用于生物乙醇生产的与结晶和无定形纤维素相关的低聚物系统的反应性评估:DFT 研究。

IF 2.1 4区 化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY Journal of Molecular Modeling Pub Date : 2024-09-20 DOI:10.1007/s00894-024-06141-6
Sâmique K. C. Araujo Camargo, Augusto Batagin-Neto, Gustavo Ventorim, Bruno S. Camargo, Fábio H. A. Vieira, Cristiane K. C. Araújo, Camilla K. C. Araújo
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引用次数: 0

摘要

背景:利用可再生原料生产生物乙醇是许多国家经济发展的决定性因素。然而,由于工艺复杂,实验变量众多,因此需要深入了解生物乙醇生产过程中发生的化学反应,以确定最佳参数。在此,我们采用基于密度泛函理论的计算方法,通过考虑结晶和无定形纤维素模型来研究低聚物体系的局部反应性,从而更好地了解纸浆预处理过程的一些细节。我们的研究结果表明,纤维素的无定形部分对通常在酸水解过程中使用的化学品具有更高的化学敏感性。此外,我们还观察到纤维素水解产生的葡萄糖单体可能会发生氧化,从而形成羟甲基糠醛(HMF)、乙酸、甲酸和乙酰丙酸等副产品。对局部化学软度指数的分析表明,纤维素水解可能与中间化学步骤有关。最后,我们研究了不同溶剂(介电常数)对系统局部反应性的影响,证明了溶剂介电常数对葡萄糖中纤维素降解的相关作用:方法:构建初始三维结构。采用哈特里-福克(HF)方法,利用 PM7 半经验哈密顿方程进行了预优化。然后通过密度泛函理论(DFT)对结构进行了重新优化。通过凝聚原子福井指数(CAFI)对这些体系进行了局部反应性研究。在几何优化和 CAFI 计算中还考虑了介电常数的系统变化,以估计溶剂对系统反应性的影响。
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Reactivity assessment of oligomeric systems associated with crystalline and amorphous cellulose for bioethanol production: a DFT study

Context

The production of bioethanol from renewable raw materials is a decisive factor in the economic development of many countries. However, the complexity of the processes and the numerous experimental variables involved require a deeper understanding of the chemical reactions that take place during bioethanol production to define optimal parameters. Here, we have employed density functional theory–based calculations to investigate the local reactivity of oligomeric systems by considering crystalline and amorphous cellulose models to better understand some details regarding pulp pretreatment processes. Our results evidence a higher chemical susceptibility of amorphous portions of cellulose to chemicals typically employed in acid hydrolysis. Additionally, we observed that glucose monomers coming from cellulose hydrolysis may undergo oxidation, leading to the formation of byproducts such as hydroxymethylfurfural (HMF), acetic acid, formic acid, and levulinic acid. The analysis of local chemical softness indexes indicated that cellulose hydrolysis may be associated with intermediate chemical steps. Finally, we investigated the influence of distinct solvents (dielectric constants) on the local reactivity of the systems, evidencing a relevant role of the solvent dielectric constant for cellulose degradation in glucose.

Methods

Initial three-dimensional structures were constructed. Pre-optimizations were performed in a Hartree–Fock (HF) approach employing the PM7 semi-empirical hamiltonian. The structures were then re-optimized via density functional theory (DFT). The local reactivity study of the systems was conducted through the condensed-to-atoms Fukui indexes (CAFI). Systematic changes of the dielectric constants were also considered in geometry optimization and CAFI calculations to estimate the influence of solvents on the reactivity of the systems.

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来源期刊
Journal of Molecular Modeling
Journal of Molecular Modeling 化学-化学综合
CiteScore
3.50
自引率
4.50%
发文量
362
审稿时长
2.9 months
期刊介绍: The Journal of Molecular Modeling focuses on "hardcore" modeling, publishing high-quality research and reports. Founded in 1995 as a purely electronic journal, it has adapted its format to include a full-color print edition, and adjusted its aims and scope fit the fast-changing field of molecular modeling, with a particular focus on three-dimensional modeling. Today, the journal covers all aspects of molecular modeling including life science modeling; materials modeling; new methods; and computational chemistry. Topics include computer-aided molecular design; rational drug design, de novo ligand design, receptor modeling and docking; cheminformatics, data analysis, visualization and mining; computational medicinal chemistry; homology modeling; simulation of peptides, DNA and other biopolymers; quantitative structure-activity relationships (QSAR) and ADME-modeling; modeling of biological reaction mechanisms; and combined experimental and computational studies in which calculations play a major role.
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