Porous zinc-based bone repair scaffold coated with MoS2 and GaP coating as well as preparation method and application of porous zinc-based bone repair scaffold

Abstract

The invention belongs to the technical field of biomedical materials, and particularly relates to a porous zinc-based bone repair scaffold coated with a MoS2 and GaP coating and a preparation method and application thereof.The porous zinc-based bone repair scaffold comprises a porous zinc-based bone repair scaffold template and the MoS2 and GaP coating coated on the surface of the porous zinc-based bone repair scaffold template, hydrothermal reaction treatment is carried out on the surface of the porous zinc-based bone repair scaffold to prepare the porous zinc-based bone repair scaffold of which the surface is coated with a molybdenum disulfide doped gallium phosphate (MoS2 at GaP) coating, and the porous zinc-based bone repair scaffold is endowed with a synergistic function of degradation regulation, tumor resistance and bone repair promotion.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical materials, and in particular relates to a porous zinc-based bone repair scaffold covered with a MoS2@GaP coating, and a preparation method and application thereof. Background Art

[0002] In recent years, the research focus of bone repair scaffolds after tumor surgery has shifted from simple structural support to intelligent design with both anti-tumor and bone-promoting functions. Traditional degradable scaffold materials such as hydroxyapatite and polylactic acid-glycolic acid copolymer have good biocompatibility but lack anti-tumor function. In contrast, degradable zinc-based scaffolds can show unique value in bone repair through material degradation behavior, mechanical adaptability and controlled release of bioactive ions. Zinc-based scaffolds provide initial mechanical support (elastic modulus close to cortical bone to avoid stress shielding), and the Zn released during degradation 2+ Ions accelerate bone healing by activating Wnt / β-catenin signaling pathways.

[0003] However, excessive Zn is produced during the degradation of Zn-based scaffolds. 2+ Ions and Zn required for bone tissue regeneration 2+ Due to the mismatch of ion concentration, it is usually necessary to prepare a phosphating coating on the stent surface to control the degradation rate. At the same time, most zinc-based materials do not have significant anti-tumor effects. Currently, those skilled in the art are often using a variety of functional modification strategies to improve the anti-tumor effects of the above-mentioned repair materials, such as gallium (Ga 3+ ) ions and molybdenum disulfide (MoS2) can show significant anti-tumor effects. Among them, the sustained release of Ga by gallium salts 3+ Ions can competitively inhibit key proteins of iron metabolism in tumor cells (transferrin receptor TfR1 and ribonucleotide reductase RRM2), block DNA synthesis and induce cell cycle arrest. 3+ Ions can also downregulate osteoclast activity by inhibiting the NF-κB signaling pathway. In addition, as a new type of two-dimensional nanomaterial, MoS2 has also shown unique dual-functional effects in the fields of anti-tumor and bone repair. Its mechanism of action is mainly based on its special physical and chemical properties and biological activity. With the help of Fenton / Fenton-like reaction catalytic properties, MoS2 can be used to synthesize the 4+ / Mo 6+ Valence conversion promotes the decomposition of H2O2 into highly toxic OH, which triggers oxidative stress and kills tumor cells. At the same time, MoS2 can also release Mo through degradation. 6+ Ions activate the Wnt / β-catenin signaling pathway to promote osteoblast differentiation and upregulate the expression of osteogenic markers such as Runx2 and ALP. The nanosheet structure of MoS2 can mimic the topology of the extracellular matrix, providing physical cues for stem cell adhesion and promoting cell extension and proliferation.

[0004] In view of this, the present invention provides a porous zinc-based bone repair scaffold coated with MoS2@GaP coating, and a preparation method and application thereof, so as to endow the porous zinc-based bone repair scaffold with multiple synergistic functions of "degradation regulation-anti-tumor-promoting bone repair" by forming a MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold. Summary of the Invention

[0005] The purpose of the present invention is to address the above-mentioned technical problems and provide a porous zinc-based bone repair scaffold covered with a MoS2@GaP coating, as well as a preparation method and application thereof.

[0006] In view of this, the present invention provides a porous zinc-based bone repair scaffold covered with a MoS2@GaP coating, comprising: a porous zinc-based bone repair scaffold template and a MoS2@GaP coating covered on the surface of the porous zinc-based bone repair scaffold template.

[0007] Furthermore, the porous zinc-based bone repair scaffold template is made of pure zinc and / or Zn-X alloy material, wherein X in the Zn-X alloy is one or more elements of Cu, Mg, Sr, Ca, Ge, Ti, Se, Li, Fe, Sn, Ag, Mn, RE, Ga, Zr, and Au.

[0008] Furthermore, the porous zinc-based bone repair scaffold template also includes an external or in-situ self-generated reinforcement phase, and the reinforcement phase is one or more of Mg2Ge, Mg2Si, Mg2Sn, ZrO2, Al2O3, ZnO, CuO2, MgO, SiN, TiC, carbon fiber, carbon nanotubes, and graphene.

[0009] Furthermore, the porous zinc-based bone repair scaffold template has a porosity of 50-95% and a pore size of 50-600 μm.

[0010] The present invention also provides a method for preparing the above-mentioned porous zinc-based bone repair scaffold covered with MoS2@GaP coating, comprising the following steps: S100, preparation of porous zinc-based bone repair scaffold template; S200, surface etching of porous zinc-based bone repair scaffold template; S300, MoS2@GaP coating was prepared on the surface of porous zinc-based bone repair scaffold template by hydrothermal reaction.

[0011] Furthermore, the surface etching process of the porous zinc-based bone repair scaffold template in step S200 is as follows: The porous zinc-based bone repair scaffold template was placed in a 0.5-3 mol / L dilute hydrochloric acid solution for surface etching for 10-60 minutes.

[0012] Furthermore, the process of preparing the MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold template in step S300 is as follows: The porous zinc-based bone repair scaffold template is placed in a hydrothermal reactor filled with a phosphating solution for a hydrothermal reaction of 10 to 120 minutes to form a MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold template; Among them, the hydrothermal reaction temperature is 80~150℃, the hydrothermal reaction treatment is carried out entirely on an electromagnetic vibration table equipped with a cooling device, and the reactor and the electromagnetic vibration table are placed in a heating furnace.

[0013] Furthermore, the phosphating solution contains: Gallium nitrate: 0.01~0.7mol / L; Phosphoric acid: 0.02~1.4mol / L; MoS2: 0.002~1.0mol / L; Wherein, the particle size of the MoS2 is 50~3000nm; The pH of the phosphating solution is adjusted to 2.0-3.5 with acid or alkali solution.

[0014] Furthermore, the hydrothermal reaction process is: At the set reaction temperature, first increase the pressure in the reactor to 0.5~2.5MPa and maintain the temperature and pressure for 3~5min; Then, the pressure in the reactor was quickly reduced to below 0.2 MPa within 30 s; Then, the pressure in the reactor is increased to 0.5-2.5 MPa again, and after maintaining the temperature and pressure for 30-60 minutes, the pressure in the reactor is slowly reduced to normal pressure at a speed of no more than 0.3 MPa / min.

[0015] The present invention also includes the use of the above-mentioned porous zinc-based bone repair scaffold covered with MoS2@GaP coating in the preparation of bone defect repair products.

[0016] The beneficial effects of the present invention are: The porous zinc-based bone repair scaffold was placed in a composite phosphating solution containing two materials through hydrothermal treatment to obtain a porous zinc-based bone repair scaffold with a MoS2@GaP coating on the surface. In this way, not only the anti-tumor effect of the porous zinc-based bone repair scaffold can be enhanced through the synergistic effect of multiple materials, but also the Ga released by the MoS2@GaP coating can be used to 3+ and MoS2 degradation products (MoO4 2-) co-activate the Wnt / β-catenin pathway, significantly increasing alkaline phosphatase (ALP) activity and calcium nodule formation. Therefore, the present invention can prepare a porous zinc-based bone repair scaffold coated with molybdenum disulfide-doped gallium phosphate (MoS2@GaP) by performing a hydrothermal reaction on the surface of the porous zinc-based bone repair scaffold, imparting the synergistic functions of "degradation regulation, anti-tumor, and bone repair promotion." BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The surface SEM image and corresponding EDS point scanning results of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating prepared in Example 1 of the present invention; Figure 2 Polarization curves of the porous zinc-based bone repair scaffold with and without MoS2@GaP coating in Hanks' solution according to Example 1 of the present invention; Figure 3 The morphology of the clones and the corresponding statistical graph of the number of clones of DLM8C3H mouse osteosarcoma cells in the extract of the porous zinc-based bone repair scaffold with or without MoS2@GaP coating in Example 1 of the present invention are shown; Figure 4 Statistical graphs of cell migration morphology and corresponding cell migration rates of DLM8C3H mouse osteosarcoma cells in the extract of porous zinc-based bone repair scaffolds with and without MoS2@GaP coating in Example 1 of the present invention. DETAILED DESCRIPTION

[0018] The technical solutions in this application will be described in detail below with reference to specific embodiments. Obviously, the embodiments described are only part of the embodiments of this application, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments in this application are within the scope of protection of this application.

[0019] In the description of this application, it should be noted that the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the exemplary embodiments according to this application. For ease of description, the techniques, methods, and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the techniques, methods, and devices should be considered part of the authorization specification. In all examples shown and discussed herein, any specific values should be interpreted as merely exemplary and not as limitations. Therefore, other examples of the exemplary embodiments may have different values.

[0020] It should be noted that, in the present application, the terms "comprise", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, an element defined by the statement "comprises a ..." does not exclude the presence of other identical elements in the process, method, article or device comprising the element. In addition, it should be pointed out that the scope of the methods and devices in the embodiments of the present application is not limited to performing functions in the order shown or discussed, and may also include performing functions in a substantially simultaneous manner or in the opposite order according to the functions involved. For example, the described method may be performed in an order different from that described, and various steps may also be added, omitted, or combined. In addition, the features described with reference to certain examples may be combined in other examples.

[0021] After tumor resection, residual cancer cells are the main cause of local recurrence and metastasis. Traditional bone scaffolds only play a role in space occupation and mechanical support. They cannot deal with problems such as local recurrence caused by incomplete surgical resection, secondary lesions caused by micrometastases, and lack of intervention in the microenvironment where cancer cells survive. By introducing anti-tumor functions into porous zinc-based bone repair scaffolds, residual tumor cells can be killed on site through synergistic functions, reducing the risk of postoperative tumor recurrence. At the same time, tumor-related bone defects are usually large, often accompanied by bone destruction or chemotherapy that inhibits bone growth. In this case, porous zinc-based bone repair scaffolds with osteogenic induction / osteogenesis-promoting reconstruction functions can support and guide bone tissue regeneration, shorten the recovery cycle, reduce medical costs, and improve comprehensive clinical benefits. Ultimately, the function of the porous zinc-based bone repair scaffold will be transformed from a "single support" to a multifunctional mode of "treatment + repair", realizing the transformation of regenerative medicine after bone tumor surgery towards precise treatment, personalized repair, and multifunctional synergy.

[0022] However, there is no report in domestic and foreign literature on the preparation method and corresponding performance research of a porous zinc-based bone repair scaffold coated with MoS2@GaP coating with controllable degradation, osteopromoting and anti-tumor properties. Therefore, it is proposed to use this degradable zinc bone repair scaffold in the next stage of bone defect repair.

[0023] Porous zinc-based bone repair scaffolds coated with MoS2@GaP First, the present invention provides a porous zinc-based bone repair scaffold covered with a MoS2@GaP coating, which includes: a porous zinc-based bone repair scaffold template and a MoS2@GaP coating covered on the surface of the porous zinc-based bone repair scaffold template.

[0024] Specifically, the porous zinc-based bone repair scaffold template is made of pure zinc and / or Zn-X alloy material, wherein X in the Zn-X alloy is one or more elements selected from Cu, Mg, Sr, Ca, Ge, Ti, Se, Li, Fe, Sn, Ag, Mn, RE, Ga, Zr, and Au.

[0025] Preferably, in the Zn-X alloy, the total mass content of element X is 0.1-6%, and the rest is Zn.

[0026] Furthermore, the porous zinc-based bone repair scaffold template also includes an external or in-situ self-generated reinforcement phase, and the reinforcement phase is one or more of Mg2Ge, Mg2Si, Mg2Sn, ZrO2, Al2O3, ZnO, CuO2, MgO, SiN, TiC, carbon fiber, carbon nanotubes, and graphene.

[0027] Preferably, the mass content of the reinforcing phase in the porous zinc-based bone repair scaffold template is 0.05-10%.

[0028] Furthermore, the porous zinc-based bone repair scaffold template has a porosity of 50-95% and a pore size of 50-600 μm.

[0029] Preparation method of porous zinc-based bone repair scaffold coated with MoS2@GaP coating The present invention also provides a method for preparing a porous zinc-based bone repair scaffold coated with a MoS2@GaP coating, comprising the following steps: S100, preparation of porous zinc-based bone repair scaffold template; S200, surface etching of porous zinc-based bone repair scaffold template; S300, MoS2@GaP coating was prepared on the surface of porous zinc-based bone repair scaffold template by hydrothermal reaction.

[0030] As some examples of the present invention, in step S100, the porous zinc-based bone repair scaffold template can be prepared by using infiltration casting, additive manufacturing technology, electrodeposition technology, etc.

[0031] As some examples of the present invention, the infiltration casting method is to cast the metal solution into a porous gypsum mold and then wash it with hot water to obtain a porous zinc-based bone repair scaffold template, wherein the casting temperature is 650~750°C.

[0032] As some examples of the present invention, the process for preparing a porous zinc-based bone repair scaffold template using additive manufacturing technology is as follows: the laser power is adjusted to 80-200W, the scanning speed is adjusted to 50-800mm / s, and the layer thickness is set to 10-50μm. The porous zinc-based bone repair scaffold template is prepared using an atomized or ball-milled mixed powder of pure zinc and / or Zn-X alloy with a particle size of 1-100μm. In addition, during the preparation of the porous zinc-based bone repair scaffold template, a certain reinforcing phase material can be added to form a reinforcing phase within the porous zinc-based bone repair scaffold template.

[0033] As some examples of the present invention, the process of preparing a porous zinc-based bone repair scaffold template using electrodeposition technology is as follows: The porous polyurethane was immersed in a mixed solution containing 100-300 g / L zinc sulfate heptahydrate, 50-100 g / L sodium sulfate and 20-40 g / L boric acid at a pH of 2.5-4.0 and a temperature of 20-50 °C. 2 After electroplating for 20 to 120 minutes, the polyurethane was removed in a vacuum tube furnace heated to 250 to 300°C, and then the furnace was cooled to room temperature to obtain a porous zinc-based bone repair scaffold template.

[0034] Furthermore, the surface etching process of the porous zinc-based bone repair scaffold template in step S200 is as follows: The porous zinc-based bone repair scaffold template is placed in a 0.5-3 mol / L dilute hydrochloric acid solution for surface etching for 10-60 minutes, then taken out, cleaned with anhydrous alcohol, and dried in a vacuum drying oven.

[0035] In the present invention, by etching the surface of the porous zinc-based bone repair scaffold template in a dilute hydrochloric acid solution, the surface roughness and porosity of the porous zinc-based bone repair scaffold template can be increased and the bonding strength of the coating formed subsequently can be improved.

[0036] Furthermore, the process of preparing the MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold template in step S300 is as follows: The porous zinc-based bone repair scaffold template is placed in a hydrothermal reactor filled with a phosphating solution for a hydrothermal reaction of 10 to 120 minutes to form a MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold template; Among them, the hydrothermal reaction temperature is 80~150℃, the hydrothermal reaction treatment is placed on an electromagnetic vibration table equipped with a cooling device throughout the process, and the reactor and the electromagnetic vibration table are placed in a heating furnace, which can be an annealing furnace, a box-type resistance furnace, a tubular resistance furnace, a muffle furnace, etc.

[0037] Preferably, during the hydrothermal reaction, the loading amount of the liquid-solid mixture inside the reactor accounts for 70% to 80% of the total volume of the entire reactor cavity.

[0038] During the hydrothermal reaction, MoS2 has a high density and is easy to sink to the bottom, and ultrasonic vibration makes it difficult to evenly distribute it in the phosphating solution. Therefore, the entire hydrothermal reaction process is placed on an electromagnetic vibration table equipped with a cooling device, and the reactor and electromagnetic vibration table are placed in a heating furnace.

[0039] In the present invention, by placing the reactor and the electromagnetic vibration table in a heating furnace, the heating furnace can provide the hydrothermal reactor with a more stable and uniform external thermal field, thereby avoiding the occurrence of temperature gradients in the hydrothermal reactor due to uneven self-heating, especially the occurrence of obvious temperature gradients inside the porous support, improving the reaction reproducibility, and promoting the phosphating reaction of GaP and the uniform deposition of MoS2 nanosheets.

[0040] Furthermore, the phosphating solution contains: Gallium nitrate: 0.01~0.7mol / L; Phosphoric acid: 0.02~1.4mol / L; MoS2: 0.002~1.0mol / L; Wherein, the particle size of the MoS2 is 50~3000nm; The pH of the phosphating solution is adjusted to 2.0-3.5 with acid or alkali solution.

[0041] Furthermore, the vibration frequency of the electromagnetic vibration table is 10-300 Hz, and the mode is frequency modulation or fixed frequency, and the amplitude is 0.01-2 mm.

[0042] Furthermore, after the hydrothermal treatment, the porous zinc-based bone repair scaffold covered with the MoS2@GaP coating is taken out, rinsed in deionized water and alcohol respectively, and then placed in a vacuum drying oven for drying to obtain the finished product of the porous zinc-based bone repair scaffold covered with the MoS2@GaP coating described in the present invention.

[0043] As other examples of the present invention, the process of preparing the MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold template in step S300 is: The porous zinc-based bone repair scaffold template is placed in a hydrothermal reactor filled with phosphating solution; At 80-150°C, first increase the pressure in the reactor to 0.5-2.5 MPa and maintain the temperature and pressure for 3-5 minutes; Then, the pressure in the reactor was quickly reduced to below 0.2 MPa within 30 s; Then, the pressure in the reactor is increased to 0.5-2.5 MPa again, and after maintaining the temperature and pressure at 80-150°C for 30-60 minutes, the pressure in the reactor is slowly reduced to normal pressure at a rate of no more than 0.3 MPa / min.

[0044] During the hydrothermal reaction, a multi-stage pressure control strategy of "rapid pressure increase - rapid pressure reduction - re-pressure increase and heat preservation - slow pressure release" was adopted. This pressure control method has obvious advantages for constructing a uniform MoS2@GaP composite functional coating and achieving interface densification. Specifically: (1) The multi-stage pressure control strategy provided by the present invention can promote the phosphating reactants to quickly generate a large number of original crystal nuclei (such as GaP, MoS2 primary particles) on the surface of the porous zinc-based bone repair scaffold template by first increasing the pressure + short-term heat preservation (3-5min), and then quickly reduce the pressure to <0.2MPa, resulting in local "non-equilibrium disturbance" of the system, and the crystals re-precipitate or the growth direction suddenly changes; the subsequent re-increasing the pressure + long-term reaction makes these crystal nuclei grow along the new orientation, forming a more uniform, dense and closely attached coating to the metal surface, and finally achieving the effect of inducing crystal nucleation and reconstruction, improving the density and adhesion of the coating; (2) The multi-stage pressure control strategy provided by the present invention can create a "capillary suction + pressure-driven diffusion" process by rapidly increasing and decreasing pressure, which can promote better penetration of Mo, Ga, P ions or precursors into the pores, and ultimately promote the formation of a comprehensive coverage of the internal surface of the porous zinc-based bone repair scaffold, which helps to improve its osteogenic activity and anti-tumor / antibacterial properties, and achieve the effect of promoting the penetration of reactants into the interior of the porous structure and improving the overall coating coverage; (3) The multi-stage pressure control strategy provided by the present invention can break the agglomeration trend of the precursor particles by rapidly increasing and decreasing the pressure, which helps to form an interlocking structure of flaky MoS2 and granular GaP, ultimately achieving the purpose of reducing agglomeration, controlling grain size, increasing specific surface area, enhancing biological activity, and controlling the nanostructure morphology of the coating; (4) The multi-stage pressure control strategy provided by the present invention can prevent the rapid escape of gas in the pores through slow pressure release in the final stage, which would cause the accumulation of tensile stress inside the coating and the risk of cracking / falling off the coating. Ultimately, the structural integrity and interface stability of the coating can be guaranteed through a controlled pressure reduction strategy.

[0045] As some examples of the present invention, during the reaction process, the pressure within the reactor can be raised to 0.5-2.5 MPa by relying on "autogenous pressure" within the enclosed space or by adding a volatile precursor (such as a hydrogen-containing phosphating agent) or a pressure regulator (such as ethylene glycol or ethanolamine). The amount of pressure regulator added can be determined through experimentation based on factors such as the hydrothermal reaction temperature and the amount of phosphating solution added.

[0046] The porous zinc-based bone repair scaffold was placed in a composite phosphating solution containing two materials through hydrothermal treatment to obtain a porous zinc-based bone repair scaffold with a MoS2@GaP coating on the surface. In this way, not only the anti-tumor effect of the porous zinc-based bone repair scaffold can be enhanced through the synergistic effect of multiple materials, but also the Ga released by the MoS2@GaP coating can be used to 3+ and MoS2 degradation products (MoO4 2- ) co-activate the Wnt / β-catenin pathway, significantly increasing alkaline phosphatase (ALP) activity and calcium nodule formation. Therefore, the present invention can prepare a porous zinc-based bone repair scaffold coated with molybdenum disulfide-doped gallium phosphate (MoS2@GaP) by performing a hydrothermal reaction on the surface of the porous zinc-based bone repair scaffold, imparting the synergistic functions of "degradation regulation, anti-tumor, and bone repair promotion."

[0047] In addition, the present invention also provides a bone repair material, which includes a metal matrix and a MoS2@GaP coating covered on the surface of the metal matrix.

[0048] It should be noted that, in addition to bone repair scaffolds, the bone repair materials provided by the present invention for preparing porous zinc-based bone repair scaffolds coated with MoS2@GaP coatings can also be used to prepare bone filling particles, bone repair particles, bone plates, bone nails, intramedullary nails and other internal fixation systems, as well as customized 3D printed bone replacement structures, bone repair membranes, craniomaxillary / spinal reconstruction scaffolds and other bone defect repair products.

[0049] The following specific examples illustrate the porous zinc-based bone repair scaffold coated with MoS2@GaP coating and the preparation method thereof according to the present invention: Example 1 First, a porous zinc-based bone repair scaffold template was prepared using high-purity zinc as raw material. The porous zinc-based bone repair scaffold template was prepared using electrodeposition technology, with a porosity of 85% and a pore size of 303μm.

[0050] The process of preparing porous zinc-based bone repair scaffold template using electrodeposition technology is as follows: First, the porous polyurethane was immersed in a mixed solution containing 200 g / L zinc sulfate heptahydrate, 75 g / L sodium sulfate and 20 g / L boric acid at a pH of 3.0 and a temperature of 40°C. 2 After electroplating for 60 minutes, the polyurethane was removed in a vacuum tube furnace heated to 300°C, and then the furnace was cooled to room temperature to obtain a porous zinc-based bone repair scaffold template. The porous zinc-based bone repair scaffold template was etched in a 1 mol / L dilute hydrochloric acid solution for 30 min to increase the surface roughness and porosity and enhance the coating bonding strength. It was then cleaned with anhydrous alcohol and dried in a vacuum drying oven. The porous zinc-based bone repair scaffold template was then placed in a hydrothermal reactor filled with a phosphating solution for a 30-minute hydrothermal reaction to deposit a MoS2@GaP composite coating on the surface of the porous zinc-based bone repair scaffold template. The phosphating solution was a mixed solution adjusted to a pH of 2.5 and contained 0.08 mol / L gallium nitrate, 0.16 mol / L phosphoric acid, and 0.2 mol / L MoS2 with a particle size of 2000 nm. The hydrothermal reaction temperature was 100°C, and the liquid-solid mixture inside the reactor accounted for 70% of the total volume of the reactor cavity. During the hydrothermal reaction, because MoS2 has a high density and tends to sink to the bottom, ultrasonic vibrations make it difficult to evenly distribute it in the phosphating solution. Therefore, the entire hydrothermal reaction was performed on an electromagnetic vibrator equipped with a cooling device, with the reactor and the electromagnetic vibrator placed in an annealing furnace. The electromagnetic vibration frequency was 80 Hz, the mode was fixed, and the amplitude was 0.5 mm. After the hydrothermal treatment, the porous zinc-based bone repair scaffold template was removed, rinsed in deionized water and ethanol, and dried in a vacuum drying oven. The resulting porous zinc-based bone repair scaffold was coated with MoS2@GaP.

[0051] Performance testing: (1) Micromorphology and composition detection Scanning electron microscopy and EDS were used to detect the microstructure and composition of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating obtained in Example 1. Figure 1 The microscopic morphology shown: from Figure 1 The SEM images in the figure show that the surface of the MoS2@GaP-coated porous zinc-based bone repair scaffold is covered with a large number of fine GaP coatings containing Ga, P, and O with an average particle size of 287±20nm, and a small number of MoS2 flakes with an average width of 2.3±0.8μm, containing O, Mo, and S, with a Mo / S atomic ratio close to 1:2. The MoS2@GaP-coated porous zinc-based bone repair scaffold has a porosity of 80.4% and a coating thickness of 3.8±0.5μm.

[0052] (2) Mechanical properties testing The compression properties and corresponding compression performance attenuation rates of the porous zinc-based bone repair scaffolds with and without MoS2@GaP coatings prepared in Example 1 and immersed in Hanks' solution for 3 months were tested and compared, and the results are shown in Table 1 below: Table 1 above shows the compressive performance data of the pure zinc bracket template and the pure zinc bracket sample covered with MoS2@GaP coating. Among them, the compressive yield strength of the pure zinc bracket not covered with MoS2@GaP coating is 7.3MPa, the stable compressive strength is 14.8MPa, and the elastic modulus is 0.86GPa; the compressive yield strength of the pure zinc bracket covered with MoS2@GaP coating is 8.6MPa, the stable compressive strength is 19.5MPa, and the elastic modulus is 0.93GPa.

[0053] After immersion in Hanks' solution for 3 months, the mechanical properties of the pure zinc scaffold without MoS2@GaP coating decreased significantly, with a compressive yield strength of 5.7 MPa, a stable compressive strength of 10.3 MPa, and an elastic modulus of 0.75 GPa. However, after immersion in Hanks' solution for 3 months, the mechanical properties of the pure zinc scaffold coated with MoS2@GaP coating still maintained more than 80% of the unimmersed sample, with a compressive yield strength of 7.9 MPa, a stable compressive strength of 16.8 MPa, and an elastic modulus of 0.85 GPa, showing excellent mechanical stability and its mechanical properties are between those of human cancellous bone and compact bone.

[0054] (3) Corrosion resistance testing Polarization test was conducted on the pure zinc stent with or without MoS2@GaP coating prepared in Example 1, and the results were as follows: Figure 2 The polarization curves shown in FIG and the electrochemical performance parameters of the pure zinc scaffold with or without MoS2@GaP coating in Hanks' solution fitted after the polarization test shown in Table 2 and its degradation rate after immersion in Hanks' solution for 1 month.

[0055] from Figure 2 The polarization curves and Figure 2 From the corrosion parameters obtained by fitting the Tafel interval (see Table 2), it can be seen that the corrosion potential, current density and corrosion rate of the pure zinc stent covered with MoS2@GaP coating obtained by polarization test in Hanks' solution are -0.960V, 1.3μA / cm 2 The MoS2@GaP coating significantly reduces the degradation rate of pure zinc scaffolds. (IV) Osteogenesis ability test (a) The Zn ion release rate of the pure zinc scaffold coated with MoS2@GaP in cell culture medium (DMEM+fetal bovine serum) was 2.7 μg / mL, which is between the Zn ion concentrations required to promote osteoblast proliferation (0.065~6.5 μg / mL), indicating that the MoS2@GaP coating can effectively regulate the degradation of the zinc scaffold to meet bone repair and regeneration.

[0056] (b) Furthermore, after three days of culture, the viability of pre-osteoblastic mouse cell line MC-3T3 cells in extracts containing 100%, 50%, and 25% pure zinc scaffolds was 15.6%, 52.7%, and 74.6%, respectively. In contrast, the viability of cells in extracts containing MoS2@GaP-coated porous zinc-based bone repair scaffolds was 75.9%, 88.6%, and 97.8%, respectively, demonstrating that the MoS2@GaP coating significantly improved the cytocompatibility of the pure zinc scaffolds. The extracts for the pure zinc scaffolds and the MoS2@GaP-coated porous zinc-based bone repair scaffolds were prepared by placing the pure zinc scaffolds or the MoS2@GaP-coated porous zinc-based bone repair scaffolds in culture medium and immersing them at 37°C for 48 hours to ensure full release of the alloy components. After immersion, extracts of varying concentrations were prepared according to research needs for subsequent cell experiments or biocompatibility assessments. The same applies below and will not be further detailed.

[0057] At the same time, the ALP multiples of MC-3T3 cells in the extract of porous zinc-based bone repair scaffolds coated with MoS2@GaP coating were 3.4 and 2.3 times that of the control group (pure titanium standard) and the single pure zinc scaffold, respectively, indicating that MoS2@GaP coating can significantly enhance the differentiation ability of osteoblasts.

[0058] (V) Anti-tumor ability testing (a) The clone morphology of DLM8C3H mouse osteosarcoma cells in the extract of porous zinc-based bone repair scaffolds with and without MoS2@GaP coating was observed, and the corresponding clone numbers were counted. Figure 3 The clone morphology and corresponding clone number statistics of DLM8C3H mouse osteosarcoma cells in the extract of porous zinc-based bone repair scaffolds with or without MoS2@GaP coating are shown, where: Figure 3 A is the clone morphology of DLM8C3H mouse osteosarcoma cells. Figure 3 B is a statistical diagram of the number of osteosarcoma cell clones in DLM8C3H mice.

[0059] from Figure 3The clonal morphology of DLM8C3H mouse osteosarcoma cells in A shows that the osteosarcoma cell clones in the control group (pure titanium standard) and the single pure zinc scaffold extract are densely distributed, with almost no osteosarcoma cell shrinkage and no cell fragments. In contrast, the osteosarcoma cell clones in the extract of the porous zinc-based bone repair scaffold coated with MoS2@GaP are sparsely distributed or even completely absent, with irregular edges, and obvious tumor cell shrinkage and increased cell fragments.

[0060] from Figure 3 As can be seen from the number of DLM8C3H mouse osteosarcoma cell clones in B, the number of osteosarcoma cell clones in the control group, the single pure zinc scaffold and the porous zinc-based bone repair scaffold coated with MoS2@GaP coating gradually decreased, indicating that the MoS2@GaP coating can significantly inhibit the proliferation of tumor cells.

[0061] (b) The cell migration morphology of DLM8C3H mouse osteosarcoma cells in the extract of porous zinc-based bone repair scaffolds with and without MoS2@GaP coating was observed, and the corresponding cell migration rates were calculated. Figure 4 The cell migration morphology and corresponding cell migration rate statistics of DLM8C3H mouse osteosarcoma cells in the extract of porous zinc-based bone repair scaffolds with or without MoS2@GaP coating are shown, where: Figure 4 A is the cell migration morphology of DLM8C3H mouse osteosarcoma cells, Figure 4 B is the statistical graph of the corresponding cell migration rate.

[0062] from Figure 4 The cell scratch morphology of DLM8C3H mouse osteosarcoma cells in A shows that the osteosarcoma cells in the control group (pure titanium standard) and the single pure zinc scaffold extract showed different degrees of migration after 24 hours of culture. In contrast, the osteosarcoma cells in the porous zinc-based bone repair scaffold extract coated with MoS2@GaP coating showed almost no cell migration. Figure 4 As can be seen from the scratch rates of DLM8C3H mouse osteosarcoma cells in Figure B, the scratch rates of osteosarcoma cells in the control group, the single pure zinc scaffold and the porous zinc-based bone repair scaffold coated with MoS2@GaP coating gradually decreased significantly, indicating that the MoS2@GaP coating can significantly inhibit the proliferation and migration of tumor cells.

[0063] Example 2 The only difference between it and the above-mentioned embodiment 1 is: In the preparation process of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating, after the porous zinc-based bone repair scaffold template is placed in a dilute hydrochloric acid solution for etching, the porous zinc-based bone repair scaffold template is placed in a hydrothermal reactor filled with phosphating solution for hydrothermal reaction. The hydrothermal reaction process is as follows: At 100°C, first increase the pressure in the reactor to 1.5 MPa and maintain the temperature and pressure for 5 minutes; Then, the pressure in the reactor was quickly reduced to below 0.2 MPa within 30 s; The pressure in the reactor was then increased to 1.5 MPa again, and after maintaining the temperature and pressure at 100°C for 30 minutes, the pressure in the reactor was slowly reduced to normal pressure at a rate of 0.2 MPa / min. After hydrothermal treatment, the porous zinc-based bone repair scaffold template was taken out, rinsed in deionized water and alcohol respectively, and then dried in a vacuum drying oven to finally obtain a porous zinc-based bone repair scaffold covered with MoS2@GaP coating.

[0064] Performance testing: (1) Microscopic morphology observation The surface of the porous zinc-based bone repair scaffold coated with MoS2@GaP was characterized by a large number of fine GaP coatings containing Ga, P, and O with an average particle size of 213±20 nm, and a small number of MoS2 flakes with an average width of 1.9±0.6 μm containing O, Mo, and S with a Mo / S atomic ratio close to 1:2. The MoS2@GaP-coated porous zinc-based bone repair scaffold had a porosity of 78.4% and a coating thickness of 3.2±0.5 μm.

[0065] (2) Mechanical properties testing The compression properties and corresponding compression performance attenuation rates of the porous zinc-based bone repair scaffolds with and without the MoS2@GaP coating prepared in Example 2 and soaked in Hanks' solution for 3 months were tested and compared, and the results are shown in Table 3 below: From the mechanical property test results in Table 3, it can be seen that after the hydrothermal reaction is carried out according to the multi-stage pressure control strategy of "first rapid pressure increase - rapid pressure reduction - then pressure increase and heat preservation - slow pressure release" in Example 2, the mechanical properties of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating are even better, and after being immersed in Hanks' solution for 3 months, the mechanical properties can be maintained at a higher level.

[0066] (3) Corrosion resistance testing The corrosion potential, corrosion current density, corrosion rate and degradation rate of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating obtained by polarization test in Hanks' solution were -0.912 V, 1.1 μA / cm 2 , 16μm / y and 17μm / y.

[0067] (IV) Osteogenesis ability test (a) The Zn ion release rate of the porous zinc-based bone repair scaffold coated with MoS2@GaP in cell culture medium was 2.5 μg / mL, which is between the Zn ion concentrations required to promote osteoblast proliferation (0.065~6.5 μg / mL), indicating that the MoS2@GaP-coated Zn-1Cu alloy scaffold can meet the requirements of bone repair and regeneration.

[0068] (b) After culturing MC-3T3 cells for three days in extracts from porous zinc-based bone repair scaffolds coated with MoS2@GaP at concentrations of 100%, 50%, and 25%, the cell viability was 78.4%, 92.1%, and 99.6%, respectively, demonstrating good cytocompatibility. Furthermore, the ALP multiple of MC-3T3 cells in the extracts from the porous zinc-based bone repair scaffolds coated with MoS2@GaP was 3.6 times higher than that in the control group (pure titanium standard), indicating that it promotes osteoblast differentiation.

[0069] (V) Anti-tumor ability testing The clone number of DLM8C3H mouse osteosarcoma cells in the extract of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating was only 0.54 times that of the control group (pure titanium standard), indicating that the porous zinc-based bone repair scaffold coated with MoS2@GaP coating can significantly inhibit the proliferation of tumor cells.

[0070] In addition, the cell migration rate of DLM8C3H mouse osteosarcoma cells in the extract of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating was 0.39 times that of the control group (pure titanium standard), indicating that the porous zinc-based bone repair scaffold coated with MoS2@GaP coating can also significantly inhibit the proliferation and migration of tumor cells.

[0071] Example 3 Firstly, a porous zinc-based bone repair scaffold template was prepared using Zn-1Cu alloy as raw material. The porous zinc-based bone repair scaffold template was prepared using additive manufacturing technology with a porosity of 75% and a pore size of 500μm.

[0072] The process of preparing porous zinc-based bone repair scaffold template using additive manufacturing technology is as follows: First, the laser power was adjusted to 150W, the scanning speed was adjusted to 700mm / s, and the layer thickness was set to 30μm. A porous zinc-based bone repair scaffold template was prepared using Zn-1Cu alloy atomized powder with a particle size of 5μm. The porous zinc-based bone repair scaffold template was etched in a 1 mol / L dilute hydrochloric acid solution for 30 min to increase the surface roughness and porosity and enhance the coating bonding strength. It was then cleaned with anhydrous alcohol and dried in a vacuum drying oven. The Zn-1Cu alloy scaffold template was then placed in a hydrothermal reactor filled with a phosphating solution for a 60-minute hydrothermal reaction to deposit a MoS2@GaP composite coating on the surface of the porous zinc-based bone repair scaffold template. The phosphating solution was a mixed solution adjusted to a pH of 2.5 and contained 0.1 mol / L gallium nitrate, 0.2 mol / L phosphoric acid, and 0.3 mol / L MoS2 with a particle size of 100 nm. The hydrothermal reaction temperature was 80°C, and the liquid-solid mixture inside the reactor accounted for 80% of the total volume of the reactor cavity. During the hydrothermal reaction, because MoS2 has a high density and tends to sink to the bottom, ultrasonic vibrations make it difficult to evenly distribute it in the phosphating solution. Therefore, the entire hydrothermal reaction was performed on an electromagnetic vibrator equipped with a cooling device, with the reactor and the electromagnetic vibrator placed in an annealing furnace. The electromagnetic vibration frequency was 100 Hz, with either a modulated or fixed frequency mode and an amplitude of 0.5 mm. After the hydrothermal treatment, the Zn-1Cu alloy scaffold template was removed, rinsed in deionized water and ethanol, and dried in a vacuum drying oven. This yielded a porous Zn-1Cu alloy bone repair scaffold coated with MoS2@GaP.

[0073] Performance testing: (1) Micromorphology and composition detection The MoS2@GaP coating on the surface of the Zn-1Cu alloy stent is in the form of fine particles with no obvious cracks. The coating thickness is 1.9 μm and the average particle size of the GaP coating is 176±12 nm, indicating that adjusting the process parameters of electromagnetic vibration treatment and hydrothermal treatment can regulate the morphology, thickness and crack condition of the MoS2@GaP coating.

[0074] (2) Mechanical properties testing The compression properties and corresponding compression performance attenuation rates of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating prepared in Example 3 above and soaked in Hanks' solution for 3 months were tested and compared, and the following results were obtained: The compressive yield strength of the MoS2@GaP coating-coated Zn-1Cu alloy stent is 12.6 MPa, the stable compressive strength is 23.2 MPa, and the elastic modulus is 1.34 GPa.

[0075] After being immersed in Hanks' solution for 3 months, the MoS2@GaP coating-coated Zn-1Cu alloy stent still maintained relatively high mechanical properties and mechanical stability, with a compressive yield strength of 11.8 MPa, a stable compressive strength of 21.7 MPa, and an elastic modulus of 1.27 GPa. The mechanical properties still remained above 90% of those of the unimmersed sample, indicating that the mechanical stability of the MoS2@GaP coating-coated Zn-1Cu alloy stent was significantly improved compared with the MoS2@GaP coating-coated porous pure zinc stent in Example 1.

[0076] (3) Corrosion resistance testing The corrosion potential, corrosion current density, corrosion rate and degradation rate of the MoS2@GaP coating-coated Zn-1Cu alloy stent obtained from the polarization test in Hanks' solution were -1.438 V, 6.8 μA / cm2, 98 μm / y and 113 μm / y respectively.

[0077] (IV) Osteogenesis ability test (a) The Zn ion release rate of the MoS2@GaP-coated Zn-1Cu alloy scaffold in the cell culture medium was 3.6 μg / mL, which is between the Zn ion concentrations required to promote osteoblast proliferation (0.065~6.5 μg / mL), indicating that the MoS2@GaP-coated Zn-1Cu alloy scaffold can meet the requirements of bone repair and regeneration.

[0078] (b) The cell viability of pre-osteoblastic mouse cell line MC-3T3 cells in the extracts of 100%, 50% and 25% MoS2@GaP coated Zn-1Cu alloy scaffolds were 67.5%, 82.7% and 95.3%, respectively.

[0079] At the same time, the ALP multiples of MC-3T3 cells in the extract of MoS2@GaP coated Zn-1Cu alloy scaffold were 2.8 times that of the control group (pure titanium standard), indicating that it is conducive to osteoblast differentiation.

[0080] (V) Anti-tumor ability testing The clone number of DLM8C3H mouse osteosarcoma cells in the extract of MoS2@GaP coated Zn-1Cu alloy scaffold was only 0.57 times that of the control group, indicating that MoS2@GaP coated Zn-1Cu alloy scaffold can also significantly inhibit tumor cell proliferation.

[0081] The cell migration rate of DLM8C3H mouse osteosarcoma cells in the extract of MoS2@GaP-coated Zn-1Cu alloy scaffolds was 0.53 times that of the control group (pure titanium standard), indicating that MoS2@GaP-coated Zn-1Cu alloy scaffolds can also significantly inhibit the proliferation and migration of tumor cells.

[0082] Example 4 The only difference between it and the above-mentioned embodiment 3 is that: During the preparation of porous zinc-based bone repair scaffolds coated with MoS2@GaP, 0.2% ZrO2 was added as an external reinforcement phase.

[0083] Performance testing: (2) Micromorphology and composition detection The MoS2@GaP coating on the surface of the Zn-1Cu alloy stent is in fine granular form with no obvious cracks in the coating. The coating thickness is 1.8 μm and the average particle size of the GaP coating is 173 ± 12 nm.

[0084] (2) Mechanical properties testing The compression properties and corresponding compression performance attenuation rates of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating prepared in Example 4 above and soaked in Hanks' solution for 3 months were tested and compared, and the following results were obtained: The compressive yield strength of the MoS2@GaP coating-coated Zn-1Cu alloy stent is 14.2 MPa, the stable compressive strength is 25.1 MPa, and the elastic modulus is 1.32 GPa.

[0085] After being immersed in Hanks' solution for three months, the MoS2@GaP-coated Zn-1Cu alloy scaffold still maintained high mechanical properties and mechanical stability, including a compressive yield strength of 13.3 MPa, a stable compressive strength of 22.6 MPa, and an elastic modulus of 1.28 GPa. The mechanical properties still remained above 90% of those of the unimmersed sample.

[0086] (3) Corrosion resistance test The corrosion potential, corrosion current density, corrosion rate and degradation rate of the MoS2@GaP coating-coated Zn-1Cu alloy stent obtained from the polarization test in Hanks' solution were -1.416 V, 6.3 μA / cm2, 84 μm / y and 102 μm / y respectively.

[0087] (IV) Osteogenesis ability test (a) The Zn ion release rate of the MoS2@GaP-coated Zn-1Cu alloy scaffold in the cell culture medium was 3.4 μg / mL, which is between the Zn ion concentrations required to promote osteoblast proliferation (0.065~6.5 μg / mL), indicating that the MoS2@GaP-coated Zn-1Cu alloy scaffold can meet the requirements of bone repair and regeneration.

[0088] (b) The cell viability of pre-osteoblastic mouse cell line MC-3T3 cells in the extracts of 100%, 50% and 25% MoS2@GaP coated Zn-1Cu alloy scaffolds was 67.3%, 82.9% and 96.1%, respectively.

[0089] At the same time, the ALP multiples of MC-3T3 cells in the extract of MoS2@GaP coated Zn-1Cu alloy scaffold were 2.9 times that of the control group (pure titanium standard), indicating that it is conducive to osteoblast differentiation.

[0090] (V) Anti-tumor ability testing The clone number of DLM8C3H mouse osteosarcoma cells in the extract of MoS2@GaP coated Zn-1Cu alloy scaffold was only 0.55 times that of the control group, indicating that MoS2@GaP coated Zn-1Cu alloy scaffold can also significantly inhibit tumor cell proliferation.

[0091] The cell migration rate of DLM8C3H mouse osteosarcoma cells in the extract of MoS2@GaP-coated Zn-1Cu alloy scaffolds was 0.52 times that of the control group (pure titanium standard), indicating that MoS2@GaP-coated Zn-1Cu alloy scaffolds can also significantly inhibit the proliferation and migration of tumor cells.

[0092] The embodiments of the present application are described above in conjunction with the accompanying drawings. Unless there is a conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present application is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of this application, ordinary technicians in this field can also make many forms without departing from the purpose of this application and the scope of protection of the claims, all of which are within the protection of this application.

Claims

1. A porous zinc-based bone repair scaffold coated with MoS2@GaP coating, characterized in that: include: A porous zinc-based bone repair scaffold template and a MoS2@GaP coating covered on the surface of the porous zinc-based bone repair scaffold template.

2. The porous zinc-based bone repair scaffold coated with MoS2@GaP coating according to claim 1, characterized in that: The porous zinc-based bone repair scaffold template is made of pure zinc and / or Zn-X alloy material, wherein X in the Zn-X alloy is one or more elements selected from Cu, Mg, Sr, Ca, Ge, Ti, Se, Li, Fe, Sn, Ag, Mn, RE, Ga, Zr, and Au.

3. The porous zinc-based bone repair scaffold coated with MoS2@GaP coating according to claim 2, characterized in that: The porous zinc-based bone repair scaffold template also includes an external or in-situ self-generated reinforcement phase, and the reinforcement phase is one or more of Mg2Ge, Mg2Si, Mg2Sn, ZrO2, Al2O3, ZnO, CuO2, MgO, SiN, TiC, carbon fiber, carbon nanotubes, and graphene.

4. The porous zinc-based bone repair scaffold coated with MoS2@GaP coating according to claim 1, characterized in that: The porous zinc-based bone repair scaffold template has a porosity of 50-95% and a pore size of 50-600 μm.

5. The method for preparing a porous zinc-based bone repair scaffold coated with a MoS2@GaP coating according to any one of claims 1 to 4, characterized in that: The following steps are involved: S100, preparation of porous zinc-based bone repair scaffold template; S200, surface etching of porous zinc-based bone repair scaffold template; S300, MoS2@GaP coating was prepared on the surface of porous zinc-based bone repair scaffold template by hydrothermal reaction.

6. The method for preparing a porous zinc-based bone repair scaffold coated with MoS2@GaP coating according to claim 5, characterized in that: The surface etching process of the porous zinc-based bone repair scaffold template in step S200 is as follows: The porous zinc-based bone repair scaffold template was placed in a 0.5-3 mol / L dilute hydrochloric acid solution for surface etching for 10-60 minutes.

7. The method for preparing a porous zinc-based bone repair scaffold coated with MoS2@GaP coating according to claim 5, characterized in that: The process of preparing the MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold template in step S300 is as follows: The porous zinc-based bone repair scaffold template is placed in a hydrothermal reactor filled with a phosphating solution for a hydrothermal reaction of 10 to 120 minutes to form a MoS2@GaP coating on the surface of the porous zinc-based bone repair scaffold template; Among them, the hydrothermal reaction temperature is 80~150℃, the hydrothermal reaction treatment is carried out entirely on an electromagnetic vibration table equipped with a cooling device, and the reactor and the electromagnetic vibration table are placed in a heating furnace.

8. The method for preparing a porous zinc-based bone repair scaffold coated with a MoS2@GaP coating according to claim 7, characterized in that: The phosphating solution contains: Gallium nitrate: 0.01~0.7mol / L; Phosphoric acid: 0.02~1.4mol / L; MoS2: 0.002~1.0mol / L; Wherein, the particle size of the MoS2 is 50~3000nm; The pH of the phosphating solution is adjusted to 2.0-3.5 with acid or alkali solution.

9. The method for preparing a porous zinc-based bone repair scaffold coated with MoS2@GaP coating according to claim 7, characterized in that: The hydrothermal reaction process is: At the set reaction temperature, first increase the pressure in the reactor to 0.5~2.5MPa and maintain the temperature and pressure for 3~5min; Then, the pressure in the reactor was quickly reduced to below 0.2 MPa within 30 s; Then, the pressure in the reactor is increased to 0.5-2.5 MPa again, and after maintaining the temperature and pressure for 30-60 minutes, the pressure in the reactor is slowly reduced to normal pressure at a speed of no more than 0.3 MPa / min.

10. Use of the porous zinc-based bone repair scaffold coated with MoS2@GaP coating according to any one of claims 1 to 4 in the preparation of bone defect repair products.

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