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研究生： 陳毅祥
Chen, Yi-Hsiang
論文名稱： 具膽紅素模版高分子外層矽球載體之製備及對膽紅素吸附之探討
Preparation of silica spherical carriers coated with bilirubin imprinted polymer shell and the investigation on the adsorption of bilirubin
指導教授： 許梅娟
Syu, Mei-Jywan
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： 49
中文關鍵詞： 膽紅素 、分子模版高分子 、奈米氧化矽球
外文關鍵詞： bilirubin, molecularly imprinted polymer, nano silica particle
相關次數： 點閱：114  下載：0 
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    • 膽紅素 (Bilirubin)，為血紅素 (hemoglobin) 蛋白質代謝分解之產物，其濃度高低可反映出肝膽功能之正常與否。正常人體每日可以生成 250 ~ 350 mg 的膽紅素，在生理檢測上，總膽紅素 (total bilirubin) 濃度的標準值為 0.2 ~ 1.5 mg/dL，直接膽紅素 (direct bilirubin) 的標準值則小於 0.4 mg/dL，兩者之間的差值即為間接膽紅素 (indirect bilirubin) 的濃度。當人體總膽紅素濃度大於 2 mg/dL，即膽紅素濃度偏高，代謝不正常，因此會出現黃疸現象。因此對血中膽紅素濃度之檢測就極為重要。
    為了達到較優之吸附專一性，於本研究中引用分子模版高分子之觀念，乃是藉由功能性單體與目標模版分子膽紅素作用先形成複合物，再依序加入交聯劑、起始劑進行聚合，其中交聯劑對模版材料形成孔洞結構之穩定性與保有性扮演極重要的角色。再以適當溶劑萃洗或化學斷鍵，自高分子中移除內含之膽紅素，即可得具特定孔洞的模版高分子。
    於製備具膽紅素特定吸附孔洞之模印高分子，本研究之特色在於：在聚合過程中摻混奈米二氧化矽球 (NSP, nano silica particles)，並以矽醇修飾其表面，因此使模版分子膽紅素可與矽球表面作用，以利模版高分子膜更牢固地形成於矽球表面；除此之外，使用相對低含量的交聯劑，試圖在奈米矽球擔體形成較均勻之薄層模版材料，以避免機械研磨對模版材料專一吸附孔洞之破壞。矽球表面修飾用的矽醇乃是選用具化學官能基的 3-aminopropyltriethoxysilane (APTES)，再將 methacrylic acid (MAA) 與之偶合接枝形成 MAA-APTES-NSP，接著再加入單體 MAA、交聯劑 ethylene glycol dimethacrylate (EGDMA) 及 起始劑 2,2-azo-bis-isobutyronitrile (AIBN) 進行熱起始聚合。
    分別以 SEM、TEM、TGA 進行分析鑑定，已成功將 MIP 聚合在 NSP 矽球表面。檢測吸附結果，對膽紅素之模印因子可達 3.676 ± 0.260。以胎牛血清進行對膽紅素專一吸附之干擾測試，得到模印因子也有 1.445 ± 0.044。結果顯示，本研究製備的 MIP-NSP 載體 確實具有對膽紅素分子特異吸附之孔洞。

    Molecularly imprinted polymer (MIP) was prepared by interaction between the template molecule and the functional monomer. During the polymerization, the cross-linker was added to create a three-dimensions matrix to confine the template molecule. Later, remove the template molecule by solvent extraction or break the chemical bonding away from polymer. Then , in this way, we get the MIP who has specific cavities can recognize the template molecule.
    In this research, try to made surface coated bilirubin imprinted polymer. The spherical carrier choose nano silica particles (NSP) because NSP is easy to make an monodisperse particle diameter by stöber method. And NSP surface modified by 3-aminopropyltriethoxysilane (APTES). Meth acrylic acid (MAA) was monomer, ethylene glycol dimethacrylate (EGDMA) was cross-linker, and initiate polymerization by heated. In here, choose 2,2-azo-bis-isobutyronitrile (AIBN) as initiator.The results indicate that NSP was coated with bilirubin-imprinted polymer shell. The imprinted factor was 3.676 ± 0.260 in aqueous solution and 1.445 ± 0.044 in fetal bovine serum.

    第一章 緒論 1 1-1 分子模版高分子 (Molecularly imprinted polymer, MIP) 1 1-1-1 製備流程 2 1-1-2 分子模版高分子的組成 2 1-1-2-1 模版分子 2 1-1-2-2 功能性單體 3 1-1-3-3 交聯劑 3 1-1-3-4 溶劑 4 1-1-4 模印型態 4 1-1-4-1 非共價性模印 4 1-1-4-2 共價性模印 5 1-1-4-3 共價與非共價式模印 5 1-1-5 聚合方式 5 1-1-6 分子模版高分子近期發展 6 1-2 生物化學感測器 6 1-2-1 生化感測元件 (Biological sensing element) 6 1-2-2 生化感測分析 8 1-2-2-1 光學式感測器 8 1-2-2-2 質量式感測器 8 1-2-2-3 電化學感測器 (Electrochemical sensor) 8 1-3 氧化矽球 (Silica particle) 9 1-4 膽紅素 (Bilirubin) 10 1-4-1 膽紅素的生成 10 1-4-2 膽紅素在血液中的輸送 11 1-4-3 黃疸症狀 (Jaundice) 12 1-4-4 膽紅素結構 13 1-4-5 膽紅素之檢測方法 15 第二章 實驗方法與材料 17 2-1 膽紅素的測定 17 2-1-1 呈色法 17 2-2 氧化矽球 (Nano silica particle, NSP) 製備與修飾 19 2-2-1 氧化矽球表面接枝 APTES (APTES-NSP) 19 2-2-2 將APTES開環合成APTES-MAA (APTES-MAA-NSP) 19 2-3 膽紅素模版高分子(膽紅素 MIP)之製備 19 2-3-1 膽紅素 MIP 模印效果之測試 19 2-3-2 膽紅素 MIP 選擇性吸附測試 20 2-3-3 於胎牛蛋白血清(fetal bovine serum, FBS)中對膽紅素之吸附測試 20 2-4 模版高分子物性分析 23 2-4-1 掃描式電子顯微鏡 23 2-4-2 穿透式電子顯微鏡 23 2-4-3 熱重分析儀 23 2-4-4 傅立葉紅外線光譜儀 23 2-5 實驗藥品目錄 24 2-6 實驗儀器目錄 25 第三章 結果與討論 26 3-1 FT-IR 圖譜分析 27 3-2 氧化矽球與模版高分子的表面及結構分析 29 3-3 模印高分子製備條件討論 36 3-3-1 不同的矽烷基團於 NSP 表面接枝之差異 36 3-3-2單體種類的影響 38 3-3-3 交聯劑配比之改變 39 3-4 選擇性與干擾性測試 41 3-4-1 膽紅素與膽綠素的選擇性 41 3-4-2 血清之干擾性感測 42 3-5 空白吸附驗證 44 第四章 結論 45 參考文獻 46

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