O-Methylation in Carbohydrates: An NMR and MD Simulation Study with Application to Methylcellulose
| Autor: | Göran Widmalm, Jakob Wohlert, Alessandro Ruda |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Substituent
Carbohydrates Dihedral angle Methylcellulose Molecular Dynamics Simulation Physical Chemistry Methylation Article Coatings and Films chemistry.chemical_compound Molecular dynamics Computational chemistry Materials Chemistry Carbohydrate Conformation Molecule Physical and Theoretical Chemistry chemistry.chemical_classification Coupling constant Fysikalisk kemi Force field (physics) Solvation Polymer Surfaces Coatings and Films Surfaces chemistry |
| Zdroj: | The Journal of Physical Chemistry. B |
| ISSN: | 1520-5207 1520-6106 |
| Popis: | Methylated carbohydrates are important from both biological and technical perspectives. Specifically, methylcellulose is an interesting cellulose derivative that has applications in foods, materials, cosmetics, and many other fields. While the molecular dynamics simulation technique has the potential for both advancing the fundamental understanding of this polymer and aiding in the development of specific applications, a general drawback is the lack of experimentally validated interaction potentials for the methylated moieties. In the present study, simulations using the GROMOS 56 carbohydrate force field are compared to NMR spin–spin coupling constants related to the conformation of the exocyclic torsion angle ω in d-glucopyranose and derivatives containing a 6-O-methyl substituent and a 13C-isotopologue thereof. A 3JCC Karplus-type relationship is proposed for the C5–C6–O6–CMe torsion angle. Moreover, solvation free energies are compared to experimental data for small model compounds. Alkylation in the form of 6-O-methylation affects exocyclic torsion only marginally. Computed solvation free energies between nonmethylated and methylated molecules were internally consistent, which validates the application of these interaction potentials for more specialized purposes. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|