Degassing polyacrylamide gel solutions prevents oxygen inhibition during free-radical polymerization.
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Peer-reviewed literature establishes that oxygen inhibits free-radical polymerization during the formation of polyacrylamide hydrogels, and removing oxygen from the system prevents this inhibition to yield uniformly cross-linked surfaces.
Hydrogel surfaces are of great importance in numerous applications ranging from cell-growth studies and hydrogel-patch adhesion to catheter coatings and contact lenses. A common method to control the structure and mechanical/tribological properties of hydrogel surfaces is by synthesizing them in various mold materials, whose influence has been widely ascribed to their hydrophobicity. In this work, we examine possible mechanisms for this “mold effect” on the surface of hydrogels during polymerization. Our results for polyacrylamide gels clearly rule out the effect of mold hydrophobicity as well as any thermal-gradient effects during synthesis. We show unequivocally that oxygen diffuses out of certain molding materials and into the reaction mixture, thereby inhibiting free-radical polymerization in the vicinity of the molding interface. Removal of oxygen from the system results in homogeneously cross-linked hydrogel surfaces, irrespective of the substrate material used. Moreover, by varying the amount of oxygen at the surface of the polymerizing solutions using a permeable membrane we are able to tailor the surface structures and mechanical properties of PAAm, PEGDA and HEMA hydrogels in a controlled manner.
Surface gel layers on commercially available contact lenses have been shown to reduce frictional shear stresses and mitigate damage during sliding contact with fragile epithelial cell layers in vitro. Spencer and co-workers recently demonstrated that surface gel layers could arise from oxygen-inhibited free-radical polymerization. In this study, polyacrylamide hydrogel shell probes (7.5 wt % acrylamide, 0.3 wt % N,N'-methylenebisacrylamide) were polymerized in three hemispherical molds listed in order of decreasing surface energy and increasing oxygen permeability: borosilicate glass, polyether ether ketone (PEEK), and polytetrafluoroethylene (PTFE). Hydrogel probes polymerized in PEEK and PTFE molds exhibited 100× lower elastic moduli at the surface ( = 80 ± 31 and = 106 ± 26 Pa, respectively) than those polymerized in glass molds ( = 31,560 ± 1,570 Pa), in agreement with previous investigations by Spencer and co-workers. Biotribological experiments revealed that hydrogel probes with surface gel layers reduced frictional shear stresses against cells (τPEEK = 35 ± 15 and τPTFE = 22 ± 16 Pa) more than those without (τglass = 68 ± 15 Pa) and offered greater protection against cell damage when sliding against human telomerase-immortalized corneal epithelial (hTCEpi) cell monolayers. Our work demonstrates that the “mold effect” resulting in oxygen-inhibition polymerization creates hydrogels with surface gel layers that reduce shear stresses in sliding contact with cell monolayers, similar to the protection offered by gradient mucin gel networks across epithelial cell layers.
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