Thin hydrogel films with nanoconfined surface reactivity by photoinitiated chemical vapor deposition

Several property requirements have led to the modification of hydrogels by incorporating functional groups. The current work seeks to achieve graded functional group incorporation into hydrogel thin films using the one-step technique of photoinitiated CVD (piCVD). The functional group pentafluorophenyl-methacrylate (PFM) is copolymerized with hydroxyethyl methacrylate (HEMA). Because PFM reacts easily with amine groups, the incorporation of PFM results in a platform for subsequent functionalization. The graded copolymer confines the PFM to the near surface region (̃20 nm) allowing the control of the hydrogel film properties independently of the surface reactivity. Although homogeneous incorporation of PFM in the hydrogel matrix inhibits swelling, the swollen water content of pure pHEMA is nearly preserved in the graded copolymer. FTIR spectroscopy shows that the absorption peaks corresponding to the fluorinated phenyl ring in the graded copolymer disappear after functionalization with 0,0-bis (2- aminoethyl) polyethylene (PEG-diamine), suggesting a nearly complete conversion of the PFM bonds.