The role of hydrogen-bonding interactions in acidic sugar reaction pathways Original Research Article

Previously, theoretical multiple sugar (β-d-xylose and β-d-glucose) reaction pathways were discovered that depended on the initial protonation site on the sugar molecules using Car–Parrinello-based molecular dynamics (CPMD) simulations [Qian, X. H.; Nimlos, M. R.; Davis, M.; Johnson, D. K.; Himmel, M. E. Carbohydr. Res. 2005, 340, 2319–2327]. In addition, simulation results showed that water molecules could participate in the sugar reactions, thus altering the reaction pathways. In the present study, the temperature and water density effects on the sugar degradation pathways were investigated with CPMD. We found that changes in both temperature and water density could profoundly affect the mechanisms and pathways. We attributed these effects to both the strength of hydrogen bonding and proton affinity of water.