Computational Study of Bond Dissociation Enthalpies for a Large Range of Native and Modified Lignins
Computational Study of Bond Dissociation Enthalpies for a Large Range of Native and Modified Lignins
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DOI：
10.1021/jz201182w
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发表时间：
2011-11-17
影响因子：
5.7
通讯作者：
Beckham, Gregg T.
中科院分区：
文献类型：
--
作者：
Kim, Seonah;Chmely, Stephen C.;Beckham, Gregg T.
木质素是植物细胞壁的主要成分，其通常在可再生燃料和化学品的选择性转化策略中未被充分利用。热处理和催化处理解构木质素的机制仍然难以捉摸，这是量子力学计算可以提供基本见解的地方。在这里，我们计算均裂键解离的异构体（BDEs）的四个普遍的连接在69个木质素模型化合物，包括β-O-4，α-O-4，β-5，和联苯键与大范围的天然和氧化取代基。这些计算包括从头算基准值外推到完整的基组限制和完整的构象搜索每个化合物。结果量化了常见木质素键之间的相对BDE和天然和氧化取代基对木质素中官能团的影响。这些数据产生的洞察热木质素解构为一个大范围的普遍的联系，并在催化裂解的目标识别援助。
Lignin is a major component of plant cell walls that is typically underutilized in selective conversion strategies for renewable fuels and chemicals. The mechanisms by which thermal and catalytic treatments deconstruct lignin remain elusive, which is where quantum mechanical calculations can offer fundamental insights. Here, we compute homolytic bond dissociation enthalpies (BDEs) for four prevalent linkages in 69 lignin model compounds, including beta-O-4, alpha-O-4, beta-5, and biphenyl bonds with a large range of natural and oxidized substituents. These calculations include ab initio benchmark values extrapolated to the complete basis set limit and full conformational searches for each compound. The results quantify both the relative BDEs among common lignin bonds and the effect of native and oxidized substituents on the functional groups in lignin. These data yield insights into thermal lignin deconstruction for a large range of prevalent linkages and aid in the identification of targets for catalytic cleavage.