喹啉基粘度荧光探针的合成及其检测应用

doi:10.6023/A23040138

化学学报 ›› 2023, Vol. 81 ›› Issue (8): 905-911.DOI: 10.6023/A23040138 上一篇下一篇

研究论文

喹啉基粘度荧光探针的合成及其检测应用

武虹乐, 郭锐, 迟涵文, 唐永和, 宋思睿, 葛恩香, 林伟英^*()

广西大学光功能材料与化学生物学研究院广西电化学能源材料重点实验室广西大学化学化工学院省部共建特色金属材料与组合结构全寿命安全国家重点实验室广西南宁 530004

投稿日期:2023-04-20 发布日期:2023-09-14
基金资助:
国家自然科学基金(21877048); 国家自然科学基金(22077048); 国家自然科学基金(22277014); 国家自然科学基金(22104019); 广西壮族自治区自然科学基金(2019GXNSFBA245068); 广西壮族自治区自然科学基金(2021GXNSFDA075003); 广西壮族自治区自然科学基金(AD21220061); 广西大学启动基金(A3040051003)

Viscosity Fluorescent Probes Based on Quinoline Group and Its Applications

Hongyue Wu, Rui Guo, Hanwen Chi, Yonghe Tang, Sirui Song, Enxiang Ge, Weiying Lin()

Institute of Optical Materials and Chemical Biology, Guangxi Key Laboratory of Electrochemical Energy Materials, School of Chemistry and Chemical Engineering, State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi University, Nanning, Guangxi 530004

Received:2023-04-20 Published:2023-09-14
Contact: *E-mail: weiyinglin2013@163.com
Supported by:
National Natural Science Foundation of China(21877048); National Natural Science Foundation of China(22077048); National Natural Science Foundation of China(22277014); National Natural Science Foundation of China(22104019); Natural Science Foundation of Guangxi Province(2019GXNSFBA245068); Natural Science Foundation of Guangxi Province(2021GXNSFDA075003); Natural Science Foundation of Guangxi Province(AD21220061); Startup Fund of Guangxi University(A3040051003)

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摘要/Abstract

作为细胞微环境的一个重要参数, 粘度通过影响生物分子之间的相互作用实现对生物功能的调节. 粘度的异常会导致多种疾病, 如阿尔茨海默病、肺炎等. 因此, 实现粘度变化的精准检测对相关疾病的预防和诊断具有重要意义. 本工作构建了新型喹啉基荧光探针QUI-VI. 通过分子内的空间扭转(扭曲的光诱导分子内电荷转移机制), 该探针实现了对粘度的检测. 光学实验表明探针QUI-VI具有高化学和光稳定性能以及灵敏的粘度检测性能等优点. 通过光谱实验、细胞成像以及组织成像实验, 表明该探针具有显著的粘度敏感性, 荧光强度会随着测试体系粘度的增强而增强. 结合首次报道的小鼠肺炎组织粘度成像实验表明探针QUI-VI有望对肺炎的早期诊断提供一定的理论支撑.

关键词: 粘度, 荧光探针, 荧光成像, 肺炎, 喹啉

As one of the important parameters of biological microenvironment, viscosity is closely related to many life activities, when diseases appear in the organism, such as pneumonia, diabetes, Alzheimer's disease, atherosclerosis, malignant tumors, etc., the cytoplasmic viscosity in the organelle also changes, the new crown pneumonia is becoming more and more serious, and it is urgent to detect the viscosity in the organism. Based on the fluorescence mechanism of twisted intramolecular charge transfer (TICT), a viscosity-mediated fluorescent probe QUI-VI is rationally designed and constructed, and its related properties are explored and applied to detect physiological viscosity changes in vivo to achieve the purpose of disease monitoring. The two conjugates were connected by the carbon-carbon double bond formed by the condensation of aminotrinitrobenzene and benzopyridine quaternary ammonium salts by methyl and aldehyde groups, forming a large conjugated system. This not only increases the free transfer of electrons in the conjugated system, so that the constructed probe molecules have a long emission wavelength, but also regulates the fluorescence signal of the probe molecules because the freely rotatable carbon-carbon double bond can respond to the change of viscosity. The regulation process is: when QUI-VI is in a high-viscosity environment, the free rotation of the carbon-carbon double bond is greatly limited, so that the two conjugated systems on the molecule are in the same plane, at this time, the probe molecule is the lowest energy state, when irradiated by 450 nm light, absorb one photon energy. The molecule is excited in the excited state, and can emit long-wavelength fluorescence when transitioning back to the ground state. On the contrary, when it is in a medium with low viscosity, the free rotation of the carbon-carbon double bond is no longer hindered, and when the two conjugated systems rotate to the same plane perpendicularly, they are in the highest energy state, and the molecules emit shorter wavelengths of fluorescence when absorbing the energy of a photon and transitioning back to the ground state, that is, it is blue-shifted by 10 nm on the fluorescence spectrum. All in all, the fluorescence change of the probe QUI-VI constructed based on the TICT mechanism is controllable.

Key words: viscosity, fluorescent probes, fluorescence imaging, pneumonia, quinolone

引用此文

武虹乐, 郭锐, 迟涵文, 唐永和, 宋思睿, 葛恩香, 林伟英. 喹啉基粘度荧光探针的合成及其检测应用[J]. 化学学报, 2023, 81(8): 905-911.

Hongyue Wu, Rui Guo, Hanwen Chi, Yonghe Tang, Sirui Song, Enxiang Ge, Weiying Lin. Viscosity Fluorescent Probes Based on Quinoline Group and Its Applications[J]. Acta Chimica Sinica, 2023, 81(8): 905-911.

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图/表 11

图式1. 探针QUI-VI的机理

Scheme 1. The mechanism of QUI-VI

图式2. QUI-VI的合成路线

Scheme 2. Synthetic route of QUI-VI Reagents and conditions: (i) Compound 1, tetrahydrofuran, aqueous ammonia, 25 ℃, 1 h. (ii) Compound 3, iodoethane, acetonitrile, 85 ℃, 12 h. (iii) Compound 2, compound 4, methanol, 65 ℃, 1 h

图1. (A) QUI-VI (10 μmol/L)在不同极性溶剂中的紫外吸收光谱. (B) QUI-VI (10 μmol/L)在不同极性溶剂中的荧光发射光谱

Figure 1. (A) UV absorption spectra of QUI-VI (10 μmol/L) in different polar solvents. (B) Fluorescence emission spectra of QUI-VI (10 μmol/L) in different polar solvents (λem=450 nm)

图2. QUI-VI (10 μmol/L)在甘油-水混合溶剂体系中的荧光发射光谱 (λem=450 nm)

Figure 2. Fluorescence emission spectra of QUI-VI (10 μmol/L) in glycerol-water mixed solvent system (λem=450 nm)

图3. 探针QUI-VI (10 μmol/L)在不同无机离子和氨基酸的溶液体系中荧光发射柱状图

Figure 3. Fluorescence emission histograms of QUI-VI (10 μmol/L) in solution systems of different inorganic ions and amino acids The numbers represent: 1. NaClO; 2. L-Cys; 3. NaF; 4. GSH; 5. H2O2; 6. DL-Hcy; 7. KI; 8. MgCl2; 9. MnCl2; 10. Na2S; 11. Na2SO4; 12. ZnCl2; 13. L-Met; 14. TBHP; 15. L-Arg; 16. L-Lys; 17. Na2SO3 (λem=450 nm)

图4. (A) 用QUI-VI (10 μmol/L)和油酸(OA) (400 μmol/L)处理的4种不同细胞系的共聚焦成像(λex=580 nm, λem=610~750 nm), 比例尺=30 μm; (B) (A)的红色通道的相对荧光强度(*p<0.05)

Figure 4. (A) Confocal imaging of four different cell lines treated with QUI-VI (10 μmol/L) and OA (400 μmol/L) (λex=580 nm, λem=610~750 nm), scale bar=30 μm; (B) the relative fluorescence intensities of the red channels of (A) (*p<0.05)

图5. (a~c) QUI-VI (10 μmol/L)以及制霉菌素(20 μmol/L)处理后的3T3细胞成像; (d~f) QUI-VI (10 μmol/L)以及莫能菌素(20 μmol/L)处理后的3T3细胞成像; (g~i) QUI-VI (10 μmol/L)处理后的3T3细胞成像; (j) 三组成像实验结果对比图

Figure 5. (a~c) 3T3 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Nys (20 μmol/L); (d~f) 3T3 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Mon (20 μmol/L); (g~i) 3T3 cell imaging after treatment with probe QUI-VI (10 μmol/L); (j) fluorescence intensity comparison chart of three groups of cell imaging

图6. (a~c) QUI-VI (10 μmol/L)以及制霉菌素(20 μmol/L)处理后的4T1细胞成像; (d~f) QUI-VI (10 μmol/L)以及莫能菌素(20 μmol/L)处理后的4T1细胞成像; (g~i) QUI-VI (10 μmol/L)处理后的4T1细胞成像; (j) 三组成像实验结果对比图

Figure 6. (a~c) 4T1 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Nys (20 μmol/L); (d~f) 4T1 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Mon (20 μmol/L); (g~i) 4T1 cell imaging after treatment with probe QUI-VI (10 μmol/L); (j) fluorescence intensity comparison chart of three groups of cell imaging

图7. (a~c) QUI-VI (10 μmol/L)以及制霉菌素(20 μmol/L)处理后的HL-7702细胞成像; (d~f) QUI-VI (10 μmol/L)以及莫能菌素(20 μmol/L)处理后的HL-7702细胞成像; (g~i) QUI-VI (10 μmol/L)处理后的HL-7702细胞成像; (j) 三组成像实验结果对比图

Figure 7. (a~c) HL-7702 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Nys (20 μmol/L); (d~f) HL-7702 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Mon (20 μmol/L); (g~i) HL-7702 cell imaging after treatment with probe QUI-VI (10 μmol/L); (j) fluorescence intensity comparison chart of three groups of cell imaging

图8. (a~c) QUI-VI (10 μmol/L)以及制霉菌素(20 μmol/L)处理后的HepG-2细胞成像; (d~f) QUI-VI (10 μmol/L)以及莫能菌素(20 μmol/L)处理后的HepG-2细胞成像; (g~i) QUI-VI (10 μmol/L)处理后的HepG-2细胞成像; (j) 三组成像实验结果对比图

Figure 8. (a~c) HepG-2 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Nys (20 μmol/L); (d~f) HepG-2 cell imaging after treatment with probe QUI-VI (10 μmol/L) and Mon (20 μmol/L); (g~i) HepG-2 cell imaging after treatment with probe QUI-VI (10 μmol/L); (j) fluorescence intensity comparison chart of three groups of cell imaging

图9. QUI-VI在(A) 正常肺组织和(B) 肺炎组织的成像; (C) QUI-VI在不同肺组织成像的荧光强度对比图

Figure 9. Different fluorescence intensities of probe QUI-VI in (A) normal lung and (B) pneumonia; (C) comparative diagram of the fluorescence intensity of probe QUI-VI in different lungs

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喹啉基粘度荧光探针的合成及其检测应用

Viscosity Fluorescent Probes Based on Quinoline Group and Its Applications

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