PROTEIN ADSORPTION AND ENDOTHELIAL-CELL ATTACHMENT AND PROLIFERATION ON PAPI-BASED ADDITIVE MODIFIED POLY(ETHER URETHANE UREAS)

To better understand vascular interactions with poly-(ether urethane urea) (PEUU) materials, protein adsorption, and endothelial cell attachment and proliferation assays were performed on a base PEUU formulation, on PEUU formulations loaded with hydrophobic and amphiphilic poly(methylene-[polyphenyl isocyanate]) (PAPI) based additives, and on PEUU formulations in which some of the polymer chains had been endcapped with either diisopropylaminoethyl (DIPAA) or decyl (DA) moieties. Protein adsorption experiments with PAPI-based additives showed that additive loaded PEUU formulations adsorbed significantly lower amounts of the studied proteins than did the unloaded PEUU. Protein adsorption to the DA and DIPAA endcapped PEUU films was found not to vary consistently from that of the unloaded PEUU film. Endothelial cell attachment and proliferation experiments with PAPI-DA and polyethylene glycol-PAPI-DA (PEG-PAPI-DA) loaded PEUU films showed that many of the films exhibited attachment and proliferation that was significantly enhanced compared to PEUU A' and that approached or equaled that of the tissue culture polystyrene control. Experiments with PAPI-DIPAA and PEG-PAPI-DIPAA loaded PEUU films exhibited attachment and proliferation data that was often below 10% of the tissue culture polystyrene control values. Experiments with the DA and DIPAA endcapped PEUU films showed endothelial cell attachment and proliferation that was statistically indistinguishable from the PEUU A' values. Contact angle analysis was carried out on the endcapped PEUU films, on the PAPI-based additive loaded PEUU films, and on PEUU A' using the sessile drop method. The advancing and receding contact angle behavior of the PAPI-based additive loaded PEUU films deviated markedly from the behavior of PEUU A', suggesting that the additives were present at the PEUU-water interface. The contact angle behavior of the endcapped PEUUs was similar to that of PEUU A', suggesting that the DA and DIPAA endcap moieties did not exist at the hydrated PEUU surface in appreciable quantities. To explain the differences in protein adsorption and endothelial cell behavior on the air side of additive loaded PEUUs when compared to the base PEUU, it was assumed that the additives near this region of the solvent swollen PEUU matrix may have migrated to, at, or near the PEUU-air interface during film formation, creating an additive enriched PEUU surface region. Once at this surface region, it was suggested that dynamic surface reorientation in response to an aqueous medium ensured that the additives with hydrophilic moieties (PEG-PAPI-DA, PEG-PAPI-DIPAA, PAPI-DIPAA) were significantly able to influence protein adsorption and endothelial cell behavior if they interacted with aqueous media more favorably than the PEUU. Furthermore, the additive without hydrophilic moieties (PAPI-DA) could influence protein adsorption and endothelial cell behavior only if it existed at the PEUU-air interface in such high concentrations that dynamic surface reorientation in response to an aqueous media would not be completely able to expose the more hydrophilic PEUU polymer chains.