CN115920110A - Preparation method of nano metal boride composite material - Google Patents

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

A kind of preparation method of nano metal boride composite material

technical field

The invention belongs to the field of new materials, and relates to a preparation method of a nanometer metal boride composite material.

Background technique

Bacterial infection is a threat to human health. It not only causes skin and soft tissue infection, induces inflammatory diseases, but also causes other lesions and complications such as sepsis if the wound is not healed for a long time. With the widespread use of antibiotics, bacterial resistance has become a major problem threatening the safety of humans and animals around the world. In particular, the emergence of "super-resistant bacteria" has greatly weakened the therapeutic effect of antibiotics. It is imperative to develop new broad-spectrum antibacterial materials. must do. Compared with antibiotics, inorganic nanomaterials can be used as antibacterial drug-loaded materials due to their unique structure, large specific surface area, stable physical and chemical properties, and excellent photothermal conversion efficiency. They can release antibacterial components, generate ROS, interrupt Material or energy transfer, inhibition of enzyme activity and other ways to exert its antibacterial effect make bacteria less resistant to drug resistance, providing a new strategy for the treatment of wound healing and infectious diseases caused by bacteria.

Metal borides are hard compounds formed by transition metals and boron, and have been widely used in the fields of flame retardancy, heat resistance, high hardness, high strength, catalysis, and superconductivity. Metal borides have a layered structure of boron atoms similar to graphite, and the M-B bond between boron atoms and metal atoms, which makes this type of compound have certain electrical conductivity and light-to-heat conversion ability; at the same time, due to the presence of boron element, It may endow it with greater biological activity and compatibility, and it can also participate in human metabolism, regulate human hormones and have certain anti-inflammatory effects. However, there is still a lack of convenient methods for preparing nano-metal borides. The boride powders prepared by traditional high-temperature synthesis, boron thermochemistry, molten electrolysis, and carbothermal methods have large sizes, poor dispersion, and are prone to aggregation and sedimentation. The antibacterial activity of borides is not high, and it is difficult to meet the requirements of the actual antibacterial field.

Contents of the invention

Aiming at the problems of difficult preparation of nano-metal borides, easy agglomeration, low single antibacterial performance, and powder application limitations, the purpose of the present invention is to provide a preparation method of nano-metal boride composite materials, which can be stripped by surfactant-assisted ultrasonic stripping Bulk metal borides, obtaining nanosheets and modifying their surface, loading indocyanine green with photodynamic antibacterial function on the surface of the material to obtain metal boride nanocomposites with excellent multi-effect synergistic antibacterial function, and using Electrospinning technology and co-spinning of polymers are used to prepare wound dressings.

Technical scheme of the present invention is:

A preparation method of nanometer metal boride composite material, the steps are as follows:

Step 1, freeze the metal boride with liquid nitrogen and disperse it in an organic solvent, add a surfactant, peel off at a temperature of 0-20°C with the assistance of ultrasound, centrifuge, wash with absolute ethanol and deionized water, and dry to obtain Metal boride nanosheets; wherein, the mass ratio of surfactant to metal boride is 1:20-1:1, the ultrasonic power is 200-800w, and the time is 1-5h;

Step 2, adding the metal boride nanosheets obtained in step 1 into an aqueous solution containing a modifier, mixing and stirring in a constant temperature water bath, washing and drying to prepare modified metal boride nanosheets; wherein, the modified The concentration of the agent is 5-20mg/mL, the mass ratio of the modifier to the metal boride is 2:1-25:1, the stirring time is 6-24h, and the reaction temperature is 20-50°C;

Step 3, mixing the modified metal boride nanosheets obtained in step 2 with the indocyanine green solution, stirring at high speed for 0.5-2 hours, and then stirring the self-assembly reaction at a low speed in a water bath at 0-35° C. After completion, centrifuge, wash, and dry to obtain nano-metal boride composite powder materials; among them, the high speed is 600-1000rpm, and the low speed is 100-300rpm;

Step 4, dispersing the nano-metal boride composite powder material obtained in step 3 in a solution containing a spinning aid, adding an organic polymer solution, blending and stirring evenly to prepare an electrospinning liquid; using electrospinning technology Carry out spinning, and collect nano-metal boride composite materials with a receiver; wherein, the stirring time is 3-24 hours; the electrospinning temperature is 10-30°C; the voltage is 13-22kV; the injection speed is 0.5-3.5mL/ h; The receiver distance is 5-25cm, and the rotation speed is 50-150rpm.

In step 1, the liquid nitrogen freezing time is 0.5-12 hours.

The metal boride in step 1 is one of zirconium diboride, niobium diboride, titanium diboride, hafnium diboride, chromium diboride and magnesium diboride.

The concentration of the metal boride in the organic solvent in step 1 is 0.5-2.0 mg/mL.

The organic solvent in step 1 is one of ethylene glycol, DMF, N-methylpyrrolidone, isopropanol, N,N-dimethylformamide, ethanol, acetonitrile or a mixed solvent with water.

In step 1, the surfactant is one of polyether P123, sodium dodecylbenzenesulfonate, polyether F68, cetyltrimethylammonium bromide, polyvinylpyrrolidone, and dodecylsulfuric acid.

The concentration of the surfactant in the stripping system in step 1 is 100-1000 μg/mL.

The modifying agent in step 2 is one of chitosan, quaternized chitosan, biguanide chitosan, amino polyethylene glycol, mercapto polyethylene glycol, and hyaluronic acid.

In step 3, the solvent of the indocyanine green solution is one of water, ethanol and PBS.

In step 3, the concentration of indocyanine green in the reaction system is 0.05-1 mg/mL; the mass ratio of indocyanine green to the modified metal boride nanosheets is 1:2-50; the drying condition is freeze-drying , Vacuum drying or blast 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 step 4, the spinning aid is one or a mixture of two or more of ethanol, polyvinylpyrrolidone (PVP), and polyethylene glycol.

In step 4, the mass ratio of the nano metal boride composite powder material to the organic high polymer is 1:10-100.

Compared with the prior art, the effect and benefit of the present invention are that the dispersibility of the metal boride nanosheets can be improved through auxiliary agent-assisted ultrasonic solution stripping and surface modification methods, and the adhesion of the material to bacteria can also be enhanced; by loading indole Cyan Green constructs a near-infrared responsive photothermal and photodynamic antibacterial material, which can achieve high-efficiency antibacterial effects against Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus; functional wounds can be prepared by electrospinning technology Antibacterial dressing with good biocompatibility. The material preparation process is green and environmentally friendly, and the operation is simple and easy. The prepared composite antibacterial material has the characteristics of broad-spectrum antibacterial, persistence, and no drug resistance. It can be used in antibacterial sprays, protective coatings, medical dressings, etc., and has broad application prospects in the field of integrated diagnosis and treatment.

Description of drawings

Figure 1 is the AFM image of the prepared zirconium diboride nanosheets.

Fig. 2 is the SEM image of the prepared titanium diboride/chitosan/indocyanine green/polylactic acid-based composite nanofiber membrane.

Detailed ways

In order to enable those skilled in the art to understand the technical solution of the present invention more clearly, the technical solution of the present invention will be described below in conjunction with specific embodiments.

It should also be understood that the following examples are only used to further illustrate the present invention, and should not be construed as limiting the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art according to the above contents of the present invention all belong to the present invention scope of protection.

The specific process parameters and the like in the following examples are only examples of suitable ranges, that is, those skilled in the art can make a selection within a suitable range through the description herein, and are not limited to the specific values exemplified below.

Example 1

1. Freeze 60mg of zirconium diboride powder in liquid nitrogen for 1 hour and disperse it in 90mL of ethylene glycol, then add 60mg of surfactant polyether F68, perform ultrasonic peeling at 400w power for 2 hours in a water bath at 5°C, and disperse at 2500r Centrifuge at a speed of 12000r/min for 5min, remove the blocky unstripped zirconium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20min, collect the precipitate, and wash with absolute ethanol and deionized water Alternately washed three times respectively, freeze-dried for 24 hours to prepare zirconium diboride nanosheets.

2. Disperse 5 mg of zirconium diboride nanosheets prepared in 5 mL of aqueous solution, dissolve 80 mg of quaternary ammonium chitosan in 5 mL of deionized water to prepare an aqueous solution of quaternary ammonium chitosan, and mix the two evenly under the action of ultrasound , Stir at room temperature for 6h. The suspension was washed three times with deionized water and freeze-dried for 24 hours to prepare quaternized chitosan-modified zirconium diboride nanosheets.

3. Mix 5 mg of modified zirconium diboride nanosheets with 5 mL of 300 μg·mL ^-1 indocyanine green PBS solution, stir at high speed for 0.5 h, and then assemble at 15°C with low speed stirring in the dark for 12 h; after that, centrifuge and wash with PBS 3 times, the zirconium diboride nanosheet composite material was obtained after vacuum drying.

4. 1 g of polylactic acid was dissolved in 10.5 mL of dichloromethane, and 50 mg of zirconium diboride nanosheet composite material and 60 mg of PVP were dispersed in 10.5 mL of dichloromethane. The two solutions were mixed and stirred for 10 h in the dark. The composite fiber membrane material was prepared by spinning at a voltage of 19kV, an injection speed of 1mL/h, a receiver distance of 12cm, a rotation speed of 75rpm, and a temperature of 20°C.

The test results show that the temperature of the prepared zirconium diboride nanosheet composite can rise to 45℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ^～2 for 10min at a concentration of 250μg·mL ^-1 . The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 95.52% and 96.96%, respectively. The temperature of the prepared electrospun membrane can rise to 55° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm ² for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 99.68% and 99.91%, respectively. The wound infection healing experiment showed that after 14 days, the healing rate of the blank group was 80.56%, and the healing rate of the wound using the composite fiber membrane was 99.25%.

Example 2

1. Disperse 80mg of niobium diboride powder frozen in liquid nitrogen for 1.5h in 80mL of DMF, add 40mg of surfactant PVP, perform ultrasonic peeling of the probe at 300w power in a 5°C water bath for 3.5h, and use 2500r/ Centrifuge at a speed of 12000r/min for 8min to remove the lumpy unstripped niobium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min for 20min, collect the precipitate, and separate it with absolute ethanol and deionized water. Alternately washed three times, freeze-dried for 24 hours to prepare dry niobium diboride nanosheets.

2. Disperse 10 mg of niobium diboride nanosheets in 10 mL of deionized water, dissolve 100 mg of chitosan in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 18 hours. The suspension was washed three times with deionized water and freeze-dried for 24 hours to prepare chitosan-modified niobium diboride nanosheets.

3. Mix 10 mg of modified nanosheets with 10 mL of ethanol solution of indocyanine green at a concentration of 500 μg·mL ^-1 , stir at high speed for 1 h, and then assemble at 20° C. under low-speed stirring in the dark for 6 h. Centrifuge, wash with absolute ethanol for 3 times, and freeze-dry to prepare the niobium diboride nanosheet composite material.

4. Disperse 0.5g of polyvinyl alcohol in 10mL of deionized water, 10mg of niobium diboride nanosheet composite and 25mg of PVP in 8mL of deionized water. The two solutions were mixed and stirred in the dark for 16h. The voltage is 16kV, the injection speed is 2mL/h, the receiver distance is 10cm, and the rotation speed is 120rpm. Spinning is performed at a temperature of 20° C. to prepare a composite fiber membrane.

The test results show that when the concentration of the prepared niobium diboride nanosheet composite is 250μg·mL ^-1 , the temperature can rise to 45℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ^～2 for 10min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 90.24% and 92.78%, respectively. The temperature of the prepared electrospun membrane can rise to 45° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm ² for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 93.87% and 95.02%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 95.25%, and the healing rate of the blank group was 80.56%.

Example 3

1. Disperse 120 mg of hafnium diboride powder frozen in liquid nitrogen for 4 hours in 100 mL of N-methylpyrrolidone, add 80 mg of surfactant polyether P123, and perform ultrasonic peeling of the probe for 4.5 hours in a 10°C water bath with a power of 550w , centrifuge at a speed of 2500r/min for 10min, remove the blocky unstripped hafnium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20min, collect the precipitate, and wash with absolute ethanol and The deionized water was alternately washed three times, and dried for 24 hours to obtain dry hafnium diboride nanosheets.

2. Disperse hafnium diboride nanosheets in 3ml of deionized water, dissolve 90mg of chitosan biguanide salt in 3mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 12h. The suspension was washed three times with deionized water to remove unloaded chitosan biguanide salt, and dried for 24 hours to prepare chitosan biguanide salt-modified hafnium diboride.

3. Mix 6 mg of modified nanosheets with 6 mL of indocyanine green aqueous solution at a concentration of 300 μg·mL ^-1 , stir at high speed for 0.5 h, and then assemble at 25°C for 10 h at low speed in the dark. After centrifugation, washing with deionized water three times, and freeze-drying, the hafnium diboride nanosheet composite material was obtained.

4. Dissolve 0.8g of polylactic acid in 9.5mL of chloroform, and disperse 25mg of hafnium diboride nanosheet composite in a mixed solution of 9.5mL of chloroform and 10.5mL of ethanol. The two solutions were mixed and stirred in the dark for 12h. The voltage is 20.5kV, the injection speed is 1.5mL/h, the receiver distance is 15cm, and the rotation speed is 55rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.

The test results show that when the prepared hafnium diboride nanosheet composite material has a concentration of 200 μg·mL ^-1 and is irradiated with 808nm near-infrared light with a power of 1.5W/cm ^～2 for 10min, the temperature can rise to 53℃; The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 99.44% and 99.21%, respectively. The prepared electrospun membrane was irradiated with 808nm near-infrared light with a power of 1.5W/cm ^~2 for 5min, and the temperature could rise to 50°C; 98.79% and 99.13%. The wound infection healing experiment showed that after 14 days, the healing rate of the blank group was 80.56%, and the healing rate of the wound using the composite fiber membrane was 98.64%.

Example 4

1. Disperse 100 mg of titanium diboride powder frozen in liquid nitrogen for 1 h in 150 m of isopropanol, add 100 mg of cetyltrimethylammonium bromide, and perform ultrasonic stripping of the probe at 300 w in a water bath at 10 ° C for 5 h , centrifuged at a speed of 2500r/min for 5min, removed the massive unstripped titanium diboride powder, retained the supernatant, and centrifuged for a second time at a speed of 12000r/min, centrifuged for 20min, collected the precipitate, and washed with absolute ethanol and The deionized water was alternately washed three times, and dried for 24 hours to obtain dry titanium diboride nanosheets.

2. Disperse 10 mg of titanium diboride nanosheets in 10 mL of deionized water, dissolve 120 mg of mercaptopolyethylene glycol in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 24 hours. The suspension was washed three times with deionized water, and freeze-dried for 24 hours to prepare titanium diboride nanosheets modified with mercaptopolyethylene glycol.

3. Mix 6 mg of modified nanosheets with 6 mL of indocyanine green PBS solution at a concentration of 600 μg·mL ⁻¹ , stir at high speed for 2 h, and then assemble at 30° C. under low-speed stirring in the dark for 6 h. After centrifugation, washing with PBS three times, and freeze-drying, the titanium diboride nanosheet composite material was obtained.

4. Dissolve 1g of polycaprolactone in 10mL of dimethylformamide, and disperse 45mg of titanium diboride nanosheet composites and 100mg of PVP in 5mL of dimethylformamide solution. The two solutions were mixed and stirred for 10 h in the dark. The voltage is 20kV, the injection speed is 0.5mL/h, the receiver distance is 20cm, and the rotation speed is 125rpm. Spinning is carried out at a temperature of 20° C. to prepare a composite fiber membrane material.

The test results show that when the concentration of the prepared titanium diboride nanosheet composite is 200μg·mL ^-1 , the temperature can rise to 48℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ^～2 for 10min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 96.32% and 97.89%, respectively. The test results show that the temperature of the prepared electrospun membrane can rise to 55°C under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ^~2 for 5min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 99.05% and 99.84%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 93.19%, and the healing rate of the blank group was 80.56%.

Example 5

1. Disperse 75mg of chromium diboride powder frozen in liquid nitrogen for 10h in 75mL of ethylene glycol, add 25mg of surfactant P123, perform ultrasonic stripping of the probe at 250w power in a 5°C water bath for 5h, and use 2500r/min Centrifuge at a speed of 5 minutes, remove the massive unstripped chromium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20 minutes, collect the precipitate, and wash alternately with absolute ethanol and deionized water Three times, drying for 24 hours to obtain dry chromium diboride nanosheets.

2. Disperse 12 mg of chromium diboride nanosheets in 10 mL of deionized water, dissolve 120 mg of hyaluronic acid in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 24 hours. The suspension was washed three times with deionized water to remove unloaded hyaluronic acid, and freeze-dried for 24 hours to prepare hyaluronic acid-modified chromium diboride nanosheets.

3. Mix 10 mg of the modified nanosheets with 10 mL of ethanol solution of indocyanine green at a concentration of 450 μg·mL ^-1 , stir at high speed for 2 h, and then assemble at 20 ° C for 12 h in the dark under low speed stirring. Centrifuge, wash with ethanol three times, and freeze-dry to obtain the chromium diboride nanosheet composite material.

4. Dissolve 1.5g of polyacrylonitrile in 13.5mL of dimethylformamide, and disperse 100mg of chromium diboride nanosheet composite in a mixed solution of 9mL of dimethylformamide and 1.5mL of ethanol. The two solutions were mixed and stirred in the dark for 24h. The voltage is 13.8kV, the injection speed is 0.5mL/h, the receiver distance is 10cm, and the rotation speed is 100rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.

The test results show that when the concentration of the prepared chromium diboride nanosheet composite is 400μg·mL ^-1 , the temperature can rise to 49℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ^～2 for 10min. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 96.55% and 97.38%, respectively. The temperature of the prepared electrospun membrane can rise to 53° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm ² for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 97.11% and 98.25%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 92.25%, and the healing rate of the blank group was 80.56%.

Example 6

1. Disperse 100mg of zirconium diboride powder in 100mL of acetonitrile, add 50mg of surfactant dodecyl sulfuric acid, perform ultrasonic peeling of the probe at 500w power in a water bath at 10°C for 3h, and centrifuge at 2500r/min for 5min , remove the bulk unstripped zirconium diboride powder, retain the supernatant, and centrifuge twice at a speed of 12000r/min for 20min to collect the precipitate, wash it alternately three times with absolute ethanol and deionized water, and dry Dry zirconium diboride nanosheets were prepared in 24 hours.

2. Disperse 10 mg of zirconium diboride nanosheets in 10 mL of deionized water, dissolve 100 mg of chitosan biguanide salt in 10 mL of deionized water, mix the two evenly under the action of ultrasonic bath, and stir at room temperature for 12 hours. The suspension was washed three times with deionized water to remove unloaded chitosan biguanide salt, and freeze-dried for 24 hours to prepare chitosan biguanide salt-modified zirconium diboride nanosheets.

3. Dissolve 1 g of polyacrylonitrile in 10.5 mL of dimethylformamide, and disperse 80 mg of zirconium diboride nanosheet composite material in 8 mL of dimethylformamide. The two solutions were mixed and stirred in the dark for 18h. The voltage is 15.6kV, the injection speed is 2.5mL/h, the receiver distance is 16cm, and the rotation speed is 120rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.

The test results show that the temperature of the prepared zirconium diboride nanosheet composite can rise to 44℃ under the irradiation of 808nm near-infrared light with a power of 1.5W/cm ^～2 for 10min at a concentration of 300μg·mL ^-1 . The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 50.89% and 52.27%, respectively. The temperature of the prepared electrospun membrane can be raised to 50° C. under the irradiation of 808 nm near-infrared light with a power of 1.5 W/cm ² for 5 minutes. The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 75.68% and 78.23%, respectively. The wound infection healing experiment showed that after 14 days, the wound healing rate of the composite fiber membrane was 85.33%, and the healing rate of the blank group was 80.56%.

Example 7

1. Disperse 80 mg of hafnium diboride powder frozen in liquid nitrogen for 2 hours in 80 mL of ethylene glycol, add 20 mg of surfactant polyvinylpyrrolidone, and perform ultrasonic peeling of the probe at 400w power in a water bath at 10°C for 2.5 hours to Centrifuge at a speed of 2500r/min for 10min, remove the massive unstripped hafnium diboride powder, retain the supernatant, and centrifuge for a second time at a speed of 12000r/min, centrifuge for 20min, collect the precipitate, and use absolute ethanol and deionized Water was alternately washed three times, and dried for 24 hours to obtain dry hafnium diboride nanosheets.

2. Dissolve 1.2g of polylactic acid in 10mL of dichloromethane, and disperse 45mg of hafnium diboride nanosheets in a mixed solution of 8mL of dichloromethane and 6.5mL of ethanol. The two solutions were mixed and stirred in the dark for 24h. The voltage is 17.5kV, the injection speed is 0.5mL/h, the receiver distance is 18cm, and the rotation speed is 80rpm. Spinning is carried out at a temperature of 25° C. to prepare a composite fiber membrane material.

The test results show that when the prepared hafnium diboride nanosheet composite material has a concentration of 300 μg·mL ^-1 and is irradiated with 808nm near-infrared light with a power of 1.5W/cm ^～2 for 10min, the temperature can rise to 47℃; The antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 49.24% and 50.01%, respectively. The prepared electrospun membrane was irradiated with 808nm near-infrared light with a power of 1.5W/cm ^~2 for 5 minutes, and the temperature could rise to 46°C; the antibacterial rates against methicillin-resistant Staphylococcus aureus and Escherichia coli were 58.56% and 59.03%. The wound infection healing experiment showed that after 14 days, the healing rate of the blank group was 80.56%, and the healing rate of the wound using the composite fiber membrane was 81.02%.

Claims (5)

1. A preparation method of nanometer metal boride composite material, characterized in that, the steps are as follows: Step 1, freeze the metal boride with liquid nitrogen and disperse it in an organic solvent, add a surfactant, peel off at a temperature of 0-20°C with the assistance of ultrasound, centrifuge, wash with absolute ethanol and deionized water, and dry to obtain Metal boride nanosheets; wherein, the mass ratio of surfactant to metal boride is 1:20-1:1, the ultrasonic power is 200-800w, and the time is 1-5h; Step 2, adding the metal boride nanosheets obtained in step 1 into an aqueous solution containing a modifier, mixing and stirring in a constant temperature water bath, washing and drying to prepare modified metal boride nanosheets; wherein, the modified The concentration of the agent is 5-20mg/mL, the mass ratio of the modifier to the metal boride is 2:1-25:1, the stirring time is 6-24h, and the reaction temperature is 20-50°C; Step 3, mixing the modified metal boride nanosheets obtained in step 2 with the indocyanine green solution, stirring at high speed for 0.5-2 hours, and then stirring the self-assembly reaction at a low speed in a water bath at 0-35° C. After completion, centrifuge, wash, and dry to obtain nano-metal boride composite powder materials; among them, the high speed is 600-1000rpm, and the low speed is 100-300rpm; Step 4, dispersing the nano-metal boride composite powder material obtained in step 3 in a solution containing a spinning aid, adding an organic polymer solution, blending and stirring evenly to prepare an electrospinning liquid; using electrospinning technology Carry out spinning, and collect nano-metal boride composite materials with a receiver; wherein, the stirring time is 3-24 hours; the electrospinning temperature is 10-30°C; the voltage is 13-22kV; the injection speed is 0.5-3.5mL/ h; The receiver distance is 5-25cm, and the rotation speed is 50-150rpm. 2. preparation method according to claim 1, is characterized in that, In step 1, 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 ethylene glycol, DMF, N-methylpyrrolidone, isopropanol, N,N-dimethylformamide, ethanol, acetonitrile or a mixed solvent with water; The surfactant is one of polyether P123, sodium dodecylbenzenesulfonate, polyether F68, cetyltrimethylammonium bromide, polyvinylpyrrolidone, and dodecylsulfuric acid. The concentration in the stripping system is 100-1000μg/mL; The liquid nitrogen freezing time is 0.5~12h. 3. preparation method according to claim 1, is characterized in that, In step 2, The modifying agent is one of chitosan, quaternized chitosan, biguanide chitosan, amino polyethylene glycol, mercapto polyethylene glycol and hyaluronic acid. 4. preparation method according to claim 1, is characterized in that, In step 3, The solvent of indocyanine green solution is one of water, ethanol and PBS, and the concentration of indocyanine green in the reaction system is 0.05～1mg/mL; The mass ratio is 1:2~50; the drying conditions are freeze drying, vacuum drying or blast drying. 5. preparation method according to claim 1, is characterized in that, In step 4, The organic polymer is one of polyvinyl alcohol, polylactic acid, polyacrylonitrile and polycaprolactone; The solvent of the organic polymer solution is one of water, dimethylformamide, ethanol, dichloromethane and chloroform; Contains one or more mixtures of ethanol, polyvinylpyrrolidone and polyethylene glycol as spinning aids; The mass ratio of the nano metal boride composite powder material to the organic high polymer is 1:10-100.

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