有机化学 ›› 2014, Vol. 34 ›› Issue (9): 1780-1785.DOI: 10.6023/cjoc201405012 上一篇    下一篇

研究论文

Al3+可视化水溶性分子荧光探针的合成及其作用研究

马拓, 张瑾, 刘龙珠, 贺云, 张尊听   

  1. 教育部药用资源与天然药物化学重点实验室, 西北濒危药材资源开发国家工程实验室, 陕西师范大学化学化工学院, 西安 710062
  • 收稿日期:2014-03-08 修回日期:2014-03-24 出版日期:2014-09-25 发布日期:2014-06-03
  • 通讯作者: 张尊听 E-mail:zhangzt@snnu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21372150)、高校基本科研业务费专项资金(No. GK261001095)资助项目.

Synthesis and Characterization of a Visualization and Water-Soluble Fluorescent Probe for Al3+

Ma Tuo, Zhang Jin, Liu Longzhu, He Yun, Zhang Zunting   

  1. Key Laboratory of the Ministry of Education for Medicinal Resources and Natural Pharmaceutical Chemistry, National Engineering Laboratory for Resource Development of Endangered Crude Drugs in Northwest of China and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062
  • Received:2014-03-08 Revised:2014-03-24 Online:2014-09-25 Published:2014-06-03
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21372150), and the Fundamental Research Funds for the Central Universities (No. GK261001095).

设计并合成了3种嘧啶并[1,6-a]苯并咪唑磺化物:4-(2'-羟基苯基)嘧啶并[1,6-a]苯并咪唑-5'-磺酸钠(L1)、4-(2'-羟基苯基)嘧啶并[1,6-a]苯并咪唑-3',5',10-三磺酸钠(L2)和4-(2',4'-二羟基苯基)嘧啶并[1,6-a]苯并咪唑-5'-磺酸钠(L3),运用质谱和核磁等方法对其结构进行表征. 利运用荧光光谱法考察了L1,L2和L3对Al3+的识别作用,结果表明:在水溶液中L2能与Al3+配合,配合后的荧光光谱强度增强,而加入其它金属离子(Cu2+,Hg2+,K+,Mg2+,Na+,Ni2+,Pb2+,Zn2+,Cr3+,Fe3+)基本没有变化,表明L2对Al3+具有专一的识别性. 通过Job's plot曲线和荧光滴定实验确定L2和Al3+以1:2的比例进行配合,L2对Al3+的检出限为0.073 μmol/L,并且L2能够可视化检测Al3+.

关键词: 配位, 铝离子, 荧光探针, 激发态内分子质子转移, 可视化检测

In order to improve the water-solubility of 4-(2'-hydroxyphenyl)-pyrimido[1,6-a]benzimidazole and 4-(2'-hydrx- yphenyl-4'-isopropoxy)-pyrimido[1,6-a]benzimidazoles, they were sulfonated in 98% H2SO4. Sodium 4-(2'-hydroxyphenyl)- pyrimido[1,6-a]benzimidazole-5-sulfonate (L1), sodium 4-(2'-hydroxyphenyl)-pyrimido[1,6-a]benzimidazole-3',5',10'-three- sulfonate (L2), sodium 4-(2',4'-dihydroxyphenyl)pyrimido[1,6-a]benzimidazol-5-sulfonate (L3) were obtained and indentified by the method of NMR, IR and MS. Fluorescence spectra of L1, L2 and L3 were detected, and they have the ESIPT effect with a large Stokes shift (175~225 nm). The structures of these compounds could be complex with Al3+, and the fluorescence spectra of Al3+ in L1, L2 and L3 were analyzed. The results showed that L2 exhibited good sensitivity selectivity to Al3+. The fluorescence of L2 was strengthened dramatically in the presence of Al3+. Other metal ions, such as Cu2+, Hg2+, K+, Mg2+, Na+, Ni2+, Pb2+, Zn2+, Cr3+, Fe3+ induced negligible fluorescence strengthening for L2 under the same conditions. When the concentration (0~20 μmol/L) of Al3+ was increased, the fluorescence intensity of L2 (10 μmol/L) was also increased. The Job’s plot and fluorescence titration indicated that the stoichiometry of L2-Al3+ was 1:2 and the detection limit of Al3+ was 0.073 μmol/L. Moreover, L2 was used for the visual detection of Al3+.

Key words: coordinate, aluminum ions, fluorescent probe, excited state intramolecular proton transfer (ESIPT), visual detection