Acid Treatment Enhances the Antioxidant Activity of Enzymatically Synthesized Phenolic Polymers

Phenolic polymers produced by enzymatic oxidation under biomimetic and eco-friendly reaction conditions are usually endowed with potent antioxidant properties. These properties, coupled with the higher biocompatibility, stability and processability compared to low-molecular weight phenolic compounds, open important perspectives for various applications. Herein, we report the marked boosting effect of acid treatment on the antioxidant properties of a series of polymers obtained by peroxidase-catalyzed oxidation of natural phenolic compounds. Both 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing/antioxidant power (FRAP) assays indicated a remarkable increase in the antioxidant properties for most phenolic polymers further to the acid treatment. In particular, up to a ca. 60% decrease in the EC₅₀ value in the DPPH assay and a 5-fold increase in the Trolox equivalents were observed. Nitric oxide- and superoxide-scavenging assays also indicated highly specific boosting effects of the acid treatment. Spectroscopic evidence suggested, in most cases, that the occurrence of structural modifications induced by the acid treatment led to more extended π-electron-conjugated species endowed with more efficient electron transfer properties. These results open new perspectives toward the design of new bioinspired antioxidants for application in food, biomedicine and material sciences.