Acta Chim. Sinica ›› 2015, Vol. 73 ›› Issue (5): 409-415.DOI: 10.6023/A15010039 Previous Articles     Next Articles

Article

基于荧光树状聚合物的高灵敏化学反应型汞离子传感器

张崇洋, 孟玉珠, 匡金志, 徐岚   

  1. 西南大学化学化工学院 重庆 400715
  • 收稿日期:2015-01-15 出版日期:2015-05-14 发布日期:2015-03-17
  • 通讯作者: 徐岚 E-mail:xulan@swu.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No. 51103120)资助.

Highly Sensitive Detection of Hg2+ by a Reaction-Based Dendritic Fluorescent Polymer Chemosensor

Zhang Chongyang, Meng Yuzhu, Kuang Jinzhi, Xu Lan   

  1. School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China
  • Received:2015-01-15 Online:2015-05-14 Published:2015-03-17
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 51103120).

In this work, spherical polymer-based fluorescent sensor with high sensitivity for Hg2+ was first designed and synthesized. Dendritic hyperbranched poly(phenylene sulfide) (HPPS) with an average molecular weight of 10.910 kD and spherical conformation was synthesized via one-pot reaction procedure with 2,4-dichlorothiophenol as monomer. Because of aryl groups conjugated with sulfur atoms and dendritic topology, HPPS displayed remarkable chemical stability, fluorescent and multiple reaction sites. It inspires us to employ it as a smart matrix to develop polymer fluorescent sensor. Through the nucleophilic substitution and hydrolysis reaction, peripheral Cl atoms of HPPS were modified by NH2 groups, and the resulted HPPS-NH2 was achieved. The fluorescent sensor (HPPSNT) was fabricated by HPPS-NH2 azo N=N covalently bonded to small probe molecule Benzamide, N-[[[2-(phenylamino)ethyl]amino]thioxomethyl], which can react with Hg2+sensitively and selectively, causing desulfurization and cyclization. The results showed that HPPSNT sensor exhibited excellent sensitivity towards Hg2+, and can selectively recognize Hg2+ over other metal ions, such as Al3+, Ba2+, Cd2+, Cu2+, Fe3+, Zn2+, Pb2+, Mg2+, K+, Ag+. It was found that the decreased absorption of fluorescent signal intensity was proportional to the mercury content concentration in a range of 2.5~100 nmol/L with a coefficient of correlation R of 0.9931, and a detection limit of 0.46 nmol/L. The mechanism of high sensitivity was discussed. HPPS was rich in sulfur atoms inside, which has a strong affinity for Hg2+, Cu2+, Fe3+, Ag+, consequently, fluorescence of HPPS-NH2 was quenched dramatically in the presence of these ions. As the peripheral small probe molecules preferentially reacted with Hg2+ via desulfurization and cyclization reaction, it is by such reactions instead of by quenching to cause fluorescence intensity of HPPSNT weakened. The decline of fluorescence intensity via desulfurization and cyclization reaction can be explained through the simulation calculation of bond length by Gaussian 09.

Key words: dendritic polymer, hyperbranched poly(phenylene sulfide), mercury ions, fluorescene, highly sensitive sensor