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Solution conformation and dynamics of a tetrasaccharide related to the LewisX antigen deduced by NMR relaxation measurements

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Abstract

1H-NMR cross-relaxation rates and nonselectivelongitudinal relaxation times have been obtained at two magnetic fields (7.0and 11.8 T) and at a variety of temperatures for the branchedtetrasaccharide methyl3-O-α-N-acetyl-galactosaminyl-β-galactopyranosyl-(1→4)[3-O-α-fucosyl]-glucopyranoside (1), an inhibitor of astrocyte growth. Inaddition, 13C-NMR relaxation data have also been recorded atboth fields. The 1H-NMR relaxation data have been interpretedusing different motional models to obtain proton–proton correlationtimes. The results indicate that the GalNAc and Fuc rings display moreextensive local motion than the two inner Glc and Gal moieties, since thosepresent significantly shorter local correlation times. The13C-NMR relaxation parameters have been interpreted in termsof the Lipari–Szabo model-free approach. Thus, order parameters andinternal motion correlation times have been deduced. As obtained for the1H-NMR relaxation data, the two outer residues possess smallerorder parameters than the two inner rings. Internal correlation times are inthe order of 100 ps. The hydroxymethyl groups have also different behaviour,with the exocyclic carbon on the glucopyranoside unit showing the highestS2. Molecular dynamics simulations using a solvated systemhave also been performed and internal motion correlation functions have beendeduced from these calculations. Order parameters and interproton distanceshave been compared to those inferred from the NMR measurements. The obtainedresults are in fair agreement with the experimental data.

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Authors and Affiliations

  1. Servicio Interdepartamental de Investigación, Universidad Autónoma de Madrid, Cantoblanco, E-28049, Madrid, Spain

    Ana Poveda

  2. Grupo de Carbohidratos, Instituto de Química Orgánica, CSIC, Juan de la Cierva 3, E-28006, Madrid, Spain

    Juan Luis Asensio, Manuel Martín-Pastor & and Jesús Jiménez-Barbero

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  1. Ana Poveda
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  2. Juan Luis Asensio
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  3. Manuel Martín-Pastor
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  4. and Jesús Jiménez-Barbero
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Poveda, A., Asensio, J.L., Martín-Pastor, M. et al. Solution conformation and dynamics of a tetrasaccharide related to the LewisX antigen deduced by NMR relaxation measurements. J Biomol NMR 10, 29–43 (1997). https://doi.org/10.1023/A:1018395627017

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