Construction of metal-organic framework materials with dual enzyme-like activities and I-type and II-type double characteristic ROS and antibacterial application of their hydrogels

The Fe-TCPP/MnOx MOF material with peroxidase (POD)-like and oxidase (OXD)-like activities was constructed, and it also has the ability to generate type I and type II dual-characteristic reactive oxygen species (ROS) under ultrasonic excitation. • The Fe-TCPP/MnOx exhibited dual enzyme-like activity, with the POD catalytic pathway being dominant, and its catalytic behavior conformed to the Michaelis-Menten kinetic model. • Under ultrasonic stimulation, this material significantly promoted the generation of ROS, capable of producing type I superoxide anion (O2. •- ) radicals and type II singlet oxygen ( 1 O 2 ). • By introducing Fe-TCPP/MnOx MOF into the polyvinyl alcohol-chitosan (PVA-CS) matrix, a hydrogel with excellent adhesion, self-repairing properties, and outstanding mechanical properties can be obtained. • Based on the antibacterial and moisturizing properties of PVA-CS-Fe-TCPP/MnOx hydrogel, it displayed good preservation ability for fruits such as blueberries and strawberries, reduced spoilage and weight loss, and effectively extended the storage time. Metal-organic frameworks (MOF) have exhibited broad application prospects in food preservation, antibacterial packaging, biomedical materials and other fields in recent years due to their high specific surface area, tunable pore structure and abundant active sites. In this study, a Fe-TCPP/MnOx MOF material with peroxidase (POD)-like and oxidase (OXD)-like activities was constructed, and it also has the ability to generate type I and type II dual-characteristic reactive oxygen species (ROS) under ultrasonic excitation. The TMB colorimetric experiment indicated that Fe-TCPP/MnOx exhibited dual enzyme-like activity, with the POD catalytic pathway being dominant, and its catalytic behavior conformed to the Michaelis-Menten kinetic model. Under ultrasonic stimulation, this material significantly promoted the generation of ROS, capable of producing type I superoxide anion (O 2 •- ) radicals and type II singlet oxygen ( 1 O 2 ). By introducing Fe-TCPP/MnOx MOF into the polyvinyl alcohol-chitosan (PVA-CS) matrix, a hydrogel with excellent adhesion, self-repairing properties, and outstanding mechanical properties can be obtained. This hydrogel also exhibited strong antibacterial properties, capable of effectively inhibiting the growth of Escherichia coli and Staphylococcus aureus . Based on the antibacterial and moisturizing properties of PVA-CS-Fe-TCPP/MnOx hydrogel, it displayed good preservation ability for fruits such as blueberries and strawberries, reduced spoilage and weight loss, and effectively extended the storage time. In summary, this study designed a multifunctional and performance-characterized MOF material, which not only has dual enzyme activities and dual-type ROS production capabilities, but also can be effectively embedded in other composite structures to generate various applications such as enzyme catalysis, antibacterial and preservation.