雙離子共聚物以光化學接枝抗汙塗層於熱塑型聚氨酯導管;Surface Modification of Thermoplastic Polyurethane Catheter by Photografting Zwitterionic Copolymers

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题名:	雙離子共聚物以光化學接枝抗汙塗層於熱塑型聚氨酯導管;Surface Modification of Thermoplastic Polyurethane Catheter by Photografting Zwitterionic Copolymers
作者:	李培榕;Li, Pei-Rong
贡献者:	生物醫學工程研究所
关键词:	雙離子材料;2-甲基丙烯酰氧乙基磷酸膽鹼;生醫塗層;抗沾黏塗層;熱塑型聚氨酯;zwitterionic materials;2-methacryloyloxyethyl phosphorylcholine (MPC);medical coatings;non-specific adsorption;thermoplastic polyurethane
日期:	2020-07-14
上传时间:	2020-09-02 15:29:06 (UTC+8)
出版者:	國立中央大學
摘要:	熱塑型聚氨酯(Thermoplastic polyurethane, TPU)因具有良好的生物相容性與機械性質，成為生醫器材的重要材料，如:人工血管、透析幫浦、導管等，但是，導管使用容易引起尿道感染與血液感染。歸究其因，TPU 表面的疏水性質使細菌、蛋白容易貼附，讓醫材的使用效率降低、引發發炎反應及感染等問題，同時，放置導管對病人來說是相當不適與疼痛。兩性雙離子材料磷脂酰膽鹼具有優異的生物相容性、潤滑與抗汙能力，能有效提高表面親水性質，並降低細菌與蛋白質等貼附，可作為醫療器材的抗汙塗層使用。本實驗嘗試開發一種在大氣環境中，透過浸塗與照射 UV 光源的方式，將兩性雙離子聚合物 2-甲基丙烯酰氧乙基磷酸膽鹼-甲基丙烯酸月桂酯 (poly(2-methacryloyloxyethyl phosphorylcholine-co-dodecyl methacrylate), P(MPC-DMA))以共價接枝上 TPU 導管。在吸收 UV 光源的輻射能量後，光引發劑 4-丙烯酰氧基二苯甲酮 (4-benzoylphenyl acrylate, BPA)被激發，會抓取聚合物及 TPU 導管碳原子上的氫原子，協助雙離子材料 P(MPC-DMA) 與 TPU 導管共價交聯，得到親水潤滑的表面。第一部分我們使用核磁共振光譜儀 (nuclear magnetic resonance ,NMR) 鑑定高分子的化學結構與轉化率，以及使用全反射-傅立葉轉換紅外線光譜儀 (attenuated total reflection-Fourier-transform infrared spectroscopy, ATR-FTIR )來確認導管表面與雙離子材料 P(MPC-DMA) 的鍵結，利用摩擦力測試、抗蛋白貼附測試、抗菌貼附測試，檢視改質後的 TPU 導管表面的抗汙潤滑特性，並與具潤滑效果的聚乙烯吡咯烷酮 (Poly(N-vinylpyrrolidone), PVP) 塗布導管比較。第二部分討論三種 P(MPC-DMA)不同分子比例的雙離子共聚物，在不同條件下的表面貼附動力學與粒徑大小關係、抗蛋白能力、溶解度及多種材料上的修飾效果差異。本論文，我們使用簡易操作且有效的改質方式，以雙離子聚合物 P(MPCDMA) 共價鍵結於 TPU 表面，使表面具有抗汙且潤滑的性能，並對表面修飾的機制提出見解，期許未來可以更進一步優化配方與製程技術，以滿足於更多的醫療器材應用。 ;Thermoplastic polyurethane (TPU) has been widely applied in various medical devices, such as artificial blood vessels, dialysis pumps and catheters, due to its good mechanical and biocompatible properties. However, bacterial infection occurs often in urinary and central venous catheters, which is attributed to the hydrophobic property of TPU, leading to non-specific adsorption of bacteria. Meanwhile, placement of catheters can be uncomfortable and painful for a patient. It has been found that zwitterionic phosphatidylcholine materials possess excellent biocompatible, lubricant and antifouling properties. In this study, we attempt to develop an efficient and facile way to graft zwitterionic polymers on TPU by dip coating and photoreaction in an ambient environment. Amphiphilic copolymers, poly(2-methacryloyloxyethyl phosphorylcholine-co-dodecyl methacrylate), P(MPC-DMA), were covalently grafted onto TPU substrate through photografting of the ketone structure in photoinitiator under UV irradiation. The chemical structures and conversion rate of as-prepared polymers were characterized by nuclear magnetic resonance (NMR) and attenuated total reflection-Fourier-transform infrared spectroscopy (ATR-FTIR). P(MPC-DMA) modified TPU tubes were examined by friction test, UV-Vis spectroscopy, anti-protein adhesion, antibacterial adhesion in comparison with poly(N-vinylpyrrolidone) (PVP) modified tubes. Additionally, we discussed the anti-fouling property and adsorption kinetics of P(MPC-DMA) copolymers with the different molecular ratios to correlate with their colloidal dimensions in solutions with an attempt to explore binding mechanism of polymers. Consequently, we demonstrated a facile and less footprint method to covalently modify P(MPC-DMA) polymeric coatings on TPU surfaces for good lubrication and antifouling capabilities. In the future works, we will dedicate to optimization of the coating process and formulation with an aim to meet the demanded requirements of medical applications.
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