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首页> 美国卫生研究院文献>Frontiers in Chemistry >Theoretical Elucidation of β-O-4 Bond Cleavage of Lignin Model Compound Promoted by Sulfonic Acid-Functionalized Ionic Liquid
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Theoretical Elucidation of β-O-4 Bond Cleavage of Lignin Model Compound Promoted by Sulfonic Acid-Functionalized Ionic Liquid

机译：磺酸功能化离子液体促进木质素模型化合物β-O-4键断裂的理论解释

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摘要

While the depolymerization of lignin to chemicals catalyzed by ionic liquids has attracted significant attention, the relevant molecular mechanism, especially the cleavage of specific bonds related to efficient depolymerization, still needs to be deeply understood for the complexity of this natural aromatic polymer. This work presents a detailed understanding of the cleavage of the most abundant β-O-4 bond in the model system, guaiacylglycerol β-guaiacyl ether, by a Brønsted acidic IL (1-methyl-3-(propyl-3-sulfonate) imidazolium bisulfate ([C3SO3Hmim][HSO4]) using density functional theory calculation and molecular dynamics simulation. It has been found that [C3SO3Hmim][HSO4] generates zwitterion/H2SO4 via proton transfer with an energy barrier of 0.38 kcal/mol, which plays a dominant role in the lignin depolymerization process. Subsequently, the reaction can be carried out via three potential pathways, including (1) the dehydration of α-C-OH, (2) dehydration of γ-C-OH, and (3) the protonation of β-O. The electrophilic attack of H2SO4 and the hydrogen-bonding interaction between GG and zwitterion are the two most important factors to promote the depolymerization reaction. In all steps, the dehydration of α-C-OH route is computed to be favored for the experiment. The relatively higher energy barrier for β-O-4 bond dissociation among these reaction steps is attributed to the hindrance of the self-assembled clusters of GG in the mixed system. Further, the dense distribution of H13([C3SO3Hmim]) surrounding O21(GG), indicated by sharp peaks in RDFs, reveals that -SO3H in cations plays a substantial role in solvating lignin. Hopefully, this work will demonstrate new insights into lignin depolymerization by functionalized ILs in biomass conversion chemistry.
机译：尽管木质素由离子液体催化分解为化学物质引起了人们的广泛关注，但由于这种天然芳香族聚合物的复杂性，相关的分子机制，尤其是与有效解聚有关的特定键的裂解仍然需要深入理解。这项工作对布朗斯台德酸性IL（1-甲基-3-（丙基-3-磺酸酯）咪唑鎓盐对模型系统中最丰富的β-O-4键对愈创甘油甘油β-愈创甘油醚的裂解有详细的了解用密度泛函理论计算和分子动力学模拟研究[C3SO3Hmim] [HSO4]，发现[C3SO3Hmim] [HSO4]通过质子转移以0.38 kcal / mol的能垒产生两性离子/ H2SO4。随后，该反应可通过三个潜在途径进行，包括（1）α-C-OH的脱水，（2）γ-C-OH的脱水和（3） β-O的质子化。H2SO4的亲电子攻击以及GG和两性离子之间的氢键相互作用是促进解聚反应的两个最重要的因素。在所有步骤中，计算出α-C-OH路径的脱水受实验青睐相对较高的能量屏障这些反应步骤中β-O-4键解离的r归因于混合系统中GG自组装簇的阻碍。此外，由RDF中的尖峰表明，O21（GG）周围的H13（[C3SO3Hmim]）的密集分布表明，阳离子中的-SO3H在溶剂化木质素方面起着重要作用。希望这项工作将展示生物质转化化学中功能化IL对木质素解聚的新见解。

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