1H-NMR assignments of GM1-oligosaccharide in deuterated water at 500 MHz by two-dimensional spin-echo J-correlated spectroscopy

Richard L. Ong, Robert K Yu

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Abstract

The 1H-NMR spectra of the oligosaccharide derived from monosialoganglioside GM1 (GM1 = β-d-galactosyl-(1-3)-β-d-N-acetylgalactosaminyl-(1-4)-[α-N-acetylneuraminyl-(2-3)]-β-d-galactosyl-( 1-4)-β-d-glucosylceramide) (GM1OS) and its reduced form (GM1OS-R) have been obtained at 500 MHz in D2O. Through the combined use of one-dimensional and homonuclear two-dimensional spin-echo J-correlated (2D SECSY) spectra of GM1OS-R, the assignments for the ring protons of GM1OS are made. Data on chemical shifts and coupling constants of GM1OS including the α-linked neuraminic acid protons, in aqueous solution, are tabulated. Due to the very small coupling constants (<2 Hz) and the closeness in chemical shifts (<0.04 ppm) for the pair of correlated peaks in the two-dimensional spectrum, the information on the connectivities of the H5 ring protons of the neutral sugar residues is missing. Second-order coupling also blurs this information. Data are compared with those obtained for ganglioside GM1 in dimethyl sulfoxide (DMSO;the actual composition therein was 97% DMSO-d6 and 3% D2O) by T.A.W. Koerner, J. H. Prestegard, P. C. Demou, and R. K. Yu (1983, Biochemistry 22, 2676). While the heterogeneity of chemical shifts for the H5, H6a, and H6b protons diminishes in D2O, that for A-9a and A-9b remains. The latter suggests an intraneuraminic acid conformation involving the glycerol side chain unaffected by the solvent. Moreover, the chemical shifts of the III-1, III-2, and A-4 protons (and perhaps the II-4, IV-2, and A-8 protons) in D2O exhibit unusual upfield shifts compared with those in DMSO. This indicates that the intramolecular interactions between GalNAc residue III and neuraminic acid present in DMSO are weakened in D2O. The effect of temperature on the conformation is also examined and appears to be minimal (<0.02 ppm) in the range 22-50 °C.

Original languageEnglish (US)
Pages (from-to)157-166
Number of pages10
JournalArchives of Biochemistry and Biophysics
Volume245
Issue number1
DOIs
StatePublished - Feb 15 1986
Externally publishedYes

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Protons
Dimethyl Sulfoxide
Spectrum Analysis
Nuclear magnetic resonance
Chemical shift
Spectroscopy
Water
Neuraminic Acids
Conformations
Glucosylceramides
G(M1) Ganglioside
Biochemistry
Oligosaccharides
Sugars
Glycerol
G(M1)-oligosaccharide
Proton Magnetic Resonance Spectroscopy
Temperature
Acids
Chemical analysis

ASJC Scopus subject areas

  • Biochemistry
  • Biophysics
  • Molecular Biology

Cite this

@article{e46b157b800648b4a51ad9d484e0305e,
title = "1H-NMR assignments of GM1-oligosaccharide in deuterated water at 500 MHz by two-dimensional spin-echo J-correlated spectroscopy",
abstract = "The 1H-NMR spectra of the oligosaccharide derived from monosialoganglioside GM1 (GM1 = β-d-galactosyl-(1-3)-β-d-N-acetylgalactosaminyl-(1-4)-[α-N-acetylneuraminyl-(2-3)]-β-d-galactosyl-( 1-4)-β-d-glucosylceramide) (GM1OS) and its reduced form (GM1OS-R) have been obtained at 500 MHz in D2O. Through the combined use of one-dimensional and homonuclear two-dimensional spin-echo J-correlated (2D SECSY) spectra of GM1OS-R, the assignments for the ring protons of GM1OS are made. Data on chemical shifts and coupling constants of GM1OS including the α-linked neuraminic acid protons, in aqueous solution, are tabulated. Due to the very small coupling constants (<2 Hz) and the closeness in chemical shifts (<0.04 ppm) for the pair of correlated peaks in the two-dimensional spectrum, the information on the connectivities of the H5 ring protons of the neutral sugar residues is missing. Second-order coupling also blurs this information. Data are compared with those obtained for ganglioside GM1 in dimethyl sulfoxide (DMSO;the actual composition therein was 97{\%} DMSO-d6 and 3{\%} D2O) by T.A.W. Koerner, J. H. Prestegard, P. C. Demou, and R. K. Yu (1983, Biochemistry 22, 2676). While the heterogeneity of chemical shifts for the H5, H6a, and H6b protons diminishes in D2O, that for A-9a and A-9b remains. The latter suggests an intraneuraminic acid conformation involving the glycerol side chain unaffected by the solvent. Moreover, the chemical shifts of the III-1, III-2, and A-4 protons (and perhaps the II-4, IV-2, and A-8 protons) in D2O exhibit unusual upfield shifts compared with those in DMSO. This indicates that the intramolecular interactions between GalNAc residue III and neuraminic acid present in DMSO are weakened in D2O. The effect of temperature on the conformation is also examined and appears to be minimal (<0.02 ppm) in the range 22-50 °C.",
author = "Ong, {Richard L.} and Yu, {Robert K}",
year = "1986",
month = "2",
day = "15",
doi = "10.1016/0003-9861(86)90200-6",
language = "English (US)",
volume = "245",
pages = "157--166",
journal = "Archives of Biochemistry and Biophysics",
issn = "0003-9861",
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TY - JOUR

T1 - 1H-NMR assignments of GM1-oligosaccharide in deuterated water at 500 MHz by two-dimensional spin-echo J-correlated spectroscopy

AU - Ong, Richard L.

AU - Yu, Robert K

PY - 1986/2/15

Y1 - 1986/2/15

N2 - The 1H-NMR spectra of the oligosaccharide derived from monosialoganglioside GM1 (GM1 = β-d-galactosyl-(1-3)-β-d-N-acetylgalactosaminyl-(1-4)-[α-N-acetylneuraminyl-(2-3)]-β-d-galactosyl-( 1-4)-β-d-glucosylceramide) (GM1OS) and its reduced form (GM1OS-R) have been obtained at 500 MHz in D2O. Through the combined use of one-dimensional and homonuclear two-dimensional spin-echo J-correlated (2D SECSY) spectra of GM1OS-R, the assignments for the ring protons of GM1OS are made. Data on chemical shifts and coupling constants of GM1OS including the α-linked neuraminic acid protons, in aqueous solution, are tabulated. Due to the very small coupling constants (<2 Hz) and the closeness in chemical shifts (<0.04 ppm) for the pair of correlated peaks in the two-dimensional spectrum, the information on the connectivities of the H5 ring protons of the neutral sugar residues is missing. Second-order coupling also blurs this information. Data are compared with those obtained for ganglioside GM1 in dimethyl sulfoxide (DMSO;the actual composition therein was 97% DMSO-d6 and 3% D2O) by T.A.W. Koerner, J. H. Prestegard, P. C. Demou, and R. K. Yu (1983, Biochemistry 22, 2676). While the heterogeneity of chemical shifts for the H5, H6a, and H6b protons diminishes in D2O, that for A-9a and A-9b remains. The latter suggests an intraneuraminic acid conformation involving the glycerol side chain unaffected by the solvent. Moreover, the chemical shifts of the III-1, III-2, and A-4 protons (and perhaps the II-4, IV-2, and A-8 protons) in D2O exhibit unusual upfield shifts compared with those in DMSO. This indicates that the intramolecular interactions between GalNAc residue III and neuraminic acid present in DMSO are weakened in D2O. The effect of temperature on the conformation is also examined and appears to be minimal (<0.02 ppm) in the range 22-50 °C.

AB - The 1H-NMR spectra of the oligosaccharide derived from monosialoganglioside GM1 (GM1 = β-d-galactosyl-(1-3)-β-d-N-acetylgalactosaminyl-(1-4)-[α-N-acetylneuraminyl-(2-3)]-β-d-galactosyl-( 1-4)-β-d-glucosylceramide) (GM1OS) and its reduced form (GM1OS-R) have been obtained at 500 MHz in D2O. Through the combined use of one-dimensional and homonuclear two-dimensional spin-echo J-correlated (2D SECSY) spectra of GM1OS-R, the assignments for the ring protons of GM1OS are made. Data on chemical shifts and coupling constants of GM1OS including the α-linked neuraminic acid protons, in aqueous solution, are tabulated. Due to the very small coupling constants (<2 Hz) and the closeness in chemical shifts (<0.04 ppm) for the pair of correlated peaks in the two-dimensional spectrum, the information on the connectivities of the H5 ring protons of the neutral sugar residues is missing. Second-order coupling also blurs this information. Data are compared with those obtained for ganglioside GM1 in dimethyl sulfoxide (DMSO;the actual composition therein was 97% DMSO-d6 and 3% D2O) by T.A.W. Koerner, J. H. Prestegard, P. C. Demou, and R. K. Yu (1983, Biochemistry 22, 2676). While the heterogeneity of chemical shifts for the H5, H6a, and H6b protons diminishes in D2O, that for A-9a and A-9b remains. The latter suggests an intraneuraminic acid conformation involving the glycerol side chain unaffected by the solvent. Moreover, the chemical shifts of the III-1, III-2, and A-4 protons (and perhaps the II-4, IV-2, and A-8 protons) in D2O exhibit unusual upfield shifts compared with those in DMSO. This indicates that the intramolecular interactions between GalNAc residue III and neuraminic acid present in DMSO are weakened in D2O. The effect of temperature on the conformation is also examined and appears to be minimal (<0.02 ppm) in the range 22-50 °C.

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U2 - 10.1016/0003-9861(86)90200-6

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