臺灣博碩士論文加值系統

摘要
近二十年來科學家致力於合成高共軛的導電高分子，不論是在光學活性上或是一些的電性質上，都有很濃厚的興趣。一般的導電高分子呈現不規則的構形，近年來部分科學家致力於合成旋光性之導電高分子，得到具有旋光性構形的導電高分子，將導電高分子之應用範圍擴展至對掌性分子之合成及分離、特殊之生化感測器、三維圓柱液晶、導電液晶分子結晶工學、螺旋超分子光化學光物理等之相關應用領域。
由於缺乏有效的合成策略，所以要合成一個具有旋光性構形的導電高分子，且進一步控制旋光性構形是困難的，而文獻上所報導的範例的適切性，也有許多引人爭議的地方。為了要形成具有旋光性構形的聚合物，我們利用本實驗室開發的方法同步還原與取代反應（concurrent reduction and substitution ）設計一個新的合成策略，將L-半胱氨酸（L-cysteine）做為親核試劑對聚苯胺進行同步還原與取代反應，以期形成具有旋光性取代基的聚合物，同時保有聚苯胺的導電性質、且高分子主鏈經誘導形成旋光性構形。利用X光-光電子能譜儀（XPS）、全反射式紅外線光譜儀（ATR-IR）、循環伏特安培法（cyclic voltammetry）、紫外光光譜儀（UV-vis）、圓二分儀（CD）、四點探針導電儀等方法鑑定其物理及化學性質。
研究的結果顯示，本論文所使用的方法確實已經有效地合成了具有L-半胱氨酸取代之聚苯胺共聚合物（PAN-L-Cys），由聚苯胺反應後XPS的能譜可以發現S元素的存在，且由其化學能態（chemical state）知道S（2p）的束縛能（binding energy）約為163.6 eV，此乃是L-半胱氨酸與聚苯胺反應所生成sulfide（Ar-S-R）價橋鍵的證據，由ATR-IR的鑑定可以發現產物在1600 cm-1（Q＝N＝Q sym str）吸收峰強度變弱，證實聚苯胺的氧化態已明顯的降低（即被還原了），及觀察到L-半胱氨酸取代基之特性吸收峰，證實L-半胱氨酸確實與聚苯胺發生反應，此外隨著重複同步還原取代反應次數的增加（從一至六次）其產物之L-半胱氨酸取代基之特性吸收峰也隨之增加，由CV光譜發現L-半胱氨酸與聚苯胺重複同步還原取代反應次數的增加（從一至六次）之陽極氧化與還原峰的平均電位值呈現先降後升之趨勢，從一至六次依次為110.5 mV、83.5 mV、95 mV、120.5 mV、135 mV，、161 mV。L-半胱氨酸取代基引入聚苯胺主鏈，增加了聚苯胺主鏈之電子密度，降低聚苯胺主鏈之平均氧化還原電位，且電流密度都明顯提高，意味氧化及還原的速率在新的L-半胱氨酸取代之聚苯胺共聚合物（PAN-L-Cys）似乎也較快且容易。當重複進行取代反應，氧化還原電位隨著反應次數增加而提升，說明L-半胱氨酸取代基的推電子效應及立體效應對聚苯胺主鏈所造成的影響。UV-vis的光譜紅位移現象的出現，證實推電子取代基之電子效應，增加聚苯胺主鏈之電子密度，對導電度有一定程度的幫助。其導電度為2 S/cm，所得到的導電度值相較於經由外加質子酸進行摻雜處理後的聚苯胺（1 ~ 10 S /cm）而言，導電性並無明顯破壞，而相對於傳統文獻中所指出烷基、烷氧基及N-烷基取代之聚苯胺衍生物而言，則明顯改善。由CD之鑑定結果，證實藉由所引進的半胱氨酸取代基的立體位向及其與聚苯胺主鏈間的作用力誘導聚苯胺主鏈形成非中心對稱性之螺旋結構，因而衍生旋光性，且L-半胱氨酸（L-cysteine）與聚苯胺反應所生成之衍生聚苯胺與D-半胱氨酸反應所得之衍生聚苯胺擁有相反的旋光性，可知其彼此相對應之螺旋體擁有不同之對掌性。

Abstract
New chiral aniline copolymers containing L-cysteine substituent have been first prepared from unsubstituted polyaniline, utilizing a concurrent reduction and substitution reaction performed in the solid-state matrix of polyaniline.
The chemical, electrical and chiroptical properties of the resultant copolymer powder have been characterized by XPS, ATRIR, CV, UV-vis, CD ( circular dichroism ) spectroscopy. The resultant copolymer powder was found to contain ca. 24 mol % (based on atomic ratio S/(N-S) measured by XPS ) of L-cysteine group and are very conductive (2 S/cm ). XPS spectra of PAN-L-Cys show a newly appeared S 2p line at around 163.6 eV, confirming the formation of the sulfide linkage. The ATRIR spectrum of the resulting aniline copolymer powder clearly showed reduction in the intensities of the peaks associated with diiminoquinoid ring at 1600 cm-1 (C=C stretching vibration of diiminoquinoid ring ). The oxidation potential E0 of the resulting aniline copolymer was lower than that of parent polyaniline. This result is consistent with the expectation that the attachment of electron-donating L-cysteine group that help lower the oxidation potential of polyaniline backbone . The UV-vis spectra of the resulting aniline copolymer showed that the lmax of the p-p* transition band is longer than the corresponding band of the parent unsubstituted polyaniline, possibly due to the enhanced electron density of the copolymer backbone as contributed by the electron-donating L-cysteine group. The corresponding CD spectra for PAN-L-Cys and PAN-D-Cys ( in NMP solutions ) are mirror image of each other, indicating that these two chiral form of polyaniline possess opposite handedness.

目錄
摘要
圖目錄
表目錄
第一章 緒論
1-1 前言 1
1-2 共軛導電高分子的簡介 1
1-3 研究目標 4
第二章 文獻回顧
2-1聚苯胺之合成 7
2-1-1 化學法 7
2-1-2 電化學法 8
2-2聚苯胺各種氧化還原態之化學構形 9
2-2-1 聚苯胺之紅外線光譜分析 9
2-2-2 聚苯胺之 UV-vis-NIR 光譜分析 10
2-2-3 聚苯胺之X光-光電子能譜分析 11
2-3 聚苯胺之摻雜與去摻雜機構 12
2-4 旋光性導電高分子的發展 13
2-4-1 旋光性聚咯 15
2-4-2 旋光性聚噻吩 17
2-4-3 旋光性聚苯胺 20
第三章 實驗內容
3-1 藥品 34
3-2 合成方法 35
3-2-1 去摻雜形式聚苯胺（dedoped polyaniline）之合成 35
3-2-2 利用同步還原與取代反應製備L-半胱氨酸取代
聚苯胺, poly(aniline-L-cysteine)(PAN-L-Cys) 36
3-2-3 利用同步還原與取代反應製備D-半胱氨酸取代
聚苯胺, poly(aniline-D-cysteine)(PAN-D-Cys) 42
3-3 實驗儀器裝置與條件 44
1.傅立葉轉換紅外線光譜儀（FT-IR） 44
2.紫外光-可見光-近紅外線光譜儀（UV-Vis-NIR
Spectroscopy；UV-Vis-NIR） 44
3. X光-光電子能譜儀（X-ray Photoelectron Spectroscopy ;
XPS） 45
4.圓二分儀(Circular Dichroism & Optical Rotatory Dispersion
Spectrometer；CD-ORD) 45
5.導電儀（Conductivity Measurement Equipment） 46
6.電化學分析儀器（Potentiostat / Galvanostat） 46
7.電化學分析儀器（Potentiostat / Galvanostat） 47
第四章 旋光性聚苯胺（PAN-L-Cys）的合成---------結構鑑定與分析
4-1 X光-光電子能譜儀的結果分析與討論 48
4-2全反射式紅外線光譜的結果分析與討論 65
4-3循環伏特安培法的結果分析與討論 76
4-4紫外線-可見光光譜儀的結果分析與討論 82
4-5圓二分儀的結果分析與討論 90
4-6導電度量測 96
第五章 綜合討論 102
5-1 L-半胱氨酸取代之聚苯胺共聚合物之時間效應 110
5-2 L-半胱氨酸取代之聚苯胺共聚合物之溶劑效應 118
第六章 總結與展望 121
第七章 參考文獻 123

第七章
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