Co-degradation of coexisting pollutants methylparaben (mediators) and amlodipine in enzyme-mediator systems: Insight into the mediating mechanism

Catalyzed oxidative reactions mediated by enzymes have been proposed as an effective remediation strategy to remove micropollutants. However, enzyme-catalyzed oxidation processes are usually limited to the substrates of phenols and amine compounds. The addition of synthetic redox mediators could extend the types of enzymecatalyzed substrates. However, the actual applications were hindered by the high cost and potential toxicity of mediators. Here, we discovered a potential HRP-mediator system by exploring the removal of co-existing pollutants amlodipine (AML) and methylparaben (MeP). It was found that MeP served as a redox mediator could efficiently mediate the removal of AML by HRP/H2O2 system. Surface electrostatic potential analysis of AML molecule suggested that MeP radicals (MePox) could abstract hydrogen from the N-H site on dihydropyridine moiety of AML and then be reduced to MeP. By exploring the mediating effects of substances with MeP-like structure, Hirshfeld charge was used to evaluate the mediating efficiency of mediators. For mediating the degradation of AML, when the Hirshfeld charge of mediator radical was around - 0.3000, the mediating efficiency was the highest. This study improved the HRP-mediated system and provided an efficient and green method for the degradation of co-existing pollutants AML and MeP.