Three-dimensional
(3D) bioprinting, where cells, hydrogels, and
structural polymers can be printed layer by layer into complex designs,
holds great promise for advances in medicine and the biomedical sciences.
In principle, this technique enables the creation of highly patient-specific
disease models and biomedical implants. However, an ability to tailor
surface biocompatibility and interfacial bonding between printed components,
such as polymers and hydrogels, is currently lacking. Here we demonstrate
that an atmospheric pressure plasma jet (APPJ) can locally activate
polymeric surfaces for the reagent-free covalent attachment of proteins
and hydrogel in a single-step process at desired locations. Polyethylene
and poly-ε-caprolactone were used as example polymers. Covalent
attachment of the proteins and hydrogel was demonstrated by resistance
to removal by rigorous sodium dodecyl sulfate washing. The immobilized
protein and hydrogel layers were analyzed using Fourier transform
infrared and X-ray photoelectron spectroscopy. Importantly, the APPJ
surface activation also rendered the polymer surfaces mildly hydrophilic
as required for optimum biocompatibility. Water contact angles were
observed to be stable within a range where the conformation of biomolecules
is preserved. Single and double electrode designs of APPJs were compared
in their characteristics relevant to localized surface functionalization,
plume length, and shape. As a proof of efficacy in a biological context,
APPJ-treated polyethylene functionalized with fibronectin was used
to demonstrate improvements in cell adhesion and proliferation. These
results have important implications for the development of a new generation
of 3D bioprinters capable of spatially patterned and tailored surface
functionalization performed during the 3D printing process in situ.