Mass spectrometry of uronic acid derivatives Part IV. The fragmentation of methyl ester methyl glycosides of methylated aldotriouronic acids

Kováčik, Vladimı́r; Bauer, Štefan; Rosík, J.

doi:10.1016/s0008-6215(00)82235-1

Cited by 42 publications

(5 citation statements)

References 8 publications

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“…The ions at mlz 372 (baA1) and m/z 543 (alditol cleavage) confirm the presence of the internal 6-deoxyhexosyl residue. The ion at m/z 263 (ald J0) indicates that the internal 6-deoxyhexosyl residue is 3 linked, since this ion, 46 mass units greater than the old J2 ion, has been shown to occur only in the case of 3-linked residues (25). Although the b ald J2 ion at mlz 397 was not observed, an ion at mlz 457 (b ald J1) demonstrates that the terminal 6-deoxyhexosyl residue (residue a, Fig.…”

Section: Resultsmentioning

confidence: 98%

See 1 more Smart Citation

Structure and relevance of the oligosaccharide hapten of Mycobacterium avium serotype 2

Camphausen¹,

Jones²,

Brennan³

1986

J Bacteriol

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The type-specific antigen of Mycobacterium avium serotype 2, the most ubiquitous of serotypes within the M. avium complex and a major cause of disseminated and localized infections, was isolated and purified. It is of the glycopeptidolipid (mycoside C) class with a characteristic oligosaccharide hapten. This was released as the oligosaccharide alditol by base-catalyzed reductive s-elimination, and the structure was established by a combination of gas chromatography-mass spectrometry, methylation analysis, fast atom bombardment mass spectrometry, and 13C and 'H nuclear magnetic resonance as 2,3-di-0-methyl-L-fucopyranosyl-(al-*3)-Lrhamnopyranosyl-(al---2)-6-deoxytalitol. A feature of the work was the elucidation of the absolute (enantiomeric) configuration of the sugars. This same structure, in much less detail, was previously reported as the species-specific hapten of strains of Mycobacterium paratuberculosis. Thus, the work raises the intriguing possibility that some M. avium serotypes are synonymous, at least in outer cell wall anatomy, with the agent(s) of paratuberculosis (Johne's disease), an insidious disease of vast proportions in ruminants. In addition, recognition of a specific determinant will allow a precise study of the epidemiology of M. avium infections in humans and animals.Mycobacterium avium, particularly serotype 2, long recognized as a pathogen for birds (33) and other animals (27), has also been identified as a ubiquitous organism capable of causing chronic infections in humans (35). In certain instances, such as those described by Wolinsky (39), such infections may develop into disease. The startling observation in recent years that a variety of serotypes of M. avium and Mycobacterium intracellulare are responsible for disseminated infections in many of the patients with acquired immunodeficiency syndrome (2, 16) has resulted in renewed interest in these environmental mycobacteria. M. avium and M. intracellulare have slow growth rates (29) and may cause disease clinically similar to that caused by Mycobacterium tuberculosis (39). However, they differ from M. tuberculosis in several respects, particularly in resistance to most antituberculosis drugs (18,39). Accordingly, there is a need to distinguish such agents of "atypical mycobacterioses" from those responsible for mammalian tuberculosis. We conform to the principle that a study of the physiology of Mycobacterium spp., notably that of the cell wall, will provide information pertinent to drug resistance, persistence, and differentiation; the last is particularly important in tracing the epidemiology of infections. Previously, we had shown that the type-specific antigens of serotypes of M. avium and M. intracellulare (the so-called M. avium complex) (3-5) and a few other mycobacteria (37), including strains of Mycobacterium paratuberculosis (8), are of the mycoside C, glycopeptidolipid (GPL) class, composed of an invariant core, fatty acyl-D-Phe-D-allo-Thr-D-Ala-L-alaninol-0-(3,4-di-O-methyl-rhamnose), with a type-specific oligosaccharide h...

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Section: Resultsmentioning

confidence: 98%

“…Evidence gained from direct insertion electron impact MS of the perdeuteriomethylated r-Ose and application of the principles of Kochetkov and Chizhov (24), Kovacik et al (25,26), and Sharp and Albersheim (34) helped establish the sequence and linkage pattern. Ions at m/z 192 (aA1, Fig.…”

Section: Resultsmentioning

confidence: 99%

Structure and relevance of the oligosaccharide hapten of Mycobacterium avium serotype 2

Camphausen¹,

Jones²,

Brennan³

1986

J Bacteriol

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“…4) the ions at mje values of 219 (aA,) and 187 (aA,) are formed by the cleavage of a hexose unit from the oligosaccharide followed by the elimination of methanol [14] and the ions at m/e values of 189 (bA,) and 157 (bA,) are formed similarly by the cleavage of a deoxyhexose unit [13]. (For the nomenclature of the fragmentation series see Kochetkov and Chizhov [34], and KovaEik et al [35].) The fragments at m/e=423 (abcJ1) and m/e = 453 (bacJ,) are obtained by cleavage of the linkages between C-1 and C-2 and between C-1 and the oxygen of the ring structure in the terminal hexose and deoxyhexose residues, respectively, and rearrangement of a methyl group [34].…”

Section: Specific Degradation Of Glycopeptides By Deaminationmentioning

confidence: 99%

Characterization of a Novel Sugar Sequence from Rat-Brain Glycoproteins Containing Fucose and Sialic Acid

Krusius

Finne

1978

Eur J Biochem

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The structure of a major fucose-containing sugar sequence of rat brain glycoproteins was investigated. Glycopeptides obtained by proteolytic digestion of the lipid-free residue of whole rat brain were fractionated by affinity chromatography on Sepharose bound to concanavalin A and wheat-germ agglutinin. An N-glycosidic glycopeptide fraction corresponding to about 65 % o'f the protein-bound fucose was obtained. Methylation analysis before and after treatment with a-fucosidase or mild acid demonstrated that a major proportion of fucose is linked to the C-3 of N-acetylglucosamine. Studies involving neuraminidase digestion, partial acid hydrolysis, chromium trioxide oxidation and uronic acid degradation revealed that the fucose-containing sugar sequence has the structure :The structure of the Gal@ 1-4) [Fuc(a1-3)]GlcNAc sequence was also confirmed by gas-liquid chromatography and mass spectrometry after preparation of an oligosaccharide derivative by specific degradation with nitrous acid deamination.The sugar sequence, which has not previously been described in glycoproteins, is a sialosylated derivative of the so-called X antigen structure and it accounts for most of the fucose present in brain glycoproteins. The sugar sequence occurs mainly in membrane-bound glycoproteins, but is also found in the soluble fraction.The biological function of glycoproteins and glycolipids depends in many cases on the structure of the terminal sugar sequence of the carbohydrate chains. Thus, in blood-group-active glycoconjugates the expression of H, Lea, Leb and X antigen determinants is known to depend on the pattern of fucose substitution [l]. On the other hand, neuraminic-acid-containing sugar sequences are also involved in the expression of many biologically active structures [2]. Therefore, in studies on biological function of glycoproteins and glycolipids, determination of the structure of the peripheral parts of their carbohydrate chains seems to be indicated.In a previous study [3] we have shown that brain glycoproteins are characterized by a high relative ~_ _ _ _ ~ Abbreviations. AcNeu, N-acetylneuraminic acid; Fuc, fucose; Gal, galactose; Man, mannose; GlcNAc, N-acetylglucosamine; GlcNAcoI, N-acetylglucosaminitol.Enzymes. Vibrio cholerae neuraminidase (EC 3.2.1.18); beef kidney a-L-fucosidase (EC 3.2.1.51) ; Aspergillus niger and Jack bean /j'-o-galactosidase (EC 3.2.1.23).amount of fucose. The relative amount of fucose in brain glycoproteins is about 2 and 4 times higher than in kidney and liver glycoproteins, respectively. In brain glycoproteins a major proportion of fucose is linked to the C-3 of N-acetylglucosamine. One third of fucose is bound to the C-6 of N-acetylglocusamine, and only traces are linked to the C-2 of galactose, whereas in kidney and liver glycoproteins fucose is mainly bound to the C-6 of N-acetylglucosamine [3].In the present work the nature of the fucosecarrying sugar sequence of brain glycoproteins was studied in more detail. A major fucose-rich N-glycosidic glycopeptide fraction was isolated by ...

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“…The mass spectra were taken by the technique described above. Assignments were made in agreement with the fragmentation patterns as elucidated by Heyns, Grutzmacher, Scharmann & Muller (1966), Kochetkov & Chizhov (1966), Kovaiik, Bauer, Rosik & Kova6 (1968a) and Kovaiik, Bauer & Rosik (1968b). To denote the fragment ions, the symbols proposed by Kovacik et al (1968a) were used.…”

Section: Resultsmentioning

confidence: 99%

Bilirubin conjugates of human bile. The excretion of bilirubin as the acyl glycosides of aldobiouronic acid, pseudoaldobiouronic acid and hexuronosylhexuronic acid, with a branched-chain hexuronic acid as one of the components of hexuronosylhexuronide

Kuenzle

1970

Biochemical Journal

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Structure elucidations have been performed on the bilirubin conjugates isolated from human hepatic bile as the phenylazo derivatives. The major bilirubin conjugates are excreted, not as was formerly thought in the form of glucuronides, but as the acyl glycosides of aldobiouronic acid, pseudoaldobiouronic acid and hexuronosylhexuronic acid. The isolated aldobiouronides are proposed to have the structures of an acyl 6-O-hexopyranosyluronic acid-hexopyranoside, an acyl 4-O-hexofuranosyluronic acid-d-glucopyranoside, and an acyl 4-O-beta-d-glucofuranosyluronic acid-d-glucopyranoside respectively, with the acyl radicals being those of the phenylazo derivative of bilirubin. The pseudoaldobiouronide is suggested to be the acyl 4-O-alpha-d-glucofuranosyl-beta-d -glucopyranosiduronic acid, with the acyl radical being that of the phenylazo derivative of vinylneoxanthobilirubinic acid. The hexuronosylhexuronide presumably is the acyl 4-O-(3-C-hydroxymethylribofuranosyluronic acid)-beta-d-glucopyranosiduronic acid, with the acyl radical being that of the phenylazo derivative of bilirubin. The 3-C-hydroxymethylriburonic acid, isolated as one of the components of the hexuronosylhexuronide, is the first natural branched-chain hexuronic acid to be detected, and the first branched-chain sugar ever detected in humans.

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Mass spectrometry of uronic acid derivatives Part IV. The fragmentation of methyl ester methyl glycosides of methylated aldotriouronic acids

Cited by 42 publications

References 8 publications

Structure and relevance of the oligosaccharide hapten of Mycobacterium avium serotype 2

Structure and relevance of the oligosaccharide hapten of Mycobacterium avium serotype 2

Characterization of a Novel Sugar Sequence from Rat-Brain Glycoproteins Containing Fucose and Sialic Acid

Bilirubin conjugates of human bile. The excretion of bilirubin as the acyl glycosides of aldobiouronic acid, pseudoaldobiouronic acid and hexuronosylhexuronic acid, with a branched-chain hexuronic acid as one of the components of hexuronosylhexuronide

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