CN113398327A - Preparation method of MXene/bioglass microsphere composite material with high biological activity - Google Patents
Preparation method of MXene/bioglass microsphere composite material with high biological activity Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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Abstract
The invention discloses a preparation method of a MXene/bioglass microsphere composite material with high biological activity. Preparing MXene by adopting an in-situ synthesis hydrofluoric acid etching method, preparing the bioglass microsphere by combining a sol-gel method and a template method, and finally preparing the MXene/bioglass microsphere composite material by using an electrostatic self-assembly method. As the MXene surface has special surface groups including polar groups such as hydroxyl (-OH), oxygen (-O) or fluorine (-F) and can be used as active sites after being compounded with the bioglass, the precipitation amount of the hydroxyapatite can be promoted to be increased, and the MXene has high surface charge (the negative Zeta potential exceeds-40 mV) and can more quickly adsorb Ca, P and the like in body fluid and accelerate the generation of the hydroxyapatite precipitate, the MXene/bioglass microsphere composite material has high bioactivity.
Description
Technical Field
The invention belongs to the field of biological functional materials, and particularly relates to a preparation method of a MXene/bioglass microsphere composite material with high biological activity.
Background
At present, the clinical treatment of patients with bone defects generally adopts traditional autologous bone transplantation and allogeneic bone transplantation. However, due to limited source of autologous bone transplantation and insufficient donor, there is a certain risk of immunological rejection and disease infection in allogeneic bone transplantation. The bioglass has good in-vitro mineralization performance, can generate bone-like carbonate hydroxyapatite crystals on the surface of bioglass after being soaked in simulated body fluid for a period of time, and can form good chemical bonding with human bones. The osseointegration performance of bioglass is mainly because hydroxyapatite generated on the surface of the glass matrix can be effectively combined with bone tissues after the glass matrix is immersed in body fluid, can adsorb related proteins, combines collagen fibers, promotes the adhesion and differentiation of osteoprogenitor cells and the metabolism of extracellular matrix of bone cells, and promotes the communication between the collagen fibers and damaged bones by forming bonding between the collagen fibers and the damaged bones.
The bioglass is invented in 1971 by the professor Larry L Hench in the United states, and is considered to be a bone repair material superior to other crystalline inorganic nonmetal bioactive materials due to the advantages of unique inorganic amorphous structure, promotion of bone cell activity, improvement of biomineralization speed and the like.
The sol-gel method is combined with a template agent, and a substance with high surface activity is introduced to be used as a structural template to synthesize the micro-nano particles with specific morphology. The main action mechanism is as follows: hydrolyzing the inorganic precursor in the system, adsorbing the inorganic precursor and a surfactant mutually and cooperatively assembling to form a specific structure, and removing the template agent through heat treatment to obtain the bioglass with a specific morphology. The method can adjust and control the size of the microspheres to be 200-800 nm by changing the using amount of the dodecylamine, and the bioglass microspheres synthesized by the method have good monodispersity, larger specific surface area, stable shape and size and ordered mesoporous structure, and are more excellent in ion release performance, cell compatibility and the like.
However, many challenges still exist in biomedical applications, and on one hand, new functions need to be imparted to the bioglass microspheres, and on the other hand, the biological activity of the bioglass microspheres needs to be improved, so that people continuously explore the structure and components of the bioglass microspheres, and adopt various means, including compounding the bioglass microspheres with hydrogel, loading drug factors, and the like.
MXene is generally represented by Mn +1AXn, where M represents a transition metal element, A represents an 13/14 th main group element, and X is carbon or nitrogen. The two-dimensional MXene has a unique planar nano structure, and a series of excellent physicochemical properties determined by the structure give the potential for wide application in the field of biomedicine. For example, in a Near Infrared (NIR) I area and a Near Infrared (NIR) II area, two-dimensional MXene has stronger optical absorption and photothermal conversion efficiency, and is very likely to assist the development of a photothermal therapy method of tumors; the high specific surface area can effectively load chemotherapeutic drugs, suggesting the potential of being a highly effective drug carrier; MXene can generate a large amount of heat after being irradiated by a Near Infrared (NIR) I area and a Near Infrared (NIR) II area, and the sharp edge of the two-dimensional MXene is combined to break the structure of a bacterial membrane and influence the material exchange between the bacteria and the surrounding environment when contacting the bacteria, so that the MXene is endowed with unique antibacterial performance. Compared with two-dimensional materials such as graphene and the like, MXene has excellent capability in the aspects of biological medicine application such as antibacterial activity, drug delivery, photothermal therapy and the like. In addition, MXene usually has special surface groups, including polar groups such as hydroxyl (-OH), oxygen (-O) or fluorine (-F), so that the surface of MXene has better hydrophilicity and high surface charge (the negative Zeta potential exceeds-40 mV), and the surfactant-free colloid has higher stability in solution. The hydrophilicity and the negative potential of MXene can promote ion exchange between the bioglass microspheres and an aqueous solution, increase the deposition amount of hydroxyapatite and further promote the bioactivity of the bioglass microspheres. However, no report about the compounding of the bioglass microspheres and MXene is found yet.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of an MXene/bioglass microsphere composite material with high biological activity, and aims to solve the technical problems in the preparation process of the MXene/bioglass microsphere composite material. The method has the advantages of strong process controllability, simplicity, high efficiency, low cost and the like, aims to improve the biological activity of the bioglass by combining MXene/bioglass microspheres, and has great industrial prospect and medical application value.
The technical scheme of the invention is as follows:
a preparation method of MXene/bioglass microsphere composite material with high biological activity comprises the following steps:
(1) preparing MXene by adopting an in-situ synthesis hydrofluoric acid etching method: placing 20 ml of 6M HCl in a polytetrafluoroethylene beaker, adding 500 mg of LiF, and weighing 500 mg of Ti after LiF is completely dissolved3AlC2Slowly adding the powder into the solution, continuously stirring for 24 h, taking the supernatant, carrying out ultrasonic treatment for 1 h, then centrifuging for 1 h at 3500 r/min, collecting the supernatant, and carrying out freeze drying for 24 h to obtain MXene powder;
(2) the preparation method comprises the following steps of (1) preparing the bioglass microspheres by combining a sol-gel method with a template method: firstly weighing 1.1057 g of dodecylamine as a template agent, pouring the dodecylamine into 24 wt% ethanol solution, selecting tetraethyl orthosilicate, calcium nitrate tetrahydrate and triethyl phosphate as a silicon source, a calcium source and a phosphorus source, adding the tetraethyl orthosilicate, the calcium nitrate tetrahydrate and the triethyl phosphate into the solution according to the molar ratio of Si to Ca to P =60 to 30.8 to 9.2, stirring the solution for 5 hours to obtain white suspension solution, centrifuging the white suspension solution to obtain white precipitate, and calcining the white precipitate to obtain white bioglass microsphere powder;
(3) preparing MXene/bioglass microsphere composite material by adopting an electrostatic self-assembly method: adding the prepared bioglass microspheres into a poly (diallyldimethylammonium chloride) solution with the concentration of 1-5 wt%, preparing a bioglass microsphere mixed solution with the concentration of 5 mg/ml, preparing an MXene solution with the concentration of 0.5-1 mg/ml, adding the MXene solution into the mixed solution, stirring for 30 min, carrying out ultrasonic treatment for 1 h, carrying out vacuum filtration on the uniform mixed solution, and carrying out freeze drying for 12 h to obtain MXene/bioglass microsphere powder.
During the etching process of in-situ synthesis hydrofluoric acid, the temperature needs to be kept at 40 ℃, and the stirring speed is 550 rpm.
In the process of in-situ synthesis hydrofluoric acid etching, after etching is finished, deionized water is used for cleaning for multiple times, and 3500 r/min is used for centrifuging for multiple times until the pH value is more than or equal to 6.
In the process of in-situ synthesis hydrofluoric acid etching, argon atmosphere protection is required during ultrasonic treatment, the ultrasonic power is 600W, and the frequency is 40 KHz.
In the sol-gel process, the centrifugal speed of the white suspension is 7000 r/min, the time is 3 min, the precipitate is taken out after centrifugation, and the white gel is obtained by repeatedly washing three times at 7000 r/min.
In the sol-gel process, the white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Compounding MXene and bioglass microspheres according to different volume ratios, wherein the MXene solution comprises the following components: biological glass microsphere mixed solution =x：100-x (x=5~20)。
In the electrostatic self-assembly process, the ultrasonic power is 600W, and the frequency is 40 KHz.
The invention has the following remarkable advantages:
1. according to the invention, the surface of the biological glass microsphere modified by MXene and poly (diallyldimethylammonium chloride) has opposite potential, the MXene and the poly (diallyldimethylammonium chloride) are strongly combined by utilizing electrostatic action, the composite material obtained by centrifugation, cleaning and drying has uniform size, the preparation process is simple and easy, the cost is low, the preparation can be carried out on a large scale, and the preparation method has wide industrial prospect.
2. The MXene/bioglass microsphere composite material prepared by the method has special surface groups on the surface, wherein the special surface groups comprise polar groups such as hydroxyl (-OH), oxygen (-O) or fluorine (-F), the groups can be used as active sites and can promote the increase of the precipitation amount of hydroxyapatite, and the MXene has high surface charge (negative Zeta potential is more than-40 mV) and can more quickly adsorb Ca, P and other ions in body fluid and accelerate the generation of the hydroxyapatite precipitation and increase the precipitation amount of the hydroxyapatite, so the MXene/bioglass microsphere composite material has high bioactivity and has great application prospect in the field of biomedicine.
3. Compared with the graphene/biological glass microsphere composite material, MXene not only has the characteristic of large specific surface area of graphene, but also has some special polar groups on the surface, is used as an active site of a hydroxyapatite nucleus and is combined with high negative potential on the MXene surface, and the MXene/biological glass microsphere composite material is obviously superior to the graphene composite biological glass microsphere material in biological activity performance.
Drawings
FIG. 1 is a schematic flow chart of the high bioactivity MXene/bioglass microsphere composite material of the invention;
FIG. 2 is an SEM image of an MXene/bioglass microsphere composite obtained by the electrostatic self-assembly method in example 3;
FIG. 3 is an SEM image of MXene-free bioglass microspheres prepared in example 3 mineralized in simulated body fluid SBF for 7 days;
FIG. 4 is an SEM image of the graphene/bioglass microsphere composite material prepared in the comparative example mineralized in simulated body fluid SBF for 7 days
FIG. 5 is an SEM image of the MXene/bioglass microsphere composite prepared in example 3 mineralized in simulated body fluid SBF for 7 days;
FIG. 6 is a graph showing the antibacterial effect of the comparative example of the present invention cultured without a sample;
FIG. 7 is a graph showing the antibacterial effect of graphene/bioglass microspheres prepared in a comparative example of the present invention;
FIG. 8 is a graph showing the antibacterial effect of the MXene/bioglass microsphere composite material prepared in example 3 after being irradiated by 808 nm infrared light.
Detailed Description
The invention provides a preparation method of a MXene/bioglass microsphere composite material with high biological activity, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of MXene/bioglass microsphere composite material with high biological activity comprises the following steps:
(1) preparing MXene by adopting an in-situ synthesis hydrofluoric acid etching method: placing 20 ml of 6M HCl in a polytetrafluoroethylene beaker, adding 500 mg of LiF, and weighing 500 mg of Ti after LiF is completely dissolved3AlC2Slowly adding the powder into the solution, stirring for 24 hr, subjecting the supernatant to ultrasonic treatment for 1 hr, centrifuging at 3500 r/min for 1 hr, collecting supernatant, and freeze drying for 24 hr to obtain MXene (Ti)3C2) And (3) powder.
(2) The preparation method comprises the following steps of (1) preparing the bioglass microspheres by combining a sol-gel method with a template method: firstly weighing 1.1057 g of dodecylamine as a template agent, pouring the dodecylamine into 24 wt% ethanol solution, selecting tetraethyl orthosilicate, calcium nitrate tetrahydrate and triethyl phosphate as a silicon source, a calcium source and a phosphorus source, adding the tetraethyl orthosilicate, the calcium nitrate tetrahydrate and the triethyl phosphate into the solution according to the molar ratio of Si to Ca to P =60 to 30.8 to 9.2, stirring the solution for 5 hours to obtain white suspension solution, centrifuging the white suspension solution to obtain white precipitate, and finally calcining the white precipitate to obtain white bioglass microsphere powder.
(3) Preparing MXene/bioglass microsphere composite material by adopting an electrostatic self-assembly method: adding the prepared bioglass microspheres into a poly (diallyldimethylammonium chloride) solution with the concentration of 1 wt%, preparing a bioglass microsphere mixed solution with the concentration of 5 mg/ml, preparing an MXene solution with the concentration of 0.5 mg/ml, adding the MXene solution into the mixed solution, stirring for 30 min, carrying out ultrasonic treatment for 1 h, carrying out vacuum filtration on the uniform mixed solution, and carrying out freeze drying for 12 h to obtain MXene/bioglass microsphere powder.
During the etching process of in-situ synthesis hydrofluoric acid, the temperature needs to be kept at 40 ℃, and the stirring speed is 550 rpm.
In the process of in-situ synthesis hydrofluoric acid etching, after etching is completed, deionized water is used for cleaning for multiple times, and 3500 r/min is used for centrifuging for multiple times until the PH value is more than or equal to 6.
In the process of in-situ synthesis hydrofluoric acid etching, argon atmosphere protection is required during ultrasonic treatment, the ultrasonic power is 600W, and the frequency is 40 KHz.
In the sol-gel process, the centrifugal speed of the white suspension is 7000 r/min, the time is 3 min, the precipitate is taken out after centrifugation, and the white gel is obtained by repeatedly washing three times at 7000 r/min.
In the sol-gel process, the white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Mixing MXene and bioglass microspheres according to the volume ratio of the solution, wherein the ratio of the MXene solution to the bioglass microsphere is as follows: bioglass microsphere mixed solution = 5: 95, compounding.
In the electrostatic self-assembly process, the ultrasonic power is 600W, and the frequency is 40 KHz.
Example 2
A preparation method of MXene/bioglass microsphere composite material with high biological activity comprises the following steps:
(1) preparing MXene by adopting an in-situ synthesis hydrofluoric acid etching method: placing 20 ml of 6M HCl in a polytetrafluoroethylene beaker, adding 500 mg of LiF, and weighing 500 mg of Ti after LiF is completely dissolved3AlC2Slowly adding the powder into the solution, stirring for 24 hr, subjecting the supernatant to ultrasonic treatment for 1 hr, centrifuging at 3500 r/min for 1 hr, collecting supernatant, and freeze drying for 24 hr to obtain MXene (Ti)3C2) And (3) powder.
(2) The preparation method comprises the following steps of (1) preparing the bioglass microspheres by combining a sol-gel method with a template method: firstly weighing 1.1057 g of dodecylamine as a template agent, pouring the dodecylamine into 24 wt% ethanol solution, selecting tetraethyl orthosilicate, calcium nitrate tetrahydrate and triethyl phosphate as a silicon source, a calcium source and a phosphorus source, adding the tetraethyl orthosilicate, the calcium nitrate tetrahydrate and the triethyl phosphate into the solution according to the molar ratio of Si to Ca to P =60 to 30.8 to 9.2, stirring the solution for 5 hours to obtain white suspension solution, centrifuging the white suspension solution to obtain white precipitate, and finally calcining the white precipitate to obtain white bioglass microsphere powder.
(3) Preparing MXene/bioglass microsphere composite material by adopting an electrostatic self-assembly method: adding the prepared bioglass microspheres into a poly (diallyldimethylammonium chloride) solution with the concentration of 5 wt%, preparing a bioglass microsphere mixed solution with the concentration of 5 mg/ml, preparing an MXene solution with the concentration of 1 mg/ml, adding the MXene solution into the mixed solution, stirring for 30 min, carrying out ultrasonic treatment for 1 h, carrying out vacuum filtration on the uniform mixed solution, and carrying out freeze drying for 12 h to obtain MXene/bioglass microsphere powder.
During the etching process of in-situ synthesis hydrofluoric acid, the temperature needs to be kept at 40 ℃, and the stirring speed is 550 rpm.
In the process of in-situ synthesis hydrofluoric acid etching, after etching is completed, deionized water is used for cleaning for multiple times, and 3500 r/min is used for centrifuging for multiple times until the PH value is more than or equal to 6.
In the process of in-situ synthesis hydrofluoric acid etching, argon atmosphere protection is required during ultrasonic treatment, the ultrasonic power is 600W, and the frequency is 40 KHz.
In the sol-gel process, the centrifugal speed of the white suspension is 7000 r/min, the time is 3 min, the precipitate is taken out after centrifugation, and the white gel is obtained by repeatedly washing three times at 7000 r/min.
In the sol-gel process, the white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Mixing MXene and bioglass microspheres according to the volume ratio of the solution, wherein the ratio of the MXene solution to the bioglass microsphere is as follows: bioglass microsphere mixed solution = 10: 90 are compounded.
In the electrostatic self-assembly process, the ultrasonic power is 600W, and the frequency is 40 KHz.
Example 3
A preparation method of MXene/bioglass microsphere composite material with high biological activity comprises the following steps:
(1) preparing MXene by adopting an in-situ synthesis hydrofluoric acid etching method: placing 20 ml of 6M HCl in a polytetrafluoroethylene beaker, adding 500 mg of LiF, and weighing 500 mg of Ti after LiF is completely dissolved3AlC2Slowly adding the powder into the solution, stirring for 24 hr, collecting supernatant, and ultrasonic treating for 1 hrCentrifuging at 3500 r/min for 1 h, collecting supernatant, and freeze drying for 24 h to obtain MXene powder.
(2) The preparation method comprises the following steps of (1) preparing the bioglass microspheres by combining a sol-gel method with a template method: firstly weighing 1.1057 g of dodecylamine as a template agent, pouring the dodecylamine into 24 wt% ethanol solution, selecting tetraethyl orthosilicate, calcium nitrate tetrahydrate and triethyl phosphate as a silicon source, a calcium source and a phosphorus source, adding the tetraethyl orthosilicate, the calcium nitrate tetrahydrate and the triethyl phosphate into the solution according to the molar ratio of Si to Ca to P =60 to 30.8 to 9.2, stirring the solution for 5 hours to obtain white suspension solution, centrifuging the white suspension solution to obtain white precipitate, and finally calcining the white precipitate to obtain white bioglass microsphere powder.
(3) Preparing MXene/bioglass microsphere composite material by adopting an electrostatic self-assembly method: adding the prepared bioglass microspheres into a poly (diallyldimethylammonium chloride) solution with the concentration of 5 wt%, preparing a bioglass microsphere mixed solution with the concentration of 5 mg/ml, preparing an MXene solution with the concentration of 1 mg/ml, adding the MXene solution into the mixed solution, stirring for 30 min, carrying out ultrasonic treatment for 1 h, carrying out vacuum filtration on the uniform mixed solution, and carrying out freeze drying for 12 h to obtain MXene/bioglass microsphere powder.
During the etching process of in-situ synthesis hydrofluoric acid, the temperature needs to be kept at 40 ℃, and the stirring speed is 550 rpm.
In the process of in-situ synthesis hydrofluoric acid etching, after etching is completed, deionized water is used for cleaning for multiple times, and 3500 r/min is used for centrifuging for multiple times until the PH value is more than or equal to 6.
In the process of in-situ synthesis hydrofluoric acid etching, argon atmosphere protection is required during ultrasonic treatment, the ultrasonic power is 600W, and the frequency is 40 KHz.
In the sol-gel process, the centrifugal speed of the white suspension is 7000 r/min, the time is 3 min, the precipitate is taken out after centrifugation, and the white gel is obtained by repeatedly washing three times at 7000 r/min.
In the sol-gel process, the white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Mixing MXene and bioglass microspheres according to the volume ratio of the solution, wherein the ratio of the MXene solution to the bioglass microsphere is as follows: bioglass microsphere mixed solution = 20: 80, compounding.
In the electrostatic self-assembly process, the ultrasonic power is 600W, and the frequency is 40 KHz.
Comparative example
A preparation method of a graphene/bioglass microsphere composite material comprises the following steps:
(1) the preparation method comprises the following steps of (1) preparing the bioglass microspheres by combining a sol-gel method with a template method: firstly weighing 1.1057 g of dodecylamine as a template agent, pouring the dodecylamine into 24 wt% ethanol solution, selecting tetraethyl orthosilicate, calcium nitrate tetrahydrate and triethyl phosphate as a silicon source, a calcium source and a phosphorus source, adding the tetraethyl orthosilicate, the calcium nitrate tetrahydrate and the triethyl phosphate into the solution according to the molar ratio of Si to Ca to P =60 to 30.8 to 9.2, stirring the solution for 5 hours to obtain white suspension solution, centrifuging the white suspension solution to obtain white precipitate, and finally calcining the white precipitate to obtain white bioglass microsphere powder.
(3) Preparing a graphene/biological glass microsphere composite material by adopting an electrostatic self-assembly method: adding the prepared biological glass microspheres into a poly (diallyldimethylammonium chloride) solution with the concentration of 5 wt%, preparing a 5 mg/ml biological glass microsphere mixed solution, preparing a 1 mg/ml graphene (purchased) solution, adding the graphene (purchased) solution into the mixed solution, stirring for 30 min, carrying out ultrasonic treatment for 1 h, carrying out vacuum filtration on the uniform mixed solution, and carrying out freeze drying for 12 h to obtain graphene/biological glass microsphere powder.
In the sol-gel process, the centrifugal speed of the white suspension is 7000 r/min, the time is 3 min, the precipitate is taken out after centrifugation, and the white gel is obtained by repeatedly washing three times at 7000 r/min.
In the sol-gel process, the white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
Preparing graphene and bioglass microspheres according to a solution volume ratio, wherein the graphene solution: bioglass microsphere mixed solution = 20: 80, compounding.
In the electrostatic self-assembly process, the ultrasonic power is 600W, and the frequency is 40 KHz.
As can be seen from FIG. 2, the MXene/bioglass microsphere composite material is successfully prepared, the MXene wraps bioglass microspheres in a film form, and the MXene and the bioglass microspheres have strong bonding force under the action of static electricity, and experiments show that the method for preparing the MXene/bioglass microspheres is feasible.
In order to research the biological activity of the material prepared by the invention, a prepared sample of 0.1 g is soaked in 20 ml of simulated body fluid SBF, the temperature is kept at 37 ℃, the simulated body fluid is replaced once every 2 days, and the biological activity of the material is judged by observing the deposition amount and the morphology of hydroxyapatite generated on the surface of the material after soaking for 7 days. By comparing fig. 3, fig. 4 and fig. 5, it is found by observing fig. 3 that after immersing the MXene-free bioglass microspheres in the simulated body fluid SBF for 7 days, the strip-shaped hydroxyapatite precipitates are generated on the surface of the bioglass microspheres, and larger pores exist among the rod-shaped hydroxyapatite precipitates, while after mineralizing the graphene/bioglass microsphere composite material in the simulated body fluid SBF for 7 days in fig. 4, the larger pores do not exist, the concentration is improved, after mineralizing the MXene/bioglass microsphere composite material in the simulated body fluid SBF for 7 days in fig. 5, a large amount of hydroxyapatite precipitates with high concentration appear, and the phenomenon that additional hydroxyapatite is accumulated to form balls on the surface occurs, and the hydroxyapatite precipitates all present independent flower flakes. Therefore, the MXene/bioglass microsphere composite material has biological activity obviously superior to that of the graphene/bioglass microsphere composite material and bioglass microspheres.
To investigate the antibacterial properties of the samples prepared according to the present invention, 10 mg of the sterilized prepared sample was added to 0.9 ml of LB medium, and 0.1 ml of 108cfu/ml of Staphylococcus aureus, incubated at 37 ℃ for 6 h. The mixed solution is then diluted 104And (4) carrying out 808 nm infrared lamp light irradiation for 20 min, incubating for 24 h under the dark condition of 37 ℃ after irradiation is finished, observing the growth condition of the bacterial colony, and calculating. Comparing fig. 6, fig. 7 and fig. 8, it is found that the graphene/bioglass microsphere composite material in fig. 7 does not exhibit significant antibacterial property compared with the culture medium without the sample in fig. 6, and the MXene/bioglass microsphere composite material in fig. 8 generates a large amount of heat after being irradiated by infrared light of 808 nm, which can cause 99% of bacteria to die, so that the graphene/bioglass microsphere composite material has excellent antibacterial property.
The MXene/bioglass microsphere composite material is prepared by adopting an in-situ synthesis hydrofluoric acid etching method, then preparing bioglass microspheres by combining a sol-gel method and a template method, and finally preparing the MXene/bioglass microsphere composite material by using an electrostatic self-assembly method. As the MXene surface has special surface groups including polar groups such as hydroxyl (-OH), oxygen (-O) or fluorine (-F) and can be used as active sites after being compounded with the bioglass, the precipitation amount of the hydroxyapatite can be promoted to be increased, and the MXene has high surface charge (the negative Zeta potential exceeds-40 mV) and can more quickly adsorb Ca, P and the like in body fluid and accelerate the generation of the hydroxyapatite precipitate, the MXene/bioglass microsphere composite material has high bioactivity. The method has strong controllability, simplicity, high efficiency and low cost, and has no report about the compounding of the bioglass microspheres and MXene. The MXene/bioglass microsphere composite material has great industrialization and application prospects in the biomedical field.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of MXene/bioglass microsphere composite material with high biological activity is characterized in that: the method comprises the following steps:
(1) preparing MXene by adopting an in-situ synthesis hydrofluoric acid etching method: placing 20 ml of 6M HCl in a polytetrafluoroethylene beaker, adding 500 mg of LiF, and weighing 500 mg of Ti after LiF is completely dissolved3AlC2Slowly adding the powder into the solution, continuously stirring for 24 h, taking the supernatant, carrying out ultrasonic treatment for 1 h, then centrifuging for 1 h at 3500 r/min, collecting the supernatant, and carrying out freeze drying for 24 h to obtain MXene powder;
(2) the preparation method comprises the following steps of (1) preparing the bioglass microspheres by combining a sol-gel method with a template method: firstly weighing 1.1057 g of dodecylamine as a template agent, pouring the dodecylamine into 24 wt% ethanol solution, selecting tetraethyl orthosilicate, calcium nitrate tetrahydrate and triethyl phosphate as a silicon source, a calcium source and a phosphorus source, adding the tetraethyl orthosilicate, the calcium nitrate tetrahydrate and the triethyl phosphate into the solution according to the molar ratio of Si to Ca to P =60 to 30.8 to 9.2, stirring the solution for 5 hours to obtain white suspension solution, centrifuging the white suspension solution to obtain white precipitate, and calcining the white precipitate to obtain white bioglass microsphere powder;
(3) preparing MXene/bioglass microsphere composite material by adopting an electrostatic self-assembly method: adding the prepared bioglass microspheres into a poly (diallyldimethylammonium chloride) solution with the concentration of 1-5 wt% to prepare a bioglass microsphere mixed solution with the concentration of 5 mg/ml, adding 0.5-1 mg/ml MXene solution into the mixed solution, stirring for 30 min, carrying out ultrasonic treatment for 1 h, carrying out vacuum filtration on the uniform mixed solution, and carrying out freeze drying for 12 h to obtain MXene/bioglass microsphere powder.
2. The method of claim 1, wherein: during the etching process of in-situ synthesis hydrofluoric acid, the temperature needs to be kept at 40 ℃, and the stirring speed is 550 rpm.
3. The method of claim 1, wherein: in the process of in-situ synthesis hydrofluoric acid etching, after etching is finished, deionized water is used for cleaning for multiple times, and 3500 r/min is used for centrifuging for multiple times until the pH value is more than or equal to 6.
4. The method of claim 1, wherein: in the process of in-situ synthesis hydrofluoric acid etching, argon atmosphere protection is required during ultrasonic treatment, the ultrasonic power is 600W, and the frequency is 40 KHz.
5. The method of claim 1, wherein: in the sol-gel process, the centrifugal speed of the white suspension is 7000 r/min, the time is 3 min, the precipitate is taken out after centrifugation, and the white gel is obtained by repeatedly washing three times at 7000 r/min.
6. The method of claim 5, wherein: in the sol-gel process, the white gel needs to be dried before calcination, the drying temperature is 60 ℃, the drying time is 24 hours, and after drying, the sample needs to be ground into powder and then calcined.
7. The method of claim 1, wherein: compounding MXene and bioglass microspheres according to different volume ratios of solutions, wherein the ratio of the MXene solution to the bioglass microspheres is as follows: biological glass microsphere mixed solution =x：100-x，x=5~20。
8. The method of claim 1, wherein: in the electrostatic self-assembly process, the ultrasonic power is 600W, and the frequency is 40 KHz.
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| CN113976080A (en) * | 2021-10-12 | 2022-01-28 | 安徽农业大学 | Preparation method of two-dimensional material and method for adsorbing phosphorus in water by using two-dimensional material |
| CN113976080B (en) * | 2021-10-12 | 2022-11-11 | 安徽农业大学 | Preparation method of two-dimensional material and method for adsorbing phosphorus in water by using two-dimensional material |
| CN114163134A (en) * | 2021-12-30 | 2022-03-11 | 西安交通大学 | Bioactive glass and preparation method thereof |
| CN114163134B (en) * | 2021-12-30 | 2022-12-27 | 西安交通大学 | Bioactive glass and preparation method thereof |
| CN115231914A (en) * | 2022-07-15 | 2022-10-25 | 中国科学院上海硅酸盐研究所 | Bionic MXene/calcium silicate layered bioceramic and preparation method and application thereof |
| CN116642876A (en) * | 2023-05-05 | 2023-08-25 | 北京先通国际医药科技股份有限公司 | Method for determining content of related metal elements in yttrium-containing glass microspheres and application thereof |
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