臺灣博碩士論文加值系統

生物活性玻璃是一種70年代初期發現的材料，因為其在身體的環境中能夠與體內組織相連結的緣故而得名。此種材料的組成多為矽酸鹽與氧化鈣或是氧化鈉的非晶相混合物，在身體的環境中會在材料表面誘發羥基磷灰石的成長，而進一步與骨骼等組織相連結。目前已經成功的通過多種骨骼取代及骨骼缺陷填補的臨床測試。
文獻上對於羥基磷灰石在生物活性玻璃表面的生長機制有不同的意見：一種是先誘發非晶相礦物質層的沉積而進一步結晶，另一種是材料表面生成活化位置直接誘發晶體的成長。在本篇論文中，我們採用固態核磁共振來深入探討矽鈣玻璃生物活性的形成機制，因為技術上，許多不同的脈衝序列可以成功的測量系統中同核或是異核之空間環境。在生物活性玻璃的合成上，我們使用溶凝膠法合成出2-3微米的矽鈣玻璃系統，內含30%氧化鈣及70%氧化矽。將此系統浸泡在模擬體液中不同的時間，以觀測羥基磷灰石的成長。除了使用文獻中的一些常規技術做定性的測量外，我們採用許多先進的固態核磁共振技術，如雙共振、雙量子技術測量材料表面的化學環境。
實驗結果支持先誘發非晶相礦物質層的沉積而進一步結晶的反應機制。我們發現在晶體成長的過程中涉及到礦物質的脫水。實驗結果也顯示此結晶相與B類碳酸鹽磷灰石不同，但是與羥基磷灰石相似。我們相信，此論文所採用的固態核磁共振技術也可以有效地研究其他相類似的生物活性材料。

The molecular mechanism of apatite formation on bioactive glass surface is studied using the techniques of XRD, EDX, SEM, FT-IR, and solid-state NMR. Using the sol-gel method a bioactive glass system containing glass beads of 2 to 3 microns in size is prepared with the composition containing 30 % CaO – 70 % SiO2. Our experimental data support the apatite formation mechanism proposed by Hench concerning the precipitation and crystallization of calcium phosphate. The phosphate ions initially deposited on the glass surface are largely amorphous and have substantial amount of water molecules in the surrounding. As the soaking time in simulated body fluid increases, some of the water molecules diffuse out of the phosphate lattice, leading to the formation of a crystalline phase. Our data show that the structure of the crystalline phase is different from type B carbonate apatite but similar to hydroxyapatite.

第1章 緒論............................................1
1-1生物活性玻璃簡介...................................1
1-2生物活性簡介.......................................2
1-3研究動機與目的.....................................5
1-4參考文獻...........................................7

第2章 核磁共振.......................................11
2-1 核磁共振簡介.....................................11
2-2 核磁共振系統的量子力學敘述.......................12
2-2-1 核自旋(Nuclear spin)...........................12
2-2-2 塞曼交互作用(The Zeeman Interaction)...........13
2-2-3 密度矩陣(The density matrix)...................14
2-2-4 熱平衡下的密度矩陣.............................16
2-2-5 密度操作子之運動方程...........................17
2-3 簡單的核磁共振實驗...............................18
2-4 系統間相互作用力.................................21
2-4-1 化學遮蔽作用力.................................21
2-4-2 核間偶極-偶極直接交互作用......................22
2-4-2-1 異核偶極-偶極交互作用........................23
2-4-2-2 同核偶極-偶極交互作用........................23
2-5 魔角旋轉.........................................24
2-6 自旋空間平均化...................................25
2-6-1 相互作用座標...................................25
2-6-2 自旋去耦.......................................26
2-6-3 自旋鎖定(Spin Locking).........................27
2-6-4 Lee-Goldburg照射...............................28
2-7 極化傳遞.........................................29
2-7-1 同核自旋的極化傳遞.............................29
2-7-2 異核自旋的極化傳遞.............................29
2-7-3 在魔角旋轉下的Hartmann-Hahn配對................30
2-7-4 自旋溫度.......................................31
2-7-5 變接觸時間交叉極化魔角旋轉實驗.................32
2-8 雙量子相干.......................................33
2-8-1 雙量子訊號.....................................33
2-8-2 雙量子訊號的激發、演進和偵測...................34
2-8-3同核多量子技術..................................35
2-9 參考文獻.........................................36

第3章 合成與鑑定.....................................38
3-1 化學藥品.........................................38
3-2生物活性玻璃的製備................................39
3-2-1 膠體合成與老化(Aging)..........................39
3-2-2 膠體的乾燥.....................................40
3-2-3 矽鈣玻璃系統穩定化.............................41
3-3 玻璃的鑑定.......................................42
3-3-1 X光繞射分析(XRD)...............................42
3-3-2 傅利葉紅外光光譜(FT-IR)........................43
3-3-3 比表面積孔洞分析儀.............................43
3-3-4 感應耦合電漿質譜...............................46
3-3-5場發射掃描式電子顯微鏡及能量分散光譜儀…........47
3-3-6 熱重分析及低溫熱差分析儀.......................49
3-4 生物活性.........................................50
3-4-1 配製模擬體液...................................50
3-4-2 浸泡模擬體液...................................51
3-5 31P固態核磁共振光譜..............................51
3-5-1 31P魔角旋轉光譜................................52
3-5-2變接觸時間31P{1H}交叉極化魔角旋轉實驗….........52
3-5-3 31P{1H}Lee-Goldburg交叉極化雙共振關聯光譜......52
3-5-4 31P雙量子實驗..................................53
3-6 29Si魔角旋轉光譜.................................54
3-7 29Si{1H}交叉極化雙共振實驗.......................55
3-8 參考文獻.........................................55

第4章 實驗結果與討論.................................56
4-1 玻璃製備.........................................56
4-2 SEM、EDX和BET比表面積............................57
4-3 FT-IR和XRD.......................................59
4-4熱重分析和熱差分析................................61
4-5感應耦合電漿質譜..................................64
4-6 31P 魔角旋轉NMR..................................65
4-7 31P{1H}Lee-Goldburg交叉極化雙共振實驗............66
4-8 31P{1H}變化傳遞時間的交叉極化魔角旋轉實驗........71
4-9 31P雙量子NMR.....................................73
4-10 29Si魔角旋轉NMR.................................76
4-11 29Si{1H}交叉極化雙共振實驗......................77
4-12 討論............................................83
4-12-1 球狀生物活性玻璃..............................83
4-12-2 31P{1H}LG交叉極化雙共振光譜...................84
4-12-3 31P-31P二階偶極矩.............................85
4-12-4羥基磷灰石的成長...............................86
4-13 參考文獻........................................89

第5章 總結與未來展望.................................93
5-1 論文總結.........................................93
5-2 未來展望.........................................94
5-3 參考文獻.........................................95

第6章 附錄...........................................97
6-1 DSC結果討論......................................97
6-2 31P{1H}交叉極化實驗結果討論......................99

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第5章 參考文獻
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