Novel bionic bone material with carbon fiber graphene structure

Abstract

The invention relates to the field of implant hygienic materials, in particular to a bone material with carbon fibers, graphene and polyether-ether-ketone as base materials, a bioglass coating covering the base materials and bioglass-loaded bacterial drugs, so that the surface of the base materials has hydrophilicity, surface energy and protein white matter adsorption are remarkably improved, and the bioglass-loaded bacterial drugs can be used for preparing the bioglass-loaded bone material. The antibacterial and anti-infection performance of the surface of the bone repair material is improved, and the growth of bacteria is remarkably inhibited; meanwhile, adhesion, proliferation, differentiation and osteogenesis related gene expression of rBMSC are promoted, new bone regeneration is remarkably promoted in vivo, good bony combination with surrounding new bones is achieved, and infection is prevented. The surface is coated; and infection is prevented. The lysozyme loaded on the surface of the coating has excellent antibacterial and osteogenesis dual biological functions, and has wide application prospects in the field of bone repair materials.

Description

[0001] Technical field: It relates to implants, in particular to a new type of bionic bone material with carbon fiber and graphene structure.

[0002] The surface properties (roughness, hydrophilicity, surface energy and protein adsorption) and chemical composition of bone repair materials significantly affect their cell response and bone-promoting abilities. When bone repair materials are implanted in the body, they should promote new bone regeneration and form bone integration with the surrounding new bone to achieve early load and long-term stability. In addition, ideal bone repair materials should also have good antibacterial and anti-infection functions, inhibit bacterial adhesion to their surfaces, maintain the bone-binding interface, and achieve long-term stability of the implant. When implanted in the body, they can form bone integration with new bone and prevent infection.

[0003] PEKK (polyetherketoneketone) has good mechanical properties and biocompatibility, and its elastic modulus is close to that of bone implants. However, it is biologically inert and it is difficult to promote new bone formation. It is difficult to integrate with surrounding bone tissue after implantation, and it is easy to loosen or even fail after implantation. PEKK itself has no antibacterial activity, and many scholars have found that one of the key factors for the failure of bone implant materials is that they do not have antibacterial and anti-infection properties. The occurrence of infection will damage the tight interface between the implant and the host bone, causing the implant to loosen and eventually lead to implant failure. Therefore, the research and development of non-metallic bone implant materials has become an important topic in medicine and biology.

[0004] Invention content: The present invention aims to at least solve the technical problems and deficiencies in the prior art. To this end, the present invention proposes a bone repair material with excellent antibacterial and anti-infection properties and excellent bone formation ability, and provides the use of the bone repair material in the preparation of orthopedic implants such as bone plates, bone nails, frontal planes, cranial ribs, artificial joints, and vertebral implants.

[0005] The technical scheme of the present invention is further described below in conjunction with specific examples. The raw materials used in the following examples, unless otherwise specified, can all be obtained from conventional commercial sources; the processes used, unless otherwise specified, all adopt conventional processes in the art.

[0006] Example 1

[0007] Preparation of substrate: Graphene oxide (GO) dispersion was directly sprayed on the surface of sulfonated carbon fiber (S-CF) and polyetheretherketone (PEEK) prepreg, and graphene oxide, sulfonated carbon fiber, and polyetheretherketone were prepared by hot pressing.

[0008] Preparation of graphene oxide, sulfonated carbon fiber and polyetheretherketone composites

[0009] The sulfonated carbon fiber and polyetheretherketone prepreg were developed by Shanxi Coal Chemistry Research Institute. The sulfonated carbon fiber reinforced in the unidirectional expectation was prepared by 1700S powder method. The content ratio of sulfonated carbon fiber and polyetheretherketone was 70WT%. 30WT%. Graphene oxide was provided by Shanxi Coal Chemistry Research Institute. After graphene oxide was prepared by modified HUNNMERS method, graphene oxide was thermally stripped at 1000C to obtain the required graphene. First, the sulfonated carbon fiber and polyetheretherketone prepreg (S-CF-PEEK) were cut into mold size. After the phase, the corresponding mass fraction (0.1WT%, 0.3WT%, 0.5WT%) of graphene is dispersed in anhydrous ethanol under the assistance of ultrasound, and the dispersion is sprayed on the cut sulfonated carbon fiber and polyetheretherketone prepreg surface with a spray gun. In order to ensure that the graphene is evenly distributed on the prepreg surface, the spraying operation is carried out on a heating plate, and the temperature is controlled at 80C to ensure the rapid evaporation of the solvent ethanol. The process is carried out in an air atmosphere, and then the sulfonated carbon fiber coated with 16 layers of graphene is placed. The polyetheretherketone prepreg is placed in a mold, hot-pressed at 400C.30MPA for one hour, and the pressure is maintained for one hour to obtain a graphene oxide, sulfonated carbon fiber, polyetheretherketone composite material-substrate (GO-S-CF-PEEK)

[0010] 2) Electrophoretic deposition of bioglass coating

[0011] The GO-S-CF-PEEK composite material was attached to an electrode sheet and immersed in a suspension of bioglass (the chemical composition of bioglass is ZnO-CaO-SiO2, prepared by sol-gel method, and the concentration in the suspension is about 1g / mL), and electrophoretic deposition (deposition voltage: 20V, deposition time: 2min) was performed to form a bioglass coating on the surface of the GO-S-PEEK composite material. The material obtained after the electrophoretic deposition was marked as MBGN.

[0012] (3) Loading lysozyme

[0013] Weigh 10.0 mg of lysozyme and dissolve it in a small amount of deionized water, transfer it to a 10 mL volumetric flask and dilute it to 10 mL with water to prepare a 1 mg / mL lysozyme aqueous solution. Use a pipette to draw 2, 20, 200, 400, 1000, 1500, and 1700 μL in turn into their respective 2 mL volumetric flasks, add water to the scale line, and prepare 1, 10, 100, 200, 500, 750, and 850 μg / mL standard solutions. Use a microplate reader (Multiskan Spectrum, Thermo Scientific) to test the optical density of the solution at 280 nm to obtain a standard curve of lysozyme in aqueous solution.

[0014] Prepare an aqueous solution of lysozyme (10 g / mL), soak MBGN in the aqueous solution of lysozyme, perform electrophoretic deposition (deposition voltage: 20 V, deposition time: 2 min), load lysozyme in the bioglass coating of MBGN, and label the obtained material as LY. Calculate the loading efficiency of lysozyme using a standard curve.

[0015] Comparative Example 1

[0016] Compared with Example 1, this comparative example replaces the electrophoretic deposition method in step (3) with a common immersion adsorption method.

[0017] Specifically, the bone repair material was prepared in the following manner:

[0018] The MBGN prepared according to steps (1) and (2) of Example 1 was immersed in an aqueous solution of lysozyme (10 g / mL) and adsorbed for 2 minutes to obtain a bone repair material.

[0019] Structural and performance testing:

[0020] 1. Physical and chemical properties

[0021] (1) Infrared spectrometer spectrum and X-ray diffraction analysis

[0022] As shown in the infrared spectrometer analysis of GO-S-CF-PEEK, MBGN and LY, * is the characteristic peak of PEKK, ^ is the characteristic peak of GO, and ● is the characteristic peak of bioglass. The results show that compared with GO-S-CF-PEEK, the characteristic peak of PEKK in MBGN and LY basically disappears. This is due to the presence of the bioglass coating on the surface. The bioglass coating covers the substrate PEKK, so only the infrared characteristic peak of the bioglass is displayed. X-ray diffraction shows that bioglass is an amorphous structure with a very low degree of crystallization. It can quickly release ions with the surrounding body fluids in the body and has excellent osteogenic activity. In addition, due to the low content of lysozyme, its characteristic peak is not displayed.

[0023] c and d are the loading efficiency and release curves of lysozyme loaded onto MBGN by different methods (traditional immersion adsorption and electrophoretic deposition EPD). It can be seen that the loading efficiency of the EPD method is significantly higher than that of the traditional immersion coating, and the release of lysozyme loaded by the EPD method in PBS aqueous solution shows sustained release, while the traditional immersion coating LY shows a sudden release at the beginning.

[0024] (2) Electron microscope and X-ray spectrometer analysis

[0025] SEM observations show that before the preparation of the bioglass coating, the GO in the substrate GO-S-CF-PEEK is evenly distributed in PEKK, providing good conductivity. After the preparation of the bioglass coating, the surface of the sample is a uniform bioglass coating, the coating is uniform, and there are no cracks; and the bioglass coating is composed of regularly arranged nano-bioglass particles. The results of the X-ray energy spectrometer show that after the preparation of the bioglass coating, the characteristic peak of GO disappears, and the bioglass covers the surface of the material. After loading lysozyme, the surface morphology and EDS elemental analysis of the material did not change significantly compared with MBGN.

[0026] (3) Hydrophilicity, surface energy, protein adsorption analysis, ion release, pH analysis

[0027] Test method: The water contact angle and diiodomethane contact angle of the sample surface were measured by contact angle meter, and the surface energy of the sample was obtained according to Owens two-liquid method; the protein adsorption capacity of the material surface was measured by BCA kit (Shanghai Biyuntian Biotechnology Co., Ltd.); GO-S-CF-PEEK, MBGN and LY were immersed in 10mL SBF solution (simulated body fluid), and the pH value of the solution was measured at different time points (0.5 days, 1 day, 3 days, 7 days, 10 days and 14 days). Test results.

[0028] The water contact angle and diiodomethane contact angle of three samples, GO-S-CF-PEEK, MBGN and LY, were displayed. The results showed that the hydrophilicity of the material was significantly improved after the preparation of the bioglass coating. There was no significant change in the water contact angle and diiodomethane contact angle on the surface of the material before and after loading lysozyme. In addition, it was shown that after the preparation of the bioglass coating, the surface energy of the material was also significantly improved, while there was no significant difference in the surface energy between MBGN and LY. The adsorption of proteins (bovine serum albumin BSA and fibronectin Fn) on the three samples was displayed. The results showed that after the preparation of the bioglass coating, the protein adsorption on the surface of the material was significantly improved, which has a positive effect on the subsequent cell adhesion and anchoring.

[0029] The pH value changes over time when GO-S-CF-PEEK, MBGN and LY are immersed in SBF. No significant change in pH was observed in GO-S-CF-PEEK (approximately stable at pH = 7.4), while for MBGN (about pH = 7.7) and LY (about pH = 7.8), the pH value gradually increased over time and stabilized after 10 days, with the stable pH of MBGN being about 7.7 and the stable pH of LY being about 7.8, both showing weak alkalinity. Existing studies have shown that a weakly alkaline environment has a positive effect on cell adhesion, proliferation and differentiation.

[0030] 2. In vitro antibacterial properties

[0031] The antibacterial activity of GO-S-CF-PEEK, MBGN or LY was determined by bacterial plate count method, and the results show digital photos of Staphylococcus aureus and Escherichia coli colonies isolated from GO-S-CF-PEEK, MBGN and LY on agar after 24 hours of bacterial culture on the material surface. A large number of Staphylococcus aureus and Escherichia coli colonies were found on GO-S-CF-PEEK, indicating that GO-S-CF-PEEK has no antibacterial function. However, the number of colonies of MBGN and LY was less, indicating that they have effective antibacterial activity.

[0032] The reduction percentages of Staphylococcus aureus and Escherichia coli in the samples are shown. Compared with GO-S-CF-PEEK, MBGN has an inhibition rate of 82.19% against Staphylococcus aureus and 80.47% against Escherichia coli. The inhibition rate of LY against Staphylococcus aureus is 99.61% and against Escherichia coli is 99.12%, demonstrating that LY has excellent in vitro antibacterial properties.

[0033] 3. In vitro cytocompatibility

[0034] Test method: rBMSC cells (density of 105 cells / well) were co-cultured with GO-S-CF-PEEK, MBGN or LY for different time periods. Laser confocal microscopy (CLSM) was used to observe the cell morphology on the surface of the material. The cell samples were fixed and the CKK-8 method was used to detect the adhesion rate of cells on the surface of GO-S-CF-PEEK, MBGN or LY.

[0036] (1) Cell Adhesion

[0037] CLSM images show the cytoskeletal morphology and distribution of nuclei (blue) and cellular actin (i.e., skeleton, green) of rBMSC cells on samples stained with FITC-Phalloidin and DAPI. On day 1, cells on MBGN and LY had filamentous protrusions, while cells on GO-S-CF-PEEK had no obvious filamentous protrusions. On day 3, there were more filopodial cells and lamellipodial cells on MBGN and LY than on GO-S-CF-PEEK, and there were a large number of cells on the surface of MBGN and LY, while the number of cells on the surface of GO-S-CF-PEEK was relatively small.

[0038] (2) Cell proliferation and osteogenic differentiation

[0039] The adhesion rate of cells after different culture times is shown. There is no significant difference among the three groups at 12 hours. At 24 hours and later, a large number of cells adhere to the surface of MBGN and LY, and the adhesion rate is higher than that of GO-S-CF-PEEK, but there is no significant difference between MBGN and LY. The proliferation of rBMSC cells on the samples after different culture times is shown (expressed as OD value). The proliferation of GO-S-CF-PEEK, MBGN and LY cells increases with time. On the 1st, 3rd and 7th days, the cell proliferation of MBGN and LY was significantly higher than that of GO-S-CF-PEEK, but there was no significant difference between the two.

[0040] The quantitative analysis of ALP activity of rBMSC cells on samples after 7, 10, and 14 days of culture is shown in Figure GO-S-CF-PEEK. The ALP activity of , MBGN, and LY cells increased over time. On days 10 and 14, the ALP activity of LY was higher than that of MBGN, and the ALP activity of MBGN was higher than that of PT40, indicating that LY and MBGN can better stimulate the positive response of cells (adhesion and spreading, proliferation, and osteogenic differentiation) compared with GO-S-CF-PEEK.

[0041] (a-d) are the expression of osteogenic genes (ALP, OPN, OCN and Runx2) of cells on GO-S-CF-PEEK, MBGN and LY, among which the primers for TRT-PCR test of ALP, OPN, OCN and Runx2 were GO-S-CF-PEEK. The expression of ALP, OCN and Runx2 genes on , MBGN and LY increased with time. On the 3rd day, there was no significant difference in the expression of ALP, OPN, OCN and Runx2 among all samples. On the 7th day, the gene expression of OPN, OCN and Runx2 in MBGN and LY was higher than that in GO-S-CF-PEEK. On the 14th day, the expression of OPN, OCN and Runx2 in LY was higher than that in MBGN, while the expression of these genes in MBGN was higher than that in GO-S-CF-PEEK. Therefore, compared with GO-S-CF-PEEK, the coated MBGN material can significantly promote the osteogenic differentiation of cells, and the trend of osteogenic differentiation is further enhanced after loading LY.

[0042] IV. Evaluation of anti-infection performance in vivo

[0043] A rat femoral intramedullary nail infection prevention model was established, and different materials were implanted into rats. X-rays of the rat femurs on the 14th day after implantation showed signs of osteomyelitis in GO-S-CF-PEEK, which were manifested by obvious cortical bone destruction and periosteal reaction. The osteomyelitis and periosteal reaction of MBGN and LY were mild, indicating that MBGN and LY had good anti-infection effects. The implants were further removed to evaluate their anti-infection properties, and a large number of bacteria were isolated from GO-S-CF-PEEK, while significantly fewer bacteria were found in MBGN and LY. Therefore, the anti-infection activity of MBGN and LY was significantly higher than that of GO-S-CF-PEEK. The reduction percentage of Escherichia coli in the in vivo samples was shown, of which GO-S-CF-PEEK had no anti-infection activity, MBGN had an inhibition rate of 78.67% against Escherichia coli, and LY had an inhibition rate of 99.53% against Escherichia coli, respectively.

[0044] 5. In vivo evaluation of osteogenesis and osseointegration

[0045] Testing method: A right femoral condyle defect model of New Zealand white rabbits was created, and GO-S-CF-PEEK, MBGN and LY were implanted into it. At the specified time points (4 weeks and 12 weeks after surgery), the repair of the bone defect was evaluated by synchrotron radiation micro-CT (SRμCT). After 4 weeks and 12 weeks of implantation, the femoral samples were hard tissue sectioned and VG stained. The new bone regeneration and bone integration were observed under an inverted microscope, and the new bone tissue-implant contact rate was analyzed by Image Pro software. The push-out strength of the samples was tested using a universal materials testing machine.

[0046] Statistical analysis was performed using one-way analysis of variance (ANOVA). The quantitative data in this chapter are the mean ± standard deviation of at least three independent experimental test results. When *p < 0.05, **p < 0.01 or #p < 0.05, it indicates that there is a statistically significant difference between the data.

[0047] (1) SRμCT analysis

[0048] As shown in the two-dimensional reconstruction images (SRμCT) of the new bone tissue around the implant at different times of implantation, it can be seen that the content of new bone around GO-S-CF-PEEK, MBGN and LY gradually increases with the increase of implantation time. After 4 and 12 weeks of implantation, the amount of NB tissue around MBGN and LY implants was higher than that of GO-S-CF-PEEK. There was no significant difference in NB around the LY group and MBGN, and the GO-S-CF-PEEK group had the lowest NB. It can be seen that compared with GO-S-CF-PEEK, LY and MBGN have better osteogenic effects.

[0049] (2) Histological analysis, implant-bone contact rate, and push-out strength evaluation

[0050] These are histological images after implantation at different times. At the 4th and 12th weeks, more NB tissues were visible on the surface of LY and MBGN, while only a relatively small amount of NB tissues were visible on the surface of GO-S-CF-PEEK. At the 12th week, there was still an obvious gap between the GO-S-CF-PEEK and NB interfaces, while the NB tissues were in closer contact with LY and MBGN, and had good bone integration. It can be seen that compared with GO-S-CF-PEEK, MBGN and LY have stronger abilities to promote new bone regeneration and bone integration.

[0051] The quantitative analysis of implant bone contact rate (BIC) after different implantation times is shown. The BIC of GO-S-CF-PEEK, MBGN, and LY increased significantly from 4 to 12 weeks after implantation. The BIC of MBGN and LY was significantly higher than that of GO-S-CF-PEEK at 4 and 12 weeks. At 12 weeks, there was no significant difference in the BIC between MBGN and LY.

[0052] b shows the push-out strength of GO-S-CF-PEEK, MBGN and LY after 4 and 12 weeks of implantation. The push-out strength of GO-S-CF-PEEK, MBGN and LY increased from the 4th week to the 12th week. At the 4th and 12th week after implantation, the push-out strength of MBGN and LY was significantly higher than that of GO-S-CF-PEEK. At 12 weeks, there was no significant difference in the push-out strength of MBGN and LY. It was proved that MBGN and LY have excellent performance in promoting bone regeneration and bone integration. In summary, GO particles are more uniformly distributed on the surface of GO-S-CF-PEEK. After electrophoretic deposition, MBGN is uniformly coated on the surface of GO-S-CF-PEEK, the coating is uniform and crack-free, and the bioglass nanoparticles are evenly distributed on the surface of the material, and lysozyme is further loaded by electrophoretic deposition.

[0053] 6. Discussion

[0054] In Example 1, GO particles are relatively evenly distributed on the surface of GO-S-CF-PEEK. After electrophoretic deposition, MBGN is evenly coated on the surface of GO-S-CF-PEEK. The coating is uniform and crack-free. Bioglass nanoparticles are evenly distributed on the surface of the material and lysozyme is further loaded by electrophoretic deposition.

[0055] The hydrophilic surface of the bone implant material can promote the early stages of cell adhesion and proliferation. In Example 1, the surface hydrophilicity of MBGN is higher than that of GO-S-CF-PEEK due to the presence of MBGN particles. In addition, there is no significant difference in the hydrophilicity of MBGN and LY, because there is no significant change in the surface morphology before and after drug loading.

[0056] Surface energy is another surface property that affects the cell response of implant materials, and surfaces with high surface energy will adsorb more proteins. In the biological microenvironment, protein adsorption is conducive to further attracting surrounding cells. In Example 1, due to the presence of nano-bioglass particles, the surface energy of MBGN and LY is higher than that of GO-S-CF-PEEK. In addition, compared with MBGN, the surface energy of LY did not change significantly. Protein adsorption on the surface of implantable materials is conducive to the initial adhesion / spreading and proliferation of cells, because the adsorbed proteins act as ligands and bind to the membrane protein receptors (such as integrins) of cells. In Example 1, due to the presence of bioglass nanoparticles, the protein adsorption of MBGN and LY is significantly higher than that of GO-S-CF-PEEK. In addition, compared with MBGN, the protein adsorption of LY did not change significantly because the protein adsorption capacity of the two is similar. These results show that covering the surface of GO-S-CF-PEEK with a bioglass coating and further loading lysozyme can improve surface properties (hydrophilicity, surface energy, and protein adsorption).

[0057] For implantable materials, bacteria can easily attach to their surface, colonize to produce bacterial biofilms, thereby causing inflammatory reactions and ultimately leading to implant failure. Implant materials with antibacterial activity can inhibit bacterial infection and ensure long-term stability of implantation. In Example 1, GO-S-CF-PEEK has no antibacterial activity, and after electrophoretic deposition of the bioglass coating, the MBGN obtained will create a weakly alkaline microenvironment, so MBGN has good antibacterial activity; and LY exhibits excellent antibacterial properties against both Staphylococcus aureus and Escherichia coli, because it continuously releases lysozyme, and the release of lysozyme can effectively inhibit bacterial adhesion.

[0058] Cell adhesion and proliferation on implants generally depend on surface characteristics (e.g., surface morphology, hydrophilicity, surface energy, and protein adsorption). Cell adhesion and spreading on the implant surface are key to subsequent cell proliferation and differentiation

[174] . In Example 1, mesenchymal stem cells adhered better to MBGN and LY than to GO-S-CF-PEEK, while there was no significant difference between MBGN and LY. rBMSC cells proliferated better on MBGN and LY than on GO-S-CF-PEEK, while there was no significant difference between MBGN and LY. The improved cell adhesion and proliferation on MBGN and LY compared to GO-S-CF-PEEK is due to the presence of bioglass nanoparticles on the surface.

[0059] In Example 1, the expressions of Runx2, ALP, OPN and OCN of MBGN and LY were significantly higher than those of GO-S-CF-PEEK. The improvement of osteogenic differentiation of rBMSC cells on MBGN was due to the presence of bioglass particles on its surface, which promoted the osteogenic differentiation of cells.

[0060] The in vivo anti-infection properties of GO-S-CF-PEEK, MBGN and LY were evaluated by establishing a rat femoral intramedullary nail infection prevention model. The results showed that the improvement in the anti-infection properties of MBGN and LY compared with GO-S-CF-PEEK was due to the bioactive coating introduced by electrophoretic deposition modification. In addition, the significant improvement in the anti-infection properties of LY in vivo was attributed to the loading of lysozyme. Since LY continuously releases lysozyme, it has an inhibitory effect on the growth of bacteria, and the inhibition rate of LY is higher than that of MBGN. Therefore, the in vitro antibacterial properties of LY are consistent with the in vivo infection properties of the sample.

[0061] Due to the presence of LY nanoparticle coating, the new bone regeneration of LY and MBGN was higher than that of GO-S-CF-PEEK, while there was no significant difference between MBGN and LY. Histological images showed that there was a clear gap between GO-S-CF-PEEK and the bone tissue interface after 4 weeks of implantation, that is, there was no bone integration. In contrast, the bone tissue was tightly integrated with MBGN and LY, and there was no gap at the 12th week, showing good bone integration. The push-out strength was used to detect the bone integration of the implant at different implantation times. Compared with GO-S-CF-PEEK, MBGN and LY showed higher push-out strength, indicating that better bone integration was formed after coating. For bone implants, it is crucial to achieve tight integration with the host bone tissue, which ensures the long-term successful bone integration quality of the implant.

[0062] The surface properties of the material (such as morphology, composition, hydrophilicity) significantly affect the response of osteoblasts and bone regeneration and bone integration around the implant. In Example 1, the bioglass coating improves the surface properties of the substrate and plays a vital role in the reaction of rBMSC activation in vitro, thereby promoting bone regeneration and bone integration in vivo. In addition, compared with GO-S-CF-PEEK, the presence of MBGN and LY further improves the surface properties, thereby further promoting in vitro cell response and in vivo bone regeneration and bone integration. LY not only has osteogenic bioactivity, but also has antibacterial activity. In short, after preparing a bioglass coating on the surface of GO-S-CF-PEEK and loading lysozyme, a new type of LY implantable bone repair material is formed, and the hydrophilicity, surface energy, and protein adsorption of the material surface are significantly improved, and bacterial growth is significantly inhibited in vitro, among which LY has an antibacterial rate of more than 99% against Escherichia coli and Staphylococcus aureus. MBGN and LY significantly promoted the adhesion, proliferation, differentiation and osteogenesis-related gene expression of rBMSCs, significantly promoted new bone regeneration in vivo, formed good bone integration with surrounding new bones, and prevented infection. The coating surface loaded with lysozyme has excellent antibacterial and osteogenesis dual biological functions, which can prevent infection and enhance bone integration, and has broad application prospects in the field of bone repair materials.

Claims

1. Preparation of substrate: Spray the graphene oxide dispersion directly onto the surface of sulfonated carbon fiber and polyetheretherketone prepreg. The lamination was prepared by hot pressing method to form graphene oxide, sulfonated carbon fiber, polyetheretherketone composite material-skeleton substrate: Preparation of graphene oxide, sulfonated carbon fiber and polyetheretherketone composites The sulfonated carbon fiber and polyetheretherketone prepreg are prepared by a 1700S powder method, and the content of the sulfonated carbon fiber and polyetheretherketone is 70 WT%. 30 WT%. Graphene oxide is prepared by a modified HUNNMERS method, and then the graphene oxide is thermally stripped at 1000°C to obtain the required graphene. First, the sulfonated carbon fiber and polyetheretherketone prepreg are cut into mold size. After that, the graphene with the corresponding mass fraction (0.1 WT%, 0.3 WT%. 0.5 WT%) is dispersed in anhydrous ethanol under the assistance of ultrasound, and the dispersion is sprayed on the cut sulfonated carbon fiber and polyetheretherketone prepreg surface with a spray gun. In order to ensure that the graphene is evenly distributed on the prepreg surface, the spraying operation is carried out on a heating plate, and the temperature is controlled at 80°C to ensure the rapid evaporation of the solvent ethanol. The process is carried out in an air atmosphere, and then the sulfonated carbon fiber coated with 16 layers of graphene is coated. The polyetheretherketone prepreg was placed in a mold, hot-pressed at 400C.30MPA for one hour, and kept under pressure for one hour to obtain graphene oxide, sulfonated carbon fiber, and polyetheretherketone composite material-matrix (PEEK-CF-GR).

2. A bone repair material, characterized in that: The bone repair material comprises a substrate and a bioglass coating covering the surface of the substrate, wherein the bioglass coating is loaded with antibacterial drugs.

3. The bone repair material according to claim 2, characterized in that: The thickness of the bioglass coating is 200-500nm.

4. The bone repair material according to claim 2, characterized in that: The bioglass coating comprises nano bioglass particles, and the nano bioglass particles have a pore structure.

5. The bone repair material according to claim 4, characterized in that: The particle size of the nano bioglass particles is 200-400 nm, and the pore size is 1-10 nm.

6. The bone repair material according to any one of claims 2 to 5, characterized in that: The antibacterial drug comprises at least one of lysozyme and antibacterial peptide.

7. The bone repair material according to claim 6, characterized in that: The mass content of the antibacterial drug in the bioglass coating is 2-10%.

8. The method for preparing the bone repair material according to any one of claims 2 to 7, characterized in that: The steps include: The surface of the substrate is covered with a bioglass coating; the antibacterial drug is loaded on the bioglass coating to obtain a bone repair material.

9. The preparation method according to claim 8, characterized in that: The step of loading the antimicrobial drug on the surface of the bioglass coating is specifically to immerse the substrate covered with the bioglass coating in an antimicrobial drug solution, and load the antimicrobial drug on the surface of the bioglass coating by electrophoretic deposition.

10. The preparation method according to claim 9, characterized in that: The voltage used in the electrophoretic deposition is 10 to 30 V, and the deposition time is 1 to 5 minutes.

11. Use of the bone repair material according to any one of claims 2 to 7 in the preparation of bone plates, bone nails, frontal surfaces, cranial ribs, artificial joints or vertebral implants.