A New Structural Model of Enzymatic Lignin with Multiring Aromatic Clusters

[Image: see text] Lignin is a natural aromatic compound in plants. Several lignin structural models have been proposed in the past years, but all the models cannot be converted to benzene carboxylic acids (BCAs) for all aromatic rings connected to oxygen. This inspired us to explore the structures of lignin. Based on the yields of BCAs, the results of (13)C NMR and ethanolysis residues, and gas chromatography–mass spectrometry and electrospray ionization mass spectrometry of ethanolysis of lignin, we have constructed a structural model of lignin with a formula C(6407)H(6736)O(2590)N(147)S(3). The model not only satisfies the results of analyses, but also explains the generation of BCAs from lignin oxidation and the ethanolysis products. Importantly, double-ring and triple-ring aromatic clusters are found in lignin, and some of them are connected by alkyl bridges, which results in conventional low conversions of lignin. Our findings in the structures of lignin may significantly influence the structures and applications of lignin.