Adsorption of proteins onto poly(ether urethane) with a phosphorylcholine moiety and influence of preadsorbed phospholipid

Abstract

In a previous report we demonstrated that the blood compatibility of poly(ether urethane) (PEU) was improved by grafting phosphorylcholine (PC) groups on the surface. The improved blood compatibility was indicated by decreased platelet adsorption/activation and reduced thrombin formation at the polymer surface in experiments in which the surfaces were contacted with platelet-rich plasma in vitro. In the present study, we investigated the effect of grafted PC groups at a PEU surface on protein and phospholipid adsorption. Adsorption of human fibrinogen (Fg), human serum albumin (Alb), human high-molecular-weight kininogen (HMWK), and dioleoyl phosphatidylcholine (DOPC) vesicles was measured by ellipsometry. For this purpose, thin PEU films were cast on silicon wafers. The polymer film was photochemically modified with a PC-containing aryl azide. The presence of PC groups on the polymer surface was demonstrated by ESCA (Electron Spectroscopy for Chemical Analysis). The hydrophilicity of the polymer surface increased by the surface modification, as indicated by a decrease of the contact angle from 59 degrees before to 43 degrees after modification. Our data show that the presence of PC groups has little effect on the adsorption of proteins to a PEU surface. The highest adsorption was observed for Fg (0.49 microgram/cm2 on PC-modified PEU and 0.50 microgram/cm2 on PEU), followed by HMWK (0.28 microgram/cm2 on both PC-modified PEU and PEU), and Alb (0.16 microgram/cm2 on PC-modified PEU and 0.18 microgram/cm2 on PEU). Protein adsorption was further studied on a "biomembrane-like" DOPC bilayer formed on hydrophilic silicon. We found no protein adsorption on this DOPC bilayer. The adsorption of small unilamellar DOPC vesicles on the polymer surfaces amounted to about 0.06 microgram/cm2 (corresponding to circa 30% of monolayer coverage) and was similar for PC-modified PEU and PEU. Despite this partial surface coverage, preadsorbed DOPC on the polymer surface diminished the subsequent adsorption of proteins considerably. These results show that the mere presence of phosphorylcholine groups on a PEU surface is insufficient to suppress protein adsorption. The highly ordered structure of natural phospholipid bilayers seems to be required to suppress protein adsorption effectively.

Synthesis of a Novel Biodegradable Polyurethane with Phosphatidylcholines

“…In order to further improve their blood compatibility, lots of modification methods have been developed. Among them, the imitation of cell membrane by introducing PC into PURs is a very effective way [2–5]. For example, aryl azides consisting of a photoactivatable 4-azidobenzoyl group and a PC end group have been synthesized and then the PC-containing aryl azides were coupled to poly (etherurethane) surfaces.…”

Recent progress of phospholipid polymers

“…The platelet density in 10 ¹m £ 10 ¹m was 6.10 and 0.34 for V-SPU-S and V-SPU-S-P, respectively. These results indicated phosphatidylcholine polar headgroup-grafted polymers did not support platelet adhesion [131][132][133]. Platelet adhesion to phosphatidylcholine polar headgroup-grafted polymer V-SPU-S-P was inhibited 95% compared with unmodi ed V-SPU [90].…”

Overview of PES biocompatible/hemodialysis membranes: PES–blood interactions and modification techniques

“…One theory suggests that the formation of an artificial organized bilayer of the PC and its derivatives at the polymer surface acts as a shield to the material's surface from the protein interaction [93,94] as depicted in Fig. 11.…”