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研究生: 林妍希
Lin, Yen-Hsi
論文名稱: 引入鹼金屬陽離子以增強鈷鐵普魯士藍奈米粒子之氧化還原反應活性
Enhancement of the Redox Activity of Co–Fe Prussian Blue Nanoparticles Through Alkali Metal Cation Insertion
指導教授: 葉晨聖
Yeh, Chen-Sheng
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2025
畢業學年度: 113
語文別: 中文
論文頁數: 115
中文關鍵詞: 普魯士藍類似物鹼金屬離子活性氧物質氧化還原活性
外文關鍵詞: Prussian blue analogue, alkali metal cation, reactive oxygen species, redox activity
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  • 化學動力療法(chemodynamic Therapy, CDT)的效果常受限於腫瘤組織中內源性過氧化氫(H2O2)濃度不足,進而限制羥基自由基的(·OH)生成效率。為解決此問題,本研究透過陽離子摻雜策略,有效促進鈷鐵普魯士藍(Co–Fe Prussian Blue, CFPB)的水驅動連續反應(H2O→O2→H2O2→·OH),顯著增強活性氧物種(reactive oxygen species, ROS)的生成。
    本實驗利用沉澱法在冰浴條件下合成出鈷鐵普魯士藍奈米粒子(Co-Fe Prussian blue, CFPB),接著利用自發性吸附反應將鹼金屬離子(Li⁺、Na⁺、K⁺、Rb⁺、Cs⁺)引入CFPB,形成CFPB/A(A = Li、Na、K、Rb、Cs)。Rb⁺與Cs⁺摻雜之CFPB可有效增強O2 → H2O2以及H2O2 → ·OH兩項還原反應;其中,Cs⁺摻雜組別觀察到明顯的Fe3+還原,進而提高結構中Co2+–NC–Fe2+的比例,顯著增強CFPB/Cs所產生的·OH量,為未摻雜之對照組的47倍。此外,密度泛函理論(density functional theory, DFT)計算則進一步驗證,隨著鹼金屬摻雜數量增加,材料的還原能力隨之提升。總結而言,本實驗透過鹼金屬摻雜方法來促進·OH的生成,預期能在化學動力療法中展現良好的治療結果。

    In this study, alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) were introduced into cobalt–iron Prussian blue (CFPB) nanoparticles via a simple absorption process. Experimental results revealed that CFPB exhibited the highest adsorption capacity for Cs⁺. Moreover, the insertion of Cs⁺ induced the reduction of Fe3+ to Fe2+, thereby increasing the proportion of Co2+–NC–Fe3+ configurations, which in turn enhanced the Fenton-like reaction. Further analysis using density functional theory (DFT) calculations and projected density of states (PDOS) confirmed that the improved reductivity primarily originated from the increased number of incorporated cations. As a result, CFPB/Cs generated ·OH radicals at levels 47 times higher than undoped CFPB. This study presents a novel concept of tuning catalytic activity through alkali metal doping, offering a promising strategy for future applications in cancer therapy.

    摘要I 英文延伸摘要(Extended Abstract)II 致謝XIII 目錄XIV 表目錄XVII 圖目錄XVIII 第一章 緒論1 1-1 前言1 1-2 化學動力療法2 1-2-1 化學動力療法之優勢與瓶頸3 1-2-2 提升過氧化氫濃度之策略5 1-2-2-1 外源性供應過氧化氫5 1-2-2-2 內源性產生過氧化氫6 1-3 普魯士藍及其類似物12 1-3-1 化學結構13 1-3-2 晶體結構14 1-3-1 陽離子對PB/PBAs的影響15 1-3-2 製備方法18 1-3-2-1 共沉澱法18 1-3-2-2 水熱法與溶劑熱法19 1-3-2-3 微乳液法21 1-3-2-4 模板輔助法22 1-3-3 PB/PBAs應用於癌症治療25 1-3-3-1 光熱治療25 1-3-3-2 光動力治療27 1-3-3-3 化學動力治療29 1-3-3-4 氣體治療33 1-4 鹼金屬陽離子增強催化反應36 1-5 脂質體38 1-5-1 脂質囊泡分類38 1-5-2 脂質體主要成分38 1-5-3 脂質體的標靶輸送41 第二章 實驗藥品與儀器43 2-1 材料合成與鑑定之相關藥品43 2-2 儀器設備44 第三章 研究動機與實驗方法47 3-1 研究動機47 3-2 實驗方法48 3-2-1 合成鈷鐵普魯士藍奈米粒子(CFPB)48 3-2-2 鹼金屬摻雜之鈷鐵普魯士藍奈米立方體(CFPB/A)49 3-2-3 製備脂質體(Liposome)49 3-2-4 製備CFPB@lipo及CFPB/Cs@lipo50 3-2-5 CFPB對鹼金屬陽離子的吸附量50 3-2-6 氧氣O2)生成之偵測方法50 3-2-7 過氧化氫(H2O2)生成之偵測方法51 3-2-8 羥基自由基(·OH)生成之偵測方法51 3-2-8-1 Aminophenyl fluorescein solution (APF)螢光偵測法52 3-2-8-2 DMPO捕捉 •OH之電子自旋共振(ESR)偵測法52 3-2-9 穩定性實驗52 第四章 實驗結果與討論53 4-1 材料結構及性質鑑定53 4-1-1 鈷鐵普魯士藍奈米粒子(CFPB)53 4-1-2 引入鹼金屬陽離子(CFPB/A)56 4-1-3 CFPB對鹼金屬陽離子之吸附能力62 4-1-4 活性物質生成能力63 4-1-4-1 氧氣生成63 4-1-4-2 過氧化氫生成64 4-1-4-3 羥基自由基生成66 4-2 脂質體修飾之鈷鐵普魯士藍奈米粒子68 4-2-1 結構鑑定69 4-2-2 活性物質生成情形71 4-2-3 穩定性實驗73 4-3 機制探討74 4-3-1 結構變化74 4-3-2 陽離子種類76 4-3-3 陽離子數量77 第五章 結論80 參考文獻81

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