分子印跡技術合成人工麝香及香豆素吸附劑及其基於磁性修飾的樣品前處理應用

Synthesis of Musk-T and Coumarin Absorbents by Molecular Imprinting Technique and Its Application on Sample Pretreatment Based on Magnetic Modification

蔣昭歡(Zhao-Huan Jiang)

指導教授 ： 凌永健

國立清華大學/工學院/奈米工程與微系統研究所/碩士(2014年)

摘要

合成香料在生活中廣泛被使用，但由於其性質穩定，不易降解，隨生活污水進入生物圈後不僅破壞環境，也危害人類健康。本研究選取麝香中的Musk-T（ethylene glycol brassylate）和香豆素作為基本研究對象合成以分子印跡技術（Molecularly Imprinted Technique, MIT）為基礎的吸附劑，並對其進行磁性修飾，應用於分析化學中的關鍵前處理過程，對複雜基質中待測物做初步分離。
本研究分別以合成麝香Musk-T和香豆素為模板分子，MAA作為與其產生非共價作用結合位點之功能單體， EGDMA作為交聯劑，AIBN作為起始劑，在有機溶劑中沉澱聚合製備分子印跡高分子微球MIPs( Molecularly Imprinted Polymers)。其中以Musk-T為模板製備的MIPs平均粒徑主要集中在400-500 nm之間，粒徑分佈集中，在研究濃度範圍0.05-1 mmol/L中，吸附劑吸附容量可達13.80 mg/g，最低1.88 mg/g，印跡因數最高4.1，最低2.4，且選擇性良好。以香豆素為模板製備的MIPs平均粒徑主要集中在300-400 nm之間，粒徑分佈集中，在研究濃度範圍0.02-0.5 mmol/L中，吸附劑吸附容量可達2.89 mg/g，最低0.39 mg/g，印跡因數最高10.1，最低2.7，且選擇性良好。經過Scatchard模型分析發現所合成兩種吸附劑均存在特異性結合和非特異性結合兩種結合位點。再利用EDC/NHS系統將帶有氨基的磁性奈米粒子修飾與帶有羧基的MIPs表面得到具磁性MIPs微球，方便用作人工香料吸附劑。本研究製備之MIPs吸附劑，相較於傳統吸附劑，具有高選擇性、易於合成、耐用、易回收等特點，有助於落實綠色分析化學之目標。

關鍵字

分子印跡高分子 ； 合成麝香 ； 香豆素 ； 吸附劑 ； 綠色

並列摘要

Artificial fragrances widely used in cosmetics, perfumes, detergents and other daily necessities are good alternatives to expensive natural flavors. Consequently, domestic sewage containing significant amount of artificial fragrances is discharged into the aquatic environment. Artificial fragrances are usually non-biodegradable, and results in bioaccumulation, disturbing the biological chain. Musk is very popular since ancient times. Deer musk is expensive and rare, therefore synthetic musk has gained more popularity. Musk-T, one of the synthetic musk, is used in my research. Another chemical is coumarin, which is also widely used as a fragrance in our daily life. But it is reported by the Health and Consumers Department of the European Union that coumarin is an allergen.
In my research, MIPs for Musk-T and coumarin are successfully prepared, where MAA is used as the functional monomer, EGDMA as the cross-linker, and the polymerization reaction is initiated by AIBN. The average size of MIPs for Musk-T is 400-500 nm, and for the concentration of 0.05mM-1mM, the adsorption capacity is in between 1.88mg/g and 13.80mg/g. The highest imprinting factor is 4.1, and the lowest is 2.4. The size of MIPs for coumarin is 300-400 nm, the adsorption capacity is between 0.39-2.89 mg/g during the sample concentration of 0.02-0.5 mM. The imprinting factor is between 2.7 and 10.1, and has a good selectivity. The data is also analyzed by Scatchard Equation. Results show that there are two kinds of adsorption on the surface of both MIPs, specific binding and nonspecific binding.
At last, the MIPs is modified by Fe3O4 using the EDC/NHS system, which makes the MIPs more convenient when it is used in the pretreatment process.

並列關鍵字

molecularly imprinted polymer ； synthesis musk ； coumarin ； adsorbent ； green

參考文獻

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