CN115920110A - Preparation method of nano metal boride composite material - Google Patents
Preparation method of nano metal boride composite material Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention belongs to the field of new materials, and discloses a preparation method of a nano metal boride composite material. The preparation process of the material is green and environment-friendly, the operation is simple and easy to implement, and the prepared composite material and composite fiber film have the characteristics of broad-spectrum antibiosis, durability, no generation of drug resistance and the like, and can be used in the fields of antibacterial spray, protective coating, medical dressing and the like.
Description
Technical Field
The invention belongs to the field of new materials, and relates to a preparation method of a nano metal boride composite material.
Background
Bacterial infection threatens human health, not only can cause skin and soft tissue infection to induce inflammatory diseases, but also can cause other pathological changes after the wound is not healed for a long time, and causes complications such as septicemia and the like. With the wide use of antibiotics, bacterial drug resistance has become a major problem threatening the safety of human beings and animals all over the world, and particularly, the appearance of 'super drug-resistant bacteria' greatly weakens the therapeutic effect of the antibiotics, and the development of novel broad-spectrum antibacterial materials is imperative. Compared with antibiotic antibiosis, the inorganic nano material can be used for an antibacterial drug-carrying material by virtue of unique structure, larger specific surface area, stable physicochemical property, excellent photo-thermal conversion efficiency and the like, can play an antibacterial role by various modes such as releasing antibacterial components, generating ROS, interrupting substance or energy transfer, inhibiting enzyme activity and the like, enables bacteria not to easily generate drug resistance, and provides a brand new strategy for treating wound healing and infectious diseases caused by bacteria.
The metal boride is a hard compound generated by transition metal and boron, and has wide application in the fields of flame retardance, heat resistance, high hardness, high strength, catalysis, superconduction and the like. The metal boride has a boron atom layered structure similar to graphite and M-B bonds between boron atoms and metal atoms, so that the compound has certain conductivity and photothermal conversion capacity; meanwhile, due to the existence of boron, the boron-containing nano-particles can be endowed with greater biological activity and compatibility, can participate in human metabolism, regulate human hormone and have certain anti-inflammatory effect. However, a simple method for preparing the nano metal boride is still lacked at present, boride powder prepared by the traditional high-temperature synthesis, boron thermochemical method, melting electrolysis method and carbothermic method is large in size, poor in dispersity and easy to aggregate and settle, and a single metal boride is low in antibacterial activity and hardly meets the requirements of the actual antibacterial field.
Disclosure of Invention
Aiming at the problems of difficult preparation, easy agglomeration, low single antibacterial performance, powder application limitation and the like of nano metal boride, the invention aims to provide a preparation method of a nano metal boride composite material.
The technical scheme of the invention is as follows:
a preparation method of a nano metal boride composite material comprises the following steps:
step 1, freezing metal boride by using liquid nitrogen, dispersing the metal boride in an organic solvent, adding a surfactant, stripping under the condition of 0-20 ℃ by ultrasonic assistance, performing centrifugal separation, washing by using absolute ethyl alcohol and deionized water, and drying to obtain metal boride nanosheets; wherein the mass ratio of the surfactant to the metal boride is 1:20 to 1:1, the ultrasonic power is 200-800 w, and the time is 1-5 h;
step 2, adding the metal boride nanosheets obtained in the step 1 into an aqueous solution containing a modifier, mixing and stirring under the condition of constant-temperature water bath, washing, and drying to obtain modified and modified metal boride nanosheets; wherein the concentration of the modifier is 5-20 mg/mL, and the mass ratio of the modifier to the metal boride is 2:1 to 25:1, stirring for 6-24 h, wherein the reaction temperature is 20-50 ℃;
step 3, mixing the modified and modified metal boride nanosheets obtained in the step 2 with a indocyanine green solution, stirring at a high speed for 0.5-2 h, then stirring in a water bath at a low speed in a dark place at a temperature of 0-35 ℃ for self-assembly reaction, and after the reaction is completed, centrifuging, washing and drying to obtain a nano metal boride composite powder material; wherein the high speed is 600-1000 rpm, and the low speed is 100-300 rpm;
step 4, dispersing the nano metal boride composite powder material obtained in the step 3 into a solution containing a spinning auxiliary agent, adding an organic polymer solution, and blending and stirring uniformly to prepare an electrostatic spinning solution; spinning by adopting an electrostatic spinning technology, and collecting by using a receiver to obtain the nano metal boride composite material; wherein the stirring time is 3-24 h; the electrostatic spinning temperature is 10-30 ℃; the voltage is 13-22 kV; the sample introduction speed is 0.5-3.5 mL/h; the distance of the receiver is 5-25 cm, and the rotating speed is 50-150 rpm.
The liquid nitrogen freezing time in the step 1 is 0.5-12 h.
In the step 1, the metal boride is one of zirconium diboride, niobium diboride, titanium diboride, hafnium diboride, chromium diboride and magnesium diboride.
In the step 1, the concentration of the metal boride in the organic solvent is 0.5-2.0 mg/mL.
In the step 1, the organic solvent is one of or a mixed solvent of ethylene glycol, DMF, N-methyl pyrrolidone, isopropanol, N-dimethylformamide, ethanol and acetonitrile and water.
In the step 1, the surfactant is one of polyether P123, sodium dodecyl benzene sulfonate, polyether F68, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and dodecyl sulfuric acid.
In the step 1, the concentration of the surfactant in the stripping system is 100-1000 mug/mL.
The modifier in the step 2 is one of chitosan, quaternized chitosan, biguanidinium chitosan, amino polyethylene glycol, sulfhydryl polyethylene glycol and hyaluronic acid.
In the step 3, the solvent of the indocyanine green solution is one of water, ethanol and PBS.
In the step 3, the concentration of the indocyanine green in the reaction system is 0.05-1 mg/mL; the mass ratio of the indocyanine green to the modified metal boride nanosheet is 1:2 to 50 percent; the drying condition is freeze drying, vacuum drying or forced air drying.
In step 4, the organic polymer is one of polyvinyl alcohol (PVA), polylactic acid (PLA), polyacrylonitrile (PAN) and Polycaprolactone (PCL).
In step 4, the solvent of the organic polymer solution is one of water, dimethylformamide, ethanol, dichloromethane and chloroform.
In the step 4, the spinning auxiliary agent is one or a mixture of more than two of ethanol, polyvinylpyrrolidone (PVP) and polyethylene glycol.
In the step 4, the mass ratio of the nano metal boride composite powder material to the organic polymer is 1:10 to 100.
Compared with the prior art, the method has the advantages that the dispersibility of the metal boride nanosheet is improved by the aid of auxiliary agent assisted ultrasonic solution stripping and surface modification methods, and the adhesion effect of the material on bacteria can be enhanced; the near-infrared response type photo-thermal and photodynamic combined antibacterial material is constructed by loading indocyanine green, so that high-efficiency antibacterial effects on escherichia coli, staphylococcus aureus and methicillin-resistant staphylococcus aureus can be realized; the functional wound antibacterial dressing can be prepared by an electrostatic spinning technology, and has good biocompatibility. The preparation process of the material is green and environment-friendly, and the operation is simple and easy. The prepared composite antibacterial material has the characteristics of broad-spectrum antibacterial property, durability, no drug resistance and the like, can be used in the fields of antibacterial spray, protective coating, medical dressing and the like, and also has wide application prospect in the field of diagnosis and treatment integration.
Drawings
Figure 1 is an AFM image of prepared zirconium diboride nanoplates.
Fig. 2 is an SEM image of the prepared titanium diboride/chitosan/indocyanine green/polylactic acid-based composite nanofiber membrane.
Detailed Description
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described below with reference to specific embodiments.
It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings.
The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
1. Freezing 60mg of zirconium diboride powder in liquid nitrogen for 1 hour, dispersing the zirconium diboride powder in 90mL of ethylene glycol, adding 60mg of polyether F68 as a surfactant, carrying out ultrasonic stripping for 2 hours in water bath at 5 ℃ with 400w of power, centrifuging for 5min at the rotating speed of 2500r/min, removing blocky un-stripped zirconium diboride powder, reserving supernatant, centrifuging for two times at the rotating speed of 12000r/min, centrifuging for 20min, collecting precipitates, respectively and alternately washing for three times by using absolute ethyl alcohol and deionized water, and carrying out freeze drying for 24 hours to obtain the zirconium diboride nanosheets.
2. Dispersing 5mg of prepared zirconium diboride nanosheets in 5mL of aqueous solution, dissolving 80mg of quaternary ammonium salt chitosan in 5mL of deionized water to prepare the quaternary ammonium salt chitosan aqueous solution, uniformly mixing the quaternary ammonium salt chitosan aqueous solution and the quaternary ammonium salt chitosan aqueous solution under the action of ultrasound, and stirring at room temperature for 6 hours. And washing the suspension with deionized water for three times, and freeze-drying for 24 hours to obtain the quaternized chitosan modified zirconium diboride nanosheet.
3.5 mg of the modified zirconium diboride nanosheet and 5mL of 300 mu g/mL -1 Mixing the indocyanine green PBS solution, stirring at high speed for 0.5h, and then stirring and assembling at low speed for 12h at 15 ℃ in a dark place; and centrifuging, washing for 3 times by PBS, and drying in vacuum to obtain the zirconium diboride nanosheet composite material.
4. 1g of polylactic acid was dissolved in 10.5mL of dichloromethane, and 50mg of zirconium diboride nanoplate composite and 60mg of PVP were dispersed in 10.5mL of dichloromethane. The two solutions were mixed and stirred for 10h in the dark. The composite fiber membrane material is prepared by spinning at the voltage of 19kV, the sample introduction speed of 1mL/h, the receiver distance of 12cm, the rotating speed of 75rpm and the temperature of 20 ℃.
Test results show that the prepared zirconium diboride nanosheet composite material has a concentration of 250 mug. ML -1 When the power is 1.5W/cm ～2 The temperature can be raised to 45 ℃ under the irradiation of 808nm near infrared light for 10 min. The bacteriostatic rates on methicillin-resistant staphylococcus aureus and escherichia coli are 95.52 percent and 96.96 percent respectively. The power of the prepared electrostatic spinning film is 1.5W/cm ～2 The temperature can be raised to 55 ℃ under the irradiation of 808nm near infrared light for 5 min. The bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are respectively 99.68% and 99.91%. The wound infection healing experiment shows that after 14 days, the blank group has a healing rate of 80.56 percent and the wound healing experiment uses the composite fiber membraneThe wound healing rate was 99.25%.
Example 2
1. Dispersing niobium diboride powder frozen for 1.5h in 80mg liquid nitrogen into 80mL DMF, adding 40mg PVP as a surfactant, carrying out probe ultrasonic stripping for 3.5h in water bath at 5 ℃ with the power of 300w, centrifuging for 8min at the rotating speed of 2500r/min, removing blocky non-stripped niobium diboride powder, reserving supernatant, centrifuging for two times at the rotating speed of 12000r/min, centrifuging for 20min, collecting precipitates, respectively and alternately washing for three times by using absolute ethyl alcohol and deionized water, and carrying out freeze drying for 24 hours to obtain the dried niobium diboride nanosheets.
2. Dispersing 10mg of niobium diboride nanosheets in 10mL of deionized water, dissolving 100mg of chitosan in 10mL of deionized water, uniformly mixing the two in the presence of bath ultrasound, and stirring at room temperature for 18h. And washing the suspension with deionized water for three times, and freeze-drying for 24 hours to obtain the chitosan modified niobium diboride nanosheet.
3. 10mg of the modified nanosheet was mixed with 10mL of 500. Mu.g.mL -1 Mixing the indocyanine green ethanol solution with the concentration, stirring at a high speed for 1h, and then stirring and assembling at a low speed for 6h at a low speed in a dark place at 20 ℃. Centrifuging, washing for 3 times by using absolute ethyl alcohol, and freezing and drying to obtain the niobium diboride nanosheet composite material.
4. 0.5g of polyvinyl alcohol was dispersed in 10mL of deionized water, and 10mg of niobium diboride nanoplatelet composite and 25mg of PVP were dispersed in 8mL of deionized water. The two solutions were mixed and stirred for 16h in the dark. Under the voltage of 16kV, the sample injection speed of 2mL/h, the receiver distance of 10cm and the rotation speed of 120rpm. Spinning at 20 deg.c to prepare the composite fiber film.
The test result shows that the prepared niobium diboride nanosheet composite material has the concentration of 250 mug. ML -1 When the power is 1.5W/cm ～2 The temperature can be raised to 45 ℃ under the irradiation of 808nm near infrared light for 10 min. The bacteriostatic rates on methicillin-resistant staphylococcus aureus and escherichia coli are 90.24% and 92.78% respectively. The power of the prepared electrostatic spinning film is 1.5W/cm ～2 808nm near infrared light for 5min, the temperature can be raised to 45 ℃. The bacteriostatic rates to methicillin-resistant staphylococcus aureus and escherichia coli are 93.87% and 95.02% respectively. Wound healing deviceInfection healing experiments show that after 14 days, the wound healing rate of the composite fiber membrane is 95.25%, and the blank healing rate is 80.56%.
Example 3
1. Dispersing the hafnium diboride powder frozen in 120mg of liquid nitrogen for 4 hours in 100mL of N-methyl pyrrolidone, adding 80mg of surfactant polyether P123, carrying out probe ultrasonic stripping for 4.5 hours in a water bath at 10 ℃ with 550w of power, centrifuging for 10 minutes at the rotating speed of 2500r/min, removing blocky unpeeled hafnium diboride powder, reserving supernatant, centrifuging for two times at the rotating speed of 12000r/min, centrifuging for 20 minutes, collecting precipitates, respectively and alternately washing for three times by using absolute ethyl alcohol and deionized water, and drying for 24 hours to obtain the dried hafnium diboride nanosheets.
2. Dispersing hafnium diboride nanosheets in 3mL of deionized water, dissolving 90mg of chitosan biguanide salt in 3mL of deionized water, uniformly mixing the two under the bath ultrasonic action, and stirring at room temperature for 12 hours. And washing the suspension with deionized water for three times to remove the unloaded chitosan biguanide salt, and drying for 24 hours to obtain the chitosan biguanide salt modified hafnium diboride.
3. 6mg of the modified nanosheet was mixed with 6mL of 300. Mu.g.mL -1 Mixing the indocyanine green aqueous solution with concentration, stirring at high speed for 0.5h, and then stirring and assembling at low speed at a dark place and a low speed for 10h at 25 ℃. Centrifuging, washing for 3 times by using deionized water, and freeze-drying to obtain the hafnium diboride nanosheet composite material.
4. 0.8g of polylactic acid was dissolved in 9.5mL of chloroform, and 25mg of the hafnium diboride nanosheet composite was dispersed in a mixed solution of 9.5mL of chloroform and 10.5mL of ethanol. The two solutions were mixed and stirred for 12h in the dark. Under the voltage of 20.5kV, the sample injection speed of 1.5mL/h, the receiver distance of 15cm and the rotation speed of 55rpm. Spinning at 25 deg.c to prepare the composite fiber membrane material.
The test result shows that the prepared hafnium diboride nanosheet composite material has the concentration of 200 mu g/mL -1 When the power is 1.5W/cm ～2 The temperature can be increased to 53 ℃ under the irradiation of 808nm near infrared light for 10 min; the bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are respectively 99.44% and 99.21%. The power of the prepared electrostatic spinning film is 1.5W/cm ～2 The temperature can be raised to 50 ℃ under the irradiation of 808nm near infrared light for 5 min; the bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are respectively 98.79% and 99.13%. The wound infection healing experiment shows that after 14 days, the blank group healing rate is 80.56%, and the wound healing rate by using the composite fiber membrane is 98.64%.
Example 4
1. Dispersing 100mg of liquid nitrogen frozen titanium diboride powder for 1h in 150m isopropanol, adding 100mg of hexadecyl trimethyl ammonium bromide, carrying out probe ultrasonic stripping for 5h in water bath at 10 ℃ and with the power of 300w, centrifuging for 5min at the rotating speed of 2500r/min, removing blocky un-stripped titanium diboride powder, reserving supernatant, centrifuging for two times at the rotating speed of 12000r/min, centrifuging for 20min, collecting precipitates, respectively washing for three times by using absolute ethyl alcohol and deionized water alternately, and drying for 24h to obtain the dried titanium diboride nanosheets.
2. Dispersing 10mg of titanium diboride nanosheets into 10mL of deionized water, dissolving 120mg of mercaptopolyethylene glycol into 10mL of deionized water, uniformly mixing the two under the bath ultrasonic action, and stirring for 24 hours at room temperature. And washing the suspension with deionized water for three times, and freeze-drying for 24 hours to obtain the thiol-polyethylene glycol modified titanium diboride nanosheet.
3. 6mg of the modified nanosheet was mixed with 6mL of 600. Mu.g.mL -1 Mixing indocyanine green PBS solution with concentration, stirring at high speed for 2h, and then stirring and assembling at low speed at a temperature of 30 ℃ in a dark place for 6h. Centrifuging, washing for 3 times by PBS, and freeze-drying to obtain the titanium diboride nanosheet composite material.
4. 1g of polycaprolactone was dissolved in 10mL of dimethylformamide, and 45mg of titanium diboride nanoplate composite and 100mg of PVP were dispersed in 5mL of dimethylformamide solution. The two solutions were mixed and stirred for 10h in the dark. Under the voltage of 20kV, the sample injection speed of 0.5mL/h, the receiver distance of 20cm and the rotating speed of 125rpm. Spinning at 20 deg.c to prepare the composite fiber membrane material.
The test result shows that the prepared titanium diboride nanosheet composite material has the concentration of 200 mu g/mL -1 When the power is 1.5W/cm ～2 808nm near infrared light for 10min, the temperature can be raised to 48 ℃. For methicillin-resistant goldThe bacteriostasis rates of the staphylococcus aureus and the escherichia coli are 96.32% and 97.89% respectively. The test result shows that the prepared electrostatic spinning membrane has the power of 1.5W/cm ～2 808nm near infrared light for 5min, the temperature can be raised to 55 ℃. The bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are respectively 99.05% and 99.84%. The wound infection healing experiment shows that after 14 days, the wound healing rate of the composite fiber membrane is 93.19%, and the blank group healing rate is 80.56%.
Example 5
1. The method comprises the steps of dispersing 75mg of liquid nitrogen frozen chromium diboride powder for 10 hours in 75mL of ethylene glycol, adding 25mg of surfactant P123, carrying out probe ultrasonic stripping for 5 hours in a water bath at 5 ℃ with the power of 250w, centrifuging for 5 minutes at the rotating speed of 2500r/min, removing blocky non-stripped chromium diboride powder, retaining supernatant, centrifuging for two times at the rotating speed of 12000r/min, centrifuging for 20 minutes, collecting precipitates, alternately washing for three times with absolute ethyl alcohol and deionized water respectively, and drying for 24 hours to obtain the dried chromium diboride nanosheets.
2. Dispersing 12mg of chromium diboride nanosheets in 10mL of deionized water, dissolving 120mg of hyaluronic acid in 10mL of deionized water, uniformly mixing the two under the action of bath ultrasound, and stirring for 24 hours at room temperature. And washing the suspension with deionized water for three times to remove the unloaded hyaluronic acid, and freeze-drying for 24 hours to obtain the hyaluronic acid modified chromium diboride nanosheet.
3. 10mg of the modified nanosheet was mixed with 10mL of 450. Mu.g.mL -1 Mixing the indocyanine green ethanol solution with concentration, stirring at high speed for 2h, and then stirring and assembling at low speed for 12h at 20 ℃ in a dark place. Centrifuging, washing with ethanol for 3 times, and freeze-drying to obtain the chromium diboride nanosheet composite material.
4. 1.5g of polyacrylonitrile was dissolved in 13.5mL of dimethylformamide, and 100mg of chromium diboride nanosheet composite was dispersed in a mixed solution of 9mL of dimethylformamide and 1.5mL of ethanol. The two solutions were mixed and stirred for 24h in the dark. Under the voltage of 13.8kV, the sample injection speed of 0.5mL/h, the receiver distance of 10cm and the rotation speed of 100rpm. Spinning at 25 deg.c to prepare the composite fiber membrane material.
The test result shows that the prepared chromium diboride sodiumThe rice flake composite material has the concentration of 400 mu g/mL -1 When the power is 1.5W/cm ～2 The temperature can be raised to 49 ℃ under the irradiation of 808nm near infrared light for 10 min. The bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are respectively 96.55 percent and 97.38 percent. The prepared electrostatic spinning film has the power of 1.5W/cm ～2 The temperature can be raised to 53 ℃ under the irradiation of 808nm near infrared light for 5 min. The bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are 97.11 percent and 98.25 percent respectively. The wound infection healing experiment shows that the wound healing rate of the composite fiber membrane is 92.25% and the blank group healing rate is 80.56% after 14 days.
Example 6
1. Dispersing 100mg of zirconium diboride powder in 100mL of acetonitrile, adding 50mg of surfactant dodecyl sulfuric acid, carrying out probe ultrasonic stripping for 3h in water bath at 10 ℃ and with the power of 500w, centrifuging for 5min at the rotating speed of 2500r/min, removing blocky un-stripped zirconium diboride powder, retaining supernatant, centrifuging for two times at the rotating speed of 12000r/min, centrifuging for 20min, collecting precipitates, respectively and alternately washing for three times by using absolute ethyl alcohol and deionized water, and drying for 24h to obtain the dried zirconium diboride nanosheets.
2. Dispersing 10mg of zirconium diboride nanosheets in 10mL of deionized water, dissolving 100mg of chitosan biguanide salt in 10mL of deionized water, uniformly mixing the two in the presence of bath ultrasound, and stirring at room temperature for 12h. And washing the suspension with deionized water for three times to remove the unloaded chitosan biguanide salt, and freeze-drying for 24 hours to obtain the chitosan biguanide salt modified zirconium diboride nanosheet.
3.1 g of polyacrylonitrile was dissolved in 10.5mL of dimethylformamide, and 80mg of the zirconium diboride nanosheet composite was dispersed in 8mL of dimethylformamide. The two solutions were mixed and stirred for 18h in the dark. Under the voltage of 15.6kV, the sample injection speed of 2.5mL/h, the receiver distance of 16cm and the rotation speed of 120rpm. Spinning at 25 deg.c to prepare the composite fiber membrane material.
Test results show that the prepared zirconium diboride nanosheet composite material has the concentration of 300 mu g/mL -1 When the power is 1.5W/cm ～2 808nm near infrared light for 10min at a temperature ofThe temperature was raised to 44 ℃. The bacteriostatic rates on methicillin-resistant staphylococcus aureus and escherichia coli are respectively 50.89% and 52.27%. The prepared electrostatic spinning film has the power of 1.5W/cm ～2 808nm near infrared light for 5min, the temperature can be raised to 50 ℃. The bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are 75.68% and 78.23% respectively. The wound infection healing experiment shows that the wound healing rate of the composite fiber membrane is 85.33% and the blank group healing rate is 80.56% after 14 days.
Example 7
1. Dispersing hafnium diboride powder frozen in 80mg of liquid nitrogen for 2 hours in 80mL of ethylene glycol, adding 20mg of polyvinylpyrrolidone serving as a surfactant, carrying out probe ultrasonic stripping for 2.5 hours in a water bath at 10 ℃ at a power of 400w, centrifuging for 10 minutes at a rotating speed of 2500r/min, removing blocky unpeeled hafnium diboride powder, retaining supernatant, centrifuging for two times at a rotating speed of 12000r/min, centrifuging for 20 minutes, collecting precipitates, respectively and alternately washing for three times by using absolute ethyl alcohol and deionized water, and drying for 24 hours to obtain the dried hafnium diboride nanosheets.
2. 1.2g of polylactic acid was dissolved in 10mL of dichloromethane, and 45mg of hafnium diboride nanoplatelets were dispersed in a mixed solution of 8mL of dichloromethane and 6.5mL of ethanol. The two solutions were mixed and stirred for 24h in the dark. Under the voltage of 17.5kV, the sample injection speed of 0.5mL/h, the receiver distance of 18cm and the rotation speed of 80rpm. Spinning at 25 deg.c to prepare the composite fiber membrane material.
The test result shows that the prepared hafnium diboride nanosheet composite material has the concentration of 300 mu g/mL -1 When the power is 1.5W/cm ～2 The temperature can be increased to 47 ℃ under the irradiation of 808nm near infrared light for 10 min; the bacteriostasis rates to methicillin-resistant staphylococcus aureus and escherichia coli are 49.24 percent and 50.01 percent respectively. The prepared electrostatic spinning film has the power of 1.5W/cm ～2 The temperature can be raised to 46 ℃ under the irradiation of 808nm near infrared light for 5 min; the bacteriostatic rates to methicillin-resistant staphylococcus aureus and escherichia coli are 58.56% and 59.03% respectively. The wound infection healing experiment shows that after 14 days, the healing rate of a blank group is 80.56%, and the healing rate of the wound using the composite fiber membrane is 81.02%.
Claims (5)
1. A preparation method of a nano metal boride composite material is characterized by comprising the following steps:
step 1, freezing metal boride by using liquid nitrogen, dispersing the metal boride in an organic solvent, adding a surfactant, stripping under the condition of 0-20 ℃ by ultrasonic assistance, performing centrifugal separation, washing by using absolute ethyl alcohol and deionized water, and drying to obtain metal boride nanosheets; wherein the mass ratio of the surfactant to the metal boride is 1:20 to 1:1, the ultrasonic power is 200-800 w, and the time is 1-5 h;
step 2, adding the metal boride nanosheets obtained in the step 1 into an aqueous solution containing a modifier, mixing and stirring under the condition of constant-temperature water bath, washing, and drying to obtain modified and modified metal boride nanosheets; wherein the concentration of the modifier is 5-20 mg/mL, and the mass ratio of the modifier to the metal boride is 2:1 to 25:1, stirring for 6-24 h, wherein the reaction temperature is 20-50 ℃;
step 3, mixing the modified and modified metal boride nanosheet obtained in the step 2 with a indocyanine green solution, stirring at a high speed for 0.5-2 h, then stirring in a water bath at a low speed for self-assembly reaction in a dark place at 0-35 ℃, and after the self-assembly reaction is completed, centrifuging, washing and drying to obtain a nano metal boride composite powder material; wherein the high speed is 600-1000 rpm, and the low speed is 100-300 rpm;
step 4, dispersing the nano metal boride composite powder material obtained in the step 3 into a solution containing a spinning auxiliary agent, adding an organic high polymer solution, and blending and stirring uniformly to prepare an electrostatic spinning solution; spinning by adopting an electrostatic spinning technology, and collecting by using a receiver to obtain the nano metal boride composite material; wherein the stirring time is 3-24 h; the electrostatic spinning temperature is 10-30 ℃; the voltage is 13-22 kV; the sample introduction speed is 0.5-3.5 mL/h; the distance of the receiver is 5-25 cm, and the rotating speed is 50-150 rpm.
2. The production method according to claim 1,
in the step 1, the method comprises the following steps of,
the metal boride is one of zirconium diboride, niobium diboride, titanium diboride, hafnium diboride, chromium diboride and magnesium diboride, and the concentration of the metal boride in the organic solvent is 0.5-2.0 mg/mL;
the organic solvent is one of or a mixed solvent of glycol, DMF, N-methyl pyrrolidone, isopropanol, N-dimethylformamide, ethanol and acetonitrile and water;
the surfactant is one of polyether P123, sodium dodecyl benzene sulfonate, polyether F68, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone and dodecyl sulfuric acid, and the concentration of the surfactant in a stripping system is 100-1000 mu g/mL;
the liquid nitrogen freezing time is 0.5-12 h.
3. The production method according to claim 1,
in the step (2), the first step is that,
the modifier is one of chitosan, quaternized chitosan, biguanidinium chitosan, amino polyethylene glycol, sulfhydryl polyethylene glycol and hyaluronic acid.
4. The production method according to claim 1,
in the step (3), the step (c),
the solvent of the indocyanine green solution is one of water, ethanol and PBS, and the concentration of the indocyanine green in the reaction system is 0.05-1 mg/mL; the mass ratio of the indocyanine green to the modified metal boride nanosheet is 1:2 to 50 percent; the drying condition is freeze drying, vacuum drying or forced air drying.
5. The production method according to claim 1,
in the step 4, the process of the method,
the organic high polymer is one of polyvinyl alcohol, polylactic acid, polyacrylonitrile and polycaprolactone;
the solvent of the organic high polymer solution is one of water, dimethylformamide, ethanol, dichloromethane and trichloromethane;
the spinning auxiliary agent is one or more than two of ethanol, polyvinylpyrrolidone and polyethylene glycol;
the mass ratio of the nano metal boride composite powder material to the organic polymer is 1:10 to 100.
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