Thermoresponsive hydrogel scaffolds with tailored hydrophilic pores

Thermoresponsive hydrogels with efficient water-release channels were prepared by incorporating star-shaped macromolecular pore precursors, with degradable disulfide crosslinked cores and hydrophilic poly(ethylene oxide) (PEO) arms, into the gel network. The gel framework exhibiting lower critical solution temperature (LCST) behavior was synthesized by atom transfer radical polymerization (ATRP) of 2-(2-methoxyethoxy)ethyl methacrylate and ethylene glycol dimethacrylate. The incorporation of degradable star macromolecules (dSM) was facilitated by growing the gel from ATRP initiator sites contained within their cores. Following the formation of the gel, the dSM cores were degraded, yielding uniform pores lined with hydrophilic PEO chains. The effect of hydrophilic pores on thermoresponsive hydrogel performances was studied by comparing hydrogels containing hydrophilic pores with analogous hydrogels with neutral pores or with pore-free controls. Dye absorption/release experiments pointed to the suitability of newly synthesized hydrogels as controlled-release media, for example, for drug delivery. Cell culture experiments confirmed their nontoxicity and biocompatibility (cell viability>98%). With arms wide open: Thermoresponsive hydrogels based on poly(2-(2-methoxyethoxy)ethyl methacrylate) were synthesized by ATRP, using core-degradable, hydrophilic-arm-containing star macroinitiators. The subsequent degradation of disulfide crosslinks generated hydrogels with hydrophilic porous domains. This unique strategy enabled the preparation of highly swelling and rapidly deswelling hydrogels.