title: Conformational Analysis of Arabinofuranosides: Prediction of (3)JH,H Using MD Simulations with DFT-Derived Spin-Spin Coupling Profiles.
abstract: A molecular dynamics (MD) investigation on a series of oligo-α-arabinofuranosides (1-8) using the AMBER force field and the GLYCAM carbohydrate parameter set is reported. The validation of the method was carried out by direct comparison of experimental vicinal proton-proton coupling constants ((3)JH,H) with those obtained by using an empirically determined Karplus equation and density functional theory (DFT)-derived relationships specifically tailored for α-arabinofuranosyl systems. A simple code was developed to implement the determination of (3)JH,H by applying these relationships to the probability distributions of rotamers and ring conformations displayed by the simulations. The empirical Karplus relationship and the DFT-derived equations yielded, in most cases, the same trend as experiment for intra-ring (3)JH,H values. This direct comparison circumvents additional sources of errors that may arise from the assumptions introduced by the deconvolution procedures often used to calculate population of rotamers and ring conformations from experimental (3)JH,H.
authors.affiliation: Department of Chemistry and Alberta Ingenuity Centre for Carbohydrate Science, Gunning-Lemieux Chemistry Centre, University of Alberta, Edmonton, AB, Canada T6G 2G2, and Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
authors.forename: Hashem A
authors.initials: HA
authors.lastname: Taha
authors.affiliation: Department of Chemistry and Alberta Ingenuity Centre for Carbohydrate Science, Gunning-Lemieux Chemistry Centre, University of Alberta, Edmonton, AB, Canada T6G 2G2, and Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
authors.forename: Norberto
authors.initials: N
authors.lastname: Castillo
authors.affiliation: Department of Chemistry and Alberta Ingenuity Centre for Carbohydrate Science, Gunning-Lemieux Chemistry Centre, University of Alberta, Edmonton, AB, Canada T6G 2G2, and Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
authors.forename: Devin N
authors.initials: DN
authors.lastname: Sears
authors.affiliation: Department of Chemistry and Alberta Ingenuity Centre for Carbohydrate Science, Gunning-Lemieux Chemistry Centre, University of Alberta, Edmonton, AB, Canada T6G 2G2, and Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
authors.forename: Roderick E
authors.initials: RE
authors.lastname: Wasylishen
authors.affiliation: Department of Chemistry and Alberta Ingenuity Centre for Carbohydrate Science, Gunning-Lemieux Chemistry Centre, University of Alberta, Edmonton, AB, Canada T6G 2G2, and Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
authors.forename: Todd L
authors.initials: TL
authors.lastname: Lowary
authors.affiliation: Department of Chemistry and Alberta Ingenuity Centre for Carbohydrate Science, Gunning-Lemieux Chemistry Centre, University of Alberta, Edmonton, AB, Canada T6G 2G2, and Department of Chemistry, University of Waterloo, Waterloo, ON, Canada N2L 3G1.
authors.forename: Pierre-Nicholas
authors.initials: PN
authors.lastname: Roy