Supplementary data for: "Conformational Free Energy Landscape of β-glucose in the Gas-Phase and Aqueous Solution: Energetic, Structural and Electronic Changes"

This data set contains files related to the article "Conformational Free Energy Landscape of β-glucose in the Gas-Phase and Aqueous Solution: Energetic, Structural and Electronic Changes" by Qinghua Liao, Mariana A.B. Morais, Carme Rovira and Alba Nin-Hill ABSTRACT The conformational flexibility of β-glucose is critical for the enzymatic breakdown of carbohydrates such as cellulose and starch. Detailed knowledge of its ring conformations supports the rational design of therapeutic agents and functional molecules, including glucosidase activity-based probes. Although quantum mechanical methods have been employed to study β-glucose conformations, a comprehensive analysis of the Cremer−Pople conformational space, particularly accounting for solventeffects, remains incomplete. Using density functional theory (DFT), we systematically characterize β-glucose conformations in both gas and aqueous phases. We apply three metadynamics approaches-standard, well-tempered, and parallel bias-using Cremer−Pople polar coordinates and ring dihedral angles as collective variables. Consistent conformational stability trends are observed across methods and environments. In both gas and aqueous phases, the free energy landscape (FEL) identifies the 4C1 chair as the global minimum, followed by equatorial conformers and the inverted 1C4 chair, which is less stable in solution than in the gas phase. In the gas phase, the most stable distorted conformers (in the 2SO−B3,O−1S3 region) exhibit structural and electronic features characteristic of an oxocarbenium ion, including a high C1−O1/C1−O5 bond length ratio, a pronounced anomeric effect, and negative charge accumulation at O1 and O5. These features are significantly diminished in aqueous solution, suggesting that the gas-phase FEL better reflects the conformational preferences of the saccharide at the -1 subsite in enzyme−substrate complexes of glucosidases. These findings provide a valuable framework for investigating saccharide conformations, establishing β-glucose as a model system for computational and methodological benchmarking. DESCRIPTION OF THE DATASET The data is compressed in two different .zip files in where we could find the trajectory files generated from the ab initio and QM/MM molecular dynamics simulations. bGlc_pbmetad-mw.zip: Data related to the gas phase and aqueous simulations of the β-glucose molecule using parallel bias metadynamics with multiple walkers and the dihedral torsions as CVs. bGlc_metad_cremerpople.zip: Data related to the gas phase and aqueous simulations of the β-glucose molecule using standard and well-tempered metadynamics and the cartesian Cremer and Pople coordinates as CVs.