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研究生： 陳姵珊
Chen, Pei-Shan
論文名稱： 酸鹼敏感型聚胺基酸水膠：特性探討及仿生多孔性複合材料之合成
pH-Sensitive Polypeptide Hydrogels: Characterization and Biomimetic Synthesis of Porous Oxides
指導教授： 詹正雄
Jan, Jeng-Shiung
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： 2011
畢業學年度： 99
語文別： 中文
論文頁數： 113
中文關鍵詞： 聚胺基酸 、水膠 、複合材料 、交聯 、仿生合成 、二氧化矽
外文關鍵詞： polypeptide, hydrogels, hybrid materials, crosslink, biomimetic synthesis, porous silica
相關次數： 點閱：144  下載：7 
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    • 本研究是利用聚胺基酸高分子(polypeptide)上的胺基與交聯劑(genipin)進行反應後製備出具有酸鹼敏感型的水膠，藉由改變聚胺基酸高分子的分子量、親疏水鏈段比、聚胺基酸溶液濃度以及加入交聯劑與高分子的莫耳數比進行調控和探討水膠物理性質的變化，並可利用仿生合成方法進行有機/無機複合材料的製備，最後將有機物質經由鍛燒去除可得到仿生多孔性的二氧化矽。
    在第一部分的研究中，我們控制胺基酸的分子量及親疏水鏈段比再經由開環聚合後就可得到聚胺基酸高分子，接著再加入交聯劑於聚胺基酸溶液中即可製備出聚胺基酸水膠。藉由交聯時間及膨潤比測量、機械強度以及生物毒性測試、FTIR和SEM來瞭解聚胺基酸水膠的物理性質，並做進一步的探討。從交聯時間及機械強度的結果中發現聚胺基酸的分子量、親疏水鏈段比、聚胺基酸溶液濃度以及交聯劑莫耳數比皆會影響物理性質；由FTIR中可發現聚胺基酸高分子經過交聯反應後二級結構會有些許的改變；由SEM可觀察到水膠的結構是具有高孔洞性及孔洞大小約為10~30 μm；膨潤比的結果可得知聚胺基酸水膠的膨潤比會隨酸鹼值不同而有改變；材料生物毒性的測試說明聚胺基酸經過交聯反應後可提高細胞的存活率。
    第二部分的研究是利用仿生合成方法進行製備聚胺基酸-二氧化矽之有機/無機複合水膠材料。由TGA結果顯示控制矽化作用時間可得到不同有機/無機含量的複合材料；從FTIR的結果中可確定有二氧化矽的形成；在機械強度測試中可知聚胺基酸-二氧化矽複合水膠材料的強度會隨著矽化作用時間增加而下降；而聚胺基酸-二氧化矽複合水膠材料經由生物毒性測試後可得知此材料對於纖維母細胞來說是不具有生物毒性，故此新穎複合材料極具有潛力可應用於蛋白質/藥物的包覆及傳輸，以及組織工程中；最後再經由鍛燒後的TEM及BET結果可得知二氧化矽是具有多孔性的結構，且此孔洞大小的主要分布是介於2~10 nm。

    In this study, pH-sensitive polypeptide hydrogels were prepared by using genipin to crosslink amine groups on polypeptide. We investigated the influence of the molecular weight of polypeptide, ratio of hydrophilic and hydrophobic segments, polypeptide solution concentration and molar ratio of genipin and polypeptide on the properties of the as-prepared hydrogels. The polypeptide-silica organic/inorganic hybrid materials can be prepared using biomimetic synthesis approach. According to our study, the obtained silicas after calcination were porous.
    In the first part, homopolypeptides and amphiphilic block copolypeptides with different molecular weights or block ratios were via the ring-opening polymerization and genipin was used to crosslink these polypeptides in aqueous solution to form hydrogels. The properties of as-prepared hydrogels were characterized by a variety of analytical techniques including gelation time and swelling ratio measurements, compression and cytotoxicity tests, FTIR, and SEM. The results show that the gelation time and compressive modulus were influenced by the molecular weight, block ratio, polypeptide concentration, and the molar ratio of genipin and polypeptide. FTIR analysis revealed that the polypeptides underwent conformational changes after crosslinking reaction. The structure of hydrogels was found to be highly porous with sizes between 10 and 30 μm by SEM characterization. The degree of swelling was found to vary with the solution conditions (that is, pH value). The cytotoxicity tests suggested that the genipin-crosslinked polypeptide hydrogels can enhance the cell viability comparing with the polypeptides without crosslinking.
    The second part demonstrated that the polypeptide-silica organic/inorganic hybrid materials can be prepared using biomimetic synthesis approach. TGA analysis showed that the weight ratio of the organic and inorganic compounds in the hybrid materials can be controlled by varying the silification time. FTIR analysis revealed that the covalent bond formation between polypeptide and silica. The compressive strength of polypeptide-silica hydrogel was decreased with increasing the silification time. The as-prepared hybrid materials were found to be not cytotoxic to fibroblast cells, so these novel hybrid materials have potential applications including protein/drug delivery, encapsulation, and tissue engineering. Based on TEM and BET characterization, the silicas obtained by calcination were to found be highly porous with sizes mainly between 2 and 10 nm.

    摘要 I Abstract III 誌謝 V 目錄 VI 圖目錄 XI 表目錄 XVII 第一章 緒論 1 1.1 前言 1 1.1.1 生物性材料簡介 1 1.1.2 水膠的發展 3 1.2 研究動機與目的 4 第二章 文獻回顧 5 2.1 胺基酸基本性質 5 2.1.1 簡介胺基酸及其結構 5 2.1.2 蛋白質的結構 8 2.2 水膠的定義與種類 12 2.2.1 水膠的定義 12 2.2.2 智慧型水膠的種類 12 2.3 水膠的物理性質 16 2.3.1 膨潤行為理論 16 2.4有機/無機複合材料 19 2.4.1 生物材料與礦化作用的發展 19 2.4.2 有機/無機複合材料簡介 20 2.4.3 聚賴胺酸沉析二氧化矽 21 2.5多孔性複合材料 26 2.5.1 中孔洞二氧化矽的重要性 27 2.5.2 中孔洞二氧化矽發展 28 第三章 實驗步驟與實驗原理 30 3.1 實驗藥品與儀器設備 30 3.1.1 實驗藥品 30 3.1.2 儀器設備 32 3.2 聚胺基酸高分子之合成 34 3.2.1 起始劑之合成 34 3.2.2 溶劑之乾燥方式 34 3.2.3 胺基酸之N-carboxyanhydrides(NCAs)的製備 35 3.2.4 聚胺基酸之開環反應 36 3.2.5 聚胺基酸之保護基(R-group)去除 37 3.3 聚胺基酸水膠之物理性質測試 38 3.3.1 聚胺基酸水膠之製備 38 3.3.2 聚胺基酸水膠之凝膠時間點(Gelation time)測試 38 3.3.3 聚胺基酸水膠之膨潤比測試 38 3.3.4 聚胺基酸水膠之機械性質 39 3.3.5 聚胺基酸水膠之生物毒性測試 39 3.4 聚胺基酸水膠之二氧化矽複合材料製備 40 3.4.1 聚胺基酸水膠之沉析無機物 40 3.4.2 聚胺基酸水膠之中孔複合材料製備 40 3.5 特性分析與性質測試 40 3.5.1 核磁共振光譜儀 40 3.5.2 凝膠滲透層析儀 41 3.5.3 高解析場發射掃描式電子顯微鏡 43 3.5.4 穿透式電子顯微鏡 44 3.5.5反射式紅外線光譜儀 45 3.5.6 紅外線光譜儀 46 3.5.7 圓二色光譜儀 47 3.5.8 萬能材料試驗機 49 3.5.9 熱重分析儀 50 3.5.10 氮氣吸脫附儀 51 第四章 結果與討論 57 4.1聚胺基酸高分子之定義 57 4.1.1聚胺基酸高分子之比例 57 4.1.2 聚胺基酸高分子之分子量與鏈長 60 4.2聚胺基酸水膠之物理性質 62 4.2.1聚胺基酸水膠之形成 62 4.2.2聚胺基酸水膠之交聯時間(Gelation time) 65 4.2.3聚胺基酸水膠之二級結構變化 69 4.2.4聚胺基酸水膠之型態與構造 75 4.2.5聚胺基酸水膠之膨潤比(Swelling ratio) 78 4.2.6聚胺基酸水膠之機械強度 81 4.2.7聚胺基酸水膠之生物毒性測試 85 4.3仿生多孔性複合材料 86 4.3.1 聚胺基酸-二氧化矽複合水膠材料之製備 86 4.3.2 聚胺基酸-二氧化矽複合水膠材料之二級結構 89 4.3.3 聚胺基酸-二氧化矽複合水膠材料之機械強度 91 4.3.4 聚胺基酸-二氧化矽複合水膠材料之生物毒性 93 4.3.5 二氧化矽複合材料之形態 94 4.3.6二氧化矽複合材料之中孔(mesopore)特性 97 第五章 結論 105 參考文獻 108

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