CN112661500B - Biological ceramic bracket with micro-nano structure on surface and preparation method and application thereof - Google Patents
Biological ceramic bracket with micro-nano structure on surface and preparation method and application thereof Download PDFInfo
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- CN112661500B CN112661500B CN202110017383.3A CN202110017383A CN112661500B CN 112661500 B CN112661500 B CN 112661500B CN 202110017383 A CN202110017383 A CN 202110017383A CN 112661500 B CN112661500 B CN 112661500B
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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
Technical Field
The invention relates to a biological ceramic bracket with a micro-nano structure on the surface, a preparation method and application thereof, in particular to a biological ceramic bracket modified by ferroferric sulfide micro-flower and a preparation method and application thereof, belonging to the field of biological materials.
Background
The treatment of malignant bone tumor has been a great clinical problem. Currently, there are many means for treating malignant bone tumors, such as surgical resection, chemotherapy, radiotherapy, and the like. Surgical resection leaves a large defect at the resection site, which must be repaired by an implant, and surgical resection does not completely remove tumor cells. Radiotherapy and chemotherapy can cause great damage to normal tissues around the tumor and also can cause tumor cells to have certain resistance to the drugs. Therefore, the development of biomaterials with both tumor-removing and bone-repairing capabilities remains a great challenge. The chemokinetic therapy utilizes the hydrogen peroxide accumulated in a tumor microenvironment for efficient disproportionation of ferrous ions to generate active oxygen with strong oxidizing property, so as to further cause a series of oxidative damages such as protein denaturation, DNA breakage, mitochondrial destruction and the like of tumor cells, and further cause the apoptosis of the tumor cells. In addition, the use of the magnetocaloric therapy can help promote the generation efficiency of hydroxyl radicals in the chemokinetic therapy, and the treatment of tumors by the magnetocaloric regulation chemokinetic therapy is realized. The magnetic hyperthermia is not affected by the depth, has high efficiency and little side effect, and can be used for treating deep tumors such as bone tumors. The microstructure on the surface of the three-dimensional scaffold can promote osteogenic differentiation of the bone marrow mesenchymal stem cells.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a biological ceramic scaffold with tumor removal and bone repair capabilities.
On one hand, the invention provides a biological ceramic scaffold material modified by ferroferric sulfide micro-flowers, which comprises an akermanite scaffold and ferroferric sulfide layer micro-flower grains growing on the surface of the akermanite scaffold, wherein the diameter of a pore channel of the akermanite scaffold 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.
Ferroferric sulfide micro-flower modified biological ceramic support, ferroferric sulfide grown on the surface of the support has ferromagnetism, can be rapidly heated up under the induction of an alternating magnetic field due to hysteresis effect, relaxation effect and other reasons, can release over-expressed hydrogen peroxide in a tumor microenvironment catalyzed by iron ions under an acid environment, and generates hydroxyl radicals through Fenton or Fenton-like reaction, and the specific reaction process is as follows: fe2+ + H2O2 → Fe3+ + OH-OH, the magnetic heat can improve the generation efficiency of active oxygen so as to achieve the synergistic effect of the magnetic heat and the chemo-kinetic therapy to effectively kill tumor cells. Meanwhile, the micro-nano structure can pass through the integrinAlpha 5 beta 1 and other mediated actin F-actin are used for regulating and controlling cell behaviors and further promoting osteogenic differentiation, so that the micro-nano structure has certain advantages in the aspect of promoting bone repair. The micro-nano structure formed by the ferroferric sulfide micro flowers on the surface of the bracket can regulate the differentiation capacity of the mesenchymal stem cells by regulating the cell morphology through integrin-mediated actin F-actin, thereby playing a role in repairing bone defects. In addition, the akermanite has good osteogenic activity, the akermanite support can release active ions (such as Ca, Mg and Si) to promote bone repair, and the ferroferric sulfide microstructure can cooperate with the active ions to further improve the osteogenic performance of the akermanite support. Therefore, the ferroferric sulfide micro-flower modified biological ceramic scaffold has good capacity of removing tumor and repairing bone defect, and can be used for postoperative treatment of bone tumor.
Preferably, 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. The hydrothermal reaction temperature is preferably 160-200 ℃, and the reaction time is 12-24 hours.
Preferably, the FeSO is in the 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.
Preferably, the ferroferric sulfide micro-flowers grow in situ on the surface of the akermanite support, and the thickness of the whole formed layer is 1-10 μm.
On the other hand, the invention provides a preparation method of the ferroferric sulfide micro-flower modified biological ceramic bracket, which comprises the steps of preparing an akermanite ceramic bracket; the akermanite ceramic bracket is supported on FeSO4•7H2And carrying out hydrothermal treatment in an aqueous solution of O and L-cysteine to obtain the ferroferric sulfide micro-flower modified biological ceramic scaffold.
In one scheme, the akermanite bioactive ceramic scaffold is prepared by the following method:
mixing akermanite powder: mixing the binder with the mass ratio of (1-1.5) to 1 to obtain paste;
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.
Preferably, the binder comprises common binders such as sodium alginate, pluronic F127 aqueous solution, and/or polyvinyl alcohol.
The obtained akermanite bracket is supported on FeSO4•7H2In the hydrothermal treatment process in the aqueous solution of O and L-cysteine, the concentration of the ferroferric sulfide hydrothermal precursor is preferably 0.01-0.05 mol/L.
According to the invention, the akermanite stent is prepared by a three-dimensional printing technology, the preparation method is simple, and the stent with a complex shape can be prepared. In addition, the ferroferric sulfide micro-flowers can be modified on the surface of the bracket by a hydrothermal method, and the preparation is simple and the repeatability is good.
On the other hand, the invention also provides application of the ferroferric sulfide micro-flower modified biological ceramic stent in a bone tumor postoperative treatment and repair material.
Drawings
Fig. 1 is an optical photograph (a) of pure akermanite and a ferriferrous sulfide modified akermanite stent, an SEM image (b 1-b 3) of the pure akermanite stent, and a ferriferrous sulfide modified akermanite stent (c 1-f 3) under different hydrothermal conditions, wherein the specific corresponding reaction conditions are as follows: (c 1-c 3) 0.02 mol/L of precursor, the reaction temperature is 160 ℃, the reaction time is 12 hours, and the name is 0.02L-FS-AKT; (d 1-d 3) 0.04 mol/L precursor, the reaction temperature is 160 ℃, the reaction time is 12 hours, and the name is 0.04L-FS-AKT; (e 1-e 3) 0.02 mol/L of precursor, the reaction temperature is 180 ℃, the reaction time is 12 hours, and the name is 0.02F-FS-AKT; (F1-F3) 0.04 mol/L precursor, the reaction temperature is 180 ℃, the reaction time is 12 hours, and the name is 0.04F-FS-AKT, wherein, as can be seen from e1-e3, the micro popcorn structure with uniform size is formed on the surface of the bracket under the condition;
FIG. 2 shows the magnetocaloric performance of a ferroferric sulfide modified scaffold; the curves in the figure are respectively from bottom to top: 6A, 7A, 8A;
FIG. 3 shows the performance of ferriferous sulfide modified akermanite supports in catalyzing hydrogen peroxide to generate active oxygen;
FIG. 4 shows the absorbance (a), the expression levels of osteogenesis-related genes Osteocalcin (OCN) (b), Osteopontin (OPN) (c), and osteocyte-specific transcription factor (RUNX 2) (d) of bone marrow mesenchymal stem cells cultured on scaffolds for 1, 3, and 7 days; from left to right in FIG. 4 (a) are AKT, 0.02L-FS-AKT, 0.04L-FS-AKT, 0.02F-FS-AKT, 0.04F-FS-AKT (as specifically illustrated in FIG. 1), respectively, and it can be seen that 0.02F-FS-AKT is effective in promoting proliferation of mesenchymal stem cells and significantly increasing expression of osteogenesis-related genes as compared to the other groups;
FIG. 5 shows the survival rate of LM-8 osteosarcoma cells under the synergistic effect of scaffold magnetocaloric energy and reactive oxygen species;
FIG. 6 shows the antitumor ability of the scaffold in the subcutaneous model of tumor in nude mice, the temperature-increasing curve (a), the change in tumor volume (b), the photographs of nude mice on days 0 and 14 (c), the photograph of tumor tissue (d) and the H of tumor tissue&E staining pattern (E); in fig. 6 (b), the curves are from top to bottom: blank group, Fe3S4Group of-AKT, Fe3S4-a set of AKT + Alternating Magnetic Fields (AMF);
FIG. 7 shows the CT analysis results of the bone defect model animal experiment of white rabbit in New Zealand.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting.
According to the invention, ferroferric sulfide is modified on the surface of the akermanite stent through a hydrothermal reaction, on one hand, the ferroferric sulfide can generate active oxygen by utilizing magnetocaloric heat and catalytic hydrogen peroxide, and kill tumor cells in a synergistic manner; on the other hand, the ferroferric sulfide micro-flowers can regulate and control osteogenic differentiation of the bone marrow mesenchymal stem cells, and the akermanite is beneficial to adhesion, proliferation and osteogenic differentiation of the bone marrow mesenchymal stem cells. Therefore, the akermanite support modified by the ferroferric sulfide micro-flowers has good capabilities of removing tumors and repairing bones (see a bioactivity test described later), can be used as a material for postoperative treatment of bone tumors, and has double functions of tumor treatment and bone tissue regeneration.
One embodiment of the invention provides a ferroferric sulfide micro flower modified biological ceramic bracket, which comprises a akermanite bracket and a ferroferric sulfide micro flower layer growing on the surface of the magnesioderma feldspar bracket, wherein the ferroferric sulfide grows on the surface of the bracket by a hydrothermal method, the hydrothermal method takes L-cysteine as a sulfur source (the L-cysteine can be dissolved in water to form a uniform aqueous solution, is acidic, and has active mercapto (-SH) property capable of reacting with metal ions), and FeSO is used for modifying the biological ceramic bracket4·7H2And O is an iron source, and ferroferric sulfide micro-flowers uniformly grow on the surface of the bracket by a one-step method. FIG. 1 shows optical photographs (a) and SEM images (b 1-f 3) of an akermanite scaffold and a ferriferrous sulfide-modified akermanite scaffold according to an example of the present invention. As can be seen from the figure, ferroferric sulfide uniformly grows on the surface of the akermanite support, and the diameter of the micro-flowers can be 5-50 μm.
The preparation of the ferroferric sulfide modified biological ceramic scaffold can comprise the following steps: preparing the akermanite support by using a 3D printing technology; placing the prepared akermanite support in FeSO4•7H2Carrying out hydrothermal treatment in an aqueous solution of O and L-cysteine, cleaning and drying to obtain the ferroferric sulfide micro-flower modified biological ceramic scaffold.
In one example of preparing the akermanite stent by using a 3D printing technology, akermanite powder is used as a raw material, the powder and a binder are uniformly mixed, and the mixing ratio of the akermanite powder and the binder is adjusted, for example, the mass ratio of the akermanite powder to the binder is (1-1.5): 1, wherein the binder can be sodium alginate, Pluronic (F127), polyvinyl alcohol or the like. And then printing by using 3D printing software (mainly comprising design of specific parameters of the bracket, regulation of the shape and the size of the bracket and the like).
And sintering the 3D printed akermanite green body to obtain the akermanite ceramic support. Wherein the sintering condition can be 1300-1400 ℃ for 3-5 hours.
Ferroferric sulfide micro flower grains grow on the surface of the akermanite support by a hydrothermal method. In one example, the method of hydrothermal growth is to place the scaffold in FeSO4•7H2Carrying out hydrothermal reaction in an aqueous solution of O and L-cysteine, and then washing and drying. Wherein the concentration of the hydrothermal precursor is 0.01-0.05 mol/L, and the FeSO4•7H2The concentration of O is 0.01-0.05 mol/L, the concentration of L-cysteine is 0.01-0.05 mol/L, when the concentration of the precursor is lower than 0.01mol/L, a uniform micron flower layer is difficult to form on the surface of the stent, and when the concentration is higher than 0.05mol/L, the ferroferric sulfide on the surface of the stent is excessive, so that the biological activity of the stent is influenced; the hydrothermal reaction temperature is 160-200 ℃, and the reaction time is 12-24 hours.
Hereinafter, a method for preparing the ferriferrous sulfide modified akermanite scaffold of the present invention will be described as an example.
Uniformly mixing the akermanite powder and the F127 aqueous solution according to the mass ratio of (1-1.5) to 1, and preparing the akermanite green-body support by using a 3D printing technology.
And sintering the printed support green body at 1300-1400 ℃ for 3-5 hours to obtain the akermanite ceramic support.
Placing the prepared akermanite support in FeSO4•7H2Carrying out hydrothermal treatment in an aqueous solution of O and L-cysteine to obtain the ferroferric sulfide micro-flower modified biological ceramic scaffold.
And characterizing the appearance of the bracket by an optical photo and a scanning electron microscope.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
5g of pure akermanite powder is uniformly mixed with 4gF127, and a 3D printing technology is utilized to prepare an akermanite support;
calcining the green akermanite support blank at 1360 ℃ for 4 hours to obtain a pure akermanite support;
adding 0.02 mol/L FeSO into the akermanite4•7H2Carrying out hydrothermal treatment on the O and L-cysteine in an aqueous solution at the temperature of 180 ℃ for 12 hours;
and (3) after hydrothermal treatment, washing the support with deionized water and absolute ethyl alcohol, and drying in a 60 ℃ drying oven to obtain the ferroferric sulfide micro-flower modified biological ceramic support. The structure of the material is characterized, and the result is shown in figure 1, and the diameter of the pore channel of the akermanite support can be seen to be 100-400 mu m; ferroferric sulfide uniformly grows on the surface of the akermanite support; the micro-flower rice particles are formed by staggered assembly of flaky particles with the diameter of 0.5-3 mu m, and the diameter of the micro-flower rice is 5-50 mu m. Then, the osteogenic activity and antitumor ability were evaluated by the following methods.
Magnetocaloric properties of the support
Changing the output current of the magnetic field, and testing the magnetocaloric performance of the bracket in a dry state and a wet state: the stent is placed in an alternating magnetic field (magnetic field parameters, coil diameter: 10cm, frequency: 560kHz, output current: 6A/7A/8A), the temperature change of the stent is monitored in real time by using a thermal imager and FLIR R & D software, and a temperature change curve is output, and the results are shown in FIGS. 2.a and 2. b. As can be seen from figure 2, the stent has good magnetic thermal performance, and can be rapidly heated in a short time to reach the temperature of over 45 ℃ required by tumor treatment.
The performance of the bracket for catalyzing hydrogen peroxide to generate active oxygen
Placing the ferroferric sulfide micro-flower modified scaffold in 1mL disodium hydrogen phosphate-citric acid buffer solution (pH =6.5, containing 200 μm H)2O2And 25mg/L methylene blue), adjusting the temperature of the stent to 42, 47, 52 and 57 ℃ by using a magnetic field, keeping for 10min, testing the absorption spectrum of the solution at 664nm, comparing with the original solution,the results are shown in FIG. 3. It can be seen that the efficiency of active oxygen generation increases with increasing temperature.
Interaction of ferroferric sulfide modified ceramic scaffold and mesenchymal stem cells
And respectively planting the mesenchymal stem cells on the akermanite bracket and the akermanite bracket modified by ferroferric sulfide, culturing for 1, 3 and 7 days, and respectively detecting the proliferation capacity of the stem cells by adopting a CCK8 method. The expression of osteogenic differentiation related genes of the mesenchymal stem cells on the scaffold was tested by RT-PCR, and the results are shown in fig. 4. In the figure 4, the mesenchymal stem cells can keep good proliferation after being cultured on the ferroferric sulfide micro-flower modified scaffold for 1, 3 and 7 days, and the osteogenesis related genes OCN, OPN and RUNX2 in 3 days are obviously up-regulated, so that the results show that the ferroferric sulfide modified scaffold can still keep the biological activity, can promote the proliferation of the stem cells and can improve the expression of the osteogenesis related genes, and the ferroferric sulfide micro-flower modified magnesium yellow feldspar scaffold can induce the osteogenic differentiation of the mesenchymal stem cells.
In vitro anti-tumor capacity of ferroferric sulfide modified stent
LM-8 osteosarcoma cells were seeded in 48-well plates and after 12 hours of culture, half of the medium in the wells was changed to pH =6.5, 200 μm H2O2Then putting the culture medium into a bracket respectively, raising the temperature to 42 ℃, 47 and 52 ℃ respectively under the control of a magnetic field, and preserving the temperature for 10 minutes. The treated cells were cultured for another 12 hours, and the survival rate of the cells was measured using CCK8 kit (Biyuntian Biotech Co., Ltd., product No. C0038), and the results are shown in FIG. 5. In fig. 5, under the synergistic effect of magnetocaloric heat and active oxygen at 52 ℃, the survival rate of the tumor is only 1.5%, and the result shows that the scaffold can catalyze hydrogen peroxide to generate active oxygen and the scaffold can synergistically kill tumor cells with high efficiency under magnetocaloric heat.
In vivo anti-tumor capability of ferroferric sulfide modified biological ceramic scaffold
LM-8 osteosarcoma cells were injected subcutaneously into nude mice to establish a subcutaneous tumor model. Then the stent is implanted into a tumor part, the temperature is raised under an alternating magnetic field, a temperature-raising curve is recorded, the temperature is kept at about 51 ℃ for ten minutes, and four days of continuous treatment are carried out. Tumor volumes were recorded every two days, nude mice were sacrificed at day 14 and tumor tissue was removed for H & E staining analysis with results shown in figure 6. Fig. 6 shows that after 3 days of treatment with magnetocaloric heat and active oxygen, the tumor volume gradually decreases, the tumor disappears in 14 days, and no tumor cells exist in the H & E staining chart, which indicates that the ferroferric sulfide modified scaffold has excellent anti-tumor performance.
In vivo anti-tumor capability of ferroferric sulfide modified biological ceramic scaffold
Constructing a bone defect model with the diameter of 6mm at the femur of a white rabbit in New Zealand, implanting a ferroferric sulfide micro flower modified bracket, taking materials after 12 weeks, and performing CT scanning analysis. The Micro-CT results (see fig. 7) show that more new bone was formed at the defect site by implanting the ferriferrous sulfide Micro flower modified bioceramic scaffold. The results show that the ferroferric sulfide micro-flower modified scaffold can efficiently inhibit bone tumor under the synergistic action of magnetic heat and active oxygen, and the bioactive ions and the surface microstructure can jointly promote bone repair, so that the scaffold has good capability of promoting bone defect repair in vivo.
Example 2
5g of pure akermanite powder is uniformly mixed with 4gF127, and a 3D printing technology is utilized to prepare an akermanite support;
calcining the green akermanite support blank at 1360 ℃ for 4 hours to obtain a pure akermanite support;
adding 0.04 mol/L FeSO into the akermanite4•7H2Carrying out hydrothermal treatment on the O and L-cysteine aqueous solution at 160 ℃ for 24 hours;
and (3) after hydrothermal treatment, washing the support with deionized water and absolute ethyl alcohol, and drying in a 60 ℃ drying oven to obtain the ferroferric sulfide micro-flower modified biological ceramic support.
Example 3
5g of pure akermanite powder is uniformly mixed with 5gF127, and a 3D printing technology is utilized to prepare the akermanite support;
calcining the akermanite support green blank at 1300 ℃ for 3 hours to obtain a pure akermanite support;
adding 0.02 mol/L FeSO into the akermanite4•7H2Carrying out hydrothermal treatment on the O and L-cysteine in water solution at the temperature of 160 ℃ for 12 hours;
and (3) after hydrothermal treatment, washing the support with deionized water and absolute ethyl alcohol, and drying in a 60 ℃ drying oven to obtain the ferroferric sulfide micro-flower modified biological ceramic support.
Example 4
5g of pure akermanite powder is uniformly mixed with 4.5g of F127, and a 3D printing technology is utilized to prepare an akermanite support;
calcining the green akermanite support blank at 1350 ℃ for 3 hours to obtain a pure akermanite support;
adding 0.04 mol/L FeSO into the akermanite4•7H2Carrying out hydrothermal treatment on the O and L-cysteine in an aqueous solution at the temperature of 200 ℃ for 24 hours;
and (3) after hydrothermal treatment, washing the support with deionized water and absolute ethyl alcohol, and drying in a 60 ℃ drying oven to obtain the ferroferric sulfide micro-flower modified biological ceramic support.
Example 5
5g of pure akermanite powder is uniformly mixed with 4gF127, and a 3D printing technology is utilized to prepare an akermanite support;
calcining the akermanite support green blank at 1300 ℃ for 5 hours to obtain a pure akermanite support;
adding 0.05mol/L FeSO into the akermanite4•7H2Carrying out hydrothermal treatment on the O and L-cysteine in an aqueous solution at 180 ℃ for 24 hours;
and (3) after hydrothermal treatment, washing the support with deionized water and absolute ethyl alcohol, and drying in a 60 ℃ drying oven to obtain the ferroferric sulfide micro-flower modified biological ceramic support.
Then, the method of the embodiment 1 is adopted to evaluate the osteogenic activity and the anti-tumor capacity of the scaffolds manufactured in the embodiments 2 to 5, and the result shows that the ferroferric sulfide modified scaffold has good magnetocaloric properties; can catalyze hydrogen peroxide to generate active oxygen and induce bone marrow mesenchymal stem cells to undergo osteogenic differentiation, and can synergistically and efficiently kill tumor cells by catalyzing hydrogen peroxide to generate active oxygen and magnetic heat, so that the in vivo and in vitro anti-tumor capacity is excellent.
The ferroferric sulfide micro-flower modified biological ceramic scaffold provided by the invention has excellent magnetocaloric performance, can catalyze hydrogen peroxide in a tumor microenvironment to generate active oxygen, and can efficiently kill tumor cells under the cooperation of magnetocaloric performance and the active oxygen. The nude mouse subcutaneous tumor experiment further proves that the ferroferric sulfide modified stent has good anti-tumor capability. The ferroferric sulfide modified akermanite support has a surface microstructure capable of regulating and controlling osteogenic differentiation of mesenchymal stem cells, and is favorable for adhesion, proliferation and osteogenic differentiation of the mesenchymal stem cells. Therefore, the ferriferous sulfide micro-flower modified akermanite scaffold has excellent anti-tumor capacity and capacity of promoting 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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