A 1H-NMR and MD study of intramolecular hydrogen bonds in methyl β-cellobioside

Leeflang, Bas R.; Vliegenthart, Johannes F.G.; Kroon-Batenburg, Loes M. J.; Eijck, B.P. van; Kroon, Jan

doi:10.1016/s0008-6215(00)90512-3

Cited by 105 publications

(56 citation statements)

References 25 publications

(1 reference statement)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For the spectra of 5, 7, 12, and 13 in CDCl 3 , the J(HOÀC(5),HÀC(5)) value of ca. 2.6 ± 2.9 Hz is similar to the corresponding value for cellobiose [14]. However, while the J in cellobiose reflects the intramolecular H-bond to OÀC(5) of the neighbouring unit, HOÀC(5) of 5, 7, 12, and 13 may form an intramolecular H-bond to OÀC (4), as confirmed by the IR band at ca.…”

supporting

confidence: 75%

Oligosaccharide Analogues of Polysaccharides, Part 16, Cross-Coupling of Partially Protected Dialkynyl Monosaccharides

Bohner

Beaudegnies

Vasella

1999

HCA

View full text Add to dashboard Cite

supporting

confidence: 75%

Oligosaccharide Analogues of Polysaccharides, Part 16, Cross-Coupling of Partially Protected Dialkynyl Monosaccharides

Bohner

Beaudegnies

Vasella

1999

HCA

View full text Add to dashboard Cite

“…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: 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

View full text Add to dashboard Cite

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.

show abstract

“…H-bonded hydroxy groups usually show resonances that are more deshielded than those of free OH groups. [47,51] (3) The temperature dependence of the OH [52,53] and NH [54Ϫ56] resonances permits H bonds to be detected and H-bond energies evaluated. [57] In dilute samples in nonpolar organic solvents, the value of ∆δ/∆T reflects the perturbation of possible H bonds with temperature, and weak interactions with the solvent (weak H bonds in CDCl 3 or van der Waals interactions in CCl 4 or CH 2 Cl 2 ).…”

Section: H Nmr and Ft-ir Datamentioning

confidence: 99%

Carbohydrate Hydrogen-Bonding Cooperativity − Intramolecular Hydrogen Bonds and Their Cooperative Effect on Intermolecular Processes − Binding to a Hydrogen-Bond Acceptor Molecule

et al. 2002

View full text Add to dashboard Cite

The high hydroxy (OH) group content in carbohydrates makes the study of carbohydrate OH···XH and OH···X Hbond energetics fundamental to understanding of carbohydrate recognition. There is, however, a relative lack of knowledge concerning the factors that allow a carbohydrate to participate in recognition events stabilised by intermolecular H bonds. We therefore present here a systematic study on the factors that determine the formation of a well-defined intramolecular H-bonding network between carbohydrate hydroxy groups, and its cooperative or anti-cooperative influence on selected intermolecular processes mediated by H bonds. With this in mind, we first determined the H-bonding networks of a series of carbohydrate derivatives − monoalcohols, 1,2-and 1,3-diols and amidoalcohols − by 1 H NMR and FT-IR spectroscopy. The hydroxy groups of these compounds showed different abilities to form intramolecular H bonds, depending on their relative positions and configurations on

show abstract

A 1H-NMR and MD study of intramolecular hydrogen bonds in methyl β-cellobioside

Abstract: The existence of an HO-3 .

Cited by 105 publications

References 25 publications

Oligosaccharide Analogues of Polysaccharides, Part 16, Cross-Coupling of Partially Protected Dialkynyl Monosaccharides

Oligosaccharide Analogues of Polysaccharides, Part 16, Cross-Coupling of Partially Protected Dialkynyl Monosaccharides

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

Carbohydrate Hydrogen-Bonding Cooperativity − Intramolecular Hydrogen Bonds and Their Cooperative Effect on Intermolecular Processes − Binding to a Hydrogen-Bond Acceptor Molecule

Contact Info

Product

Resources

About