A conformational study of the vicinally branched trisaccharide ?-D-Glcp-(1 ? 2)[?-D-Glcp-(1 ? 3)]?-D-Manp-OMe by nuclear Overhauser effect spectroscopy (NOESY) and transverse rotating-frame Overhauser effect spectroscopy (TROESY) experiments: Comparison to Monte Carlo and Langevin dynamics simulations

Kjellberg, Alexandra; Widmalm, Göran

doi:10.1002/(sici)1097-0282(19991005)50:4<391::aid-bip5>3.0.co;2-s

Cited by 36 publications

(29 citation statements)

References 53 publications

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“…Proton-proton cross-relaxation rates were measured using the 1D 1 H, 1 H-DPFGSE T-ROESY experiment10 and a 1D 1 H, 1 H-DPFGSE NOESY11 experiment with zero-quantum suppression 12. Selective excitations of H1, H1′ and H4 resonances were enabled using 30–40 ms long SNOB-2 shaped pulses.…”

Section: Experimental Methodsmentioning

confidence: 99%

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: Experimental Methodsmentioning

confidence: 99%

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

et al. 2010

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“…Proton–proton cross‐relaxation rates were measured at 600 and 700 MHz with the 1D T‐ROESY experiment 44. Selective excitation of H1′ in the DPFGSE part of the pulse sequence was performed using i‐SNOB‐2 or r‐SNOB shaped pulses45 of 80 ms duration flanked by pulsed field gradients with the duration of 1 ms.…”

Section: Methodsmentioning

confidence: 99%

Direct Detection of Inter‐residue Hydrogen Bonds in Polysaccharides by Single‐Molecule Force Spectroscopy

et al. 2005

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“…Proton ± proton cross-relaxation rates (s NOE and s T-ROE ) were measured at 600 MHz using one-dimensional DPFGSE NOESY [77,78] and DPFGSE T-ROESY [79] experiments, respectively. Proton ± proton cross-relaxation rates (s NOE and s T-ROE ) were measured at 600 MHz using one-dimensional DPFGSE NOESY [77,78] and DPFGSE T-ROESY [79] experiments, respectively.…”

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confidence: 99%

Oligosaccharides Display Both Rigidity and High Flexibility in Water as Determined by13C NMR Relaxation and1H,1H NOE Spectroscopy: Evidence ofanti-φ andanti-ψ Torsions in the Same Glycosidic Linkage

Höög¹,

Landersjö²,

Widmalm³

2001

Chem. Eur. J.

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The trisaccharide beta-D-Glcp-(1-->2)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-OMe has been investigated by molecular dynamics (MD) simulations and NMR experiments in water. 13C spin-lattice (T1) and spin-spin (T2) relaxation times, together with 1H,13C NOE data were measured at two magnetic field strengths (9.4 and 14.1 T) in a 277 K D2O solution. Relaxation data interpreted by means of the model-free formalism revealed a rigid (S2 approximately 0.9) oligosaccharide tumbling in solution. 1H,1H Cross-relaxation rates were determined at 600 MHz by 1D DPFGSE NOESY and T-ROESY experiments, which provided high quality data and subsequently proton-proton distances within the trisaccharide. The presence of anti conformers at both torsions of a glycosidic linkage is demonstrated for the first time. MD simulations were carried out to facilitate analysis of the NOE data. In total, 15 simulations-starting from five different conformational states--were performed, with production runs of up to 10 ns, resulting in 83 ns of oligosaccharide dynamics in water. anti Conformers were populated to different degrees in the simulations, especially at the phi2 torsion angle. By combining the results from the NOE experiments and the MD simulations, the anti conformers at the (1-->2)-linkage were quantified as 7% anti-phi2 and 2% anti-psi2, revealing a highly flexible trisaccharide in which large conformational changes occur. From the MD simulations, interresidue hydrogen bonding, from HO2" to O2 or O3, was significantly populated (approximately 40%) in both of the anti conformational states. The contentious issue over rigidity versus flexibility in oligosaccharides has thus been thoroughly examined, showing that the dynamics should be taken into account for a relevant description of the molecular system.

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Cited by 36 publications

References 53 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

Direct Detection of Inter‐residue Hydrogen Bonds in Polysaccharides by Single‐Molecule Force Spectroscopy

Oligosaccharides Display Both Rigidity and High Flexibility in Water as Determined by13C NMR Relaxation and1H,1H NOE Spectroscopy: Evidence ofanti-φ andanti-ψ Torsions in the Same Glycosidic Linkage

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