A1H NMR Spectroscopic Approach to the Unambiguous Determination of Glycosyl Linkage Positions in Oligosaccharides

Sheng, Shuqun; Cherniak, Robert; Halbeek, Herman van

doi:10.1006/abio.1997.2454

Cited by 17 publications

(11 citation statements)

References 7 publications

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“…A powerful tool in carbohydrate analysis is methylation analysis, which provides information about which hydroxyl groups are substituted. Van Halbeek and co-workers investigated oligosaccharides in H 2 O at temperatures below 0 °C either by supercooling or addition of acetone- d 6 to prevent freezing . During the studies the authors noticed that the method can be used to identify positions in the monosaccharide residues of oligosaccharides which are glycosidically linked .…”

Section: B New Nmr Methodsmentioning

confidence: 99%

“…Van Halbeek and co-workers investigated oligosaccharides in H 2 O at temperatures below 0 °C either by supercooling or addition of acetone-d 6 to prevent freezing. 172 During the studies the authors noticed that the method can be used to identify positions in the monosaccharide residues of oligosaccharides which are glycosidically linked. 172 The aliphatic protons at carbons with OH attached will show couplings to the OH group at low temperature and can be identified by comparison of spectra obtained in D 2 O and H 2 O using, e.g., 1D TOCSY or by the line broadening.…”

Section: B New Nmr Methodsmentioning

confidence: 99%

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Carbohydrate Structural Determination by NMR Spectroscopy: Modern Methods and Limitations

2000

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I. Introduction and Scope 4589 II. NMR Methods for Structural Determination 4591 A. Carbohydrate Structural Elements and Classical NMR Methods 4591 1. Number of Sugar Residues 4592 2. Constituent Monosaccharides 4592 3. Anomeric Configuration 4593 4. Linkage and Sequence 4594 5. Position of Appended Groups 4594 6. Classical NMR Methods 4594 B. New NMR Methods 4596 C. Computer-Assisted Structural Analysis 4598 D. NMR Spectroscopy of Mixtures 4599 III. Large and Unusual Oligosaccharides 4600 IV. Polysaccharides 4603 V. NMR Analysis of Small Sample Amounts 4604 A. NMR Probes and Sample Tubes 4605 B. Examples of Structural Analysis with Small Sample Amounts 4606 VI. Conclusions 4610 VII. Acknowledgments 4610 VIII. References 4610 † This paper is dedicated to the late Professor R. U. Lemieux in memory of an always exiting and stimulating collaboration on structural studies of oligosaccharides.Jens Ø. Duus received his M.Sc. degree in Chemical Engineering from the Technical University of Denmark in 1989. Following this, he continued his graduate study with Professor Klaus Bock at the Carlsberg Laboratory and was granted his Ph.D. degree from the Technical University of Denmark in 1993. During his graduate study he was twice a Visiting Scientist at Dupont Experimental Station in Wilmington, DE working with Dr. S. Sabesan. From 1993 to 1994 he was a Research Fellow in Chemistry at the Beckman Institute at the California Institute of Technology working with Professor Harry B. Gray. After returning to the Carlsberg Laboratory, he was appointed Senior Scientist. His main fields of research are structure and dynamics of biomolecules with emphasis on carbohydrates using NMR and fluroescence.

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Section: B New Nmr Methodsmentioning

confidence: 99%

Section: B New Nmr Methodsmentioning

confidence: 99%

Carbohydrate Structural Determination by NMR Spectroscopy: Modern Methods and Limitations

2000

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“…There are no quaternary carbons in either disaccharide, so there must be eight positions in the molecule that do not bear an −OH group. 46 In the case of nigerose, four of these carbon atoms are associated with the internal oxygens of the two pyranose rings (δ C 78.6 (C-5(β))/74.0 (C-5(α)) and δ C 74.3 (C-5′(β))/74.3 (C-5′(α)), which have similar chemical shifts to those of glucopyranose in the previous section. The remaining four carbons, which appear as annotations on the 13 C projection of the HSQC-TOCSY spectrum in Figure 12, must be associated with the glycosidic linkage.…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, it is immediately apparent that 8 out of 24 carbons are not involved in correlations in the −OH region of the HSQC-TOCSY spectra for either nigerose or gentiobiose (bottom left Figures and ). There are no quaternary carbons in either disaccharide, so there must be eight positions in the molecule that do not bear an −OH group . In the case of nigerose, four of these carbon atoms are associated with the internal oxygens of the two pyranose rings (δ C 78.6 (C-5(β))/74.0 (C-5(α)) and δ C 74.3 (C-5′(β))/74.3 (C-5′(α)), which have similar chemical shifts to those of glucopyranose in the previous section.…”

Section: Resultsmentioning

confidence: 99%

A Solution NMR Approach To Determine the Chemical Structures of Carbohydrates Using the Hydroxyl Groups as Starting Points

et al. 2018

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An efficient NMR approach is described for determining the chemical structures of the monosaccharide glucose and four disaccharides, namely, nigerose, gentiobiose, leucrose and isomaltulose. This approach uses the 1 H resonances of the −OH groups, which are observable in the NMR spectrum of a supercooled aqueous solution, as the starting point for further analysis. The 2D-NMR technique, HSQC-TOCSY, is then applied to fully define the covalent structure (i.e., the topological relationship between C–C, C–H, and O–H bonds) that must be established for a novel carbohydrate before proceeding to further conformational studies. This process also leads to complete assignment of all 1 H and 13 C resonances. The approach is exemplified by analyzing the monosaccharide glucose, which is treated as if it were an “unknown”, and also by fully assigning all the NMR resonances for the four disaccharides that contain glucose. It is proposed that this technique should be equally applicable to the determination of chemical structures for larger carbohydrates of unknown composition, including those that are only available in limited quantities from biological studies. The advantages of commencing the structure elucidation of a carbohydrate at the −OH groups are discussed with reference to the now well-established 2D-/3D-NMR strategy for investigation of peptides/proteins, which employs the −NH resonances as the starting point.

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“…But it is also possible that hydrogen bonds play a deciding role in selecting between two or more conformations of otherwise similar energies. Too few data involving hydroxy protons for conformational studies are yet available [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] to answer these questions and this work is a part of a study done to investigate if and how the NMR data obtained for the hydroxy protons can be used to better characterize the conformation of oligosaccharides in aqueous solution.…”

Section: Introductionmentioning

confidence: 99%

The use of chemical shifts of hydroxy protons of oligosaccharides as conformational probes for NMR studies in aqueous solution. Evidence for persistent hydrogen bond interaction in branched trisaccharides

Sandström¹,

Baumann²,

Kenne³

1998

J. Chem. Soc., Perkin Trans. 2

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BranchedTrisaccharides.-NMR studies of branched trisaccharides (I)-(IV) show that there is a persistent hydrogen bond interaction between the O(2')H of the 3-linked sugar moiety and the O(5") of the 4-linked sugar moiety in trisaccharides (Ia), (Id), and (IVa) not only in DMSO but also in aqueous solution. Further studies of the correlation between chemical shifts of hydroxy protons and conformation of oligosaccharides are of interest.

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A1H NMR Spectroscopic Approach to the Unambiguous Determination of Glycosyl Linkage Positions in Oligosaccharides

Cited by 17 publications

References 7 publications

Carbohydrate Structural Determination by NMR Spectroscopy: Modern Methods and Limitations

Carbohydrate Structural Determination by NMR Spectroscopy: Modern Methods and Limitations

A Solution NMR Approach To Determine the Chemical Structures of Carbohydrates Using the Hydroxyl Groups as Starting Points

The use of chemical shifts of hydroxy protons of oligosaccharides as conformational probes for NMR studies in aqueous solution. Evidence for persistent hydrogen bond interaction in branched trisaccharides

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