Mass spectrometry of partially methylated alditol acetates

Björndal, Håkan; Lindberg, Bengt; Svensson, Sigfrid

doi:10.1016/s0008-6215(00)81115-5

Cited by 469 publications

(110 citation statements)

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“…The m/e values in the mass spectra of both alditol acetates agreed well with those in the literature (Bjorndal et al, 1967). These results showed that the six oligosaccharides were all (1 -+ 6)-a-linked manno-oligosaccharides.…”

supporting

confidence: 89%

Studies on Fungal Polysaccharides: The Immunological Determinant of the Serologically Active Substances from Absidia cylindrospora, Mucor hiemalis and Rhizopus nigricans

Miyazaki

Hayashi

Ohshima

et al. 1979

Journal of General Microbiology

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Six manno-oligosaccharides were isolated from the partial acid hydrolysate of pronasetreated extracellular glycan (pt-ACE-11) of Absidia cylindrospora by gel filtration on Bio Gel P-2 and descending paper chromatography. The pentasaccharide and the higher molecular weight oligosaccharides significantly inhibited the precipitation reaction of intracellular glycans from Absidia cylindrospora (ACI-B), Mucor hiemalis (MhI-B) and Rhizopus nigricans (RnI-B) with anti-ACE serum. Structural analysis showed that these six oligosaccharides were composed of linear ( 1 + 6)-a-linked mannopyranosyl residues. INTRODUCTIONPreviously (Hayashi et al., 1978a, b) we have described the isolation, purification and partial characterization of the serologically active fucomannan-peptide of Absidia cylindrospora, a member of the Mucorales. Rabbit antiserum (anti-ACE serum) against the extracellular non-dialysable fraction of A. cylindrospora reacted not only with this fucomannanpeptide but also with antigenic fractions from four Mucor spp. and Rhizopus nigricans. However, anti-ACE serum did not cross-react with the purified mannans of Candida albicans and Saccharomyces cerevisiae, so it would appear that the chemical structure of the serologically active determinant might be different from those of the mannans of C. albicans and S. cerevisiae.In the present paper, the purification of six manno-oligosaccharides and the results of precipitation inhibition tests with these oligosaccharides are described. The common determinant in the serologically active substances of A. cylindrospora, M. hiemalis and R. nigricans is discussed. METHODSAnalytical methods. Quantitative analyses of carbohydrate, protein and phosphate were performed by the methods of Dubois et al. (1956( ), Lowry et al. (1951 and of Fiske & Subbarow (1925), respectively, using mannose, bovine serum albumin and KHzPOB as the standards.For paper and thin-layer chromatography (t.1.c.) the following solvent systems were used: A, ethyl acetate/pyridine/acetic acid/water (5: 5: 1 : 3, by vol.); By 1-butanol/ethanol/water (3 : 1 : 1 , by vol.). Carbohydrates on paper and thin-layer chromatograms were detected with the alkaline silver nitrate reagent (Trevelyan et al., 1950) or the periodate-benzidine reagent (Cifonelli & Smith, 1954). (The use of benzidine in the UK is prohibited under the Carcinogenic Substances Regulations, 1968). Gas-liquid chromatography (g.1.c.) was performed using a Shimadzu GC-6A chromatograph (Shimadzu, Tokyo, Japan) as described previously (Hayashi et al., 1978a). A glass column packed with 3 % (w/w) ECNSS-M on Chromosorb W (AW-DMCS, 60 to 80 mesh) was used for identification of the partially methylated alditol acetates. G. T. M I Y A Z A K I A N D OTHERScolumn packed with 3 % (w/w) silicone OV-225 on Chromosorb W (AW-DMCS, 80 to 100 mesh) at 170 "C and operated at an ionization voltage of 70 eV, a trap current of 60 ,uA and an ion source at 310 "C. Infrared spectra were recorded with a Hitachi-215 spectrometer. Preparation of ACI-By MhI-B and RnI-B.The s...

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confidence: 89%

Studies on Fungal Polysaccharides: The Immunological Determinant of the Serologically Active Substances from Absidia cylindrospora, Mucor hiemalis and Rhizopus nigricans

Miyazaki

Hayashi

Ohshima

et al. 1979

Journal of General Microbiology

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“…The analysis and identification of partially methylated hexosamine in the form of methyl hexosaminide and neutral sugars in the form of alditol acetates were performed as described previously [5] with the use of the data of Bjorndal et al [12] on fragmentation patterns of methylated alditol acetates.…”

Section: E Thy La T Ion a Nalysismentioning

confidence: 99%

Somatic Antigens of Shigella

Dmitriev

Knirel

Kochetkov

et al. 1976

European Journal of Biochemistry

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The O-specific polysaccharide obtained from the lipopolysaccharide of Shigella dysenteriae type 1 (Shigella shiga) by mild acid hydrolysis followed by fractionation on Sephadex G-50 was found to be identical to that described by Morgan's group and was composed of L-rhamnose, D-galactose and N-acetyl-D-glucosamine in a ratio 2 : 1 : 1. On the basis of methylation analysis data the polysaccharide was proved to be a linear chain of monosaccharide residues in pyranose forms substituted at position 3, except for that of galactose substituted at position 2.Selective cleavage, based on the N-deacetylation reaction of the polymer, together with determination of linkage configurations by chromic anhydride oxidation showed that the O-specific polysaccharide is built up of repeating tetrasaccharide units whose proposed structure is given belowwhere Rhap = rhamnopyranose, Galp = galactopyranose, and GlcNAcp = N-acetyl-glucosamine.The present findings confirmed the considerations of Heidelberger on the substitution patterns of L-rhamnose and D-galactose residues from the results of serological studies.Sliigella dysenteriae type 1 (Sh. shigu) is the most investigated from ten serotypes of Slzigella dysenteriae subgroup and its O-specific polysaccharide was found to be composed of L-rhamnose, D-galactose and N-acetyl-D-glucosamine residues [l, 21. Moreover, as follows from the data of Heidelberger and coworkers [3] on serological relationship between this polysaccharide and two K-specific polysaccharides from Pneumococcus types 2 and 6, it was proposed that rhamnose and galactose residues in the Sh. dysenteriue polysaccharide were substituted at positions 3 and 2 respectively. In spite of these findings, the complete chemical structure of the antigenic polysaccharide from Sh. dysenteriae type 1 has not previously been established.In the course of systematic structural investigations on Sh. dysenteriae lipopolysaccharides, we have performed the chemotyping of all ten lipopolysaccharides of this subgroup [4], determined the structures of polysaccharide chains of serotypes 3 [5,6] and 6 [7], and discovered a new type of acidic monosaccharides [8] which were found to be the components of these O-antigens.

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“…( Mass spectrometry has shown a unique ability to resolve certain structural ambiguities. Permethylation is a well developed but time-consuming GC-MS method in linkage analysis of oligosaccharides [1,2]. Other methods implementing the derivatization of saccharides have been used to obtain their structural information [3][4][5][6][7][8][9][10][11].…”

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confidence: 99%

Rapid and sensitive differentiation of anomers, linkage, and position isomers of disaccharides using High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS)

Gabryelski

Froese

2003

J. Am. Soc. Mass Spectrom.

128

124

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A challenging aspect of structural elucidation of carbohydrates is gaining unambiguous information for anomers, linkage, and position isomers. Such isomers with identical mass can't be easily distinguished in mass spectrometry and a separation step is required prior to mass spectrometry identification. In our laboratory, gas-phase separation and differentiation of anomers, linkage, and position isomers of disaccharides was achieved using High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS). The FAIMS method responds to changes in ion mobility at high field rather than absolute values of ion mobility, and was shown to provide efficient separation and identification of disaccharide isomers at high sensitivity. Separation of analyzed disaccharide isomers can be accomplished at low nM level in a matter of seconds without sample purification or fractionation. Capability for examining a large population of ionic species of disaccharides by this method allowed for correlating structural details of disaccharide isomers with their separation properties in FAIMS. Results for disaccharide isomers indicate that this method could be applied to a larger group of carbohydrates. ( Mass spectrometry has shown a unique ability to resolve certain structural ambiguities. Permethylation is a well developed but time-consuming GC-MS method in linkage analysis of oligosaccharides [1,2]. Other methods implementing the derivatization of saccharides have been used to obtain their structural information [3][4][5][6][7][8][9][10][11]. The soft mass spectrometry ionization techniques such as fast atom bombardment (FAB) [12][13][14][15][16], liquid secondary ionization mass spectrometry (LSIMS) [17,18], along with matrix-assisted laser desorption ionization (MALDI) [19 -23], and electrospray ionization (ESI) [24 -28] have gained attention as approaches to investigate underivatized oligosaccharides. Collision-induced dissociation (CID) offers the possibility to assign details of carbohydrate structure such as sugar sequence for linear oligosaccharides [12], linkage position [12,[15][16][17]29], and differentiation of anomers [25,30]. In addition to analyzing protonated or deprotonated molecular ions of saccharides in CID, alkali metal adduct ions have been used to promote fragmentation of ligand-carbohydrate complexes. In the positive ion mode, calcium and magnesium adducts of oligosaccharides were investigated for the elucidation of the linkage position of trisaccharides [26] and cobalt complexes have been used to differentiate the anomeric configuration of disaccharides [30]. In the negative ion mode, decomposition of chloride adducts was investigated for differentiation of the linkage position of disaccharides [31].Despite recent advances in tandem mass spectrometry of carbohydrates, the spectral differences for some isomers are very small and they do not provide unambiguous identification. This is especially true when a mixture of isomers with the same m/z has to be analyzed. In such applications a separation step is required ...

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Mass spectrometry of partially methylated alditol acetates

Cited by 469 publications

References 2 publications

Studies on Fungal Polysaccharides: The Immunological Determinant of the Serologically Active Substances from Absidia cylindrospora, Mucor hiemalis and Rhizopus nigricans

Studies on Fungal Polysaccharides: The Immunological Determinant of the Serologically Active Substances from Absidia cylindrospora, Mucor hiemalis and Rhizopus nigricans

Somatic Antigens of Shigella

Rapid and sensitive differentiation of anomers, linkage, and position isomers of disaccharides using High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS)

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