臺灣博碩士論文加值系統

分子模版高分子（molecularly imprinted polymer, MIP）為單體與模版分子形成錯合物，並以高比例之交聯劑進行交聯聚合反應，合成具有高度吸附選擇性之聚合物，對模版分子或其結構相似的分子有良好之辨識能力。
本研究以膽固醇為模版分子，黃體酮及荳固醇為競爭分子，MAA為單體，DVB及EGDMA為交聯劑，1-hydroxycyclohexylphenyl ketone為光起始劑，以紫外光（254nm）光化學聚合反應的方式製備模版高分子顆粒及薄膜，並使用高效能液相層析儀(HPLC)測量膽固醇模版高分子對膽固醇的吸附量以及選擇率。
由顆粒狀分子模版高分子吸附實驗結果得知，（a）在單一溶質吸附液與混合溶質吸附液中，MIP對膽固醇及黃體酮之吸附量不同，對膽固醇的選擇性較高於黃體酮，尤其長時間的吸附作用下，膽固醇的選擇效應更加明顯，顯示顆粒狀MIP確實具有辨識膽固醇之模版位置，同時，MIP辨識性質深受流動相溶液影響，原因為吸附液中溶劑的極性能改變MIP的吸附效能，以甲醇/水(90/10)的比例為吸附液溶劑結果顯示分子模版高分子對膽固醇的吸附量不僅提高，且選擇性亦更明顯。
由薄膜型膽固醇模版高分子吸附結果發現，MIP薄膜與NIP薄膜可附著於鋁片（Al plate）及鍍鋁玻璃（Al-coated glass）表面，MIP在單一溶質吸附液與混合溶質吸附液中，對膽固醇與荳固醇的吸附量不同，NIP則顯現較小的吸附量，且兩者吸附量大約相同。在各種不同組成的聚合溶液中，以95 mole％，DVB為交聯劑之組成，合成製備之模版高分子薄膜對膽固醇具有較高的選擇性。

The technique to synthesize molecularly imprinted polymer(MIP)involves complexation of template molecule and functional monomer, followed by polymerization of this complex with crosslinker to form a highly crosslinking polymer, MIP exhibits specific recognition ability to template molecule due to the affinity between functional group and template molecule and it’s well-defined shape which allows the template molecule specifically to fit in.
The purpose of this study is to synthesize cholesterol-imprinted polymerization, UV(254nm) stimulated polymerization with methacrylic acid (MAA) as functional monomer, divinylbenzene (DVB) and Ethylene glycol dimethacrylate (EGDMA) as crosslinker and 1-hydroxycyclohexylphenyl ketone as initiator. The adsorption determined by analyzing the concentration change of solute in adsorption solution using HPLC.
For MIP particles, the results showed that cholesterol-imprinted polymer adsorbed different amount of cholesterol and progesterone when they were placed in the adsorption solution of single solute and in the adsorption solution of binary solute. Cholesterol was more selectivity adsorbed by MIP particle than progesterone. Especially for long-period of adsorption, selectivity characteristics for cholesterol was more significant. This results indicated that the synthesized MIP did possess template site which could recognize cholesterol molecule. In addition, the adsorption amount of cholesterol and selectivity factor for cholesterol were enhanced when the polarty of solvent in adsorption solution was increased.
For MIP composite membranes, it was found that both MIP membrane and NIP membrane were still retained on the surface of both Al plate and Al-coated glass after series of treatment including extraction, adsorption and re-extraction. Cholesterol-imprinted polymer membrane adsorbed more cholesterol than stigmasterol. NIP membrane adsorbed about the same amount of both cholesterol and stigmasterol. The amount of cholesterol and stigmasterol adsorbed by NIP membrane was smaller than that adsorbed by MIP membrane. The results suggested that MIP membrane did exhibit the ability to recognize cholesterol. With polymerization solution of 95 mole% DVB, the synthesized MIP membrane showed the better selective characteristics toward cholesterol.

中文摘要 ---------------------------------------------------------------------------------- I
英文摘要 -------------------------------------------------------------------------------- III
誌謝 -------------------------------------------------------------------------------------- V
目錄 ------------------------------------------------------------------------------------ VI
圖目錄---------------------------------------------------------------------------------- VIII
表目錄--------------------------------------------------------------------------------- XIX
第 一 章 緒論 -------------------------------------------------------------------------- 1
1.1前言------------------------------------------------------------------------------ 1
1.2分子模版技術（Molecular imprinting technique）------------------------ 2
1.3分子模版的應用--------------------------------------------------------------- 5
1.4薄膜技術工程應用於分子模版高分子的合成-------------------------- 12
1.5檢測膽固醇的方法----------------------------------------------------------- 13
1.6 MIPs技術於膽固醇分析的應用------------------------------------------- 18
1.7 研究動機---------------------------------------------------------------------- 19
第二章 原理----------------------------------------------------------------------------- 21
2.1 分子模版高分子的原理--------------------------------------------------- 21
2.1.1自組結合--------------------------------------------------------------- 24
2.1.2 單體聚合------------------------------------------------------------- 24
2.1.3 模版移除------------------------------------------------------------- 25
2.2 分子模版高分子的製備---------------------------------------------------- 25
2.3 目標物分子-膽固醇 （Cholesterol）------------------------------------- 30
2.3.1 膽固醇的特性與合成---------------------------------------------- 30
2.3.2 膽固醇的結構------------------------------------------------------- 34 2.3.3 膽固醇在人體內的運輸與代謝---------------------------------- 36
2.3.4 膽固醇與血管硬化及心臟病之關係---------------------------- 38
2.3.5 黃體酮（Progesterone）--------------------------------------------- 40
2.3.6 荳固醇（Stigmasterol）--------------------------------------------- 42
2.4功能性單體（Functional monomer）----------------------------------- 42
2.5 交聯劑（Crosslinker）-------------------------------------------------------- 48
2.6 聚合方式---------------------------------------------------------------------- 50
2.6.1 共價鍵鍵結方式---------------------------------------------------- 50
2.6.2 非共價鍵結合------------------------------------------------------- 52
2.6.2.1 酸鹼性官能基單體---------------------------------------- 52
2.6.2.2 金屬離子官能基單體------------------------------------- 55
2.6.2.3 金屬離子模版分子---------------------------------------- 55
2.6.2.4 無機化合物單體------------------------------------------- 57
2.6.2.5 微生物模版分子------------------------------------------- 61
2.7 聚合膽固醇模版高分子---------------------------------------------------- 63
第三章 實驗------------------------------------------------------------------- 68
3.1 實驗藥品與儀器------------------------------------------------------------- 68
3.1.1 實驗藥品------------------------------------------------------------- 68
3.1.2 實驗儀器------------------------------------------------------------- 70
3.2 顆粒狀分子模版高分子---------------------------------------------------- 71
3.2.1 分子模版高分子之製備------------------------------------------- 71
3.2.2 分子模版高分子中膽固醇之移除------------------------------- 75
3.2.3 分子模版高分子之吸附效能測試------------------------------- 76
3.2.3.1 膽固醇（Cholesterol）/ 黃體酮（Progesterone）
系統--------------------------------------------------------- 76
3.2.3.2 HPLC分析系統-------------------------------------------- 77
3.3 薄膜型分子模版高分子---------------------------------------------------- 77
3.3.1 以多孔性氧化鋁Anopore®為基材之分子模版高分子複
合膜-------------------------------------------------------------------77
3.3.1.1 分子模版高分子複合膜之製備------------------------- 77
3.3.1.2 Anopore®表面改質----------------------------------------- 78
3.3.1.3 分子模版高分子之脫附作用---------------------------- 78
3.3.1 .4 MIP/ Anopore®複合膜之特性分析--------------------- 81
3.3.1.4.1 氣體穿透儀分析------------------------------ 82
3.3.1.4.2 掃瞄式電子顯微鏡（SEM）分析------------ 86
3.3.2 以鋁片(Al plate)為基材之分子模版高分子複合膜----------- 86
3.3.2.1 分子模版高分子複合膜之製備------------------------- 86
3.3.2.1.1 DVB/MAA/Cholesterol聚合溶液-------- 86
3.3.2.1.2 EGDMA/MAA/Cholesterol聚合溶液---- 88
3.3.2.2 分子模版高分子薄膜中膽固醇之移除---------------- 89
3.3.2.3 分子模版高分子複合膜效能測試---------------------- 89
3.3.2.4 MIP/Al複合膜之特性分析----------------------------- 92
3.3.2.4.1 掃瞄式電子顯微鏡分析--------------------- 92
3.3.2.4.2 液相層析儀分析------------------------------ 93
3.3.3 以鍍鋁玻璃為基材之分子模版高分子複合膜---------------- 93
3.3.3.1 分子模版高分子複合膜之製備------------------------- 93
3.3.3.1.1 DVB/MAA/Cholesterol聚合溶液-------- 93
3.3.3.1.2 EGDMA/MAA/Cholesterol聚合溶液---- 93
3.3.3.2 MIP/鍍鋁玻璃複合膜中膽固醇之移除---------------- 95
3.3.3.3 分子模版高分子複合膜之吸附效能測試------------- 95
3.3.3.4 分子模版高分子複合膜特性分析---------------------- 95
3.3.3.4.1 掃瞄式電子顯微鏡分析--------------------- 95
3.3.3.4.2 液相層析儀分析------------------------------ 97
第四章 結果---------------------------------------------------------------------------- 98
4.1 顆粒狀分子模版高分子---------------------------------------------------- 98
4.1.1分子模版高分子中膽固醇之移除--------------------------------- 98
4.1.2 吸附效能測試------------------------------------------------------ 101
4.1.2.1 DVB/MAA/Cholesterol聚合溶液---------------------- 101
4.1.2.1.1膽固醇 / 黃體酮系統----------------------- 101
4.2 薄膜型分子模版高分子-------------------------------------------------- 119
4.2.1 以多孔性氧化鋁Anopore®為基材之分子模版高分子複
合膜----------------------------------------------------------------- 119
4.2.1.1膜厚與紫外光光照時間及氧氣穿透係數的關係-- 119
4.2.1.2分子模版高分子薄膜中膽固醇之移除-------------- 122
4.2.2 合成膽固醇分子模版高分子薄膜於改質之Anopore®
表面----------------------------------------------------------------- 122
4.2.2.1以3-(Trimethoxysilyl)propyl ester
(CH2=CHCOO(CH2)3Si(OCH3)3)改質Anopore®
之結果---------------------------------------------------- 123
4.2.2.2 以Allyl mercaptan（CH2=CHCH2SH）改質
Anopore® 之結果----------------------------------- 123
4.2.3以鋁片（Al plate）為基材之分子模版高分子複合膜----------- 130
4.2.3.1分子模版高分子薄膜中膽固醇之移除--------------- 130
4.2.3.2 模版高分子薄膜之吸附效能測試之結果----------- 134
4.2.3.2.1 DVB/MAA/Cholesterol聚合溶液---------- 139
4.2.3.2.2 EGDMA/MAA/Cholesterol聚合溶液----- 146
4.2.4以鍍鋁玻璃為基材之分子模版高分子複合膜---------------- 150
4.2.4.1 EGDMA/MAA/Cholesterol聚合溶液------------------ 150
4.2.4.1.1 分子模版高分子薄膜中膽固醇移除------- 150
4.2.4.1.2 模版高分子薄膜吸附效能測試之結果--- 153
第五章 討 論-------------------------------------------------------------------------- 158
5.1 顆粒狀分子模版高分子對膽固醇與黃體酮選擇性之探討----------- 158
5.1.1 單一溶質吸附吸液中之選擇特性--------------------------------- 159
5.1.2 混合溶質吸附液中之選擇特性---------------------------------- 159
5.2 不同基材製備薄膜型分子模版------------------------------------------- 162
5.3 聚合溶液組成對薄膜型分子模版高分子選擇效能之影響---------- 165
第六章 結 論-------------------------------------------------------------------------- 172
第七章 建 議-------------------------------------------------------------------------- 175
參考文獻-------------------------------------------------------------------------------- 176

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