臺灣博碩士論文加值系統

本論文改良 R. A. Bartsh 的合成方法合成全環，並利用簡單的 Williamson 醚類合成法引入側臂以合成一系列新的碳軸側臂雙苯十九環冠醚，用以探討對鹼金屬、銀離子之錯合現象及形式；利用快速原子撞擊質譜法迅速地測知冠醚與金屬離子錯合的能力，亦可看出十九環碳軸冠醚與鈉離子、鉀離子、銣離子及銀離子均形成1:1錯合。
利用13C-NMR金屬誘導變化效應輔以1H-NMR光譜變化，可看出冠醚與金屬離子錯合時構形的改變情形；十九環碳軸冠醚與鉀離子及銀離子之13C、1H峰線的位移會隨著金屬鹽類濃度增加而改變，至1:1時達最大值，由此可知其以1:1形式錯合且橋頭碳上的氧在配位上佔有重要的地位。
引入不同的發光團側臂可以螢光光譜在定性上測得金屬離子對冠醚螢光訊號的影響：鹼金屬離子使螢光強度增強，銀離子使螢光強度減弱。利用錯合常數的公式及Stern-Volmer equation可得知冠醚與金屬錯合能力大小，得知冠醚對K+有最大的錯合常數。
利用十九環冠醚對鉀離子的選擇性，可用作選擇性薄膜電極的材料。實驗結果顯示：以冠醚3a-PVC-NaTPB-NPOE 的比例為5:50:1:100製成鉀離子選擇薄膜電極，得到56.4mV/decade接近於能士特的理論值；且對鉀的選擇性皆比其它鹼金、鹼士族金屬離子為佳。

A new series of sym-dibenzo─19-crown-6 ethers with different sidearms have been synthesized. This thesis improves R. A. Bartsh’s synthesis,using the simple Willamson’s ethers to synthesize a series of c-pivot lariat ethers. Fast-atom-bombardment (FAB) mass spectrometry was used as a fast scanning method to study the stoichrometry of the complexes. It is shown that sym-dibenzo-19-crown-6 derivatives form 1:1 complexes with Na+、K+、Rb+ and Ag+ ions.
13C and 1 H NMR spectroscopies were used to investigate the complex formation between these lariat crown ethers with K+ and Ag+ ions. Form the results of metal-induced change in NMR spectra, boh 13C and 1 H NMR showed chemical shift vary with metal salt concentration added. Results show that these C-pivot sidearm lariat crown ethers form 1:1 complexes with K+ and Ag+ ions. In addition, the oxygen atom on the top of the bridged carbon chain plays an important role in the complexing formation.
Crown ether linked different fluorophores are well suited for the study of trace metal ions by fluorescence spectra. The addition of K+ ion enhances the fluorescence emission intensity while the addition of Ag+ quenches the fluorescence emission intensity. With the calculated stability constant and Stern-Volmer equation, we can compare these lariat crown ethers’s complexing abilities and calculate their complexation constants.
Poly(vinyl chloride)(PVC) membrane electrodes based on sym-dibenzo-19-crown-6 ionophors were prepared and test for selective detection of the potassium ion. The membrane electrode made of lariat crown ether 3a-PVC-NaTPB-NPOE at a ratio of 5:50:1:100 yielded 56.4 mV/decade response，near the Nerstain response.The electrode revealed good selectivities with respect to the other alkali metal and alkaline earth metal ions.

第一章 緒論---------------------------------------------1
第二章 實驗部分-----------------------------------------9
2-1儀器--------------------------------------------------9
2-2藥品--------------------------------------------------9
2-3實驗步驟----------------------------------------------11
第三章 結果與討論-------------------------------------- 21
3-1十九環碳軸冠醚之合成----------------------------------21
3-2 利用FAB-MS初步探討錯合性質------------------------ 23
3-3 13C-NMR的結果與討論---------------------------------35
3-4 1H-NMR 的結果與討論---------------------------------52
3-5 以螢光光譜法研究冠狀醚與金屬離子的錯合---------------57
3-6 螢光生命期的測量-------------------------------------76
第四章 結論---------------------------------------------80
第五章發展十九冠六醚對鉀離子的離子選擇性薄膜電極---------81
5-1 研究動機---------------------------------------------81
5-2 實驗部份---------------------------------------------81
5-3 結果與討論-------------------------------------------82
5-4 結論-------------------------------------------------88
參考文獻------------------------------------------------ 90
附錄-----------------------------------------------------93

1. Pederson, C. J. J. Am. Chem. Soc. 1967,89,7017.
2.(a) Wild, S. B. Pure Appl. Chem. 1990,62,1139.
(b) Melson, G. A. Coordination Chemistry of Macrocyclic
Compounds, Plenum, New York. 1979.
3. Weber, E. Toner, J. L. Laidler, D. A. Stoddart, J. F. Bartsch, R. A. Ed. Crown Ethers and Analogs, Wiely＆Sons, New York. 1989.
4. Kida, K. Kida, T, Nakatsuji, Y. Ikeda, I. J.Chem. Soc.,Perkin Trans 1. 1998,3857.
5. Ouchi, M. Inoue, Y. Sakmoto, H. Yamahira, A. Yoshinaga, M. Hakushi, T. J. Org. Chem. 1983,48,3168.
6.Strzelbicki, J. Bartsch, R. A. Anal. Chem. 1981,53,1894.
7.Pederson, C. J. J. Am. Chem. Soc. 1970,92,386.
8.Izatt, R. M. Eatough, D. J. Christernsen, Chem.Rev. 1974,74,351. 9.Walkowiak, W. Kang, S. I. Bartsch, R. A. Anal.Chem. 1990,62,2024.
10.Charewicz, W. A. Bartsch, R. A. Anal. Chem. 1982,54,2300
11.Walkowiak, W. Charewicz, W. A. Kang, S. I. Yang, I. W. Bartsch, R. A. Anal.Chem. 1990,62,2313.
12. Simon, J. D. Moomaw, W. R. Ceckler, T. M. J. Phys. Chem. 1985, 89,5659.
13. Tang, J. Wei, C. M. Anal. Chem. 1986,58,3233.
14.Shamsipur, M. Popov, A. J. J. Am. Chem. Soc. 1979,101,4051.
15.Stoss,S. Kleinpeter, E. Schroth, W. Magn. Reson. Chem. 1992,30,425.
16.Stoss,S. Kleinpeter, E. Holdt, H. J. Magn. Reson. Chem. 1991,29,999.
17.Nishids, H. Katayama, Y. Katasuki, H. Nakamura, H. Takagi, M. Ueno, K. Tetrahedron.Lett. 1982,1853.
18.Nakashima, K. Nakatsuji, S.；Akiyama, S. Tanigawa, I. Kaneda, T. Misumi, S. Talanta. 1984,31,749.
19.De Silva, A. P. De Silva, S. A. J. Chem. Soc. Chem. Commun. 1986,1709.
20.Fery-Forgues, S. Le Bris, M. T. Guett’e, J. P. Valeur, B. J. Chem. Soc. Chem.Commun. 1988,384.
21.Huston, M. Czarnik, A. W. J. Am. Chem. Soc. 1990,112,7054.
22.De Silva, A. P. Sandanayake, K. R. A. S. Angew. Chem. Int. Ed. Engl. 1990,29,5193.
23.De Silva, A. P.；Sandanayake, K. R. A. S. Tetrahedron Lett. 1991,32,421.
24.Thanabal, V.；Krishnan, V. J. Am. Chem. Soc. 1982,104,3463.
25.Heo,G. S, Bartsch,R. A, Schlobohm, L. L, Lee, J. G, J. Org. Chem. 1981,46,3574.
26. Nakashima, K. Nagaoka, Y. Nakatsuji, S. Kaneda, T. Tanigawa, I. Hirose, K. Misumi, S. Akiyama, S. Bull. Chem. Soc. Jan. 1987,60,3219.
27. Kubo, K. Kato, N. Sakurai, T. Bull. Chem. Soc. Jan. 1997,70,3041.
28. Bourson,J. Borrel, M. N. Valrur,B. Anal. Chim. Acta. 1992,257,189.
29. Kleipeter, E. Stoss, S. Schroth, W. Magn. Reson. Chem. 1989,27, 676.
30. DeBoer, J. A. A. and Reinhoudt, D. N. J. Am. Chem. Soc. 1985,107,5347.
31. Zhu, C.Y. Bradshaw, J. S. Oscarson, J. L. and Izatt, R. M.
J. Incl.Phenom. 1992,12.275.
32. R, Ishige. Kubo, K. Kubo, J. Sakurai, T. Talant,1999, 48,181.
33. Kubo, K. Sakaguchi, S. Sakurai, T. Talant. 1999,49,735.
34. Warmke, H. Wiczk, W. Ossowski, T. Talant. 2000,52,449.
35. Gunaratne, A. P. Gunnlaugsson, H. Q. N. Huxley, T. McCoy, A. J. M. Rademacher, C. P. Rice, J. T. Rice, T. E. Chem. Rev. 1997,97,1515.
36. Nakatsuji, Y. Hirofumi, K. K. Zhang, W. Kida, T. Ikeda, I. J.Am.Chem.Soc. 2000, 122,6307.
37.Ji, H. F. Dabestani, R. Brown, G. M. Sacheben, R. A. J. Chem. Soc., Chem. Commun. 2000,833.
38.Janta. J.Anal. Chem. 1987,59,1351.
39.Anzai, J. C. Anal.Chim.Acta. 1991,323.
40.Bakker, E. Anal. Chem. 1997,69,1061.
41. Bakker, E.Chem.Rev. 1998,98,1593.