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研究生： 陳柏誠
Chen, Bo-chen
論文名稱： 以γ-聚麩胺酸改質聚酯型脂肪族聚氨基甲酸酯之製備、特性與血小板貼附性研究
Preparation, characterization, and platelet adhesion of gamma-poly(glutamic acid)-modified aliphatic poly(ester ureathane)s
指導教授： 林睿哲
Lin, Jui-che
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2008
畢業學年度： 96
語文別： 中文
論文頁數： 58
中文關鍵詞： 聚氨基甲酸酯 、聚麩胺酸 、血液相容性
外文關鍵詞： Blood compatibility, Gamma-poly(glutamic acid), Polyurethane
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    • 本研究使用1,6-己二異氰酸酯、聚己內酯與1,4-丁二醇合成具有不同平均硬鏈長度的脂肪族聚氨基甲酸酯，再將其摻混不同量的天然高分子聚麩胺酸來改善聚氨基甲酸酯的血液相容性。利用傅利葉紅外線光譜儀、微差掃描熱卡儀、吸水量測量、接觸角測試儀及體外血小板貼附實驗來探討加入聚麩胺酸對高分子的整體性質、表面性質及血液相容性的影響。研究結果顯示聚麩胺酸改質後的聚氨基甲酸酯具有較低的硬鏈段結晶區域熔融溫度、較小的接觸角及較高的吸水量，體外血小板貼附實驗結果得知，將聚麩胺酸摻混至聚氨基甲酸酯內，會降低血小板在聚氨基甲酸酯表面上的貼附數目及活化程度。

    Aliphatic polyurethanes based on 1,6-hexanethylene diisocyanate, polycaprolactone and 1,4-butanediol were synthesized. The polyurethanes with different average length of hard segments were blended with various weight percentage of poly(γ-glutamic acid) (γ-PGA), a natural polymer, to improve their blood compatibility. The polymer's bulk, surface and platelet-contacting properties were studied using Fourier transform infrared spectrophotometry, differential scanning calorimetry, water absorption analysis, static contact angle analysis and in vitro platelet adhesion experiments. The effects of γ-PGA incorporation on the thermal transition property, hydrophilicity/hydrophobicity and platelet-contacting property of the polyurethanes are discussed. γ-PGA modified polyurethanes exhibit a lower melting temperature of hard segment domains, smaller contact angle, and higher water absorption value than the polyurethanes without γ-PGA. In vitro platelet adhesion studies indicated that the addition of γ-PGA into aliphatic polyurethanes leads to a reduction in platelet adhesion and activation.

    目錄 目錄 ………………………………………………………………Ⅰ 圖目錄 ………………………………………………………………Ⅳ 表目錄 ………………………………………………………………Ⅴ 第一章 緒論…………………………………………………………1 1-1 生醫材料簡介………………………………………………1 1-2 凝血機制……………………………………………………4 1-2-1 血小板構造…………………………………………………4 1-2-2 血小板機能…………………………………………………5 1-3 聚氨基甲酸酯………………………………………………6 1-4 聚氨基甲酸酯組成…………………………………………7 1-4-1 二異氰酸酯…………………………………………………7 1-4-2 軟鏈段………………………………………………………10 1-4-3 鏈延長劑……………………………………………………11 1-4-4 催化劑………………………………………………………12 1-5 聚氨基甲酸酯生醫材料……………………………………13 1-6 研究動機……………………………………………………14 第二章 文獻回顧……………………………………………………16 2-1 影響血液相容性的因素……………………………………16 2-1-1 親水性表面…………………………………………………16 2-1-2 微相分離結構的表面………………………………………17 2-1-3 具有生物活性分子的表面…………………………………17 2-1-4 負電荷的表面………………………………………………19 2-2 聚己內酯……………………………………………………21 2-3 聚麩胺酸……………………………………………………21 第三章 實驗內容……………………………………………………24 3-1 藥品…………………………………………………………24 3-2 合成…………………………………………………………27 3-2-1 合成脂肪族聚氨基甲酸酯…………………………………27 3-2-2 酸處理γ-PGA………………………………………………28 3-2-3 γ-PGA摻混脂肪族聚氨基甲酸酯…………………………28 3-3 儀器設備……………………………………………………29 3-3-1 整體性質分析………………………………………………29 3-3-2 表面性質分析………………………………………………31 3-3-3 血小板貼附性分析…………………………………………32 第四章 結果與討論…………………………………………………34 4-1 聚氨基甲酸酯組成與分子量………………………………34 4-2 傅利葉紅外線光譜分析……………………………………36 4-3 熱轉移行為…………………………………………………38 4-4 吸水率………………………………………………………42 4-5 水面下水接觸角……………………………………………44 4-6 血小板貼附實驗……………………………………………46 第五章 總結與未來展望……………………………………………50 參考文獻 ………………………………………………………………51 圖目錄 Figure 1-1.　The structure of commercial medical polymer: (a) PU, (b) silicon rubber, (c) PVC, (d) Nylon, (e) PMMA, (f) Teflon, and (g) Dacron…………………………………………3 Figure 1-2.　Structure of the platelet…………………………4 Figure 1-3.　The main reaction between isocyanates and (a) alcohol,(b) amine, and (c) water…………………………………8 Figure 1-4.　Typical catalysts used for polyurethane synthesis………………………………………………………………12 Figure 2-1.　Structures of heparin sulfate and heparin…………………………………………………………………18 Figure 2-2.　Structures of (a) ionic γ-PGA, and (b)γ-PGA………………………………………………………………………22 Figure 3-1.　Synthesis scheme for the preparation of the polyurethanes…………………………………………………………27 Figure 3-2.　Measure the contact angle by captive bubble method…………………………………………………………………31 Figure 4-1.　FTIR spectra of γ-PGA, PU, and γ-PGA/PU blend……………………………………………………………………37 Figure 4-2.　DSC thermographs of the PU1, PU2, and Pellethane……………………………………………………………40 Figure 4-3.　DSC thermographs of (a) γ-PGA/PU1, and (b) γ-PGA/PU2…………………………………………………………………41 Figure 4-4.　SEM photographs after 1 h of platelet adhesion for (a) Pellethane, (b) PU1, and (c) PU2…………47 Figure 4-5.　SEM photographs after 1 h of platelet adhesion for (a) PU1-G5, (b) PU1-G7.5, (c) PU1-G10, (d) PU1-12.5, and (e) PU1-G15…………………………………………48 Figure 4-6.　SEM photographs after 1 h of platelet adhesion for (a) PU2-G5, (b) PU2-G7.5, (c) PU2-G10, (d) PU2-12.5, and (e) PU2-G15…………………………………………49 表目錄 Table 1-1.　Cooper’s classification scheme for platelet adsorption………………………………………………………………6 Table 1-2.　Typical diisocyanates used for polyurethane synthesis………………………………………………………………9 Table 1-3.　Typical polyol soft segments used for polyurethane synthesis……………………………………………10 Table 1-4.　Typical chain extenders used for polyurethane synthesis………………………………………………………………11 Table 3-1.　The composition of Hepes-Tyrodes buffer solution………………………………………………………………33 Table 4-1.　The composition and molecular weights of polyurethanes…………………………………………………………35 Table 4-2.　Element analysis of polyurethanes………………35 Table 4-3.　Thermal analysis data………………………………39 Table 4-4.　Water absorption data………………………………43 Table 4-5.　Captive bubble (underwater) static contact angle……………………………………………………………………45

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