Self-assembled artificial enzyme from hybridized porous organic cages and iron oxide nanocrystals

Although it is well-accepted that iron oxide nanoparticles are considered as artificial enzymes when their surface is hydrophilic, the enzyme-like properties of iron oxide nanoparticles with hydrophobic surface coating is unexplored. This work demonstrates that hydrophobic iron oxide nanocrystals coated with a layer of oleic acid could serve as artificial enzymes when their surface is covered by a layer of ionic surfactant. Furthermore, the co-assembly of iron oxide nanocrystals and porous organic cages could modulate their enzyme-like activities.

Co-assembly of iron oxide (Fe₃O₄) nanocrystals with different size and porous organic cages (POCs) was performed by an emulsion-confined strategy to achieve hybridized Fe₃O₄/POCs co-assemblies. The peroxidase-mimic activity of these co-assemblies were assessed in the presence of 3, 3', 5, 5'-Tetramethylbenzidine (TMB) and hydrogen peroxide. Finally, these co-assemblies were applied as sensors to detect glucose and hydrogen peroxide.

Co-assembly of Fe₃O₄ nanocrystals and POCs resulted in the self-assembly of Fe₃O₄ nanoparticles into two-dimensional nanoparticle superlattices on the eight (111) facets of the octahedral POCs colloidal crystals. The unique oil-in-water (O/W) emulsion confined assembly method switches the Fe₃O₄ nanoparticles and POC crystals from hydrophobic to hydrophilic because of the strong hydrophobic interactions. Importantly, these co-assemblies dispersed in water showed strong peroxidase-mimic activity in water despite that their surface is covered by a bilayer of aliphatic chains. Furthermore, the intrinsic enzymatic activity of the co-assemblies is highly dependent on the size of the nanocrystals, and a higher catalytic activity is achieved from a larger sized Fe₃O₄ nanocrystal.