次氯酸及汞(Ⅱ)離子螢光化學感測分子之合成與應用

Abstract

本論文以 7-hydroxycoumarin 為基底，設計合成螢光化學感測分子 HS1、MS1。化合物 HS1 藉由藍色螢光增強的方式辦識 NaOCl ，在其他 ROS 及 RNS 的存在下，仍對 NaOCl 具有高度選擇性，並能在 pH 值範圍為 7.0－12.0 內偵測到 NaOCl 的存在。藉由 1H-NMR 及 Mass 等相關數據，推測 NaOCl 可選擇性地對化合物 HS1 上的 oxime 進行氧化反應，逕而產生藍色螢光。此外，更可進一步應用於 RAW 264.7 cells 內偵測 NaOCl 之存在。 化合物 MS1 藉由藍色螢光增強的方式辦識 Hg2+，在其他金屬離子的存在下，仍對 Hg2+ 具有高度選擇性，並能在 pH 值範圍為 6.5－9.0 內偵測到 Hg2+ 的存在。由 1H-NMR 可知，化合物 MS1 以 imine 及 amine 上的氮跟 OH group 上的氧與 Hg2+ 鍵結。由 Job plot 可得 MS1－Hg2+ 的錯合比例為 1：1。藉由 Benesi-Hildebrand plot 算出 MS1－Hg2+ 的結合常數為 6.85 × 103 M-1。化合物 MS1 偵測 Hg2+ 的偵測極限為 0.193 μM。此化學感測分子亦成功應用於觀測HeLa 細胞內 Hg2+ 之分布。

In this thesis, 7-hydroxycoumarin was used as a signal unit for chemosensors HS1 and MS1. Chemosensor HS1 indicated the presence of NaOCl among other ROS and RNS with high selectivity by a remarkable blue emission. According to 1H NMR and Mass studies, the oxime was selectively oxidized by NaOCl to be a cyano group. The best pH range for detecting NaOCl by Chemosensor HS1 was from pH 7.0 to 12.0. In addition, Chemosensor HS1 can be used as a fluorescent probe for detecting NaOCl in living cells. Chemosensor MS1 indicated the presence of Hg2+ among other metal ions with high selectivity by a remarkable blue emission. According to 1H NMR studies, Hg2+ binding with chemosensor MS1 is mainly through the hydrazine group and OH group. The binding ratio of MS1－Hg2+ complexes was determined as 1:1 according to Job plot. According to Benesi-Hildebrand plot, the association constant of MS1－Hg2+ complexes was decided as 6.85 × 103 M-1. The best pH range for detecting Hg2+ by chemosensor MS1 was from pH 6.5 to 9.0. In addition, chemosensor MS1 can be used as a fluorescent probe for detecting Hg2+ in living cells.