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

doi:10.6023/A26020054

Abstract

In recent years, supramolecular polymers constructed in the participation of lanthanide metal coordination, which 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 proved to be a convenient and efficient synthesis pathway for pillararene dimers. Due to its dual-ring cavities, this macrocyclic molecule is highly suitable to act as a host to encapsulate specific guest molecules, thereby achieving supramolecular cross-linking assembly. In order to introduce luminescence center into supramolecular assembly, an 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 an aliphatic nitrile-modified terbium ion complex. Subsequently, the host-guest interaction between bridged bis-pillar[5]arene and aliphatic nitrile-modified terbium ion complex facilitated the formation of 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 this, a fluorescent film was prepared by loading this supramolecular polymer onto hydrophobic substrates. Experimental results demonstrated that the film enables 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

Cite this article

Guanghui Yang, Jie Han, Qingshui Chi, Jiaxuan Li, Yupeng Wang, Xia Tian, Wei Su, Yingzhuang Xu, Jianrong Han. Copper Ion Fluorescence Sensing Film Based on Pillar[5]arene Supramolecular Polymer[J]. Acta Chimica Sinica, 2026, 84(6): 812-819.

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Fig. & Tab. 8

Figure 1. Schematic diagram of the synthetic routes for H1 (a) and G1 (b)

Figure 2. (a) Image of G1 solid under 254 nm UV light; (b) Image of G1 methanol solution under 254 nm UV light; (c) Fluorescence excitation spectrum of G1 methanol solution; (d) Fluorescence emission spectrum of G1 methanol solution

理论值					实测值
C/%	N/%	H/%			C/%	N/%	H/%
45.42	7.57	3.95			45.44	7.52	3.83

Table 1. Elemental analysis data of G1

Figure 3. Fluorescence titration experiment of the coordination reaction between Tb3+ and G0: (a) a, b represent the fluorescence emission spectra of Tb³⁺ and G0 aqueous solutions, respectively, c~l correspond to the fluorescence emission spectra of G0 aqueous solution after cumulatively adding 0.1~1.0 equiv. Tb3+ in sequence; (b) Calibration curve of the solution fluorescence values as a function of n(Tb3+)/n(G0)

Figure 4. SEM image (a) and TEM image (b) of the supramolecular polymer at a concentration of 1×10−3 mol/L; SEM image (c) and TEM image (d) of the supramolecular polymer at a concentration of 1×10−5 mol/L; Tyndall effect image (e) of equimolar mixtures of H1 and G1 at a concentration of 1×10−5 mol/L; Fluorescence emission spectra (f) of supramolecular polymer before and after formation in DMF solution at a concentration of 1×10−5 mol/L (λex=272 nm)

Figure 5. Schematic diagram of the formation process of supramolecular polymer

Figure 6. (a) Fluorescence emission spectra of a series of S1 solution after adding different metal ions (0.5 equiv.) in aqueous. (b) Fluorescence emission spectra of S1 solution after cumulative addition of Cu2+ (0~0.8 equiv.) in aqueous. Insert: Curve of solution fluorescence values as a function of the Cu²⁺ to S1 concentration ratio. (c) Linear correlation curve between S1 solution fluorescence values and Cu²⁺ concentration within a specific range. (d) Fluorescence emission spectrum of the film in 0~0.01 mol/L Cu²⁺ aqueous solution. Insert: Linear correlation curve between film fluorescence values and Cu²⁺ concentration within a specific range

Figure 7. Images of detection film (S1@PMMA 5.0%) under 254 nm ultraviolet irradiation. Top image: film in a gradient concentration of copper ion aqueous solution (a~e represent Cu2+ concentration increasing from 1×10−5 to 1×10−4 mol/L); Bottom image: film in a series of metal ion salt solutions (concentration of all metal ions is 1.67×10−4 mol/L)

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