It has become an important technique in biochemistry and biology, not only because the molecular weight of the native material at that level of accuracy is in itself very useful information, but also because the changes thereof upon chemical or enzymatic treatment provide further insight into the structure or biological significance of parts of the native molecule (12). These manipulations are often necessary to obtain structural information because little excess energy is transferred to the analyte during the MALDI process, and "prompt" fragmentation is therefore rarely observed. This feature is an advantage in the analyses of mixtures, as long as the components can be resolved.Although most of the compounds in the above-mentioned categories are amenable to MALDI, it is difficult to ionize highly acidic compounds, even in the negative mode of the mass spectrometer, where they are detected as anions. In that mode, most efforts have been devoted to oligonucleotides (7,8). It is even more difficult to ionize polysulfate esters or polysulfonic acids. This is due, in part, to the fact that these substances tenaciously attach cations (such as Na+, K+, etc.) that give rise to broad unresolved peaks, the centroid of which corresponds to the average mass of all these partial salts.When attempting to use the oxidized A chain of bovine insulin (A...

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Section: Resultsmentioning

confidence: 99%

Mass spectrometric molecular-weight determination of highly acidic compounds of biological significance via their complexes with basic polypeptides.

Juhász

Biemann

1994

Proc. Natl. Acad. Sci. U.S.A.

141

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“…Due to the presence of sulphate and hexuronic acid in these molecules, negative ion mode MS has usually been the method of choice. Historically, fast atom bombardment and liquid secondary desorption/ionisation techniques for analysing glycosaminoglycans or depolymerised glycosaminoglycans [7][8][9][10], have been substituted by negative ion electrospray (ES) mass spectrometry [11][12][13][14][15][16][17][18]. Matrix assisted timeof-flight (MALDI-TOF) mass spectrometry has also been successfully used for this analysis [19], including coupling of the negatively charged glycosaminoglycans to positively charged polypeptides enabling glycosaminoglycans to be detected in positive ion mode [20,21].…”

Section: Introductionmentioning

confidence: 99%

Use of graphitised carbon negative ion LC–MS to analyse enzymatically digested glycosaminoglycans

Karlsson¹,

Schulz²,

Packer³

et al. 2005

Journal of Chromatography B

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“…In this context, a high number of publications have been focused on the study of sulfated sugar-containing macromolecules through the mass spectrometric analysis of their enzymatically or chemically produced oligosaccharides [8 -12]. The earlier studies [13,14] [8,9], and mucopolysaccharides [24] have served as models for the improvement of the knowledge of mass spectrometric methods involving these types of molecules.Many of the aforementioned studies have been dedicated to determine the sulfation position of isomeric oligosaccharides. Evaluation of the losses of monosaccharide units by sequencing mass spectrometry is normally sufficient to determine the sulfation pattern of isomers bearing sulfate groups on different monosaccharide units [10,17].…”

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ESI-MS differential fragmentation of positional isomers of sulfated oligosaccharides derived from carrageenans and agarans

Gonçalves

Ducatti

Grindley

et al. 2010

J. Am. Soc. Mass Spectrom.

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We have prepared a number of isomeric red seaweed galactan-derivative sulfated oligosaccharides to determine whether there were diagnostic differences among the isomeric mass spectra obtained using ESI CID MS/MS (triple quadrupole instrument). Fragmentation of the single or multicharged molecular ions from di-, tetra-, and hexasaccharides indicated that the relative positioning of the sulfate groups and type of monosaccharide unit affect the rate of cleavage of the glycosidic bonds. We also performed a comparative [M-Na] Ϫ fragmentation study of positional isomers of sulfated disaccharides that present all four monosulfation possibilities on the galactopyranosidic ring. In this case, negative-ion ESI CID MS/MS approach gave diagnostic product ions from cross-ring cleavages along with the same main B 1 ion (from sulfated Galp), at m/z 241, for all isomers. The isomeric disaccharides were also submitted to increased spray energy conditions inducing in-source fragmentation; preformed B 1 ions were then fragmented to give similar product ions as those found in [M-Na] Ϫ analysis. [4,5]. It is now recognized that the regiochemistry and stereochemistry of the positions of the sulfates are highly significant for their recognition, the "sulfation code" [6,7]. Thus, the development of diverse tools for the structural determination of sulfated sugars has become extremely important. In this context, a high number of publications have been focused on the study of sulfated sugar-containing macromolecules through the mass spectrometric analysis of their enzymatically or chemically produced oligosaccharides [8 -12]. The earlier studies [13,14] [8,9], and mucopolysaccharides [24] have served as models for the improvement of the knowledge of mass spectrometric methods involving these types of molecules.Many of the aforementioned studies have been dedicated to determine the sulfation position of isomeric oligosaccharides. Evaluation of the losses of monosaccharide units by sequencing mass spectrometry is normally sufficient to determine the sulfation pattern of isomers bearing sulfate groups on different monosaccharide units [10,17]. In cases where the differences are only related to the position occupied by the sulfate groups in the same monosaccharide ring, the determination of the positional isomer is more difficult. Most of the studies carried out with this aim have been performed to determine the location and degree of sulfation for 4-and/or 6-sulfated HexNAc of chondroitin sulfate-oligosaccharides. For this purpose, control of the charge state of the parent ion followed by determination of the relative abundance of the product ions generated from the cleavage of the glycosidic linkage Address reprint requests to Dr. M. D. Noseda,

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Analysis of glycosaminoglycan-derived oligosaccharides using fast-atom-bombardment mass-spectrometry

Cited by 43 publications

References 16 publications

Mass spectrometric molecular-weight determination of highly acidic compounds of biological significance via their complexes with basic polypeptides.

Mass spectrometric molecular-weight determination of highly acidic compounds of biological significance via their complexes with basic polypeptides.

Use of graphitised carbon negative ion LC–MS to analyse enzymatically digested glycosaminoglycans

ESI-MS differential fragmentation of positional isomers of sulfated oligosaccharides derived from carrageenans and agarans

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