基于四芳基咪唑的聚集诱导发光染料及其细胞成像应用

doi:10.6023/cjoc202210002

摘要/Abstract

1,2,4,5-四苯基咪唑呈螺旋桨状高扭曲构象, 具有发展成为聚集诱导发光分子的潜力. 通过四组分“一锅煮”反应, 高产率地合成了2个基于四芳基咪唑的荧光分子(TAI-m和TAI-q), 通过核磁共振和高分辨质谱对其进行了结构表征, 单晶结构证实了它们高度扭曲的分子构象. TAI-m和TAI-q都表现出优异的聚集诱导发光性质. 对其自聚集纳米颗粒及F-127封装纳米颗粒的细胞染色及荧光成像性能做了比较研究. 结果表明二者的染色行为明显不同, 自聚集纳米颗粒染色的细胞显示清晰的细胞轮廓, 但细胞内部染色效果较差, 而F-127封装纳米颗粒能快速分布于整个细胞.

关键词: 聚集诱导发射, 四芳基咪唑, 自聚集纳米颗粒, 封装的纳米颗粒, 细胞成像

1,2,4,5-Tetraphenylimidazole takes a highly twisted propeller-like conformation, which results in its potential to be developed into aggregation-induced emission (AIE)-active molecules. Herein, two tetraarylimidazole-based aggregation- induced emission luminogens (TAI-m and TAI-q) were easily synthesized through a one-pot, four-component reaction in high yields. Their structures were fully characterized by nuclear magnetic resonance (NMR) and high-resolution mass spectra (HRMS). Furthermore, the crystal structures of them confirmed their highly twisted conformation. Both TAI-m and TAI-q exhibited good AIE properties. The self-aggregation nanoparticles and the pluronic F-127 encapsulated nanoparticles of them were prepared for comparative study of their cell imaging performance. The findings indicated that they showed the distinct staining behaviors. The cells stained with the self-aggregates showed clear cell outlines but fuzzy cell interiors. By comparison, the pluronic F-127 encapsulated nanoparticles can be distributed in the whole cell.

Key words: aggregation-induced emission, tetraarylimidazole, self-aggregation nanoparticles, encapsulated nanoparticles, cell imaging

引用此文

赵洋, 陈盼盼, 李高楠, 钮智刚, 王恩举. 基于四芳基咪唑的聚集诱导发光染料及其细胞成像应用[J]. 有机化学, 2023, 43(6): 2156-2162.

Yang Zhao, Panpan Chen, Gaonan Li, Zhigang Niu, Enju Wang. Tetraarylimidazole-Based Aggregation-Induced Emission Luminogens and Their Cell-Imaging Application[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2156-2162.

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图/表 8

Scheme 1. Synthetic route to TAI-m and TAI-q

Figure 1. Fluorescence spectra of TAI-m (A) in CH3CN/H2O mixtures and TAI-q (B) in EtOH/H2O mixtures with different water fractions, and their images in dissolved state and in aggregation state taken under 365 nm UV excitation (10 μmol/L, λex=370 nm for TAI-m, λex=397 nm for TAI-q) Fluorescence spectra of TAI-m (A) in CH3CN/H2O mixtures and TAI-q (B) in EtOH/H2O mixtures with different water fractions, and their images in dissolved state and in aggregation state taken under 365 nm UV excitation (10 μmol/L, λex=370 nm for TAI-m, λex=397 nm for TAI-q)

Figure 2. Oak Ridge thermal ellipsoid plot (ORTEP) drawing of TAI-m (A) and TAI-q (C) with 50% probability ellipsoids The red letters were used to indicate the aromatic rings attached to imidazole. Crystal packing arrangement of TAI-m (B) viewed along the c-axis and TAI-q (D) viewed along the a-axis

Figure 3. Fluorescence spectra of TAI-m in CH3CN/glycerol mixtures (A) and TAI-q in EtOH/glycerol mixtures (B) with different glycerol fractions

Figure 4. Fluorescence spectra of TAI-m (A) and TAI-q (B) in different solvents and their images in different solvents taken under 365 nm

Figure 5. Viability of HeLa cells in the presence of different concentrations of TAI-m and TAI-q for 10 h

Figure 6. Confocal images of HeLa cells stained with the self-aggregation nanoparticles of TAI-m (A, B, C, D) and TAI-q (E, F, G, H) A and E images in brightfield mode, B and F images in blue channel, C and G images in green channel, and D and H images in red channel

Figure 7. Confocal images of HeLa cells stained with the pluronic F-127 encapsulated nanoparticles of TAI-m (A, B, C, D) and TAI-q (E, F, G, H)

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