臺灣博碩士論文加值系統

第一部份:我們已研發出了兩個以 4-nitrobenzo[c][1,2,5]oxadiazole (NBD) 為架構的人工感測劑，(E)-N1-(2,5-dimethoxybenzylidene)-N2-
(7-nitrobenzo[c][1,2,5]oxadiazol-4-yl)benzene-1,2-diamine (15) 和 (E)-N1-(3-methoxybenzylidene)-N2- (7-nitrobenzo[c][1,2,5]oxadiazol-4-
yl)benzene-1,2-diamine (16)，藉著胺類和醛類進行縮合反應脫水，即可得化合物，合成方法簡單，而且產率高，並探討其是否會與陰離子產生可見光及螢光的變化。感測劑 15 和 16 是荷希夫鹼衍生物，在酸性溶液中很容易產生水解反應，在混合溶液 (乙腈與水的體積比為 4：1) 中，對於硫酸氫根離子 (pKa = 1.99) 有特別優異的靈敏性及選擇性，可藉由不同的顏色變化快速的來辨識硫酸氫根離子，其中感測劑 15 能與硫酸氫根離子產生螢光增強的現象，其對於硫酸氫根離子的偵測極限為 (0.24 ± 0.03) uM。我們將水解產物經過分離，及 1H NMR 光譜、 ESI-MS 分析和 X-ray 鑑定確定其結構，並證實感測劑偵測硫酸氫根離子的反應機構是水解反應。另外，我們模擬了感測劑可應用在環境中，藉由顏色的變化偵測硫酸氫鹽類。
第二部份:本實驗室設計出三個新的感測劑 16-18 偵測一系列的羧酸鹽陰離子異構物，化合物 16 與 18 能用肉眼來區分順式-丁烯二羧酸鹽與反式-丁烯二羧酸鹽及 2-氫氧基丁二羧酸鹽與 2,3-二氫氧基丁二羧酸鹽且具有很好的敏感性與選擇性，除此之外，化合物 16 對於順式-丙-1-烯基-1,2,3-三羧酸鹽與反式-丙-1-烯基-1,2,3-三羧酸鹽 亦有獨特的顏色變化可以用來辨識它們。

Part 1 :Two new receptors have been prepared based on 4-nitrobenzo[c][1,2,5]oxadiazole (NBD), (E)-N1-(2,5-dimethoxybenzylidene)-N2-(7-nitrobenzo[c][1,2,5]oxadiazol-4-yl)benzene-1,2-diamine (15) and (E)-N1-(3-methoxybenzylidene)-N2- (7-nitrobenzo[c][1,2,5]oxadiazol-4-yl)benzene-1,2-diamine (16). Receptors 15 and 16 were obtained by simple and high-yielding condensation of an amine and aldehyde, and their fluorescent and naked eye visible color changes in the presence of anions and cations were investigated. Receptors 15 and 16 are Schiff base derivatives, which hydrolyze easily in acidic solution. In acetonitrile and water (4:1) solution, they show remarkable sensitivity and selectivity to hydrogen sulfate ions. Among them, receptor 15 shows fluorescence enhancement in the presence of hydrogen sulfate, with a detection limit of (0.24 ± 0.03) uM. We isolated the hydrolysis product and determined its structure through 1H NMR, ESI-MS, and X-ray crystallography. In addition, we confirmed the effectiveness of the receptor in applications in the natural environment.
Part 2 :Three new colorimetric anion receptors 16-18 were synthesized and characterized. Among them, both 16 and 18 showed good sensitivity and selectivity for discrimination of maleate versus fumarate or malate versus tartrate by dramatic colour changes in DMSO. Thus, both 16 and 18 can be used as optical chemosensors for recognition of maleate versus fumarate or malate versus tartrate anion. Besides that, the receptor 16 has also a unique colour change for recognition of either cis-aconitate or trans-aconitate in DMSO, accordingly it can be used for detection of each isomer and discrimination of cis-aconitate from trans-aconitate anion.

第一部份
謝誌Ι
摘要Ⅱ
AbstractⅢ
目錄Ⅳ
圖目錄Ⅴ
表目錄Ⅵ
壹、緒論1
一、前言1
二、研究動機13
三、螢光離子感應器的訊號傳遞機制14
貳、實驗部份21
一、測試儀器21
二、實驗試藥及溶劑22
叁、實驗結果與討論23
肆、結論62
伍、合成步驟與光譜數據63
陸、文獻資料81
第二部份
摘要ΧΙΙΙ
AbstractΧⅣ
目錄ΧⅤ
圖目錄ΧⅥ
表目錄ΧΧⅥ
壹、緒論84
一、前言84
二、研究動機93
貳、實驗部份94
一、測試儀器94
二、實驗試藥及溶劑95
叁、實驗結果與討論96
肆、結論171
伍、合成步驟與光譜數據172
陸、文獻資料199
柒、附錄 (已發表文章)201

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