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基于柱[5]芳烃超分子聚合物的铜离子荧光检测薄膜

杨广慧a,b, 韩捷b, 迟清水a, 李佳轩a, 王雨鹏a, 田霞a, 苏伟a, 许应桩a, 韩建荣*,a   

  1. (a河北科技大学 理学院 石家庄 050018);
    (b沧州职业技术学院 沧州 061001)
  • 投稿日期:2026-02-10
  • 基金资助:
    河北省中央引导地方科技发展资金项目(No. 236Z2601G).

Copper Ion Fluorescence Sensing Film Based on Pillar[5]arene Supramolecular Polymer

Yang Guanghuia b, Han Jieb, Chi Qingshuia, Li Jiaxuana, Wang Yupenga, Tian Xiaa, Su Weia, Xu Yingzhuanga, Han, Jianrong*,a   

  1. (aSchool of Sciences, Hebei University of Science and Technology, Shijiazhuang 050018);
    (bCangzhou Technical College, Cangzhou 061001)
  • Received:2026-02-10
  • Contact: *E-mail: han_jianrong@126.com
  • Supported by:
    Central Guidance on Local Science and Technology Development Fund of Hebei Province (No. 236Z2601G).

In recent years, supramolecular polymers constructed in the participation of lanthanide metal coordination commonly combine excellent luminescence properties with dynamic reversibility, have been widely reported for designing or developing intelligent sensing materials. In this paper, a bridged bis-pillar[5]arene macrocyclic molecule was synthesized in one step by the bicyclic oligomerization method. This strategy was proved to be a convenient and efficient synthesis path for pillararene dimers. Due to its double-ring cavities, this macrocyclic molecule is highly suitable for acting as a host to encapsulate specific guest molecules, thereby achieving supramolecular cross-linking assembly. In order to introduce luminescence center into supramolecular assembly, a aliphatic nitrile-modified pyridine-2,6-dicarboxylic acid molecule was designed and synthesized for the first time. Its β-dicarboxylic acid structure serves as a coordination site for binding Terbium ions, while the aliphatic nitrile structure acts as a host-guest interaction site for complexing with the bridged bis-pillar[5]arene. Firstly, it underwent coordination reaction with Terbium ions to form a aliphatic nitrile-modified terbium ion complex. Subsequently, the host-guest interaction between bridged bis-pillar[5]arene and aliphatic nitrile-modified terbium ion complex was performed to form a lanthanide luminescent supramolecular polymer through cross-linking assembly in solution. The study revealed the fluorescence properties, aggregation morphologies of supramolecular polymer and described its formation process. Furthermore, fluorescence properties of the supramolecular polymer were utilized to investigate its stimulus-responsive behaviors toward a series of metal ions. It was found that the addition of copper ions could affect the luminescent capability of the supramolecular polymer, thus leading to a significant reduction of the system's fluorescence intensity. Based on it, fluorescent film was prepared by loading this supramolecular polymer onto hydrophobic substrates. Experimental results demonstrated that the film enable both qualitative detection and quantitative analysis of trace copper ions in water. making it an environmentally friendly, safe, sensitive, and convenient fluorescent probe for copper ions.

Key words: supramolecular polymer, pillar[5]arene, lanthanide luminescence, fluorescent probe, copper ion