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研究生: 邱顯裕
Chiu, Hsien-Yu
論文名稱: 睪酮分子模版的吸附性質與電化學感測特性之研究
A study of adsorption properties and electrochemical sensing characteristics with imprinted polymer
指導教授: 楊明長
Yang, Ming-Chang
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: 2006
畢業學年度: 94
語文別: 中文
論文頁數: 118
中文關鍵詞: 分子模版交流阻抗睪酮
外文關鍵詞: Impedance, Testosterone, Molecularly imprinted polymer, Molecular imprinting, Silicon
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  • 本研究為睪酮分子模版(molecularly imprinted polymer, MIP)的分析應用,主要分成三部分。
    第一部分是合成對睪酮分子有高吸附性的塊狀模版,探討聚合時不同的單體與溶劑對模版吸附量與選擇性的影響。選擇MAA與HEMA兩種單體分別合成高分子,結果顯示,以MAA為單體的模版有較高的目標物吸附量74.8ppm與較佳選擇性4.5;而以環己烷比甲醇更適合當高選擇性模版的溶劑。
    第二部分為合成薄膜狀的分子模版,探討聚合溫度對吸附力的影響,以及模版對於目標物與競爭物的吸附性質。結果顯示,在45℃有最佳聚合溫度,模版對目標物的吸附量透過Scatchard’s plot可計算出內部的可辨識孔洞數0.41μmole /cm2•g與吸附平衡常數Ka = 9.85 ppm-1。
    第三部分則是薄膜分子模版的感測能力,吸附過的分子模版製成電極進行交流阻抗測試。實驗結果顯示,阻抗值隨著吸附液濃度增高與模版吸附量增多而減少。合成模版時,模印分子含量0.5g,單體/交聯劑比值為0.33時,有最高感測靈敏度。目標物與干擾物的感測現象相同但有不同的阻抗值。然而非分子模版卻因為孔洞沒有膨潤現象,使得阻抗值趨勢有不同的結果。每組數據均重複四次以上實驗,並取平均值所得之結果。

    In this study, the molecularly imprinted polymer (MIP) with testosterone was investigated in three parts.
    The first part refered to the synthesis of bulk polymers having a high affinity for testosterone. Various monomers and solvents for polymerization were examined in order to determine their influence on the binding amount and selectivity. Two kinds of monomers, methacrylic acid (MAA) and 2-hydroxyethylmethacrylate (HEMA), were used to prepare bulk MIP. It was found that the polymer synthesized with MAA monomer had higher selectivity (4.5) and adsorption amount (78.4ppm) than that with HEMA monomer; and the cyclohexane is a better porgen for selective MIP than methanol.
    In the second part, thin-film imprinted polymer was synthesized and investigated. The polymerization temperature effect and the adsorption properties for template and analog were in discussion. It were that there was a optimum polymerization temperature (45℃) for membrane MIP. By calculating the adsorption amount of the MIP through Scatchard’s plot, equilibrium constant (9.85 ppm-1) and the amount of recognition sites (0.41μmole /cm2•g) could be found.
    The last part is about the sensing ability of the membrane MIP. MIP electrodes was produced by the adsorbed thin film MIP and then tested A.C. Impedance spectroscopy. Charge transfer resistance of the adsorbed MIP decreased with the increase of the adsorption amount and adsorption solution concentration. The MIP composed with 0.5g template and 0.33 monomer/cross-linker ratio had the highest sensitivity. Sensing the template and the analog had the same phenomenon but different resistance values. Non-imprinted polymer had opposite electrochemical behavior compared with imprinted polymer because of the swelling effect of the recognition site. All data were got from experiments at least four times.

    目錄 中文摘要 i Abstract ii 目錄. iii 圖目錄. vii 表目錄. x 第一章 序論 1 1-1 前言 1 1-2 分子模版技術之簡介1 1-2-1 分子模版之組成2 1-2-2 分子模版技術之應用4 1-3類固醇分子模版之文獻回顧6 1-3-1 模版組成物質與形成6 1-3-2 分析方法9 1-3-3 睪酮、黃體素對於人體之影響12 1-4研究動機與目的15 第二章 原理16 2-1 分子模版技術16 2-1-1分子模版之原理16 2-1-2 目標物分子17 2-1-3 官能基單體18 2-1-4 交聯劑21 2-1-5 溶劑22 2-1-6 分子模版形式22 2-2 分子模版之偵測方法與原理24 2-2-1 電化學偵測24 2-2-2 重量偵測29 2-3 分析參數的定義 31 2-3-1 吸附力31 2-3-2 選擇性32 2-3-3 模印係數33 2-3-4 平衡常數33 第三章 實驗藥品設備及實驗步驟35 3-1 實驗藥品及儀器設備35 3-1-1 實驗藥品35 3-1-2 實驗儀器設備37 3-2 粉體分子模版研究之實驗步驟39 3-2-1 粉體分子模版之合成39 3-2-2 粉體分子模版之清洗40 3-2-3 粉體分子模版之吸附測試42 3-3 薄膜分子模版研究之實驗步驟44 3-3-1 矽晶片之清洗44 3-3-2 薄膜分子模版之合成44 3-3-3 薄膜分子模版之清洗及吸附測試45 3-3-4 薄膜分子模版之交流阻抗測試45 3-4 分子模版之分析 48 3-4-1 表面輪廓儀分析48 3-4-2 高效能層析儀分析50 2-2-1 電化學分析儀分析51 第四章 結果與討論52 4-1 塊狀分子模版52 4-1-1利用不同單體合成之塊狀分子模版52 4-1-2利用不同溶劑合成之塊狀分子模版58 4-2薄膜分子模版60 4-2-1吸附時間對分子模版吸附值的影響61 4-2-2聚合溫度對吸附值的影響64 4-2-3吸附液濃度對分子模版吸附值的影響64 4-2-4 Scatchard’s plot 68 4-2-5薄膜分子模版與非分子模版71 4-2-6薄膜分子模版吸附目標物與競爭物74 4-3由電子轉移阻抗感測目標物與競爭物濃度78 4-3-1平衡電位測試78 4-3-2薄膜分子模版感測行為81 4-3-3模印分子含量對電子轉移阻抗值的影響88 4-3-4分子模版單體/鎖鏈劑比例對電子轉移阻抗的影響91 4-3-5薄膜分子模版對目標物與競爭物的電子轉移阻抗97 4-3-6薄膜分子模版與非分子模版對目標物的感測靈敏度100 第五章 結論與建議105 5-1 結論105 5-1-1塊狀分子模版105 5-1-2薄膜分子模版105 5-1-3交流阻抗感測結果106 5-2 建議106 參考文獻108 附錄115

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