三苯基咪唑衍生物的聚集诱导发光性质及其细胞成像应用

doi:10.6023/cjoc202212004

摘要/Abstract

聚集诱导发光(AIE)材料在生物医学领域有很大优势, 尤其为生物成像研究开启了新局面. 通过2,4,5-三苯基咪唑衍生物与1,4-二溴丁烷/1-溴丁烷亲核取代反应, 合成了2个丁烷桥联的双咪唑衍生物及2个1-位丁基取代的单咪唑衍生物. 4个产物都表现出优异的AIE性质, 其中含有甲氧基助色团的衍生物具有更长的发射波长. 机理研究表明限制扭曲的分子内电荷转移是这类结构具有AIE活性的原因, 因此, 2-位强吸电子芳基是它们具有AIE活性的决定因素. 此外, 咪唑环1-位取代基的空间效应对AIE也非常重要, 因为较大体积的1-位取代基使分子呈扭曲构象, 从而限制聚集态π-π堆积作用. 最后, 研究了1-位丁基取代的单咪唑衍生物的细胞染色和成像性能, 结果显示二者在蓝色、绿色及红色通道都表现出不错的荧光成像能力, 但在不同颜色通道观察到的细胞被染色区域不完全相同.

关键词: 聚集诱导发光(AIE), 三苯基咪唑, 扭曲的分子内电荷转移, 扭曲构象

Aggregation-induced emission (AIE)-active materials have great advantages in the biomedical field and open up a whole new world of opportunity for bioimaging. Herein, two butylidene-bridged bisimidazole derivatives and two butyl-sub- stituted monoimidazole derivatives were easily synthesized from dibromobutane/bromobutane and 2,4,5-triphenyl-1H-imida- zole derivatives. All the obtained imidazole derivatives showed excellent AIE properties, and the derivatives containing methoxy groups exhibited red-shifted emission. The research on AIE mechanism indicated that the restriction of twisted intramolecular charge transfer (TICT) mechanism was responsible for the AIE behaviors of these imidazole derivatives. Therefore, the strong electron-withdrawing nitro group is crucial for their AIE property. In addition, the steric effect of the substituent group at 1-position of imidazole ring is also indispensable for AIE, because it results in the twisted conformation and thus hampers the intermolecular π-π stacking interactions. Ultimately, the cell staining and bioimaging behaviour of butyl-substituted monoimidazole derivatives were investigated. Both of them displayed an excellent bioimaging performance in blue, green and red channels, but the different staining regions in cells were observed in different channels.

Key words: aggregation-induced emission (AIE), triphenylimidazole, twisted intramolecular charge transfer (TICT), twisted conformation

引用此文

赵洋, 陈盼盼, 韩立志, 王恩举. 三苯基咪唑衍生物的聚集诱导发光性质及其细胞成像应用[J]. 有机化学, 2023, 43(7): 2454-2461.

Yang Zhao, Panpan Chen, Lizhi Han, Enju Wang. Aggregation-Induced Emission and Cell Imaging of Triphenylimidazole Derivatives[J]. Chinese Journal of Organic Chemistry, 2023, 43(7): 2454-2461.

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图/表 7

图式1. 三苯基咪唑衍生物的合成路线

Scheme 1. Synthetic route to the triphenylimidazole derivatives

图1. BTPI-H, BTPI-OMe, BBI-H及BBI-OMe在DMSO(实线)中及在DMSO/H2O (V∶V=1∶9) (短划线)中的吸收光谱

Figure 1. Absorption spectra of BTPI-H, BTPI-OMe, BBI-H and BBI-OMe in DMSO (solid line) and DMSO/H2O (V∶V=1∶9) (dashed line)

图2. BBI-H (A), BBI-OMe (B), BTPI-H (C)及BTPI-OMe (D)在不同含水量的DMSO/H2O混合溶剂中的荧光谱图及其在365 nm紫外光激发下的照片(E)

Figure 2. Fluorescence spectra of BBI-H (A), BBI-OMe (B), BTPI-H (C) and BTPI-OMe (D) in DMSO/H2O mixtures with different water fractions (fw), and photos (E) of them taken under 365 nm UV excitation 10 μmol/L, λex=377 nm for BBI-H and BTPI-H, and λex=394 nm for BBI-OMe and BTPI-OMes

图3. BTPI-H在不同溶剂中的荧光谱图(A)及365 nm紫外光激发下的照片(B)

Figure 3. Fluorescence spectra of BTPI-H in different solvents (A) and photographs taken under 365 nm UV excitation (B)

图4. BTPI-H及BTPI-OMe的HOMO-LUMO分布

Figure 4. HOMO-LUMO distributions of BTPI-H and BTPI-OMe

图5. TriPI-NO2 (A)和TetraPI-NO2 (B)在不同含水量的DMSO/H2O混合溶剂中的荧光谱图(λex=377 nm)

Figure 5. Fluorescence spectra of TriPI-NO2 (A) and TetraPI-NO2 (B) in DMSO/H2O mixtures with different water fractions (λex=377 nm)

图6. Hela细胞分别与聚集态BTPI-H (A, B, C, D)和BTPI-OMe (E, F, G, H)孵育20 min后的共聚焦成像图

Figure 6. Confocal images of HeLa cells stained with the self-aggregation nanoparticles of BTPI-H (A, B, C, D) and BTPI-OMe (E, F, G, H) for 20 min (A and E) images in brightfield mode, (B and F) images in blue channel (λex=405 nm, λem=430~475 nm), (C and G) images in green channel (λex=488 nm, λem=500~550 nm), (D and H) images in red channel (λex=640 nm, λem=663~737 nm)

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