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  Secondary H/D isotope effect on hydrogen-bonded hydroxyl groups as a tool for recognizing distance constraints in conformational analysis of oligosaccharides

Dabrowski, J., Grosskurth, H., Baust, C., & Nifantev, N. E. (1998). Secondary H/D isotope effect on hydrogen-bonded hydroxyl groups as a tool for recognizing distance constraints in conformational analysis of oligosaccharides. Journal of Biomolecular NMR, 12(1), 161-172. doi:10.1023/A:1008237308320.

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Genre: Journal Article
Alternative Title : Secondary H/D isotope effect on hydrogen-bonded hydroxyl groups as a tool for recognizing distance constraints in conformational analysis of oligosaccharides

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JBiomolNMR_12_1998_161.pdf (Any fulltext), 261KB
 
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Dabrowski, Janusz1, Author           
Grosskurth, Horst2, Author           
Baust, Carmen3, Author           
Nifantev, Nicolay E., Author
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1Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society, ou_1497706              
2Department of Molecular Neurobiology, Max Planck Institute for Medical Research, Max Planck Society, ou_1497704              
3Max Planck Institute for Medical Research, Max Planck Society, ou_1125545              

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 Abstract: An 'isotopomer-selected NOE' (ISNOE) method for the unequivocal identification of mutually hydrogen-bond-linked hydroxyl groups is described. It relies on the fact that the OH group's signal patterns obtained for a partially deuterated sample originate from both isotopomers of the 'partner' hydroxyl, whereas a NOE for this group can originate from cross-relaxation with the protio isotopomer of this hydroxyl only. Hence, the isotopically shifted component of this group's signal does not appear in a ROE difference spectrum obtained with selective excitation of the 'partner' hydroxyl. This method is also applicable in those cases when only one of two mutually hydrogen-bonded groups exhibits resolvable isotope shifts. Furthermore, it is shown that isotope shifts may occur even for pairs of OH groups that are not mutually hydrogen-bonded, if these participate in hydrogen bonds with other hydroxyls and thereby affect conformational equilibria. The ISNOE experiment enables one to distinguish between these two sources of isotope shifts. Since the O[Symbol: see text][Symbol: see text][Symbol: see text]O distance for hydrogen-bonded hydroxyls in sugars is known to lie between 2.7 and 3.0 A , the hydrogen bonds established by ISNOE can be used in conformational analysis as reliable, motionally non-averaged distance constraints for the conformations containing these bonds.

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Language(s): eng - English
 Dates: 1997-11-181998-03-021998-07-01
 Publication Status: Published in print
 Pages: 12
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 Rev. Type: Peer
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Title: Journal of Biomolecular NMR
  Abbreviation : J. Biomol. NMR
Source Genre: Journal
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Publ. Info: Dordrecht, The Netherlands : Springer Science+Business Media
Pages: - Volume / Issue: 12 (1) Sequence Number: - Start / End Page: 161 - 172 Identifier: ISSN: 0925-2738
CoNE: https://pure.mpg.de/cone/journals/resource/954925566734