基于柱[5]芳烃超分子聚合物的铜离子荧光检测薄膜

doi:10.6023/A26020054

摘要/Abstract

近年来, 由镧系金属配位作用参与构筑的超分子聚合物, 兼具镧系离子优异的发光性能和超分子的动态可逆性, 被广泛报道用于智能传感材料的设计与开发. 本工作合成了一种桥联双柱[5]芳烃大环分子, 通过主客体作用与制备的长链腈修饰的铽离子配合物经交联组装形成了具有镧系发光性能的超分子聚合物. 利用荧光性能探究了超分子聚合物对多种金属离子的识别作用, 结果显示其对铜离子有特异性的识别能力. 应用该超分子聚合物制成了荧光薄膜, 该薄膜可作为荧光探针用于水中铜离子的检测, 具有良好的选择性和灵敏度.

关键词: 超分子聚合物, 柱[5]芳烃, 镧系发光, 荧光探针, 铜离子

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

引用此文

杨广慧, 韩捷, 迟清水, 李佳轩, 王雨鹏, 田霞, 苏伟, 许应桩, 韩建荣. 基于柱[5]芳烃超分子聚合物的铜离子荧光检测薄膜[J]. 化学学报, 2026, 84(6): 812-819.

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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图/表 8

图1. 主体分子H1 (a)和客体分子G1 (b)的合成路线示意图

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

图2. (a) 254 nm紫外灯下的G1固体图像; (b) 254 nm紫外灯下的G1甲醇溶液图像; (c) G1甲醇溶液的荧光激发光谱; (d) G1甲醇溶液的荧光发射光谱

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

表1. G1的元素分析数据

Table 1. Elemental analysis data of G1

图3. Tb3+与G0配位过程的荧光滴定实验: (a) a、b分别为Tb3+、G0水溶液的荧光发射光谱, c~l依次对应的是G0水溶液中累计滴加0.1~1.0 equiv. Tb3+后的荧光发射光谱; (b)溶液荧光值随n(Tb3+)/n(G0)变化的工作曲线

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)

图4. 超分子聚合物在1×10−3 mol/L浓度下的扫描电镜图(a)和透射电镜图(b); 超分子聚合物在1×10−5 mol/L浓度下的扫描电镜图(c)和透射电镜图(d); 1×10−5 mol/L浓度下H1与G1等物质的量混合液的丁达尔效应图(e); 1×10−5 mol/L浓度下超分子聚合物在DMF溶液中生成前后的荧光发射光谱(λex=272 nm) (f)

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)

图5. 超分子聚合物的形成过程示意图

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

图6. (a)一系列S1溶液中加入不同金属离子(0.5 equiv.)水溶液后的荧光发射光谱; (b) S1溶液中累计滴加Cu2+ (0~0.8 equiv.)水溶液后的荧光发射光谱. 插图: 溶液荧光值随Cu2+与S1浓度比变化的工作曲线; (c) S1溶液荧光值与Cu2+浓度在一定范围内的线性相关曲线; (d)薄膜在0~0.01 mol/L Cu2+水溶液中的荧光发射光谱. 插图: 薄膜荧光值与Cu2+浓度在一定范围内的线性相关曲线

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

图7. 254 nm紫外灯下的荧光检测薄膜(S1@PMMA 5.0%)图像. 上图为薄膜在不同浓度铜离子水溶液(a~e: Cu2+浓度由1×10−5递增为1×10−4 mol/L)中的图像; 下图为薄膜在不同金属离子水溶液中的图像(金属离子浓度均为1.67×10−4 mol/L)

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)

参考文献 23

[1]	Brunsveld, L.; Folmer, B. J.; Meijer, E. W.; Sijbesma, R. P. Chem. Rev. 2001, 101, 4071. pmid: 11740927
[2]	De Greef, T. F.; Smulders, M. M.; Wolffs, M.; Schenning, A. P.; Sijbesma, R. P.; Meijer, E. W. Chem. Rev. 2009, 109, 5687. doi: 10.1021/cr900181u pmid: 19769364
[3]	Fouquey, C.; Lehn, J. M.; Levelut, A. M. Adv. Mater. 1990, 2, 254. doi: 10.1002/adma.v2:5
[4]	Yang, L.; Tan, X.; Wang, Z.; Zhang, X. Chem. Rev. 2015, 115, 7196. doi: 10.1021/cr500633b
[5]	Yao, H.; Wang, J.; Tian, W. Acta Polym. Sin. 2021, 52, 578 (in Chinese).
	(姚灏, 王景霞, 田威, 高分子学报, 2021, 52, 578.)
[6]	Huo, Y.; He, Z.; Wang, C.; Zhang, L.; Xuan, Q.; Wei, S.; Wang, Y.; Pan, D.; Dong, B.; Wei, R. Chem. Commun. 2021, 57, 1413. doi: 10.1039/D0CC07247H
[7]	Clemons, T. D.; Stupp, S. I. Prog. Polym. Sci. 2020, 111, 101310. doi: 10.1016/j.progpolymsci.2020.101310
[8]	Dong, R.; Zhou, Y.; Huang, X.; Zhu, X.; Lu, Y.; Shen, J. Adv. Mater. 2015, 27, 498. doi: 10.1002/adma.v27.3
[9]	Wang, H.; Ji, X.; Li, Z.; Huang, F. Adv. Mater. 2017, 29, 1606117. doi: 10.1002/adma.v29.14
[10]	Roy, N.; Schädler, V.; Lehn, J.-M. Acc. Chem. Res. 2024, 57, 349. doi: 10.1021/acs.accounts.3c00683
[11]	Li, Z.; Liu, X.; Wang, G.; Li, B.; Chen, H.; Li, H.; Zhao, Y. Nat. Commun. 2021, 12, 1363. doi: 10.1038/s41467-021-21677-4
[12]	Yu, H.-J.; Zhou, X.-L.; Dai, X.; Shen, F.-F.; Zhou, Q.; Zhang, Y.-M.; Xu, X.; Liu, Y. Chem. Sci. 2022, 13, 8187. doi: 10.1039/D2SC02384A
[13]	Zhou, W.-L.; Dai, X.-Y.; Lin, W.; Chen, Y.; Liu, Y. Chem. Sci. 2023, 14, 6457. doi: 10.1039/D3SC01425H
[14]	Li, F.; Yi, S.; Wang, J.; Liu, X.; Gao, W.; Li, J.; Zhang, H. Acta Chim. Sinica 2025, 83, 453 (in Chinese). doi: 10.6023/A25010009
	(李菲, 伊思静, 王姣, 刘晓霞, 高文梅, 李婧婧, 张海峰, 化学学报, 2025, 83, 453.) doi: 10.6023/A25010009
[15]	Kotova, O.; Bradberry, S. J.; Savyasachi, A. J.; Gunnlaugsson, T. Dalton Trans. 2018, 47, 16377. doi: 10.1039/c8dt03768j pmid: 30379167
[16]	Zheng, B.; Hou, Y.; Gao, L.; Zhang, M. Chin. J. Chem. 2019, 37, 843. doi: 10.1002/cjoc.v37.8
[17]	Sun, N.; Xiao, X.; Jiang, J. Polym. Chem. 2015, 6, 5015. doi: 10.1039/C5PY00683J
[18]	Xia, B.; He, J.; Abliz, Z.; Yu, Y.; Huang, F. Tetrahedron Lett. 2011, 52, 4433.
[19]	Cragg, P. J.; Sharma, K. Chem. Soc. Rev. 2012, 41, 597. doi: 10.1039/C1CS15164A
[20]	Li, C.; Han, K.; Li, J.; Zhang, H.; Ma, J.; Shu, X.; Chen, Z.; Weng, L.; Jia, X. Org. Lett. 2012, 14, 42. doi: 10.1021/ol2027834
[21]	Wang, Y.; Ping, G.; Li, C. Chem. Commun. 2016, 52, 9858. doi: 10.1039/C6CC03999E
[22]	Zhang, H.; Li, J.; Hu, Z.; Ji, X. Chin. J. Chem. 2024, 42, 2699. doi: 10.1002/cjoc.v42.22
[23]	Lv, T.; Wu, S.; Jin, Y.; Ma, J.; Jiang, S.; Xue, Y.; Wang, F. Chin. J. Chem. 2024, 42, 135. doi: 10.1002/cjoc.v42.2