Synthesis of a porous hollow magnetic molecularly imprinted microsphere by O/W/O composite emulsion polymerization for specifically recognizing bovine serum albumin

•A porous hollow molecularly imprinted microsphere was synthesized by O/W/O composite emulsion polymerization.•The obtained microspheres were superparamagnetic and thermo-responsive.•The HMMIM adsorption capacity toward BSA was 89.9 mg/g and a good separation efficacy toward BSA was observed in bovine whole blood. Molecular imprinting technology is highly successful for low-molecular-weight molecules, but is still confronted with many challenges for proteins. This study introduces a strategy to synthesize hollow magnetic molecularly imprinted microspheres (HMMIMs) under Fe3O4 magnetic nanoparticles matrix, by oil-in-water-in-oil composite emulsion polymerization with alkylphenol ethoxylates and Span-80 as emulsifiers. The synthesis conditions after optimization were 1.0 mmol thermo-sensitive functional monomer N-isopropylacrylamide, 1.0 mmol cross-linker N, N-methylene bisacrylamide, 2.0 wt% vinyl-modified silk fibroin, and 50 mg Fe3O4@COOH nanoparticles. The morphology structure and the forming process of the acquired HMMIMs were well characterized by POM, SEM, TEM and FT-IR. The HMMIMs were synthesized successfully with a porous structure and large specific surface area. The particle size of the obtained HMMIMs was at 10–20 µm. The obtained microspheres were superparamagnetic and thermo-responsive. The HMMIM adsorption capacity at 25 °C toward bovine serum albumin (BSA) was 89.9 mg/g and the BSA separation factor in BSA/BHb mixtures was 2.12. A good separation efficacy toward BSA was also observed in bovine whole blood. The prepared HMMIM possessed heterogeneous active sites, the BSA adsorption process on HMMIM was chemisorption controlled.