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