13C- and 1H-N.M.R. spectroscopy of permethylated gluco-, galacto-, and manno-pyranoses and their 6-deoxy analogues

Haverkamp, Johan; Bie, M. J. A. De; Vliegenthart, Johannes F.G.

doi:10.1016/s0008-6215(00)86130-3

Cited by 38 publications

(10 citation statements)

References 14 publications

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“…4) to that of the synthetic tri-0-methyl fucose (not shown) allowed the assignment of resonances at 3.55, 3.00 and 1.00 ppm to the 4, 5 and 6 protons of sugar residue C; since these chemical shifts are consistent with those of the synthetic sugar, it is concluded that the H-3 of residue C may have its resonance between those of H-2 and H-4 (3.55 13.70 ppm). The chemical shifts of 2,3,4-tri-O-methyl a-L-fucopyranose resonances deduced from the 2D-COSY analysis lead to the revision of the previous values obtained by one-dimensional 'H-NMR [6].…”

Section: Two-dimensionul Chem Icul-shift Correlu Ted Spectroscopymentioning

confidence: 72%

“…In the region of 0.5 -2.0 ppm the very intense broad signal at 1.25 ppm is attributable to the polymethylenic chain; two doublets centred at 1.35 and 1.28 ppm ( J = 6.5 Hx) may be assigned to methyl protons of 6-dcoxysugar residues [6] whereas the doublet at 1.14 ppm is characteristic of the methyl protons of cc-methyl branched fatty esters (protons 5, Fig. 1).…”

Section: One-dimensional Studiesmentioning

confidence: 99%

“…It also appears that there are two rhamnose (or mannose) residues on the basis of the small poorly resolved J1,2 couplings in sugar residues A and S at 5.51 and 4.95 ppm [4]. The third sugar residue (unit ~ C, d1,2 = 3.7 Hz) is attributable to the resonance of a-Lfucoside (or galactoside) [6].…”

Section: One-dimensional Studiesmentioning

confidence: 99%

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Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

Daffé

Servin

1989

European Journal of Biochemistry

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Two-dimensional chemical shift correlated (COSY>. nuclear Overhauser (NOESYj and J-resolved spectroscopy were used to determine the complete structure of the major triglycosyl dimycocerosyl phenol phthiocerol of the tubercle bacillus (strain Canctti) without any other analytical technique. The COSY spectrum of the native glycolipid allowed the composition of the trisaccharide and the location of one methoxyl group to be determined through the assignment of the resonances of the non-anomeric methine protons. Information with respect to the configuration of the sugar residues, the pyranose structure and the linkage sites of the trisaccharide were obtained by the analysis of the COSY spectrum of the peracetylated glycolipid. The NOESY spectrum confirmed the linkage sites through the inter-residue connectivity across glycosidic linkages and allowed the determination of the sequence of the oligosaccharidc and the configuration of its sugar residues from the through-space connectivities. The J-resolved spectroscopy was used to elucidate thc structure of the glycolipid and gave additional data showing the presence of 11 non-equivalent methyl groups and allowing the recognition of two other analogucs of the phenol phthiocerol derivative in the mixture. Thus, the non-destructive 2D-NMR spectroscopy was found to be satisfactory for the analysis of mycobacterial mycosides.Most mycobacteria are endowed with large quantities of glycolipids which contain within them small oligosaccharides of sufficient antigenicity to evoke antibodies of such exquisite specificity as to allow unequivocal identification of species or subspecies [l]. This concept w-as originally formulated by Smith et al. who gave the name 'mycosides' to type-specific glycolipids of mycobacteria limited in distribution to a single species or organism 121. These specific components are of three classes: the C-mycosides (glycopeptidolipidsj, the treh, '1 1 osecontaining lipooligosaccharides, and the phenolic glycolipids To determine the primary structure of the carbohydrate moiety ol' these glycolipids, modern spectroscopic techniques, in conjunction with elaborate derivatization of substances, have been widely used. To date, no secondary structural information (conformation), which is important for understanding thc biological activities of these substances, has been publishcrl. Furthermore, proton nuclear magnetic resonance ('€1-NMK) spectroscopy, which is very suitable for providing primary and secondary structural information on glycolipids [3], yielded only fragmentary data (composition and configuration of sugar residues) in studies on mycosides.Recently, we elucidated the complete primary structure of NMR and by application of a combination of compositional analysis, mass spectrometry and chemical degradations [4, 51. The spin-decoupling method in one-dimensional NMR was found to be a powerful method for assigning the rhamnosyl ring H-1 to H-6 chemical shifts, and for analyzing the linkage sites using peracetylated glycolipids [4, 51. However, the assign...

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Section: Two-dimensionul Chem Icul-shift Correlu Ted Spectroscopymentioning

confidence: 72%

Section: One-dimensional Studiesmentioning

confidence: 99%

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Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

Daffé

Servin

1989

European Journal of Biochemistry

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“…As compared to authentic 6-deoxy-D-glucose, the 6-deoxy-L-glucose generated in the current study gave the same spectrum. Haverkamp et al 45) reported the inclinations of the 13 C NMR spectra of 6-deoxy-D-glucose and D-glucose, and they sug- gested that the C-6 of 6-deoxy-L-glucose underwent a large upfield shift as compared to glucose, and that the C-4 and C-5 of 6-deoxy-D-glucose were shifted slightly downfield and upfield, respectively, as compared to D-glucose. The 13 C NMR spectra also revealed similar patterns between L-fucose and D-galactose, and between L-rhamnose and D-mannose.…”

Section: )mentioning

confidence: 99%

Enzymatic production of three 6-deoxy-aldohexoses from l-rhamnose

Shompoosang

Yoshihara

Uechi

et al. 2014

Bioscience, Biotechnology, and Biochemistry

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6-Deoxy-l-glucose, 6-deoxy-l-altrose, and 6-deoxy-l-allose were produced from l-rhamnose with an immobilized enzyme that was partially purified (IE) and an immobilized Escherichia coli recombinant treated with toluene (TT). 6-Deoxy-l-psicose was produced from l-rhamnose by a combination of l-rhamnose isomerase (TT-PsLRhI) and d-tagatose 3-epimerase (TT-PcDTE). The purified 6-deoxy-l-psicose was isomerized to 6-deoxy-l-altrose and 6-deoxy-l-allose with l-arabinose isomerase (TT-EaLAI) and l-ribose isomerase (TT-AcLRI), respectively, and then was epimerized to l-rhamnulose with immobilized d-tagatose 3-epimerase (IE-PcDTE). Following purification, l-rhamnulose was converted to 6-deoxy-l-glucose with d-arabinose isomerase (TT-BpDAI). The equilibrium ratios of 6-deoxy-l-psicose:6-deoxy-l-altrose, 6-deoxy-l-psicose:6-deoxy-l-allose, and l-rhamnulose:6-deoxy-l-glucose were 60:40, 40:60, and 27:73, respectively. The production yields of 6-deoxy-l-glucose, 6-deoxy-l-altrose, and 6-deoxy-l-allose from l-rhamnose were 5.4, 14.6, and 25.1%, respectively. These results indicate that the aldose isomerases used in this study acted on 6-deoxy aldohexoses.

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“…t Mass spectroscopy of the mixture is m/e 204>m/e 217. § See for reference the J..2 values of Streefkerk et al (1973) and of Haverkamp et al (1975). 11 Because of the very small amounts, 1H-n.m.r.…”

Section: Fig 1 Gas Chromatogram Ofpertrimethylsilyl Methyl Glycosidesmentioning

confidence: 99%

Characterization by gas-liquid chromatography-mass spectrometry and proton-magnetic-resonance spectroscopy of pertrimethylsilyl methyl glycosides obtained in the methanolysis of glycoproteins and glycopeptides

Kamerling

Gerwig

Vliegenthart

et al. 1975

Biochemical Journal

339

137

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The quantitative analysis by gas chromatography of monosaccharides present in glycoproteins and glycopeptides using methanolysis, followed by re-N-acetylation and trimethylsilylation, gives rise to several peaks for each monosaccharide. The identity of these peaks for xylose, fucose, mannose, galactose, glucose, N-acetylglucosamine, N-acetylgalactosamine and N-acetylneuraminic acid was established for alpha- and beta-methyl pyranosides and furanosides by combined g.l.c.-mass spectrometry and proton-magnetic-resonance spectroscopy. These data provide for the unambiguous interpretation of the gas chromatograms obtained in the application of this g.l.c. method, and supply basic information for the further application of mass spectrometry in this field.

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13C- and 1H-N.M.R. spectroscopy of permethylated gluco-, galacto-, and manno-pyranoses and their 6-deoxy analogues

Abstract: The 13C-(25.16 MHz) and 'H-n.m.r. (220,300 MHz) spectra of permethylated mannopyranoses, their 6-deoxy analogues, and permethylated 6_deoxy-ghrco-and

Cited by 38 publications

References 14 publications

Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

Enzymatic production of three 6-deoxy-aldohexoses from l-rhamnose

Characterization by gas-liquid chromatography-mass spectrometry and proton-magnetic-resonance spectroscopy of pertrimethylsilyl methyl glycosides obtained in the methanolysis of glycoproteins and glycopeptides

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