具多乙氧基之亞胺酚基螢光化學感測器之合成、鑑定與其在不同溶劑系統中之金屬離子辨識行為研究探討

Polyethoxy Salicylideneimines as Fluorescence Chemosensors: Design, Synthesis and Sensing in Different Solvent Media

張惟智(Wei-Chih Chang)

指導教授 ： 吳景雲

國立暨南國際大學/科技學院/應用化學系/碩士(2013年)

https://doi.org/10.6837/NCNU.2013.00176

摘要

在本篇論文中我們合成了兩個螢光化學感測器，分別為1,4-Bis(2-(2-(2-(3,5-di-tert-butyl-salicyald-2-imine)phenoxy)ethoxy)ethoxy)ethoxy)benzene (以下簡稱化合物DT)及1,4-Bis(2-(2-(2-(3,5-dichloro-salicyald-2-imine)phenoxy)ethoxy)ethoxy)ethoxy)benzene (以下簡稱化合物DC)，利用兩個不同取代基的亞胺酚基化合物作為辨識單元，多乙氧基鏈作為架橋基，並利用紫外光-可見光吸收光譜儀(UV-Vis)以及螢光光譜儀，分別探討這兩種化合物在不同溶劑系統下與各種金屬離子的紫外光-可見光吸收變化以及螢光表現，結果顯示這兩種化合物皆可以對Zn2+離子具有辨識能力且造成螢光強度的差異。
(1) 在甲醇溶液系統中：競爭反應實驗結果顯示，DT-Zn系統僅有鋁、鉻、銅及鉛離子能將鋅離子取代。在DC-Zn系統則是有鈷、鉻、銅、鎳及鉛離子可以將鋅離子取代。
值得注意的是在DT-Zn系統中，加入鋇離子可以使得螢光強度增強，推測是藉由協同效應的影響所致。
此外在滴定實驗及Job′s plot實驗結果，我們可以得知這兩種化合物對鋅離子皆以2 : 3的方式結合。
(2) 在 10 mM HEPES溶液系統中：化合物DT及DC僅對鋅離子具有辨識能力，而且在競爭反應實驗結果，我們可以發現沒有其他金屬離子可以將鋅離子取代掉。

關鍵字

亞胺酚基 ； 化學感測器 ； 螢光 ； 鋅

並列摘要

Two new fluorescence chemosensors, 1,4-Bis(2-(2-(2-(3,5-di-tert-butyl-salicyald-2-imine)phenoxy)ethoxy)ethoxy)ethoxy)benzene ( named as compound DT ) and 1,4-Bis(2-(2-(2-(3,5-dichloro-salicyald-2-imine)phenoxy)ethoxy)ethoxy)ethoxy)benzene ( named as compound DC ) hereafter, containing polyethoxy chain and salicyaldimine moiety has been designed and synthesized.
The cation recognition abilities of DT and DC toward various cations ( Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Ag+, Al3+, Cd2+, Co2+, Cr3+, Cu2+, Mn2+, Ni2+, Pb2+ and Zn2+ ) in different solvent media have been examined by UV-Vis and fluorescence spectroscopies. In methanol and 10 mM HEPES media, sensors DT and DC also showed 〃Off-On〃 fluorescence signaling behavior when interacted with Zn2+ ion.
(I) Methanol as media: According to the competitive studies, in the DT-Zn system, Zn2+ ion would be replaced by Al3+, Cr3+, Cu2+ and Pb2+ ions while in the DC-Zn system, Zn2+ ion would be replaced by Co2+, Cr3+, Cu2+, Ni2+ and Pb2+ ions, as observations of absorption change in the UV-vis spectra and fluorescence quenching in the fluorescence spectra. Interestingly, when adding Ba2+ ion into the solution of DT-Zn system and adding Al3+ ion into the solution of DC-Zn system, the fluorescence intensity for both systems are enhanced, signifying noticeable co-operative effect and substitution effect, respectively. On the basis of titration and Job′s plot, sensors DT and DC bind with Zn2+ both in a 2:3 stoichiometry.
(II) 10 mM HEPES as media: Sensors DT and DC recognize only the Zn2+ ion. No other metal ion can replace Zn2+ ion in the DT-Zn and DC-Zn complexes.

並列關鍵字

salicylideneimine ； chemosensors ； fluorescence ； Zn2+

參考文獻

1. J.-M. Lehn. Angew. Chem., Int. Ed. Engl. 1988, 27, 89-112.

2. J. -M. LehnLehnLehn . Angew. Chem. Angew. Chem.Angew. Chem. Angew. Chem. Angew. Chem. , Int. Ed. Engl. Int. Ed. Engl. 1990 , 29 , 1304 -1319 .

3. J. S.J. S. J. S. LindseyLindsey Lindsey. New J. Chem.New J. Chem.New J. Chem.New J. Chem. New J. Chem. New J. Chem.New J. Chem.New J. Chem. 1991 , 15 , 153 -180 .

4. D. PhilpPhilp Philp.; J. F.J. F. J. F. StoddartStoddart Stoddart, Synlett Synlett , 1991 , 445 -458 .

5. G. G. StokesStokes . Philos. Philos. Trans. R. Trans. R. Soc . LondonLondon , A 1852 1852 , 142, 463 -562 . 6. M. J. Culzoni, A. Munoz de la Pena, A. Machuca, H. C. Goicoechea and R. Babiano, Anal. Methods, 2013, 5, 30-49.