Molecularly engineered lignin to polyphenol via organocatalysis as an active sunscreen ingredient

Abstract

Phenolation is one of the effective strategies to synthesize lignin-based polyphenols, improve lignin's properties, and extend its value-added applications in biological, medicinal and cosmetic fields. Herein, by taking the structural feature advantage of lignin, an effective and green strategy was developed to molecularly engineer lignin into a robust lignin-3-(2-hydroxyphenyl)propionate ester (LPPE) derivative via a transesterification reaction between 3,4-dihydrocoumarin (DHC) and the aliphatic hydroxyls in lignin under organocatalysis. The strategy is optimized and the novel derivative was systematically characterized by ¹H, ¹³C and ³¹P nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy. The findings indicated that the successful introduction of 3-(2-hydroxyphenyl)propionate groups using a OH groups/DHC/organic base molar ratio of 1꞉1꞉0.3 at 120 °C for 6 h increased the content of phenolic hydroxyl groups from 1.793 1 to 3.017 9 mmol/g, and the LPPE exhibited excellent ultraviolet-absorbing and antioxidant performance with up to 90% free radical scavenging activity within 20 min using 5 mg/mL of LPPE. In addition, good biocompatibility and a high Sun protection factor (SPF) value of 40.9 were achieved at 5% (w) dosage of LPPE in the cream, indicating its significant application potential in sunscreen.