Evidence for a Transient Interresidue Hydrogen Bond in Sucrose in Aqueous Solution Obtained by Rotating-Frame Exchange NMR Spectroscopy Under Supercooled Conditions

Sheng, Shuqun; Vanhalbeek, H.

doi:10.1006/bbrc.1995.2493

Cited by 41 publications

(19 citation statements)

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“…The NMR data for the disaccharides alone in solution (Table 1) are in good agreement with what has been reported in the previous studies described above, but performed under slightly different experimental conditions [48,53,55]. Besides temperature coefficients, coupling constants and chemical exchange, it has been shown previously that the chemical shift difference Δδ (chemical shift of a hydroxy proton in an oligosaccharide minus chemical shift of the hydroxy proton in the constituent monosaccharide) can also be used as a conformational probe to study hydrogen bond interaction, hydration and spatial proximity to other hydroxy protons, ring oxygen or bulky substituents [59,60,61].…”

Section: Resultssupporting

confidence: 90%

“…According to the DOSY experiments, the diffusion of trehalose and lactose, when in mixture, are comparable at the temperatures at which the hydroxy protons will be studied. The occurrence of hydrogen bond interactions in aqueous solutions of trehalose, lactose and sucrose have been previously investigated using MD simulation [23,28,30,52] as well as NMR of hydroxy protons [48,53,54,55]. Thus, hydroxy protons involved in hydrogen bonding are expected to have smaller temperature coefficients, a slower rate of exchange with water, and coupling constants which do not represent conformational averaging but instead indicate a restricted rotation around the H–C–O–H bond.…”

Section: Resultsmentioning

confidence: 99%

“…In supercooled lactose, the presence of a hydrogen bond between GalO5' and GlcOH3 was deduced [48] from the decrease in the chemical exchange rate of GlcOH3 as well as from the small value of its 3 J CH, OH (3.1 Hz) that deviate from the value of 5.5 ± 0.5 Hz which would indicate free rotation around the H–C–O–H bond [56]. In sucrose the existence of a transient hydrogen bond between the GlcOH2 and FruOH1' groups was evidenced under supercooled conditions from the chemical exchange cross-peak observed in the ROESY spectra between glucosyl OH2 and fructosyl OH1 protons [55]. For trehalose, the 3 J CH, OH and 2,3 J C,OH of the hydroxy protons, measured at a concentration of 1.7 M in a 97:3 D 2 O/H 2 O solvent at −3 °C, suggested that intramolecular hydrogen bonding interaction was not present [53] in good agreement with MD simulation and X-ray data [25,57,58].…”

Section: Resultsmentioning

confidence: 99%

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NMR Study on the Interaction of Trehalose with Lactose and Its Effect on the Hydrogen Bond Interaction in Lactose

Vilén

Sandström

2013

Molecules

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Trehalose, a well-known stress-protector of biomolecules, has been investigated for its effect on the mobility, hydration and hydrogen bond interaction of lactose using diffusion-ordered NMR spectroscopy and NMR of hydroxy protons. In ternary mixtures of trehalose, lactose and water, the two sugars have the same rate of diffusion. The chemical shifts, temperature coefficients, vicinal coupling constants and ROE of the hydroxy protons in trehalose, lactose and sucrose were measured for the disaccharides alone in water/acetone-d 6 solutions as well as in mixtures. The data indicated that addition of trehalose did not change significantly the strength of the hydrogen bond interaction between GlcOH3 and GalO5' in lactose. Small upfield shifts were however measured for all hydroxy protons when the sugar concentration was increased. The chemical shift of the GlcOH3 signal in lactose showed less change, attributed to the spatial proximity to GalO5'. Chemical exchange between hydroxy protons of lactose and trehalose was observed in the ROESY NMR spectra. Similar effects were observed with sucrose indicating no specific effect of trehalose at the concentrations investigated (73 to 763 mg/mL) and suggesting that it is the concentration of hydroxy groups more than the type of sugars which is guiding intermolecular interactions.

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Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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NMR Study on the Interaction of Trehalose with Lactose and Its Effect on the Hydrogen Bond Interaction in Lactose

Vilén

Sandström

2013

Molecules

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“…17 Direct detection of H-bonds was reported for proteins and nucleic acids. 14,15,18,19 Indirect evidence for H-bonding in carbohydrates has been presented, 20–23 but to our knowledge no through-H-bond correlation was directly detected by NMR, for carbohydrates in H 2 O.…”

mentioning

confidence: 88%

Evidence for Helical Structure in a Tetramer of α2-8 Sialic Acid: Unveiling a Structural Antigen

et al. 2012

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Characteristic hydrogen bonding (H-bonding) patterns define secondary structure in proteins and nucleic acids. We show that similar patterns apply for α2-8 linked SiA (sialic acid) in H2O; and that H-bonds define its structure. A 15N,13C α2-8 SiA tetramer was used as a model system for the polymer. At 263K, we detected intra-residue through-bond J couplings between 15N and C8 for residues I, II and III of the tetramer, which indicate H-bonds between the 15Ns and the O8s of these residues. Additional J couplings between the 15Ns and C2s of the adjacent residues confirm the putative H-bonds. The NH groups showing this long-range correlation also experience slower 1H/2H exchange rate. Additionally, detection of couplings between H7 and C2 for residues II and III imply that the conformations of the linkers between these residues are different than the monomer's. These structural elements are consistent with two left handed helical models: 1) two residues per turn (24 helix) and 2) four residues per turn (14 helix). To discriminate between models, we resorted to 1H, 1H NOEs. The 24 helical model is in better agreement with the experimental data, for which all of the observed NOEs are predicted. On the other hand, for the 14 helix 87% of the observed intra-residue NOEs are predicted. In this report we provide direct evidence of H-bonding for a tetramer of α2-8 linked SiA and show how H-bonds can be a determining factor for shaping the carbohydrate three-dimensional structure.

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“…These observations concerning solvent‐exposed H‐bonding are particularly important considering that experimental techniques such as nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy permit nowadays the detection of individual H‐bonds in solvated (bio)molecules, see e.g . Refs . for NMR studies, Refs .…”

Section: Introductionmentioning

confidence: 99%

Solvent‐Modulated Influence of Intramolecular Hydrogen‐Bonding on the Conformational Properties of the Hydroxymethyl Group in Glucose and Galactose: A Molecular Dynamics Simulation Study

Lonardi

Oborský

Hünenberger

2016

Helvetica Chimica Acta

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Intramolecular hydrogen‐bonding (H‐bonding) is commonly regarded as a major determinant of the conformation of (bio)molecules. However, in an aqueous environment, solvent‐exposed H‐bonds are likely to represent only a marginal (possibly adverse) conformational driving as well as steering force. For example, the hydroxymethyl rotamers of glucose and galactose permitting the formation of an intramolecular H‐bond with the adjacent hydroxyl group are not favored in water but, in the opposite, least populated. This is because the solvent‐exposed H‐bond is dielectrically screened as well as subject to intense H‐bonding competition by the water molecules. In the present study, the effect of a decrease in the solvent polarity on this rotameric equilibrium is probed using molecular dynamics simulation. This is done by considering six physical solvents (H2O, DMSO, MeOH, CHCl3, CCl4, and vacuum), along with 19 artificial water‐like solvent models for which the dielectric permittivity and H‐bonding capacity can be modulated independently via a scaling of the O–H distance and of the atomic partial charges. In the high polarity solvents, the intramolecular H‐bond is observed, but arises as an opportunistic consequence of the proximity of the H‐bonding partners in a given rotameric state. Only when the polarity of the solvent is decreased does the intramolecular H‐bond start to induce a conformational pressure on the rotameric equilibrium. The artificial solvent series also reveals that the effects of the solvent permittivity and of its H‐bonding capacity mutually enhance each other, with a slightly larger influence of the permittivity. The hydroxymethyl conformation in hexopyranoses appears to be particularly sensitive to solvent‐polarity effects because the H‐bond involving the hydroxymethyl group is only one out of up to five H‐bonds capable of forming a network around the ring.

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Evidence for a Transient Interresidue Hydrogen Bond in Sucrose in Aqueous Solution Obtained by Rotating-Frame Exchange NMR Spectroscopy Under Supercooled Conditions

Cited by 41 publications

References 0 publications

NMR Study on the Interaction of Trehalose with Lactose and Its Effect on the Hydrogen Bond Interaction in Lactose

NMR Study on the Interaction of Trehalose with Lactose and Its Effect on the Hydrogen Bond Interaction in Lactose

Evidence for Helical Structure in a Tetramer of α2-8 Sialic Acid: Unveiling a Structural Antigen

Solvent‐Modulated Influence of Intramolecular Hydrogen‐Bonding on the Conformational Properties of the Hydroxymethyl Group in Glucose and Galactose: A Molecular Dynamics Simulation Study

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