A general photoiniferter approach to the surface functionalization of acrylic and methacrylic structures written by two-photon stereolithography

Two-photon stereolithography (TPS) is an established additive fabrication technique allowing the voxel-by-voxel direct writing of even intricate 3D nano/microstructures via the polymerization of a photoresin. An obvious way to tune the chemical functionalities of such nano/microstructures is formulating a photoresin with the desired functional monomer(s). Unfortunately, this makes every photoresin "unique" in terms of viscosity and reactivity, thus requiring a tedious and often time-consuming optimization of its printing parameters. In this work, we describe a general approach for the chemical functionalization of TPS-written structures based on two commercial photoresins. Our strategy entailed the grafting of functional polymer layers via an innovative approach based on photoiniferter coupling to unreacted double bonds and photopolymerization. After writing woodpiles as 3D model structures, we demonstrated the viability of this approach by anchoring a photoiniferter via its photoinduced addition to the residual CC on the structure's surface triggered by green light. This in turn allowed for the blue light-mediated, surface-initiated photopolymerization of functional monomers. Molecularly imprinted polymer films were also easily synthesized by using the same approach on model honeycombs. The imprinted layers resulted in only a minimal increase in size with no effect on the geometrical features of the honeycombs. Overall, this strategy offers a general approach for the surface modification of TPS-written (meth)acrylic structures with a wide variety of functional polymers via photoiniferter polymerization.