Penetration behavior and subsurface grafting of dansyl cadaverine and polyethylene glycol (PEG) derivatives in poly(ethylene-co-acrylic acid) (EAA) film

Dansyl cadaverine and polyethylene glycol (PEG) derivatives were grafted on the surface of EAA film and in its subsurface region through formation of amides and esters, respectively. A two-step reaction was conducted. First, EAA film was activated with PCl5 at room temperature. Second, the acid chloride was reacted with dansyl cadaverine or a PEG derivative to form a modified film. ATR-FTIR spectroscopy and fluorometry were employed to analyze the modified films after each step. It was found that dichloromethane yielded the highest grafting efficiency, with the dansyl cadaverine penetrating throughout the ATR-FTIR analysis region (∼400 nm) in a few minutes. As the grafting depth increased with time, so did the amount of fluorescence intensity of grafted dansyl cadaverine. ATR-FTIR spectra for PEG grafting indicated that the acid chloride peak decreased with time, while the ester peak increased. However, hydrolysis occurred at later times, consuming the acid chloride groups within the film. A marked decrease of static water contact angle was observed for EAA grafted with PEG99 (PEG that contains 99 ethylene glycol repeat units), almost 40° lower than that of neat EAA (∼99°). For other PEG-grafted films, the surface hydrophilicity was also improved.