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研究生: 邱求三
Chiou, Chyow-San
論文名稱: 大環醚在壓電昌體偵測器及液體層上之應用
Application of Macrocylic Polyethers in Piezoelectric Quartz Detector and Liquid Chromatography
指導教授: 施正雄
Shih, Jeng-Shong
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 86
語文別: 中文
論文頁數: 182
中文關鍵詞: 大環醚壓電晶體
論文種類: 學術論文
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  • 本研究嘗試將大環醚類及大環醚類和碳六十之化合物應用於毛細管電泳當修試劑、壓電晶體偵測器及層析管柱材質研製等應用。
    大環胺醚添加於毛細管電泳之緩衝溶液中,具有分離陰離子及陽離子等雙功效功能。實驗中成功利用大環胺醚以分離K+,Na+及NH4+;並可利用緩衝溶液pH值的控制,而將大環胺醚質子化,此質子化的大環胺醚,於緩衝溶液中可扮演類似長鏈烷基四級銨鹽之修飾劑角色,可將EOF反向,並和陰離子間產生不同的作用力,而達到將其分離之目的,實驗中成功分離I-, NO3-, SCN-, BrO3-, IO3-, CrO42-等六種無機陰離子,及對硝基苯甲酸等五種有機陰離子。
    於壓電晶體偵測器部份,實驗中合成具長鏈烷基的大環胺醚及碳六十/大環胺醚化合物,作為壓電晶體電極的表面塗佈物,經由電極表面吸附重量的改變,而導致晶體頻率的變化,而達到偵測的目的。實驗中利用此壓電晶體偵測器,對有機化合物及陰、陽離子作檢測,並將所得訊號和商用之電導度及紫外光/可見光偵測器做比較,發現壓電偵測器具相當競爭性,而其偵測極限,對不同的有機物,約在10-4M,而對不同的陰、陽離子則約在10-5M。
    本研究亦合成碳六十-聚苯乙烯-二乙烯苯(CG-161m)-大環胺醚的樹脂,以作為離子層析管柱之填充材質,實驗中藉由衝提溶液pH值的控制,而將管柱材質中的大環胺醚質子化,即可應用於分離甲、乙、丙、丁酸根離子,及順、反丁烯二酸根離子等同分異構化合物;而將大環胺醚去質子化後,則可利用來分離陽離子。由於管柱材質之母體為聚苯乙烯-二乙烯苯及碳六十,故亦成功的利用此層析管柱以分離酚等芳香族化合物。

    Marcocyclic polyethers and C60-cryptand were synthesized and appliedincapillary electrophoresis, piezoelectric quartz crystal detector and ion chromatography as modifiers, coating material and packing materials respectively to separate or detect anions, cations and organic molecules.
    Macrocyclic cryptand-22 was employed as a bifuctional modifier to separate of cations and anions via capillary electrophoresis. The remarkable cation complexing ability of cryptand-22 caused an improvement in the separation resolution of some cations, e.g., K+, Na+ and NH4+ ions with capillary electrophoresis. The cryptand-22 was protonated as cryptand-2H2+at pH<7 and the protonated cryptand-22 was applied as a capillary surface modifier to seperate various organic / inorganic anions with capillary electrophoresis. This modifier treament caused the electroosmotic flow (EOF) and electrophoretic mobility of anions to have the same direction, thereby causing a greater column efficiency. The capillary electrophoresis system with the protonated cryptand modifier was successfully employed to separate and analyze various inorganic anions, e.g., I-, NO3-, SCN-, BrO3-, IO3-, CrO42-, and various carboxylate anions, e.g., p-nitro-benzoic acid, p-chloro-benzoic acid, p-hydroxy-benzoic acid, benzoic acid and terephthalic acid.
    A reusable and sensitive multifunctional piezoelectric quartz crystal liquid chromato graphic detector was developed for detection of cations, anions and organic molecules in solutions. The quartz crystal coated with dioctadecanoyl-cryptand-22 or C60- cryptand could be applied to detect organic molecules, e.g., benzoic acid, in solutions. The dioctadecanoyl-cryptand-22 coated crystal detector also could adsorb cations or anions which depends on the cryptand was protonated or not. The adsorption of cations such as Cr3+ or anions such as NO3- resulted in the oscillating frequency of the cryptand coated quartz crystal. The cryptand coated crystal detector showed good competition with a commercial conductivity detector for cations or anions and UV-Vis detector for organic molecules. The detection limits of the cryptand coated piezoelectric detector for ions and organic molecules were estimated as about 10-5M and 10-4M respectively.
    Poly (styrene / divinyl benzene) resin with C60-cryptand as an anchoring group was synthesized and applied in ion chromatography as a packing material for separations of organic anions, inorganic cations and aromatic compouds. The cryptand can not only form strong complexes with metal cations, but it has also shown a remarkable complexing ability with organic anions after protonation at pH<7. The protonated C60-cryptand resin has been applied as an anion exchanger to successfully separate some organic carboxylicate anions including HCOO-, CH3COO-, CH3CH2COO-, and CH3(CH2)2COO-, and some geometric isomers, e.g., fumarate and maleate ions. Alternately, after deprotonated at pH>7, the C60-cryptand resin can be switched as a cation exchanger to separate inorganic cations. And, because of the poly (styrene / divinyl benzene) and C60-, the syntesized resin could also be applied to separate some aromatic compounds, e.g., phenol, p-chloro phenol, p-nitro phenol and m-cresol.

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