臺灣博碩士論文加值系統

癌症為人類死亡主因之一，對於癌症治療的問題，學術界積極尋找新的治療技術，期望能減少病患痛苦，並降低副作用。磁性熱治療與光熱治療是目前最具潛力的癌症治療技術。有鑑於此，本研究以具有良好生物相容性之聚己內酯(PCL)，包覆氧化鐵(Fe3O4)奈米粒子、普魯士藍(Prussian blue)奈米粒子，結合具有良好延展性之聚二甲基矽氧烷 (PDMS)，發展出同軸靜電紡絲磁性複合纖維材料，使其可應用於癌症磁性熱治療與光熱治療技術。
本實驗包含: 1. 利用水熱法合成出磁性氧化鐵奈米粒子(Fe3O4)，並利用界面活性劑聚乙烯吡咯烷酮(PVP)，控制磁性氧化鐵奈米粒子的粒徑大小，增強其在溶液中分散性。接著探討聚己內酯(PCL)、聚二甲基矽氧烷 (PDMS)同軸靜電紡絲型態，製備出磁性奈米纖維複合材料，並在高頻率交流磁場下，探討磁性複合纖維膜對加熱效果之影響及型態變化; 2.合成普魯士藍奈米粒子，並結合聚己內酯、聚二甲基矽氧烷成為同軸靜電紡絲型態，製備出奈米纖維複合材料。再利用其吸收700 nm區間紅光之特性，研究不同波長與激光功率，對材料升溫效果之影響。預期本研究之實驗成果，將有助於癌症熱治療及光熱治療之應用。

Cancer is one of the main causes of human death. Many academic researchers are actively looking for new therapeutic technologies that can help to reduce the pains of patients and the side effects. Currently, magnetic hyperthermia and photothermal therapy are the most potent cancer treatment technology. Therefore, this study utilizes biocompatible polycaprolactone (PCL), iron oxide (Fe3O4) nanoparticles, Prussian blue (PB) nanoparticles and ductile polydimethylsiloxane (PDMS) to develop co-axial electrospun composite fibers that can be applied on the magnetic hyperthermia and photothermal therapy cancer treatment.
This study synthesized magnetic Fe3O4 nanoparticles using a hydrothermal method. Polyvinylpyrrolidone (PVP) was introduced to control the particle size and to improve the dispersibility of nanoparticles in solution. Next, the morphology of the electrospun Fe3O4/PCL/PDMS composite fibers were systematically investigated and their heating performance was evaluated under alternating electromagnetic field. Furthermore, electrospun PB/PCL/PDMS composite fibers were also developed and their heating performance was studied by exposing to visible red light with a wavelength near 700nm. These results are expected to contribute the advance of hyperthermia and photothermal therapy.

目錄
摘要 I
Abstract II
目錄 III
圖目錄 VII
表目錄 X
第一章 緒論 1
1.1. 前言 1
1.2. 研究動機及目的 4
第二章 文獻回顧 7
2.1. 磁性奈米粒子 7
2.1.1. 磁性理論 7
2.1.2 磁滯曲線 12
2.1.3 超順磁 13
2.1.4 磁性與粒徑的關係 13
2.1.5 磁性粒子升溫機制 15
2.2. 靜電紡絲 (Electrospinning) 19
2.2.1. 靜電紡絲理論 19
2.2.2. 影響靜電紡絲的因素 21
2.2.3. 同軸靜電紡絲製程 29
2.2.4. 靜電紡絲複合材料之應用 31
2.2.5. 聚乙烯吡咯烷酮 (polyvinyl pyrrolidone，PVP) 33
2.2.6. 聚己內酯 (Polycaprolactone，PCL) 33
2.2.7. 聚二甲基矽氧烷 (Polydimethylsiloxane，PDMS) 34
2.2.8. 普魯士藍 (Prussian blue) 34
2.3. 熱療 (Hyperthermia) 36
2.3.1. 熱療的歷史 36
2.3.2. 熱療的機制 36
2.3.3. 熱療文獻 37
第三章 實驗 39
3.1. 實驗藥品 39
3.2. 實驗儀器 42
3.3.　實驗步驟 44
3.3.1. 磁性氧化鐵粒子製備 44
3.3.2. 普魯士藍粒子製備 45
3.3.3. 靜電紡絲溶液配製 45
3.3.4. 單軸/同軸靜電紡絲實驗 45
3.3.5. 加熱實驗 46
3.3.6. 照光實驗 46
第四章 結果與討論 47
4.1. 合成 Fe3O4@PVP奈米粒子之性質研究 47
4.1.1. 物性分析 47
4.1.2. PVP分子量的影響 49
4.1.3. PVP濃度的影響 50
4.1.4. TGA分析 53
4.1.5. FTIR分析 55
4.1.6. SQUID分析 56
4.2. 紡絲溶液設計 58
4.2.1. PVP電紡絲纖維表面型態研究 58
4.2.2. PCL電紡絲纖維表面型態研究 60
4.2.3. 紡絲溶液選擇分析 62
4.3. 靜電紡絲製備Fe3O4奈米粒子與其高分子複合纖維 63
4.3.1. PVP與PDMS同軸電紡複合纖維研究 63
4.3.2. PCL與PDMS同軸電紡複合纖維研究 66
4.3.3. PCL/PDMS與Fe3O4奈米粒子同軸電紡複合纖維研究 69
4.3.4. 同軸電紡複合纖維之鑑定與分析 73
4.4. 靜電紡絲製備普魯士藍與其高分子複合纖維 80
4.4.1. PCL/PDMS/普魯士藍同軸複合纖維研究 80
4.4.2. 可見光加熱實驗研究 82
第五章 結論 84
參考文獻 85

 
圖目錄
圖2.1- 1相鄰磁區間磁化方向變化情形 8
圖2.1- 2不同磁性表現之磁矩分布 11
圖2.1- 3 (a)磁性物質之磁滯曲線，其中Mr為殘留磁化量、Hc為矯頑力、Ms磁化強度 (b)超順磁的磁化量與外加磁場之曲線 12
圖2.1- 4超順磁粒子示意圖 13
圖2.1- 5磁性粒子磁區構造圖 14
圖2.1- 6奈米粒子矯頑力與粒徑的關係 14
圖2.1- 7摩擦損耗示意圖 18
圖2.2- 1 典型電紡裝置示意圖 20
圖2.2- 2 泰勒錐形成示意圖 20
圖2.2- 3 同軸靜電紡絲裝置示意圖 30
圖2.2- 4 同軸奈米纖維之TEM圖 30
圖2.2- 5 同軸電紡複合液滴流動模式 31
圖2.2- 6 電紡絲纖維應用示意圖 32
圖2.2- 7 普魯士藍應用示意圖 35
圖3.3- 1 氧化鐵奈米粒子製備示意圖 44
圖4.1- 1 合成之氧化鐵奈米粒子形貌圖 48
圖4.1- 2 不同PVP分子量下合成Fe3O4奈米粒子TEM影像圖 49
圖4.1- 3 添加不同濃度PVP之TEM形貌圖 52
圖4.1- 4 添加不同莫耳比率的PVP之粒徑分布圖 53
圖4.1- 5 熱重分析後氧化為Fe2O3 54
圖4.1- 6 磁性氧化鐵粒子之TGA分析圖 54
圖4.1- 7 Fe3O4@PVP奈米粒子之FTIR圖 55
圖4.1- 8 不同PVP添加量下奈米粒子磁化強度與施加磁場關係圖 57
圖4.2- 1 PVP (Mw=29,000)纖維之SEM圖 59
圖4.2- 2 PCL 10 wt %纖維之SEM圖 61
圖4.3- 1 PVP/PDMS在不同濃度下複合纖維之SEM圖 64
圖4.3- 2 PVP/PDMS複合纖維之TEM圖 65
圖4.3- 3 PCL/PDMS在不同濃度下複合纖維之SEM圖 67
圖4.3- 4 PCL/PDMS複合纖維之TEM圖 68
圖4.3- 5 PVP/PDMS同軸複合纖維之外觀與型態 70
圖4.3- 6 PCL/PDMS/Fe3O4同軸複合纖維TEM圖 72
圖4.3- 7 PDMS纖維結構SEM圖 74
圖4.3- 8 PDMS纖維結構EDS分析 75
圖4.3- 9 複合纖維膜加熱前後形貌變化圖 76
圖4.3- 10 不同濃度之PDMS複合纖維在頻率磁場對持溫效果的影響 78
圖4.3- 11 PCL/PDMS/ Fe3O4奈米粒子同軸複合纖維之應力-應變曲線 79
圖4.3- 12 普魯士藍粒子形貌圖 80
圖4.3- 13 普魯士藍UV-vis鑑定曲線圖 80
圖4.3- 14 PCL/PDMS/普魯士藍同軸複合纖維形貌與SEM圖 81
圖4.3- 15 PCL/PDMS/普魯士藍同軸複合纖維TEM圖 81
圖4.3- 16 不同激發之光源照射之溫度隨時間曲線圖 83
圖4.3- 17 不同激光功率照射之溫度隨時間曲線圖 83

表目錄
表2.2- 1 電紡常用溶劑之導電度 24
表4.1- 1 各種氧化鐵的物理性質 48
表4.1- 2 改變PVP濃度之實驗條件參數 50
表4.1- 3 添加不同莫耳比率的PVP之平均粒徑 53
表4.2- 1 PVP 電紡絲實驗參數 58
表4.2- 2 PCL 10 wt% 電紡絲參數 60
表4.3- 1 PVP / PDMS複合纖維參數 63
表4.3- 2 PCL / PDMS複合纖維參數 66
表4.3- 3 PCL/PDMS與Fe3O4奈米粒子同軸複合纖維實驗條件 71
表4.3- 4 複合纖維之應力與應變 79

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