鋅(Ⅱ)離子、焦磷酸根及氰(Ⅰ)離子螢光化學感測分子之合成與應用

Abstract

本論文分別以 BODIPY 及 7-hydroxycoumarin 為基底，設計合成螢光化學感測分子 1、CS1。化合物 1 藉由綠色螢光增強的方式辦識 Zn2+，在其他金屬離子的存在下，仍對 Zn2+ 具有高度選擇性。由核磁共振氫譜可知，化合物 1 以胺基與 Zn2+ 鍵結。由 Job plot 可得 1－Zn2+ 的錯合比例為 1：1。藉由Benesi-Hildebrand plot 算出 1－Zn2+ 的結合常數為 5.9 × 104 M-1。化合物 1 偵測 Zn2+ 最佳 pH 值範圍為 5.0－10.0。進一步錯合物 1－Zn2+ 可藉由綠色螢光減弱的方式辦識 pyrophosphate (PPi)，在其他陰離子的存在下，仍對 PPi 具有高度選擇性。由 Job plot 可得 1－Zn2+－PPi 的錯合比例為 1：1。藉由Benesi-Hildebrand plot 算出 1－Zn2+－PPi 的結合常數為 6.9×104 M-1。於生物應用上，在有 Zn2+ 存在下，細胞內會產生綠色螢光，當進一步加入 PPi，細胞內的綠色螢光會有減弱的現象。 化合物 CS1 藉由藍色螢光增強的方式辦識 CN-，在其他陰離子的存在下，仍對 CN- 具有高度選擇性。藉由 1H-NMR 及 Mass 等相關數據，推測 CN- 可選擇性地對化合物 CS1 上的 levulinoyl ester 進行去保護的反應，進而產生藍色螢光。化合物 CS1 偵測 CN- 最佳 pH 值範圍為 6.5－7.5。

In this thesis, BODIPY and 7-hydroxycoumarin were used as signal units for chemosensor 1 and CS1, respectively. Chemosensor 1 indicated the presence of Zn2+ among other metal ions with high selectivity by a remarkable green emission. According to 1H NMR studies, Zn2+ binding with chemosensor 1 is mainly through the amine (NH) group. The binding ratio of 1－Zn2+ complexes was determined as 1:1 according to Job plot. According to Benesi-Hildebrand plot, the association constant of 1－Zn2+ complexes was decided as 5.9 × 104 M-1. The best pH range for detecting Zn2+ by chemosensor 1 was from pH 5.0 to 10.0. Furthermore, 1－Zn2+ complexes indicated the presence of PPi among other anions with high selectivity by fluorescence quenching. The binding ratio of 1－Zn2+－PPi complexes was determined as 1:1 according to Job plot. According to Benesi-Hildebrand plot, the association constant of 1－Zn2+ complexes was decided as 6.9×104 M-1. For applications, the fluorescent enhancement was observed with addition of 1 to the living cells preloaded with Zn2+, the decrease of fluorescent intensity was observed after further addition of PPi. CS1 indicated the presence of CN- among other anions with high selectivity by a remarkable blue emission. According to 1H NMR and Mass studies, it was inferred that the levulinoyl ester could be easily and selectively deprotected by CN-. The best pH range for detecting CN- by CS1 was from pH 6.5 to 8.0.