Serse, Francesco;
Trespi, Silvio;
Paloni, Matteo;
Salvalaglio, Matteo;
Mazzotti, Marco;
(2025)
Solvent-mediated mechanism and kinetics of glucose mutarotation from enhanced sampling simulations.
The Journal of Chemical Physics
, 163
(16)
, Article 164504. 10.1063/5.0288357.
Preview |
Text
164504_1_5.0288357.pdf - Published Version Download (5MB) | Preview |
Abstract
Understanding how solvent molecules participate in chemical reaction mechanisms remains a central challenge in molecular simulations. Here, we investigate the mechanism and kinetics of glucose mutarotation in aqueous solution using a combined well-tempered metadynamics and mean force integration approach, within the framework of canonical transition state theory. We compute free energy landscapes and kinetic rate coefficients for the α → β mutarotation in pure water, as well as in systems representative of water/methanol and water/acetone mixtures. Our simulations indicate that ring opening and closure occur via concerted, solvent-assisted pathways, with ring opening identified as the rate-determining step. The temperature dependence of the predicted kinetic constant is quantitatively consistent with experimental data, while the reactivity modulation by organic co-solvents is captured qualitatively. Overall, the results provide molecular-level insight into solvent-mediated carbohydrate chemistry, demonstrating that the solvent participates in all key reactive steps and highlighting how enhanced sampling techniques can yield mechanistic and kinetic information in explicitly solvated reactive systems.
| Type: | Article |
|---|---|
| Title: | Solvent-mediated mechanism and kinetics of glucose mutarotation from enhanced sampling simulations |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/5.0288357 |
| Publisher version: | https://doi.org/10.1063/5.0288357 |
| Language: | English |
| Additional information: | © 2025 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
| Keywords: | Free energy landscapes, Molecular simulations, Metadynamics, Isomerism, Reaction mechanisms, Solvents, Transition state theory, Carbohydrates |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10217130 |
Archive Staff Only
 |
View Item |
