以溶膠凝膠法製備磺胺二甲嘧啶分子拓印高分子在管柱層析之應用

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黃郁婷(Yu-Ting Huang) 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

以溶膠凝膠法製備磺胺二甲嘧啶分子拓印高分子在管柱層析之應用
(Application of Sulfamethazine-Molecularly Imprinted Polymer on Liquid Chromatography Prepared by Sol-Gel Process)

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摘要(中)

本研究以磺胺二甲嘧啶 (Sulfamethazine，SMZ) 為模板分子，四乙氧基矽烷 (Tetraethoxysilane，TEOS)為單體，經溶膠-凝膠程序與後處理程序製備分子拓印高分子(molecularly imprinted polymer, MIP)與無分子拓印高分子(non-molecularly imprinted polymer, NIP)。所討論的變數為(1)溶膠-凝膠程序之R值(H2O/TEOS) (2)後處理程序 (3)移動相pH值 (4)移動相組成，經溶膠-凝膠程序所得之產物因其網目架橋密度低、極性官能基多且須移除模板分子(SMZ)，須經後處理程序即萃取、HMDS修飾反應與進一步反應等步驟才能得到具有層析分離之MIP，故探討下列以下變數(1)HMDS修飾反應時間 (2)後處理程序的順序 (3)進一步反應時間 (4)鍛燒移除模板分子之溫度 (5) 移除模板分子方法即鍛燒與萃取比較，將製備之MIP作為層析靜置相，最後再以高效能液相層析儀(high performance liquid chromatographic method，HPLC) 測量SMZ與相似物磺胺甲噁唑 (Sulfamethoxazole，SMO)滯留時間進而算出選擇率(selectivity，α)與拓印因子(Imprinting factor，IF )，以及利用SMZ與SMO兩吸收峰的基部寬度進而計算出解析度(Resolution，Rs)與理論板數( Theoretical Plate Number，N )。
結果顯示溶膠-凝膠程序之R值會影響MIP之模板分子辨識位置，HMDS修飾反應時間、進一步反應的時間與移除模板分子之溫度會影響MIP及NIP之SMZ與SMO之滯留時間與層析分離之效果。萃取與鍛燒移除模板方法中，利用萃取所得之MIP其Rs與N高。移動相pH值接近模板分子的pKa值時(pH=7.4)及移動相含水量為90％時，有較高的α、IF、Rs與N。本法顯示先進行HMDS修飾反應60分鐘後在300℃反應2小時，最後利用甲醇萃取移除模板分子(SMZ)，移動相pH值及含水量比分別為7.4及90 ％，使MIP具有較高之α(4.03)、IF(2.19)、Rs(4.61)與N(361)

摘要(英)

The synthesis of inorganic molecularly imprinted polymer (MIP) as a stationary phase of high performance liquid chromatography (HPLC), for the efficient determination of template (sulfamethazine, SMZ) and analogue (sulfamethoxazole, SMO) has been developed. MIP was prepared by reaction of tetraethoxysilane (TEOS) via sol-gel process and post treatment. The template was dissolved in acid aqueous solution and added into TEOS to form the precursor solution. The solution was adjusted the pH by adding ammonium hydroxide (NH4OH). There were three steps in post treatment , modification with HMDS, farther reaction, and extraction, to improve the crosslink density of MIP and remove template. The best recognizability of MIP was obtained by the following conditions: the ratio of water to TEOS (R=5), extraction (MeOH, 17hr), post treatment sequence (modification 1h, reaction 2h, extraction 17hr), the value of pH (pH= pka = 7.4) and composition of mobile phase (MeCN:H2O = 10:90).

關鍵字(中)

★ 理論板數
★ 解析度
★ 膠-凝膠程序
★ 磺胺二甲嘧啶
★ 選擇率
★ 拓印因子

關鍵字(英)

★ sol-gel Process
★ sulfamethazine (SMZ)
★ selectivi

論文目次

頁次
中文摘要 ………………………………………………………… I
英文摘要 ………………………………………………………… III
誌謝 ………………………………………………………… IV
目錄 ………………………………………………………… V
圖索引 ………………………………………………………… VIII
表索引 ………………………………………………………… X
一、前言…………………………………………………… 1
1-1 分子拓印高分子發展及應用………………………… 1
1-2 分子拓印高分子技術與原理………………………… 2
1-3 溶膠－凝膠程序……………………………………… 4
1-3-1 系統之pH值對溶膠－凝膠程序的影響……………… 4
1-3-2 含水量對溶膠－凝膠程序的影響…………………… 5
1-4 模板分子SMZ之介紹………………………………… 7
1-5 文獻回顧……………………………………………… 8
1-6 研究目的……………………………………………… 10
二、實驗…………………………………………………… 11
2-1 實驗藥品……………………………………………… 11
2-2 實驗儀器器…………………………………………… 13
2-3 分子拓印高分子之製備……………………………… 14
2-4 分子拓印高分子之物性測試………………………… 16
2-4-1 高效能液相層析(HPLC)參數………………………… 16
2-4-1-1 容量因子(Capacity Factor) ……………………… 16
2-4-1-2 選擇率(Selectivity) ……………………………… 16
2-4-1-3 解析度(Resolution)………………………………… 17
2-4-1-4 拓印因數(Imprinting Factor) …………………… 17
2-4-1-5 理論板數( Theoretical Plates Number ) ……… 18
2-4-2 氮氣吸附孔隙儀分析(ASAP)………………………… 18
2-4-3 化學分析電子儀分析(ESCA) ……………………… 18
2-4-4 紅外線光譜分析(FTIR)……………………………… 18
2-4-5 熱重分析儀分析(TGA)………………………………… 19
三、結果與討論…………………………………………… 20
3-1 R值對分子拓印高分子層析的影響…………………… 20
3-2 後處理程序對分子拓印高分子層析的影響………… 27
3-2-1 HMDS修飾時間對分子拓印高分子層析的影響……… 27
3-2-2 後處理程序的順序對分子拓印高分子層析的影響… 40
3-2-3 進一步反應的時間對分子拓印高分子層析的影響… 44
3-2-3 鍛燒移除模板分子溫度對分子拓印高分子層析的影響48
3-2-4 萃取與鍛燒對分子拓印高分子層析的影響………… 59
3-3 移動相之pH值對於分子拓印高分子層析的影響…… 67
3-4 移動相組成對分子拓印高分子層析的影響………… 72
四、結論…………………………………………………… 77
參考文獻 ………………………………………………………… 80
附錄A ………………………………………………………… 84

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指導教授

陳暉(Hui Chen)

審核日期

2009-6-25

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