Wang Zichen, Hao Mingtian, Li Xiaoyu, Zhang Beibei, Jiao Mingyang, Chen Bo-Zhen
School of Chemical Sciences, University of Chinese Academy of Sciences, No. 19A, Yuquan Road, Beijing 100049, P. R. China.
Shandong Energy Institute, Qingdao 266101, Shandong, China.
iScience. 2022 Jan 10;25(2):103755. doi: 10.1016/j.isci.2022.103755. eCollection 2022 Feb 18.
The extraction of higher-value products from lignin degradations under mild conditions is a challenge. Previous research reported efficient two-step oxidation and reduction strategies for lignin degradation, which has great significance to lignin degradation. In this paper, the mechanism about the C-O bond cleavage of lignin with and without Cα oxidations has been studied systematically. Our calculation results show that the degradation of anionized lignin with Cα oxidations is kinetically and thermodynamically feasible. In addition, the calculations predict that the anionized lignin compounds without Cα oxidation also could be degraded under mild conditions. Moreover, we propose special lignin catalytic degradation systems containing the characteristic structure of "double hydrogen bonds." The double hydrogen bonds structure could further decrease the energy barriers of the C-O bond cleavage reaction. This provides a versatile strategy to design novel lignin degradation.
在温和条件下从木质素降解产物中提取高价值产品是一项挑战。先前的研究报道了用于木质素降解的高效两步氧化还原策略，这对木质素降解具有重要意义。本文系统研究了有和没有Cα氧化时木质素C-O键断裂的机理。我们的计算结果表明，经Cα氧化的阴离子化木质素的降解在动力学和热力学上是可行的。此外，计算预测未经Cα氧化的阴离子化木质素化合物在温和条件下也可降解。而且，我们提出了具有“双氢键”特征结构的特殊木质素催化降解体系。双氢键结构可进一步降低C-O键断裂反应的能垒。这为设计新型木质素降解提供了一种通用策略。
