Metal-Phenolic Network-Functionalized Magnetic Nanoparticles for Enzyme Immobilization.

Metal-phenolic network (MPN) coating is an emerging class of surface functionalization method and has attracted ever-growing interest in areas of bioengineering and biotechnology. Although various applications for MPN coatings, including drug delivery, cytoprotection, and antimicrobial surfaces, have been studied in the form of films and capsules, their interaction with enzyme molecules and the subsequent influence of biocatalytic properties are poorly understood. Herein, MPN coatings composed of different types of metal ions (CuII, FeIII, ZnII, MnII, AuIV) coordinated with tannic acid (TA) were fabricated on Fe3O4 nanoparticles as a facile nanoplatform for immobilizing alcohol dehydrogenase (ADH). The results show that the different polarization capacities of metal ions (i.e., Lewis acids) could affect the hydrophilicity and hydrophobicity of the coordinated MPN coatings, while the enzyme immobilization rate, biocatalytic activity, and stability are in turn influenced by the surface properties of the MPN coatings. Among the different metal ions, the Fe3O4-TA-ZnII showed the highest enzyme immobilizing efficiency (91.53%) and catalytic activity (60.45 U/mg ADH). Besides, the enzyme re-usability and tolerance to extreme conditions were both enhanced after immobilization. These results highlight an advanced strategy for the interfacial construction of hybrid heterogeneous biocatalytic systems with potential use in biomedical applications.