A fluorescent probe with AIE activity, preparation method thereof and use thereof

Abstract

The present invention discloses a fluorescent probe with AIE activity, a preparation method thereof, and a use thereof. The fluorescent probe with AIE activity has the following structure: #imgabs0# The fluorescent probe with AIE activity of the present invention has a simple preparation process, a yield of up to 98%, and is easy to prepare and promote on a large scale; the luminescence quantum efficiency of this type of compound can reach 96%, and it can quickly stain the cell membrane of Hela cervical cancer cells with high brightness; it can stain Zn 2+ Fluorescence detection is performed, and the luminescence will be red-shifted, with a detection limit of 10 ‑ 9 M plays an important role in the fields of fluorescent imaging materials and fluorescent probes.

Description

Technical Field

[0001] The present invention relates to a fluorescent probe with AIE activity, a preparation method and application thereof, and belongs to the technical field of new materials. Background Art

[0002] Five- and six-membered metallocyclic platinum complexes have attracted significant attention due to their unique phosphorescent properties. By forming a five- and six-membered metallocyclic ring, the coordination configuration of the platinum complex approaches a planar tetragonal structure, maximizing the strength of the ligand field and minimizing non-radiative metal center transitions. However, the introduction of a six-membered metallocyclic ring increases the flexibility of the molecular framework, which can adversely affect the luminescence efficiency of the compound. Consequently, the preferred planar tetragonal structure of the five- and six-membered metallocyclic platinum complex is insufficient to induce a large d orbital splitting, resulting in thermally accessible non-radiative dd transitions. This results in weak luminescence, low luminescence efficiency, and poor selectivity for metal ions in the five- and six-membered metallocyclic platinum chloride complexes. Summary of the Invention

[0003] The present invention provides a fluorescent probe with AIE activity, a preparation method thereof, and uses thereof, which significantly improve the luminescence efficiency and selectivity for metal ions and can be used for fluorescence imaging, detection of zinc ions, etc.

[0004] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0005] A fluorescent probe with AIE activity has the following structure:

[0006]

[0007] The above-mentioned fluorescent probes with AIE activity solve the problems of low luminescence efficiency of platinum complexes and poor selectivity for metal ions, and will play an important role in the fields of fluorescence imaging and metal ion detection.

[0008] The inventors discovered that the high-field alkynyl ligands of the present invention can lead to a larger energy difference between the lowest excited state and the d–d state, effectively suppressing non-radiative dd transitions. Replacing the chloride ion at the fourth coordination site of a cyclometallated platinum complex with a polypyridine alkynyl auxiliary ligand not only enhances luminescence, but also allows the active N site of the polypyridine to connect with other metal ions, enabling selective recognition of certain specific metal ions.

[0009] In order to improve the luminescence efficiency and selectivity for metal ions, the fluorescent probe with AIE activity of the present invention preferably has the following structure: Most preferably:

[0010]

[0011] A method for preparing a fluorescent probe with AIE activity is disclosed. The probe is generated by coordinating a pinene-modified cyclometallated primary ligand and a polypyridine alkyne auxiliary ligand with a platinum metal ion. To improve luminous efficiency and selectivity for metal ions, the polypyridine alkyne auxiliary ligand is at least one of 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine, 4'-ethynyl-2,2':6',2"-terpyridine, or 5-ethynyl-2,2'-bipyridine.

[0012] The structure of the above-mentioned pinene-modified cyclometallated primary ligand is

[0013] This application includes the following preferred embodiments:

[0014] Complex (-)-Pt1: The cyclometallated primary ligand is selected from The auxiliary ligand is selected from 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine.

[0015] Complex (-)-Pt2: The cyclometallated primary ligand is selected from The auxiliary ligand is selected from 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine.

[0016] Complex (-)-Pt3: The cyclometallated primary ligand is selected from The auxiliary ligand is selected from 4'-ethynyl-2,2':6',2"-terpyridine.

[0017] Complex (-)-Pt4: The cyclometallated primary ligand is selected from The auxiliary ligand is selected from 4'-ethynyl-2,2':6',2"-terpyridine.

[0018] Complex (-)-Pt5: The cyclometallated primary ligand is selected from The auxiliary ligand is selected from 5-ethynyl-2,2'-bipyridine.

[0019] Complex (-)-Pt6: The cyclometallated primary ligand is selected from The auxiliary ligand is selected from 5-ethynyl-2,2'-bipyridine.

[0020] In order to improve the product yield, as one preferred embodiment, the preparation method of the fluorescent probe having AIE activity comprises the following steps:

[0021] 1) dissolving the polypyridine alkyne auxiliary ligand in dichloromethane to obtain an auxiliary ligand liquid;

[0022] 2) dissolving sodium hydroxide in methanol to obtain a sodium hydroxide methanol solution;

[0023] 3) The pinene-modified cyclometallated platinum chloride complex precursor is dissolved in dichloromethane to obtain a complex precursor liquid;

[0024] 4) Under argon protection, the auxiliary ligand solution and the sodium hydroxide methanol solution were stirred and mixed, and after reacting at room temperature for 0.5 to 5 hours, the complex precursor solution was added dropwise. After the addition was complete, stirring was continued at room temperature for 1 to 24 hours. The solvent was evaporated, and the solid was washed with methanol and vacuum dried to obtain a fluorescent probe with AIE activity: a five-membered six-membered ring metal platinum polypyridine alkyne complex.

[0025] The above-mentioned slow dropping speed is preferably 1 mL / min.

[0026] The molar amount of the polypyridine alkyne auxiliary ligand is 1 to 5 times the molar amount of the pinene-modified cyclometallated platinum chloride complex precursor; the molar amount of sodium hydroxide is 2 to 8 times the molar amount of the pinene-modified cyclometallated platinum chloride complex precursor.

[0027] In the above step 1), the concentration of the auxiliary ligand solution is 0.0075 to 0.075 mol / L; in step 2), the concentration of the sodium hydroxide methanol solution is 0.015 to 0.12 mol / L (the molar content of sodium hydroxide in 1 L of methanol); in step 3), the concentration of the complex precursor solution is 0.0075 to 0.015 mol / L.

[0028] The fluorescent probe having AIE activity can be used as a fluorescent probe, or as a fluorescent imaging material, or as a dyeing material.

[0029] The above-mentioned AIE-active fluorescent probes can detect Zn 2+ Significant light change for Zn 2+ Quantitative detection of Zn 2+ There is a good linear relationship between the concentration and the fluorescence intensity. The detection limit is 10 -9 M.

[0030] The fluorescent probe with AIE activity is used for rapid staining of Hela cervical cancer cells distributed on the cell membrane. The luminescence quantum efficiency of the fluorescent probe with AIE activity reaches 96%.

[0031] The technologies not mentioned in this invention are all referred to the prior art.

[0032] Beneficial effects of the present invention:

[0033] 1. The fluorescent probe with AIE activity of the present invention has a luminescence quantum efficiency of up to 96%, and can quickly stain the cell membrane of Hela cervical cancer cells with high brightness.

[0034] 2. The fluorescent probe with AIE activity of the present invention can detect Zn in water. 2+Fluorescence detection is performed, and the luminescence will be red-shifted, and the detection limit can reach 10 -9 M.

[0035] 3. The fluorescent probe with AIE activity of the present invention has a simple preparation process, a yield of up to 98%, and is easy to prepare and promote on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 The five-membered and six-membered ring metal platinum complex coordinated by 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine prepared in Example 1 1 H NMR spectrum;

[0037] Figure 2 The five-membered and six-membered ring metal platinum complex coordinated by 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine prepared in Example 1 13 C NMR spectrum;

[0038] Figure 3 The five-membered six-membered ring metal platinum complex coordinated by 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine prepared in Example 2 1 H NMR spectrum;

[0039] Figure 4 The five-membered six-membered ring metal platinum complex coordinated by 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine prepared in Example 2 13 C NMR spectrum;

[0040] Figure 5 The five-membered and six-membered ring metal platinum complex coordinated by 4'-ethynyl-2,2':6',2"-terpyridine prepared in Example 3 1 H NMR spectrum;

[0041] Figure 6 The five-membered and six-membered ring metal platinum complex coordinated by 4'-ethynyl-2,2':6',2"-terpyridine prepared in Example 3 13 C NMR spectrum;

[0042] Figure 7 The five-membered and six-membered ring metal platinum complex coordinated by 4'-ethynyl-2,2':6',2"-terpyridine prepared in Example 4 1 H NMR spectrum;

[0043] Figure 8 The five-membered and six-membered ring metal platinum complex coordinated by 4'-ethynyl-2,2':6',2"-terpyridine prepared in Example 4 13 C NMR spectrum;

[0044] Figure 9 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 1 H NMR spectrum;

[0045] Figure 10 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 13 C NMR spectrum;

[0046] Figure 11 The crystal structure of the five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5;

[0047] Figure 12 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 6 1 H NMR spectrum;

[0048] Figure 13 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 6 13 C NMR spectrum;

[0049] Figure 14 The AIE performance of the five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 in a DMSO / H2O mixed solvent;

[0050] Figure 15 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 is used for Zn 2+ recognition performance;

[0051] Figure 16 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 is used for Zn 2+ Detection limit test;

[0052] Figure 17 This is a confocal image of HeLa cells stained with the 5-ethynyl-2,2'-bipyridine coordinated five- and six-membered ring metal platinum complex prepared in Example 5. DETAILED DESCRIPTION

[0053] In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

[0054] In each case, the preparation of the pinene-modified cyclometallated platinum chloride complex precursors (-)-(N^C*N)PtCl and (-)-(N^N*C)PtCl was based on Zhang H.-H., Wu, S.-X., and Wang, Y.-Q. et al., Mechanochromicluminescent property and anti-counterfeiting application of AIE-active cyclometalated platinum(II) complexes featuring a fused five-six-membered metallacycle[J]. Dyes and Pigments, 2022, 197: 109857.

[0055] The room temperature in each case was 15-25° C.; the stirring speed was 200 r / min unless otherwise specified.

[0056] Example 1 Synthesis of complex Pt1

[0057] Five-membered and six-membered ring metal platinum complexes coordinated by 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine (-)-(N ^ C * N) Synthesis of PtC≡CR:

[0058] 25 mg (0.075 mmol) of 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine was dissolved in 10 mL of dichloromethane to obtain solution 1 (concentration: 0.0075 mol / L); 6 mg (0.15 mmol) of sodium hydroxide was dissolved in 10 mL of methanol to obtain solution 2 (concentration: 0.015 mol / L); 49 mg (0.075 mmol) of pinene-modified cyclometallated platinum chloride precursor (-)-(N ^ C * N) PtCl was dissolved in 10 mL of dichloromethane to obtain solution 3 (concentration: 0.0075 mol / L); under argon protection, solution 1 and solution 2 were stirred and mixed, reacted at room temperature for 0.5 h, and then solution 3 was slowly added dropwise (drop rate: 1 mL / min). After the addition was complete, stirring was continued at room temperature for 1 h. The solvent was spin-dried and the solid was washed with methanol three times (20 mL×3, i.e., 20 mL of methanol was used for each wash) and vacuum dried to obtain the target product 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine-coordinated five-membered and six-membered ring metal platinum complex as a yellow solid (yield: 70%), recorded as Pt1, and the corresponding 1 H NMR spectra and 13 C NMR spectrum see Figure 1-2 , we can see from the figure that we get the target structure

[0059] Example 2 Synthesis of complex Pt2

[0060] Five-membered and six-membered ring metal platinum complexes coordinated by 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine (-)-(N ^ N * C) Synthesis of PtC≡CR:

[0061] 150 mg (0.45 mmol) of 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine was dissolved in 10 mL of dichloromethane to obtain solution 1 (concentration: 0.045 mol / L); 24 mg (0.6 mmol) of sodium hydroxide was dissolved in 10 mL of methanol to obtain solution 2 (concentration: 0.06 mol / L); 98 mg (0.15 mmol) of pinene-modified cyclometallated platinum chloride precursor (-)-(N ^ N * C) PtCl was dissolved in 10 mL of dichloromethane to obtain solution 3 (concentration: 0.015 mol / L); under argon protection, solution 1 and solution 2 were stirred and mixed, reacted at room temperature for 3 h, and then solution 3 was slowly added dropwise (drop rate: 1 mL / min). After the addition was complete, stirring was continued at room temperature for 10 h. The solvent was spin-dried and the solid was washed with methanol three times (20 mL × 3, i.e., 20 mL of methanol was used for each wash) and vacuum dried to obtain the target product, 4'-(4-ethynylphenyl)-2,2':6',2"-terpyridine-coordinated five-membered and six-membered ring platinum complex, as an orange solid (yield: 88%), denoted as Pt2. The corresponding 1 H NMR spectra and 13 C NMR spectrum see Figure 3-4 , we can see from the figure that we get the target structure

[0062] Example 3 Synthesis of complex Pt3

[0063] Five-membered and six-membered ring metal platinum complexes coordinated by 4'-ethynyl-2,2':6',2"-terpyridine (-)-(N ^ C * N) Synthesis of PtC≡CR:

[0064] 190 mg (0.75 mmol) of 4'-ethynyl-2,2':6',2"-terpyridine was dissolved in 10 mL of dichloromethane to obtain solution 1 (concentration: 0.075 mol / L); 48 mg (1.2 mmol) of sodium hydroxide was dissolved in 10 mL of methanol to obtain solution 2 (concentration: 0.12 mol / L); 98 mg (0.15 mmol) of pinene-modified cyclometallated platinum chloride precursor (-)-(N ^ C * N) PtCl was dissolved in 10 mL of dichloromethane to obtain solution 3 (concentration: 0.015 mol / L); under argon protection, solution 1 and solution 2 were stirred and mixed, reacted at room temperature for 5 h, and then solution 3 was slowly added dropwise (drop rate: 1 mL / min). After the addition was complete, stirring was continued at room temperature for 24 h. The solvent was spin-dried and the solid was washed with methanol three times (20 mL×3, i.e., the amount of methanol used for each wash was 20 mL), and vacuum dried to obtain the target product 4'-ethynyl-2,2':6',2"-terpyridine coordinated five-membered and six-membered ring metal platinum complex as a yellow solid (yield: 80%), recorded as Pt3, the corresponding 1 H NMR spectra and 13 C NMR spectrum see Figure 5-6 , we can see from the figure that we get the target structure

[0065] Example 4 Synthesis of Complex Pt4

[0066] Five-membered and six-membered ring metal platinum complexes coordinated by 4'-ethynyl-2,2':6',2"-terpyridine (-)-(N ^ N * C) Synthesis of PtC≡CR:

[0067] 190 mg (0.75 mmol) of 4'-ethynyl-2,2':6',2"-terpyridine was dissolved in 10 mL of dichloromethane to obtain solution 1 (concentration: 0.075 mol / L); 30 mg (0.75 mmol) of sodium hydroxide was dissolved in 10 mL of methanol to obtain solution 2 (concentration: 0.075 mol / L); 98 mg (0.15 mmol) of pinene-modified cyclometallated platinum chloride precursor (-)-(N ^ N *C) PtCl was dissolved in 10 mL of dichloromethane to obtain solution 3 (concentration: 0.015 mol / L); under argon protection, solution 1 and solution 2 were stirred and mixed, reacted at room temperature for 3 h, and then solution 3 was slowly added dropwise (drop rate: 1 mL / min). After the addition was complete, stirring was continued at room temperature for 10 h. The solvent was spin-dried and the solid was washed with methanol three times (20 mL × 3, i.e., 20 mL of methanol was used for each wash) and vacuum dried to obtain the target product, 4'-ethynyl-2,2':6',2"-terpyridine-coordinated five-membered and six-membered ring metal platinum complex, as an orange solid (yield: 85%), denoted as Pt4. The corresponding 1 H NMR spectra and 13 C NMR spectrum see Figure 7-8 , we can see from the figure that we get the target structure

[0068] Example 5 Synthesis of Complex Pt5

[0069] Five-membered and six-membered ring metal platinum complexes coordinated by 5-ethynyl-2,2'-bipyridine (-)-(N ^ C * N) Synthesis of PtC≡CR:

[0070] 108 mg (0.6 mmol) of 5-ethynyl-2,2'-bipyridine was dissolved in 10 mL of dichloromethane to obtain solution 1 (concentration: 0.06 mol / L); 36 mg (0.9 mmol) of sodium hydroxide was dissolved in 10 mL of methanol to obtain solution 2 (concentration: 0.09 mol / L); 98 mg (0.15 mmol) of pinene-modified cyclometallated platinum chloride precursor (-)-(N ^ C * N) PtCl was dissolved in 10 mL of dichloromethane to obtain solution 3 (concentration: 0.015 mol / L); under argon protection, solution 1 and solution 2 were stirred and mixed, reacted at room temperature for 4 h, and then solution 3 was slowly added dropwise (drop rate: 1 mL / min). After the addition was complete, stirring was continued at room temperature for 15 h. The solvent was spin-dried and the solid was washed with methanol three times (20 mL×3, i.e., 20 mL of methanol was used for each wash) and vacuum dried to obtain the target product, a five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine, as a yellow solid (yield: 98%), denoted as Pt5. The corresponding 1 H NMR spectra and 13 C NMR spectrum see Figure 9-10 , we can see from the figure that we get the target structure The crystal structure of Pt5 is as follows Figure 11 shown.

[0071] Example 6 Synthesis of Complex Pt6

[0072] Five-membered and six-membered ring metal platinum complexes coordinated by 5-ethynyl-2,2'-bipyridine (-)-(N ^ N * C) Synthesis of PtC≡CR:

[0073] 81 mg (0.45 mmol) of 5-ethynyl-2,2'-bipyridine was dissolved in 10 mL of dichloromethane to obtain solution 1 (concentration: 0.045 mol / L); 24 mg (0.6 mmol) of sodium hydroxide was dissolved in 10 mL of methanol to obtain solution 2 (concentration: 0.06 mol / L); 98 mg (0.15 mmol) of pinene-modified cyclometallated platinum chloride precursor (-)-(N ^ C * N) PtCl was dissolved in 10 mL of dichloromethane to obtain solution 3 (concentration: 0.015 mol / L); under argon protection, solution 1 and solution 2 were stirred and mixed, reacted at room temperature for 4 h, and then solution 3 was slowly added dropwise (drop rate: 1 mL / min). After the addition was complete, stirring was continued at room temperature for 15 h. The solvent was spin-dried and the solid was washed with methanol three times (20 mL×3, i.e., 20 mL of methanol was used for each wash) and vacuum dried to obtain the target product, a five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine, as an orange solid (yield: 92%), denoted as Pt6, and the corresponding 1 H NMR spectra and 13 C NMR spectrum see Figure 12-13 , we can see from the figure that we get the target structure

[0074] Test of luminescence quantum efficiency: The HORIBA JY instrument was used to test the Pt1-Pt6 in DMSO / H2O (volume fraction of H2O f w The luminescence quantum efficiency of the mixed solution is 50%), and the concentration of Pt1-Pt6 is 10 -4 M, the excitation wavelength is 420nm. The test results are shown in Table 1.

[0075] Table 1

[0076]

[0077] Table 1 shows the luminescence quantum efficiency of the AIE-active five-membered and six-membered ring metal platinum polypyridine alkyne complexes prepared in each example. It can be found that the platinum complex obtained in Example 5 has the highest luminescence quantum efficiency, reaching 96%.

[0078] AIE performance test: The HORIBA JY instrument was used to test the AIE performance of Pt5 in DMSO / H2O (volume fraction of H2O wThe luminescence quantum efficiency of the mixed solution is 0%, 30%, 50%, 70%, 75%, 80%, and 90% respectively. The concentration of Pt5 is 10 -4 M, the excitation wavelength is 420 nm.

[0079] Figure 14 The AIE performance of the five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 in a DMSO / H2O mixed solvent is shown in FIG. w The maximum luminescence quantum efficiency in the 50% solution reached 96%, which is nearly 20 times that in the pure DMSO solution.

[0080] Zn 2+ Detection performance: In the DMSO / H2O (H2O volume fraction f of Pt5 w 20%), 0.1 times the equivalent of ZnCl2 was added, and the emission curve was tested. The concentration of Pt5 was 10 -4 M, the excitation wavelength is 420nm. When other metal ions exist in the solution, the luminescence intensity does not change. 2+ No interference with detection.

[0081] Prepare a series of different concentrations of Zn 2+ Solution, in DMSO / H2O (volume fraction of H2O f w Add a certain amount of ZnCl2 into the solution (20%), test the emission intensity, the excitation wavelength is 420nm, and examine the effect of Pt5 on Zn 2+ The quantitative detection performance was evaluated and the detection limit was calculated.

[0082] Figure 15 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 is used for Zn 2+ The detection performance of Zn 2+ Make a significant light change. Figure 16 The five-membered and six-membered ring metal platinum complex coordinated by 5-ethynyl-2,2'-bipyridine prepared in Example 5 is used for Zn 2+ Quantitative detection was performed with a detection limit of 1.13×10 -9 M, linear correlation coefficient R 2 =0.99728.

[0083] Zn 2+ Detection limit test: prepare a series of different concentrations of Zn 2+ Solution, in the DMSO / H2O (volume fraction of H2O f wA certain amount of ZnCl2 was added to the solution (20%), and the emission intensity was tested. The concentration of Pt1-Pt6 was 10 -4 M, the excitation wavelength is 420 nm, and the detection limit is calculated.

[0084] Table 2

[0085]

[0086] Table 2 shows the AIE activity of the five-membered and six-membered ring metal platinum polypyridine alkyne complexes prepared in each case for Zn 2+ The detection limit of the identified platinum complex obtained in Example 5 can be found to be 2+ The detection limit is the lowest, which can complete the detection of trace Zn 2+ The detection of heavy metal ions will play an important role in the field of heavy metal ion detection.

[0087] Staining Performance: Cultured HeLa cells were seeded in glass-bottomed cell culture dishes. After overnight culture, the cells were stained with 10 μmol / L of the 5-ethynyl-2,2'-bipyridine-coordinated five- and six-membered ring platinum complex prepared in Example 5 in a DMSO / DMEM mixture (volume ratio 5:95) for 15 minutes. After washing with PBS buffer to remove the extracellular fluorescent dye, the cells were imaged using a confocal laser scanning fluorescence microscope in the blue, green, and red channels. HeLa cells were obtained from the Cell Resource Center of the Institute of Basic Medicine, Chinese Academy of Medical Sciences; DMEM medium was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.

[0088] Figure 17 This is a confocal image of HeLa cells stained with the 5-ethynyl-2,2'-bipyridine coordinated five-membered and six-membered ring metal platinum complex prepared in Example 5. HeLa cells can be stained quickly, and the luminescent five-membered and six-membered ring platinum complex is mainly distributed on the cell membrane.

Claims

1. A fluorescent probe with AIE activity, characterized in that: Its structure is as follows: 。 2. The fluorescent probe with AIE activity according to claim 1, wherein: Its structure is as follows: 、 and .

3. The fluorescent probe having AIE activity according to claim 2, wherein: Its structure is as follows: 。 4. A method for preparing a fluorescent probe having AIE activity according to any one of claims 1 to 3, characterized in that: The ligand is formed by coordinating a pinene-modified cyclometallated primary ligand and a polypyridine alkyne auxiliary ligand with a platinum metal ion; wherein the polypyridine alkyne auxiliary ligand is at least one of 4'-(4-ethynylphenyl)-2,2':6',2''-terpyridine, 4'-ethynyl-2,2':6',2''-terpyridine, or 5-ethynyl-2,2'-bipyridine; The structure of the pinene-modified cyclometallated primary ligand is or .

5. The method for preparing a fluorescent probe having AIE activity according to claim 4, wherein: The steps include: 1) Dissolve the polypyridine alkyne auxiliary ligand in dichloromethane to obtain an auxiliary ligand liquid; 2) Dissolve sodium hydroxide in methanol to obtain sodium hydroxide methanol solution; 3) The pinene-modified cyclometallated platinum chloride complex precursor is dissolved in dichloromethane to obtain a complex precursor liquid; 4) Under argon protection, the auxiliary ligand solution and the sodium hydroxide methanol solution were stirred and mixed. After reacting at room temperature for 0.5-5 hours, the complex precursor solution was added dropwise. After the addition was complete, stirring was continued at room temperature for 1-24 hours. The solvent was dried, and the solid was washed with methanol and vacuum dried to obtain a fluorescent probe with AIE activity.

6. The method for preparing a fluorescent probe having AIE activity according to claim 5, wherein: The molar amount of the polypyridine alkyne auxiliary ligand is 1 to 5 times the molar amount of the pinene-modified cyclometallated platinum chloride complex precursor; the molar amount of sodium hydroxide is 2 to 8 times the molar amount of the pinene-modified cyclometallated platinum chloride complex precursor; in step 1), the concentration of the auxiliary ligand solution is 0.0075 to 0.075 mol / L; in step 2), the concentration of the sodium hydroxide methanol solution is 0.015 to 0.12 mol / L; in step 3), the concentration of the complex precursor solution is 0.0075 to 0.015 mol / L.

7. Use of the fluorescent probe with AIE activity according to any one of claims 1 to 3, characterized in that: Used as Zn 2+ The fluorescent probe for detection can be used to prepare fluorescent imaging materials or dyeing materials for rapid dyeing of Hela cervical cancer cells distributed on the cell membrane.

8. The use of the fluorescent probe with AIE activity according to claim 7, characterized in that: For Zn 2+ Quantitative detection of .

9. The use of the fluorescent probe with AIE activity according to claim 8, characterized in that Zn 2+ The detection limit reached 10 -9 M.

10. The use of the fluorescent probe with AIE activity according to claim 7, characterized in that: The luminescence quantum efficiency of the fluorescent probe with AIE activity reached 96%.

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