利用矽氧烷化合物製備分子拓印高分子

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許玉瑩(Yu-Ying Hsu) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

利用矽氧烷化合物製備分子拓印高分子

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摘要(中)

摘要
本研究利用溶膠-凝膠法以四甲氧基矽烷 (TMOS) 或與矽偶合劑為單體，製備出具有吸附及辨識咖啡因的分子拓印高分子材料，並探討不同製備條件即pH值、R值 (H2O/Si)、偶合劑的種類及添加量對分子拓印之影響。本研究所得分子拓印高分子材料可經由煅燒的方式將模版分子移除，而留下具有與拓印物質互補的辦識位置。
分子拓印高分子的性質可利用高效能液相層析儀 (HPLC) 測量咖啡因鍵結量及選擇性 (α，咖啡因鍵結量與類似物茶鹼鍵結量之比值)，且可經由氮氣吸附孔隙儀 (ASAP) 得知，所製備之分子拓印高分子是否具多孔性質。
本研究結果顯示，單獨利用 TMOS 所製備之分子拓印高分子具有狹窄的孔徑分佈，並具有高比表面積 (434.5 m2/g)，故可得到較高之咖啡鍵結量 (17 μmol/g)。而反應系統中藉由二官能基矽烷 (KBM-22) 或三官能基矽烷 (KBM-13) 的添加，可改變所得分子拓印高分子的比表面積與孔徑大小。隨著 KBM-13 添加比例的增加，可使咖啡因的鍵結量下降，但是提升分子拓印高分子的選擇性，最高可達7。
而利用煅燒升溫梯度的改變，所得分子拓印高分子之性質也有所不同。在改變煅燒升溫梯度下所得的咖啡因鍵結量，以利用 KBM-13所製備的提升效果較佳，可提升2 ~ 3倍，且選擇性也有明顯提升，最高可達48。

關鍵字(中)

★ 溶膠凝膠法
★ 分子拓印

關鍵字(英)

★ sol-gel
★ MIP

論文目次

目錄
目錄…………………………………………………………………… I
圖索引………………………………………………………………… III
表索引………………………………………………………………… V
第一章前言………………………………………………………….. 1
1-1 分子拓印原理………………………………………………… 2
1-2 共價鍵與非共價鍵型分子拓印……………………………… 5
1-3 溶膠-凝膠技術之簡介………………………………………... 9
1-4 溶膠-凝膠法之分子拓印材料………………………………... 17
1-5 咖啡因模版分子之介紹……………………………………… 23
1-6 研究目的……………………………………………………… 25
第二章實驗………………………………………………………….. 27
2-1 實驗藥品……………………………………………………… 28
2-2 實驗儀器……………………………………………………… 30
2-3 分子拓印高分子材料之製備………………………………… 31
2-4 分子拓印高分子材料之物性測試…………………………… 34
第三章結果與討論………………………………………………….. 36
3-1 四甲氧基矽烷製備分子拓印高分子………………………… 37
3-1-1 pH值對分子拓印高分子之影響………………………… 37
3-1-2 咖啡因添加量對分子拓印高分子之影響………………... 41
3-1-3 R值對分子拓印高分子之影響………………………… 43
3-2 四甲氧基矽烷與矽偶合劑製備分子拓印高分子…………… 46
3-2-1 R值對分子拓印高分子之影響……………………………. 46
3-2-1-1 高R值對分子拓印高分子之影響…………………….. 46
3-2-1-2 低R值對分子拓印高分子之影響…………………….. 53
3-2-2 pH值對分子拓印高分子之影響………………………… 55
3-2-3 二官能基矽烷含量對分子拓印高分子之影響…………... 61
3-2-4 三官能基矽烷含量對分子拓印高分子之影響…………... 67
3-2-5 不同煅燒溫度移除模版分子之探討……………………... 72
3-2-6 分子拓印高分子之結構鑑定……………………………... 78
3-2-7 咖啡因拓印之驗證………………………………………... 84
第四章結論………………………………………………………….. 87
參考文獻……………………………………………………………… 89
圖索引
Figure 1-1 A way to make artificial locks for molecular keys………... 3
Figure 1-2 Schematic illustration of non-covalent molecular imprinting………………………………………………... 4
Figure 1-3 Covalent imprinting of mannopyranoside using itsp-vinylbenzenboronic acid as a functional monomer…….. 7
Figure 1-4 Non-covalent imprinting by theophylline………………… 8
Figure 1-5 The hydrolysis and condensation of silane……………….. 12
Figure 1-6 Sol-gel reaction process…………………………………... 13
Figure 1-7 Gel structure for acid and base catalyst reaction………….. 14
Figure 1-8 Polymerization behavior of aqueous silica……………….. 15
Figure 1-9 Scheme of relative reaction kinetics of alkoxysilanes versus pH…………………………………………………. 16
Figure 1-10 Preparation procedures used to create the imprinted silicas……………………………………………………. 18
Figure 1-11 Chemical structure of template molecules………………. 20
Figure 1-12 Scheme of formation of chiral cavity in a sol-gel matrix... 20
Figure 1-13 The structure of three dye molecules and schematic representation of the preparation of their imprinted polysiloxanes……………………………………………. 21
Figure 1-14 Scheme of a sol-gel method using TEOS and acetic anhydride………………………………………………… 22
Figure 1-15 A plausible mechanism of the formation of pore void suitable for the selective adsorption of steroid skeletons... 22
Figure 2-1 The structural formula of template and silanes…………. 29
Figure 2-2 Systhesis process of preparing MIP via sol gel process…... 32
Figure 2-3 Systhesis process of preparing MIP via sol gel process…... 33
Figure 3-1 Relationship between caffeine bound and pH value of MIP 40
Figure 3-2 Relationship between caffeine bound and R of MIP……… 45
Figure 3-3 Nitrogen adsorption-desorption isotherms and Pore sizedistributions of C-1, D-1………………………………….. 51
Figure 3-4 Relationship between selectivity and R of MIP…………... 52
Figure 3-5 Nitrogen adsorption-desorption isotherms and Pore size distributions of F-2………………………………………... 59
Figure 3-6 Nitrogen adsorption-desorption isotherms and Pore size distributions of F-2, F-4…………………………………... 60
Figure 3-7 Nitrogen adsorption-desorption isotherms and Pore size distributions of G-3……………………………………….. 65
Figure 3-8 Nitrogen adsorption-desorption isotherms and Pore size distributions of G-1, G-3…………………………………. 66
Figure 3-9 Nitrogen adsorption-desorption isotherms and Pore sizedistributions of H-1, H-3…………………………………. 71
Figure 3-10 TGA analysis of caffeine………………………………… 74
Figure 3-11 Different calcination temperature program……………… 75
Figure 3-12 TGA analysis of MIP prepared by different TMOS:KBM-13…………………………………………. 80
Figure 3-13 FTIR spectra of sample A-5 (A) before and (B) after calcination at 600℃……………………………………... 81
Figure 3-14 FTIR spectra of sample G-1 (A) before and (B) after calcination at 600℃……………………………………... 82
Figure 3-15 FTIR spectra of sample H-1 (A) before and (B) after calcination at 600℃……………………………………... 83
Figure 3-16 Selectivity of caffeine imprinted and non-imprinted……. 86
表索引
Table 1-1 Advantages and disadvantages of covalent and non-covalent imprinting……………………………………. 6
Table 1-2 Caffeine concentration among of the retail beverages…….. 24
Table 3-1 Preparation conditions and characteristics of MIP prepared by different pH value via sol-gel process………………….. 39
Table 3-2 Preparation conditions and characteristics of MIP prepared by different caffeine amounts via sol-gel process………….. 42
Table 3-3 Preparation conditions and characteristics of MIP prepared by different R(H2O：Si ratio) via sol-gel process................. 44
Table 3-4 Pore properties of MIP……………………………………... 49
Table 3-5 Preparation conditions and characteristics of MIP preparedby different R(H2O：Si ratio) via sol-gel process................. 50
Table 3-6 Preparation conditions and characteristics of MIP preparedby different R(H2O：Si ratio) via sol-gel process................. 54
Table 3-7 Preparation conditions and characteristics of MIP preparedby different pH via sol-gel process………………………… 57
Table 3-8 Pore properties of MIP prepared by different pH via sol-gelprocess……………………………………………………… 58
Table 3-9 Preparation conditions and characteristics of MIP preparedby different content of coupling agent via sol-gel process… 63
Table 3-10 Pore properties of MIP prepared by different content of coupling agent via sol-gel process………………………... 64
Table 3-11 Preparation conditions and characteristics of MIP preparedby different content of coupling agent via sol-gel process.. 69
Table 3-12 Pore properties of MIP prepared by different content of coupling agent via sol-gel process……............................... 70
Table 3-13 Preparation conditions and characteristics of MIP via sol-gel process and removed the template by differentcalcinations temperature………………………………….. 76
Table 3-14 Preparation conditions and characteristics of MIP viasol-gel process and removed the template by different calcinations temperature………………………………….. 77
Table 3-14 Preparation conditions and characteristics of MIPprepared by different content of coupling agent via sol-gel process…………………………………………………….. 85

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指導教授

陳暉(Hui Chen)

審核日期

2005-6-22

推文