A combined nuclear magnetic resonance and molecular dynamics study of the two structural motifs for mixed-linkage β-glucans: methyl β-cellobioside and methyl β-laminarabioside

Christensen, N. J.; Pb, Hansen; Larsen, Flemming H.; Folkerman, Tore; Motawia, Mohammed Saddik; Engelsen, Søren Balling

doi:10.1016/j.carres.2009.12.009

Cited by 22 publications

(26 citation statements)

References 57 publications

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“…Assuming hydrogen bonding is occurring when donor H to acceptor distances are 2.5 Å or less, the probability of intramolecular hydrogen bonding between O5′ and HO3 in aqueous solution in both methyl α - and β -cellobioside is approximately 60%. This result is similar those calculated previously where the O5′-HO3 hydrogen bond was determined to persist for 35%50 and 70%52.…”

Section: Resultssupporting

confidence: 92%

“…In our analysis hydrogen bonding is defined as any H-bond donor to acceptor distance < 2.5 Å. It is surmised that methyl β -cellobioside contains an intramolecular hydrogen bond between O5′ and HO3 because of the short interatomic distance between these atoms observed in the x-ray crystal structure4 and from previous NMR and computational studies 48–50. What is unclear is to what extent this intramolecular hydrogen bond is maintained in the aqueous phase.…”

Section: Resultsmentioning

confidence: 99%

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Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

et al. 2010

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An investigation of the conformational properties of methyl β-maltoside, methyl α-cellobioside and methyl β-cellobioside disaccharides, using NMR spectroscopy and molecular dynamics (MD) techniques, is presented. Emphasis is placed on validation of a recently presented force field for hexopyranose disaccharides followed by elucidation of the conformational properties of two different types of glycosidic linkages, α-(1→4) and β-(1→4). Both gas-phase and aqueous-phase simulations are performed to gain insight into the effect of solvent on the conformational properties. A number of transglycosidic J-coupling constants and proton-proton distances are calculated from the simulations and are used to identify the percent sampling of the three glycosidic conformations, syn, anti-φ and anti-ψ, and, in turn, describe the flexibility around the glycosidic linkage. The results show the force field to be in overall good agreement with experiment, though some very small limitations are evident. Subsequently, a thorough hydrogen bonding analysis is performed to obtain insights into the conformational properties of the disaccharides. In methyl β-maltoside competition between HO2′-O3 intramolecular hydrogen bonding and intermolecular hydrogen bonding of those groups with solvent lead to increased sampling of syn φ,ψ conformations and better agreement with NMR J-coupling constants. In methyl α and β-cellobioside, O5′-HO6 and HO2′-O3 hydrogen bonding interactions are in competition with intermolecular hydrogen bonding involving the solvent molecules. This competition leads to retention of the O5′-HO3 hydrogen bond and increased sampling of the syn region of the φ/ψ map. Moreover, glycosidic torsions are correlated to the intramolecular hydrogen bonding occurring in the molecules. The present results verify that in the β-(1→4)-linkage intramolecular hydrogen bonding in the aqueous phase is due to the decreased ability of water to successfully compete for the O5′ and HO3 hydrogen bonding moieties in contrast to that occurring between the O5′ and HO6 atoms in this α-(1→4)-linkage.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

et al. 2010

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“…At equivalent β-glucan concentration in solutions (2.5% BBG 67 ≈ 2.5% OBG 68 and 5% BBG 67 ≈ 5% OBG 68 ) the viscosity for OBG 68 is approximately 100 fold higher than for BBG 67 . This dramatic increase in viscosity rely partially on the changed block structure of the β-glucan polymer (Christensen et al, 2010) and is in good agreement with measurements reported elsewhere, where high molar mass β-glucans have significant higher viscosities compared to low molar mass β-glucans (Varum et al, 1991;Wood, Beer, & Butler, 2000).…”

Section: Viscositysupporting

confidence: 79%

Comparative spectroscopic and rheological studies on crude and purified soluble barley and oat β-glucan preparations

Mikkelsen

Jespersen

Møller

et al. 2010

Food Research International

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“…But it is not clear which conformer is the most stable one, depending on the computational method used. 18,[21][22][23] NMR studies have suggested that the syn-// syn-w conformer is the most stable one in solution. 7,17,[25][26][27] But the population of the other two states cannot be agreed on and is actively debated.…”

Section: Introductionmentioning

confidence: 99%

“…Conformational analyses of saccharides, especially lactose and cellobiose, have been carried out by using X-ray crystallography, 5 NMR 6 (such as NOE, 7 Jcoupling constant, 8,9 residual dipolar couplings (RDCs), [10][11][12] and paramagnetic pseudocontact shifts (PCSs) 13 ), and theoretical calculations. [14][15][16][17][18][19][20][21][22][23][24] The cellobiose or lactose flexibility mainly arises from two dihedral angles / (H1 0 -C1 0 -O 0 -C4) and w (C1 0 -O 0 -C4-H4), which in principle vary from À180°to 180° (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

DFT application in conformational determination of cellobiose

Yan

Yao

2015

Carbohydrate Research

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A combined nuclear magnetic resonance and molecular dynamics study of the two structural motifs for mixed-linkage β-glucans: methyl β-cellobioside and methyl β-laminarabioside

Cited by 22 publications

References 57 publications

Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

Conformational Properties of Methyl β-Maltoside and Methyl α- and β-Cellobioside Disaccharides

Comparative spectroscopic and rheological studies on crude and purified soluble barley and oat β-glucan preparations

DFT application in conformational determination of cellobiose

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