CN114732906A - Barium titanate-graphene composite material and preparation method and application thereof - Google Patents
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Abstract
A barium titanate-graphene composite material and a preparation method and application thereof belong to the technical field of nano materials, solve the technical problem of accelerating healing at each stage of wound repair, and comprise the following steps: s1, preparing a graphene dispersion liquid; s2, adding a 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride solution and N-hydroxysuccinimide into the graphene dispersion liquid; s3, centrifuging to take precipitates, cleaning and dispersing the precipitates into ultrapure water; and S4, dropwise adding the aminated nano barium titanate, stirring at room temperature, cleaning and drying to obtain the barium titanate-graphene composite material. The barium titanate-graphene composite material prepared by the invention is used in medicines for resisting bacteria and promoting cell proliferation and migration, particularly in medicines for wound healing, and can improve the antibacterial effect of the composite material and accelerate the inflammatory phase; after a certain compression is given to the wound, micro-current can be generated to promote the proliferation period and the maturation period so as to accelerate the whole wound repair process.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a barium titanate-graphene composite material and a preparation method and application thereof.
Background
The wound healing (wound healing) process is a multi-stage, orderly physiological process that mainly includes three stages: inflammatory phase (inflammation), proliferative phase (proliferation) and maturation phase (proliferation). In the inflammatory phase, bacterial infection is easy to occur, and the use of a large amount of antibiotics generates super bacteria, so that the wound healing is delayed; the proliferation and migration of fibroblasts and keratinocytes play an important role during the proliferation and maturation phase, and therefore the development of drugs with antibacterial and cell proliferation and migration promoting properties is an important challenge for wound healing.
Currently, a wide variety of nanomaterials are widely used to accelerate the wound healing process. However, most of them are designed for a single stage of wound healing, such as the inflammatory or proliferative phase, and are not layered to step forward multiple stages of wound healing. Moreover, some nanomaterials, such as carbon nanotubes, silver nanoparticles, and metal oxide nanoparticles, may risk causing inflammation and even tumorigenesis, metastasis, etc. after high dose or prolonged exposure. Therefore, the development of safe, novel and programmed nano-systems respectively corresponding to each stage of wound repair to accelerate wound healing is the development trend of the current wound repair agent.
Barium titanate (BaTiO)3) The nanometer material is a thermoelectric material with good biocompatibility, excellent thermoelectric conversion performance and higher piezoelectric coefficientOr a piezoelectric material. Has been widely applied in the field of biological medicine as nano medicine material, such as sterilization, cell differentiation induction, tissue regeneration and the like. The barium titanate nano material is used as a thermoelectric material, the self-polarizability of the material is reduced under a heating state, so that electrons and holes which are asymmetrically distributed on the surface of the material are released and react with surrounding media to generate active oxygen radicals, thereby killing bacteria. As a piezoelectric material, when subjected to external mechanical stress, the piezoelectric material can generate weak current instantly, thereby inducing cell differentiation and proliferation. However, the barium titanate nano material has some disadvantages at present:
（1）、BaTiO3as a thermoelectric material, since it does not have a capability of generating heat by itself, the heat required for generating radicals can only depend on physical heating from the outside;
（2）、BaTiO3as a thermoelectric material, the thermoelectric material has weak response capability to external temperature change and longer response time;
(3) electrons and holes generated under thermal excitation are easy to recombine, thereby reducing BaTiO3Antibacterial property of the nano material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a barium titanate-graphene composite material and a preparation method and application thereof, so that a medicament can generate weak current stimulation under the irradiation of visible light to promote wound healing.
In order to realize the purpose, the invention is realized according to the following technical scheme:
a barium titanate-graphene composite material comprises the following components in parts by weight: 50 parts of barium titanate solution and 100 parts of graphene solution.
A preparation method of a barium titanate-graphene composite material comprises the following steps:
s1, weighing 50-100mg of graphene powder, adding the graphene powder into ultrapure water, and performing ultrasonic dispersion to prepare a graphene dispersion liquid;
s2, adding 1mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride solution with the concentration of 1-10mM and 1mL of N-hydroxysuccinimide with the concentration of 2-50mM into the graphene dispersion liquid prepared in the step S1, and stirring at room temperature in a dark place to prepare a mixed solution;
s3, centrifuging the mixed solution prepared in the step S2 to obtain a precipitate, repeatedly cleaning the precipitate for at least 3 times by using ultrapure water, and then dispersing the precipitate into the ultrapure water to prepare a dispersion liquid;
s4, dropwise adding 100mg of aminated nano barium titanate into the dispersion liquid prepared in the step S3, stirring at room temperature for 24 hours, repeatedly cleaning the precipitate for at least 3 times by using ultrapure water, and drying the precipitate to prepare the barium titanate-graphene composite material.
Further, in the step S1, the volume of ultrapure water is 80 mL.
Further, in the step S1, the method for preparing graphene powder includes the following steps:
s1-1, weighing 1g of graphite powder and 0.5g of sodium nitrate, adding into a reaction vessel, adding 25mL of concentrated sulfuric acid into the reaction vessel, and fully stirring until the mixture is uniformly mixed to obtain a reaction mixed solution;
s1-2, placing the reaction container in an ice bath, weighing 3g of potassium permanganate and slowly adding the potassium permanganate into the reaction mixed solution;
s1-3, moving the reaction container into an oil bath, wherein the oil bath temperature is 35 ℃, and stirring for 2 h;
s1-4, adding 46mL of ultrapure water into the reaction vessel, controlling the temperature at 98 ℃, and stirring for 15 min;
s1-5, adding 140mL of 15% hydrogen peroxide solution into the reaction container, centrifuging to obtain a precipitate after the temperature is reduced to room temperature, repeatedly washing the precipitate for 5 times by using 10% hydrochloric acid solution, dispersing the precipitate in ultrapure water, and freeze-drying to obtain graphene powder.
Further, in the step S4, the method for preparing the aminated nano barium titanate includes the following steps:
s4-1, mixing nano barium titanate and H2O2Adding the solution into a reaction vessel, wherein the weight of the nano barium titanate is 400mg, and H2O2The volume of the solution is 25mL, and ultrasonic dispersion is carried out for 20 minutes;
s4-2, placing the reaction container in an oil bath, connecting a condensation pipe above the reaction container, controlling the temperature of the oil bath at 110 ℃, stirring at a speed of 750rad/min, and carrying out condensation reflux for 4 hours;
s4-3, centrifuging the condensate prepared in the step S4-2 for 5min at 10000rpm, discarding the supernatant, washing the obtained solid particles with ultrapure water for 2 times in sequence, then washing with ethanol for 2 times, and finally dispersing the solid particles into 20mL of ethanol;
s4-4, placing the ethanol solution with the hydroxylated barium titanate prepared in the step S4-3 into a flask, then placing the flask into an oil bath, wherein the oil bath temperature is 80 ℃, a condenser pipe is connected above the flask, and 400 mu L of tri-aminopropyl triethylsilane is added into the flask, and the reaction time is 48 h;
s4-5, centrifuging the solution after the reaction in the step S4-4 at 10000rpm for 5min, discarding the supernatant, washing the solid particles with ethanol for 2 times, then washing with water for 2 times, dispersing the solid particles into 10mL of water, and freeze-drying to obtain the aminated nano barium titanate.
The barium titanate-graphene composite material prepared by the method is used for medicines for resisting bacteria and promoting cell proliferation and migration.
The barium titanate-graphene composite material prepared by the method is used in a medicine for wound healing.
Compared with the prior art, the invention has the beneficial effects that:
the barium titanate-graphene composite material, the preparation method and the application thereof provided by the invention effectively synergistically unify graphene with photo-thermal capability and barium titanate with thermoelectric capability on the same nano material:
on the one hand, the barium titanate-graphene composite material has excellent photothermal properties under visible light irradiation, and thus can generate a large amount of active oxygen radicals induced by pyroelectricity. The barium titanate-graphene composite material can well inhibit the recombination of electrons and holes, so that the capacity of the barium titanate-graphene composite material for generating active oxygen free radicals is effectively improved, the antibacterial effect of the composite material is further improved, and the inflammatory phase is accelerated. The barium titanate-graphene composite material has the sterilization rate of more than 70% to escherichia coli and staphylococcus aureus under visible light.
On the other hand, the barium titanate-graphene composite material is a piezoelectric material, can generate weak current instantly when being subjected to external mechanical stress, so as to induce cell differentiation and proliferation, and the graphene has a two-dimensional plane structure which provides a good platform for cell adhesion and proliferation and can promote cell differentiation and proliferation. Thus, upon a given compression at the wound, micro-current is generated to promote the proliferative and maturation phases and thus accelerate the overall wound repair process.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a transmission electron microscope photograph of a barium titanate-graphene composite;
FIG. 2 is a graph of the generation of reactive oxygen species from a barium titanate-graphene composite under visible light irradiation;
FIG. 3 is a bacterial growth curve diagram of the barium titanate-graphene composite material for inhibiting the growth of Escherichia coli;
FIG. 4 is a graph showing the survival rate of bacteria by the barium titanate-graphene composite material for inhibiting the growth of Escherichia coli;
FIG. 5 is a photograph showing the detection of the growth inhibition of Escherichia coli by the barium titanate-graphene composite material;
FIG. 6 is a bacterial growth curve diagram of the barium titanate-graphene composite material for inhibiting the growth of Staphylococcus aureus;
FIG. 7 is a graph showing the bacterial survival rate of the barium titanate-graphene composite material for inhibiting the growth of Staphylococcus aureus;
FIG. 8 is a photograph showing the performance of barium titanate-graphene composite material in inhibiting the growth of Staphylococcus aureus;
FIG. 9 is a graph showing the results of cell proliferation and migration experiments;
FIG. 10 is a graph showing the results of a wound repair experiment in mice;
fig. 11 is a transmission electron micrograph of the barium titanate-graphene composite prepared in example 2;
fig. 12 is a transmission electron micrograph of the barium titanate-graphene composite prepared in example 3.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
Example 1
A barium titanate-graphene composite, wherein: the composite material comprises the following raw materials in parts by weight: 50 parts of barium titanate solution and 100 parts of graphene solution.
A preparation method of a barium titanate-graphene composite material comprises the following steps:
s1, weighing 50mg of graphene powder, adding the graphene powder into ultrapure water, wherein the volume of the ultrapure water is 80mL, and performing ultrasonic dispersion to prepare graphene dispersion liquid;
the method for preparing graphene powder comprises the following steps:
s1-1, weighing 1g of graphite powder and 0.5g of sodium nitrate, adding into a reaction vessel, adding 25mL of concentrated sulfuric acid into the reaction vessel, and fully stirring until the mixture is uniformly mixed to obtain a reaction mixed solution;
s1-2, placing the reaction container in an ice bath, weighing 3g of potassium permanganate and slowly adding the potassium permanganate into the reaction mixed solution;
s1-3, moving the reaction container into an oil bath, wherein the oil bath temperature is 35 ℃, and stirring for 2 hours;
s1-4, adding 46mL of ultrapure water into the reaction vessel, controlling the temperature at 98 ℃, and stirring for 15 min;
s1-5, adding 140mL of 15% hydrogen peroxide solution into the reaction container, centrifuging to obtain a precipitate after the temperature is reduced to room temperature, repeatedly washing the precipitate for 5 times by using 10% hydrochloric acid solution, dispersing the precipitate into ultrapure water, and freeze-drying to obtain graphene powder;
s2, adding 1mL of 10mM 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride solution and 1mL of 50mM N-hydroxysuccinimide into the graphene dispersion liquid prepared in the step S1, and stirring at room temperature in a dark place to prepare a mixed solution;
s3, centrifuging the mixed solution prepared in the step S2 to obtain a precipitate, repeatedly cleaning the precipitate for 3 times by using ultrapure water, and then dispersing the precipitate into the ultrapure water to prepare a dispersion liquid;
s4, dropwise adding 100mg of aminated nano barium titanate into the dispersion liquid prepared in the step S3, stirring at room temperature for 24 hours, repeatedly cleaning the precipitate for 3 times by using ultrapure water, and drying the precipitate to prepare the barium titanate-graphene composite material, wherein the barium titanate-graphene composite material is shown in figure 1;
the method for preparing the aminated nano barium titanate comprises the following steps:
s4-1, mixing nano barium titanate and H2O2Adding the solution into a reaction vessel, wherein the weight of the nano barium titanate is 400mg, and H2O2The volume of the solution is 25mL, and ultrasonic dispersion is carried out for 20 minutes;
s4-2, placing the reaction container in an oil bath, connecting a condensation pipe above the reaction container, controlling the temperature of the oil bath at 110 ℃, stirring at a speed of 750rad/min, and carrying out condensation reflux for 4 hours;
s4-3, centrifuging the condensate prepared in the step S4-2 for 5min at 10000rpm, discarding the supernatant, washing the obtained solid particles with ultrapure water for 2 times in sequence, then washing with ethanol for 2 times, and finally dispersing the solid particles into 20mL of ethanol;
s4-4, putting the ethanol solution with the hydroxylated barium titanate prepared in the step S4-3 into a flask, then putting the flask into an oil bath, wherein the oil bath temperature is 80 ℃, a condenser pipe is connected above the flask, and 400 mu L of tri-aminopropyl triethylsilane is added into the flask, and the reaction time is 48 hours;
s4-5, centrifuging the solution after the reaction of the step S4-4 at 10000rpm for 5min, discarding the supernatant, washing the solid particles with ethanol for 2 times in sequence, then washing with water for 2 times, finally dispersing the solid particles into 10mL of water, and freeze-drying to obtain the aminated nano barium titanate.
The barium titanate-graphene composite material prepared by the method is used for medicines for resisting bacteria and promoting cell proliferation and migration.
The barium titanate-graphene composite material prepared by the method is used in a medicine for wound healing.
The following is a validation test of the barium titanate-graphene composite material.
Detecting the capability of the barium titanate-graphene composite material to generate active oxygen free radicals under the irradiation of visible light:
barium titanate nanomaterial as a thermoelectric material has a reduced self-polarizability in a heated state because electrons and holes asymmetrically distributed on the surface of the material are released and react with the surrounding medium to generate Reactive Oxygen Species (ROS), which are measured using 2 ', 7' -dichlorofluoroxanthate diacetate (DCFH-DA) (Sigma) reagent.
First, H2DCFDA was dissolved in ethanol to prepare a DCF stock solution at a concentration of 1 mg/mL. Then, 10 uL of DCF stock solution was mixed with 1384 uL of 0.01M sodium hydroxide solution. The resulting solution was incubated at room temperature for 30 minutes and 7000. mu.L of phosphate buffered saline (PBS, 10mM, pH 7.4) was added to form a 29. mu.M DCF working solution. 80 μ L of the above DCF working solution was added to a 96-well multi-well black plate (Costar, Corning, NY), and then 20 μ L of 1 mg/mL barium titanate-graphene composite nanomaterial was added to each well, followed by incubation for 2 hours. DCF fluorescence emission spectra in the range of 500-600 nm were collected using a microplate reader with an excitation wavelength of 490 nm, and the curves of the barium titanate-graphene composite material generating active oxygen radicals under visible light irradiation are shown in FIG. 2.
(II) the antibacterial property of the barium titanate-graphene composite material is used for accelerating the inflammation-stopping period:
s1 bacterial culture
1) Preparing a liquid bacteria culture solution: weighing 10g of tryptone, 5g of yeast powder and 5g of sodium chloride, adding the tryptone, the yeast powder and the sodium chloride into 1L of ultrapure water, adjusting the pH value to 7.2 by using 5mol/L sodium hydroxide solution, placing the mixture into an autoclave for sterilization, and taking the mixture out for later use;
2) preparing a solid bacteria culture solution: weighing 10g of tryptone, 5g of yeast powder, 5g of sodium chloride and 20g of agar, adding the weighed materials into 1L of ultrapure water, adjusting the pH value to 7.2 by using 5mol/L of sodium hydroxide solution, placing the materials into an autoclave for sterilization, taking out the materials at 60 ℃, pouring the materials into a culture product, and cooling the materials for later use;
3) adding antibiotics into the sterilized culture medium, wherein the final concentration is 20 mug/mL, adding frozen bacteria strains 15 mug L into 20mL of culture solution, and carrying out shake cultivation overnight at 37 ℃ with the rotation number of 150 rpm;
s2, weighing 5mg of barium titanate-graphene composite material, adding the barium titanate-graphene composite material into 1mL of bacterial culture solution, and preparing into 5mg/mL of solution;
s3, diluting the well-grown bacterial solution by different times, measuring the absorption value at 600nm, and adjusting the absorption value =0.1 for later use;
s4, antibacterial detection of the barium titanate-graphene composite material: adding 144 mu L of prepared 5mg/mL barium titanate-graphene composite material bacterial culture solution into 156 mu L of prepared bacterial culture solution to prepare 2.4mg/mL solution, diluting the solution in duplicate to obtain solutions with concentrations of 1.2 mg/mL, 0.6 mg/mL, 0.3 mg/mL and 0.15 mg/mL, adding 50 mu L of each solution into a 96-well plate, repeating the steps three times for each well, adding 100 mu L of bacterial solution with an absorption value =0.1 into each well, transferring the solution into a bacterial culture shaker after 20 minutes, culturing at 37 ℃ and 150rpm, detecting the absorption value at 600nm of bacterial growth every 1 hour, and drawing a growth curve, as shown in figure 3 (Escherichia coli) and figure 6 (Staphylococcus aureus).
And 4, performing antibacterial detection on the barium titanate-graphene composite material by adopting a coating flat plate method, and specifically comprising the following steps:
adding 160 mu L of prepared 5mg/mL barium titanate-graphene composite material bacterial culture solution into 840 mu L of bacterial solution with absorption value = 0.1; taking the bacterial solution with the absorption value of 840 muL =0.1 and 160 muL of bacterial culture solution as a comparison; putting the bacterial culture solution with or without the barium titanate-graphene composite material into a bacterial culture shaker, and culturing for 30 minutes at 37 ℃ and 150 rpm; diluting the bacterial culture solution with and without the barium titanate-graphene composite material by 10000 times respectively, adding 30 mu L of the bacterial culture solution into a solid culture medium, uniformly coating the bacterial culture solution, culturing the bacterial culture solution at 37 ℃ for 24 hours, and taking a picture as shown in fig. 5.
And (III) promoting cell differentiation and proliferation and accelerating proliferation and maturation stages by using the barium titanate-graphene composite material.
The graphene in the barium titanate-graphene composite material has certain proliferation promoting and strong migration promoting effects on vascular endothelial cells and skin fibroblasts, and as shown in fig. 9, barium titanate is used as a thermoelectric material and can generate micro-current to promote cell differentiation and proliferation after being heated. In order to simulate the microenvironment of the wound site, a Transwell system was used, in which macrophages raw264.7 were implanted in the upper chamber and fibroblasts 3T3 were implanted in the lower chamber, and scarification was performed. And adding the barium titanate-graphene composite material into the upper cavity, releasing cytokines to act on the 3T3 cells in the lower cavity, and observing the evaluation of the barium titanate-graphene composite material on the wound healing of the mouse.
Selecting a female BALB/c mouse as an animal model, cutting a 1.5 cm-long wound on the back of the mouse after anesthetizing the mouse as shown in figure 10, dripping a barium titanate-graphene composite material, and pinching with fingers to generate micro-current under certain pressure. Wound size was measured daily and wound healing curves were plotted. After 14 days, the mice were sacrificed, and the wound tissues were stained with hematoxylin-eosin to study the pathological changes of the wound, and it was found that epithelial keratinocytes gradually moved to the wound and the scar at the wound became gradually smaller, and the wound treated with the barium titanate-graphene composite was almost completely healed. Hydroxyproline is the main component of collagen and plays a major role in the wound healing process.
Example 2
A barium titanate-graphene composite, wherein: the composite material comprises the following raw materials in parts by weight: 50 parts of barium titanate solution and 150 parts of graphene solution.
A preparation method of a barium titanate-graphene composite material comprises the following steps:
s1, weighing 50mg of graphene powder, adding the graphene powder into ultrapure water, wherein the volume of the ultrapure water is 80mL, and performing ultrasonic dispersion to prepare graphene dispersion liquid;
the method for preparing graphene powder comprises the following steps:
s1-1, weighing 1g of graphite powder and 0.5g of sodium nitrate, adding into a reaction vessel, adding 25mL of concentrated sulfuric acid into the reaction vessel, and fully stirring until the mixture is uniformly mixed to obtain a reaction mixed solution;
s1-2, placing the reaction container in an ice bath, weighing 3g of potassium permanganate and slowly adding the potassium permanganate into the reaction mixed solution;
s1-3, moving the reaction container into an oil bath, wherein the oil bath temperature is 35 ℃, and stirring for 2 hours;
s1-4, adding 46mL of ultrapure water into the reaction vessel, controlling the temperature at 98 ℃, and stirring for 15 min;
s1-5, adding 140mL of 15% hydrogen peroxide solution into the reaction container, centrifuging to obtain a precipitate after the temperature is reduced to room temperature, repeatedly washing the precipitate for 5 times by using 10% hydrochloric acid solution, dispersing the precipitate in ultrapure water, and freeze-drying to obtain graphene powder;
s2, adding 1mL of 10mM 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride solution and 1mL of 50mM N-hydroxysuccinimide into the graphene dispersion liquid prepared in the step S1, and stirring at room temperature in a dark place to prepare a mixed solution;
s3, centrifuging the mixed solution prepared in the step S2 to obtain a precipitate, repeatedly cleaning the precipitate for 3 times by using ultrapure water, and then dispersing the precipitate into the ultrapure water to prepare a dispersion liquid;
s4, dropwise adding 150mg of aminated nano barium titanate into the dispersion liquid prepared in the step S3, stirring at room temperature for 24 hours, repeatedly cleaning the precipitate for 3 times by using ultrapure water, and drying the precipitate to prepare the barium titanate-graphene composite material, wherein the barium titanate-graphene composite material is shown in figure 1;
the method for preparing the aminated nano barium titanate comprises the following steps:
s4-1, mixing nano barium titanate and H2O2Adding the solution into a reaction vessel, wherein the weight of the nano barium titanate is 400mg, and H2O2The volume of the solution is 25mL, and ultrasonic dispersion is carried out for 20 minutes;
s4-2, placing the reaction container in an oil bath, connecting a condensation pipe above the reaction container, controlling the temperature of the oil bath at 110 ℃, stirring at a speed of 750rad/min, and carrying out condensation reflux for 4 hours;
s4-3, centrifuging the condensate prepared in the step S4-2 for 5min at 10000rpm, discarding the supernatant, washing the obtained solid particles with ultrapure water for 2 times in sequence, then washing with ethanol for 2 times, and finally dispersing the solid particles into 20mL of ethanol;
s4-4, putting the ethanol solution with the hydroxylated barium titanate prepared in the step S4-3 into a flask, then putting the flask into an oil bath, wherein the oil bath temperature is 80 ℃, a condenser pipe is connected above the flask, and 400 mu L of tri-aminopropyl triethylsilane is added into the flask, and the reaction time is 48 hours;
s4-5, centrifuging the solution after the reaction in the step S4-4 at 10000rpm for 5min, discarding the supernatant, washing the solid particles with ethanol for 2 times, then washing with water for 2 times, dispersing the solid particles into 10mL of water, and freeze-drying to obtain the aminated nano barium titanate.
Fig. 11 is a transmission electron microscope photograph of the barium titanate-graphene composite prepared in example 2, and it is observed that the barium titanate-graphene composite is successfully prepared and has a uniform structure.
The barium titanate-graphene composite material prepared in this example has the ability of generating active oxygen radicals under visible light irradiation, accelerating the inflammation arrest phase, promoting cell differentiation and proliferation, and accelerating the proliferation phase and the maturation phase, which are prepared in example 1, due to excellent antibacterial properties.
Example 3
A barium titanate-graphene composite, wherein: the composite material comprises the following raw materials in parts by weight: 100 parts of barium titanate solution and 100 parts of graphene solution.
A preparation method of a barium titanate-graphene composite material comprises the following steps:
s1, weighing 25mg of graphene powder, adding the graphene powder into ultrapure water, wherein the volume of the ultrapure water is 80mL, and performing ultrasonic dispersion to prepare a graphene dispersion liquid;
the method for preparing graphene powder comprises the following steps:
s1-1, weighing 1g of graphite powder and 0.5g of sodium nitrate, adding into a reaction vessel, adding 25mL of concentrated sulfuric acid into the reaction vessel, and fully stirring until the mixture is uniformly mixed to obtain a reaction mixed solution;
s1-2, placing the reaction vessel in an ice bath, weighing 3g of potassium permanganate and slowly adding the potassium permanganate into the reaction mixed solution;
s1-3, moving the reaction container into an oil bath, wherein the oil bath temperature is 35 ℃, and stirring for 2 hours;
s1-4, adding 46mL of ultrapure water into the reaction vessel, controlling the temperature at 98 ℃, and stirring for 15 min;
s1-5, adding 140mL of 15% hydrogen peroxide solution into the reaction container, centrifuging to obtain a precipitate after the temperature is reduced to room temperature, repeatedly washing the precipitate for 5 times by using 10% hydrochloric acid solution, dispersing the precipitate in ultrapure water, and freeze-drying to obtain graphene powder;
s2, adding 1mL of 10mM 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride solution and 1mL of 50mM N-hydroxysuccinimide into the graphene dispersion liquid prepared in the step S1, and stirring at room temperature in a dark place to prepare a mixed solution;
s3, centrifuging the mixed solution prepared in the step S2 to obtain a precipitate, repeatedly cleaning the precipitate for 3 times by using ultrapure water, and then dispersing the precipitate into the ultrapure water to prepare a dispersion liquid;
s4, dropwise adding 100mg of aminated nano barium titanate into the dispersion liquid prepared in the step S3, stirring at room temperature for 24 hours, repeatedly cleaning the precipitate for 3 times by using ultrapure water, and drying the precipitate to prepare the barium titanate-graphene composite material, wherein the barium titanate-graphene composite material is shown in figure 1;
the method for preparing the aminated nano barium titanate comprises the following steps:
s4-1, mixing nano barium titanate and H2O2Adding the solution into a reaction vessel, wherein the weight of the nano barium titanate is 400mg, and H2O2The volume of the solution is 25mL, and ultrasonic dispersion is carried out for 20 minutes;
s4-2, placing the reaction container in an oil bath, connecting a condensation pipe above the reaction container, controlling the temperature of the oil bath at 110 ℃, stirring at a speed of 750rad/min, and carrying out condensation reflux for 4 hours;
s4-3, centrifuging the condensate prepared in the step S4-2 for 5min at 10000rpm, discarding the supernatant, washing the obtained solid particles with ultrapure water for 2 times in sequence, then washing with ethanol for 2 times, and finally dispersing the solid particles into 20mL of ethanol;
s4-4, putting the ethanol solution with the hydroxylated barium titanate prepared in the step S4-3 into a flask, then putting the flask into an oil bath, wherein the oil bath temperature is 80 ℃, a condenser pipe is connected above the flask, and 400 mu L of tri-aminopropyl triethylsilane is added into the flask, and the reaction time is 48 hours;
s4-5, centrifuging the solution after the reaction in the step S4-4 at 10000rpm for 5min, discarding the supernatant, washing the solid particles with ethanol for 2 times, then washing with water for 2 times, dispersing the solid particles into 10mL of water, and freeze-drying to obtain the aminated nano barium titanate.
Fig. 12 is a transmission electron microscope photograph of the barium titanate-graphene composite prepared in example 3, and it is observed that the barium titanate-graphene composite is successfully prepared and has a uniform structure.
The barium titanate-graphene composite material prepared in this example has the ability of generating active oxygen radicals under visible light irradiation, accelerating the inflammation arrest phase, promoting cell differentiation and proliferation, and accelerating the proliferation phase and the maturation phase, which are prepared in example 1, due to excellent antibacterial properties.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. A barium titanate-graphene composite material is characterized in that: the composite material comprises the following components in parts by weight: 50 parts of barium titanate solution and 100 parts of graphene solution.
2. A method for preparing the barium titanate-graphene composite material according to claim 1, comprising the steps of:
s1, weighing 50-100mg of graphene powder, adding the graphene powder into ultrapure water, and performing ultrasonic dispersion to prepare a graphene dispersion liquid;
s2, adding 1mL of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride solution with the concentration of 1-10mM and 1mL of N-hydroxysuccinimide with the concentration of 2-50mM into the graphene dispersion liquid prepared in the step S1, and stirring at room temperature in a dark place to prepare a mixed solution;
s3, centrifuging the mixed solution prepared in the step S2 to obtain a precipitate, repeatedly cleaning the precipitate for at least 3 times by using ultrapure water, and then dispersing the precipitate into the ultrapure water to prepare a dispersion liquid;
s4, dropwise adding 100mg of aminated nano barium titanate into the dispersion liquid prepared in the step S3, stirring at room temperature for 24 hours, repeatedly cleaning the precipitate for at least 3 times by using ultrapure water, and drying the precipitate to prepare the barium titanate-graphene composite material.
3. The method for preparing a barium titanate-graphene composite material according to claim 2, wherein: in step S1, the volume of ultrapure water is 80 mL.
4. The preparation method of the barium titanate-graphene composite material according to claim 2, characterized in that: in step S1, the method for preparing graphene powder includes the following steps:
s1-1, weighing 1g of graphite powder and 0.5g of sodium nitrate, adding into a reaction vessel, adding 25mL of concentrated sulfuric acid into the reaction vessel, and fully stirring until the mixture is uniformly mixed to obtain a reaction mixed solution;
s1-2, placing the reaction container in an ice bath, weighing 3g of potassium permanganate and slowly adding the potassium permanganate into the reaction mixed solution;
s1-3, moving the reaction container into an oil bath, wherein the oil bath temperature is 35 ℃, and stirring for 2 h;
s1-4, adding 46mL of ultrapure water into the reaction vessel, controlling the temperature at 98 ℃, and stirring for 15 min;
s1-5, adding 140mL of 15% hydrogen peroxide solution into the reaction container, centrifuging to obtain a precipitate after the temperature is reduced to room temperature, repeatedly washing the precipitate for 5 times by using 10% hydrochloric acid solution, dispersing the precipitate in ultrapure water, and freeze-drying to obtain graphene powder.
5. The preparation method of the barium titanate-graphene composite material according to claim 2, characterized in that: in the step S4, the method for preparing aminated nano barium titanate includes the following steps:
s4-1, adding nano barium titanate and a H2O2 solution into a reaction container, wherein the weight of the nano barium titanate is 400mg, the volume of the H2O2 solution is 25mL, and ultrasonically dispersing for 20 minutes;
s4-2, placing the reaction container in an oil bath, connecting a condensation pipe above the reaction container, controlling the temperature of the oil bath at 110 ℃, stirring at a speed of 750rad/min, and carrying out condensation reflux for 4 hours;
s4-3, centrifuging the condensate prepared in the step S4-2 for 5min at 10000rpm, discarding the supernatant, washing the obtained solid particles with ultrapure water for 2 times in sequence, then washing with ethanol for 2 times, and finally dispersing the solid particles into 20mL of ethanol;
s4-4, putting the ethanol solution with the hydroxylated barium titanate prepared in the step S4-3 into a flask, then putting the flask into an oil bath, wherein the oil bath temperature is 80 ℃, a condenser pipe is connected above the flask, and 400 mu L of tri-aminopropyl triethylsilane is added into the flask, and the reaction time is 48 hours;
s4-5, centrifuging the solution after the reaction in the step S4-4 at 10000rpm for 5min, discarding the supernatant, washing the solid particles with ethanol for 2 times, then washing with water for 2 times, dispersing the solid particles into 10mL of water, and freeze-drying to obtain the aminated nano barium titanate.
6. Use of a barium titanate-graphene composite material prepared according to the method of claim 2, wherein: the barium titanate-graphene composite material is used in medicines for resisting bacteria and promoting cell proliferation and migration.
7. Use of a barium titanate-graphene composite material prepared according to the method of claim 2, wherein: the barium titanate-graphene composite material is used in a medicine for wound healing.
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