The water-catalyzed mechanism of the ring-opening reaction of glucose
文献信息
Wojciech Plazinski, Anita Plazinska, Mateusz Drach
The hexopyranose mutarotation is an important focus for carbohydrate chemistry for more than 150 years. The paper describes the results of advanced computational studies aimed at elucidating the ring-opening reaction of glucose. Molecular simulations based on the combination of the DFT method with the molecular dynamics formalism allowed for a detailed insight into the mechanism of the process accompanied by the information of the kinetic and dynamic nature. The results indicate that the process is initiated by deprotonation of the anomeric hydroxyl group by water molecules and the subsequent proton transfer to the ring oxygen atom. The latter event has been identified as a ‘bottleneck’ of the process triggering the ring cleavage. The most time-consuming steps of the ring-opening reaction are the orientational rearrangements of water molecule(s) participating in the proton transfer(s) and the final extension of the newly-formed aldehyde chain. The orientational preferences of the aldehyde group present in the acyclic form of D-hexopyranoses are responsible for the anomeric equilibrium characteristics.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.




