臺灣博碩士論文加值系統

本研究利用高溫摻雜以及氨水熱法製備含氮官能基氧化石墨烯量子點(ANGODs)。摻雜含氮官能基以及調控氧化石墨烯量子點尺寸大小，可以修補其結構上的缺陷、調整電子結構、增強量子侷限效應來提升其光催化活性。更重要的是，ANGODs具有優異的生物相容性，搭配其在光照射下能夠催化產生活性氧化物質(reactive oxygen species)，使得ANGODs在光動力治療上有相當大的潛力。
由研究結果可知，製備的ANGODs自身有能力催化產生足夠量的單重態氧(1O2)，此為Type II光動力治療反應。然而在抗壞血酸或三乙醇胺水溶液中，ANGODs具有催化水氧化產生大量過氧化氫的能力(Type I光動力治療反應)，這表示抗壞血酸或是三乙醇胺能夠還原ANGODs之光生電洞而轉變光動力治療的反應機制，提升ANGODs光生電子產生過氧化氫的利用率。經過腫瘤細胞毒殺測試，ANGODs在光照下能夠有效地殺死腫瘤細胞，而不會對正常細胞造成嚴重影響，說明其有良好的腫瘤對正常細胞的選擇性。在抗壞血酸存在下，光照ANGODs 10分鐘，肺癌細胞、頭頸癌、及大腸癌細胞僅約3%存活，而正常細胞存活率超過60%。生物相容性測試中，ANGODs有高度的生物相容性以及極低的生物毒性。
ANGODs的化學穩定性高且與生物體的鍵結力強，使其在生物體液、細胞表面、或抗體鍵結上的光動力治療及其他生物醫療有廣泛的應用層面與極大發展潛力。

This study utilized high temperature doping and hydrothermal treatment to synthesize nitrogen-doped graphene oxide quantum dots (ANGODs). Introducing nitrogen functional group and tuning the size of graphene oxide quantum dots would repair the structural defects, tuning electronic structure, and enhance quantum confinement effect to elevate photocatalytic activity. More importantly, ANGODs have great potential on photodynamic therapy because of their excellent biocompatibility and capability to generate reactive oxygen species under illumination. In our study, as-prepared ANGODs have ability to catalyze sufficient amount of singlet oxygen (1O2) through Type II photodynamic therapy. However, ANGODs promote water oxidation to generate large amount of hydrogen peroxide in ascorbic acid (AA) or triethanolamine (TEOA) solution (Type I photodynamic therapy), which indicate AA or TEOA would reduce photogenerated holes from ANGODs to switch photodynamic therapy mechanism in order that enhance the efficiency of photogenerated electron to produce hydrogen peroxide. In cancer killing test, ANGODs selectively killed cancer cells under illumination without severely affecting normal cells, which demonstrates that ANGODs have high tumor-to-normal tissue ratio. In the presence of AA, the cell viability of ANGODs-treated lung cancer cells, head and neck cancer cells, and colon cancer cells remained merely 3% after 10 min irradiation while that of normal cells remained over 60%. In biocompatibility test, ANGODs exhibit high biocompatibility and extremely low cytotoxicity. High chemical stability and strong binding force to organism which make ANGODs have great potential on biofluid, cell surface, or antibody binding related photodynamic therapy and wide application of biomedicine.

中文摘要 I
英文延伸摘要 Ⅱ
誌謝 XV
本文目錄 XVIII
表目錄 XXII
圖目錄 XXVI
第一章 緒論 1
1-1 前言 1
1-2 光動力治療之起源 3
1-3 光動力治療機制 4
1-4 光催化原理與反應機制 6
1-5 犧牲試劑工作原理 8
1-6 抗壞血酸在治療上的應用 9
1-7 研究動機 10
第二章 文獻回顧 11
2-1 光敏化劑簡介 11
2-1-1 第一代光敏化劑 12
2-1-2 第二代光敏化劑 13
2-1-3 第三代光敏化劑 15
2-1-4 半導體量子點(semiconductor quantum dots) 15
2-1-5 碳奈米材料 18
2-2 氧化石墨烯結構與性質 23
2-3 氧化石墨烯改良方法 26
2-3-1 材料表面結構改質 27
2-3-2 尺寸大小改變 27
2-4 光催化產過氧化氫 29
第三章 實驗方法與儀器原理介紹 36
3-1 藥品、材料與儀器設備 36
3-1-1 藥品與材料 36
3-1-2 儀器與實驗設備 37
3-2 氧化石墨烯量子點的製備 38
3-3 光催化反應檢測方法與分析 40
3-3-1 Amplex® Red方法之原理 40
3-3-2 過氧化氫生成與濃度檢測 41
3-4 細胞實驗 42
3-4-1 生物相容性(biocompatibility)評估 42
3-4-2 光動力治療與過氧化氫生物毒性評估 43
3-4-3 H2DCFDA測定法檢測細胞內ROS水平 44
3-5 分析儀器原理簡介 45
3-5-1 穿透式電子顯微鏡(Transmission Electron Microscope, TEM) 45
3-5-2 X射線光電子能譜及紫外光電子能譜(X-ray Photoelectron Spectroscopy, XPS ＆ Ultraviolet Photoelectron Spectroscopy, UPS) 47
3-5-3 原子力顯微鏡(Atomic Force Microscope) 50
3-5-4 傅立葉轉換紅外光譜儀(Fourier Transform- Infrared Spectroscopy, FT-IR) 53
3-5-5 拉曼光譜分析儀(Raman Spectroscopy) 54
3-5-6 紫外-可見光分光光度計(UV-Visible Spectrophotometer) 56
3-5-7 光致螢光光譜儀(Photoluminescence, PL) 58
3-5-8 電子順磁共振光譜儀(Electron Paramagnetic Resonance spectrometer, EPR) 59
第四章 結果與討論 62
4-1 穿透式電子顯微鏡(TEM)分析 62
4-2 X射線光電子能譜(XPS)分析 63
4-3 原子力顯微鏡(AFM)分析 66
4-4 傅立葉轉換紅外光譜儀(FTIR)分析 67
4-5 拉曼光譜(Raman)分析 68
4-6 紫外光-可見光吸收光譜圖譜(UV-vis)與光致螢光圖譜(PL)分析 69
4-7 紫外光電子能譜(UPS)與電子結構分析 71
4-8 電子順磁共振光譜儀(EPR)分析與光動力治療機制探討 72
4-9 光催化產過氧化氫之測試 76
4-10 生物相容性測試 78
4-11 光動力治療與過氧化氫毒性評估 79
4-12 細胞內活性氧化物質水平檢測 81
4-13 細胞凋亡測定 82
第五章 結論 85
參考文獻 86

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