LAUSR.org creates dashboard-style pages of related content for over 1.5 million academic articles. Sign Up to like articles & get recommendations!

The impact of conformational sampling on first-principles calculations of vicinal COCH J-couplings in carbohydrates.

Photo from wikipedia

Dihedral angles in organic molecules and biomolecules are vital structural parameters that can be indirectly probed by NMR measurements of vicinal J-couplings. The empirical relations that map the measured couplings… Click to show full abstract

Dihedral angles in organic molecules and biomolecules are vital structural parameters that can be indirectly probed by NMR measurements of vicinal J-couplings. The empirical relations that map the measured couplings to dihedral angles are typically determined by fitting using static structural models, but this neglects the effects of thermal fluctuations at the finite temperature conditions under which NMR measurements are often taken. In this study, we calculate ensemble-averaged J-couplings for several structurally rigid carbohydrate derivatives using first-principles molecular dynamics simulations to sample the thermally accessible conformations around the minimum energy structure. Our results show that including thermal fluctuation effects significantly shifts the predicted couplings relative to single-point calculations at the energy minima, leading to improved agreement with experiments. This provides evidence that accounting for conformational sampling in first-principles calculations can improve the accuracy of NMR-based structure determination for structurally complex carbohydrates.

Keywords: principles calculations; impact conformational; sampling first; first principles; conformational sampling

Journal Title: Glycobiology
Year Published: 2022

Link to full text (if available)


Share on Social Media:                               Sign Up to like & get
recommendations!

Related content

More Information              News              Social Media              Video              Recommended



                Click one of the above tabs to view related content.