Conjugated polymer with aggregation-induced luminescent properties, preparation method and use thereof

Abstract

The invention belongs to the technical field of polymer materials, and discloses a conjugated polymer having an aggregation-induced emission property, and a preparation method and a use thereof. The structural formula of the conjugated polymer is formula I. In the formula I, R<1> independently is an aryl or heteroaryl group having an aggregation-induced emission property; R<2> independently is anaryl group or a heteroaryl group; R<3> and R<4> independently are an alkyl group, halogen, a mercapto group or -RY, R in the RY is obtained through substituting one or more carbon atoms in an alkylenegroup with one or more hetero atoms which are not directly mutually connected, the hetero atom(s) is / are O and / or S, and Y in the RY is an end group; R<3> can be same to or different from R<4>; and mis an integer in a range of 1 to 200. The conjugated polymer has the aggregation-induced emission property, has a very high selectivity on living cells, is not affected by (early stage and late stage) apoptotic cells, necrotic cells and microbes, and has a good biocompatibility and a long tracing time. The conjugated polymer can be applied to specifically marked living cells.

Description

technical field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a conjugated polymer with aggregation-induced luminescent properties, a preparation method thereof and an application in specific labeling of living cells. Background technique

[0002] The development of a highly sensitive, high luminous efficiency and high selectivity live cell probe for in vitro detection of cell viability and evaluation of the cytotoxicity of drug molecules is very important for the development of new drugs, toxicology research and the final clinical application of drug molecules. significance. The fluorescent labeling method has significant advantages for the specific analysis of living cells, such as: high sensitivity, simple operation, low cost and easy adjustment of optical properties. However, the current commercial dyes are mainly fluorescent materials with aggregation-induced fluorescence quenching (ACQ) properties, which are pro...

Examples

Embodiment 1

[0055] Preparation of conjugated polymer (polymer P(TPE-2EG)) with aggregation-induced luminescence properties: the reaction equation is as follows:

[0056]

[0057] (1) Synthesis of compound 3

[0058] Compound 1 (0.27g, 1mmol) and potassium carbonate (0.28mg, 2mmol) were added to a 100mL two-neck flask, dissolved in 20mL of acetone, and then compound 2 (0.82g, 3mmol) and a catalytic amount (about 10mg) of octadecine Six (18-crown-6), heated to reflux overnight (12h). After the reaction is cooled to room temperature, pour into the water phase to quench the reaction, and extract three times with dichloromethane, combine the organic phase and wash the organic phase with water three times, dry and filter with anhydrous magnesium sulfate, spin off the solvent, and use petroleum ether / acetic acid Ethyl ester (3 / 1, v / v) was used as eluent, and the white solid compound 3 was obtained by column separation with a yield of 81% (0.307g).

[0059] 1 H NMR (500MHz, CDCl 3 ):δ7.79(...

Embodiment 2

[0069] Preparation of conjugated polymer (polymer P2) with aggregation-induced luminescence properties: the reaction equation is as follows:

[0070]

[0071] (1) Synthesis of Compound 6

[0072] Add compound 1 (0.27g, 1mmol) and potassium carbonate (0.28mg, 2mmol) into a 100mL two-neck flask, dissolve it with 20mL of acetone, add compound 5 (0.9g, 3mmol) and a catalytic amount of octadecadecanohexa (18- crown-6), heated to reflux overnight (12h); after the reaction was cooled to room temperature, poured into the water phase to quench the reaction, and extracted three times with dichloromethane, combined the organic phase and then washed the organic phase with water three times, and washed the organic phase with anhydrous magnesium sulfate After drying and filtering, the solvent was spun off, and petroleum ether / ethyl acetate (3 / 1, v / v) was used as the eluent, and the white solid compound 6 was obtained by column separation with a yield of 75% (0.321g).

[0073] (2) Synthe...

Embodiment 3

[0077] Example 3: Specific detection and cytotoxicity detection of live cells

[0078] (1) Cytotoxicity detection: HeLa cells were cultured for 24 hours in medium (DMEM (10% FBS) co-cultivation of polymer P (TPE-2EG)) containing different concentrations of polymer P (TPE-2EG), The concentration of P(TPE-2EG) was 0, 1, 2, 4, 8, 16, 32, 64μM, and the cell viability was measured. The test results were as follows: figure 1 as shown in (C); figure 1 (C) is a histogram of the cell viability of HeLa cells cultured in medium containing different concentrations of P(TPE-2EG) for 24 hours;

[0079] HeLa cells were cultured for 24 hours in media containing different concentrations of calcein. The concentrations of calcein were 0, 0.5, 1, 2, 4, 8, 10, 15, and 20 μM, and the cell viability was measured. The test results were as follows: figure 1 Shown in (D); 1 (D) is a histogram of the cell viability of HeLa cells cultured in media containing different concentrations of calcein for 24 h...

technical field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a conjugated polymer with aggregation-induced luminescent properties, a preparation method thereof and an application in specific labeling of living cells. Background technique

[0002] The development of a highly sensitive, high luminous efficiency and high selectivity live cell probe for in vitro detection of cell viability and evaluation of the cytotoxicity of drug molecules is very important for the development of new drugs, toxicology research and the final clinical application of drug molecules. significance. The fluorescent labeling method has significant advantages for the specific analysis of living cells, such as: high sensitivity, simple operation, low cost and easy adjustment of optical properties. However, the current commercial dyes are mainly fluorescent materials with aggregation-induced fluorescence quenching (ACQ) properties, which are pro...

Examples

Embodiment 1

[0055] Preparation of conjugated polymer (polymer P(TPE-2EG)) with aggregation-induced luminescence properties: the reaction equation is as follows:

[0056]

[0057] (1) Synthesis of compound 3

[0058] Compound 1 (0.27g, 1mmol) and potassium carbonate (0.28mg, 2mmol) were added to a 100mL two-neck flask, dissolved in 20mL of acetone, and then compound 2 (0.82g, 3mmol) and a catalytic amount (about 10mg) of octadecine Six (18-crown-6), heated to reflux overnight (12h). After the reaction is cooled to room temperature, pour into the water phase to quench the reaction, and extract three times with dichloromethane, combine the organic phase and wash the organic phase with water three times, dry and filter with anhydrous magnesium sulfate, spin off the solvent, and use petroleum ether / acetic acid Ethyl ester (3 / 1, v / v) was used as eluent, and the white solid compound 3 was obtained by column separation with a yield of 81% (0.307g).

[0059] 1 H NMR (500MHz, CDCl 3 ):δ7.79(...

Embodiment 2

[0069] Preparation of conjugated polymer (polymer P2) with aggregation-induced luminescence properties: the reaction equation is as follows:

[0070]

[0071] (1) Synthesis of Compound 6

[0072] Add compound 1 (0.27g, 1mmol) and potassium carbonate (0.28mg, 2mmol) into a 100mL two-neck flask, dissolve it with 20mL of acetone, add compound 5 (0.9g, 3mmol) and a catalytic amount of octadecadecanohexa (18- crown-6), heated to reflux overnight (12h); after the reaction was cooled to room temperature, poured into the water phase to quench the reaction, and extracted three times with dichloromethane, combined the organic phase and then washed the organic phase with water three times, and washed the organic phase with anhydrous magnesium sulfate After drying and filtering, the solvent was spun off, and petroleum ether / ethyl acetate (3 / 1, v / v) was used as the eluent, and the white solid compound 6 was obtained by column separation with a yield of 75% (0.321g).

[0073] (2) Synthe...

Embodiment 3

[0077] Example 3: Specific detection and cytotoxicity detection of live cells

[0078] (1) Cytotoxicity detection: HeLa cells were cultured for 24 hours in medium (DMEM (10% FBS) co-cultivation of polymer P (TPE-2EG)) containing different concentrations of polymer P (TPE-2EG), The concentration of P(TPE-2EG) was 0, 1, 2, 4, 8, 16, 32, 64μM, and the cell viability was measured. The test results were as follows: figure 1 as shown in (C); figure 1 (C) is a histogram of the cell viability of HeLa cells cultured in medium containing different concentrations of P(TPE-2EG) for 24 hours;

[0079] HeLa cells were cultured for 24 hours in media containing different concentrations of calcein. The concentrations of calcein were 0, 0.5, 1, 2, 4, 8, 10, 15, and 20 μM, and the cell viability was measured. The test results were as follows: figure 1 Shown in (D); 1 (D) is a histogram of the cell viability of HeLa cells cultured in media containing different concentrations of calcein for 24 h...

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