Biodegradable polymer brush as nanocoupled interface for improving the durability of polymer coating on metal surface

Abstract

Metal-based drug-eluting stents (DESs) have severe drawbacks such as peeling-off and cracking of the coated polymer. To prevent the fracture of polymer-coated layer and improve the durability of DES, poly(l-lactide) (PLLA) brushes were synthesized onto cobalt-chromium (Co-Cr or CC) surface through atom transfer radical polymerization (ATRP) of 2-hydroxyethylmethacrylate (HEMA) followed by surface-initiated ring opening polymerization (SI-ROP) of l-lactide. The polymer brushes were then characterized by attenuated total reflection-Fourier transform infrared (ATR-FTIR), water contact angle, ellipsometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). All of the unmodified and modified Co-Cr surfaces were coated with a matrix of poly(d,l-lactide) (PDLLA) and sirolimus (SRL). The in vitro drug release profile was measured for 70 days. The PLLA-modified Co-Cr showed a biphasic release pattern in the initial burst followed by a slow release. On the other hand, the unmodified Co-Cr showed fast drug release and detachment of the coated polymer layer due to the instability of the polymer layer on Co-Cr surface. In comparison, the PLLA-modified Co-Cr preserved a uniform coating without detachment even after 6 weeks of degradation test. The platelet morphology and low density of platelet adhered on the modified layer and the SRL-in-PDLLA coated Co-Cr surfaces demonstrated that these samples would be blood compatible. Therefore, the introduction of PLLA brush onto Co-Cr surface is proved to dramatically improve the durability of the coating layer, and it is a promising strategy to prevent the coating defects found in DESs.

Keywords: Atom transfer radical polymerization; Drug release; Drug-eluting stent; Poly(l-lactide) brush; Ring opening polymerization.