博碩士論文 107827607 詳細資訊

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姓名 阮艷垂(Diem Thuy Nguyen)  查詢紙本館藏   畢業系所 生醫科學與工程學系
(Preparation of lubricant and antifouling medical coating on thermalplastic polyurethane)
★ Deposition of Photoactive Layer on Thermoplastic Polyurethane Tubes for Photo-grafting poly(2-methacryloyloxyethyl phosphorylcholine)
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摘要(中) 醫療器材的表面性質是影響設備的關鍵因素之一。 實際上,體內留置的導管或醫材植入物中的潤滑度不足會直接影響每個患者的健康狀況。 疏水性表面還會引起細菌附著和蛋白質吸附,導致生物材料的的不穩定性與損壞。在這項研究中,我們合成了無規共聚物聚(2-甲基丙烯酰氧基氧乙基磷酰膽鹼(MPC)-r- 3-(三(三(三甲基甲矽烷氧基)甲矽烷基)甲基丙烯酸丙酯] TSM,透過簡單且快速的浸塗方法,改質在常用的人工植入物材料-熱塑性聚氨酯(TPU)導管,含有2-甲基丙烯酰氧基乙基磷酰膽鹼(MPC)的聚合物可以提供出色的生物相容性和對不良反應的高耐受性,TSM的疏水基團可使聚合物吸附於TPU導管表面。此外,我們也將聚乙烯吡咯烷酮(PVP)和丙烯酸4-苯甲酰基苯基酯(BPA)添加到塗料溶液中,以光誘導的方式增加塗層穩定性並形成緊密網絡。 傅立葉轉換紅外線光譜儀(ATR-FTIR)結果表明,改質後的TPU表面成功地形成了均勻的塗層,並以Profilometer Profilm3D(P3D)的結果證實,成功降低了材料表面粗糙度。在去離子水環境的摩擦試驗中, 經MPC7-TSM5, PVP, BPA(CsMT75)的塗料溶液改性後的導管, 成功降低了10倍以上的動摩擦係數。 此外,在PBS環境下,帶有CsMT75塗層的TPU管可以維持一個月的穩定性,並可以長時間的降低細菌和蛋白質在表面的貼附力。因此,用無規聚合物MPC-TSM,PVP和BPA (CsMT) 改性的TPU導管具有穩定的潤滑性質與抗非特異性吸附能力,具應用於醫材設備的巨大潛力。通過表面等離子體共振(SPR)和動態光散射(DLS)測試以及粘度和表面張力測量,研究了共聚物中單體的合適比例,溶劑和乾燥時間等表面改質的關鍵因素,探討並深刻了解表面修飾機制。然而,目前需使用5 wt%的聚合物溶液來修飾材料,為了降低聚合物使用濃度並保持相似的塗布效果,我們新發布三元共聚物(MPC-TSM-BPA)。將光交聯劑引入共聚物中時,不僅保留了防污潤滑劑穩定的表面,也降低主共聚物的修飾濃度至1 wt%。此外,在調整了成分和因素之後,除了聚合物濃度降低了5倍,UV時間也比之前的塗覆過程中的15分鐘減少了3倍至5分鐘,這歸功於MPC-TSM-BPA本身的交聯和共價鍵結。簡而言之,我們提供了一個製程簡單且具效益的表面修飾方式,未來期望應用於各項醫材設備。
摘要(英) Surface properties are one of determinants for the successful outcome of biomedical devices. Indeed, the high friction and insufficient lubrication in indwelling catheters or medical implants directly affect health situation of each patient. The hydrophobic surface also causes the bacterial attachment and protein adsorption, leading to the long-term instability then the failure of biomaterials. In this study, random copolymers, poly (2-methacryloyloxyethyl phosphorylcholine (MPC) -r- 3-(tris(trimethylsiloxy)silyl)propyl methacrylate (TSM) are synthesized to modify thermoplastic polyurethane (TPU) catheter, a common artificial implantable material in biomedical fields, via a simple and quick dip-coating method. The bio-inspired polymer containing 2-methacryloyloxyethyl phosphorylcholine (MPC) can provide the outstanding biocompatibility and the high resistance to unfavorable reactions. In addition, TSM in the copolymer with hydrophobic domain served as attachment material with a strong physical affinity to TPU surface. Poly vinylpyrrolidone (PVP) and 4-benzoylphenyl acrylate (BPA) were also added into the coating solution to induce the stability and form a tight network for surface membrane. Attenuated total reflection-Fourier-transform infrared (ATR-FTIR) results indicated the successfully uniform coating layer on TPU surface after modification with the significant decrease of roughness measured by Profilometer, Profilm3D (P3D). Regarding to a friction test in deionization water environment, the dynamic friction coefficient decreased over 10 times with the high stability during testing time after modification with a coating solution including MPC7-TSM5, PVP and BPA (CsMT75). Moreover, TPU tubes with CsMT75-coated membrane can be durable in PBS in one month. The anti-fouling assay also showed the significant decrease of bacterial and protein adhesion on the surface for the long period of time. Therefore, modifying TPU with coating solution including random copolymer MPC-TSM, PVP and BPA (CsMT) is potentially promising for stable lubricant coating material as well as repelling of nonspecific absorption on surface for the long term, then prevention of implant failure. Via Surface Plasmon Resonance (SPR) and Dynamic light scattering (DLS) testing as well as viscosity and surface tension measurement, the key factors such as suitable ratio of monomers in copolymer, solvents and drying time/condition were investigated to acknowledge deeply about the coating mechanism. Nevertheless, in this process, the polymer concentration is quite high up to (5 wt%), the aim to continuously decrease the concentration of polymer but still keep the similar coating efficiency has led to the newly released three-random copolymer (MPC-TSM-BPA). When photo crosslinkers were introduced into the copolymer, not only does the antifouling lubricant stable surface remain, but the main copolymer concentration was also down to only 1 wt%. After adjustment of components and factors, in addition to the 5-time decrease of polymer concentration, the UV time also reduced 3 times to 5 min compared to 15 min in the previous coating process thanks to the enhancement of crosslinking and formation of covalent bonds. Therefore, due to simple process and cost efficiency, the coating process can be applied to manufacturing and potentially used for various substrates of medical devices.
關鍵字(中) ★ 穩定的潤滑劑塗料
★ 非特異性吸收
★ 生物啟發共聚物
★ 浸塗工藝
關鍵字(英) ★ stable lubricant coating material
★ nonspecific absorption
★ bio-inspired copolymer
★ dip coating process
1-1 Thermo plastic polyurethane (TPU) 1
1-1-1 The advances of TPU in medical aspect. 1
1-1-2 The insufficiency of anti-fouling properties 3
1-1-3 The previous studies of TPU modification 4
1-2 PVP and Zwitterionic polymers 8
1-2-1 PVP 8
1-2-2 Zwitterionic polymers 10
1-3 Polymer 2-(methacryloyloxy)ethyl phosphory lcholine (MPC) co 3-(tris(trimethylsiloxy)silyl)propyl methacrylate (TSM) (MPC-TSM) for surface modification 12
1-3-1 Characteristics of MPC and TSM monomer 12
1-3-2 Polymer MPC-TSM 15
1-4 BPA and Photo-grafting method 17
3-1 Material 21
3-1-1 Chemicals 21
3-1-2 Equipments 22
3-2 Methods 22
3-2-1 P(MPC-TSM) & P(MPC-TSM-BPA) Synthesis 22
3-2-2 Preparation pf TPU substrate 23
3-2-3 Preparation of CsMTxy-coated TPU catheter 23
3-2-4 Optimization of CsMTB coating process 23
3-2-5 Surface Characterization by Attenuated total reflection (ATR-FTIR) and Profilometer (Profilm3D) 23
3-2-6 Surface Elemental Composition Analysis by X-ray Photoelectron Spectrosopy (XPS) 24
3-2-7 Surface Wettability and Water Contact Angle 24
3-2-8 Surface Density Resonance Antifouling test (SPR) 25
3-2-9 Ultraviolet–Visible spectroscopy (UV-Vis) 25
3-2-10 Friction test 25
3-2-11 Observation and Analysis of Bacterial adhesion 26
3-2-12 Protein absorption test -Immunosorbent Assay (ELISA) 26
3-2-13 Dynamic Light Scattering (DLS) 27
3-2-14 Visosity & Surface tension 27
4-1 MPC-TSM 29
4-1-1 NMR Spectrum Analysis of MPC-TSM (1H NMR) 29
4-1-2 Preparation of CsMTxy-coated TPU catheter 30
4-1-3 Surface characterizations 33
4-1-4 Lubrication and Coating stability 38
4-1-5 Antifouling assays 43
4-1-6 Key factors affecting the coating process 48
4-2 MPC-TSM-BPA 57
4-2-1 NMR Spectrum Analysis of MPC-TSM (1H NMR) 57
4-2-2 Optimization of coating components for the preparation of CsMTB-coated catheter 58
4-2-3 The advancement of MTB material in increasing the stability for coating layer. 67
4-2-4. Excellent anti-fouling performance 74
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指導教授 黃俊仁 李宇翔(Chun-Jen Huang Yu-Hsiang Lee) 審核日期 2021-1-18
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