CN110038127B - Preparation method and application of polypyrrole/gold composite hollow microsphere structure material - Google Patents
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Abstract
The invention discloses a preparation method of a polypyrrole/gold composite hollow microsphere structural material, which comprises the following steps: s1: modifying the monodisperse silicon dioxide microspheres by polyvinylpyrrolidone; s2: wrapping polypyrrole on the surface of the modified monodisperse silica microsphere to obtain a silica/polypyrrole composite microsphere; s3: and modifying the polypyrrole in the silicon dioxide/polypyrrole composite microspheres by polyvinylpyrrolidone, coating gold shells on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then melting the silicon dioxide in the silicon dioxide/polypyrrole composite microspheres coated with the gold shells to obtain the polypyrrole/gold composite hollow microsphere structural material. The material prepared by the method has good biocompatibility and biological metabolizability, good imaging function, high photothermal conversion efficiency, good photothermal stability and drug loading capacity, and the preparation method is simple and easy to operate and has high preparation efficiency.
Description
Technical Field
The invention relates to a preparation method and application of a polypyrrole/gold composite hollow microsphere structural material.
Background
At present, cancer is one of the most serious diseases, the traditional methods for treating cancer comprise surgical operation, radiotherapy, chemotherapy and the like, the traditional methods have common defects, cancer cells are killed, normal cells are killed, the immune system is damaged to a certain extent, and adverse reactions are large. The photothermal therapy technology is a minimally invasive therapy technology, near-infrared laser light energy is converted into heat energy by utilizing a photothermal material with light absorption capacity so as to kill cancer cells, and compared with the traditional chemotherapy and radiotherapy, the photothermal therapy technology has the advantages of small side effect and good treatment specificity. The key of the photothermal treatment technology is to develop a biocompatible, efficient and stable photothermal conversion material, and currently, the more researched photothermal conversion materials comprise a noble metal photothermal conversion material, a carbon-based photothermal conversion material and a semiconductor photothermal material. The noble metal photo-thermal conversion material is expensive, and the shape of the noble metal photo-thermal conversion material is easy to change after the temperature rises, so that the stability of the photo-thermal performance of the noble metal photo-thermal conversion material is influenced; the light absorption coefficient of the carbon-based photothermal conversion material is low, and the preparation and functionalization conditions of the carbon material are harsh; the semiconductor photo-thermal material contains heavy metal ions, and the problem of leaching toxicity in vivo is difficult to solve.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a polypyrrole/gold composite hollow microsphere structural material, and the material prepared by the method has good biocompatibility and biological metabolisms, good imaging function, high photothermal conversion efficiency, good photothermal stability, drug loading capacity, simple and easy operation and high preparation efficiency.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a polypyrrole/gold composite hollow microsphere structure material comprises the following steps:
s1: modifying the monodisperse silicon dioxide microspheres by polyvinylpyrrolidone;
s2: wrapping polypyrrole on the surface of the modified monodisperse silica microsphere to obtain a silica/polypyrrole composite microsphere;
s3: and modifying the polypyrrole in the silicon dioxide/polypyrrole composite microspheres by polyvinylpyrrolidone, coating gold shells on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then melting the silicon dioxide in the silicon dioxide/polypyrrole composite microspheres coated with the gold shells to obtain the polypyrrole/gold composite hollow microsphere structural material.
Further provides a preparation method of the monodisperse silica microsphere, in step S1, the preparation steps of the monodisperse silica microsphere are as follows:
mixing water, ammonia water and absolute ethyl alcohol in a proper proportion and stirring;
adding a proper amount of tetraethoxysilane and stirring;
and centrifugally separating, cleaning and drying to obtain the monodisperse silicon dioxide microspheres.
Further, 1-3 mL, 3-10 mL and 50-100 mL of water, ammonia water and absolute ethyl alcohol are respectively taken; and/or the stirring mode is magnetic stirring, the stirring time is 20-60 minutes, and the stirring speed is 100-400 revolutions per minute; and/or the temperature of the solution is 25-60 ℃; and/or 1-5 mL of ethyl orthosilicate is added, and the stirring time after the ethyl orthosilicate is added is 8-16 hours.
Further provides a specific method for modifying monodisperse silica microspheres with polyvinylpyrrolidone, and in step S1, the steps of modifying monodisperse silica microspheres with polyvinylpyrrolidone are as follows:
taking a proper amount of monodisperse silicon dioxide microspheres, and ultrasonically dispersing the monodisperse silicon dioxide microspheres into absolute ethyl alcohol;
adding a proper amount of polyvinylpyrrolidone, performing ultrasonic treatment, and stirring;
and (4) centrifugally separating, then washing and drying to obtain the modified monodisperse silica microspheres.
Further, the monodispersity silica microspheres are 0.05-0.2 g, and the absolute ethyl alcohol is 20 mL; and/or 0.1-2 g of polyvinylpyrrolidone is added, the ultrasonic treatment time after the polyvinylpyrrolidone is added is 10-30 minutes, the stirring time is 12-24 hours, and the solution temperature is 30-50 ℃.
Further provides a specific method for coating polypyrrole on the surface of the monodisperse silica microsphere, and in step S2, the step of coating polypyrrole on the surface of the monodisperse silica microsphere is as follows:
placing the monodisperse silicon dioxide microspheres modified by polyvinylpyrrolidone into a proper amount of absolute ethyl alcohol and carrying out ultrasonic treatment;
adding a proper amount of pyrrole and then carrying out ultrasonic treatment;
adding a proper amount of ammonium persulfate solution and stirring;
and (4) carrying out centrifugal separation, cleaning and drying to obtain the silicon dioxide/polypyrrole composite microspheres.
Further, the monodispersity silica microspheres are 0.05-0.2 g, the absolute ethyl alcohol is 150mL, and the ultrasonic treatment time is 10-30 minutes; and/or the amount of the added pyrrole is 0.02-0.2 mL, and the time of ultrasonic treatment after the pyrrole is added is 5-10 minutes; and/or the added ammonium persulfate solution is 2-10 mL, the mass volume concentration is 0.06g/mL, and the stirring time after the ammonium persulfate solution is added is 8-24 hours; and/or the temperature of the solution is 15-30 ℃.
Further, the specific steps of step S3 are as follows:
ultrasonically dispersing a proper amount of silicon dioxide/polypyrrole composite microspheres and a proper amount of polyvinylpyrrolidone into a proper amount of deionized water;
adding a proper amount of chloroauric acid solution and stirring;
adding a proper amount of freshly prepared sodium borohydride solution and stirring to obtain a dispersion liquid;
taking a proper amount of the dispersion, adding a proper amount of sodium hydroxide solution, oscillating, and standing;
and (4) drying after centrifugal separation to obtain the polypyrrole/gold composite hollow microsphere structural material.
Further, ultrasonically dispersing the silicon dioxide/polypyrrole composite microspheres in 50mL of deionized water to obtain a solution in which the mass volume concentration of the silicon dioxide/polypyrrole composite microspheres is 0.5-5 mg/mL; the added polyvinylpyrrolidone is 20-80 mg; and/or 0.5-3 mL of chloroauric acid solution is added, the molar concentration of the chloroauric acid solution is 0.02-0.05 mol/L, and the stirring time after the chloroauric acid solution is added is 3-5 hours; and/or 5-9 mL of the added sodium borohydride solution, wherein the molar concentration of the added sodium borohydride solution is 0.02-0.1 mol/L, and the stirring time after the sodium borohydride solution is added is 3-5 hours; and/or taking 30mL of the dispersion, adding 10-30 mL of sodium hydroxide solution, wherein the molar concentration of the sodium hydroxide solution is 0.5-2 mol/L, the oscillation treatment time is 5-10 minutes, and the standing time is 4-10 hours; and/or the speed of centrifugal treatment is 8000 rpm, and the time length of centrifugal treatment is 5 min; and/or the drying temperature is 40-60 ℃.
The invention also provides application of the polypyrrole/gold composite hollow microsphere structural material, and the polypyrrole/gold composite hollow microsphere structural material prepared by the preparation method is applied to a photothermal treatment technology as a photothermal conversion material.
After the technical scheme is adopted, the monodisperse silicon dioxide microspheres are modified by polyvinylpyrrolidone, then the polypyrrole is coated on the surfaces of the monodisperse silicon dioxide microspheres to obtain silicon dioxide/polypyrrole composite microspheres, the polypyrrole in the silicon dioxide/polypyrrole composite microspheres is modified by the polyvinylpyrrolidone, gold shells are coated on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then the silicon dioxide in the silicon dioxide/polypyrrole composite microspheres coated with the gold shells is ablated to obtain the polypyrrole/gold composite hollow microsphere structural material. The polypyrrole/gold composite hollow microsphere structural material prepared by the method has good biocompatibility and biological metabolism, good imaging function, good photo-thermal stability and high photo-thermal conversion efficiency, the hollow structure enables the polypyrrole/gold composite hollow microsphere structural material to have drug loading capacity, and photo-thermal conversion experiments show that the using power density is 0.5W/cm2The 980nm near-infrared light exciter irradiates the dispersion liquid of the polypyrrole/gold composite hollow microsphere structural material with the mass volume concentration of 0.15mg/mL, the temperature of the solution rises to 50.1 ℃ from 25.0 ℃ after 10 minutes, and the preparation method is simple and easy to operate and has high preparation efficiency.
Drawings
FIG. 1 is a particle size distribution diagram of silica/polypyrrole microspheres;
FIG. 2 is a graph showing the particle size distribution of silica/polypyrrole/gold microspheres;
FIG. 3 is a particle size distribution diagram of polypyrrole/gold hollow microspheres;
FIG. 4 is a graph showing UV-VIS absorption spectra of silica/polypyrrole and silica/polypyrrole/gold microsphere dispersion solutions;
FIG. 5 is a graph showing the temperature change of various samples after 980nm NIR irradiation.
Detailed Description
In order that the present invention may be more readily and clearly understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings.
Example one
A preparation method of a polypyrrole/gold composite hollow microsphere structure material comprises the following steps:
s1: modifying the monodisperse silicon dioxide microspheres by polyvinylpyrrolidone; to improve the hydrophilicity and biocompatibility of the monodisperse silica microspheres;
s2: wrapping polypyrrole on the surface of the modified monodisperse silica microsphere to obtain a silica/polypyrrole composite microsphere;
s3: and modifying the polypyrrole in the silicon dioxide/polypyrrole composite microspheres by polyvinylpyrrolidone to prevent the polypyrrole nanoparticle structure from collapsing, coating a gold shell on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then melting the silicon dioxide in the silicon dioxide/polypyrrole composite microspheres coated with the gold shell to obtain the polypyrrole/gold composite hollow microsphere structure material.
In step S1, the monodisperse silica microspheres may be prepared by:
mixing water, ammonia water and absolute ethyl alcohol in a proper proportion and stirring;
adding a proper amount of tetraethoxysilane and stirring;
and centrifugally separating, cleaning and drying to obtain the monodisperse silicon dioxide microspheres.
Specifically, the water, the ammonia water and the absolute ethyl alcohol can be 1-3 mL, 3-10 mL and 50-100 mL respectively, the solution temperature can be 25-60 ℃, the stirring mode is magnetic stirring, the stirring time can be 20-60 minutes, and the stirring speed can be 100-400 revolutions per minute; the amount of added tetraethoxysilane can be 1-5 mL, the stirring time after adding tetraethoxysilane can be 8-16 hours, in the embodiment, 2mL, 6mL and 75mL of water, ammonia water and absolute ethyl alcohol are respectively taken, the solution temperature is 40 ℃, the stirring time is 40 minutes, the stirring speed is 250 revolutions per minute, the amount of added tetraethoxysilane is 3mL, the stirring is carried out for 12 hours after adding tetraethoxysilane, and the cleaning time is 3 times.
In step S1, the step of modifying the monodisperse silica microspheres with polyvinylpyrrolidone may be:
taking a proper amount of monodisperse silicon dioxide microspheres, and ultrasonically dispersing the monodisperse silicon dioxide microspheres into absolute ethyl alcohol;
adding a proper amount of polyvinylpyrrolidone, performing ultrasonic treatment, and stirring;
and (4) centrifugally separating, then washing and drying to obtain the modified monodisperse silica microspheres.
Specifically, the monodispersed silica microspheres can be 0.05-0.2 g, and the absolute ethyl alcohol can be 20 mL; the added polyvinylpyrrolidone can be 0.1-2 g, the ultrasonic treatment time after the polyvinylpyrrolidone is added can be 10-30 minutes, the stirring time can be 12-24 hours, and the solution temperature can be 30-50 ℃. In this example, the monodisperse silica microspheres were 0.1g, the polyvinylpyrrolidone was added in an amount of 1g, the duration of the ultrasonic treatment after the addition of the polyvinylpyrrolidone was 20 minutes, the stirring duration was 18 hours, the solution temperature was 40 ℃, and the washing was carried out three times with absolute ethanol.
In step S2, the step of coating polypyrrole on the surface of the monodisperse silica microsphere may be:
placing the monodisperse silicon dioxide microspheres modified by polyvinylpyrrolidone into a proper amount of absolute ethyl alcohol and carrying out ultrasonic treatment;
adding a proper amount of pyrrole and then carrying out ultrasonic treatment;
adding a proper amount of ammonium persulfate solution and stirring;
and (4) carrying out centrifugal separation, cleaning and drying to obtain the silicon dioxide/polypyrrole composite microspheres.
Specifically, the monodisperse silica microspheres can be 0.05-0.2 g, the absolute ethyl alcohol can be 150mL, and the ultrasonic treatment time can be 10-30 minutes; the volume of the added pyrrole is 0.02-0.2 mL, and the duration of ultrasonic treatment after the pyrrole is added can be 5-10 minutes; the added ammonium persulfate solution can be 2-10 mL, the mass volume concentration of the ammonium persulfate solution can be 0.06g/mL, the stirring time after the ammonium persulfate solution is added can be 8-24 hours, the temperature of the solution can be 15-30 ℃, absolute ethyl alcohol and water are used for cleaning for multiple times during cleaning, then the solution is transferred to a forced air drying oven for drying, and the particle size of the monodisperse silicon dioxide microspheres can be about 400 nm. In this example, the monodisperse silica microspheres are 0.1g, the sonication time is 20 minutes, the added pyrrole is 0.1mL, and the sonication time after the addition of pyrrole is 7 minutes; 5mL of ammonium persulfate solution was added, and the time period for stirring after the addition of the ammonium persulfate solution was 18 hours, and the temperature of the solution was 22 ℃.
The specific steps of step S3 may be:
ultrasonically dispersing a proper amount of silicon dioxide/polypyrrole composite microspheres and a proper amount of polyvinylpyrrolidone into a proper amount of deionized water;
adding a proper amount of chloroauric acid solution and stirring;
adding a proper amount of freshly prepared sodium borohydride solution and stirring to obtain a dispersion liquid;
taking a proper amount of the dispersion, adding a proper amount of sodium hydroxide solution, oscillating, and standing;
and (4) drying after centrifugal separation to obtain the polypyrrole/gold composite hollow microsphere structural material.
Specifically, the silicon dioxide/polypyrrole composite microspheres are ultrasonically dispersed in 50mL of deionized water, and the mass volume concentration of the silicon dioxide/polypyrrole composite microspheres in the obtained solution can be 0.5-5 mg/mL; the added polyvinylpyrrolidone can be 20-80 mg; the added chloroauric acid solution can be 0.5-3 mL, the molar concentration can be 0.02-0.05 mol/L, and the stirring time after the chloroauric acid solution is added can be 3-5 hours; the added sodium borohydride solution can be 5-9 mL, the molar concentration can be 0.02-0.1 mol/L, and the stirring time after the sodium borohydride solution is added can be 3-5 hours; taking 30mL of the dispersion, adding 10-30 mL of sodium hydroxide solution, wherein the molar concentration of the sodium hydroxide solution can be 0.5-2 mol/L, the duration of oscillation treatment can be 5-10 minutes, the duration of standing can be 4-10 hours, the speed of centrifugal treatment can be 8000 revolutions per minute, the duration of centrifugal treatment can be 5min, and the drying temperature can be 40-60 ℃. In this embodiment, the silica/polypyrrole composite microspheres are ultrasonically dispersed in 50mL of deionized water, and the mass volume concentration of the silica/polypyrrole composite microspheres in the obtained solution is 2.5 mg/mL; the amount of polyvinylpyrrolidone added was 50 mg; adding 1.5mL of chloroauric acid solution with the molar concentration of 0.03mol/L, adding the chloroauric acid solution, and stirring for 4 hours; adding 7.5mL of sodium borohydride solution with the molar concentration of 0.06 mol/L, and stirring for 4 hours after adding the sodium borohydride solution; taking 30mL of the dispersion, adding 20mL of sodium hydroxide solution with the molar concentration of 1mol/L, carrying out oscillation treatment for 7 minutes, standing for 6 hours, wherein the speed of centrifugal treatment is 8000 revolutions per minute, the time duration of centrifugal treatment is 5 minutes, and the drying temperature is 50 ℃.
Example two
A preparation method of a polypyrrole/gold composite hollow microsphere structure material comprises the following steps:
s1: modifying the monodisperse silicon dioxide microspheres by polyvinylpyrrolidone; to improve the hydrophilicity and biocompatibility of the monodisperse silica microspheres;
s2: wrapping polypyrrole on the surface of the modified monodisperse silica microsphere to obtain a silica/polypyrrole composite microsphere;
s3: and modifying the polypyrrole in the silicon dioxide/polypyrrole composite microspheres by polyvinylpyrrolidone to prevent the polypyrrole nanoparticle structure from collapsing, coating a gold shell on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then melting the silicon dioxide in the silicon dioxide/polypyrrole composite microspheres coated with the gold shell to obtain the polypyrrole/gold composite hollow microsphere structure material.
In step S1, the monodisperse silica microspheres may be prepared by:
mixing water, ammonia water and absolute ethyl alcohol in a proper proportion and stirring;
adding a proper amount of tetraethoxysilane and stirring;
and centrifugally separating, cleaning and drying to obtain the monodisperse silicon dioxide microspheres.
Specifically, the water, the ammonia water and the absolute ethyl alcohol can be 1-3 mL, 3-10 mL and 50-100 mL respectively, the solution temperature can be 25-60 ℃, the stirring mode is magnetic stirring, the stirring time can be 20-60 minutes, and the stirring speed can be 100-400 revolutions per minute; the amount of added tetraethoxysilane can be 1-5 mL, the stirring time after adding tetraethoxysilane can be 8-16 hours, in the embodiment, 1mL, 3mL and 50mL of water, ammonia water and absolute ethyl alcohol are respectively taken, the solution temperature is 25 ℃, the stirring time is 20 minutes, the stirring speed is 100 revolutions per minute, the amount of added tetraethoxysilane is 1mL, the stirring is carried out for 8 hours after adding tetraethoxysilane, and the cleaning frequency is 3 times.
In step S1, the step of modifying the monodisperse silica microspheres with polyvinylpyrrolidone may be:
taking a proper amount of monodisperse silicon dioxide microspheres, and ultrasonically dispersing the monodisperse silicon dioxide microspheres into absolute ethyl alcohol;
adding a proper amount of polyvinylpyrrolidone, performing ultrasonic treatment, and stirring;
and (4) centrifugally separating, then washing and drying to obtain the modified monodisperse silica microspheres.
Specifically, the monodispersed silica microspheres can be 0.05-0.2 g, and the absolute ethyl alcohol can be 20 mL; the added polyvinylpyrrolidone can be 0.1-2 g, the ultrasonic treatment time after the polyvinylpyrrolidone is added can be 10-30 minutes, the stirring time can be 12-24 hours, and the solution temperature can be 30-50 ℃. In this example, the monodisperse silica microspheres were 0.05g, the polyvinylpyrrolidone was 0.2g, the duration of the ultrasonic treatment after the polyvinylpyrrolidone was added was 10 minutes, the stirring duration was 12 hours, the solution temperature was 30 ℃, and the washing was carried out three times with absolute ethanol.
In step S2, the step of coating polypyrrole on the surface of the monodisperse silica microsphere may be:
placing the monodisperse silicon dioxide microspheres modified by polyvinylpyrrolidone into a proper amount of absolute ethyl alcohol and carrying out ultrasonic treatment;
adding a proper amount of pyrrole and then carrying out ultrasonic treatment;
adding a proper amount of ammonium persulfate solution and stirring;
and (4) carrying out centrifugal separation, cleaning and drying to obtain the silicon dioxide/polypyrrole composite microspheres.
Specifically, the monodisperse silica microspheres can be 0.05-0.2 g, the absolute ethyl alcohol can be 150mL, and the ultrasonic treatment time can be 10-30 minutes; the volume of the added pyrrole is 0.02-0.2 mL, and the duration of ultrasonic treatment after the pyrrole is added can be 5-10 minutes; the added ammonium persulfate solution can be 2-10 mL, the mass volume concentration of the ammonium persulfate solution can be 0.06g/mL, the stirring time after the ammonium persulfate solution is added can be 8-24 hours, the temperature of the solution can be 15-30 ℃, absolute ethyl alcohol and water are used for cleaning for multiple times during cleaning, then the solution is transferred to a forced air drying oven for drying, and the particle size of the monodisperse silicon dioxide microspheres can be about 400 nm. In this embodiment, the monodisperse silica microspheres are 0.05g, the sonication time is 10 minutes, the added pyrrole is 0.02mL, and the sonication time after the addition of the pyrrole is 5 minutes; the amount of the ammonium persulfate solution added was 2mL, the stirring time after the ammonium persulfate solution was added was 8 hours, and the temperature of the solution was 15 ℃.
The specific steps of step S3 may be:
ultrasonically dispersing a proper amount of silicon dioxide/polypyrrole composite microspheres and a proper amount of polyvinylpyrrolidone into a proper amount of deionized water;
adding a proper amount of chloroauric acid solution and stirring;
adding a proper amount of freshly prepared sodium borohydride solution and stirring to obtain a dispersion liquid;
taking a proper amount of the dispersion, adding a proper amount of sodium hydroxide solution, oscillating, and standing;
and (4) drying after centrifugal separation to obtain the polypyrrole/gold composite hollow microsphere structural material.
Specifically, the silicon dioxide/polypyrrole composite microspheres are ultrasonically dispersed in 50mL of deionized water, and the mass volume concentration of the silicon dioxide/polypyrrole composite microspheres in the obtained solution can be 0.5-5 mg/mL; the added polyvinylpyrrolidone can be 20-80 mg; the added chloroauric acid solution can be 0.5-3 mL, the molar concentration can be 0.02-0.05 mol/L, and the stirring time after the chloroauric acid solution is added can be 3-5 hours; the added sodium borohydride solution can be 5-9 mL, the molar concentration can be 0.02-0.1 mol/L, and the stirring time after the sodium borohydride solution is added can be 3-5 hours; taking 30mL of the dispersion, adding 10-30 mL of sodium hydroxide solution, wherein the molar concentration of the sodium hydroxide solution can be 0.5-2 mol/L, the duration of oscillation treatment can be 5-10 minutes, the duration of standing can be 4-10 hours, the speed of centrifugal treatment can be 8000 revolutions per minute, the duration of centrifugal treatment can be 5min, and the drying temperature can be 40-60 ℃. In this embodiment, the silica/polypyrrole composite microspheres are ultrasonically dispersed in 50mL of deionized water, and the mass-volume concentration of the silica/polypyrrole composite microspheres in the obtained solution is 0.5 mg/mL; polyvinylpyrrolidone was added in an amount of 20 mg; adding 0.5mL of chloroauric acid solution with the molar concentration of 0.02mol/L, adding the chloroauric acid solution, and stirring for 3 hours; adding 5mL of sodium borohydride solution with the molar concentration of 0.02mol/L, and stirring for 3 hours after adding the sodium borohydride solution; taking 30mL of the dispersion, adding 10mL of sodium hydroxide solution with the molar concentration of 0.5 mol/L, carrying out oscillation treatment for 5 minutes, standing for 4 hours, wherein the speed of centrifugal treatment is 8000 revolutions per minute, the time of centrifugal treatment is 5 minutes, and the drying temperature is 40 ℃.
EXAMPLE III
A preparation method of a polypyrrole/gold composite hollow microsphere structure material comprises the following steps:
s1: modifying the monodisperse silicon dioxide microspheres by polyvinylpyrrolidone; to improve the hydrophilicity and biocompatibility of the monodisperse silica microspheres;
s2: wrapping polypyrrole on the surface of the modified monodisperse silica microsphere to obtain a silica/polypyrrole composite microsphere;
s3: and modifying the polypyrrole in the silicon dioxide/polypyrrole composite microspheres by polyvinylpyrrolidone to prevent the polypyrrole nanoparticle structure from collapsing, coating a gold shell on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then melting the silicon dioxide in the silicon dioxide/polypyrrole composite microspheres coated with the gold shell to obtain the polypyrrole/gold composite hollow microsphere structure material.
In step S1, the monodisperse silica microspheres may be prepared by:
mixing water, ammonia water and absolute ethyl alcohol in a proper proportion and stirring;
adding a proper amount of tetraethoxysilane and stirring;
and centrifugally separating, cleaning and drying to obtain the monodisperse silicon dioxide microspheres.
Specifically, the water, the ammonia water and the absolute ethyl alcohol can be 1-3 mL, 3-10 mL and 50-100 mL respectively, the solution temperature can be 25-60 ℃, the stirring mode is magnetic stirring, the stirring time can be 20-60 minutes, and the stirring speed can be 100-400 revolutions per minute; the amount of added tetraethoxysilane can be 1-5 mL, the stirring time after adding tetraethoxysilane can be 8-16 hours, in the embodiment, 3mL, 10mL and 100mL of water, ammonia water and absolute ethyl alcohol are respectively taken, the solution temperature is 60 ℃, the stirring time is 60 minutes, the stirring speed is 400 revolutions per minute, the amount of added tetraethoxysilane is 5mL, the stirring time is 16 hours after adding tetraethoxysilane, and the cleaning time is 3 times.
In step S1, the step of modifying the monodisperse silica microspheres with polyvinylpyrrolidone may be:
taking a proper amount of monodisperse silicon dioxide microspheres, and ultrasonically dispersing the monodisperse silicon dioxide microspheres into absolute ethyl alcohol;
adding a proper amount of polyvinylpyrrolidone, performing ultrasonic treatment, and stirring;
and (4) centrifugally separating, then washing and drying to obtain the modified monodisperse silica microspheres.
Specifically, the monodispersed silica microspheres can be 0.05-0.2 g, and the absolute ethyl alcohol can be 20 mL; the added polyvinylpyrrolidone can be 0.1-2 g, the ultrasonic treatment time after the polyvinylpyrrolidone is added can be 10-30 minutes, the stirring time can be 12-24 hours, and the solution temperature can be 30-50 ℃. In this example, the monodisperse silica microspheres were 0.2g, the polyvinylpyrrolidone was 2g, the duration of the ultrasonic treatment after the polyvinylpyrrolidone was added was 30 minutes, the stirring duration was 24 hours, the solution temperature was 50 ℃, and the washing was carried out three times with absolute ethanol.
In step S2, the step of coating polypyrrole on the surface of the monodisperse silica microsphere may be:
placing the monodisperse silicon dioxide microspheres modified by polyvinylpyrrolidone into a proper amount of absolute ethyl alcohol and carrying out ultrasonic treatment;
adding a proper amount of pyrrole and then carrying out ultrasonic treatment;
adding a proper amount of ammonium persulfate solution and stirring;
and (4) carrying out centrifugal separation, cleaning and drying to obtain the silicon dioxide/polypyrrole composite microspheres.
Specifically, the monodisperse silica microspheres can be 0.05-0.2 g, the absolute ethyl alcohol can be 150mL, and the ultrasonic treatment time can be 10-30 minutes; the volume of the added pyrrole is 0.02-0.2 mL, and the duration of ultrasonic treatment after the pyrrole is added can be 5-10 minutes; the added ammonium persulfate solution can be 2-10 mL, the mass volume concentration of the ammonium persulfate solution can be 0.06g/mL, the stirring time after the ammonium persulfate solution is added can be 8-24 hours, the temperature of the solution can be 15-30 ℃, absolute ethyl alcohol and water are used for cleaning for multiple times during cleaning, then the solution is transferred to a forced air drying oven for drying, and the particle size of the monodisperse silicon dioxide microspheres can be about 400 nm. In this embodiment, the monodisperse silica microspheres are 0.2g, the sonication time is 30 minutes, the added pyrrole amount is 0.2mL, and the sonication time after the addition of pyrrole is 10 minutes; the amount of the ammonium persulfate solution added was 10mL, the stirring time after the addition of the ammonium persulfate solution was 24 hours, and the temperature of the solution was 30 ℃.
The specific steps of step S3 may be:
ultrasonically dispersing a proper amount of silicon dioxide/polypyrrole composite microspheres and a proper amount of polyvinylpyrrolidone into a proper amount of deionized water;
adding a proper amount of chloroauric acid solution and stirring;
adding a proper amount of freshly prepared sodium borohydride solution and stirring to obtain a dispersion liquid;
taking a proper amount of the dispersion, adding a proper amount of sodium hydroxide solution, oscillating, and standing;
and (4) drying after centrifugal separation to obtain the polypyrrole/gold composite hollow microsphere structural material.
Specifically, the silicon dioxide/polypyrrole composite microspheres are ultrasonically dispersed in 50mL of deionized water, and the mass volume concentration of the silicon dioxide/polypyrrole composite microspheres in the obtained solution can be 0.5-5 mg/mL; the added polyvinylpyrrolidone can be 20-80 mg; the added chloroauric acid solution can be 0.5-3 mL, the molar concentration can be 0.02-0.05 mol/L, and the stirring time after the chloroauric acid solution is added can be 3-5 hours; the added sodium borohydride solution can be 5-9 mL, the molar concentration can be 0.02-0.1 mol/L, and the stirring time after the sodium borohydride solution is added can be 3-5 hours; taking 30mL of the dispersion, adding 10-30 mL of sodium hydroxide solution, wherein the molar concentration of the sodium hydroxide solution can be 0.5-2 mol/L, the duration of oscillation treatment can be 5-10 minutes, the duration of standing can be 4-10 hours, the speed of centrifugal treatment can be 8000 revolutions per minute, the duration of centrifugal treatment can be 5min, and the drying temperature can be 40-60 ℃. In this embodiment, the silica/polypyrrole composite microspheres are ultrasonically dispersed in 50mL of deionized water, and the mass-volume concentration of the silica/polypyrrole composite microspheres in the obtained solution is 5 mg/mL; polyvinylpyrrolidone was added in an amount of 75 mg; adding 3mL of chloroauric acid solution with the molar concentration of 0.05mol/L, and stirring for 5 hours after adding the chloroauric acid solution; adding 9mL of sodium borohydride solution with the molar concentration of 0.1mol/L, and stirring for 5 hours after adding the sodium borohydride solution; taking 30mL of the dispersion, adding 30mL of sodium hydroxide solution with the molar concentration of 2mol/L, carrying out oscillation treatment for 10 minutes, standing for 10 hours, wherein the speed of centrifugal treatment is 8000 revolutions per minute, the time duration of centrifugal treatment is 5 minutes, and the drying temperature is 60 ℃.
Example four
The polypyrrole/gold composite hollow microsphere structural material prepared by the preparation method in the embodiment is used as a photothermal conversion material in photothermal treatment technology, so that light energy absorbed by near-infrared laser is converted into heat energy to kill cancer cells.
The working principle of the invention is as follows:
firstly, polyvinylpyrrolidone is used for modifying monodisperse silicon dioxide microspheres, then polypyrrole is coated on the surfaces of the monodisperse silicon dioxide microspheres to obtain silicon dioxide/polypyrrole composite microspheres, polyvinylpyrrolidone is used for modifying the polypyrrole in the silicon dioxide/polypyrrole composite microspheres, gold shells are coated on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then the gold shells are coated by ablationAnd (3) obtaining the polypyrrole/gold composite hollow microsphere structural material by using the silicon dioxide in the gold-shell silicon dioxide/polypyrrole composite microsphere. The polypyrrole/gold composite hollow microsphere structural material prepared by the method has good biocompatibility and biological metabolism, good imaging function, good photo-thermal stability and high photo-thermal conversion efficiency, the hollow structure enables the polypyrrole/gold composite hollow microsphere structural material to have drug loading capacity, and photo-thermal conversion experiments show that the using power density is 0.5W/cm2The 980nm near-infrared light exciter irradiates the dispersion liquid of the polypyrrole/gold composite hollow microsphere structural material with the mass volume concentration of 0.15mg/mL, the temperature of the solution rises to 50.1 ℃ from 25.0 ℃ after 10 minutes, and the preparation method is simple and easy to operate and has high preparation efficiency.
The above embodiments are described in further detail to solve the technical problems, technical solutions and advantages of the present invention, and it should be understood that the above embodiments are only examples of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms indicating an orientation or positional relationship are based on the orientation or positional relationship shown in the drawings only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or the orientations or positional relationships that the products of the present invention are conventionally placed in use, and are only used for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
Furthermore, the terms "horizontal", "vertical", "overhang" and the like do not imply that the components are required to be absolutely horizontal or overhang, but may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the present invention, unless otherwise expressly stated or limited, the first feature may be present on or under the second feature in direct contact with the first and second feature, or may be present in the first and second feature not in direct contact but in contact with another feature between them. Also, the first feature being above, on or above the second feature includes the first feature being directly above and obliquely above the second feature, or merely means that the first feature is at a higher level than the second feature. A first feature that underlies, and underlies a second feature includes a first feature that is directly under and obliquely under a second feature, or simply means that the first feature is at a lesser level than the second feature.
Claims (1)
1. A preparation method of a polypyrrole/gold composite hollow microsphere structure material is characterized by comprising the following steps:
s1: modifying the monodisperse silicon dioxide microspheres by polyvinylpyrrolidone;
s2: wrapping polypyrrole on the surface of the modified monodisperse silica microsphere to obtain a silica/polypyrrole composite microsphere;
s3: modifying polypyrrole in the silicon dioxide/polypyrrole composite microspheres by polyvinylpyrrolidone, coating gold shells on the surfaces of the silicon dioxide/polypyrrole composite microspheres, and then melting the silicon dioxide in the silicon dioxide/polypyrrole composite microspheres coated with the gold shells to obtain a polypyrrole/gold composite hollow microsphere structural material;
in step S1, the monodisperse silica microspheres are prepared as follows:
mixing 1-3 mL of water, 3-10 mL of ammonia water and 50-100 mL of absolute ethyl alcohol, and stirring for 20-60 minutes in a magnetic stirring mode, wherein the stirring speed is 100-400 r/min, and the solution temperature is 25-60 ℃;
adding 1-5 mL of tetraethoxysilane and stirring for 8-16 hours;
centrifugally separating, cleaning and drying to obtain the monodisperse silicon dioxide microspheres;
in step S1, the step of modifying the monodisperse silica microspheres with polyvinylpyrrolidone is as follows:
ultrasonically dispersing 0.05-0.2 g of monodisperse silicon dioxide microspheres into 20mL of absolute ethyl alcohol;
adding 0.1-2 g of polyvinylpyrrolidone, carrying out ultrasonic treatment for 10-30 minutes, and then stirring for 12-24 hours, wherein the temperature of the solution is 30-50 ℃;
centrifugally separating, then washing with absolute ethyl alcohol and drying to obtain modified monodisperse silicon dioxide microspheres;
in step S2, the step of coating polypyrrole on the surface of the monodisperse silica microsphere is as follows:
putting 0.05-0.2 g of monodisperse silicon dioxide microspheres modified by polyvinylpyrrolidone into 150mL of absolute ethyl alcohol and carrying out ultrasonic treatment for 10-30 minutes;
adding 0.02-0.2 mL of pyrrole and then carrying out ultrasonic treatment for 5-10 minutes;
adding 2-10 mL of ammonium persulfate solution with the mass volume concentration of 0.06g/mL, and stirring for 8-24 hours, wherein the temperature of the solution is 15-30 ℃;
centrifugally separating, cleaning and drying to obtain the silicon dioxide/polypyrrole composite microspheres;
the specific steps of step S3 are as follows:
ultrasonically dispersing the silicon dioxide/polypyrrole composite microspheres in 50mL of deionized water to obtain a solution with the mass volume concentration of 0.5-5 mg/mL of the silicon dioxide/polypyrrole composite microspheres, and then adding 20-80 mg of polyvinylpyrrolidone;
adding 0.5-3 mL of chloroauric acid solution with the molar concentration of 0.02-0.05 mol/L and stirring for 3-5 hours;
adding 5-9 mL of freshly prepared sodium borohydride solution with the molar concentration of 0.02-0.1 mol/L, and stirring for 3-5 hours to obtain a dispersion liquid;
taking 30mL of the dispersion, adding 10-30 mL of sodium hydroxide solution with the molar concentration of 0.5-2 mol/L, oscillating for 5-10 minutes, and standing for 4-10 hours;
and (3) carrying out centrifugal separation at the speed of 8000 revolutions per minute for 5min, and drying at the temperature of 40-60 ℃ to obtain the polypyrrole/gold composite hollow microsphere structural material.
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