Mechanistic insights into glucose-to-5-HMF conversion in DES media

Askar Z. Akhmetzhanova Z. Rakhatkyzy M. Shah D. Nuraje N.
15 July 2025 Elsevier B.V.

Journal of Molecular Liquids
2025 #430

This work provides novel mechanistic insights into the conversion of glucose to 5-hydroxymethylfurfural (5-HMF) in deep eutectic solvent (DES) systems, addressing reaction pathways that remain largely unexplained. By integrating experimental approaches with molecular dynamics (MD) simulations, key parameters influencing 5-HMF formation were systematically identified. A range of DES formulations, varying in molar ratios, and preparation techniques (in-situ and ex-situ microwave) were evaluated to optimize 5-HMF production. Tetrabutylammonium chloride (TBAC)-based DES outperformed choline chloride (ChCl)-based DES, achieving higher yields at an optimal 1:28 hydrogen bond acceptor (HBA)/ hydrogen bond donor (HBD) ratio. Interestingly, the DES preparation method had a minimal impact on 5-HMF yield at this ratio. Mechanistic investigations revealed that TBAC-based DES systems exhibit enhanced catalytic efficiency due to strong ionic dissociation and synergistic roles of Cr³⁺ and free Cl⁻ ions. MD simulations revealed the mechanistic interplay between DES components, showing that increasing isopropanol content modulated ionic interactions and enhanced chloride availability for catalysis. The synergistic effect of Cl⁻ as a Brønsted base and Cr³⁺ as a Lewis acid was demonstrated through systematic changes in interaction energies, while TBAC-based systems showed superior performance due to optimized ionic distribution. These findings underscore the importance of optimizing DES composition to enhance reaction kinetics and product stability, offering a robust framework for designing advanced catalytic systems with industrial and environmental applications.

5-HMF stability , DES, 5-HMF , Fructose dehydration , Glucose , Glucose isomerization , GROMACS , Microwave irradiation

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Department of Chemical and Materials Engineering, School of Engineering and Digital Sciences, Nazarbayev University, Astana, Kazakhstan
National Laboratory Astana, Nazarbayev University, Astana, Kazakhstan

Department of Chemical and Materials Engineering
National Laboratory Astana

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