Počet záznamů: 1
Limitations in the description of conformational preferences of C-disaccharides: The (1 -> 3)-C-mannobiose case
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SYSNO ASEP 0480867 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Limitations in the description of conformational preferences of C-disaccharides: The (1 -> 3)-C-mannobiose case Tvůrce(i) Raich, I. (CZ)
Lövyová, Z. (CZ)
Trnka, L. (CZ)
Parkan, Kamil (UOCHB-X)
Kessler, Jiří (UOCHB-X) RID, ORCID
Pohl, Radek (UOCHB-X) RID, ORCID
Kaminský, Jakub (UOCHB-X) RID, ORCIDZdroj.dok. Carbohydrate Research. - : Elsevier - ISSN 0008-6215
Roč. 451, Nov 8 (2017), s. 42-50Poč.str. 9 s. Jazyk dok. eng - angličtina Země vyd. NL - Nizozemsko Klíč. slova C-disaccharides ; mannosides ; conformations ; NMR ; J-coupling constants ; molecular dynamics Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GA16-00270S GA ČR - Grantová agentura ČR Institucionální podpora UOCHB-X - RVO:61388963 UT WOS 000413320300005 EID SCOPUS 85029726149 DOI 10.1016/j.carres.2017.09.006 Anotace Conformational preferences of two C-glycosyl analogues of Manp-(1 -> 3)-Manp, were studied using a combined method of theoretical and experimental chemistry. Molecular dynamics was utilized to provide conformational behavior along C-glycosidic bonds of methyl 3-deoxy-3-C-[(alpha-D-mannopyranosyl) methyl]-alpha-D-and L-mannopyranosides. The OPLS2005 and Glycam06 force fields were used. Simulations were performed with explicit water (TIP3P) and methanol. Results were compared with a complete conformational scan at the MM4 level with the dielectric constant corresponding to methanol. In order to verify predicted conformational preferences, vicinal (3)J(HH) NMR coupling constants were calculated by the Karplus equation on simulated potential energy surfaces (PES). A set of new parameters for the Karplus equation was also designed. Predicted 3JHH were compared with experimental data. We also used reverse methodology, in which the (3)J(HH) coupling constants were calculated at the DFT level for each family of (phi, psi)-conformers separately and then experimental values were decomposed onto calculated (3)J(HH) couplings in order to obtain experimentally derived populations of conformers. As an alternative method of evaluation of preferred conformers, analysis of sensitive C-13 chemical shifts was introduced. We were able to thoroughly discuss several fundamental issues in predictions of preferred conformers of C-saccharides, such as the solvent effect, reliability of the force field, character of empirical Karplus equation or applicability of NMR parameters in predictions of conformational preferences in general. Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2018
Počet záznamů: 1