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標題: 製備多功能吸附性薄膜於吸附與感測上的應用
Preparation of Multi-Functional Adsorptive Membranes for Adsorption and Sensing Application
作者: 孫幸宜
關鍵字: 應用研究
Multi-functional adsorptive membrane
Chemical modification
Fluorescent dye
摘要: An efficient alternative for chromatographic column is adsorptive membrane which canovercome the mass-transfer limitations of packed column such as high-pressure packing,intraparticle diffusion, and high pressure drop in operation. With research experience on thisarea for a couple of years, the PI aims to develop the technique of novel multi-functionaladsorptive membrane for analytical or sensing application. This project will focus on a seriesof chemical modifications on commercial porous membrane or fiber with OH groups. Thesemodifications are either in serial or in parallel, and each modification will create one specialtype of functional groups on solid matrix for one or more adsorption applications.Three chemical modification procedures are proposed in the first year of this project. Thefirst step is to react the OH groups on solid matrix with the NCO group of MIA (4-isocyanato-4'(3,3-dimethyl-2,4-dioxo-azetidino)diphenyl-methane) such that the azetidine-2,4-dioneterminal of MIA will be exposed on the matrix surface. The azetidine-2,4-dione could quicklyreact with primary aliphatic amines at high efficiency. Thus, anticipated in the second step isthe solid matrix modification with aminosuccinic acid. The exposed groups on solid matrix willbecome di-carboxylic acid, which could adsorb heavy metal ions by chelation, or adsorbphenols and triazines via hydrogen bonding. The solid matrix with immobilized metal ions maybe further adopted as immobilized metal affinity adsorbent. The third modification suggests tocouple -PGA onto the MIA-reacted solid matrix in order to create multi-COOH groups. Theresulted matrix will serve as a weak cation exchanger for adsorbing cationic dyes or proteins.In the second year, this project will concentrate on the immobilization of fluorescent dyeonto the membrane or fiber for adsorption or sensing purpose. The first step is to couplecarbazole-9-propionyl chloride onto the solid matrix for producing a fluorescent sensingmaterial. Moreover, the exposed carbazole groups on the matrix could provide for hydrophobicadsorption. Proposed in next two modification steps in parallel is the creation of quaternaryammonium groups (by nitration, reduction, and quateramination) and sulfonic acid groups (bysulfonation) on the carbazole-9-propionyl chloride-immobilized matrix. Thus, the sensingmatrix will turn into strong ion exchangers for adsorbing anionic DNA and cationic proteins. Inaddition, primary amine groups will be produced on the solid matrix after nitration andreduction, which could further react with glutaraldehyde. The created CHO terminal may evenfurther couple with immunoproteins to form an immunoaffinity adsorbent. In this year, thechange of fluorescence on the solid matrix will also be detected for sensing application.
吸附性薄膜分離技術之能成為層析管柱替代技術之一,主要因其能解決層析管柱的高壓填充、孔洞內擴散限制、與高操作壓降等問題,提升經濟效益。本實驗室經過多年來於吸附性薄膜的研究經驗累積,希望能發展多功能吸附性薄膜的製備方法,以應用於微量分析或感測用途。因此,本計畫建議以商業具有OH 基的微過濾薄膜或玻璃纖維為基材進行一連串化學改質實驗,這些化學改質可以是並聯式或串聯式,而每一項化學改質所形成的官能基即可提供一或多重吸附用途,達到多功能的應用目標。第一年度本計畫建議進行以下的化學改質實驗:第一步為帶OH 基的薄膜或纖維與合成之化學物質MIA (4-isocyanato-4’(3,3-dimethyl-2,4-dioxo-azetidino)diphenyl-methane)進行反應,MIA 可提供一端的NCO 官能基與OH 基反應,而顯露出另一端的azetidine-2,4-dione 官能基。第二步為將帶有azetidine-2,4-dione 官能基的薄膜或纖維與aminosuccinic acid 反應,如此薄膜或纖維表面將改質為具螯合作用的雙COOH 官能基,可應用於多類吸附用途,如:螯合吸附重金屬離子;而金屬離子螯合的薄膜或纖維可再進一步做為固定化金屬親和吸附材,以吸附分離生物分子;藉氫鍵作用吸附酚類物質或三氮六環衍生物等。前兩步化學改質屬於串聯式的反應設計,第三步化學改質則與第二步化學改質為相似的應用,屬於並聯式設計。第三步化學改質建議將薄膜或纖維上的azetidine-2,4-dione 官能基與-PGA 的一級胺基反應,使其固定上薄膜或纖維,如此薄膜或纖維表面將具有多重COOH 官能基,可應用於吸附酚類物質或三氮六環衍生物,也可應用為弱陽離子交換吸附材,吸附陽離子染料或蛋白質等。第二年度本計畫建議進行固定螢光染料於薄膜或纖維的化學改質,以做為吸附或感測材之應用。第一步為帶OH 基的薄膜或纖維與carbazole-9-propionyl chloride 反應,因其具COCl 官能基,易與OH 基反應,而固定之後基材將顯露出carbazole 官能基,可應用於疏水物質的吸附。第二步化學改質為將固定有carbazole-9-propionyl chloride 的薄膜或纖維進行硝化與還原反應,以獲得具一級胺基的薄膜或纖維,可應用於吸附酚類或三氮六環衍生物等。本計畫另建議將具一級胺基的薄膜或纖維進一步在鹼性環境下與溴乙烷反應,使產生四級胺基,可做為強陰離子交換吸附材,應用於DNA 的吸附。第三步化學改質為將帶一級胺基的薄膜或纖維與兩端帶有醛基的glutaraldehyde 反應,反應後薄膜或纖維上將顯露醛基,可應用於蛋白質之化學吸附,且可更進一步應用於免疫吸附用途。第四步化學改質屬於並聯式設計, 建議將第一步化學改質所得固定有carbazole-9-propionyl chloride 的薄膜或纖維進行磺化反應,以做為強陽離子交換吸附材,應用於金屬離子或陽離子蛋白質的吸附。因本年度的化學改質一開始即將薄膜或纖維固定上螢光染料,故可藉由基材螢光性質的變化,尋找適當的檢量線,做為後續吸附/脫附實驗的定量之用,而這也正是一種感測用途。
其他識別: NSC98-2221-E005-052
Appears in Collections:化學工程學系所



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