Development of a Novel Fluorescent Probe Based on Coumarin Fluorophore for Polarity Detection and Its Imaging Applications

doi:10.6023/A22060261

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (9): 1217-1222.DOI: 10.6023/A22060261 Previous Articles Next Articles

Article

基于香豆素荧光团的新型极性检测荧光探针的开发及其成像应用

宋思睿^a, 唐永和^a, 孙良广^b, 郭锐^a, 姜冠帆^a, 林伟英^a^,^*()

a 广西电化学能源材料重点实验室广西大学光功能材料与化学生物学研究院广西大学化学化工学院南宁 530004
b 广西农业职业技术大学南宁 530007

投稿日期:2022-06-13 发布日期:2022-08-24
通讯作者: 林伟英
基金资助:
国家自然科学基金(21672083); 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(22104019); 广西省自然科学基金(2021GXNSFDA075003); 广西省自然科学基金(AD21220061); 广西省自然科学基金(2019GXNSFBA245068); 广西大学启动基金(A3040051003)

Development of a Novel Fluorescent Probe Based on Coumarin Fluorophore for Polarity Detection and Its Imaging Applications

Sirui Song^a, Yonghe Tang^a, Liangguang Sun^b, Rui Guo^a, Guanfan Jiang^a, Weiying Lin^a()

a Guangxi Key Laboratory of Electrochemical Energy Materials, Institute of Optical Materials and Chemical Biology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
b Guangxi Agricultural Vocational University, Nanning 530007, China

Received:2022-06-13 Published:2022-08-24
Contact: Weiying Lin
Supported by:
National Natural Science Foundation of China(21672083); National Natural Science Foundation of China(21877048); National Natural Science Foundation of China(22077048); National Natural Science Foundation of China(22104019); Natural Science Foundation of Guangxi Province(2021GXNSFDA075003); Natural Science Foundation of Guangxi Province(AD21220061); Natural Science Foundation of Guangxi Province(2019GXNSFBA245068); Startup Fund of Guangxi University(A3040051003)

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Abstract

Polarity is one of the important factors in cell microenvironment. Polarity, to a large extent, is involved in various physiological activities and has an important influence on many life activities of organisms. Studies show that many metabolic diseases in the body can cause polarity changes, such as diabetes, fatty liver, atherosclerosis, and so on. Therefore, it is important to detect polarity changes in living organisms. In this paper, a novel polar fluorescent probe COM-PO with large Stokes-shift was designed and synthesized by altering the push and pull electron groups on coumarin to alter the intramolecular charge transfer (ICT). The fluorescence intensity and wavelength of the probe changed with the polarity of the test system. In polar solvents, the excited state energy of COM-PO dissipates in the solvent through dipole-dipole interaction, and its fluorescence emission intensity decreases. On the contrary, the fluorescence emission intensity of the probe increases significantly in low polar solvents. Since the probe has a large Stokes shift, it can avoid the relatively high signal-to-noise ratio and the serious fluorescence self-extinguishing in the imaging process. Therefore, we applied the probe to cell diagnosis and in vivo disease diagnosis. It is well known that cancer cells are less polar than normal cells, and when the probe enters cancer cells, their fluorescence intensity increases by two to three times compared to normal cells. The fluorescence intensity of the probe COM-PO was also twice as high as that of the normal mice. The COM-PO probe was tested by solution spectroscopy, cell imaging, tissue imaging and mouse in vivo imaging. The experimental results show that the probe COM-PO has the advantages of high polarity sensitivity, high selectivity, strong pH adaptability and good biocompatibility, and can detect the polarity changes of abnormal states of cells, tissues and even livers, which is expected to realize the early diagnosis of polarity related diseases.

Key words: polarity, coumarin, fluorescent probe, fluorescence imaging

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Sirui Song, Yonghe Tang, Liangguang Sun, Rui Guo, Guanfan Jiang, Weiying Lin. Development of a Novel Fluorescent Probe Based on Coumarin Fluorophore for Polarity Detection and Its Imaging Applications[J]. Acta Chimica Sinica, 2022, 80(9): 1217-1222.

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Fig. & Tab. 9

Scheme 1. The mechanism of COM-PO

Scheme 2. Synthetic route of COM-PO Reagents and conditions: (i) Compound 1, compound 2, ethanol, 85 ℃, 4 h. (ii) Compound 3, compound 4, ethanol, 85 ℃, 8 h

Figure 1. (A) UV absorption spectra of COM-PO (10 μmol•L-1) in different polarity solvents. (B) Fluorescence emission spectra of COM-PO (10 μmol•L-1) in different polarity solvents

Solvent	ε/(mol•L^-1•cm^-1)	λ_b/λ_a (nm)	Δλ_s(斯托克斯位移)/nm
1,4-Dioxane	5.45×10³	460/564	96
THF	2.36×10³	465/590	125
MeOH	5.78×10⁴	475/620	145
DMSO	8.25×10⁴	480/625	145
Acetonitrile PBS	7.77×10³ 6.73×10³	468/580 479/627	112 148

Table 1. The spectroscopic characteristics of the probe COM-PO in different solvents

Figure 2. Fluorescence emission spectra of COM-PO (10 μmol•L-1) in dioxane-water mixed solvent system (percentage represents volume fraction of dioxane content in mixed solvent)

Figure 3. Fluorescence emission histograms of COM-PO (10 μmol•L-1) in different inorganic ions and amino acids The numbers represent: 1. CaCl2; 2. NaClO; 3. CuSO4; 4. L-Cys; 5. NaF; 6. GSH; 7. H2O2; 8. DL-Hcy; 9. KI; 10. MgCl2; 11. MnCl2; 12. Na2S; 13. Na2SO4; 14. ZnCl2; 15. L-Met; 16. TBHP; 17. L-Arg; 18. L-Lys; 19. L-Val; 20. Na2SO3 (p<0.05)

Figure 4. (a~c) Imaging plots of 3T3 cells treated with probe COM-PO (10 μmol•L-1); (d~f) imaging plots of 4T1 cells treated with probe COM-PO (10 μmol•L-1); (g~i) imaging plots of HL-7702 cells treated with probe COM-PO (10 μmol•L-1); (j~l) imaging plots of Hela cells treated with probe COM-PO (10 μmol•L-1); (m) comparison of the fluorescence intensity of the four groups of cells imaged (*p<0.05)

Figure 5. Different fluorescence intensities of probe COM-PO when using in (a) normal liver and (b) fatty liver; (c) comparative diagram of the fluorescence intensity of probe COM-PO in different livers

Figure 6. Fluorescence imaging of living mice. (A) The image of hepatitis mouse injected with COM-PO; (B) the normal mouse model injected with COM-PO; (C) the relative fluorescence intensities of mouse model (λex=480 nm, λem=570 nm)

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基于香豆素荧光团的新型极性检测荧光探针的开发及其成像应用

Development of a Novel Fluorescent Probe Based on Coumarin Fluorophore for Polarity Detection and Its Imaging Applications

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