New Mechanistic Insights into the Lignin β-O-4 Linkage Acidolysis with Ethylene Glycol Stabilization Aided by Multilevel Computational Chemistry,ACS Sustainable Chemistry & Engineering

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New Mechanistic Insights into the Lignin β-O-4 Linkage Acidolysis with Ethylene Glycol Stabilization Aided by Multilevel Computational Chemistry
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2021-01-25 , DOI: 10.1021/acssuschemeng.0c08901
Alessandra De Santi _{1,

2} , Susanna Monti ₃ , Giovanni Barcaro ₄ , Zhenlei Zhang ₂ , Katalin Barta _{1,

5} , Peter J Deuss ₂

Affiliation

Acidolysis in conjunction with stabilization of reactive intermediates has emerged as one of the most powerful methods of lignin depolymerization that leads to high aromatic monomer yields. In particular, stabilization of reactive aldehydes using ethylene glycol results in the selective formation of the corresponding cyclic acetals (1,3-dioxolane derivatives) from model compounds, lignin, and even from softwood lignocellulose. Given the high practical utility of this method for future biorefineries, a deeper understanding of the method is desired. Here, we aim to elucidate key mechanistic questions utilizing a combination of experimental and multilevel computational approaches. The multiscale computational protocol used, based on ReaxFF molecular dynamics, represents a realistic scenario, where a typical experimental setup can be reproduced confidently given the explicit molecules of the solute, catalyst, and reagent. The nudged elastic band (NEB) approach allowed us to characterize the key intermolecular interactions involved in the reaction paths leading to crucial intermediates and products. The high level of detail obtained clearly revealed for the first time the unique role of sulfuric acid as a proton donor and acceptor in lignin β-O-4 acidolysis as well as the reaction pathways for ethylene glycol stabilization, and the difference in reactivity between compounds with different methoxy substituents.

中文翻译：

多级计算化学辅助下对木质素 β-O-4 连接酸解与乙二醇稳定的新机理见解

酸解与活性中间体的稳定相结合已成为木质素解聚最有效的方法之一，可实现高芳香族单体产率。特别是，使用乙二醇稳定反应性醛会导致模型化合物、木质素甚至软木木质纤维素选择性地形成相应的环状缩醛（1,3-二氧戊环衍生物）。鉴于该方法对于未来生物精炼厂的高度实用性，需要对该方法有更深入的了解。在这里，我们的目标是利用实验和多级计算方法的结合来阐明关键的机制问题。所使用的基于 ReaxFF 分子动力学的多尺度计算协议代表了一个现实场景，在给定溶质、催化剂和试剂的明确分子的情况下，可以自信地重现典型的实验设置。微动弹性带 (NEB) 方法使我们能够表征产生关键中间体和产物的反应路径中涉及的关键分子间相互作用。获得的高水平细节首次清楚地揭示了硫酸作为质子供体和受体在木质素β-O-4酸解中的独特作用以及乙二醇稳定的反应途径，以及化合物之间反应性的差异具有不同的甲氧基取代基。

更新日期：2021-02-08

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