CN112341623B - Preparation method and application of three-dimensional polydopamine - Google Patents

Abstract

The invention relates to a preparation method and application of three-dimensional polydopamine, and belongs to the technical field of functional materials. The preparation method takes dopamine hydrochloride and metal iron salt as raw materials, and prepares the three-dimensional poly-dopamine by utilizing a self-polymerization and self-assembly method. The three-dimensional polydopamine prepared by the method has the advantages of simple method, adjustable size and shape and the like, and realizes the requirements of environmental protection by using a common water/alcohol system as a reaction solvent. The preparation method of the three-dimensional polydopamine material provided by the invention can promote the further development of polydopamine related research. The three-dimensional polydopamine prepared by the method has an excellent photo-thermal conversion effect, and compared with the traditional photo-material, the material shows excellent biocompatibility and photo-thermal conversion rate, and can promote the research of a photo-thermal agent. The three-dimensional poly-dopamine material prepared by the invention can be used for photothermal treatment of tumors, so that the three-dimensional poly-dopamine material has a good medical application prospect.

Description

Preparation method and application of three-dimensional polydopamine

Technical Field

The invention relates to a preparation method and application of three-dimensional polydopamine, and belongs to the technical field of functional materials.

Background

In recent years, the research on polydopamine has become a research hotspot of various subjects such as chemistry, materials science, biomedicine and the like due to the fact that polydopamine has the characteristics of special optics, electricity, biocompatibility and the like. In the current research, polydopamine is widely applied in the fields of catalytic chemistry, free radical scavenging, ink-jet printing, tumor treatment, energy materials and the like. For the present time, most of the research based on polydopamine is to prepare dopamine monomer into zero-dimensional globules or two-dimensional polydopamine film through certain chemical reaction. However, no report has been made on the novel morphological structure of polydopamine material, particularly polydopamine having a three-dimensional structure.

The poly-dopamine serving as a material with great significance is developed into a novel method for preparing a three-dimensional poly-dopamine material, so that the defects of the research field are made up, and the development of the poly-dopamine material in various fields is greatly promoted.

Disclosure of Invention

The invention aims to provide a method for preparing three-dimensional polydopamine, which generates three-dimensional polydopamine with flower-like structure in the presence of metal ions through polymerization of dopamine under alkaline conditions, and uses a three-dimensional polydopamine material as a photothermal conversion reagent to produce a medical effect.

The preparation method of the three-dimensional polydopamine provided by the invention comprises the following steps:

(1) mixing water, anhydrous low-carbon alcohol and 25% strong ammonia water by mass percent, wherein the mixed volume ratio of the mixed solution is as follows: water, namely anhydrous low-carbon alcohol, namely concentrated ammonia water (0.3-3) and (0.025-0.1), heating and stirring the mixed solution at the stirring speed of 600 r/min, heating to 30-90 ℃, and stirring for 10-30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the first solution is as follows: 2.5-4.5 g/L to obtain a second solution;

(3) adding metal iron salt into the second solution to ensure that the mass concentration of the metal iron salt in the second solution is as follows: 0.0003-0.001 g/L, the reaction temperature is 30-90 ℃, and the reaction time is 2-36 hours, so as to obtain a third reaction solution;

(4) and (3) carrying out centrifugal separation on the third reaction liquid, washing the precipitate obtained by the centrifugal separation with water and ethanol, carrying out centrifugal treatment on a washing liquid, repeating the step for 2-3 times, and carrying out freeze drying on the centrifugal precipitate obtained finally to obtain the three-dimensional polydopamine.

In the preparation method, the lower alcohol is ethanol, ethylene glycol, isopropanol, n-butanol or glycerol.

In the preparation method, the metal iron salt is ferric chloride hexahydrate, ferrous chloride, ferrous sulfate, ferric sulfate or ferric citrate.

The application of the three-dimensional polydopamine prepared by the method disclosed by the invention in the preparation of a photothermal conversion agent by using the polydopamine comprises the following steps:

(1) dispersing three-dimensional polydopamine in a phosphate buffer solution to enable the mass volume concentration of the polydopamine to be 50-400 mu g/mL, and carrying out ultrasonic treatment for 10-30 minutes with the ultrasonic power of 120W to obtain a fourth solution;

(2) irradiating the fourth solution by using laser with the wavelength of 808nm and the power of 0.8-2.0W for 5-15 minutes, wherein the temperature of the fourth solution is changed.

The invention provides a preparation method and application of three-dimensional polydopamine, which has the advantages that:

the preparation method of the three-dimensional polydopamine material first prepares the uniform three-dimensional polydopamine material. The three-dimensional polydopamine prepared by the method has the advantages of simple method, adjustable size and shape and the like, and realizes the requirements of environmental protection by using a common water/alcohol system as a reaction solvent. The test result shows that the size of the prepared three-dimensional polydopamine material and the size of the assembled monomer can be adjusted. The preparation method of the three-dimensional polydopamine material provided by the invention can promote the further development of polydopamine related research. The three-dimensional polydopamine prepared by the method has an excellent photo-thermal conversion effect, and compared with the traditional photo-material, the material shows excellent biocompatibility and photo-thermal conversion rate, and can promote the research of a photo-thermal agent. The three-dimensional poly-dopamine material prepared by the invention can be used for photothermal treatment of tumors, so that the three-dimensional poly-dopamine material has a good medical application prospect.

Drawings

FIG. 1 is a Scanning Electron Microscope (SEM) image of three-dimensional polydopamine prepared by ferric chloride hexahydrate as an iron salt in an ethanol/water system according to the method of the present invention.

FIG. 2 is an SEM image of three-dimensional polydopamine prepared by ferric chloride hexahydrate as ferric salt in ethanol/water system at different temperatures.

FIG. 3 is an SEM image of three-dimensional polydopamine prepared by using ferric chloride hexahydrate as an iron salt at different concentrations according to the method disclosed by the invention.

FIG. 4 is an SEM image of three-dimensional polydopamine prepared in an ethanol/water system by using ferrous sulfate as an iron salt.

Fig. 5 is an SEM image of three-dimensional polydopamine prepared in an ethylene glycol/water system using ferrous chloride as an iron salt according to the method of the present invention.

FIG. 6 is an SEM image of three-dimensional polydopamine prepared in an isopropanol/water system by using ferric sulfate as a ferric salt according to the method of the invention.

Fig. 7 is an SEM image of three-dimensional polydopamine prepared in n-butanol/water system by using ferric citrate as ferric salt according to the present invention.

Fig. 8 is an SEM image of three-dimensional polydopamine prepared in glycerol/water system using ferric chloride hexahydrate as iron salt by the method of the present invention.

FIG. 9 is a temperature time curve of a three-dimensional polydopamine material prepared by the method of the invention and using ferric chloride hexahydrate as an iron salt under laser irradiation.

Detailed Description

The preparation method of the three-dimensional polydopamine provided by the invention comprises the following steps:

(1) mixing water, anhydrous low-carbon alcohol and 25% strong ammonia water by mass percent, wherein the mixed volume ratio of the mixed solution is as follows: water, namely anhydrous low-carbon alcohol, namely concentrated ammonia water (0.3-3) and (0.025-0.1), heating and stirring the mixed solution at the stirring speed of 600 r/min, heating to 30-90 ℃, and stirring for 10-30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the second solution is as follows: 2.5-4.5 g/L to obtain a second solution;

(3) adding metal iron salt into the second solution to ensure that the mass concentration of the metal iron salt in the second solution is as follows: 0.0003-0.001 g/L, the reaction temperature is 30-90 ℃, and the reaction time is 2-36 hours, so as to obtain a third reaction solution;

(4) and (3) carrying out centrifugal separation on the third reaction liquid, washing the precipitate obtained by the centrifugal separation with water and ethanol, carrying out centrifugal treatment on a washing liquid, repeating the step for 2-3 times, and carrying out freeze drying on the centrifugal precipitate obtained finally to obtain the three-dimensional polydopamine.

In the preparation method, the lower alcohol is ethanol, ethylene glycol, isopropanol, n-butanol or glycerol.

In the above preparation method, the metal iron salt is ferric chloride hexahydrate, ferrous chloride, ferrous sulfate, ferric sulfate, or ferric citrate.

The application of the three-dimensional polydopamine prepared by the method disclosed by the invention, namely the application of polydopamine sodium in a photothermal conversion agent, comprises the following steps:

(1) dispersing three-dimensional polydopamine in a phosphate buffer solution to enable the mass volume concentration of the polydopamine to be 50-400 mu g/mL, and carrying out ultrasonic treatment for 10-30 minutes with the ultrasonic power of 120W to obtain a fourth solution;

(2) irradiating the fourth solution by using laser with the wavelength of 808nm and the power of 0.8-2.0W for 5-15 minutes, wherein the temperature of the fourth solution is changed.

The SEM image of the three-dimensional polydopamine prepared by the method of the invention and taking ferric chloride hexahydrate as an iron salt is shown in figure 1, and as can be seen from figure 1, the three-dimensional structure is successfully constructed, the size of the material is about 2 mu m, and the material has the structural characteristics similar to flowers.

Fig. 9 is a temperature-time curve of the three-dimensional polydopamine material prepared by the method of the present invention and using ferric chloride hexahydrate as an iron salt under laser irradiation, the material has a good photothermal conversion effect, and as the concentration of the prepared material increases, the temperature of the solution significantly increases under the laser irradiation with a wavelength of 808nm, and can reach 78.5 ℃ at most within 10 minutes.

The following describes embodiments of the method of the invention:

example 1:

(1) mixing water, absolute ethyl alcohol and 25% by mass of concentrated ammonia water with each other, wherein the mixing volume ratio of the mixed solution is as follows: water, anhydrous low-carbon alcohol and concentrated ammonia water in a ratio of 1:0.3:0.025, heating the mixed solution while stirring at a stirring speed of 600 r/min, heating to 30 ℃, and stirring for 10 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the solution is as follows: 2.5g/L to obtain a second solution;

(3) adding ferric chloride hexahydrate into the second solution, so that the mass concentration of the added ferric chloride hexahydrate is as follows: 0.0003g/L, the reaction temperature is 30 ℃, and the reaction time is 2 hours, so as to obtain a third reaction solution;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. The SEM image of the prepared three-dimensional polydopamine is shown in fig. 1.

Example 2:

(1) mixing water, absolute ethyl alcohol and 25% by mass of concentrated ammonia water with each other, wherein the mixing volume ratio of the mixed solution is as follows: heating the mixed solution with stirring at the stirring speed of 600 r/min, heating to 60 ℃, and stirring for 10 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the solution is as follows: 2.5g/L to obtain a second solution;

(3) adding ferric chloride hexahydrate into the second solution, so that the mass concentration of the added ferric chloride hexahydrate is as follows: 0.0003g/L, the reaction temperature is 60 ℃, and the reaction time is 7 hours, so as to obtain a third reaction solution;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. An SEM image of the prepared three-dimensional polydopamine is shown in fig. 2.

Example 3:

(1) mixing water, absolute ethyl alcohol and 25% by mass of concentrated ammonia water with each other, wherein the mixing volume ratio of the mixed solution is as follows: heating the mixed solution with stirring at the stirring speed of 600 r/min, heating to 60 ℃, and stirring for 30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution, wherein the mass volume ratio of the added dopamine hydrochloride is as follows: 3.0g/L to obtain a second solution;

(3) adding ferric chloride hexahydrate into the second solution, wherein the mass-volume ratio of the added metal iron salt is as follows: 0.001g/L, the reaction temperature is 60 ℃, and the reaction time is 6 hours, so as to obtain a third reaction solution;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. An SEM image of the prepared three-dimensional polydopamine is shown in fig. 3.

Example 4:

(1) mixing water, absolute ethyl alcohol and 25% by mass of concentrated ammonia water with each other, wherein the mixing volume ratio of the mixed solution is as follows: heating the mixed solution with stirring at the stirring speed of 600 r/min, heating to 60 ℃, and stirring for 30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution, so that the mass concentration of the added dopamine hydrochloride is as follows: 3.0g/L to obtain a second solution;

(3) adding ferrous sulfate into the second solution, so that the mass concentration of the added ferrous sulfate is as follows: 0.0015g/L, the reaction temperature is 60 ℃, and the reaction time is 6 hours, so as to obtain a third reaction solution;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. An SEM image of the prepared three-dimensional polydopamine is shown in fig. 4.

Example 5:

(1) mixing water, ethylene glycol and 25% by mass of concentrated ammonia water with each other, wherein the mixed volume ratio of the mixed solution is as follows: heating the mixed solution at a stirring speed of 600 r/min, heating to 60 ℃, and stirring for 30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution, so that the mass concentration of the added dopamine hydrochloride is as follows: 4.5g/L to obtain a second solution;

(3) adding ferrous chloride into the second solution, so that the mass concentration of the ferrous chloride added into the solution is as follows: 0.0005g/L, the reaction temperature is 60 ℃, and the reaction time is 18 hours, so as to obtain a third reaction liquid;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. An SEM image of the prepared three-dimensional polydopamine is shown in fig. 5.

Example 6:

(1) mixing water, isopropanol and 25% by mass of concentrated ammonia water with each other, wherein the mixing volume ratio of the mixed solution is as follows: heating and stirring the mixed solution at the stirring speed of 600 r/min, heating to 90 ℃, and stirring for 30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the solution is as follows: 3g/L to obtain a second solution;

(3) adding ferric sulfate into the second solution to ensure that the mass concentration of the ferric sulfate in the solution is as follows: 0.0005g/L, the reaction temperature is 90 ℃, and the reaction time is 36 hours, so as to obtain a third reaction liquid;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. An SEM image of the prepared three-dimensional polydopamine is shown in fig. 6.

Example 7:

(1) mixing water, n-butanol and 25% by mass of concentrated ammonia water with each other, wherein the mixing ratio of the mixed solution is as follows: water, namely n-butanol and concentrated ammonia water are added in a ratio of 1:2:0.1, the mixed solution is heated and stirred at a stirring speed of 600 r/min, heated to 70 ℃ and stirred for 30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the solution is as follows: 4.5g/L to obtain a second solution;

(3) adding ferric citrate into the second solution to ensure that the mass concentration of the ferric citrate in the solution is as follows: 0.006g/L, the reaction temperature is 70 ℃, and the reaction time is 36 hours, so as to obtain a third reaction solution;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. An SEM image of the prepared three-dimensional polydopamine is shown in fig. 7.

Example 8:

(1) mixing water, glycerol and 25% of strong ammonia water by mass percent, wherein the mixing proportion of the mixed solution is as follows: heating and stirring the mixed solution at the stirring speed of 600 r/min, heating to 60 ℃, and stirring for 30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the solution is as follows: 4.5g/L to obtain a second solution;

(3) adding ferric chloride hexahydrate into the second solution, so that the mass concentration of the ferric chloride hexahydrate in the solution is as follows: 0.005g/L, the reaction temperature is 60 ℃, and the reaction time is 36 hours, so as to obtain a third reaction solution;

(4) and (3) performing centrifugal separation on the third reaction liquid, washing the precipitate obtained by centrifugal separation with water and ethanol, treating the washing liquid, repeating the step for 2-3 times, and performing freeze drying on the finally obtained centrifugal precipitate to obtain the three-dimensional polydopamine. An SEM image of the prepared three-dimensional polydopamine is shown in fig. 8.

Application example 1:

(1) dispersing three-dimensional polydopamine in a solution in a phosphate buffer solution to enable the mass volume concentration of the polydopamine to be 50 mu g/mL, and carrying out ultrasonic treatment for 10 minutes with the ultrasonic power of 120W to obtain a fourth solution;

(2) irradiating the fourth solution by using laser with the wavelength of 808nm and the power of 0.8W for 5 minutes, monitoring the temperature change of the fourth solution in real time by using a temperature detector, and displaying by using a temperature sensor that the temperature can reach 50 ℃ at most.

Application example 2:

(1) dispersing three-dimensional polydopamine in a solution in a phosphate buffer solution to ensure that the mass volume concentration of the polydopamine is 200 mug/mL, and carrying out ultrasonic treatment for 10 minutes with the ultrasonic power of 120W to obtain a fourth solution;

(2) irradiating the fourth solution by using laser with the wavelength of 808nm and the power of 1.5W for 5 minutes, monitoring the temperature change of the fourth solution in real time by using a temperature detector, and displaying by using a temperature sensor that the temperature can reach 60 ℃ at most.

Application example 3:

(1) dispersing the three-dimensional polydopamine prepared by the method in a solution in a phosphate buffer solution to ensure that the mass volume concentration of the polydopamine is 400 mug/mL, and performing ultrasonic treatment for 10 minutes under the ultrasonic power of 120W to obtain a fourth solution;

(2) irradiating the fourth solution by using laser with the wavelength of 808nm and the power of 1.5W for 5 minutes, monitoring the temperature change of the fourth solution in real time by using a temperature detector, and displaying by using a temperature sensor that the temperature can reach 70 ℃ at most.

Application example 4:

(1) dispersing the three-dimensional polydopamine prepared by the method in a solution in a phosphate buffer solution to ensure that the mass volume concentration of the polydopamine is 400 mug/mL, and carrying out ultrasonic treatment for 10 minutes with the ultrasonic power of 120W to obtain a fourth solution;

(2) irradiating the fourth solution by using laser with the wavelength of 808nm and the power of 2W for 15 minutes, monitoring the temperature change of the fourth solution in real time by using a temperature detector, and displaying by using a temperature sensor that the temperature can reach 78.5 ℃ at most.

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

Claims (3)

1. A preparation method of three-dimensional polydopamine is characterized by comprising the following steps:

(1) mixing water, anhydrous low-carbon alcohol and 25% strong ammonia water by mass percent, wherein the mixed volume ratio of the mixed solution is as follows: water, namely anhydrous low-carbon alcohol, namely concentrated ammonia water (0.3-3) and (0.025-0.1), heating and stirring the mixed solution at the stirring speed of 600 r/min, heating to 30-90 ℃, and stirring for 10-30 min to obtain a first solution;

(2) adding dopamine hydrochloride into the first solution to ensure that the mass concentration of the dopamine hydrochloride in the first solution is as follows: 2.5-4.5 g/L to obtain a second solution;

(3) adding metal iron salt into the second solution to ensure that the mass concentration of the metal iron salt in the second solution is as follows: 0.0003-0.001 g/L, the reaction temperature is 30-90 ℃, and the reaction time is 2-36 hours, so as to obtain a third reaction solution, wherein the metal ferric salt is ferric chloride hexahydrate, ferrous chloride, ferrous sulfate, ferric sulfate or ferric citrate;

(4) and (3) carrying out centrifugal separation on the third reaction liquid, washing the precipitate obtained by the centrifugal separation with water and ethanol, carrying out centrifugal treatment on a washing liquid, repeating the step for 2-3 times, and carrying out freeze drying on the centrifugal precipitate obtained finally to obtain the three-dimensional polydopamine.

2. The method according to claim 1, wherein the anhydrous lower alcohol is ethanol, ethylene glycol, isopropanol, n-butanol or glycerol.

3. Use of the three-dimensional polydopamine prepared by the preparation method according to claim 1, characterized in that the polydopamine is used as a light-to-heat conversion agent, comprising the steps of:

(1) dispersing three-dimensional polydopamine in a phosphate buffer solution to enable the mass volume concentration of the polydopamine to be 50-400 mu g/mL, and carrying out ultrasonic treatment for 10-30 minutes with the ultrasonic power of 120W to obtain a fourth solution;

(2) irradiating the fourth solution by using laser with the wavelength of 808nm and the power of 0.8-2.0W for 5-15 minutes, wherein the temperature of the fourth solution is changed.

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