臺灣博碩士論文加值系統

根據二吩及三吩衍生物的研究結果，此類衍生物在照光時會有光毒性，而光毒性的來源是光敏化效果所產生的單線態氧。利用此一特性多吩類衍生物或可開發成新的光化學療劑。為此目的本研究以五種多吩類衍生物為原料，分別為2,2':5',2''-三吩（alpha-terthienyl，以下簡稱aT），1,2-二（2-吩）乙炔（1,2-bis(2-thienyl)acetylene，以下簡稱BTA），(E)-1,2-二（2-吩）乙烯（(E)-1,2-bis(2-thienyl)ethene，以下簡稱BTE），5-甲醛-2,2':5',2''-三吩（5-formyl-2,2':5',2''-terthiophene，以下簡稱FTT），和5-（2-（2-亞胺）乙基乙醇）-2,2':5',2''-三吩（(5-(2-(2-imino)-aminoethyl)-ethanol)-2,2':5',2''-terthiophene，以下簡稱IAET），用單線態氧捕捉劑2,5-dimethylfuran和1,3-diphenylisobenzofuran證明這些結構式經修飾的衍生物仍會在照光時產生單線態氧，再以高效液相層析儀分析這些衍生物在甲醇、氰甲烷、乙醇及異丙醇等四種溶劑下對其單線態氧產率的影響。實驗結果顯示，aT與FTT有最大的單線態氧產率，又以在氰甲烷中產率最高。BTA、BTE和IAET的單線態氧產率很低，此外BTE和IAET會在照光過程中發生結構式變化。此結果顯示多吩類衍生物進行的光反應途徑有兩種：產生單線態氧（如aT與FTT）或光解產物（如BTE與IAET）。其差異點在於多吩類衍生物之最大吸收波長的吸收強度，此類衍生物之最大吸收波長的吸收乃由電子的傳遞效應所引起，電子傳遞效應高者會使鍵結斷裂形成光解產物，反之則可保持結構式安定而產生單線態氧。另外單線態氧在不同溶劑下的半衰期之長短對此類衍生物的單線態氧產率恰成正比。

According to some previous research reports of bithiophene and terthiophene derivatives, singlet oxygen photosensitized by poly-thiophene derivatives would be the mechanism leading to their phototoxicity. This property has high potential to be developed into photochemotherapy agents. Here we use singlet quenchers, 2,5-dimethylfuran and 1,3-diphenylisobenzofuran to prove singlet oxygen which was generated by some polythiophene derivatives of alpha-terthienyl(aT), 1,2-bis(2-thienyl)acetylene(BTA), (E)-1,2-bis(2-thienyl)ethene(BTE), 5-formyl-2,2':5',2"-terthiophene(FTT), and (5-(2-(2-imino)-aminoethyl)-ethanol)-2,2':5',2"-terthiophene(IAET) under irradiation. The effect of different organic solvents of methanol, acetonitrile, ethanol, and propan-2-ol on singlet oxygen quantum yield was assayed by HPLC method.
The results show that aT and FTT have higher value of singlet oxygen quantum yield, and singlet oxygen can be detected more in acetonitrile than in other solvents. It is due to the lifetime of singlet oxygen in solvents. BTA, BTE, and IAET hardly generate singlet oxygen; BTE and IAET undergo photodegradation during irradiation. It suggests that there are two pathways of photochemical reactions for polythiophene derivatives to either generate singlet oxygen (such as aT and FTT) or photolysis(such as BTE and IAET). The mechanisms of photochemical reactions of polythiophene derivatives are upon the molar absorptivity of their maximum absorption band which is characteristic of an electron transfer transition. The higher value of the effect of an electron transfer transition would lead polythiophene derivatives to photolysis while the lower would lead to generate singlet oxygen.

目 錄
附圖目錄v
附表目錄viii
中文摘要ix
英文摘要xi
第一章 緒 論1
壹、多吩類衍生物（polythiophene derivatives）1
一、多吩類衍生物之背景1
二、多吩類衍生物之研究歷史3
三、多吩類衍生物之光化學反應5
（一）單線態氧的產生5
（二）電子轉移作用8
貳、單線態氧（Singlet oxygen；1O2）之簡介10
一、單線態氧之產生法10
二、單線態氧之測定11
三、單線態氧對生物體之影響11
參、光化學療法之發展13
一、光化學療法之源起13
二、光化學療法於臨床上之治療14
肆、研究目的與方法16
第二章 多吩類衍生物照光後產生單線態氧之確認實驗19
壹、實驗原理19
一、單線態氧捕捉劑19
二、DMFu及DPBF與單線態氧之反應過程22
貳、實驗材料、儀器及方法27
一、實驗材料27
二、儀器28
三、方法28
（一）五種多吩類衍生物照光變化之測量28
（二）五種多吩類衍生物照光後產生單線態氧之確認試驗28
參、實驗結果30
一、五種多吩類衍生物在四種溶劑下照光前後的光譜吸收值及光譜圖30
二、五種多吩類衍生物加入DMFu後在四種溶劑下照光前後的光譜圖37
三、五種多吩類衍生物加入DPBF後在四種溶劑下照光前後的光譜圖43
肆、討論49
一、多吩類衍生物之光譜吸收50
（一）三吩類衍生物之光譜吸收50
（二）二吩類衍生物之光譜吸收51
二、單線態氧之確認51
三、多吩類衍生物之降解情形53
伍、結論55
第三章 多吩類衍生物於不同溶劑下的單線態氧產率評比56
壹、實驗材料、儀器及方法58
一、實驗材料58
二、儀器59
三、方法59
（一）多吩類衍生物於不同溶劑下的單線態氧產率評比實驗59
（二）RP-HPLC之分析條件60
（三）DMFu之迴歸曲線的製作60
貳、實驗結果62
一、五種多吩類衍生物照光前後的HPLC圖62
二、DMFu在五種多吩類衍生物溶液中照光前後之變化情形67
參、討論72
一、多吩類衍生物之單線態氧產率的評比72
二、光解產物的形成74
三、電子傳遞效應75
四、溶劑效應77
五、結論78
第四章 結 語79
參 考 文 獻82
附圖部份86

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