阅读说明：本技术 一种特异性识别肿瘤细胞的导电高分子材料及其制备方法 (Conductive polymer material for specifically recognizing tumor cells and preparation method thereof ) 是由 向兴力 于 2020-05-17 设计创作，主要内容包括：本发明公开了一种特异性识别肿瘤细胞的导电高分子材料的制备方法,其特征在于,包括如下步骤：步骤S1、席夫碱类聚合物的制备；步骤S2、N-(2-氯乙基)-3-硼苯甲酰胺离子化改性席夫碱类聚合物。本发明还公开了根据所述特异性识别肿瘤细胞的导电高分子材料的制备方法制备得到的特异性识别肿瘤细胞的导电高分子材料及其应用。本发明公开的特异性识别肿瘤细胞的导电高分子材料对肿瘤细胞特异性识别效果佳,综合性能好,生物兼容性和稳定性优异,能有效降低非特异性染色的强度,以适应细胞生物学研究的需求。(The invention discloses a preparation method of a conductive polymer material for specifically identifying tumor cells, which is characterized by comprising the following steps: step S1, preparing Schiff base polymers; and S2, ionizing and modifying the Schiff base polymer by the N- (2-chloroethyl) -3-borabenzamide. The invention also discloses the conductive polymer material for specifically recognizing the tumor cells, which is prepared by the preparation method of the conductive polymer material for specifically recognizing the tumor cells, and an application thereof. The conductive polymer material for specifically recognizing the tumor cells disclosed by the invention has the advantages of good tumor cell specific recognition effect, good comprehensive performance, excellent biocompatibility and stability, and capability of effectively reducing the intensity of nonspecific staining so as to meet the requirements of cell biological research.)

1. A preparation method of a conductive polymer material for specifically recognizing tumor cells is characterized by comprising the following steps:

step S1, preparation of Schiff base polymers: adding 4,4' -diformyl triphenylamine and 2, 5-di (2-thienyl) -3, 4-diamine into an organic solvent, stirring and reacting for 8-12 hours at 75-85 ℃ in the atmosphere of nitrogen or inert gas, cooling to room temperature after the reaction is finished, removing the solvent by rotary evaporation, washing for 4-8 times with petroleum ether, and removing the petroleum ether by rotary evaporation to obtain a Schiff base polymer;

step S2, ionizing and modifying the Schiff base polymer by N- (2-chloroethyl) -3-boron benzamide: and (2) dissolving the Schiff base polymer prepared in the step S1 in a high-boiling-point solvent, adding N- (2-chloroethyl) -3-boron benzamide into the solvent, stirring the mixture at the temperature of between 80 and 90 ℃ for reacting for 8 to 12 hours, and then removing the solvent by rotary evaporation to obtain the N- (2-chloroethyl) -3-boron benzamide ionized modified Schiff base polymer.

2. The method of claim 1, wherein the molar ratio of the 4,4' -ditriphenylamide, 2, 5-bis (2-thienyl) -3, 4-diamine, and the organic solvent in step S1 is 1:1 (6-10).

3. The method of claim 1, wherein the organic solvent is any one of dichloromethane, tetrahydrofuran, and acetone.

4. The method of claim 1, wherein the inert gas is any one of helium, neon, and argon.

5. The method for preparing a conductive polymer material capable of specifically recognizing tumor cells according to claim 1, wherein the mass ratio of the schiff base polymer, the high-boiling-point solvent and the N- (2-chloroethyl) -3-borabenzamide in the step S2 is 1 (3-5) to 0.2.

6. The method of claim 1, wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.

7. The conductive polymer material for specifically recognizing tumor cells, which is prepared according to the preparation method of the conductive polymer material for specifically recognizing tumor cells of any one of claims 1 to 6.

8. The use of the conductive polymer material according to claim 7 for specifically recognizing tumor cells.

Technical Field

The invention relates to the technical field of functional biomedicine, in particular to a conductive polymer material for specifically identifying tumor cells and a preparation method thereof.

Background

Tumors are the first disease which endangers all human beings, are one of the leading causes of diseases and fatalities in the world, and the global tumor burden is expected to increase along with the increase of the world population and the increase of the aging population. Early diagnosis, early treatment and targeted therapy of tumors are a constant concern and research. The traditional fluorescent dye for cell biological research has many unsuspecting limitations, such as strict requirement on excitation wavelength, low fluorescence efficiency, easy overlapping of emission wavelength and excitation wavelength, poor light stability, and the like, which brings inconvenience to biological research.

Most of the existing methods for detecting tumor cells adopt relatively large-scale instruments such as flow cytometry, and the detection methods need special detection instruments, professional operators, complex sample pretreatment and the like; there are also other methods for detecting tumor cells, such as mass spectrometry, colorimetry, microcantilever methods, electrochemiluminescence, and the like. However, the existing detection methods have the problems of low sensitivity, slow detection speed and poor selectivity on tumor cells. Meanwhile, the existing tumor cell detection method has the defects of being too complex, long in detection time, expensive in detection equipment, complex in covalent modification of folic acid, low and unstable in non-covalent modification adsorption rate, low in folic acid identification and the like.

The Chinese invention patent with the application number of 201811643769.X discloses a preparation method of a conductive polymer material for specifically identifying tumor cells, which is characterized by comprising the following steps: (1) 28ml of toluene, 1.36g of 10.4mmol of 3, 4-dimethoxythiophene, 2.60g of 23.1mmol of 3-chloro-1, 2-propanediol and 0.16g of 0.92mmol of p-toluenesulfonic acid monohydrate were added to a two-necked flask under a nitrogen atmosphere, mixed and reacted at 90 ℃ for 24 hours; (2) and (2) evaporating the mixture in the step (1) and purifying by column chromatography to obtain EDOT-Cl. The invention has the following advantages: the flexible conductive polymer material for tumor cell specific recognition is synthesized and prepared, the non-labeling and non-invasive specific recognition of tumor cells is realized, and an effective means is provided for malignant tumor screening, early cancer diagnosis and instant diagnosis. However, the preparation method of the high polymer material is complex, and toxic and harmful solvents such as toluene and the like are used in the preparation process, so that the high polymer material is not environment-friendly.

Therefore, the conductive polymer material for specifically identifying the tumor cells, which has the advantages of good specific identification effect on the tumor cells, good comprehensive performance, excellent biocompatibility and stability, capability of effectively reducing the intensity of nonspecific staining so as to meet the requirements of cell biology research, meets the market requirements, has wide market value and application prospect, and has very important significance for promoting the specific identification of the tumor cells.

Disclosure of Invention

The invention aims to solve the problems and provides a conductive polymer material for specifically identifying tumor cells and a preparation method thereof, wherein the preparation method is simple and easy to implement, has low requirements on equipment and reaction conditions, has low preparation cost and is suitable for continuous large-scale production; the conductive polymer material for specifically recognizing the tumor cells, which is prepared by the method, has the advantages of good tumor cell specific recognition effect, good comprehensive performance, excellent biocompatibility and stability, and capability of effectively reducing the intensity of nonspecific staining so as to meet the requirements of cell biological research.

In order to achieve the above object, the present invention provides the following technical solution, a method for preparing a conductive polymer material specifically recognizing tumor cells, comprising the steps of:

step S1, preparation of Schiff base polymers: adding 4,4' -diformyl triphenylamine and 2, 5-di (2-thienyl) -3, 4-diamine into an organic solvent, stirring and reacting for 8-12 hours at 75-85 ℃ in the atmosphere of nitrogen or inert gas, cooling to room temperature after the reaction is finished, removing the solvent by rotary evaporation, washing for 4-8 times with petroleum ether, and removing the petroleum ether by rotary evaporation to obtain a Schiff base polymer;

step S2, ionizing and modifying the Schiff base polymer by N- (2-chloroethyl) -3-boron benzamide: and (2) dissolving the Schiff base polymer prepared in the step S1 in a high-boiling-point solvent, adding N- (2-chloroethyl) -3-boron benzamide into the solvent, stirring the mixture at the temperature of between 80 and 90 ℃ for reacting for 8 to 12 hours, and then removing the solvent by rotary evaporation to obtain the N- (2-chloroethyl) -3-boron benzamide ionized modified Schiff base polymer.

Preferably, the molar ratio of the 4,4' -diformyl triphenylamine, the 2, 5-di (2-thienyl) -3, 4-diamine and the organic solvent in the step S1 is 1:1 (6-10).

Preferably, the organic solvent is any one of dichloromethane, tetrahydrofuran and acetone.

Preferably, the inert gas is any one of helium, neon and argon.

Preferably, the mass ratio of the Schiff base polymer, the high-boiling-point solvent and the N- (2-chloroethyl) -3-boron benzamide in the step S2 is 1 (3-5) to 0.2.

Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

Another object of the present invention is to provide a conductive polymer material capable of specifically recognizing tumor cells, which is prepared according to the method for preparing a conductive polymer material capable of specifically recognizing tumor cells.

Still another object of the present invention is to provide an application of the conductive polymer material for specifically recognizing tumor cells in the specific recognition of tumor cells.

Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:

(1) the preparation method of the conductive polymer material for specifically identifying the tumor cells, provided by the invention, is simple and feasible, has low requirements on equipment and reaction conditions, has low preparation cost, and is suitable for continuous large-scale production.

(2) The conductive polymer material for specifically identifying the tumor cells overcomes the defects of complexity, long detection time, expensive detection equipment, complex covalent modification of folic acid, low and unstable non-covalent modification adsorption rate, low folic acid identification property and the like in the conventional tumor cell detection method, and has the advantages of good tumor cell specific identification effect, good comprehensive performance, excellent biocompatibility and stability, capability of effectively reducing the nonspecific staining intensity and capability of meeting the requirements of cell biological research.

(3) The conductive polymer material for specifically recognizing the tumor cells, provided by the invention, is characterized in that a Schiff base polymer prepared from 4,4' -diformyl triphenylamine and 2, 5-di (2-thienyl) -3, 4-diamine is used as a base material, so that the conductive polymer material is endowed with excellent conductivity; through N- (2-chloroethyl) -3-boratobenzamide ionization modification, a phenylboronic acid group is introduced, and the tumor cell specific recognition effect can be effectively achieved; all the structures and the components have synergistic effect, so that the comprehensive performance of the composite material is better.

(4) The conductive polymer material for specifically identifying the tumor cells, provided by the invention, introduces a quaternary ammonium salt structure, and can endow the material with the effects of antibiosis, antistatic and neutralization of negative charges of the tumor cells; can realize the non-marking and non-invasive specific recognition of tumor cells, and provides an effective means for malignant tumor screening, early cancer diagnosis and instant diagnosis.

Detailed Description

In order to make the technical solution of the present invention better understood by those skilled in the art, the following provides a detailed description of the product of the present invention with reference to the examples.

In this example, all the raw materials were purchased commercially.