High-Resolution Proton NMR Studies of Gangliosides. 1. Use of Homonuclear Two-Dimensional Spin-Echo J-Correlated Spectroscopy for Determination of Residue Composition and Anomeric Configurations

Theodore A.W. Koerner, James H. Prestegard, Peter C. Demou, Robert K Yu

Research output: Contribution to journalArticle

176 Citations (Scopus)

Abstract

The proton nuclear magnetic resonance spectra of gangliosides G M4 (6), G M3 (7), G M2 (8), and G M1 (9) and their asialo derivatives (3–5) have been obtained at 500 MHz and 30 °C in dimethyl-d 6 sulfoxide-deuterium oxide (98:2 v/v). Through chemical shift analysis of the upfield (0.6–3.0 ppm), anomeric (4.0–5.0 ppm), and olefinic (5.2–5.6 ppm) regions, well resolved in the one-dimensional spectra, a quantitative determination of NeuAc/GalNAc/Gal/Glc/ceramide ratios is obtained within the series 3–9. Through the use of homonuclear two-dimensional spin-echo J-correlated spectroscopy (2-D-SECSY), the J connectivities of 4–9 are revealed, allowing allocation of all resonances to subspectra. Each subspectrum is assigned to a specific residue through consideration of the number, J-connected pattern, and chemical shifts of its component protons and the magnitude and sequence of their vicinal coupling constants. Thus the monosaccharide composition, anomeric configurations, and aglycon structures of gangliosides and their derivatives may be obtained rapidly and nondestructively through high-field, proton 2-D-SECSY NMR, independent of congener series or other data. Formation of NeuAcα2→3Gal glycosidic linkages causes predictable 0.2–0.6 ppm deshielding of the proton directly attached to the glycosidation site. However, formation of GalNAcβ1→4Gal and Galβ1→3GalNAc glycosidic linkages causes irregular effects on the protons directly involved. The lack of chemical shift additivity in the latter cases indicates that glycosidation shift data can be unreliable in assignment of glycosidic linkage sites. Large, reciprocal long-range glycosidation shifts experienced by resonances of the GalNAc and NeuAc residues of 8 and 9 indicate through-space interactions exist between these residues, as they are disposed in these branched-chain gangliosides.

Original languageEnglish (US)
Pages (from-to)2676-2687
Number of pages12
JournalBiochemistry
Volume22
Issue number11
DOIs
StatePublished - Jan 1 1983
Externally publishedYes

Fingerprint

Gangliosides
Protons
Spectrum Analysis
Chemical shift
Nuclear magnetic resonance
Spectroscopy
sulfoxide
Chemical analysis
Deuterium Oxide
Derivatives
Monosaccharides
Ceramides
Magnetic Resonance Spectroscopy

ASJC Scopus subject areas

  • Biochemistry

Cite this

High-Resolution Proton NMR Studies of Gangliosides. 1. Use of Homonuclear Two-Dimensional Spin-Echo J-Correlated Spectroscopy for Determination of Residue Composition and Anomeric Configurations. / Koerner, Theodore A.W.; Prestegard, James H.; Demou, Peter C.; Yu, Robert K.

In: Biochemistry, Vol. 22, No. 11, 01.01.1983, p. 2676-2687.

Research output: Contribution to journalArticle

@article{c14514fa2cde49a5b72935a8b132c5b9,
title = "High-Resolution Proton NMR Studies of Gangliosides. 1. Use of Homonuclear Two-Dimensional Spin-Echo J-Correlated Spectroscopy for Determination of Residue Composition and Anomeric Configurations",
abstract = "The proton nuclear magnetic resonance spectra of gangliosides G M4 (6), G M3 (7), G M2 (8), and G M1 (9) and their asialo derivatives (3–5) have been obtained at 500 MHz and 30 °C in dimethyl-d 6 sulfoxide-deuterium oxide (98:2 v/v). Through chemical shift analysis of the upfield (0.6–3.0 ppm), anomeric (4.0–5.0 ppm), and olefinic (5.2–5.6 ppm) regions, well resolved in the one-dimensional spectra, a quantitative determination of NeuAc/GalNAc/Gal/Glc/ceramide ratios is obtained within the series 3–9. Through the use of homonuclear two-dimensional spin-echo J-correlated spectroscopy (2-D-SECSY), the J connectivities of 4–9 are revealed, allowing allocation of all resonances to subspectra. Each subspectrum is assigned to a specific residue through consideration of the number, J-connected pattern, and chemical shifts of its component protons and the magnitude and sequence of their vicinal coupling constants. Thus the monosaccharide composition, anomeric configurations, and aglycon structures of gangliosides and their derivatives may be obtained rapidly and nondestructively through high-field, proton 2-D-SECSY NMR, independent of congener series or other data. Formation of NeuAcα2→3Gal glycosidic linkages causes predictable 0.2–0.6 ppm deshielding of the proton directly attached to the glycosidation site. However, formation of GalNAcβ1→4Gal and Galβ1→3GalNAc glycosidic linkages causes irregular effects on the protons directly involved. The lack of chemical shift additivity in the latter cases indicates that glycosidation shift data can be unreliable in assignment of glycosidic linkage sites. Large, reciprocal long-range glycosidation shifts experienced by resonances of the GalNAc and NeuAc residues of 8 and 9 indicate through-space interactions exist between these residues, as they are disposed in these branched-chain gangliosides.",
author = "Koerner, {Theodore A.W.} and Prestegard, {James H.} and Demou, {Peter C.} and Yu, {Robert K}",
year = "1983",
month = "1",
day = "1",
doi = "10.1021/bi00280a014",
language = "English (US)",
volume = "22",
pages = "2676--2687",
journal = "Biochemistry",
issn = "0006-2960",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - High-Resolution Proton NMR Studies of Gangliosides. 1. Use of Homonuclear Two-Dimensional Spin-Echo J-Correlated Spectroscopy for Determination of Residue Composition and Anomeric Configurations

AU - Koerner, Theodore A.W.

AU - Prestegard, James H.

AU - Demou, Peter C.

AU - Yu, Robert K

PY - 1983/1/1

Y1 - 1983/1/1

N2 - The proton nuclear magnetic resonance spectra of gangliosides G M4 (6), G M3 (7), G M2 (8), and G M1 (9) and their asialo derivatives (3–5) have been obtained at 500 MHz and 30 °C in dimethyl-d 6 sulfoxide-deuterium oxide (98:2 v/v). Through chemical shift analysis of the upfield (0.6–3.0 ppm), anomeric (4.0–5.0 ppm), and olefinic (5.2–5.6 ppm) regions, well resolved in the one-dimensional spectra, a quantitative determination of NeuAc/GalNAc/Gal/Glc/ceramide ratios is obtained within the series 3–9. Through the use of homonuclear two-dimensional spin-echo J-correlated spectroscopy (2-D-SECSY), the J connectivities of 4–9 are revealed, allowing allocation of all resonances to subspectra. Each subspectrum is assigned to a specific residue through consideration of the number, J-connected pattern, and chemical shifts of its component protons and the magnitude and sequence of their vicinal coupling constants. Thus the monosaccharide composition, anomeric configurations, and aglycon structures of gangliosides and their derivatives may be obtained rapidly and nondestructively through high-field, proton 2-D-SECSY NMR, independent of congener series or other data. Formation of NeuAcα2→3Gal glycosidic linkages causes predictable 0.2–0.6 ppm deshielding of the proton directly attached to the glycosidation site. However, formation of GalNAcβ1→4Gal and Galβ1→3GalNAc glycosidic linkages causes irregular effects on the protons directly involved. The lack of chemical shift additivity in the latter cases indicates that glycosidation shift data can be unreliable in assignment of glycosidic linkage sites. Large, reciprocal long-range glycosidation shifts experienced by resonances of the GalNAc and NeuAc residues of 8 and 9 indicate through-space interactions exist between these residues, as they are disposed in these branched-chain gangliosides.

AB - The proton nuclear magnetic resonance spectra of gangliosides G M4 (6), G M3 (7), G M2 (8), and G M1 (9) and their asialo derivatives (3–5) have been obtained at 500 MHz and 30 °C in dimethyl-d 6 sulfoxide-deuterium oxide (98:2 v/v). Through chemical shift analysis of the upfield (0.6–3.0 ppm), anomeric (4.0–5.0 ppm), and olefinic (5.2–5.6 ppm) regions, well resolved in the one-dimensional spectra, a quantitative determination of NeuAc/GalNAc/Gal/Glc/ceramide ratios is obtained within the series 3–9. Through the use of homonuclear two-dimensional spin-echo J-correlated spectroscopy (2-D-SECSY), the J connectivities of 4–9 are revealed, allowing allocation of all resonances to subspectra. Each subspectrum is assigned to a specific residue through consideration of the number, J-connected pattern, and chemical shifts of its component protons and the magnitude and sequence of their vicinal coupling constants. Thus the monosaccharide composition, anomeric configurations, and aglycon structures of gangliosides and their derivatives may be obtained rapidly and nondestructively through high-field, proton 2-D-SECSY NMR, independent of congener series or other data. Formation of NeuAcα2→3Gal glycosidic linkages causes predictable 0.2–0.6 ppm deshielding of the proton directly attached to the glycosidation site. However, formation of GalNAcβ1→4Gal and Galβ1→3GalNAc glycosidic linkages causes irregular effects on the protons directly involved. The lack of chemical shift additivity in the latter cases indicates that glycosidation shift data can be unreliable in assignment of glycosidic linkage sites. Large, reciprocal long-range glycosidation shifts experienced by resonances of the GalNAc and NeuAc residues of 8 and 9 indicate through-space interactions exist between these residues, as they are disposed in these branched-chain gangliosides.

UR - http://www.scopus.com/inward/record.url?scp=0021111040&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0021111040&partnerID=8YFLogxK

U2 - 10.1021/bi00280a014

DO - 10.1021/bi00280a014

M3 - Article

C2 - 6307345

AN - SCOPUS:0021111040

VL - 22

SP - 2676

EP - 2687

JO - Biochemistry

JF - Biochemistry

SN - 0006-2960

IS - 11

ER -