臺灣博碩士論文加值系統

本研究使用分子模版技術以電聚合成法製備色胺酸分子感測電極，利用電化學方法探討其鏡像分子間辨識的選擇性，以及用循環伏安(CV)法分析其在白金電極上之電活性行為。研究發現在電壓+0.8 V~+1.0 V(vs. Ag/AgCl)之間，色胺酸分子在白金電極上出現強吸附的氧化電流峰，此訊號為色胺酸分子苯環結構上之π電子轉移所造成的氧化峰；相關的電活性分子對白金電極的作用電流大小將在本文一併做比較。
再者，以導電性高分子聚砒硌於白金電極上所製備出L與D-色胺酸分子模版感測器，在適當前處理條件下，再利用NaOH溶液進行對目標分子萃取，再以正電壓選擇性誘導吸附目標物分子於薄膜電極上，而後以庫倫方法計算其吸附量。本實驗分別以L與D-色胺酸製作成其分子模版感測電極，其選擇性分別為：L/D=17.8±2.4、D/L=15.1±1.2 ，電位範圍於-0.3 V~+1.2 V(vs. Ag/AgCl)，掃描速率為0.1 V/sec，L與D-色胺酸在待測液中之感測濃度為10 mM。本研究並討論辨識能力之影響因素，包括：前處理條件、目標物分子之移除方式、不同目標物分子濃度、電聚合時間、掃描速率等。

In this research, trytophan sensing electrodes were prepared by molecular imprinting technique through electropolymerization process. The entro-selectivity of the electrode was investigated by using electrochemical method. And behaviors of the electro-active molecule were analyzed by CV method. The results revealed that strong peak of anodic current of trytophan appeared between 0.8 V to 1.0 V(vs. Ag/AgCl) from its π electron transfer. The interactions of related electro-active molecules were compared in the text.
Furthermore, conducting polymer, polypyrrole, was used to prepared L and D trytophan imprinted electrode. Under some pretreatment condition, the target molecule was extracted from the imprinted electrode in NaOH solution. Then, its rebinding was induced by positive potential and quantitative adsorption was evaluated by coulomb method. The selectivity of the D and L- trytophan imprinted electrode was estimated respectively as: L/D=17.8±2.4, D/L=15.1±1.2 under the conditions: potential range -0.3 V~+1.2 V(vs. Ag/AgCl), scan rate: 0.1 V/sec, in 10 mM sample solution. This study will discuss the recognition ability affected by many factors including: pretreatment condition, extraction method of target molecules, concentration of target molecules, electropolymerization time, scanning rate, etc.

中文摘要I
英文摘要II
誌謝III
總目錄V
表目錄VII
圖目錄VIII
第一章 緒論1
1-1 前言1
1-2 分子辨識之要素2
1-3 導電性高分子簡介6
導電性高子之特性8
導電性高分子之應用9
1-4 砒硌（Pyrrole，Py）之電化學行為與聚合結構10
1-5 胺基酸之簡介11
1-6 目標物分子-色胺酸在人體內之重要性12
1-7 研究動機12
第二章 原理14
2-1 分子模版之起源與發展14
2-2 分子模版之原理15
2-3 製備分子模版所需之材料22
2-3-1 目標分子的選擇22
2-3-2 交聯劑23
2-3-3 功能性單體24
2-3-4 溶劑25
2-4 分子模版之應用領域26
2-4-1 分離26
2-4-2 生物感測器裝置28
2-4-3 催化作用與合成酵素28
2-4-4 抗體和鍵結位向模仿的接收體29
2-5 實際產品之開發30
2-6 電化學感測原理30
第三章 實驗方法31
3-1 藥品31
3-2 設備與電極材料32
3-3 分析儀器33
3-4 電化學系統介紹34
3-5 QCM原理38
震盪頻率與吸附質量的關係式-Sauerbrey Equation39
3-6 實驗流程41
3-7 實驗方法42
3-7-1 鉑工作電極前處理42
3-7-2 電聚合成分子模版電極42
3-7-3 分子模版電極中目標物分子之萃取43
3-7-4 電化學感應測試43
3-7-5 吸附值之計算(庫倫法)43
第四章 色胺酸分子的電活性行為分析45
4-1 不同電極鉑和鎳材料與色胺酸分子的作用行為45
4-2 干擾分子之電活性測試47
4-3 色胺酸分子氧化還原作用原理52
4-4 色胺酸不可逆的吸附現象54
4-5 石英晶體震盪測試56
4-6 掃描速率之影響58
4-7 不同pH之影響59
4-8 不同濃度之影響60
第五章 分子模版聚砒硌於鉑電極之特性探討62
5-1 CV前處理62
5-2 NaOH萃取過程65
5-3 L-與D-色胺酸之分子模版交叉選擇性測試68
5-4 CP聚合時間之影響70
5-5 掃描速率之影響72
5-6 目標物分子濃度與辨識之關係74
第六章 結論77
參考文獻79
表目錄
Table 2-1 共價鍵鍵結18
Table 2-2 非共價鍵鍵結19
Table 2-3 自組性與預組性系統之比較20
Table 2-4 單體與分析物結合方式之特性表21
Table 2-5 各式不同用途的目標物分子22
Table 2-6 分子模版實際應用的領域26
Table 5-1 不同CV前處理圈數下L-色胺酸分子模版薄膜之吸附庫倫值與選擇性之比較64
Table 5-2 不同CP電聚合時間下L-色胺酸分子模版薄膜之吸附庫倫值與選擇性之比較71
Table 5-3 不同掃描速率下L-色胺酸分子模版薄膜之吸附庫倫值與選擇性之比較73
Table 5-4 不同感測濃度下目標物分子L-色胺酸與干擾性分子D-色胺酸對L-色胺酸分子模版薄膜之吸附庫倫值與選擇性之比較75
圖目錄
Figure 1-1 Different kinds of electrostatic interaction3
Figure 1-2 Hydrogen bonding3
Figure 1-3 Van der waals interaction4
Figure 1-4 Hydrophobic interaction4
Figure 1-5 常見的導電性聚合物7
Figure 1-6 聚砒硌的兩種不同聚合結構10
Figure 1-7 胺基酸於生理pH值中所存在的兩極性離子11
Figure 1-8 D-和L-色胺酸的化學構造12
Figure 2-1 分子模版製作過程示意圖16
Figure 2-2 交聯劑的種類23
Figure 2-3 用於自組性分子模版製作之功能性單體的選擇24
Figure 3-1 電化學系統之電極反應中可改變的參數36
Figure 3-2 一般電化學系統裝置圖37
Figure 3-3 石英晶體在交流電場中受交流電場影響的震盪示意圖38
Figure 3-4 庫倫法計算示意圖(特徵峰經由時間t1至t2所圍的面積即為吸附之庫倫值可由電流值I對時間t積分得到)44
Figure 4-1 色胺酸分子對不同電極材料(a)鉑與(b)鎳，的CV行為比較，10 mM色胺酸，掃瞄速率0.1 V/sec，pH=6.6。46
Figure 4-2 不同分子對鉑電極的CV行為(a)色胺酸(b)酪胺酸(c)硝基酪胺酸(d)麩胺酸(e)離胺酸(f)苯丙胺酸(g)苯甲酸，10 mM待測液，掃描速率0.1 V/sec，pH=6.6。51
Figure 4-3 色胺酸分子對鉑電極的CV行為(a)背景緩衝溶液(b)色胺酸，10 mM待測液，掃描速率0.1 V/sec，pH=6.6。53
Figure 4-4 色胺酸分子對鉑電極不可逆吸附作用的CV行為，色胺酸濃度10 mM，掃描速率0.1 V/sec，pH=6.6。55
Figure 4-5 色胺酸分子對鉑電極的吸附作用之CV行為與EQCM變化，色胺酸濃度10 mM，掃描速率0.1 V/sec，pH=6.6。57
Figure 4-6 在不同掃描速率下色胺酸分子對鉑電極的CV行為，色胺酸濃度為10 mM，pH=6.6。58
Figure 4-7 在不同pH下色胺酸分子對鉑電極的CV行為，色胺酸濃度10 mM，掃描速率0.1 V/sec。59
Figure 4-8 在不同濃度下色胺酸分子對鉑電極的CV行為，掃描速率0.1 V/sec，pH=6.6。60
Figure 4-9 在不同色胺酸濃度下之峰電流(IP)關係圖，掃瞄速率0.1 V/sec，pH=6.6。61
Figure 5-1 不同CV前處理(a)無前處理(b)10圈(c)20圈，之L-色胺酸分子模版薄膜對目標物分子L-色胺酸與鏡像干擾性分子D-色胺酸的CV辨識圖譜，待測液10 mM，pH=6.6，掃描速率0.1 V/sec。63
Figure 5-2 CV前處理圈數與選擇性之趨勢關係圖64
Figure 5-3 L-色胺酸分子模版薄膜先經過(a)L-色胺酸待測液(b)D-色胺酸待測液CV前處理後在100 mM，pH=13的NaOH萃取溶劑下之CV萃取過程圖，掃描速率0.1 V/sec。66
Figure 5-4 L-色胺酸分子模版薄膜在不同萃取過程下之CV辨識圖譜(a)無萃取(b)CV萃取90圈(c)CV萃取100圈(d)CV萃取150圈，100 mM，pH=13的NaOH萃取溶劑，色胺酸待測液10 mM，pH=6.6，掃描速率0.1 V/sec。67
Figure 5-5 L-和D-色胺酸分子再吸附於(a)L-色胺酸分子模版(b)D-色胺酸分子模版的CV辨識圖譜，色胺酸待測液10 mM，pH=6.6，掃描速率0.1 V/sec。69
Figure 5-6 CP電聚合時間與選擇性之趨勢關係圖71
Figure 5-7 Log掃描速率與選擇性之趨勢關係圖73
Figure 5-8 不同感測濃度與選擇性之趨勢關係圖76

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