The use of chemical shifts of hydroxy protons of oligosaccharides as conformational probes for NMR studies in aqueous solution. Evidence for persistent hydrogen bond interaction in branched trisaccharides

Sandström, Corine; Baumann, Herbert; Kenne, Lennart

doi:10.1039/a805678a

Cited by 50 publications

(35 citation statements)

References 27 publications

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“…However, the temperature coefficients are much larger than the measured values of ¾1-3 ppb K 1 in DMSO or ¾1-6 ppb K 1 in water-acetone solutions previously reported for hydroxyl protons involved in strong intramolecular H-bonds. 8,11,17,18,24 Consequently, experimental NMR data clearly indicate that no hydroxyl proton in the guaiacylˇ-O-4 structure is involved in a strong intramolecular H-bond that persists significantly in solution, but instead suggest that H-bonding to the solvent predominates. These conclusions are consistent with those obtained from MD simulations performed in explicit solvation in which no persistent intramolecular Hbonding interaction was detected.…”

Section: Temperature Coefficientsmentioning

confidence: 91%

“…However, strong and persistent intramolecular H-bonding interactions have been found to exist for branched trisaccharides and oligosaccharides in aqueous solution. 8,17,18 In this work, we used 1 H NMR of hydroxyl protons to seek evidence for intramolecular H-bonding interactions in the threo and erythro forms of a benzylated guaiacyľ -O-4 model compound (Scheme 1) in aprotic and protic solvents. Temperature coefficients dυ/dT and coupling constants 3 J HCOH were measured in DMSO-d 6 , acetone-d 6 and acetone-d 6 -water (9 : 1, v/v).…”

Section: Introductionmentioning

confidence: 99%

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Conformational study of a guaiacyl β‐O‐4 lignin model compound by NMR. Examination of intramolecular hydrogen bonding interactions and conformational flexibility in solution

Besombes

Utille

Mazeau

et al. 2004

Magnetic Reson in Chemistry

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Intramolecular H-bonding interactions were investigated in solution for the threo and erythro diastereomeric forms of a guaiacyl beta-O-4 lignin model compound by using the NMR data obtained from hydroxyl protons. Temperature coefficients of the chemical shifts (ddelta/dT) and coupling constants (3J(HCOH)) were measured in aprotic and protic solutions: DMSO-d6, acetone-d6 and acetone-d6-water. The NMR parameters do not support the existence of strong and persistent intramolecular H-bonds that could participate in the stabilization of the guaiacyl beta-O-4 structure in solution, but instead indicate that intermolecular H-bonds to solvent predominate. 1D NOE experiments nevertheless revealed the presence of a direct chemical exchange between the hydroxyl protons, suggesting the possible existence of weak and transient intramolecular H-bonding interactions. The conformational flexibility of the threo structure was also investigated in acetone solution from the measurement of long-range 1H, 1H and 1H, 13C coupling constants and from NOESY experiments. The NMR data are not consistent with any single conformation, indicating that different conformers co-exist in solution. The experimental results support the conformational flexibility predicted by molecular dynamics simulations performed in a previous study. Finally, both experimental and theoretical approaches indicate that weak intramolecular H-bonds can exist transiently in solution, breaking and reforming as the beta-O-4 molecule undergoes conformational interconversion, but cannot be invoked as possible means of conferring rigidity to the beta-O-4 structure.

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Section: Temperature Coefficientsmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Conformational study of a guaiacyl β‐O‐4 lignin model compound by NMR. Examination of intramolecular hydrogen bonding interactions and conformational flexibility in solution

Besombes

Utille

Mazeau

et al. 2004

Magnetic Reson in Chemistry

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“…A comparison of the proton chemical shifts between the monomer and the pseudopentasaccharide was performed (Table 2). [19] The protons identified by MD as potential hydrogen-bond donors, with the exception of OH3 of GlcN II , are among those that underwent the largest variations: (i) the OH6 of In order to increase the range of temperatures for the observation of the hydroxy signals, a DMSO/water (25:75, v/v) solvent mixture was used. Under these conditions, the chemical shift variation of the hydroxy resonances with respect to the monomers were similar to those obtained in water/acetone (Table 2).…”

Section: Vsg Gpi By Nmrmentioning

confidence: 99%

“…[7] Such an investigation implies the detection of the hydroxy protons in H 2 O solution using specific NMR experiments in acetone/water solvent mixtures, which requires in general low temperatures and a careful control of the pH. [19] Once the hydroxy resonances are detected, the occurrence of stable hydrogen bonds can be deduced from the changes in chemical shift upon bonding, decrease of the solvent exchange rate, by the line width, the exchange EXSY cross-peaks, or by the temperature coefficient. [20] By using firstly the mixture acetone/water (15:85) and 1D-NMR and 2D TOCSY experiments (Supporting information), the labile protons of 6 were detected and assigned at 259 K. Unfortunately, the exchange with the solvent was still too fast as to detect NOEs or exchange peaks from the OH signals valid as indicative of hydrogen bonding even using short mixing times.…”

Section: Vsg Gpi By Nmrmentioning

confidence: 99%

Conformational Study of GPI Anchors: the Common Oligosaccharide GPI Anchor Backbone

Chevalier¹,

López-Prados²,

Pérez³

et al. 2005

Eur J Org Chem

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The solution three‐dimensional structure of pseudopentasaccharide 6, which constitutes the product from the GPI‐PLD cleavage of a GPI anchor, has been studied using a protocol which involves a systematic search of the conformational space around the glycosidic linkages, a thorough molecular dynamics study with explicit water molecules and a full NMR analysis study of intramolecular hydrogen bonding in solution. The results indicate that 6 exists in an extended conformation with a considerable flexibility compatible with a hinge‐like conformational motion. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…To explore the reasons for the increased basicity of an OH in the presence of phosphates, the 1 H NMR titration of the hydroxyl proton was performed in aqueous solution. 1 H NMR chemical shifts of hydroxyl protons were recently used as conformational probes for oligosaccharides [38][39][40] and myo-inositol 2-phosphate [41] as they contain useful data on hydrogen bonding. For compound 4, the resonances of the OH-3 proton can be observed at approximately 5.7 ppm in a pH range of 7 to 10 ( Figure 3).…”

Section: Physicochemical Studiesmentioning

confidence: 99%

3‐Hydroxybenzene 1,2,4‐Trisphosphate, a Novel Second Messenger Mimic and unusual Substrate for Type‐I myo‐Inositol 1,4,5‐Trisphosphate 5‐Phosphatase: Synthesis and Physicochemistry

Mills

Dozol²,

Vandeput

et al. 2006

ChemBioChem

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3-Hydroxybenzene 1,2,4-trisphosphate 4 is a new myo-inositol 1,4,5-trisphosphate analogue based on the core structure of benzene 1,2,4-trisphosphate 2 with an additional hydroxyl group at position-3, and is the first noninositol based compound to be a substrate for inositol 1,4,5-trisphosphate 5-phosphatase. In physicochemical studies on 2, when three equivalents of protons were added, the (31)P NMR spectrum displayed monophasic behaviour in which phosphate-1 and phosphate-2 behaved independently in most of the studied pH range. For compound 4, phosphate-2 and phosphate-4 interacted with the 3-OH group, which does not titrate at physiological pH, displaying complex biphasic behaviour which demonstrated co-operativity between these groups. Phosphate-1 and phosphate-2 strongly interacted with each other and phosphate-4 experienced repulsion because of the interaction of the 3-OH group. Benzene 1,2,4-trisphosphate 2 is resistant to inositol 1,4,5-trisphosphate type I 5-phosphatase catalysed dephosphorylation. However, surprisingly, 3-hydroxybenzene 1,2,4-trisphosphate 4 was dephosphorylated by this 5-phosphatase to give the symmetrical 2,3-dihydroxybenzene 1,4-bisphosphate 16. The extra hydroxyl group is shown to form a hydrogen bond with the vicinal phosphate groups at -15 degrees C, and (1)H NMR titration of the ring and hydroxyl protons in 4 shows the OH proton to be strongly stabilized as soon as the phosphate groups are deprotonated. The effect of the phenolic 3-OH group in compound 4 confirms a critical role for the 6-OH group of the natural messenger in the dephosphorylation mechanism that persists even in radically modified analogues.

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The use of chemical shifts of hydroxy protons of oligosaccharides as conformational probes for NMR studies in aqueous solution. Evidence for persistent hydrogen bond interaction in branched trisaccharides

Cited by 50 publications

References 27 publications

Conformational study of a guaiacyl β‐O‐4 lignin model compound by NMR. Examination of intramolecular hydrogen bonding interactions and conformational flexibility in solution

Conformational study of a guaiacyl β‐O‐4 lignin model compound by NMR. Examination of intramolecular hydrogen bonding interactions and conformational flexibility in solution

Conformational Study of GPI Anchors: the Common Oligosaccharide GPI Anchor Backbone

3‐Hydroxybenzene 1,2,4‐Trisphosphate, a Novel Second Messenger Mimic and unusual Substrate for Type‐I myo‐Inositol 1,4,5‐Trisphosphate 5‐Phosphatase: Synthesis and Physicochemistry

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