開發以喹啉及稠合喹啉衍生物為主結構單元之螢光探針並探討其螢光對環境改變之響應能力

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姓名

林信宏(LIN, HSIN-HUNG) 查詢紙本館藏

畢業系所

化學學系

論文名稱

開發以喹啉及稠合喹啉衍生物為主結構單元之螢光探針並探討其螢光對環境改變之響應能力
(Development of fluorescent probes with quinoline and fused quinoline derivatives as the main structural unit and investigation of their fluorescence response to environmental changes)

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至系統瀏覽論文 ( 永不開放)

摘要(中)

在複雜環境上量測物質或環境變化經常需要使用特定儀器，而使用螢光探
針作為量測媒介則可以簡化量測流程與工具，並可應用於可視化生物體內
各組織的狀況。
本篇論文成功以喹啉與稠合喹啉衍生物為主結構單元並合成出四個系
列的模型分子，藉由實驗量測其線性與非線性光學性質可以得知這些分子
具有以下特性:
(1) 以 D-π-A 方式組成之第一、二、三系列條形分子有明顯溶劑效應。
(2) 對同一系列分子而言，在固定推電子基團的情況下，改變拉電子基
團共軛性質會影響螢光激發效率，相比於 benzothiazole，以
triazolopyridine 與 oxadiazole 做為拉電子基團雖在高極性溶劑具有較
高的螢光量子產率，但雙光子激發截面值皆較低。
(3) 第二系列分子在結構中引入烷氧基有助於提升螢光量子產率與雙光
子螢光表現，並在不改變共軛結構下於末端連接不同標定官能基不
會對螢光性質有顯著改變。
(4) 本篇論文中化合物雖然在溶劑態時具有優秀的螢光量子產率與亮
度，但在固態的螢光量子產率表現較差。
(5) 以雙鍵延長共軛系統導致在高極性溶劑下螢光量子產率降低，但對
於環境黏稠度的改變具有敏感性。
(6) 以含氮雜環結構作為共軛系統之螢光探針對於酸性環境具有敏感
性，並可於鹼性環境回復原有光學性質。

摘要(英)

Detection of substances or environmental changes in a complex
environment often requires specific instruments. However, using fluorescent
probes as media can simplify the measurement processes and tools. And such
probes can be applied to visualize the status of various tissues in living
organisms.
In this thiesis, four series of model compound were successfully synthesized
using quinoline and fused quinoline derivatives as the main structural units.
Through the experimental measurement of linear and nonlinear optical
properties, it can be known that these molecules have the following
characteristics:
(1) Model compounds of D-π-A type show very salient solvent effect.
(2) For the same series of molecules, keeping same electron-donating group
while changing the electron-withdrawing group will affect the fluorescence
efficiency. Compare to benzothiazole, using triazolopyridine or oxadiazole as
electron-withdrawing groups lead to high fluorescence quantum yield in high
polar solvent but low two-photon excitation cross section.
(3) The introduction of alkoxy groups in the second series of model molecules
can improve the fluorescence quantum yield and two-photon emission
performance. In addition, attaching different bio-labeling functional groups to
the aforementioned model structures does not change their fluorescent
properties.
iii
(4) Although these final compounds have excellent fluorescence quantum
yields and brightness in solvents, the fluorescence quantum yields of these
compounds in the solid state are poor.
(5) Extending the conjugated system with double bonds leads to a decrease in
the fluorescence quantum yield in high polar solvents, but makes it sensitive to
the viscosity.
(6) Using heterocyclic units containing nitrogen as a part of conjugated systems
can make fluorescent probes sensitive to the pH change of the environment and
the process of fluorescence color change in accordance with the pH variation is
reversible.

關鍵字(中)

★ 喹啉
★ 稠合喹啉
★ 螢光探針
★ 生物顯影

關鍵字(英)

論文目次

摘要 ........................................................................................................................ i
Abstract ................................................................................................................. ii
目錄 ...................................................................................................................... iv
圖目錄 ................................................................................................................. vii
表目錄 ................................................................................................................... x
第一章緒論 ......................................................................................................... 1
1-1 螢光探針類型與應用 ........................................................................... 1
單光子螢光原理: .......................................................................................... 1
螢光探針作用類型: ...................................................................................... 3
螢光探針量測的優勢 ................................................................................... 7
1-2 具雙光子性質之螢光探針 ................................................................... 8
1-2-1 雙光子吸收原理 ........................................................................ 8
1-2-2 與單光子螢光探針相比之優缺點 ............................................ 9
1-2-3 雙光子探針用於生物顯影所需考量要素 .............................. 11
生物顯影因素 ............................................................................................. 11
雙光子探針光學因素 ................................................................................. 13
1-3 具雙態螢光發射之螢光分子 ............................................................. 14
1-4 研究動機與論文架構 ......................................................................... 17
第二章分子設計與合成 ................................................................................... 18
2-1 模型分子設計概念及目的 ................................................................. 18
2-2 模型分子合成途徑 ............................................................................. 22
vi
第三章光學性質量測與探討 ........................................................................... 29
3-1 光學性質鑑定實驗方法 ..................................................................... 29
3-2 溶液態之線性光學性質 ..................................................................... 33
3-3 雙光子螢光光學性質 ......................................................................... 45
3-4 其他凝態之光學性質 ......................................................................... 51
3-5 分子周遭環境的刺激對其螢光的影響 ............................................. 56
3-5-1 黏度 .......................................................................................... 56
3-5-2 吸附狀態 .................................................................................. 59
3-5-3 酸鹼 .......................................................................................... 60
3-6 結果與討論 .......................................................................................... 63
第四章作為細胞影像探針之評估 ................................................................... 65
第五章實驗藥品與合成步驟 ........................................................................... 67
5-1 合成模型分子所使用之藥品與溶劑 ................................................. 67
5-2 合成詳細步驟...................................................................................... 69
第六章結構鑑定光譜圖 ................................................................................. 100
參考文獻 ........................................................................................................... 163

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指導教授

林子超

審核日期

2023-8-17

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