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可生物降解聚合物刷作为纳米耦合界面用于提高金属表面聚合物涂层的耐久性。

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

作者信息

Bedair Tarek M, Cho Youngjin, Joung Yoon Ki, Han Dong Keun

机构信息

Center for Biomaterials, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791, Republic of Korea; Department of Biomedical Engineering, Korea University of Science and Technology, 113 Gwahangno, Yuseong-gu, Daejeon 305-333, Republic of Korea; Chemistry Department, Faculty of Science, Minia University, El-Minia 61519, Egypt.

Center for Biomaterials, Korea Institute of Science and Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791, Republic of Korea.

出版信息

Colloids Surf B Biointerfaces. 2014 Oct 1;122:808-817. doi: 10.1016/j.colsurfb.2014.08.025. Epub 2014 Aug 27.

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.

摘要

金属基药物洗脱支架(DESs)存在严重缺点,如涂层聚合物的剥落和开裂。为防止聚合物涂层断裂并提高DES的耐久性,通过甲基丙烯酸2-羟乙酯(HEMA)的原子转移自由基聚合(ATRP),随后进行丙交酯的表面引发开环聚合(SI-ROP),在钴铬(Co-Cr或CC)表面合成了聚(L-丙交酯)(PLLA)刷。然后通过衰减全反射傅里叶变换红外光谱(ATR-FTIR)、水接触角、椭偏仪、X射线光电子能谱(XPS)、原子力显微镜(AFM)和扫描电子显微镜(SEM)对聚合物刷进行表征。所有未改性和改性的Co-Cr表面均涂覆有聚(D,L-丙交酯)(PDLLA)和西罗莫司(SRL)的基质。测量了70天的体外药物释放曲线。PLLA改性的Co-Cr在初始突释后呈现双相释放模式,随后缓慢释放。另一方面,未改性的Co-Cr由于聚合物层在Co-Cr表面的不稳定性而表现出快速药物释放和涂层聚合物层的脱落。相比之下,即使经过6周的降解测试,PLLA改性的Co-Cr仍保持均匀涂层而无脱落。血小板形态以及粘附在改性层和SRL-PDLLA涂层Co-Cr表面上的血小板低密度表明这些样品具有血液相容性。因此,可以证明在Co-Cr表面引入PLLA刷可显著提高涂层的耐久性,这是防止DES中发现的涂层缺陷的一种有前景的策略。

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