近年來顯影技術越來越發達，不僅是應用在臨床診斷上，在研究領域上也有越來越多不同種類的顯影技術被發展出來。螢光顯影技術又是非常重要的技術之一，原因是螢光具有極佳的空間解析度與時間解析度 (spatial and time resolution)，應用在不管是臨床上或是研究領域當中都是非常有利的工具，而螢光顯影當中共軛半導體高分子(簡稱Pdots)是非常具有潛力的螢光探針，因其具有吸收截面係數和不錯的量子產率 (quantum yield)、極佳的光穩定性、低的細胞毒性、適當的奈米顆粒(小於30 nm)以及容易生物偶聯等優點使Pdots非常適合
利用於生物顯影當中。目前已有許多不同波長的Pdots已被設計出來，其中更包含近紅外光 (near infrared，簡稱NIR)的Pdots，而近紅外光具有較高的穿透效率、對生物體較低的傷害、和生物體當中的自體螢光干擾 (autofluorescence)不重疊等等優點，因此應用在生物顯影當中是非常合適的。
然而傳統共軛半導體高分子點大多為具有剛性且平面結構的π共軛分子，分子間會因為π-π stacking而堆疊，而在聚集的狀況下螢光會減弱，此現象即為聚集導致螢光焠滅(aggregation caused quenching,ACQ)。目前用來解決聚集導致螢光焠滅的方法，包括具聚集誘導發光(AIE)、和以鍵結立體障礙大的分子(anti-ACQ)，以立體障礙來阻止π-π stacking形式的堆疊，提高量子產率。而我的題目則會比較聚集誘導發光(AIE)和鍵結立體障礙大的分子(anti-ACQ)，何者在我們的系統上能最有效的改善光學性質。

中文關鍵字：近紅外光放光，窄峰，生物顯影，聚集誘導螢光焠滅，半導體高分子點

Since fluorescence imaging techniques provide a good range of spatial and temporal resolution, it is widely used in biological area. In recent years, fluorescence imaging techniques even applied to surgery. It makes easier for doctors on diagnosing and curing the diseases. In fluorescence imaging techniques, fluorescent probes are playing increasingly important roles. Among currently developed fluorescent probes, semiconducting polymer dots are one of the most suitable for biological application to their advantages such as high brightness, non-toxic, fast and stable emission rate, excellent photostability, easy surface modification, tunable optical properties and so on. However, Pdots with ultrahigh fluorescence brightness are extremely lacking due to aggregation-caused quenching (ACQ) caused by pi-pi stacking between the molecules.

In my first project, I want to solve the problem of aggregation-caused quenching in Pdots via aggregation-induced emission (AIE) behavior or coupling with bulky steric-hindered molecules(anti-ACQ). This article describes the design and synthesis of donor−bridge−acceptor-based semiconducting polymer dots(Pdots) that exhibit narrow-band emissions, ultrahigh brightness, and large Stokes shifts in the near-infrared (NIR) region. Finally, we prove that anti-ACQ compare to AIE can strongly effect the Pdots on optical performance. Then we chose the best performance of the Pdots for further experiment such as cell labeling、zebrafish bioimaging

Key words: near-infrared emission,narrow fluorescence,bioimaging,aggregation-caused quenching,semiconducting polymer dots.

論文審定書 i
中文摘要 ii
Abstract iv
目錄 vi
圖目錄 viii
表目錄 xii
化學結構縮寫表 xiii
第一部分 1
第一章 前言 1
第二章 實驗 19
2-1實驗藥品 19
2-2實驗儀器 21
2-3合成部分 25
2-4 Pdots的製備方法 36
2-5 Bioconjugation 37
2-6 細胞標記 38
2-7斑馬魚動物實驗 40
第三章 結果與討論 45
3-1 設計與反應探討 45
3-2 Pdots製備以及顆粒大小 48
3-3 Pdots光學性質探討 49
3-4 單晶結構分析 51
3-5高分子π-π stacking造成光譜紅移之探討 56
3-6 高分子THF/H2O混和溶液下堆疊之探討 58
3-7莫爾吸收係數的計算 61
3-8 單一顆粒亮度(Single particle brightness)與光穩定性(Photostability) 62
3-9 專一標定細胞以及細胞毒性 65
3-10動物實驗-斑馬魚血管影像觀測 67
第四章 結論 69
第二部分 70
第一章 前言 70
第二章 實驗 73
2-1實驗藥品 73
2-2實驗儀器 73
2-3合成部分 75
2-4 Pdots樣品的製備方法 76
2-4 Polymer懸浮溶液樣品的製備方法 77
2-5 偵測氫氣的方法與裝置(microsensor) 78
2-5 偵測氫氣的方法與裝置(GC-TCD) 79
第三章 結果與討論 80
3-1設計與反應探討 80
3-2 Pdots製備 81
3-3 Pdots光學性質探討 81
3-4 氫氣的偵測(microsensor) 82
3-5氫氣的偵測(GC-TCD) 85
第四章 結論 88
參考資料 89
附圖 96

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