Photoresponsive Emulsion-Templated Porous Materials via Orthogonal Photoclick Chemistry

The functionalization of emulsion-templated porous polymers (polyHIPEs) utilizing modern and efficient chemistries is an important avenue for tailoring the properties of these scaffolds for specific and specialized applications. Herein, tetrazole photoclick chemistry is utilized for the efficient functionalization of polyHIPEs synthesized from various monomer systems and polymerization chemistries. Using both radical polymerization and thiol-ene polymerization, polyHIPEs with well-defined, interconnected open-cell morphologies are synthesized with tetrazole concentrations ranging from 0 to 5 w/v %, with the pore diameters ranging from 3 to 24 μm. Analyzed by fluorescence spectroscopy, FTIR spectroscopy, and confocal microscopy, spatially controlled functionalization to generate photopatterned fluorescent polyHIPEs is demonstrated via the reaction with residual acrylate and thiol groups. In addition, the scaffolds can be readily functionalized with external dipolarophiles such as acrylates to incorporate a functionality onto the polyHIPE surface. With many functional tetrazoles also reported in the literature, a PEG-tetrazole is also used to explore the photoinduced functionalization of polyHIPEs possessing tunable ratios of thiol and acrylate groups, and the effect on fluorescence, wettability, and biocompatibility is analyzed. Overall, the reaction is shown to be a broadly applicable tool for polyHIPE functionalization with many avenues for further development toward specific applications.