Compartmentalized mesoporous core-shell protein particles with hydrophobic-hydrophilic domains for synergistic...

The development of enzyme carriers capable of concurrently enriching hydrophobic pollutants and facilitating efficient aqueous-phase biocatalysis is crucial for advanced wastewater treatment. Conventional inorganic mesoporous supports, with their uniformly hydrophilic or hydrophobic surfaces, are fundamentally limited in achieving this dual function. To address this challenge, we engineered a zein-based mesoporous particle (ZMP) that features intrinsic hydrophilic-hydrophobic partitioned structure, further stabilized by a TA/Fe^3 + coordination coating. This design creates a robust platform for high-performance enzyme immobilization, exhibiting an excellent turnover frequency. Specifically, the hierarchical architecture, comprising hydrophobic inner domains and hydrophilic outer surfaces, enables the selective adsorption of nonpolar pollutants while providing a favorable microenvironment for immobilizing hydrophilic enzyme. The TA/Fe³⁺ network enhances enzyme retention without compromising substrate permeability. During phenol removal, the TA/Fe³⁺-coated ZMP-immobilized enzyme exhibited a 2.1-fold increase in the reaction rate constant and higher substrate affinity compared to the uncoated system. Furthermore, the spatially partitioned ZMP exhibited stronger hydrophobic adsorption and superior catalytic performance versus conventional mesoporous silica carriers, maintaining over 90% naphthalene removal efficiency even in complex, multi-pollutant systems. These findings highlight the structural advantages of zein-based mesoporous carriers in achieving efficient, selective, and stable biocatalysis under complex environmental conditions.