臺灣博碩士論文加值系統

利用電化學聚合法製作掌性聚苯胺薄膜，探討添加苯胺雙體對於聚苯胺薄膜掌性形成的影響，並調整各項電聚合參數，如聚合時間、苯胺單體與掌性摻雜酸的濃度比例、聚合時的pH值、氧化還原態的控制、摻雜非掌性酸、改用苯胺單體的衍生物電聚合等，找出最佳掌性聚苯胺薄膜的合成條件，並使用循環伏安法分析電化學性質、紫外光－可見光光譜鑑定分子型態、原子力顯微鏡來觀測表面狀態。此外亦探討相同條件下，與化學聚合法聚合掌性聚苯胺之間的差異。

掌性聚苯胺測得較優異旋光強度的電化學聚合條件如下：不添加苯胺雙體時，苯胺單體與樟腦磺酸根離子濃度比為1：1.82，pH 1.80；添加苯胺雙體時，苯胺單體與樟腦磺酸根離子濃度比為1：3.64，pH 1.35；0.9V定電壓電聚合100秒、condition電壓為0.4V。添加苯胺雙體聚合掌性聚苯胺能夠增加電活性、促進聚合速率，但其表面比未添加苯胺雙體聚合的掌性聚苯胺粗糙，兩者的氧化還原態皆為emeraldine salt form。

最後此掌性聚苯胺薄膜以電化學石英晶體微天秤(EQCM)與固相微萃取(SPME)結合高效能液相層析儀等方式用於檢測掌性非類固醇類抗發炎藥物如ibuprofen等真實樣品，得知S-掌性聚苯胺對於S form化合物的親和力大於R form化合物，R-掌性聚苯胺則相反，證明掌性聚苯胺薄膜的確擁有掌性分子辨識能力。

Chiral polyaniline prepared by electrochemical polymerization was studied to explore the addition of N-phenyl–1,4diamine (aniline dimer) on chirality. The polymerization time, ratio of aniline and dopant, pH value, redox states, dopants, and aniline derivatives were studied and optimized for the chirality of polyaniline. The polyaniline film was characterized by cycle voltammetry, UV-Vis, and AFM spectroscopy. Furthermore, the differences of chemical and electrochemical polymerization were compared. The aniline dimer produced the better electroactive and the rate of polymerization was promoted. However, the surface of the polyaniline is rougher than that without aniline dimer addition. Emeraldine salt form were obtained in both methods.

The best chirality were achieved as follows : the proportion of aniline and CSA－ is 1 : 1.82, pH 1.80 in no aniline dimer；the proportion of aniline and CSA－ is 1 : 3.64, pH is 1.35 in aniline dimer；0.9V for 100 seconds in electrochemical polymerization；condition at 0.4V.

The enantioselectivity of the chiral polyaniline was examed by EQCM and the SPME combined with HPLC was used to analyzed NSAIDs. The (S)-chiral polyaniline showed better binding efficiency for (S)-form NSAIDs than (R)-form, while the inverse was true for the (R)-chiral polyaniline.

謝誌i
中文摘要ii
英文摘要iii
目錄iv
表目錄viii
圖目錄ix

1、緒論 1
1.1、聚苯胺的簡介與發展近況 1
1.2、聚苯胺的氧化還原態 1
1.3、聚苯胺的合成 3
1.4、聚苯胺的氧化還原機制 4
1.5、聚苯胺的結構與紫外光-可見光光譜(UV-Vis) 5
1.6、圓二色極化光譜(circular dichroism，CD) 7
1.7、掌性聚苯胺導電高分子 10
1.8、非類固醇類抗發炎藥物11
1.9、石英晶體微天秤(quartz crystal microbalance，QCM)簡介12
1.10、固相微萃取法(solid phase microextration) 14
1.11、原子力顯微鏡(Atomic Force Microscopy，AFM)簡介 15

2、實驗部分 17
2.1、試藥部份 17
2.2、儀器設備 18
2.3、實驗步驟 19
2.3.1、以化學聚合法合成掌性聚苯胺 19
2.3.1.1、聚合方法 19
2.3.1.2、控制單體溶液的濃度 19
2.3.1.3、控制單體溶液的pH 20
2.3.1.4、陰離子的干擾 20
2.3.2、以電化學聚合法合成掌性聚苯胺 20
2.3.2.1、聚合方法 20
2.3.2.2、控制單體溶液的濃度 21
2.3.2.3、控制單體溶液的pH 21
2.3.3、氧化還原態的控制 21
2.3.3.1、電壓的效應 21
2.3.3.2、pH值的效應 21
2.3.4、製備觀測AFM下所需的聚苯胺試片 22
2.3.5、電化學石英晶體微天秤(EQCM)的偵測 22
2.3.6、固相微萃取步驟 22
2.3.6.1、吸附步驟 22
2.3.6.2、脫附步驟 23
2.3.6.3、高效能液相層析儀(HPLC)偵測步驟 23

3、結果與討論 24
3.1、化學聚合法合成掌性聚苯胺 24
3.1.1、掌性聚苯胺溶液稀釋倍數的影響 24
3.1.2、相反旋光性的摻雜酸對於掌性聚苯胺的影響 25
3.1.3、苯胺單體與摻雜酸的濃度比例在化學聚合對於聚苯胺掌性的影響 26
3.1.4、探討苯胺單體與摻雜酸的濃度比例與添加苯胺雙體造成的效應 27
3.1.5、pH值在化學聚合對掌性聚苯胺形成的探討 28
3.1.6、紫外光－可見光光譜 30
3.1.7、非掌性摻雜酸的效應 32
3.2、電化學聚合法合成掌性聚苯胺 33
3.2.1、定電壓聚合時間對聚苯胺掌性偵測的影響 33
3.2.2、苯胺單體與摻雜酸濃度比例在電化學聚合對於聚苯胺掌性的影響 36
3.2.3、pH值在電化學聚合對掌性聚苯胺形成的探討 38
3.2.4、氧化還原態的控制對聚苯胺掌性的效應 39
3.2.5、所浸泡之電解質的pH對聚苯胺掌性的效應 41
3.2.6、掌性聚苯胺的去摻雜與再摻雜 42
3.2.7、具取代基聚苯胺之光學活性的探討 44
3.2.8、紫外光－可見光光譜 46
3.2.9、掌性聚苯胺、甲基－聚苯胺、乙基－聚苯胺薄膜的電化學性質 47
3.3、以原子力顯微鏡(AFM)觀測掌性聚苯胺之表面 48
3.4、電化學石英晶體微天秤(EQCM) 51
3.4.1、以電化學石英晶體微天秤(EQCM)做陰離子摻雜的探討 51
3.4.2、聚苯胺薄膜摻雜陰離子時，頻率變化對應質量的關係 51
3.4.3、以電化學石英晶體微天平(EQCM)偵測掌性非類固醇類抗發炎藥物 51
3.5、固相微萃取結合高效能液相層析儀偵測非類固醇類抗發炎藥物 56

4 、結論與未來展望 58

5 、參考文獻 59

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