Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16730
標題: Diamine-Salicylaldehyde共軛4-乙烯芳香基化合物之合成與對金屬探測效應之光譜研究
Synthesis and Spectral Studies of Diamine-Salicylaldehyde Conjugating 4-Vinyl Aryl Derivatives as Metal Sensor Fluorophores
作者: 洪宛華
Houng, Wang-Hua
關鍵字: Fluoresence sensor
陽離子感測器
Schiff base
解離常數
出版社: 化學系所
引用: [1] Domaille, D. W.; Que, E. L.; Chang, C. J., Nat. Chem. Bio., 2008, 4, 168 [2] (a).Valeur, B.; Leray, I., Coord. Chem. Rev., 2000, 205, 3-40.; (b). Schemehl, R. H.; Li, C. J.; Xia, W. S.; Mague, J. T.; Luo, C. P.; Guldi. D. M., J. phys. Chem. B., 2002, 106, 833. [3] 張健忠, 2007科學月刊6月號-螢光影像專輯2 [4] Wroblewski, S.; Trzebiatowska, K.; Jedrzejewska, B.; Pietrzak, M.; Gawinecki, R.; Paczkowski, J., J. Chem. Soc., Perkin Trans. 2, 1999, 1909. [5] Lippert, E. Z., Elecktrochem. 1957, 61, 962. [6] Bhattaachryya, K.; Chowdhury, M. Chem. Rev. 1993, 93, 507. [7] Rettig, W.; Zietz, B. Chem. Phys. Lett. 2000, 317, 187. [8] Wang, S. L.; Ho, T. I. J. Photochem. Photobiol., A 2000, 135, 119. [9] Zhang, X.; Guo, L.; Wu, F. Y.; Jiang, Y. B. Org. Lett. 2003, 5, 2667. [10] Mishraa, A.; Beheraa, G. B.; Krishnab, M. M. G.; Periasamyb, N., Journal of Luminescence. 2001, 92, 175. [11] Steiner, U. E.; Abdel-Kader, M. H.; Ischer, P.; Kramer, H. E. A., J. Am. Chem. Soc., 1978, 100, 3190. [12] Abdel-Halim, S. T.; Abdel-Kader, M. H.; Steiner, U. E., J. Phys. Chem. 1988, 92, 4324. [13] Yang, J.-S.; Chiou, S.-Y. ; Liau, K.-L. J. Am. Chem. Soc. 2002, 124, 2519. [14] Fung, S. Y.; Duhamel, J.; Chen, P. J. Phys. Chem. A, 2006, 110, 11446. [15] (a) Gilabert, E.; Lapouyade, R.; Rulliere, C. Chem. Phys. Lett. 1988, 145, 262.; (b) Rettig, W.; Majenz, W. Chem. Phys. Lett. 1989, 154, 335.; (c) Rullière, C.; Abraham, E.; Oberlé, J.; Jonusauskas, G.; Lapouyade, R. J. Photochem. Photobiol. A: Chem. 1997, 105, 101. [16] Rettig, W.; Létard, J.; Lapouyade, R. Chem. Phys. Lett. 1994, 222, 209. [17] Mataga, N.; Kaifu, Y.; Koizuni, M. Bull. Chem. Soc. Jpn., 1956, 29, 465.; (c) Onsager, L. J. Am. Chem. Soc., 1936, 58, 1486. [18] Lewinski, J.; Zachara, J.; Justyniak, I.; Dranka, M., Coord. Chem. Rev . , 2005, 249, 1185. [19] Chen, H.-Y.; Tang, H.-T.; Lin, C.-C., Macromolecules, 2006, 39, 3745. [20] Kaur, N.; Kumar, S., Chem. Commun. , 2007, 29, 3069. [21] Singh, N.; Kaur, N.; Mulrooney, R. C.; Callan, J. F., Terrahedron. Letters. , 2008, 49, 6690. [22] Singh N.; Mulrooney R. C.; Kaur N.; Callan, J. F., Chem. Commun. , 2008, 40, 4900. [23] He, G.; Zhao, Y.; He, C.; Liu, Y.; Duan, C., Inorganic chemistry , 2008, 47, 5169. [24] Du, H.; Fuh, R. A.; Li, J.; Corkan, A.; Lindsey, J. S. Photochemistry and Photobiology, 1998, 68, 141. [25] Congreve, M.; Aharony, David.; Albert, J.; Callaghan, O.; Campbell, J.; Robin, A. E. C., Chessari, G.; Cowan, S.; Edwards, P. D.; Frederichson M.; McMenamin, R.; Murray, C. W.; Patel, S.; Wallis, N., J. Med. Chem. 2007, 50, 1124. [26] Chang, C.-C.; Chen, K.-J.; Yu, L-J., J. Org. Chem., 1999, 64, 5603-5610. [27] Chang, C.-C.; Wu , J. -Y.; Chang, T.-C., Journal of the Chinese Chemical Society, 2003, 50, 185-188. [28] Lin, T.-C.; He, G. S,; Prasad, P. N.; Tan, L.-S., J. Mater. Chem. , 2004, 14, 982-991. [29] Basran, J.; Sutcliffe, M. J.; Scrutton, N. S. J. Biol. Chem., 2001, 276, 42887. [30] Toprak, M.; Gellert, E.; Bekaroglu, O., Transition Met. Chem., 1979, 4, 372 [31] Burdette, S. C., Lippard, S. J., J. Am. Chem. Soc.,2003, 125, 1778 [32] Hadjoudis, E.; Mavridis, I. M., Chem. Soc. Rev., 2004, 33, 579 [33] Reichardt, c.; Harbusch-Goernert, E.; Liebigs Ann. Cbem. 1983, 5, 721. [34] Burdette, S. C.; Frederickson, C. J.; Bu, W.; Lippard, S. J., J. Am. Chem. Soc., 2003, 125, 1778. [35] Jacques, P., The Journal of Physical Chemistry,1986, 90, 5535-5539.
摘要: 本論文所設計的系列化合物是以Diamine-salicylaldehyde (DS) 為主衍生出兩部份的變化;第一部份為DS上5位置的共振延伸,其連接不同推拉能力的乙烯芳香族官能基為衍生物。另外一部分著眼在 DS 的2位置上氫氧基與其取代基的研究。藉由酸鹼滴定實驗決定化合物發生質子轉移的環境,並根據所測得的pKa及pKb值,可了解每個構型存在的pH範圍。此外,藉由溶劑效應實驗,進一步探討化合物分子的 ICT 行為, ICT 行為越顯著的分子,表示其與金屬作用可能會產生明顯的光譜變化。最後利用上述實驗所得結果,篩選出最佳化的條件來探討化合物對金屬離子的敏感度及選擇性。由此獲得一些對特定金屬有鍵結能力,並可明顯光譜辨識的螢光感測器 (Fluorscence sensor)。 由實驗結果得知,改變DS 2位置的取代,並未能提供一個更好的金屬離子選擇條件,然而在5 位置的取代基改變,實驗結果發現不同的推拉電子基,會使化合物光譜性質差異甚多;在金屬感測能力方面,無法單純由連接推拉電子基來找出其規律性,而是以ICT行為扮演最大的角色。我們歸納出化合物2-((E)-(2-(dimethylamino) ethylimino)methyl)-4-((E)-2-(pyridin-4-yl)vinyl)phenol ( IIa )在MeCN的條件下,對Zn2+金屬離子有很好的作用能力。而化合物2-((E)-(2-(dimethylamino)ethylimino)methyl)-4-(4-methoxystyryl)phenol ( Ia )在MeOH:H2O=3:1中性的條件時,對Zn2+金屬離子有獨特的專一性光譜表現,根據上述實驗結果此分子有潛力可以應用於生物體的金屬偵測。
In order to develop a set of available fluorescence sensor, alternatively modifications basing on Diamine-Salicylaldehyde [DS] were performed in this thesis. First, extensive electron delocalization was achieved with conjugating 4-vinyl aryl on 5-position of phenol moiety of DS; second, the hydroxyl group of phenol moiety of DS was capped with alkyl or picoyl groups. The optimized chelating conditions to metal ions of these DS derivatives were evaluated with counting the protons exchange abilities and ICT (intramolecular charge transfer) behaviors by pKa measurement and solvent effect assays, respectively. Consequently, metal fluorescence sensor candidates can be screened depending on the fluorescence enhancement or spectra shift under variable metal-containing solvents. Base on our research results, metal-chelating factors were dominated by ICT effects of DS derivatives which were determined by substituting the electron pull-push 4-vinyl aryl functions. On the other hand, the existence of hydroxyl groups could increase the spectra diversities once the chelators interacting with metal ions. From the SAR (structure activity relationship), the DS derivatives 2-((E)-(2-(dimethylamino)ethylimino) -methyl)-4-(4-methoxystyryl)phenol (Ia) and 2-((E)-(2-(dimethylamino) ethylimino)methyl)-4-((E)-2-(pyridine-4-yl)vinyl)phenol (IIa) were suitable Zn+2 or Cd+2 metal ion fluorescence sensors. IIa was excellent recognizer for Zn+2 under MeCN system but chelated Zn+2 and Cd+2 in semi-aqueous solutions (H2O/MeOH=3/1); while Ia could specifically recognize Zn+2 well in semi-aqueous solutions. Thus, the life science application was expectable for these metal-chelated candidates.
URI: http://hdl.handle.net/11455/16730
其他識別: U0005-1606200922544100
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