Freeform Three-Dimensionally Printed Microchannels via Surface-Initiated Photopolymerization Combined with Sacrificial Molding

Precise freeform microchannels within an aqueous environment have several biomedical applications but remain a challenge to fabricate. Carbohydrate glass materials have shown potential for three-dimensionally (3D) printing precise, microscale structures and are suitable as a sacrificial material to reconstruct complex channel architectures, but due to the rapid dissolution kinetics in hydrogels and the aqueous environment, protective coatings are required. Here, conformal coatings were applied to carbohydrate structures via surface-initiated photopolymerization (SIP) by incorporating a photoinitiator (PI) into freeform 3D printed isomalt structures using a custom 3D printer. Structures were then immersed into a photocurable prepolymer bath and exposed to light for reaction initiation. To achieve uniform distribution of photoinitiator molecules in 3D printed constructs, miscibility between commercial photoinitiators and isomalt was modeled using the group contribution method. A dye-based, type-two photoinitiator, Eosin Y disodium salt (EY), was selected for its miscibility with isomalt and stability under high temperature. A previously described Eosin Y (EY)/triethanolamine (TEA) radical polymerization system was used to polymerize poly­(ethylene glycol) diacrylate (PEGDA). Attenuated total reflectance–Fourier transform infrared (ATR-FTIR), surface morphology, and swelling ratio characterizations via SIP were performed. Coatings around freeform structures and solid surfaces were presented to demonstrate the capability of coating complex architectures. This coating method should facilitate the application of 3D sacrificial molding in a variety of hydrogels toward building biomimetic vascular constructs.