標題: 以芘衍生物為基底之螢光化學感測分子用於偵測鐵(III)離子及鎘(II)離子
Selective Turn-on Fluorescent Chemosensors for Fe3+ and Cd2+ Ions based on Pyrene Derivative
作者: 鐘健豪
吳淑褓
Wu, Shu-Pao
應用化學系碩博士班
關鍵字: 螢光感測分子;鐵離子;鎘離子;細胞顯影;芘;激態複體;Fluorescence chemosensor;Iron ion;Cadmium ion;Cell imaging;Pyrene;Excimer
公開日期: 2010
摘要: 本論文使用pyrene 為發光基團,設計合成出螢光化學感測分子 (1、2、3、4、5、6)。化合物1 藉由螢光變化(由微弱變發強綠光)來 辨識Fe(III)離子,在其他金屬離子的存在下仍對Fe(III)具有高度選擇性。 當加入Fe(III)時,化合物1 與Fe3+錯合,促使pyrene 芳香環的靠近,而 造成激發複體(excimer)的放光,產生綠色螢光(507 nm)。由Job plot 可得知1-Fe(III)的錯合比例為1:1。由Benesi-Hildebrand plot 得到1 -Fe(III)之結合常數為1.27 × 10^4 M^-1。合成化合物2、5 及6 作為化合 物1 之比較,而其螢光感測的篩選能力均不及化合物1。 化合物3 藉由螢光變化(藍光變綠光)來辨識Fe(III)及Hg(II)離子。當 加入Fe(III)時,化合物3 與Fe(III)錯合,促使pyrene 芳香環靠近,而造成 由激發單體(monomer)轉變成激發複體的放光。由Job plot 可得3- Fe(III)的錯合比例為2:1。3-Fe3+之結合常數為6.57 × 10^10 M^-2。3- Hg(III)之結合常數Ka = 1.93 × 10^11 M^-2。 化合物4 藉由螢光變化(綠光變藍光)來辨識Cd2+離子。當加入 Cd(II)時,化合物4 與Cd(II)錯合,導致pyrene 堆疊的扭曲,而生成static excimer 放光(457 nm),由Job plot 得知化合物4 與Cd2+之錯合比例為 1:1。由Benesi-Hildebrand plot 得知4-Cd2+之結合常數為3.29 × 10^4 M^-1。
In this thesis, pyrene was used as a signal unit for chemosensors 1, 2, 3, 4, 5 and 6. Chemosensor 1 can detect Fe(III) by Fe(III)-induced formation of pyrene excimer, which resulted in a green emission. Upon Fe(III) addition, 1 exhibited a significant emission centered at 507 nm, which is the formation of pyrene excimer. The binding ratio of 1—Fe(III) was determined as 1:1 according to Job plot. The association constant of 1—Fe(III) complexes was found to be 1.27 × 10^4 M^-1 according to Benesi-Hildebrand plot.Chemosensor 1 is better sensor for Fe(III) than chemosensors 2, 5, 6. Chemosensor 3 can detect Fe(III) and Hg(II) from other metal ions. Upon addition of Fe(III), 3 exhibited a green emission centered at 505 nm, which comes from the formation of pyrene excimer. The binding ratio of 3-Fe(III) was decided as 2:1 according to Job plot. The association constant of 3-Fe(III) complexes was decided as 6.57 × 10^10 M^-2. Chemsensor 4 can detect Cd(II) from other metal-ion. Upon addition of Cd(II), 4 exhibited a strong emission at 457 nm due to the formation of static pyrene excimer. The binding ratio of 4-Cd(II) was found to be 1:1 according to Job plot. The association constant was determined as 3.29 × 10^4 M^-1 according to Benesi-Hildebrand plot.
URI: http://140.113.39.130/cdrfb3/record/nctu/#GT079825534
http://hdl.handle.net/11536/47624
Appears in Collections:Thesis