CN112661500B - Bioceramic scaffold with micro/nano structure on the surface and its preparation method and application - Google Patents

Abstract

A biological ceramic support with a micro-nano structure on the surface and a preparation method and application thereof are disclosed, and specifically a biological ceramic support modified by ferroferric sulfide micro-flower is characterized by comprising an akermanite support and ferroferric sulfide layer micro-flower grains growing on the surface of the akermanite support, wherein the diameter of a pore passage of the akermanite support is 100-400 μm; the ferroferric sulfide micro-flower grains are of a micro-nano structure and are assembled by flaky grains with the diameter of 0.5-3 mu m, and the diameter of the flaky grains is 5-50 mu m. The prepared ferroferric sulfide micro-flower modified biological ceramic scaffold can be used for treating and repairing bone tumor after operation.

Description

Bioceramic scaffold with micro/nano structure on the surface and its preparation method and application

technical field

The invention relates to a bioceramic scaffold with a micro-nano structure on the surface and a preparation method and application thereof, in particular to a bioceramic scaffold modified with iron tetrasulfide microflora, a preparation method and application thereof, and belongs to the field of biological materials.

Background technique

The treatment of malignant bone tumors has always been a huge clinical problem. At present, there are many methods for the treatment of malignant bone tumors, such as surgical resection, chemotherapy, radiotherapy and so on. Surgical resection leaves a large defect at the resection site, which must be repaired with an implant, and surgical resection cannot completely remove tumor cells. Radiotherapy and chemotherapy will cause greater damage to the normal tissue around the tumor, and will also make tumor cells resistant to drugs. Therefore, the development of biomaterials with both tumor clearance and bone repair capabilities remains a great challenge. Chemodynamic therapy utilizes ferrous ions to efficiently disproportionate hydrogen peroxide accumulated in the tumor microenvironment to generate highly oxidative reactive oxygen species, which in turn cause a series of oxidative damages such as protein degeneration, DNA fragmentation, and mitochondrial damage in tumor cells, thereby causing tumors apoptosis of cells. In addition, the use of magnetothermal therapy can assist in promoting the generation efficiency of hydroxyl radicals in chemodynamic therapy, and realize magnetothermal regulation of chemodynamic therapy for the treatment of tumors. Magnetothermal therapy is not affected by depth, has high efficiency, and has few side effects, so it can be used to treat deep tumors such as bone tumors. The microstructure on the surface of the three-dimensional scaffold can promote the osteogenic differentiation of bone marrow mesenchymal stem cells.

SUMMARY OF THE INVENTION

In view of the problems existing in the prior art, the purpose of the present invention is to provide a bioceramic scaffold with both tumor removal and bone repair capabilities.

In one aspect, the present invention provides a bioceramic scaffold material modified with ferric ferrite microflora, comprising a magnesite scaffold and ferric tetrasulfide layer microflora particles grown on the surface of the magnesite scaffold, wherein the pore diameter of the magnesia feldspar scaffold is in the range of 100-400 μm; the iron tetrasulfide microflora particles are micro-nano structures, assembled from flake particles with a diameter of 0.5-3 μm, and the diameter of which is 5-50 μm.

Ferrous tetrasulfide microflora-modified bioceramic scaffold, the iron tetrasulfide grown on the surface of the scaffold has ferromagnetic properties, which can rapidly heat up under the induction of an alternating magnetic field due to hysteresis effect and relaxation effect, and can be used in an acidic environment. Fe 2+ + H 2 O 2 → Fe 3+ + OH - + Fe ²⁺ + H ₂ O ₂ → Fe ³⁺ + OH ^- + • OH, magnetocaloric can improve the production efficiency of reactive oxygen species and achieve the synergistic effect of magnetocaloric and chemokinetic therapy to kill tumor cells. At the same time, micro-nano structures can regulate cell behavior by mediating actin F-actin such as integrin α5β1, thereby promoting osteogenic differentiation. Therefore, micro-nano structures have certain advantages in promoting bone repair. The micro-nano structures formed by the iron tetrasulfide microflora on the surface of the scaffolds can regulate the cell shape and then the differentiation ability of bone marrow mesenchymal stem cells through integrin-mediated actin F-actin, and play a role in repairing bone defects. In addition, magnesite has good osteogenic activity, and magnesite scaffold itself can release active ions (such as Ca, Mg and Si) to promote bone repair, while the microstructure of ferric sulfide can synergize with active ions to further the osteogenesis of magnesite scaffold performance. Therefore, the bioceramic scaffold modified with iron tetrasulfide microflora of the present invention has a good ability to remove tumors and repair bone defects, and can be used for postoperative treatment of bone tumors.

Preferably, the bioceramic scaffold is formed by growing the ferric tetrasulfide microflora particles on the surface of the MgO feldspar scaffold using a hydrothermal method in an aqueous solution of FeSO ₄ ·7H ₂ O and L-cysteine. prepared. The hydrothermal reaction temperature is preferably 160-200° C., and the reaction time is 12-24 hours.

Preferably, the concentration of FeSO ₄ •7H ₂ O in the aqueous solution is -0.01-0.05 mol/L, and the concentration of L-cysteine is 0.01-0.05 mol/L.

Preferably, the ferric tetrasulfide microflora is grown in situ on the surface of the magnesia feldspar support, and the thickness of the entire layer formed is 1-10 μm.

_In another aspect, the present invention provides a method for preparing a bioceramic scaffold modified with ferric sulfide microflora, including the preparation of a magnesia feldspar ceramic scaffold _; A bioceramic scaffold modified with ferric tetrasulfide microflora is obtained by hydrothermal treatment in an aqueous solution of amino acid.

In one embodiment, the bioactive ceramic scaffold of the magnesite feldspar is prepared by the following method:

Mix the magnesite powder: the binder in a mass ratio of (1-1.5): 1 to obtain a paste;

The obtained paste is placed in a three-dimensional printer for three-dimensional printing to obtain a green body;

The obtained green body is sintered at 1300-1400 DEG C for 3-5 hours to prepare a magnesite bioactive ceramic stent.

Preferably, the binder includes the common binder sodium alginate, aqueous solution of Pluronic F127, and/or polyvinyl alcohol and the like.

In the process of hydrothermal treatment of the obtained magnesite scaffold in an aqueous solution of FeSO ₄ •7H ₂ O and L-cysteine, the concentration of the hydrothermal precursor of iron tetrasulfide is preferably 0.01-0.05mol/L.

In the present invention, the magnesia feldspar bracket is prepared by three-dimensional printing technology, the preparation method is simple, and the bracket with complex shape can be prepared. In addition, the hydrothermal method can decorate the surface of the scaffold with FeS microflora, and the preparation is simple and reproducible.

In yet another aspect, the present invention also provides an application of a bioceramic scaffold modified with iron tetrasulfide microflora in the treatment and repair of bone tumors after surgery.

Description of drawings

Figure 1 shows the optical photos of pure magnesite and ferric sulfide modified magnesite scaffolds (a), SEM images of pure magnesite scaffolds (b1-b3), ferric tetrasulfide-modified magnesite under different hydrothermal conditions Scaffold (c1-f3), the specific corresponding reaction conditions are as follows: (c1-c3) 0.02 mol/L precursor, reaction temperature 160 ℃, reaction time 12 hours, named 0.02 L-FS-AKT; (d1-d3) 0.04 mol/L precursor, reaction temperature 160 °C, reaction time 12 hours, named 0.04L-FS-AKT; (e1-e3) 0.02 mol/L precursor, reaction temperature 180 °C, reaction time 12 hours, named as 0.02 F-FS-AKT; (f1-f3) 0.04 mol/L precursor, reaction temperature 180 °C, reaction time 12 hours, named 0.04F-FS-AKT, among which, it can be seen from e1-e3 that in this Under one condition, a micro-flower structure with uniform size was formed on the surface of the stent;

Figure 2 shows the magnetocaloric properties of the scaffold modified with ferric tetrasulfide; the curves in the figure from bottom to top are: 6A, 7A, and 8A;

Fig. 3 is the performance of ferric tetrasulfide modified magnesite scaffold to catalyze hydrogen peroxide to generate reactive oxygen species;

Figure 4 shows the absorbance (a), osteogenesis-related genes osteocalcin (OCN) (b), osteopontin (OPN) (c) and osteocytes of bone marrow mesenchymal stem cells cultured on scaffolds for 1, 3, and 7 days The expression level of specific transcription factor (RUNX2) (d); from left to right in Figure 4 (a) are AKT, 0.02 L-FS-AKT, 0.04 L-FS-AKT, 0.02 F-FS-AKT, 0.04 F-FS-AKT (specified in Figure 1), it can be seen from the figure that 0.02 F-FS-AKT can effectively promote the proliferation of bone marrow mesenchymal stem cells, and can significantly increase the expression of osteogenesis-related genes compared with other groups Express;

Figure 5 shows the survival rate of LM-8 osteosarcoma cells under the synergistic effect of scaffold magnetocaloric and reactive oxygen species;

Figure 6 shows the anti-tumor ability of the scaffold in the subcutaneous tumor model of nude mice, the heating curve (a), the change in tumor volume (b), the photos of nude mice on days 0 and 14 (c), the photos of tumor tissue (d) and the tumor The H&E staining image of the tissue (e); the curves in (b) of Figure 6 are from top to bottom: blank group, Fe ₃ S ₄ -AKT group, Fe ₃ S ₄ -AKT + alternating magnetic field (AMF) group;

Figure 7 shows the CT analysis results of the New Zealand white rabbit bone defect model animal experiment.

Detailed ways

The present invention will be further described below with reference to the accompanying drawings and the following embodiments. It should be understood that the accompanying drawings and the following embodiments are only used to illustrate the present invention, but not to limit the present invention.

In the present invention, the surface of the magnesia feldspar scaffold is modified with ferric tetrasulfide by hydrothermal reaction. On the one hand, the ferric tetrasulfide can use magnetocaloric and catalytic hydrogen peroxide to generate reactive oxygen species and synergistically kill tumor cells; Ferric sulfide microflora can regulate the osteogenic differentiation of bone marrow mesenchymal stem cells, and magnesite itself is beneficial to the adhesion, proliferation and osteogenic differentiation of bone marrow mesenchymal stem cells. Therefore, the Fe4S microflora-modified magnesia feldspar scaffold of the present invention has good tumor removal and bone repair capabilities (refer to the biological activity test described later), and can be used as a material for postoperative treatment of bone tumors, which has both tumor treatment and bone repair. Dual function of bone tissue regeneration.

One embodiment of the present invention provides a bioceramic scaffold modified with ferric tetrasulfide micro-flowers, which comprises a magnesite scaffold and a ferric tetrasulfide micro-flower layer grown on the surface of the magnesia feldspar scaffold, and the ferric tetrasulfide is a hydrothermal It is grown on the surface of the scaffold by the hydrothermal method, and L-cysteine is used as the sulfur source in the hydrothermal method (L-cysteine can be dissolved in water to form a uniform aqueous solution, which is acidic, and the sulfhydryl (-SH) in it is active and can be Metal ion reaction), using FeSO ₄ ·7H ₂ O as the iron source, one-step uniform growth of iron tetrasulfide microflora on the surface of the scaffold. FIG. 1 shows the optical photos (a) and SEM images (b1~f3) of a magnesite scaffold and a ferric tetrasulfide-modified magnesite scaffold of an example of the invention. It can be seen from the figure that the iron tetrasulfide grows uniformly on the surface of the magnesia feldspar scaffold, and the diameter of the micro-flowers can be 5-50 μm.

The preparation of the above-mentioned ferric tetrasulfide modified bioceramic scaffold may include: preparing a magnesite scaffold by 3D printing technology; performing the prepared magnesite scaffold in an aqueous solution of FeSO ₄ •7H ₂ O and L-cysteine Hydrothermal treatment, washing and drying to obtain a bioceramic scaffold modified with ferric tetrasulfide microflora.

In an example of using 3D printing technology to prepare a magnesite feldspar scaffold, magnesia feldspar powder is used as the raw material, the powder and the binder are mixed uniformly, and the mixing ratio of the two is adjusted, such as the mass ratio of magnesite feldspar powder and the binder. It is (1~1.5):1, wherein the binder can be sodium alginate, Pluronic (F127) and/or polyvinyl alcohol, etc. Then use 3D printing software (mainly including designing the specific parameters of the stent, adjusting the shape and size of the stent, etc.) to print.

The 3D printed magnesia feldspar green body is sintered to obtain a magnesia feldspar ceramic stent. The sintering conditions can be sintered at 1300~1400℃ for 3~5 hours.

Ferric tetrasulfide microflora particles were grown on the surface of magnesia feldspar scaffolds by hydrothermal method. In one example, the method of hydrothermal growth is to hydrothermalize the scaffolds in an aqueous solution of _FeSO4-7H2O and L _- cysteine, followed by washing and drying. Among them, the concentration of hydrothermal precursor is 0.01~0.05mol/L, the concentration of FeSO ₄ •7H ₂ O is 0.01~0.05mol/L, and the concentration of L-cysteine is 0.01~0.05mol/L. The current precursor concentration When the concentration is lower than 0.01mol/L, it is difficult to form a uniform micron flower layer on the surface of the stent. When the concentration is higher than 0.05mol/L, there will be too much iron tetrasulfide on the surface of the stent, which will affect the biological activity of the stent. The hydrothermal reaction temperature is 160~200℃, the reaction time is 12~24 hours.

Hereinafter, as an example, the preparation method of the ferric tetrasulfide-modified magnesite scaffold in the present invention will be described.

The magnesia feldspar powder and the F127 aqueous solution were mixed uniformly according to the mass ratio (1~1.5): 1, and the magnesite feldspar green scaffold was prepared by 3D printing technology.

The printed scaffold green body is sintered at 1300-1400° C. for 3-5 hours to obtain a magnesia feldspar ceramic scaffold.

The prepared magnesia feldspar scaffold was subjected to hydrothermal treatment in an aqueous solution of FeSO ₄ •7H ₂ O and L-cysteine to obtain a bioceramic scaffold modified with ferric sulfide microflora.

The morphology of the scaffolds was characterized by optical photographs and scanning electron microscopy.

The following further examples are given to illustrate the present invention in detail. 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 content of the present invention belong to the present invention. scope of protection. The specific process parameters and the like in the following examples are only an example of a suitable range, that is, those skilled in the art can make selections within the suitable range through the description herein, and are not intended to be limited to the specific numerical values exemplified below.

Example 1

5g of pure magnesite feldspar powder was evenly mixed with 4g F127, and the magnesia feldspar scaffold was prepared by 3D printing technology;

The green magnesia feldspar scaffold was calcined at 1360°C for 4 hours to obtain a pure magnesia feldspar scaffold;

Put the magnesite into the aqueous solution of 0.02 mol/L FeSO ₄ ·7H ₂ O and L-cysteine for hydrothermal treatment, the temperature is 180℃, and the time is 12 hours;

After the hydrothermal treatment, the scaffold was rinsed with deionized water and absolute ethanol, and dried in an oven at 60°C to obtain a bioceramic scaffold modified with iron tetrasulfide microflora. Its structure is characterized, and the results are shown in Figure 1. It can be seen from the figure that the diameter of the pores of the magnesia feldspar scaffold is 100-400 μm; the iron tetrasulfide grows evenly on the surface of the magnesia feldspar scaffold; the micro-flower particles are composed of 0.5~ It is composed of 3 μm flake particles staggered and assembled, and the diameter of the micro flower is 5 to 50 μm. Then, the following methods were used to evaluate the osteogenic activity and antitumor ability.

Magnetocaloric properties of stents

Change the output current of the magnetic field, and test the magneto-caloric properties of the stent in dry and wet states: place the stent in an alternating magnetic field (magnetic field parameters, coil diameter: 10cm; frequency: 560kHz; output current: 6A/7A/8A), The thermal imager and FLIR R&D software were used to monitor the temperature change of the stent in real time, and output the temperature change curve. The results are shown in Figures 2.a and 2.b. It can be seen from Figure 2 that the stent has good magnetocaloric properties and can rapidly heat up in a short period of time, reaching a temperature above 45°C required for tumor treatment.

Performance of scaffolds to catalyze the generation of reactive oxygen species from hydrogen peroxide

The scaffold modified with ferric tetrasulfide microflora was placed in 1 mL of disodium hydrogen phosphate-citric acid buffer solution (pH=6.5, containing 200 M H ₂ O ₂ and 25 mg/L methylene blue), and the temperature of the scaffold was adjusted to 42 using a magnetic field. , 47, 52, and 57 °C, after holding for 10 min, the absorption spectrum of the test solution at 664 nm was compared with the original solution. The results are shown in Figure 3. It can be seen from the figure that as the temperature increases, the efficiency of reactive oxygen generation increases.

Interaction between iron tetrasulfide-modified ceramic scaffolds and bone marrow mesenchymal stem cells

Bone marrow mesenchymal stem cells were seeded on magnesia feldspar scaffolds and ferric tetrasulfide-modified magnesia feldspar scaffolds, respectively, and cultured for 1, 3, and 7 days, and the proliferation ability of stem cells was detected by CCK8 method. The expression of osteogenic differentiation-related genes of bone marrow mesenchymal stem cells on the scaffold was tested by RT-PCR method, and the results are shown in FIG. 4 . In Figure 4, bone marrow mesenchymal stem cells can maintain good proliferation after 1, 3, and 7 days of culture on the iron tetrasulfide microflora-modified scaffold, and the osteogenesis-related genes OCN, OPN, and RUNX2 were significantly up-regulated at 3 days. The results showed that, The scaffolds modified with ferric sulfide can still maintain biological activity, can promote the proliferation of stem cells, and can increase the expression of osteogenesis-related genes, indicating that the ferric sulfide microflora-modified magnesite scaffolds can induce bone marrow mesenchymal stem cells into osteogenesis differentiation.

In vitro antitumor ability of ferric tetrasulfide-modified scaffolds

The LM-8 osteosarcoma cells were seeded in a 48-well plate, and after culturing for 12 hours, half of the medium in the well was replaced with a medium with pH=6.5, 200M H ₂ O ₂ , and then put into the scaffolds respectively, under the control of the magnetic field. Then, the temperature was raised to 42, 47 and 52 °C, respectively, and kept for 10 minutes. The treated cells were further cultured for 12 hours, and the cell viability was measured using the CCK8 kit (Biyuntian Biotechnology Co., Ltd., product number C0038). The results are shown in FIG. 5 . In Figure 5, the tumor survival rate was only 1.5% under the synergistic effect of magnetocaloric and reactive oxygen species at 52 °C. The results showed that the scaffold could catalyze the generation of reactive oxygen species by hydrogen peroxide and the magnetocaloric synergy to kill tumor cells efficiently.

In vivo antitumor ability of FeS-modified bioceramic scaffolds

Nude mice were injected subcutaneously with LM-8 osteosarcoma cells to establish a subcutaneous tumor model. After that, the stent was implanted into the tumor site and heated under an alternating magnetic field, and the heating curve was recorded. The temperature was kept at about 51°C for ten minutes, and the treatment was continued for four days. The tumor volume was recorded every two days, and the nude mice were sacrificed on the 14th day, and the tumor tissue was removed for H&E staining analysis. The results are shown in Figure 6. Figure 6 shows that after 3 days of treatment with magneto-caloric and reactive oxygen species, the tumor volume gradually became smaller, and the tumor disappeared after 14 days, and there were no tumor cells in the H&E staining image. .

In vivo antitumor ability of FeS-modified bioceramic scaffolds

A bone defect model with a diameter of 6 mm was constructed in the femur of New Zealand white rabbits, and a scaffold modified with triiron tetrasulfide microflora was implanted. After 12 weeks, the material was collected and analyzed by CT scan. The results of Micro-CT (see Figure 7) showed that more new bone was formed in the defect when the bioceramic scaffold modified with FeS4 microflora was implanted. The results show that the scaffold modified with FeS4 microflora can effectively inhibit bone tumor under the synergistic effect of magnetocaloric and reactive oxygen species, and bioactive ions and surface microstructure can jointly promote bone repair, which has a good in vivo promotion of bone defect repair. ability.

Example 2

5g of pure magnesite feldspar powder was evenly mixed with 4g F127, and the magnesia feldspar scaffold was prepared by 3D printing technology;

The green magnesia feldspar scaffold was calcined at 1360°C for 4 hours to obtain a pure magnesia feldspar scaffold;

Put the magnesite into 0.04 mol/L FeSO ₄ ·7H ₂ O and L-cysteine aqueous solution for hydrothermal treatment, the temperature is 160 ℃, and the time is 24 hours;

After the hydrothermal treatment, the scaffold was rinsed with deionized water and absolute ethanol, and dried in an oven at 60°C to obtain a bioceramic scaffold modified with iron tetrasulfide microflora.

Example 3

Pure magnesia feldspar powder 5g, evenly mixed with 5g F127, using 3D printing technology to prepare magnesia feldspar support;

The green magnesia feldspar scaffold was calcined at 1300 °C for 3 hours to obtain a pure magnesia feldspar scaffold;

Put the magnesite into the aqueous solution of 0.02 mol/L FeSO ₄ ·7H ₂ O and L-cysteine for hydrothermal treatment, the temperature is 160 ℃, and the time is 12 hours;

After the hydrothermal treatment, the scaffold was rinsed with deionized water and absolute ethanol, and dried in an oven at 60°C to obtain a bioceramic scaffold modified with iron tetrasulfide microflora.

Example 4

5g of pure magnesite powder, evenly mixed with 4.5g F127, the magnesia feldspar scaffold was prepared by 3D printing technology;

The green magnesia feldspar scaffold was calcined at 1350°C for 3 hours to obtain a pure magnesia feldspar scaffold;

Put magnesite into 0.04 mol/L FeSO ₄ ·7H ₂ O and L-cysteine aqueous solution for hydrothermal treatment, the temperature is 200 ℃, and the time is 24 hours;

After the hydrothermal treatment, the scaffold was rinsed with deionized water and absolute ethanol, and dried in an oven at 60°C to obtain a bioceramic scaffold modified with iron tetrasulfide microflora.

Example 5

5g of pure magnesite feldspar powder was evenly mixed with 4g F127, and the magnesia feldspar scaffold was prepared by 3D printing technology;

The green magnesia feldspar scaffold was calcined at 1300°C for 5 hours to obtain a pure magnesite scaffold;

Put the magnesite into the aqueous solution of 0.05 mol/L FeSO ₄ •7H ₂ O and L-cysteine for hydrothermal treatment, the temperature is 180 ℃, and the time is 24 hours;

After the hydrothermal treatment, the scaffold was rinsed with deionized water and absolute ethanol, and dried in an oven at 60°C to obtain a bioceramic scaffold modified with iron tetrasulfide microflora.

Then, the scaffolds manufactured in Examples 2-5 were evaluated for osteogenic activity and anti-tumor ability by the method of Example 1 above. The results showed that the scaffolds modified with ferric tetrasulfide had good magnetocaloric properties; they could catalyze peroxidation Hydrogen generates reactive oxygen species and induces osteogenic differentiation of bone marrow mesenchymal stem cells, and synergistically kills tumor cells by catalyzing hydrogen peroxide to generate reactive oxygen species and magnetothermally, thus having excellent anti-tumor ability in vitro and in vivo.

The bioceramic scaffold modified with iron tetrasulfide microflora provided by the invention has excellent magnetocaloric properties, and can catalyze hydrogen peroxide in tumor microenvironment to generate reactive oxygen species, and the magnetocaloric and reactive oxygen species can synergistically kill tumor cells efficiently. Subcutaneous tumor experiments in nude mice further confirmed that the scaffolds modified with ferric sulfide have good anti-tumor ability. The surface microstructure of the Fe4S-modified magnesite feldspar scaffold can regulate the osteogenic differentiation of bone marrow mesenchymal stem cells, and the scaffold itself is beneficial to the adhesion, proliferation and osteogenic differentiation of bone marrow mesenchymal stem cells. Therefore, the Fe4S microflora-modified magnesia feldspar scaffold has excellent antitumor ability and ability to promote bone tissue regeneration, and can be used as a bone filling material for postoperative treatment of bone tumors.

Claims (9)

1. The biological ceramic support modified by ferroferric sulfide micro-flowers is characterized by comprising an akermanite support and ferroferric sulfide micro-flower particles growing on the surface of the akermanite support, wherein the diameter of a pore passage of the akermanite support is 100-400 mu m; the ferroferric sulfide micro-flower grains are of a micro-nano structure and are assembled by flaky grains with the diameter of 0.5-3 mu m, and the diameter of the flaky grains is 5-50 mu m.

2. The ferroferric sulfide micro flower modified biological ceramic scaffold as claimed in claim 1, wherein the ferroferric sulfide micro flower grows in situ in pores of the akermanite scaffold, and the thickness of a formed micro flower layer is 1-10 μm.

3. The ferroferric sulfide micro-flower modified bioceramic scaffold according to claim 1, wherein the bioceramic scaffold is prepared by placing akermanite in FeSO₄•7H₂And (3) growing ferroferric sulfide micron flower particles on the surface of the akermanite support in an aqueous solution of O and L-cysteine by using a hydrothermal method.

4. The ferroferric sulfide micro flower modified bioceramic scaffold according to claim 3, wherein the FeSO is in aqueous solution₄•7H₂The concentration of O is 0.01-0.05 mol/L, and the concentration of L-cysteine is 0.01-0.05 mol/L.

5. The ferroferric sulfide popcorn modified biological ceramic scaffold according to claim 3 or 4, wherein the hydrothermal reaction temperature is 160-200 ℃ and the reaction time is 12-24 hours.

6. The ferroferric sulfide micro flower modified biological ceramic scaffold as claimed in claim 1, wherein the akermanite bioactive ceramic scaffold is prepared by the following method:

obtaining paste by using akermanite powder and a binder;

placing the obtained paste into a three-dimensional printer for three-dimensional printing to obtain a blank body;

sintering the obtained blank at 1300-1400 ℃ for 3-5 hours to obtain the akermanite bioactive ceramic support.

7. The ferroferric sulfide popcorn modified bioceramic scaffold according to claim 6, wherein the binder comprises sodium alginate, aqueous pluronic solution, and/or polyvinyl alcohol.

8. The ferroferric sulfide micro-flower modified biological ceramic scaffold as claimed in claim 6, wherein the paste is obtained by mixing the akermanite powder and the binder according to the mass ratio of (1-1.5): 1.

9. Use of the ferroferric sulfide micro flower modified biological ceramic scaffold according to any one of claims 1-5 in a material for treatment and repair of bone tumor after operation.

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