Nuclear magnetic resonance and conformational studies on amylose and model compounds in dimethyl sulfoxide solution

Jacques, Maurice St.; Sundararajan, P. R.; Taylor, Kenneth J. W.; Marchessault, R. H.

doi:10.1021/ja00431a007

Cited by 114 publications

(38 citation statements)

References 9 publications

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“…The difference between the downfield shifts for HOÀC(3) and HOÀC(2') indicates a ca. 2 : 1 equilibrium of M2 and M3; this is in agreement with the observed Dd/DT values (HOÀC(3): À 2.8 ppb/K, HOÀC(2'): À 4.2 ppb/K[30]). The determination of the conformational equilibrium from J(H,OH) alone is hampered by the fact that the exact J(H,OH) value for a Haccepting OH group is not known (compare[1]).…”

supporting

confidence: 91%

“…Nevertheless, Casu et al had observed a downfield shift for both HOÀC(3) and HOÀC(2') and postulated an internal Hbond, without specifying which OH acts as H-donor and which one as H-acceptor [22]. Marchessault and co-workers determined the temperature dependence for HOÀC(3), HOÀC(2'), and HOÀC(6') (À 2.8, À 4.2, and À 5.8 ppb/K, resp., as deduced from the bivariate plot in [30]) and concluded that HOÀC(3) is the H-donor. Finally, Christofides and Davies [31] analysed a 1 : 2 a/b-maltose mixture by SIMPLE 1 H-NMR spectroscopy.…”

Section: A Flip-flop Inter-residue H-bond In Maltosementioning

confidence: 96%

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Intra- and Intermolecular H-Bonds of Alcohols in DMSO, 1H-NMR Analysis of Inter-Residue H-Bonds in Selected Oligosaccharides: Cellobiose, Lactose, N,N′-Diacetylchitobiose, Maltose, Sucrose, Agarose, and Hyaluronates

Bernet

Vasella

2000

HCA

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supporting

confidence: 91%

Section: A Flip-flop Inter-residue H-bond In Maltosementioning

confidence: 96%

Intra- and Intermolecular H-Bonds of Alcohols in DMSO, 1H-NMR Analysis of Inter-Residue H-Bonds in Selected Oligosaccharides: Cellobiose, Lactose, N,N′-Diacetylchitobiose, Maltose, Sucrose, Agarose, and Hyaluronates

Bernet

Vasella

2000

HCA

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“…While some HO2′-O3 hydrogen bonding is present in solution, solvent can effectively compete for this intramolecular hydrogen bond which is indicated by the large first peak in the RDF between Ow and HO2′ (Figure 7f). While water is competing for the HO2′-O3 hydrogen bonding interaction, there is also a competition between the HO2′-O3 and O2′-HO3 51. This is evident by the large first peak on the gas phase HO2′-O3 RDF versus the small first peak in the O2′-HO3 RDF (compare Figures 7e and 7g).…”

Section: Resultsmentioning

confidence: 94%

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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“…This method has been extensively used in peptides, proteins, as well as in carbohydrates [20][21][22]. Small δ/ T values have been observed for -OH of cellulose [22], maltose and amylose [23], as well as β-chitobiose and chitin [24] in aprotic solvents and were interpreted by their participation in intramolecular hydrogen bonding. Thus, temperature coefficients below −4 ppb/ • C suggest the formation of intramolecular hydrogen bond [25].…”

Section: H-nmr Temperature Dependencementioning

confidence: 99%

Synthesis and Determination of Polymerization Rate Constants of Glucose-Based Monomers

Sharma

Durand

Pucci

2011

Designed Monomers and Polymers

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To prepare non-ionic amphiphilic polymers usable for solubilizing integral membrane proteins, hydrophilic and amphiphilic β-D-glucose-based tris(hydroxymethyl)acrylamidomethane monomers were synthesized and their radical homopolymerization rate constants (f k 2 p /k t ) were determined. The polymerization kinetics, monitored by 1 H-NMR, were carried out in THF in the presence of AIBN as radical initiator. The plot of monomer conversion as a function of time followed Tobolsky's equation. The number of hydroxyl groups, as well as the nature of the substituents grafted onto the hydroxyl groups, was found to alter the rates of polymerization. While the steric hindrance significantly affected the kinetics, intermolecular hydrogen bonds between hydroxyl groups, as demonstrated by NMR investigations at different concentrations and temperatures, may also play a role in the rate constants of polymerization.

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Nuclear magnetic resonance and conformational studies on amylose and model compounds in dimethyl sulfoxide solution

Cited by 114 publications

References 9 publications

Intra- and Intermolecular H-Bonds of Alcohols in DMSO, 1H-NMR Analysis of Inter-Residue H-Bonds in Selected Oligosaccharides: Cellobiose, Lactose, N,N′-Diacetylchitobiose, Maltose, Sucrose, Agarose, and Hyaluronates

Intra- and Intermolecular H-Bonds of Alcohols in DMSO, 1H-NMR Analysis of Inter-Residue H-Bonds in Selected Oligosaccharides: Cellobiose, Lactose, N,N′-Diacetylchitobiose, Maltose, Sucrose, Agarose, and Hyaluronates

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

Synthesis and Determination of Polymerization Rate Constants of Glucose-Based Monomers

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