Long-lasting UV-blocking Mechanism of Lignin: Origin and Stabilization of Semiquinone Radicals

Semiquinone (SQ) radicals play a critical role in the long-lasting UV-blocking application of lignin, while their origin and stable structure are unclear. Here, the organosolv lignin extracted from poplar (OL-P) is self-assembled into normal micelles (LNM) with more phenolic hydroxyl groups on the surface, and reverse micelles (LRM) with more methoxyl groups on the surface. After 12 h UV irradiation, the SQ radical contents in LNM and LRM increase 33% and 78% respectively. The performance of LNM based sunscreen keeps upswinging due to radical stabilization of phenolic hydroxyl groups. LRM based sunscreen experiences a gradual decrease after reaching maximum UV absorbance due to the quick generation and over oxidation of SQ radicals. Density functional theory (DFT) simulations reveal that methoxyl groups in OL-P has bigger bond length and smaller bond dissociation enthalpy than phenolic hydroxyl groups, and are easy to form SQ radicals. The Gibbs free energy (ΔG) needed for SQ-quinone transformation is above 26.10 kcal mol.^-1, while that for SQ-hydroquinone transformation is below -66.78 kcal mol.^-1. Hydroquinone is the stable structure of SQ radicals. This work discloses the origin and stable structure of SQ radicals in lignin under UV irradiation, and provides an important guidance for its long-lasting UV-blocking application.