NMR Coupling Constants, Karplus Equations, and Adjusted MD Statistics: Detecting Diagnostic Torsion Angles for the Solution Geometry of 6‐[α‐ d ‐Mannopyranosyl]‐ d ‐Mannopyranose (Mannobiose)
Year: 2024
Type: article
Abstract: The quantitative solution conformations of 2-(hydroxymethyl)-tetrahydropyran, α-methyl-d-mannopyranoside, and 6-[α-d-mannopyranosyl]-d-mannopyranose (mannobiose) are described. Parametrized Karplus equations for redundant spin pairs across the terminal ω-torsion and the glycosidic ω-torsion for mannobiose are developed, including ω/θ-hypersurfaces for the terminal hydroxymethylene group. Experimental NMR data, algorithmic spectral simulation (clustered Hamiltonian method), molecular dynamics (MD) simulations (GLYCAM06), energy minimizations by DFT, and adjusted torsion angle populations weighted over the Karplus-type equations are used. We demonstrate that spectral simulation is a powerful tool in the refinement of initial J values obtained from static GAIO DFT calculations. We also show that only as few as one of multiple redundant torsions can be diagnostic for conformational analysis of the disaccharide.
Source: Magnetic Resonance in Chemistry
DOI: 10.1002/mrc.5483
Authors: Andreas H. Franz, Kendall S. Bromley, Ei T. Aung, Stephen Q. L. Do, Hana M. Rosenblatt, Amelia J. Watson
Institution: University of the Pacific
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W4403500419