A heteroaromatic hyperbranched conjugated polymer, a preparation method thereof and an application thereof

Abstract

The present invention discloses a heteroaromatic hyperbranched conjugated polymer, its preparation method and application. The structural unit of the polymer is shown as follows. It is synthesized by A3-coupling reaction. The solvents and catalysts used are environmentally friendly, the reaction conditions are mild, and the reaction steps and post-treatment are simple. Hg<supgt;2+< / supgt; ions and 2'-aminoacetophenone have obvious quenching effects on the fluorescence of the polymer solution, and 17β-estradiol has obvious enhancement effects on the fluorescence of the polymer solution. It can be used for the detection of Hg<supgt;2+< / supgt> ions, 17β-estradiol and 2'-aminoacetophenone. It not only has simple operation and short response time, but also has high selectivity and low detection limit for Hg<supgt;2+< / supgt> ions, 17β-estradiol and 2'-aminoacetophenone, and is expected to be used as a chemical detector.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer, and particularly relates to a novel hyperbranched conjugated polymer with an imidazole-thiazole structure, and a preparation method and application of the polymer. Background Art

[0002] Heterocyclic-fused hyperbranched conjugated polymers have the advantages of hyperbranched polymers and heterocyclic-fused conjugated polymers, namely low viscosity, good solubility, high thermal stability, and good biological activity, including the electron transport performance and strong fluorescence emission due to the presence of the conjugated structure, and can be widely applied in various fields such as optoelectronics, catalysis, biomedicine, fluorescent probes, and sensors. Therefore, the exploration of the synthesis and properties of heterocyclic-fused hyperbranched conjugated polymers has great development prospects and is expected to become a research hotspot that attracts much attention. The traditional method for synthesizing heterocyclic-fused conjugated polymers by transition metal-catalyzed coupling reaction has a narrow substrate scope and difficult preparation of reaction monomers. In addition, the noble metal catalysts required in the experiment are not only highly toxic and environmentally unfriendly, but also expensive and costly. Considering these factors, the method of using monomers containing heteroatoms such as nitrogen, oxygen, and sulfur but without heterocyclic-fused structures to in-situ generate structurally novel heterocyclic-fused structural units through cyclization polycondensation reaction will be more advantageous.

[0003] In recent years, due to the important role of transition metal ions in living organisms and their impact on the environment, the detection technology of them has become the focus of people's attention. Hg 2+ The harm to the human body is mainly concentrated in the central nervous system, digestive system, and internal organs, and also has certain effects on the respiratory system, blood, and skin. Hg 2+ has persistence, easy mobility, and high bioaccumulation, which makes it one of the most concerned environmental pollutants at present. The main direct impact on humans is mercury pollution in water, mainly in the form of Hg 2+ form. Therefore, the rapid and sensitive detection of Hg 2+ is crucial for human survival and environmental protection.

[0004] In addition, water and air pollution caused by various harmful substances in nature have become a major environmental protection issue. For example, 17β-estradiol (E2) can promote animal growth and increase milk production in dairy cows. However, excessive intake of E2 can interfere with the body's endocrine system, leading to abnormalities in the reproductive and immune systems and even causing cancer in reproductive organs. 2'-Aminoacetophenone (2AP) is a volatile and unstable substance, which has been recognized as an important trace substance with aromatic activity that often appears in many foods abroad. When the concentration of 2AP in food exceeds a certain sensory threshold, it will cause an unpleasant odor of "atypical aging", abbreviated as the "UTA" phenomenon. This UTA phenomenon will seriously affect the taste and flavor of food. Therefore, monitoring E2 and 2'-aminoacetophenone in food is of great significance for ensuring food safety.

[0005] At present, many methods for detecting Hg 2+ , 17β-estradiol, and 2'-aminoacetophenone have been developed, such as atomic absorption spectrophotometry, inductively coupled plasma mass spectrometry, and high performance liquid chromatography. Although these detection methods have good selectivity, they require complex sample pretreatment, and the instrument operation is difficult, so their applications are limited to a certain extent. Summary of the Invention

[0006] The object of the present invention is to provide a heteroaromatic hyperbranched conjugated polymer for detecting Hg 2+ , 17β-estradiol, and 2'-aminoacetophenone, which has simple operation, short response time, and high stability and selectivity, as well as a preparation method and application of the polymer.

[0007] For the above object, the structural unit of the heteroaromatic hyperbranched conjugated polymer adopted by the present invention is shown in the following formula:

[0008]

[0009] In the formula, R represents any one of OH, Cl, Br, COOH, CN, NH 2 , NO 2 , COOCH 2 CH 3 , and n is an integer from 0 to 7; or R represents a benzene ring and n = 0.

[0010] 2,2'-Diamino-6,6'-bithiazolo[2,3-b][1,4]thiazole shown as M1, [1,1':3',1"-terphenyl]-4,4",5'-tricarbaldehyde shown as M2, an alkyne monomer shown as M3, a copper salt, and a base are added to dimethyl sulfoxide, and a polymerization reaction is carried out under the protection of an inert gas and stirring conditions at 70-90 °C. After the reaction is completed, extraction, drying, and dialysis are carried out to obtain the heteroaromatic hyperbranched conjugated polymer;

[0011]

[0012] In the above preparation method, the copper salt is any one of cuprous chloride, cuprous iodide, and cuprous bromide; the base is any one of anhydrous potassium carbonate and anhydrous sodium carbonate.

[0013] In the above preparation method, the molar ratio of 2,2'-diamino-6,6'-bi(benzothiazole) to [1,1':3',1''-terphenyl]-4,4",5'-tricarbaldehyde and the alkyne monomer is preferably 1.0 - 2.0:1:2.0 - 5.0, and the molar ratio of 2,2'-diamino-6,6'-bi(benzothiazole) to the copper salt and the base is 1:0.02 - 0.5:2.0 - 5.0.

[0014] It was found through testing that Hg 2+ has an obvious quenching effect on the fluorescence of the tetrahydrofuran solution of the heteroaromatic hyperbranched conjugated polymer of the present invention, 17β-estradiol has an obvious enhancing effect on the fluorescence of the polymer's tetrahydrofuran solution, and 2'-aminoacetophenone has an obvious quenching effect on the fluorescence of the polymer's tetrahydrofuran solution. Therefore, the heteroaromatic hyperbranched conjugated polymer of the present invention can be used to detect Hg 2+ or 17β-estradiol or 2'-aminoacetophenone. The specific detection method is as follows: Dissolve the heteroaromatic hyperbranched conjugated polymer in tetrahydrofuran to prepare a polymer solution with a concentration of 1.0×10 -6 mol / L; then add standard samples of the analyte with different concentrations thereto, detect the fluorescence intensity of the system, plot a standard curve of the maximum fluorescence intensity of the system corresponding to different concentrations of the analyte varying with the concentration of the analyte; then test the fluorescence intensity of the system when adding the sample solution of the analyte to be tested, and the content of the analyte can be determined according to the fluorescence intensity combined with the standard curve equation.

[0015] The beneficial effects of the present invention are as follows:

[0016] 1. The present invention synthesizes a novel heteroaromatic hyperbranched conjugated polymer by using the A3-Coupling reaction. Compared with traditional methods, the synthesis method of the present invention is milder, environmentally friendly, and free of metal catalyst residues.

[0017] 2. Hg 2+ ions and 2'-aminoacetophenone have an obvious quenching effect on the fluorescence of the tetrahydrofuran solution of the heteroaromatic hyperbranched conjugated polymer synthesized by the present invention, and 17β-estradiol has an obvious enhancing effect on the fluorescence of the tetrahydrofuran solution of such polymers. It can be used for the detection of Hg 2+ ions, 17β-estradiol, and 2'-aminoacetophenone in the organic phase. It not only has simple operation and short response time, but also has high sensitivity to Hg 2+Ions, 17β-estradiol, and 2'-aminoacetophenone have high selectivity and low detection limits and are promising as chemical detectors. Description of the Drawings

[0018] Figure 1 is the 1 1H-NMR spectrum of polymer P1.

[0019] Figure 2 is the IR spectrum of polymer P1.

[0020] Figure 3 is the 1 1H-NMR spectrum of polymer P2.

[0021] Figure 4 is the IR spectrum of polymer P2.

[0022] Figure 5 is the 1 1H-NMR spectrum of polymer P3.

[0023] Figure 6 is the IR spectrum of polymer P3.

[0024] Figure 7 is the 1 1H-NMR spectrum of polymer P4.

[0025] Figure 8 is the IR spectrum of polymer P4.

[0026] Figure 9 is the 1 1H-NMR spectrum of polymer P5.

[0027] Figure 10 is the IR spectrum of polymer P5.

[0028] Figure 11 is the 1 1H-NMR spectrum of polymer P6.

[0029] Figure 12 is the IR spectrum of polymer P6.

[0030] Figure 13 is the fluorescence spectrum of the fluorescence intensity of polymer P1 as a function of Hg 2+ concentration and the linear relationship diagram of the relative fluorescence intensity as a function of Hg 2+ concentration.

[0031] Figure 14 is the fluorescence spectrum of the fluorescence intensity of polymer P2 as a function of Hg 2+ concentration and the linear relationship diagram of the relative fluorescence intensity as a function of Hg 2+ concentration.

[0032] Figure 15 is the fluorescence spectrum of the fluorescence intensity of polymer P3 varying with the concentration of Hg 2+ and the linear relationship diagram of the relative fluorescence intensity varying with the concentration of Hg 2+ concentration.

[0033] Figure 16 is the comparative diagram of the relative fluorescence intensity of polymer P1 in different cation systems.

[0034] Figure 17 is the comparative diagram of the relative fluorescence intensity of polymer P2 in different cation systems.

[0035] Figure 18 is the comparative diagram of the relative fluorescence intensity of polymer P3 in different cation systems.

[0036] Figure 19 is the fluorescence spectrum of the fluorescence intensity of polymer P4 varying with the concentration of 17β - estradiol and the linear relationship diagram of the relative fluorescence intensity varying with the concentration of 17β - estradiol.

[0037] Figure 20 is the fluorescence spectrum of the fluorescence intensity of polymer P4 varying with the concentration of 2'-aminoacetophenone and the linear relationship diagram of the relative fluorescence intensity varying with the concentration of 2'-aminoacetophenone.

[0038] Figure 21 is the fluorescence spectrum of the fluorescence intensity of polymer P5 varying with the concentration of 17β - estradiol and the linear relationship diagram of the relative fluorescence intensity varying with the concentration of 17β - estradiol.

[0039] Figure 22 is the fluorescence spectrum of the fluorescence intensity of polymer P5 varying with the concentration of 2'-aminoacetophenone and the linear relationship diagram of the relative fluorescence intensity varying with the concentration of 2'-aminoacetophenone.

[0040] Figure 23 is the fluorescence spectrum of the fluorescence intensity of polymer P6 varying with the concentration of 17β - estradiol and the linear relationship diagram of the relative fluorescence intensity varying with the concentration of 17β - estradiol.

[0041] Figure 24 is the fluorescence spectrum of the fluorescence intensity of polymer P6 varying with the concentration of 2'-aminoacetophenone and the linear relationship diagram of the relative fluorescence intensity varying with the concentration of 2'-aminoacetophenone. Detailed implementation manners

[0042] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments, but the protection scope of the present invention is not limited to these embodiments.

[0043] Example 1

[0044]

[0045] Add 0.0902 g (0.302 mmol) of 2,2'-diamino-6,6'-bi(benzothiazole), 0.05 g (0.159 mmol) of [1,1':3',1''-terphenyl]-4,4",5'-tricarbaldehyde, and 0.0537 g (0.795 mmol) of 3-butyn-1-ol into a 50 mL three-necked flask, add 15 mL of anhydrous dimethyl sulfoxide to dissolve, and then add 0.0146 g (0.077 mmol) of CuI and 0.0318 g (0.230 mmol) of K 2 CO 3 , stir and heat to 80 °C under an argon atmosphere, and react at a constant temperature for 72 h. After the reaction is completed, first cool to room temperature, then add 100 mL of dichloromethane to the reaction solution, and then wash it 3 times with 50 mL of saturated brine and 50 mL of saturated ammonium chloride aqueous solution respectively. Distill under reduced pressure to obtain a crude product, and then dissolve the crude product in a mixed solution of tetrahydrofuran and water with a volume ratio of 4:1, perform dialysis treatment for 2 days, and rotary evaporate to obtain polymer P1 with a yield of 72%. The structural characterization results are as follows:

[0046] 1 H-NMR (600 MHz, DMSO-d6) δ 10.11 (1H, -CHO), 8.33 - 7.52 (8H, =CH), 4.00 (2H, -CH 2 ), 2.62 - 1.24 (3H, -CH 3 )(see Figure 1 ); FT-IR (KBr): CH=: 2928; C=C: 3020, 1605; C=N: 1702 (see Figure 2 ).

[0047] The polymer P1 was tested by gel permeation chromatography, and Mn = 46345, Mw = 73688, Mw / Mn = 1.59.

[0048] Example 2

[0049]

[0050] Add 0.0902 g (0.302 mmol) of 2,2'-diamino-6,6'-bi(benzothiazole), 0.05 g (0.159 mmol) of [1,1':3',1''-terphenyl]-4,4",5'-tricarbaldehyde, and 0.1058 g (0.795 mmol) of 4-bromobut-1-yne into a 50 mL three-necked flask, add 15 mL of anhydrous dimethyl sulfoxide to dissolve, and then add 0.0146 g (0.077 mmol) of CuI and 0.0318 g (0.230 mmol) of K2 CO 3 , Stir and heat to 80 °C in an argon atmosphere, and react at a constant temperature for 72 h. After the reaction is completed, first cool to room temperature, then add 100 mL of dichloromethane to the reaction solution, and then wash it 3 times with 50 mL of saturated brine and 50 mL of saturated ammonium chloride aqueous solution respectively. Distill under reduced pressure to obtain a crude product. Then dissolve the crude product in a mixed solution of tetrahydrofuran and water with a volume ratio of 4:1, perform dialysis treatment for 2 days, and rotary evaporate to obtain polymer P2 with a yield of 69%. The structural characterization results are as follows:

[0051] 1 H-NMR (600 MHz, DMSO-d6) δ 10.09 (2H, -CHO), 8.10 - 8.03 (3H, =CH), 3.46 (2H, -CH 2 ), 2.54 - 1.22 (8H, -CH 3 )(see Figure 3 ); FT-IR (KBr): CH=: 2934; C=C: 3020, 1605; C=N: 1698 (see Figure 4 ).

[0052] Tested by gel permeation chromatography, the Mn of polymer P2 is 45016, Mw is 203922, and Mw / Mn is 4.53.

[0053] Example 3

[0054]

[0055] Add 0.0902 g (0.302 mmol) of 2,2'-diamino-6,6'-biphenyl bisthiazole, 0.05 g (0.159 mmol) of [1,1':3',1"-terphenyl]-4,4",5'-tricarbaldehyde, and 0.0780 g (0.795 mmol) of 4-pentynoic acid into a 50 mL three-necked flask, add 15 mL of anhydrous dimethyl sulfoxide to dissolve, and then add 0.0146 g (0.077 mmol) of CuI and 0.0318 g (0.230 mmol) of K 2 CO 3 , Stir and heat to 80 °C in an argon atmosphere, and react at a constant temperature for 72 h. After the reaction is completed, first cool to room temperature, then add 100 mL of dichloromethane to the reaction solution, and then wash it 3 times with 50 mL of saturated brine and 50 mL of saturated ammonium chloride aqueous solution respectively. Distill under reduced pressure to obtain a crude product. Then dissolve the crude product in a mixed solution of tetrahydrofuran and water with a volume ratio of 4:1, perform dialysis treatment for 2 days, and rotary evaporate to obtain polymer P3 with a yield of 69%. The structural characterization results are as follows:

[0056] 1H-NMR (600 MHz, DMSO-d6) δ 10.08 (2H, -CHO), 8.01 - 7.51 (12H, =CH), 3.63 (2H, -CH 2 ), 2.54 - 1.11 (10H, -CH 3 )(see Figure 5 ); FT-IR (KBr): CH=: 2941; C=C: 3018, 1605; C=N: 1704 (see Figure 6 ).

[0057] The polymer P3 was tested by gel permeation chromatography, and the results were Mn = 43012, Mw = 240006, and Mw / Mn = 5.58.

[0058] Example 4

[0059]

[0060] 0.0902 g (0.302 mmol) of 2,2'-diamino-6,6'-bibenzo[b]thiazole, 0.05 g (0.159 mmol) of [1,1':3',1''-terphenyl]-4,4'',5'-tricarbaldehyde, and 0.0670 g (0.795 mmol) of 4-pentyn-1-ol were added to a 50 mL three-necked flask and dissolved in anhydrous dimethyl sulfoxide solvent (concentration: 0.1 mol / L). Then, 0.0146 g (0.077 mmol) of CuI and 0.0318 g (0.230 mmol) of K 2 CO 3 were added to the reaction solution. The mixture was stirred and heated to 80 °C under an argon atmosphere for 72 h. After the reaction, it was first cooled to room temperature, then 100 mL of dichloromethane was added to the reaction solution, and then it was washed three times with 50 mL of saturated brine and 50 mL of saturated ammonium chloride respectively. After vacuum distillation, a crude product was obtained. The crude product was then dissolved in a mixture of tetrahydrofuran and water with a volume ratio of 4:1, dialyzed for 2 days, and the solvent was removed by rotary evaporation to obtain polymer P4. The yield was 72%, and the results of structural characterization were as follows:

[0061] 1 H-NMR (600 MHz, DMSO-d6) δ 10.08 (d, J = 9.7 Hz, 1H), 8.46–7.35 (m, 6H), 3.57 (d, J = 38.0 Hz, 9H), 2.61 (s, 3H), 2.39 (s, 2H), 1.82–1.17 (m, 15H) (see Figure 7 ); FT-IR (KBr): CH=: 2928; C=C: 3020, 1605; C=N: 1702 (see Figure 8 ).

[0062] The Mn of this polymer is 44276, Mw is 111132, and Mw / Mn is 2.51 as tested by gel permeation chromatography.

[0063] Example 5

[0064]

[0065] 0.0902 g (0.302 mmol) of 2,2'-diamino-6,6'-biphenyl bisthiazole, 0.05 g (0.159 mmol) of [1,1':3',1"-terphenyl]-4,4",5'-tricarbaldehyde, and 0.0816 g (0.795 mmol) of 5-chloro-1-pentene were added to a 50 mL three-necked flask and dissolved in anhydrous dimethyl sulfoxide solvent (concentration: 0.1 mol / L). Then, 0.0146 g (0.077 mmol) of CuI and 0.0318 g (0.230 mmol) of K 2 CO 3 were added to the reaction solution. The mixture was stirred and heated to 80 °C under an argon atmosphere for 72 h. After the reaction, it was first cooled to room temperature, then 100 mL of dichloromethane was added to the reaction solution, and then it was washed three times with 50 mL of saturated brine and 50 mL of saturated ammonium chloride respectively. After vacuum distillation, a crude product was obtained. The crude product was then dissolved in a mixed solution of tetrahydrofuran and water with a volume ratio of 4:1, dialyzed for 2 days, and the solvent was removed by rotary evaporation to obtain polymer P5. Its yield was 69%, and the results of structural characterization were as follows:

[0066] 1 1H-NMR (600 MHz, DMSO-d6) δ 10.18–10.05 (m, 1H), 8.59–7.24 (m, 4H), 3.68 (t, J = 6.4 Hz, 1H), 2.61 (s, 1H), 2.42–1.19 (m, 15H) (see Figure 9 ); FT-IR (KBr): CH=: 2934; C=C: 3020, 1605; C=N: 1698 (see Figure 10 ).

[0067] The Mn of this polymer is 43180, Mw is 91973, and Mw / Mn is 2.13 as tested by gel permeation chromatography.

[0068] Example 6

[0069]

[0070] 0.0902 g (0.302 mmol) of 2,2'-diamino-6,6'-bi(benzothiazole), 0.05 g (0.159 mmol) of [1,1':3',1''-terphenyl]-4,4'',5'-tricarbaldehyde, and 0.0892 g (0.795 mmol) of 5-hexynoic acid were added to a 50 mL three-necked flask and dissolved in anhydrous dimethyl sulfoxide solvent (concentration: 0.1 mol / L). Then, 0.0146 g (0.077 mmol) of CuI and 0.0318 g (0.230 mmol) of K 2 CO 3 were added to the reaction solution. The mixture was stirred and heated to 80 °C under an argon atmosphere and reacted for 72 h. After the reaction, it was first cooled to room temperature, then 100 mL of dichloromethane was added to the reaction solution, and then it was washed three times with 50 mL of saturated brine and 50 mL of saturated ammonium chloride respectively. After distillation under reduced pressure, a crude product was obtained. The crude product was then dissolved in a mixed solution of tetrahydrofuran and water with a volume ratio of 4:1, and dialysis treatment was carried out for 2 days. The solvent was removed by rotary evaporation to obtain polymer P6. Its yield was 69%, and the structural characterization results were as follows:

[0071] 1 1H-NMR (600 MHz, DMSO-d6) δ 10.08 (d, J = 10.2 Hz, 1H), 8.37–7.31 (m, 14H), 5.75 (s, 0H), 5.32 (s, 0H), 2.61 (s, 1H), 2.39 (s, 1H), 2.16–1.17 (m, 8H) (see Figure 11 ); FT-IR (KBr): CH=: 2941; C=C: 3018, 1605; C=N: 1704 (see Figure 12 ).

[0072] Tested by gel permeation chromatography, the Mn of this polymer was 45029, Mw was 93660, and Mw / Mn was 2.08.

[0073] Example 7

[0074] Application of the polymer P1 prepared in Example 1 in detecting Hg 2+ , and the specific method is as follows:

[0075] The polymer P1 was dissolved in tetrahydrofuran to prepare a 1.0×10 -6 mol / L tetrahydrofuran solution of polymer P1; 3 mL of the 1.0×10 -6 mol / L tetrahydrofuran solution of polymer P1 was added to a cuvette, and a Hg 2+ standard sample was added thereto, so that the Hg in the resulting mixed solution 2+The concentrations were 0, 3.33, 6.67, 10, 13.3, 16.67, 20 μmol / L, and the fluorescence spectra of different concentrations of Hg were measured using a fluorescence spectrometer. 2+ The fluorescence spectra of the corresponding systems (see Figure 13 a), and the relative fluorescence intensities of different concentrations of Hg at the maximum absorption wavelength were plotted. 2+ The standard curve of the corresponding systems varying with the concentration of Hg 2+ (see Figure 13 b).

[0076] As can be seen from Figure 13 a, the fluorescence intensity of polymer P1 was significantly affected by the concentration of Hg. 2+ With the increase in the concentration of Hg, 2+ the fluorescence intensity of the system gradually decreased. As can be seen from Figure 13 b, when the concentration of Hg 2+ was in the range of 0 - 20 μmol / L, the relative fluorescence intensity increased linearly with the concentration of Hg. 2+ The linear equation was:

[0077] y = 0.06491x + 0.93815

[0078] where y is the relative fluorescence intensity and x is the concentration of Hg. 2+ The correlation coefficient R 2 was 0.98783. It can be seen that the linear relationship between the relative fluorescence intensity and the concentration of Hg 2+ was very good. Using the formula for the lowest detection limit to calculate the lowest detection limit, polymer P1 had a very high detection sensitivity for Hg. 2+ The detection limit was 7.743×10 -7 mol / L.

[0079] Example 8

[0080] Application of the conjugated polymer P2 prepared in Example 2 in the detection of Hg 2+ was the same as that in Example 7. As can be seen from Figure 14 a, the fluorescence intensity of polymer P2 was significantly affected by the concentration of Hg. 2+ With the increase in the concentration of Hg, 2+ the fluorescence intensity of the system gradually decreased. As can be seen from Figure 14 b, when the concentration of Hg 2+ was in the range of 0 - 20 μmol / L, the relative fluorescence intensity increased linearly with the concentration of Hg. 2+ The linear equation was:

[0081] y = 0.06293x + 0.9424

[0082] where y is the relative fluorescence intensity and x is the concentration of Hg. 2+Concentration, correlation coefficient R 2 is 0.97552. It can be seen that the relative fluorescence intensity and Hg 2+ have a good linear relationship in concentration. Using the formula for the lowest detection limit to calculate the lowest detection limit, the polymer P2 has a very high detection sensitivity for Hg 2+ , and the detection limit is 8.18×10 -7 mol / L.

[0083] Example 9

[0084] Application of the polymer P3 prepared in Example 3 in detecting Hg 2+ . The specific method is the same as that in Example 7. As shown in Figure 15 a, the fluorescence intensity of the polymer P3 is significantly affected by the Hg 2+ concentration. Along with the increase of the Hg 2+ concentration, the fluorescence intensity of the system gradually decreases. As shown in Figure 15 b, when the concentration of Hg 2+ is in the range of 0 - 20 μmol / L, the relative fluorescence intensity increases linearly with the Hg 2+ concentration, and the linear equation is:

[0085] y = 0.07325x + 0.90551

[0086] where y is the relative fluorescence intensity and x is the Hg 2+ concentration, and the correlation coefficient R 2 is 0.96847. It can be seen that the relative fluorescence intensity and Hg 2+ have a good linear relationship in concentration. Using the formula for the lowest detection limit to calculate the lowest detection limit, the polymer P3 has a very high detection sensitivity for Hg 2+ , and the detection limit is 3.53×10 -7 mol / L.

[0087] To prove the selectivity of the fused heterocyclic hyperbranched conjugated polymer of the present invention for Hg 2+ detection, the fused heterocyclic hyperbranched conjugated polymers of Examples 1, 2, and 3 are respectively used for Ag + , Ca 2+ , Cd 2+ , Cu 2+ , Mg 2+ , Mn 2+ , Ni 2+ , Co 2+ , Zn 2+ , Li 2+ , Cr 2+ and Hg 2+ these 12 heavy metal cations (where the polymer concentration is 1.0×10 -6mol / L, prepared with tetrahydrofuran as the solvent, and the metal ion concentration in the detection system is 1.0×10 -6 mol / L) was tested, and the results are shown in Figures 16 - 18 . As can be seen from the figure, when Hg 2+ is added, the fluorescence quenching effect of the detection system is the strongest, while other ions have almost no fluorescence quenching effect, indicating that the fused heterocyclic hyperbranched conjugated polymer of the present invention can detect Hg 2+ with high selectivity.

[0088] Example 10

[0089] Application of the polymer P4 prepared in Example 4 in detecting 17β-estradiol, the specific method is as follows:

[0090] Dissolve the polymer P4 in tetrahydrofuran to prepare a 1.0×10 -6 mol / L tetrahydrofuran solution of polymer P4; Add 3 mL of 1.0×10 -6 mol / L tetrahydrofuran solution of polymer P4 into a cuvette, add a 17β-estradiol standard sample to it, and make the concentration of 17β-estradiol in the resulting mixture 0, 3.33, 6.67, 10, 13.3, 16.67, 20 μmol / L respectively. Use a fluorescence spectrometer to measure the fluorescence spectra of the corresponding systems with different concentrations of 17β-estradiol (see Figure 19 a), and draw a standard curve of the relative fluorescence intensity of the corresponding systems with different concentrations of 17β-estradiol varying with the concentration of 17β-estradiol at the maximum absorption wavelength (see Figure 19 b).

[0091] As can be seen from Figure 19 a, the fluorescence intensity of the polymer P4 is significantly affected by the concentration of 17β-estradiol. As the concentration of 17β-estradiol increases, the fluorescence intensity of the system gradually increases. As can be seen from Figure 19 b, when the concentration of 17β-estradiol is in the range of 0 - 20 μmol / L, the relative fluorescence intensity increases linearly with the concentration of 17β-estradiol, and the linear equation is:

[0092] y = 0.03689x + 0.93399

[0093] In the formula, y is the relative fluorescence intensity, x is the concentration of 17β-estradiol, and the correlation coefficient R 2 is 0.97756. It can be seen that the linear relationship between the relative fluorescence intensity and the concentration of 17β-estradiol is very good. Calculate the lowest detection limit using the formula for the lowest detection limit. The polymer P4 has a very high detection sensitivity for 17β-estradiol, and the detection limit is 2.70×10 -8 mol / L.

[0094] Application of the polymer P4 prepared in Example 4 in detecting 2'-aminoacetophenone, and the specific method is as follows:

[0095] Dissolve the polymer P4 in tetrahydrofuran to prepare a 1.0×10 -6 mol / L tetrahydrofuran solution of polymer P4; add 3 mL of the 1.0×10 -6 mol / L tetrahydrofuran solution of polymer P4 into a cuvette, and add a 2'-aminoacetophenone standard sample thereto, so that the concentrations of 2'-aminoacetophenone in the obtained mixed solutions are 0, 3.33, 6.67, 10, 13.3, 16.67, 20 μmol / L respectively. Measure the fluorescence spectra of the corresponding systems with different concentrations of 2'-aminoacetophenone by using a fluorescence spectrometer (see Figure 20 a), and plot a standard curve of the relative fluorescence intensity of the corresponding systems with different concentrations of 2'-aminoacetophenone varying with the concentration of 2'-aminoacetophenone at the maximum absorption wavelength (see Figure 20 b).

[0096] As can be seen from Figure 20 a, the fluorescence intensity of the polymer P4 is significantly affected by the concentration of 2'-aminoacetophenone. Along with the increase in the concentration of 2'-aminoacetophenone, the fluorescence intensity of the system gradually decreases. As can be seen from Figure 20 b, when the concentration of 2'-aminoacetophenone is in the range of 0 - 20 μmol / L, the relative fluorescence intensity increases linearly with the concentration of 2'-aminoacetophenone, and the linear equation is:

[0097] y = 0.07021x + 0.89722

[0098] where y is the relative fluorescence intensity, x is the concentration of 2'-aminoacetophenone, and the correlation coefficient R 2 is 0.96367. It can be seen that the linear relationship between the relative fluorescence intensity and the concentration of 2'-aminoacetophenone is very good. Calculate the lowest detection limit by using the formula for the lowest detection limit. The detection sensitivity of the polymer P4 to 2'-aminoacetophenone is very high, and the detection limit is 4.24×10 -8 mol / L.

[0099] Example 11

[0100] Application of the polymer P5 prepared in Example 5 in detecting 17β-estradiol and 2'-aminoacetophenone, and the specific method is the same as that in Example 10. As can be seen from Figure 21 a and Figure 22 a, the fluorescence intensity of the polymer P5 is significantly affected by the concentrations of 17β-estradiol and 2'-aminoacetophenone. Along with the increase in the concentration of 17β-estradiol, the fluorescence intensity of the system gradually increases; along with the increase in the concentration of 2'-aminoacetophenone, the fluorescence intensity of the system gradually decreases. As can be seen from Figure 21As can be seen from Fig. 17b and Fig. 22b, when the concentrations of 17β-estradiol and 2'-aminoacetophenone are in the range of 0 - 20 μmol / L, the relative fluorescence intensity increases linearly with the concentrations of 17β-estradiol and 2'-aminoacetophenone. The linear equations are respectively:

[0101] y = 0.09415x + 0.83735

[0102] y = 0.07182x + 0.91705

[0103] In the equations, y is the relative fluorescence intensity, x is the concentration of 17β-estradiol or 2'-aminoacetophenone, and the correlation coefficients R 2 are 0.98827 and 0.98057 respectively. It can be seen that the linear relationship between the relative fluorescence intensity and the concentration of 17β-estradiol or 2'-aminoacetophenone is very good. Using the formula for the lowest detection limit to calculate the lowest detection limit, the polymer P5 has a very high detection sensitivity for 17β-estradiol or 2'-aminoacetophenone, and the detection limits are 6.75×10 -9 mol / L and 1.64×10 -8 mol / L respectively.

[0104] Example 12

[0105] Application of the polymer P6 prepared in Example 6 in detecting 17β-estradiol and 2'-aminoacetophenone. The specific method is the same as that in Example 10. From Figure 23 Fig. 21a and Figure 24 Fig. 23a, it can be seen that the fluorescence intensity of the polymer P6 is significantly affected by the concentrations of 17β-estradiol and 2'-aminoacetophenone. Along with the increase in the concentration of 17β-estradiol, the fluorescence intensity of the system gradually increases; with the increase in the concentration of 2'-aminoacetophenone, the fluorescence intensity of the system gradually decreases. From Figure 23 Fig. 25b and Fig. 27b, when the concentrations of 17β-estradiol and 2'-aminoacetophenone are in the range of 0 - 20 μmol / L, the relative fluorescence intensity increases linearly with the concentrations of 17β-estradiol and 2'-aminoacetophenone. The linear equations are respectively:

[0106] y = 0.06135x + 0.97668

[0107] y = 0.0676x + 0.90497

[0108] In the equations, y is the relative fluorescence intensity, x is the concentration of 17β-estradiol or 2'-aminoacetophenone, and the correlation coefficients R 2They are 0.9988 and 0.96714 respectively. It can be seen that the linear relationship between the relative fluorescence intensity and the concentration of 17β-estradiol or 2'-aminoacetophenone is very good. Using the formula for the lowest detection limit to calculate the lowest detection limit, the polymer P6 has a very high detection sensitivity for 17β-estradiol or 2'-aminoacetophenone, and the detection limits are 2.14×10 -9 mol / L and 1.71×10 -8 mol / L respectively.

Claims

1. A heteroaromatic hyperbranched conjugated polymer, characterized in that, the structural unit of the polymer is shown by the following formula: wherein R represents any one of OH, Cl, Br, COOH, CN, NH 2 , NO 2 , COOCH 2 CH 3 , and n is an integer from 0 to 7; or R represents a benzene ring and n = 0.

2. A method for synthesizing the heteroaromatic hyperbranched conjugated polymer according to claim 1, characterized in that: 2,2'-diamino-6,6'-bi(benzothiazole) shown as M1, [1,1':3',1"-terphenyl]-4,4",5'-tricarbaldehyde shown as M2, an alkyne monomer shown as M3, a copper salt, and a base are added to dimethyl sulfoxide, and a polymerization reaction is carried out under the protection of an inert gas and stirring conditions at 70-90 °C. After the reaction is completed, extraction, drying, and dialysis are carried out to obtain the heteroaromatic hyperbranched conjugated polymer; 3. The method for synthesizing the heteroaromatic hyperbranched conjugated polymer according to claim 2, characterized in that: the copper salt is any one of cuprous chloride, cuprous iodide, and cuprous bromide.

4. The method for synthesizing the heteroaromatic hyperbranched conjugated polymer according to claim 2, characterized in that: the base is any one of anhydrous potassium carbonate and anhydrous sodium carbonate.

5. The method for synthesizing the heteroaromatic hyperbranched conjugated polymer according to any one of claims 2 to 4, characterized in that: the molar ratio of 2,2'-diamino-6,6'-bi(benzothiazole) to [1,1':3',1"-terphenyl]-4,4",5'-tricarbaldehyde and the alkyne monomer is 1.0-2.0:1:2.0-5.

0.

6. The method for synthesizing the heteroaromatic hyperbranched conjugated polymer according to any one of claims 2 to 4, characterized in that: the molar ratio of 2,2'-diamino-6,6'-bi(benzothiazole) to the copper salt and the base is 1:0.02-0.5:2.0-5.

0.

7. Use of the heteroaromatic hyperbranched conjugated polymer according to claim 1 in detecting Hg 2+ in.

8. Application of the heteroaromatic hyperbranched conjugated polymer according to claim 1 in detecting 17β-estradiol.

9. Application of the heteroaromatic hyperbranched conjugated polymer according to claim 1 in detecting 2'-aminoacetophenone.

Images