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.
Do multinuclear 3d metal catalysts achieve O–O bond formation via radical coupling or via water nucleophilic attack? WNA leads the way in [Co4O4]n+
