Drug-eluting stents (DESs) have been associated with adverse clinical effects. Moreover, recent publications have shown that the coating of DESs suffers from defects. The purpose of this contribution is to examine a three-step process for surface modification as a means of improving the durability of DESs. In the first step, 4-(2-bromoethyl)benzenediazonium tetrafluoroborate was electrografted onto a stainless steel (SS) stent. X-ray photoelectron spectroscopy (XPS) of the modified stent confirmed the formation of the organic layer. In the second step, methyl methacrylate was polymerized onto the grafted surface by atom-transfer radical polymerization. XPS, electrochemical impedance spectroscopy, and contact-angle measurements were used to characterize the polymer brushes. The last step involved spray-coating of the stent with a drug-in-polymer matrix [poly(n-butyl methacrylate)/poly(ethylene-co-vinyl acetate) + paclitaxel]. Scanning electron microscopy confirmed the considerably improved durability of the drug-in-polymer matrix. Bare controls showed greater cracking and delamination of the coating than did the two-step modified stents after incubation under physiological (37 degrees C) and accelerated (60 degrees C) conditions. Finally, paclitaxel controlled release from the modified SS DESs was moderate compared with that of nontreated samples. In conclusion, the proposed method significantly improves the durability of drug-in-polymer matrixes on a SS DESs.
The coating of medical implants by polymeric films aims at increasing their biocompatibility as well as providing a durable matrix for the controlled release of a drug. In many cases, the coating is divided into a primer layer, which bridges between the medical implant and the drug-eluting matrix. The primer coating must be very carefully designed in order to provide optimal interactions with the surface of the medical implant and the outer layer. Here we present a simple and versatile approach for designing the primer layer based on electropolymerization of a carefully chosen blend of three different pyrrole derivatives: N-methylpyrrole (N-me), N-(2-carboxyethyl)pyrrole (PPA), and the butyl ester of N-(2-carboxyethyl)pyrrole (BuOPy). The composition and physical properties of the primer layer were studied in detail by atomic force microscopy (AFM) and a nano scratch tester. The latter provides the in-depth analysis of the adhesion and viscoelasticity of the coating. AFM phase imaging reveals a uniform distribution of the three monomers forming rough morphology. This primer layer significantly improved the morphology, stability, and paclitaxel release profile of a paclitaxel-eluting matrix based on methyl and lauryl methacrylates.
The assembly of poly(lactic acid) (PLA) nanoparticles on a 12-aminodecanoic acid (ADA) self-assembled monolayer (SAM) is described. Assembly is accomplished through electrostatic interactions between the positively charged SAM and the negatively charged PLA nanoparticles. The strategy used involves two steps in which a preliminary electrochemical coating of the ADA SAM is followed by a second step that involves immersing the SAM in a solution containing gold or PLA nanoparticles. The SAM was characterized by using cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), FTIR spectroscopy, and contact angle measurements, whereas scanning electron microscopy (SEM) was used to image the nanoparticles after electrostatic attachment was achieved. We found that the surface coverage of the nanoparticles could be controlled by modulating the electrostatic interactions between the negatively charged particles and the positively charged SAM surface by varying the pH of the nanoparticle solution, the immersion time, and the number of cyclic voltammetry scans under which the SAM was formed.
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