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1H NMR studies of molecular interactions of carbohydrates in aqueous solutions

Hakkarainen, Birgit (2007). 1H NMR studies of molecular interactions of carbohydrates in aqueous solutions. Diss. (sammanfattning/summary) Uppsala : Sveriges lantbruksuniv., Acta Universitatis Agriculturae Sueciae, 1652-6880 ; 2007:5
ISBN 978-91-576-7304-6
[Doctoral thesis]

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The formation and structure of inclusion complexes between α-cyclodextrin (α-CD) and adamantane, 1-adamantanol, 1-(hydroxymethyl)-adamantane, 2-adamantanol and 1,3-adamantanediol in aqueous solutions were studied by 1H NMR spectroscopy using both exchangeable and non-exchangeable protons. Complexes were formed with all adamantane derivatives with the exception of 1,3-adamantanediol. Similarities between the α-CD/adamantane and the α-CD/2-adamantanol complexes were evidenced by the appearance of a narrow and upfield shifted O(3)H signal for α-CD in the complex. α-CD formed 1:1 complexes with 1-adamantanol and 1-(hydroxymethyl)-adamantane. In both cases the O(2)H signal of α-CD was broadened with higher concentration of guest molecule and low temperatures. 1H NMR studies of the hydrogen bonding network in mono-altro-β-cyclodextrin and its complex with adamantane-1-carboxylic acid showed that the hydroxy proton chemical shifts, temperature coefficients and vicinal coupling constants could be used to monitor the formation of intermolecular hydrogen bonds and hydration changes. The conformational change undertaken by altrose upon addition of adamantane-1-carboxylic acid allowed a more regular hydrogen bond network between the secondary hydroxyl groups in the CD, as evidenced by the downfield shift for O(3)H of the glucose-units. In the second part of the thesis, the interactions between di- and trimannosides, substructures of oligomannose-9, and mutants of the HIV inactivating protein cyanovirin-N (CV-N) were studied using saturation transfer difference NMR spectroscopy. In one mutant CV-NMutDB, the carbohydrate-binding site on domain B was suppressed while keeping the domain A intact. In the other mutant, CV-NMutDA, the specificity of domain A for trimannose was altered while domain B was kept intact. Both mutants recognised all di- and trimannosides containing the terminal Manα(1-2)Man epitope. The binding of the mutants were similar, with a slightly stronger affinity for the trisaccharide, Manα(1-2)Manα(1-2)ManαOMe in CV-NMutDB. Isothermal titration calorimetry data for CV-NMutDB showed a binding affinity of 3.4 +/-0.5 microM for the trisaccharide, which is close to the value derived for the nonamannoside (4.3 +/-0.5 microM). No binding parameters were extracted for CV-NMutDA due to the presence of two binding sites. This study confirm previous findings showing that not only the terminal disaccharide but also the linkage to the reducing end residue is important for binding to CV-N and thereby also for antiviral activity.

Authors/Creators:Hakkarainen, Birgit
Title:1H NMR studies of molecular interactions of carbohydrates in aqueous solutions
Series Name/Journal:Acta Universitatis Agriculturae Sueciae
Year of publishing :2007
Number of Pages:53
ALLI. Bendeby, B., Kenne, L., and Sandström, C. (2004) 1H-NMR studies of the inclusion complexes between α-cyclodextrin and adamantane derivatives using both exchangeable hydroxy protons and non-exchangeable aliphatic protons. Journal of Inclusion Phenomena and Macrocyclic Chemistry 50, 173-181. II. Hakkarainen, B., Fujita, K., Immel, S., Kenne, L., and Sandström, C. (2005) 1H NMR studies on the hydrogen-bonding network in mono-altro-β-cyclodextrin and its complex with adamantane-1-carboxylic acid. Carbohydrate Research 340, 1539-1545. III. Hakkarainen, B., Lahmann, M., Oscarson, S., Matei, E., Kenne, L., Gronenborn, A.M., and Sandström, C. (2006) Atomic mapping of the sugar binding epitopes in one-site and two-site mutants of Cyanovirin-N by Saturation-Transfer Difference NMR Spectroscopy. Manuscript IV. Hakkarainen, B., Kenne, L., Lahmann, M., Oscarson, S., Sandström, C. (2006) NMR study of hydroxy protons of di- and trimannosides substructures of Man-9. Manuscript
Place of Publication:Uppsala
ISBN for printed version:978-91-576-7304-6
Publication Type:Doctoral thesis
Full Text Status:Public
Agrovoc terms:nmr spectroscopy, dextrins, lectins
Keywords:Hydroxy protons, cyclodextrin, conformation, molecular interactions, anti-viral, cyanovirin-N, Man9, mannosides.
Permanent URL:
ID Code:1300
Department:(NL, NJ) > Dept. of Chemistry (until 131231)
Deposited By: Birgit Hakkarainen
Deposited On:09 Jan 2007 00:00
Metadata Last Modified:02 Dec 2014 10:11

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