Controlling modulus and morphology of hydrogel tubes through surface modification

Crosslinked, porous poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) (PHEMA-MMA) tubes were prepared in cylindrical glass molds using a new centrifugal casting process developed in our group. The resulting hydrogel tubes have a bi-phasic wall structure, with a spongy inner layer and a gel-like outer layer, the latter of which provides mechanical strength to the tube. While many factors influence wall morphology and, thus, mechanical properties, we focused on the effect of the surface properties of the glass mold in which tubes are synthesized. Specifically, we investigated the impact of a diverse set of silane modifications of the glass mold on tube morphology, elastic modulus and mold release. We treated activated glass surfaces with one of three alkoxysilanes having either ethoxy, amine or fluorocarbon end-groups. Silane-modified glass surfaces were found to be more hydrophobic than the unmodified glass mold, with the most hydrophobic surface being that of the fluorocarbon-terminated silane. The presence of the silane layer on the mold was confirmed by X-ray photoelectron spectroscopy and the stability of this modification was confirmed by examining the surface chemistry of the hydrogel tubes. The biphasic hydrogel tube wall structure was observed for all tubes, yet those tubes synthesized in unmodified molds had a cracked outer morphology, whereas those synthesized in silane-modified molds had a smooth outer morphology. This influenced the mechanical properties of the tubes where tubes synthesized in silane-modified molds had a significantly greater elastic modulus than those tubes synthesized in unmodified molds. Release from the molds was easiest with ethoxy- and amine-functionalized silane mold modifications.