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Engineered tubular constructs made from soft biomaterials are employed in a myriad of applications in biomedical science. Potential uses of these constructs range from vascular grafts to conduits for enabling perfusion of engineered tissues and organs. The fabrication of standalone tubes or complex perfusable constructs from biofunctional materials, including hydrogels, via rapid and readily accessible routes is desirable. Here we report a methodology in which customized coaxial nozzles are 3D printed using commercially available stereolithography (SLA) 3D printers. These nozzles can be used for the fabrication of hydrogel tubes via coextrusion of two shear-thinning hydrogels: an unmodified Pluronic® F-127 (F127) hydrogel and an F127bisurethane methacrylate (F127-BUM) hydrogel. We demonstrate that different nozzle geometries can be modeled via computer-aided design and 3D printed in order to generate tubes or coaxial filaments with different cross-sectional geometries. We were able to fabricate tubes with luminal diameters or wall thicknesses as small as ~150 μm. Finally, we show that these tubes can be functionalized with collagen I to enable cell adhesion, and human umbilical vein endothelial cells can be cultured on the luminal surfaces of these tubes to yield tubular endothelial monolayers. Our approach could enable the rapid fabrication of biofunctional hydrogel conduits which can ultimately be utilized for engineering in vitro models of tubular biological structures.

Bio-sourced and biodegradable polymers for additive manufacturing could enable the rapid fabrication of parts for a broad spectrum of applications ranging from healthcare to aerospace. However, a limited number of these materials are suitable for vat photopolymerization processes. Herein, we report a two-step additive manufacturing process to fabricate robust protein-based constructs using a commercially available laser-based SLA printer. Methacrylated bovine serum albumin (MA-BSA) was synthesized and formulated into aqueous resins that were used to print complex 3D objects with a resolution comparable to a commercially available resin. The MA-BSA resins were characterized by rheometry to determine the viscosity and the cure rate, as both of these parameters can ultimately be used to predict the printability of the resin. In the first step of patterning these materials, the MA-BSA resin was 3D printed, and in the second step, the printed construct was thermally cured to denature the globular protein and increase the intermolecular noncovalent interactions. Thus, the final 3D printed part was comprised of both chemical and physical cross-links. Compression studies of hydrated and dehydrated constructs demonstrated a broad range of compressive strengths and Young's moduli that could be further modulated by adjusting the type and amount of co-monomer. The printed hydrogel constructs demonstrated good cell viability (> 95%) after a 21-day culture period. These MA-BSA resins are expected to be compatible with other vat photopolymerization techniques including digital light projection (DLP) and continuous liquid interface production (CLIP). File list (2) download file view on ChemRxiv ChemRxiv manuscript_Nelson.pdf (2.02 MiB) download file view on ChemRxiv ChemRxiv_supporting_information_Nelson.pdf (2.95 MiB)

As a machine-recognizable representation of polymer connectivity, BigSMILES line notation extends SMILES from deterministic to stochastic structures. The same framework that allows BigSMILES to accommodate stochastic covalent connectivity can be...

Mechanically robust bulk antimicrobial polymers are one way to address disease transmission via contaminated surfaces. Here, we demonstrate the visible light photo-oxidative cross-linking of amine-containing PDMS using a single-component, solvent-free system where amines have a dual role as antimicrobial functionalities and cross-linking sites. Rose Bengal, a xanthene dye used as a fluorescent stain, is thermally reacted with the polymer to give a solvent-free liquid siloxane that can generate reactive singlet oxygen upon aerobic green light irradiation, coupling the amine functionalities into imine cross-links. Photorheological experiments demonstrate that light intensity is the largest kinetic factor in the photo-oxidative curing of these polymers. Room temperature irradiation under an ambient atmosphere results in free-standing elastic materials with mechanical properties that depend on the amount of Rose Bengal present. An ultimate elongation strain of 117% and Young’s modulus of 2.15 MPa were observed for the highest dye loading, with both mechanical properties found to be higher than those for the same solution-based dye amounts. We demonstrate that the solvent-free nature of the material can be exploited to generate 3D structures using low-temperature deposition as well as direct-write patterning and photolithography on glass substrates. The antimicrobial activity was investigated, with the cross-linked material demonstrating greater efficacy against E. coli (Gram negative) compared with MRSA (Gram positive) bacterial strains and inducing complete cell lysis of incubated CHO-K1 mammalian cells, demonstrating applicability as a mechanically robust single-component antimicrobial elastomer.