Core-Shell Magnetic Mesoporous Silica Microspheres with Large Mesopores for Enzyme Immobilization in Biocatalysis

Magnetic mesoporous silica microspheres with core-shell structure and large pores are highly desired in macromolecules delivery and biocatalysis, biospeparation, and adsorption. In this work, a controllable solvent evaporation induced solution-phase interface co-assembly approach was developed to synthesize core-shell structural magnetic mesoporous silica microspheres with ultralarge mesopore size (denoted as LP-MMS). The synthesis was achieved by employing large-molecular-weight amphiphilic block copolymers poly(ethylene oxide)- block-poly(methyl methacrylate) (PEO- b-PMMA) and small surfactant cetyltrimethylammonium bromide as co-templates, which can co-assemble with silica source in tetrahydrofuran/water solutions. The obtained LP-MMS microspheres possess uniform rasberry-like morphology with a diameter of 600 nm, large primary spherical mesopores (ca. 36 nm), large specific surface area (348 m²/g), high specific pore volume (0.59 cm³/g), and fast magnetic responsivity with high magnetization (15.9 emu/g). The mesopore morphology can be transformed from spherical to cylindrical through introducing a shearing force during the interfacial co-assembly in the synthesis system. The designed LP-MMS microspheres turn out to be good carriers for enzyme (trypsin) immobilization with a high loading capacity of 80 μg/mg and demonstrate excellent biocatalysis efficiency up to 99.1% for protein digestion within 30 min and good recycling stability with negligible decay in digestion efficiency after reuse for five times.