Emulsion-Free 3D Printing of Inherently Porous Molecularly Imprinted Polymers with Tailored Macroscopic Geometries

Abstract

Molecularly imprinted polymers (MIPs) with customizable macroscopic shapes expand the scope of molecular imprints’ impressive applications. Combining 3D printing with molecular imprinting technology enables reproducible and scalable fabrication of polymers in tailored macroscopic structures while preserving molecular recognition properties. This study introduces a photocurable, 3D-printable formulation for the emulsion-free fabrication of porous MIPs in highly structured macroscopic geometries using polymerization-induced phase separation. To prove the principle, an inherently porous lattice cube imprinted with 17β-estradiol (E2) is investigated for the extraction and enrichment of this hormone. Surprisingly, incubation studies revealed that the 3D-printed MIPs exhibit approximately double the binding capacity for E2 than the porous nonimprinted control polymers despite their similar surface area. The remarkable results highlight the potential of porous additively manufactured molecularly imprinted polymers (AM-MIPs) for a plethora of exciting applications, e.g., in filters, sensors, release systems, and biomedical engineering.