臺灣博碩士論文加值系統

本研究以聚砒硌於鎳和白金電極上製備出電化學式L-酪胺酸與D-酪胺酸分子模版感測器，此分子模版藉由形狀互補的作用進行辨識。在分子模版薄膜製備完成後，可施加正電壓誘導目標物分子吸附於薄膜上，並且以庫侖計算方法計算之。以L-酪胺酸與D-酪胺酸為目標物之分子模版其各自的選擇性分別為L/D＝9.4/1、D/L＝27.2/1，掃瞄的電位固定於-0.1V?＋0.5V（vs. Ag/AgCl）之間，掃瞄速率為0.1V/s，L-酪胺酸與D-酪胺酸在溶液中的濃度皆為5mM。分子模版的最佳辨識能力將被研究包括許多影響因素例如：目標物分子洗除時間、分子模版薄膜的厚度、目標物分子的濃度與掃瞄速率…等。L-酪胺酸與D-酪胺酸目標分子在聚砒硌的擴散將被探討，研究發現熱聚法與電聚法同樣可獲得高選擇性，電聚合法可以獲得比較緻密的結構，但是需要使用NaOH處理才能具有辨識活性，目標物分子與分子模版聚砒硌間的辨識機構將在本研究中做更深入探討。

Electrochemical sensors were fabricated on nickel and platinum electrodes by molecularly imprinting D and L tyrosine on polypyrrole films to form complementary cavities for subsequent template recognition. The performance of the imprinted films was evaluated by coulometry using an applied positive potential to induce adsorption of the target molecules. Using this procedure high enantioselectivities were found for each imprinted film. In this study, the most individual selectivities for L and D tyrosine on their respective imprinted films were estimated to be L/D=9.4/1 and D/L=27.2/1, determined by applying potential at a sweep rate of 0.1V/s from -0.1 to 0.5V (vs. Ag/AgCl) with the two enantiomers being present at the same concentration(5mM). Several factors affecting rebinding, such as: extraction time, film thickness, template concentration and sweep rate were investigated to achieve optimum recognition ability. The diffusion of target molecules in the polypyrrole films was also examined. Both thermal polymerization and eletropolymerization methods can be used to prepare a tyrosine imprinted film with high selectivity. A closed pack structure of tyrosine imprinted polyprrole film is obtained by eletropolymerization with CV, but NaOH treatment is needed to activate the rebinding of the film. A recognition mechanism for the interaction of the polypyrrole film for its template under the influence of an applied positive potential is proposed in this study.

摘要I
英文摘要II
誌謝III
總目錄IV
表目錄VII
圖目錄VIII
第一章 文獻回顧1
1-1 導電性高分子1
1-1-1 簡介1
1-1-2 導電性高分子的特性3
1-1-3 導電性高分子之應用3
1-2 砒硌（Pyrrole）的結構與電化學行為4
1-3 胺基酸簡介5
1-3-1 胺基酸的性質5
1-3-2 胺基酸的分類11
1-4 酪胺酸的重要性及其應用12
1-5 研究動機13
第二章 原理16
2-1 分子模版技術16
2-1-1 分子模版技術的發展16
2-1-2 分子模版的製作過程18
2-2 分子模版聚合物於生物感測器上的應用28
2-3 電化學感測器的影響因素31
2-3-1 電極材料的選擇31
2-3-2 電解液的影響32
2-3-3 pH值的影響32
2-3-4 攪拌速率與溫度的影響33
2-3-5 聚砒硌與酸性物質結合時的反應機構33
2-4 藥物與生化分子辨識（Recognition）及鏡像選擇性（enantioselection）的應用33
2-4-1 親合性分離33
2-4-2 擬生物感測器（Bio-mimetic sensor）與智慧型分子模版34
第三章 實驗方法36
3-1 藥品與儀器設備36
3-1-1 藥品36
3-1-2 儀器設備37
3-2 電化學之原理及設備裝置介紹38
3-3 分子模版電極的製備42
3-3-1 工作電極的前處理42
3-3-2 熱聚合製備分子模版電極42
3-3-3 電聚合製備分子模版電極43
3-4 分子模版電極中目標物分子的洗除43
3-4-1 洗除以熱聚合方法製備的分子模版中之目標物分43
3-4-2 洗除以電聚合方法製備的分子模版中之目標物分子44
3-5 分子模版之表面結構觀察44
3-6 tyrosine/PPy分子模版之電化學測試44
3-7 吸附值的計算45
3-8 掃描式電子顯微鏡46
第四章 分子模版聚砒咯於鎳電極之特性探討48
4-1 鎳電極的簡介48
4-2 分子模版吸附行為50
4-3 分子模版萃取時間的影響52
4-4 D-與L-酪胺酸之分子模版交叉選擇性之測試54
4-5 目標物分子濃度與辨識的關係56
4-6 分子模版厚度對選擇性的影響59
4-7 由SEM觀察薄膜結構61
4-8 掃描速度對分子模版選擇性的影響63
4-9 分子模版中的擴散效應65
4-10 干擾物的影響67
4-11 分子模版機構討論69
4-12 pH值對分子模版選擇性的影響71
第五章 分子模版聚砒硌於鉑電極上的特性討論73
5-1 以熱聚法合成酪胺酸分子模版73
5-1-1 分子模版的洗除測試73
5-1-2 不同電壓下的濃度對電流的I - t行為75
5-1-3 由SEM觀察分子模版表面結構77
5-1-4 pH值對分子模版選擇性的影響79
5-2 以電聚法製備酪胺酸分子模版81
5-2-1 以NaOH處理的影響81
5-2-2 單體比例對選擇性的影響83
5-2-3 電聚合厚度條件的影響85
5-2-4 干擾性物質的測試87
5-3 熱聚合與電聚合方法的比較89
第六章 結論91
參考文獻92

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