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

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-05-13 DOI:10.1016/j.molliq.2025.127774

Zhaniya Askar , Zhibek Akhmetzhanova , Makpal Rakhatkyzy , Dhawal Shah , Nurxat Nuraje

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引用次数: 0

Abstract

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.

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葡萄糖到5-羟甲基糠醛在DES介质中的转化机制

这项工作为葡萄糖在深度共晶溶剂（DES）系统中转化为5-羟甲基糠醛（5-HMF）提供了新的机制见解，解决了大部分尚未解释的反应途径。通过实验方法与分子动力学（MD）模拟相结合，系统地确定了影响5-羟甲基糠醛形成的关键参数。为了优化5-羟甲基糠醛的生产，研究人员评估了一系列不同摩尔比的DES配方和制备技术（原位和非原位微波）。基于四丁基氯化铵（TBAC）的DES优于基于氯化胆碱（ChCl）的DES，在最佳的氢键受体(HBA)/氢键供体（HBD）比为1:28时获得了更高的收率。有趣的是，在此比率下，DES制备方法对5-HMF产率的影响最小。机理研究表明，基于tbac的DES系统由于Cr3+和游离Cl−离子的强离子解离和协同作用而具有更高的催化效率。MD模拟揭示了DES组分之间相互作用的机理，表明异丙醇含量的增加调节了离子相互作用，增强了氯离子的催化有效性。Cl−作为Brønsted碱和Cr3+作为Lewis酸的协同作用通过相互作用能的系统变化得到了证明，而基于tbac的体系由于优化了离子分布而表现出更优的性能。这些发现强调了优化DES组成以提高反应动力学和产品稳定性的重要性，为设计具有工业和环境应用的先进催化系统提供了强有力的框架。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.