Quantum Mechanical Calculations Suggest That Lignin Polymerization Is Kinetically Controlled

15 February 2019, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Lignin is an abundant biopolymer important for plant function while holding promise as a renewable source of valuable chemicals. Although the lignification process in plant cell walls has been long-studied, a comprehensive, mechanistic understanding on the molecular scale remains elusive. A better understanding of lignification will lead to improved atomistic models of the plant cell wall that could, in turn, inform effective strategies for biomass valorization. Here, using first-principles quantum chemical calculations, we show that a simple model of kinetically-controlled radical coupling broadly rationalizes qualitative experimental observations of lignin structure across a wide variety of biomass types, thus paving the way for predictive, first-principles models of lignification while highlighting the ability of computational chemistry to help illuminate complex biological processes.


lignin polymerization
Radical coupling
Density Functional Theory

Supplementary materials

SI forchemrxiv


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