基于π-共轭柱[5]芳烃的荧光传感器用于L-精氨酸识别

doi:10.6023/cjoc202411015

摘要/Abstract

近十年来, 人们对各种功能化柱芳烃的合成和应用特性进行了广泛的研究. 由于柱芳烃具有丰富的主客识别能力, 因此在传感器领域具有良好的应用前景. 然而, 柱芳烃的非共轭结构导致其极差的荧光效率. 通过在柱[5]芳烃骨架中引入供电子的三芳基胺(Ar₃N)和缺电子的三芳基硼(Ar₃B), 得到了一种π-共轭电荷转移体系P5BN, 显著改善了其发光性能, 并进一步用于荧光检测应用. 分子结构显示, P5BN提供了一个大环空腔, 可封装适当大小的氨基酸分子. P5BN作为一种荧光传感器, 可以选择性检测L-精氨酸(L-Arg), 最低检测浓度为2.21×10^－8 mol/L. 实验和密度泛函理论(DFT)计算证明了识别机制.

关键词: 荧光传感器, 主客体识别, 柱[5]芳烃, L-精氨酸, 密度泛函理论(DFT)计算

In the past decade, people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes. Pillararenes show good application prospects in the field of sensors due to the rich host-guest recognition in their rigid electron-rich cavities. However, most reported pillararenes are functionalized by alkoxy modification, which results in poor charge transfer nature and weak fluorescence response. A π-conjugated charge-transfer system P5BN was obtained by introducing electron-donating triarylamine (Ar₃N) and electron-deficient triarylborane (Ar₃B) into pillar[5]arene skeleton, which significantly improved its luminescence behavior and was further used for fluorescence detection applications. The molecular structure showed that P5BN provided a good macrocyclic cavity to encapsulate amino acids molecules of suitable size. It was found that P5BN, as a fluorescent sensor, showed a highly sensitive and selective response to L-arginine (L-Arg), resulting in a significant enhancement of the fluorescence at 408 nm of P5BN with the lowest detection concentration being 2.21×10^－8 mol/L. The recognition mechanism was demonstrated through experiments and DFT theoretical calculations.

Key words: fluorescent sensor, host-guest recognition, pillar[5]arene, L-arginine, density functional theory (DFT) calculations

引用此文

令小鹏, 陶绍平, 林奇, 史兵兵, 姚虹, 魏太保, 陈进发. 基于π-共轭柱[5]芳烃的荧光传感器用于L-精氨酸识别[J]. 有机化学, 2025, 45(7): 2480-2485.

Xiaopeng Ling, Shaoping Tao, Qi Lin, Bingbing Shi, Hong Yao, Taibao Wei, Jinfa Chen. A Pillar[5]arene-Based π-Conjugated Dye Used for Fluorescence Sensing of L-Arginine[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2480-2485.

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图/表 5

Scheme 1. Research foundation and design strategy of pillar[5]arene-based π-conjugated emitter P5BN with enhanced luminescence and host-guest recognition

Figure 1. Fluorescence responses P5BN (c=2.0×10－6 mol/L, λex=345 nm) to various solutions of amino acids (4.0×10－6 mol/L) in DMSO solution Inset: photographs of solutions before and after the addition of L-Arg under 365 nm UV irradiation

Figure 2. Fluorescence intensity of P5BN (c=2.0×10－6 mol/L, λex=345 nm) at 408 nm with addition of L-Arg (4.0×10－6 mol/L) in the presence of competition ions (4.0×10－6 mol/L) in DMSO solution

Figure 3. Fluorescence changes of P5BN (c=2.0×10－6 mol/L, λex=345 nm) in the presence of different equiv. of L-Arg in DMSO solution

Figure 4. (a) Calculated electrostatic potentials (ESP) mapped onto the electron density isosurfaces in P5BN, L-Arg and P5BN@L-Arg; (b) Independent Gradient Model based on Hirsh- feld partition (IGMH) diagram of P5BN@L-Arg at the B3LYP/6- 31G(d,p) level

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