臺灣博碩士論文加值系統

摘要
本論文分為三部分，第一部份在探討香豆素衍生物發色團在圓二色性光譜的應用，進而利用圓二色性激子對掌性方法鑑定天然物的絕對組態。第二部分，合成以香豆素衍生物為主架構的聚合物，以利探討在有機發光二極體材料的光學性質。第三部分，合成含有醣殘基的香豆素寡聚合物，將其應用在具有醣辨識能力的化學感測器上。
在圓二色性光譜方面：香豆素衍生物發色團具有紅位移、高靈敏性 (ε > 40,000)及螢光性質的特性，利用此發色團在圓二色性激子對掌性方法，可以鑑定含有立體中心的分子及天然物的絕對組態。我們把香豆素酸衍生物製備成香豆素醯基咪試劑，活化香豆素羧基的反應性，而提高香豆素與天然物羥基酯化偶合的反應產率。如此，香豆素發色團可以更容易用來製備其衍生物及廣泛的應用在圓二色性光譜的研究。因此，香豆素醯基咪試劑在非常微量的天然物絕對組態的鑑定上是非常有潛力。
在發光二極體材料合成方面：香豆素具有非常好的發光效率，我們合成以香豆素為主架構的單體及聚合物，探討其光物理性質，並將評估其應用在發光二極體材料的可能性。聚合物是由單體進行開環複分解聚合反應 (ROMP)所得到。因此合成策略著重於norbornene取代基的建構及香豆素內酯 (lactone)環的縮合合成。
在化學感測器方面：我們利用香豆素對於環境有靈敏的反應特點，設計開發具有醣辨識能力的化學感測器。此化學感應器是由norbornene為聚合端，香豆素為訊號傳遞單元、醣殘基為分子辨識單元及一段橋架 (spacer) 所組成的寡聚合物。此部分合成著重於醣殘基與香豆素衍生物之間橋架連結的建構。

目錄
目錄-----------------------------------------------------------I
圖目錄-------------------------------------------------------III
表目錄---------------------------------------------------------V
簡稱用語對照表------------------------------------------------VI
中文摘要----------------------------------------------------VIII
英文摘要-------------------------------------------------------X
緒論-----------------------------------------------------------1
第一章 香豆素衍生物在圓二色性光譜的應用------------------------3
1.1前言--------------------------------------------------------3
1.2圓二色性激子對掌性方法的介紹--------------------------------6
1.2.1圓二色性激子對掌性方法的原理及特徵------------------------6
1.2.2圓二色性激子對掌性方法的應用------------------------------9
結果與討論----------------------------------------------------11
1.3香豆素 (coumarin)衍生物模擬反應研究------------------------11
1.3.1香豆素發色團的合成方法及性質探討-------------------------11
1.3.2二胺及二醇類香豆素衍生物的製備---------------------------13
1.3.3香豆素衍生物的光譜性質-----------------------------------16
1.4香豆素醯基咪試劑的合成及反應活性探討---------------------27
1.5 Ponasterone A衍生物的合成及光譜研究-----------------------31
1.6香豆素醯基咪唑的超微量偶合反應-----------------------------35
1.7結論-------------------------------------------------------37
第二章 香豆素衍生物在有機發光二極體的應用---------------------38
2.1前言-------------------------------------------------------38
2.2有機分子發光原理及元件結構---------------------------------40
2.2.1發光原理-------------------------------------------------40
2.2.2有機發光二極體元件的基本結構-----------------------------41
2.2.3有機發光二極體元件組成材料的討論-------------------------43
2.3香豆素衍生物單體及高分子發光材料的合成---------------------49
2.3.1香豆素衍生物單體及高分子的合成策略-----------------------49
2.3.2香豆素衍生物合成方法的探討-------------------------------51
2.4香豆素衍生物單體的光物理性質-------------------------------61
2.5結論-------------------------------------------------------65
第三章 香豆素衍生物在化學感測器的應用-------------------------66
3.1前言-------------------------------------------------------66
3.2感測器的組成與原理-----------------------------------------69
3.3碳水化合物感測器的合成-------------------------------------71
3.3.1碳水化合物感測器的合成策略-------------------------------71
3.3.2碳水化合物感測器合成方法的探討---------------------------71
實驗部分------------------------------------------------------77
參考文獻-----------------------------------------------------108
附錄---------------------------------------------------------116

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