臺灣博碩士論文加值系統

本論文合成一系列螢光感測分子20-24，化合物20-22採用蒽基當作螢光基團，化合物24修飾上芘基螢光基團，然後運用硫冠醚和三唑基團作為金屬離子辨識單位，分別修飾在cone構形和1,3- alternate構形的芳杯上，利用光譜儀器測量這些化合物在乙腈溶液中的光物理性質，證實其化合物的負向異質變構性效應(negative heterotropic allosteric effect)。
　　首先我們從化合物20-23了解對銀和鉛離子的錯合能力，利用Stern-Volmer plot和Job plot計算出化合物22下緣的三唑基團對Pb2+離子為1:1的錯合，而其錯合常數為3.96×104 M-1。藉由銀離子對化合物22的NMR滴定實驗，以訊號的位移量(ppm)和銀離子濃度做Benesi-Hildebrand plot，算出錯合常數為1.76×103 M-1。從控制實驗化合物23得知，1,3-alternate芳杯上的硫冠醚基團皆會對銀和鉛離子有錯合能力。針對化合物22，我們以紫外可見光譜及螢光光譜的滴定，並搭配氫核磁共振光譜實驗，加入不同當量數的銀和鉛離子來調配螢光基團的放射強度，證明化合物22的負向異質變構性效應。
　　最後，我們將化合物24對15種金屬離子和9種陰離子進行初步篩選，篩選結果發現銅和汞離子對化合物24有強烈的螢光淬熄，而在陰離子方面，F-離子會造成化合物24 紫外可見光的紅位移，使芘基形成最大螢光放射約在472 nm的靜態激態雙體。AcO-離子也會形成靜態激態雙體的螢光放射，而H2PO4-離子造成動態激態雙體螢光強度減弱而單體螢光強度增加。

In this work, a series of novel fluoroionophores 20-24 were synthesized. The structure of 20-22 featured anthrance moiety and 24 featured pyrene moiety as the fluorophore. The thiacrown and triazole groups as metal ion recongnition sites were modyfied and incorporated into the cone and 1,3-alternate conformations of calix[4]arene. The photo-physical properties of compounds 20-24 in acetonitrile were measured which provided evidence for the allosteric effect of compounds.
The binding ability of compounds 20-23 toward Ag+ and Pb2+ were studied first. Stern-Volmer plot and Job plot were used to determine the binding constant of 22 with Pb2+ to be 3.96×104 M-1. From NMR titration experiment of compound 22 with Ag+ ion, we obtain its binding constant to be 1.76×103 M-1 using Benesi-Hildebrand plot of �����nvs [Ag+]. By control compound 23, we found that 1,3-alternate calix[4]thiacrown can bind both Ag+ and Pb2+. Negative allosteric effect of compound 22 with variable amount of Ag+ and Pb2+ ion were proven by UV-vis, fluorescece and 1H NMR spectroscope.
Finally, compound 24 was screened with 15 metal ions and 9 anions. We found that the fluorescence of compound 24 was selectively quenched by Cu2+ and Hg2+. The complexation of 24 with F- caused a bathochromic shift of its UV-vis absorption, furthermore, it showed a emission max at around 470 nm consistent with a static excimer formation. The complexation of 24 with acetate also showed emission spectra with λmax 472 nm, but it showed only marginal UV-vis shift. The complexation of 24 with H2PO-4 caused a selective quenched of the dynamic excimer emission but an enhancement of the monomer emission of the pyrenyl groups.

目錄

頁次
中文摘要 i
英文摘要 iii
謝誌 v
目錄 vii
圖目錄 x
式圖目錄 xiii
表目錄 xiv
附圖目錄 xiv
第一章 緒論 1
1.1 超分子化學簡介 1
1.2 芳杯簡介 2
1.3 芳杯之命名 4
1.4 芳杯之性質與特性 6
1.4.1 芳杯的性質 6
1.4.2 芳杯的構形 6
1.4.3 芳杯的構形控制 9
1.4.4 芳杯之合成 11
1.4.5 芳杯下緣衍生化反應 13
1.4.6 芳杯上緣衍生化反應 14
1.5 即合化學(Click Chemistry) 15
1.5.1 合成三氮唑(triazole)的反應機制 17
1.6 化學感應器之設計原理 19
1.6.1
光誘導電子轉移 (photoinduced electron transfer，PET) 20
1.6.2
光誘導電荷轉移 (photoinduced charge transfer，PCT) 22
1.6.3
螢光共振能量傳遞(Fluorescence Resonance Energy Transfer，FRET) 24
1.6.4
單體-激態雙體之形成(Formation of Monomer-Excimer) 27
1.6.5 異質變構性效應 (allosteric effect) 29
第二章 研究動機 33
第三章 結果與討論 34
3.1 合成策略 34
3.1.1 下緣對位雙丙炔基醚化芳杯8之合成 35
3.1.2 螢光發射基團之合成 35
3.1.2.1 疊氮甲基蒽27之合成 36
3.1.2.2 疊氮甲基醯胺芘30之合成 36
3.1.3 Cone構形芳杯衍生物之合成 37
3.1.3.1 下緣對位雙溴乙烷基醚化芳杯31之合成 38
3.1.3.2 下緣對位雙triazole硫冠醚芳杯20之合成 39
3.1.4 1,3-alternate構形芳杯衍生物之合成 40
3.1.4.1 對位雙丙炔基雙溴乙基1,3-alternate芳杯38之合成 40
3.1.4.2
對位雙丙炔基1,3-alternate硫冠醚芳杯23之合成 41
3.1.4.3
含蒽對位雙triazole 1,3-alternate芳22之合成 42
3.1.4.4
含芘對位雙triazole醯胺基1,3-alternate芳杯24之合成 43
3.2
含蒽基螢光感測器芳杯衍生物對金屬篩選能力之研究 44
3.2.1 對位雙triazole硫冠醚芳杯20對金屬離子篩選能力探討 44
3.2.2
含蒽對位雙triazole 1,3-alternate硫冠醚芳杯22對金屬離子篩選能力探討 49
3.2.3　
含蒽對位雙triazole 1,3-alternate硫冠醚芳杯22與金屬離子的異質變構性效應之研究 54
3.3
含芘基螢光感測器芳杯衍生物篩選能力之研究 81
第四章 結論 90
第五章 實驗部分 92
第六章 參考文獻 115
第七章 附錄 121

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