臺灣博碩士論文加值系統

我們設計並合成出數個同時具有醯胺（amide）及吡咯（pyrrole）的感測器分子，並分別利用三噻吩（terthiophene）、二硝基苯（dinitrobenzene）、二酚苯喹喔啉（diphenylquinoxaline）具不同推拉電子能力的基團，藉以探討電子接受子的強弱對於感測器與陰離子作用的影響。
從各感測器分子與陰離子的UV-Vis、放光光譜滴定實驗結果得知，我們所合成的感測器分子對於氟（F-）、焦磷酸根（HP2O73-）、氰根（CN-）離子有很好的結合能力，同時在放光光譜方面，呈現可增加鑑別度的”ratiometric”現象。感測器分子溶液如果在與陰離子的UV-Vis或螢光光譜實驗中，變化程度較大的陰離子，藉由氫核磁共振滴定實驗圖譜的推測，陰離子通常會對感測器分子上醯胺官能基的NH進行去質子化的反應；加入陰離子後，在UV-Vis及螢光光譜中變化程度較小者，通常要先與感測器分子中醯胺及吡咯上共四個NH的影響形成氫鍵，才會進行去質子化反應；而其他在UV-Vis及螢光光譜變化不明顯的情況下，作用力僅僅只是靠2或4個陰離子與感測器分子之間形成的氫鍵。值得注意的是，2、3能在半水溶液的條件下辨識氰根離子，我們推測應該是感測器分子與氰根離子形成共價鍵而得到” cyanohydrin”的結構。在氫核磁共振滴定圖譜及電灑質譜圖中，我們都能得到1、2、3與氰根離子形成共價鍵的有力的證據。但因為感測器分子1三噻吩為推電子基的影響，造成其無法如感測器分子2、3能在有大量水分子競爭的環境下與離子形成穩定的鍵結。
藉由氫鍵及去質子化的作用力，能讓我們設計的感測器分子1、2、3在高極性有機溶劑下，對氟、焦磷酸根離子有很好的辨識能力；感測器分子2、3在半水溶液下對氰根離子的選擇性及靈敏度都遠大於其他陰離子，因此皆為理想的氰根離子化學感測器。

We have designed and synthesized a series of chemosensors containing amide and pyrrole groups for anion recognition and sensing. The binding affinity between these chemosensors and various anions has been investigated to elucidate the influence of electronic effect generated by different functional groups such as terthiophene, dinitrobenzene, and diphenylquinoxaline in the structure of these chemosensors.
According to the changes of UV-Vis and fluorescentce spectra on addition of anions, the chemosensors 1, 2 and 3 display strong binding ability to fluoride, pyrophosphate and cyanide. Moreover, the appearance of the ratiometric phenomenon upon interaction with anions further enhances the spectral differentiation for anion sensing.
The reaction mechanism between chemosensor and anions is further investigated by the 1H-NMR titration experiments. Anions strongly intereacting with chemsensors and producing large changes during the titration in UV-Vis and fluorescent spectra usually result in deprotonation of the amide group while the weaker anions initially form hydrogen bonds with NHs on amides and pyrroles followed by deprotonation at higher anion concentration. The weakest anions, however, form only 2 or 4 hydrogen bonds with chemosensors during titration. Moreover, both sensors 2 and 3 are able to recognize cyanide under semi-aqueous environment. We proposed that the formation of covalent bonded cyanohydrin derivatives from cyanide addition to carbonyl center is responsible for the effectiveness of sensors 2 and 3 in semi-aqueous environment. The structures of the cyanide adducts have been confirmed by 1H-NMR and ESI mass spectra. On the other hand, sensor 1 could not form stable cyanide adduct under the competition with water due to the less electron-withdrawing nature of terthiophene.
Based on the hydrogen bonding and deprotonation, chemosensors 1, 2 and 3 show very good recognition ability to F- and HP2O73- in polar organic solvents. Most importantly, we have demonstrated that chemosensors 2 and 3 exhibit outstanding selectivity and sensitivity to cyanide over other anions in the semi-aqueous solution, which renders them highy promising chemosensors for cyanide.

中文摘要
英文摘要
1.緒論-------------------------------------------------------------------1
1.1辨識單元--------------------------------------------------------------1
1.2訊號傳遞與產生--------------------------------------------------------3
1.3陰離子感測器設計原理--------------------------------------------------3
1.4螢光(fluorogenic)化學感測器的機制-------------------------------------5
1.5發色改變之陰離子化學感測器機制----------------------------------------7
1.6 常用來作為陰離子感測的官能基-----------------------------------------9
1.7. Ratiometric principle----------------------------------------------15
1.8 研究動機------------------------------------------------------------17

2. 實驗部分
2.1 分析儀器及實驗方法--------------------------------------------------18
2.2 感測器1、2、3之合成途徑---------------------------------------------21


3. 實驗結果
3.1 X-ray 單晶繞射圖----------------------------------------------------23
3.2 光物理性質----------------------------------------------------------23
3.3 紫外-可見光（UV-Vis）光譜滴定---------------------------------------25
3.4 放光光譜滴定--------------------------------------------------------41
3.5 在混合溶劑（H2O與CH3CN）之紫外-可見光及放光光譜滴定-----------------52
3.6 結合常數------------------------------------------------------------56
3.7 感測器分子 1、2、3 與各種陰離子1H-NMR滴定實驗-----------------------57
3.8 感測器分子1、2、3與各陰離子ESI-Mass實驗-----------------------------76
4. 結果分析與討論-------------------------------------------------------78
5. 結論與未來展望-------------------------------------------------------81

參考文獻----------------------------------------------------------------83

A. 附錄
A1.1 感測器分子1合成步驟------------------------------------------------A1
A1.2 感測器分子2合成步驟------------------------------------------------A4
A1.3 感測器分子3合成步驟------------------------------------------------A6
A-2 各化合物氫（碳）核磁共振光譜數據------------------------------------A9
A-3 化學感測器 3 之晶體數據--------------------------------------------A27

[1] Beer, P. D.; Gale, P. A. Angew. Chem. Int. Ed. 2001, 40, 486.
[2] Martínez-Máñez, R.; Félix Sancenón, F. Chem Rev, 2003, 103, 4419.
[3] Leray, I.; Valeur, B. Coord chem. Rev, 2000, 205, 3.
[4] Pascal, R. A.; Spergel, J.; Engbersen, D.V. Tetrahedron Lett. 1986, 27, 4099.
[5] Valiyaveettil, S.; Engbersen, J. F. J.; Verboom, W.; Reinhoudt, D. N. Angew. Chem. Int. Ed. Engl. 1993, 32, 900.
[7] Sun, S.-S.; Lees, A. J. Chem. Commun. 2000, 1687.
[8] Sun, S.-S.; Lees, A. J.; Zavalij. P. Y. Inorg. Chem. 2003, 42, 2445.
[9] Kelley, T. R.; Kim, M. H. J. Am. Chem. Soc. 1994, 116, 7072.
[10] Bülmann, P.; Nishizawa, S.; Xiao, K. P.; Umezawa, Y. Tetrahedron 1997, 53, 1647
[11] Vazquez, M.; Fabbrizzi, L.; Taglietti, A.; Pedrido, R. M.; Gonzalez-Noya, A. M.; Bermejo, M. R. Angew. Chem., Int. Ed. 2004, 43, 1962
[12] Sessler, J. L.; M. J.; Lynch, V.; McGhee, E.; Ibers, J. A. J. Am. Chem. Soc. 1990, 112, 2810.
[13] Shionoya, M.; Furuta, H.; Lynch, V.; Harriman, A.; Sessler, J. L. J. Am. Chem. Soc. 1992, 114, 5714.
[14] Gale, P. A.; Sessler, J. L.; Krấl, V.; Lynch, V. J. Am. Chem. Soc. 1996, 118, 5140.
[15] Black, C. B.; Andrioletti, B.; Try, A. C.; Ruiperez, C.; Sessler, J. L. J. Am. Chem. Soc. 1999, 121, 10438.
[16] Anzenbacher, P., Jr.; Try, A. C.; Miyaji, H.; Jursı´kova´ , K.; Lynch, V. M.; Marquez, M.; Sessler, J. L. J. Am. Chem. Soc. 2000, 122, 10268.
[17] Wu, C.-Y.;Chen, M.S.; Lin, C.-A.; Lin, S.-C.; Sun, S.-S. Chem. Eur. J. 2006, 12, 2263.
[18] Andrievsky, A.; Ahuis, F.; Sessler, J. L.; Vögtle, F.; Gudat, D.; Moini, M. J. Am. Chem. Soc. 1998, 120, 9712.
[19] Yin, Z.; Li, Z.; Yu, A.; He, J.; Cheng, J. P. Tetrahedron Lett. 2004, 45, 6803
[20] Sessler, J. L.; Katayev, E.; Pantos, G. D.; Ustynyuk, Y. A. Chem. Commun. 2004, 1276.
[21] Sessler, J. L.; Katayev, E.; Pantos, G. D.; Scherbakov, P.; Reshetova, M. D.; Khrustalev, V. N.; Lynch, V. M.; Ustynyuk, Y. A. J. Am. Chem. Soc. 2005, 127, 11442.
[22] Peng, X.; Wu, Y.; Fan, J.; Tian, M.; Han, K. J. Org. Chem. 2005, 70, 10524
[23]Kubo, Y.; Yamamoto, M.; Ikeda, M.; Takeuchi, M.; Shinkai, S.; Yamaguchi, S.; Tamao, K. Angew. Chem., Int. Ed. 2003, 42 2036.
[24] Brooks, S. J.; Edwards, P. R.; Gale, P. A.; Light, M. K. New J. Chem. 2006, 30, 65
[25] Chung, Y. M.; Raman, B.; Kim, D. S.; Ahn, K. H. Chem. Commun. 2006, 186
[26] Eaton, D. F. Pure. Appl. Chem. 1988. 60. 1107-1114