Zirconium oxide surface pda-go@cu2o composite functional coating, preparation method and application thereof

Abstract

The application discloses a zirconium oxide surface PDA-GO@Cu2O composite functional coating and a preparation method and application thereof. Firstly, dopamine can be self-polymerized under weak alkaline conditions and a polydopamine adhesion layer is formed on the surface of zirconium oxide; subsequently, the abundant oxygen-containing functional groups such as hydroxyl groups, carboxyl groups and epoxy groups on the surface of graphene oxide enable the graphene oxide to adsorb and complex copper ions; then, Cu2O is uniformly loaded on the surface of GO sheet layers through an ascorbic acid / alkaline system to form a GO@Cu2O composite nanostructure; finally, the composite nanoparticles are fixed on the surface of the zirconium oxide material through the interaction between the PDA layer and the GO@Cu2O, and the composite functional coating which can be used for modifying the surface of a zirconium oxide implant is obtained. The composite functional coating has the advantages of stability, antibacterial property and bone formation promotion.

Description

Technical Field

[0001] This invention relates to the field of dental implant material development technology, and in particular to a zirconia surface PDA-GO@Cu2O composite functional coating, its preparation method and application. Background Technology

[0002] With the increase in dental implant cases, peri-implantitis and inadequate osseointegration have become two key issues affecting surgical success rates. To address these issues, researchers are optimizing implant structure, material composition, and surface design to improve their physical, mechanical, and biological properties. Current implant materials mainly include titanium, PEEK, and zirconia implants.

[0003] Titanium is a bioinert material. While it can form direct osseointegration with bone tissue, it lacks the ability to actively induce osteogenesis. In patients with poor bone quality or weak healing ability, its osteogenesis efficiency and osseointegration quality are often unsatisfactory. Secondly, titanium surfaces lack active antibacterial function, making them prone to bacterial adhesion and biofilm formation. When oral hygiene is not properly controlled, this can lead to peri-implant mucositis and even peri-implantitis, threatening the long-term stability of the implant. Furthermore, from a biosafety perspective, titanium implants may release titanium particles due to mechanical wear or corrosion during long-term use, inducing local inflammatory reactions. Finally, aesthetically, titanium alloys are grayish-black, which can easily cause gingival translucency in the anterior aesthetic zone or in patients with thin soft tissue, affecting the aesthetic outcome.

[0004] The main problem with PEEK is insufficient osseointegration due to its bioinertness. PEEK is a hydrophobic material, lacking active sites for cell adhesion, proliferation, and osteogenic differentiation. Compared to traditional implant materials like titanium, its osseointegration capacity is significantly weaker. Secondly, PEEK itself lacks active antibacterial capabilities; its hydrophobic surface easily leads to bacterial adhesion and plaque biofilm formation, resulting in a lack of antibacterial function and hindering early and stable healing of the surrounding tissues. Furthermore, the chemical inertness and lack of active functional groups on the PEEK surface make surface modification difficult, limiting the direct application of conventional chemical modification strategies and restricting its functional expansion.

[0005] Zirconia implants have become an important material for dental aesthetic restorations due to their excellent aesthetic results, lack of metal allergy risk, and good biocompatibility. However, biological limitations such as insufficient bioactivity due to surface chemical inertness and the absence of inherent antibacterial function still restrict further improvement in clinical osseointegration outcomes. Summary of the Invention

[0006] To overcome the defects and shortcomings of the existing technology, the purpose of this invention is to provide a PDA-GO@Cu2O composite functional coating on the zirconia surface, its preparation method and application.

[0007] The technical solution provided by this invention is as follows: A method for preparing a PDA-GO@Cu2O composite functional coating on a zirconia surface, the method comprising the following steps: (1) Mix the GO aqueous dispersion with 0.1 M CuSO4 solution and react at 300 rpm for 10 min; add PEG-600 solution to reaction product 1 and stir well, add 0.05 M ascorbic acid solution and 0.1 M NaOH solution and stir well. After the solution turns black, continue stirring for 30 min, let stand, and centrifuge, wash and dry the resulting reaction product 2 to obtain GO@Cu2O NPs; (2) After grinding, washing and drying, ZrO2 was positioned on the side wall of a beaker. Dopamine was added to a pH=8.5, 0.1 mM Tris·HCl solution. The resulting mixed solution was added to the beaker and the liquid level was submerged in ZrO2. The reaction was carried out at room temperature and 500 rpm for 3 h. The reaction product 3 on the side wall of the beaker was washed with pure water to obtain ZrO2-PDA. (3) Add 500 μg / mL GO@Cu2O NPs aqueous solution to the above beaker and make the liquid level cover ZrO2-PDA. React at room temperature and 500 rpm for 3 h. Wash the reaction product 4 on the side wall of the beaker with pure water to obtain zirconia implant ZrO2-PDA-GO@Cu2O.

[0008] Preferably, in step (1), in reaction product 1, the mass-to-volume ratio of GO to CuSO4 solution in the GO aqueous dispersion is 1 g: 50 mL.

[0009] Preferably, in step (2), the volume ratio of reaction product 1 to PEG-600 solution, ascorbic acid solution and 0.1 M NaOH solution is 1:1:1:1.

[0010] Preferably, in step (1), the centrifugal washing is performed by washing with deionized water and anhydrous ethanol in sequence, followed by centrifugation, in order to remove unreacted substances and impurities.

[0011] Preferably, in step (2), the mass-to-volume ratio of dopamine to Tris·HCl solution is 0.8 g: 400 mL.

[0012] Preferably, in step (2), the polishing, washing, and drying are specifically as follows: polishing with 100#, 200#, 400#, and 1000# silicon carbide sandpaper in sequence to ensure a smooth surface, followed by ultrasonic cleaning with acetone, anhydrous ethanol, and deionized water for 10 minutes in sequence to remove the debris attached to the surface, and then placing it in an oven to dry.

[0013] Preferably, in step (3), the washing process involves washing three times with ultrapure water to remove impurities.

[0014] This invention further discloses the PDA-GO@Cu2O composite functional coating on the zirconia surface prepared by the above method.

[0015] This invention further discloses the application of the above-mentioned PDA-GO@Cu2O composite functional coating on the zirconia surface in the preparation of surface modification materials for dental zirconia implants.

[0016] This invention overcomes the shortcomings of existing technologies by providing a PDA-GO@Cu2O composite functional coating on a zirconia surface, its preparation method, and its applications. This invention addresses the problems of strong bioinertness, insufficient antibacterial properties, difficulty in stably loading functional nanomaterials, and the tendency of single antibacterial components to aggregate and release uncontrollably. Specifically, graphene oxide not only serves as a loading carrier for cuprous oxide nanoparticles, improving their dispersibility and interfacial bonding stability, but also participates in antibacterial activity and osteogenic-related cell behavior regulation through its layered structure and surface oxygen-containing functional groups. The cuprous oxide nanoparticles, as copper-based active components, further endow the material with antibacterial properties and osteogenic potential, thereby achieving multi-component synergistic functional modification of the zirconia surface.

[0017] The technical concept of this invention is as follows: First, by utilizing the characteristic that dopamine can self-polymerize under weakly alkaline conditions and form a polydopamine adhesion layer on the zirconia surface, the reactivity and interfacial bonding ability of the zirconia surface are improved. Then, by utilizing the abundant oxygen-containing functional groups such as hydroxyl, carboxyl, and epoxy groups on the surface of graphene oxide, it can adsorb and complex copper ions, and provide nucleation sites for the in-situ generation of cuprous oxide nanoparticles. Furthermore, by using an ascorbic acid / alkaline system, copper ions are reduced to cuprous oxide nanoparticles, so that Cu2O can be uniformly loaded on the GO sheet surface to form a GO@Cu2O composite nanostructure. Finally, by using hydrogen bonding, π-π interaction, coordination, and physical adsorption between the PDA layer and GO@Cu2O, the composite nanoparticles are fixed on the zirconia material surface, thereby obtaining a composite functional coating with stability, antibacterial properties, and osteopromoting effects.

[0018] Compared to existing simple zirconia surface treatment methods, this invention does not merely change the surface roughness of the material through sandblasting, acid etching, or plasma treatment. Instead, it further introduces a functionally responsive nanocomposite layer, transforming the zirconia surface modification from a single physical modification to a synergistic modification of physical, chemical, and biological functions. The PDA layer improves the adhesion and hydrophilicity of the zirconia surface, providing a stable interface for subsequent nanocomponent loading; the GO sheet structure increases the effective loading area, improves the dispersibility of Cu2O NPs, and reduces their direct aggregation; Cu2ONPs can serve as a copper-based antibacterial active component, inhibiting common oral pathogens or biofilm formation through contact sterilization, copper ion release, and reactive oxygen species-related effects. The combination of these three elements forms a structurally stable, synergistically component-coated, and multifunctional composite coating on the zirconia surface.

[0019] The key technical points of this invention include: First, PDA is used as the interfacial transition layer between zirconium oxide and GO@Cu2O to solve the problem of insufficient stability of GO or Cu2ONPs directly loaded on the zirconium oxide surface. Second, GO is used as the in-situ growth carrier for Cu2O nanoparticles. The adsorption and confinement of copper ions by oxygen-containing functional groups on the GO surface improves the dispersion and loading uniformity of Cu2ONPs. Third, PEG-600 was used in the preparation process of GO@Cu2O nanoparticles to improve the dispersion stability of the reaction system and to help regulate the formation process of Cu2ONPs. Fourth, by combining GO@Cu2O NPs with the PDA-modified zirconium oxide surface, the antibacterial active components are not simply mixed or physically deposited, but rather form a more stable composite coating structure through multiple interfacial interactions.

[0020] The innovation of this invention lies in the organic combination of a PDA interface adhesion layer, a GO nanocarrier, and Cu2O NPs antibacterial active components to construct a composite functional system suitable for surface modification of zirconia dental materials. This system can improve the shortcomings of traditional zirconia materials in terms of surface functionality, and alleviate the problems of easy aggregation, insufficient stability, and low surface loading efficiency when using Cu2O NPs alone. Through the synergistic design of PDA-GO@Cu2O, this invention is expected to endow zirconia materials with better antibacterial properties, surface hydrophilicity, and biocompatibility, providing a new technical solution for the surface functionalization of zirconia implants, restorations, or other oral hard tissue substitutes.

[0021] Therefore, the core of this invention is not limited to the preparation of single cuprous oxide nanoparticles, but rather to achieving stable functional modification of the zirconia material surface through a multi-level structural design of "PDA interface layer-GO carrier-Cu2O nano-antibacterial component". This technical route has the advantages of mild preparation conditions, relatively simple operation process, clear component functions, and strong scalability, making it suitable for application in the antibacterial modification and surface biofunctional enhancement of dental zirconia materials.

[0022] The beneficial effects of this invention after adopting the above technical solution are as follows: (1) Multi-component synergistic modification significantly enhances the bioactivity of zirconium surfaces: This invention uses ZrO2 as a substrate, utilizes the universal adhesiveness of PDA to construct a stable interface layer, and further loads GO and Cu2O to achieve multi-component synergistic functionalization of the surface. This modification strategy can effectively improve the problems of strong bioinertness and limited osteogenic induction ability of traditional zirconium materials, providing a more favorable interface microenvironment for cell adhesion, spreading, proliferation and differentiation.

[0023] (2) PDA serves as an interface bridge, resulting in stable coating construction and strong applicability: PDA has excellent surface adhesion capabilities, which can firmly bond to the ZrO2 surface and provide reaction sites and connection bases for further fixation of GO and Cu2O. This method is simple to operate, has mild conditions, does not rely on complex equipment, and helps to improve the stability, uniformity and repeatability of composite coating construction, overcoming the problems of easy peeling and insufficient adhesion of single coatings.

[0024] (3) GO introduction enhances surface functionality and promotes cell behavior regulation: GO has a large specific surface area and abundant oxygen-containing functional groups, which can further improve the surface roughness, hydrophilicity and protein adsorption capacity, which is conducive to early cell adhesion and the establishment of bone-related microenvironment; at the same time, GO can also provide a good carrier for the subsequent dispersion of active components, enhancing the structural stability and functional integration of the composite surface.

[0025] (4) Cu2O endows the surface with dual potential for antibacterial and repair promotion: The introduction of Cu2O gives the material surface a certain antibacterial activity, which helps to inhibit bacterial adhesion and biofilm formation, thereby reducing the risk of peri-implant infection. At the same time, the biological effects of copper ions can also participate in angiogenesis, cell migration and osteogenic regulation to a certain extent, so that the surface has both antibacterial protection and tissue repair promotion effects.

[0026] (5) Combining osteogenic and antibacterial functions, better meeting the needs of oral implant applications: Traditional implant surface modification often focuses on a single function, while the ZrO2-PDA-GO@Cu2O surface can improve cell compatibility and osteogenic activity while also taking into account antibacterial properties, forming a dual advantage of "promoting bone integration + anti-infection". This feature is more in line with the actual needs of implant materials in the complex oral microenvironment, and helps to improve the quality of early osseointegration and long-term clinical stability.

[0027] (6) The preparation conditions are mild and the scalability is good, with certain clinical translation prospects: The surface modification strategy of this invention has a relatively mild overall process, clear steps, and a wide range of raw material sources, which has good operability and reproducibility. Compared with high temperature, high energy or complex equipment-dependent modification methods, it is easier to scale up the preparation and optimize the process, and therefore has good application potential in the functionalization of zirconium implant surfaces and clinical translation. Attached Figure Description

[0028] Figure 1 Characterization of GO, Cu2O NPs and GO@Cu2O NPs and detection of photothermal properties of GO and GO@Cu2O NPs; where (a) SEM, (b) XRD, (c) FTIR, (df) photothermal properties of GO, and (g~i) photothermal properties of GO@Cu2O NPs.

[0029] Figure 2 The results show the photodynamic properties, ROS regulation properties, and pH acid response properties of Cu2O NPs and GO@Cu2O NPs; specifically, (a~d) are the photodynamic property evaluation results of Cu2O NPs and GO@Cu2O NPs, (e~f) are the ROS regulation property evaluation results of Cu2O NPs and GO@Cu2O NPs, and (g~h) are the pH acid response property evaluation results of Cu2O NPs and GO@Cu2O NPs.

[0030] Figure 3 It’s ZrO 2、 ZrO2-PDA and ZrO2-PDA-GO@Cu2O surface characterization; (a) SEM, (b, d) EDS and elemental quantitative analysis results, (c, e) water contact angle detection, (f~i) photothermal performance and photothermal stability.

[0031] Figure 4 The evaluation focuses on the biocompatibility of GO@Cu2O NPs and ZrO2-PDA-GO@Cu2O surfaces; specifically, (a, b) biocompatibility of GO@Cu2ONPs, (c, d) biocompatibility of ZrO2-PDA-GO@Cu2O surfaces, and (e, f) hemolytic toxicity testing of GO@Cu2O NPs.

[0032] Figure 5 The antibacterial properties of GO@Cu2O NPs and ZrO2-PDA-GO@Cu2O surfaces are as follows: (a~e) Evaluation results of the antibacterial properties of GO@Cu2O NPs, (f~h) Evaluation results of the antibacterial properties of ZrO2-PDA-GO@Cu2O surfaces, and (i~k) Evaluation results of the biofilm inhibition and mature biofilm removal performance of ZrO2-PDA-GO@Cu2O surfaces.

[0033] Figure 6 It’s ZrO 2、 Evaluation of osteogenic properties of ZrO2-PDA and ZrO2-PDA-GO@Cu2O surfaces; (a) surface cytotoxicity assessment, (b-e) RT-qPCR, (f-h) alizarin red staining results and quantitative analysis results, and (i-k) immunofluorescence staining results.

[0034] Figure 7 It’s ZrO 2、 In vivo osteogenic performance evaluation of ZrO2-PDA and ZrO2-PDA-GO@Cu2O surfaces; (a) Micro-CT analysis results, (b~c) BV / TV and BMD analysis results, (d) H&E staining results of important organs. Detailed Implementation

[0035] The technical solution of the present invention will be further described in detail below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0036] Example 1: Preparation of Cu2O NPs Prepare 0.02 M PEG-600 stock solution and 0.1 M anhydrous copper sulfate (CuSO4) solution for later use. Take 50 mL of PEG-600 stock solution and mix it with 50 mL of copper sulfate solution, then stir at 300 rpm for 10 min on a magnetic stirrer to ensure thorough mixing. Subsequently, prepare 0.05 M ascorbic acid solution, 0.1 M sodium hydroxide (NaOH) solution, and 0.026 M sodium borohydride (NaBH4) solution, respectively.

[0037] Slowly add 50 mL of ascorbic acid solution and 50 mL of NaOH solution to the above mixed solution while stirring continuously. When the solution color gradually changes from blue to yellow, slowly add 50 mL of NaBH4 solution dropwise (avoid adding too quickly). At this point, the solution color turns black. Continue stirring for 30 min, then stop stirring. The reaction system is then allowed to stand at room temperature for 24 h.

[0038] After 24 hours, a dark red precipitate was observed at the bottom of the container. The supernatant was discarded, and the precipitate was resuspended in deionized water and centrifuged at 12,000 rpm. This process was repeated 2-3 times. The precipitate was then washed 2-3 times with anhydrous ethanol in the same manner to thoroughly remove unreacted substances and impurities. Finally, the precipitate was resuspended in 5 mL of deionized water, frozen at -20°C, and then freeze-dried to obtain dark red particles, denoted as Cu₂O NPs.

[0039] Example 2: Synthesis of GO@Cu2O NPs A certain amount of GO was dispersed in deionized water, and a homogeneous and stable GO dispersion was obtained by ultrasonic treatment for 10 min. Subsequently, 1 g of GO was mixed with 50 mL of 0.1 M CuSO4 solution and stirred at 300 rpm for 10 min to promote Cu... 2+ Sufficient adsorption and coordination on the GO surface.

[0040] Take 50 mL of PEG-600 solution and mix it with 50 mL of the above solution. Stir the mixture on a magnetic stirrer at 300 rpm for 10 min to ensure thorough mixing. Slowly add 50 mL of 0.05 M ascorbic acid solution and 50 mL of 0.1 M NaOH solution to the above mixture while stirring continuously. The solution turns black at this point. Continue stirring for 30 min and then stop stirring. The reaction system is then allowed to stand at room temperature for 24 h.

[0041] The reaction product was allowed to stand, centrifuged and washed (unreacted substances and impurities were removed by deionized water and anhydrous ethanol), and dried to obtain black particulate matter, denoted as GO@Cu2O NPs.

[0042] Example 3: Preparation of ZrO2-PDA-GO@Cu2O surface The ZrO2 sample was sequentially polished with 100#, 200#, 400#, and 1000# silicon carbide sandpaper to ensure a smooth surface. It was then ultrasonically cleaned for 10 min each time with acetone, anhydrous ethanol, and deionized water to remove surface debris. After cleaning, the sample was placed in an oven to dry. The treated ZrO2 sheet was fixed to the side wall of a beaker and marked on the back. 400 mL of 0.1 mM Tris·HCl solution (pH=8.5) was prepared, and 0.8 g of dopamine (DA) was added. The prepared solution was added to the beaker, and the mixture was stirred at 500 rpm for 3 h at room temperature using a magnetic stirrer. The sample was then washed three times with ultrapure water to remove impurities, yielding a ZrO2-PDA sample. The ZrO2-PDA surface was fixed in the beaker in the same manner. A 500 μg / mL GO@Cu2O NPs aqueous solution was prepared and added to the beaker, ensuring the liquid level covered the ZrO2-PDA. Then, the mixture was stirred at 500 rpm for 3 h at room temperature using a magnetic stirrer, and then washed three times with ultrapure water to remove impurities, yielding the ZrO2-PDA-GO@Cu2O sample.

[0043] Application Examples 1. Material Characterization Characterization of Cu2O NPs and GO@Cu2O NPs: SEM, XRD, FTIR, photothermal performance testing, photodynamic performance testing, and ROS modulation capability testing. Characterization results are as follows: Figure 1 and Figure 2 As shown in the figure. This study successfully prepared Cu2O NPs using a reduction method and further loaded them onto a GO surface to obtain GO@Cu2O NPs composite nanomaterials. Characterization results show that this synthesis process not only achieved effective grafting and uniform distribution of Cu2O NPs on the GO surface, but also did not significantly adversely affect the original basic properties of the material. SEM results ( Figure 1 a) shows that the prepared Cu2O NPs have a granular structure with relatively uniform particle size; after being loaded onto GO, the Cu2O NPs can be distributed relatively uniformly on the surface of GO nanosheets, indicating that the Cu2O NPs have been successfully grafted onto the GO surface. XRD results ( Figure 1 b) shows that GO, Cu2O NPs, and GO@Cu2O NPs all have corresponding characteristic diffraction peaks, and no obvious impurity peaks were observed, indicating that the prepared material has high purity. FTIR results ( Figure 1 c) The composition of GO, Cu2O NPs, and GO@Cu2O NPs was further verified at the chemical structure level, proving that the composite material retains the characteristic functional groups and structural information related to GO and Cu2O. Photothermal performance test results ( Figure 1The results (d~i) show that GO and GO@Cu2O NPs have similar photothermal heating performance, indicating that the grafting process of Cu2ONPs did not significantly weaken the photothermal conversion ability and good photothermal stability of GO nanosheets. Photodynamic performance and pH response detection results ( Figure 2 (a~f) shows that GO@Cu2O NPs still possess similar reactive oxygen species (ROS) generation capabilities to Cu2O NPs, indicating that the composite material preparation process did not significantly damage the chemical structure and photodynamic activity of Cu2O NPs. Furthermore, the ROS regulation capability detection results ( Figure 2 The results (g~h) indicate that both GO@Cu2O NPs and Cu2O NPs have certain ROS regulation capabilities and can scavenge or absorb excess ROS, suggesting that the composite material may have certain potential for oxidative stress regulation while maintaining antibacterial activity.

[0044] Characterization of ZrO2-PDA-GO@Cu2O: SEM, EDS, water contact angle measurement, and photothermal performance testing. Characterization results are as follows: Figure 3 As shown, a PDA coating was successfully constructed on the ZrO2 surface, and GO@Cu2O NPs were grafted onto its surface through the PDA coating. SEM results ( Figure 3 a~b, Figure 3 d) shows that a uniform PDA coating was formed on the ZrO2 surface, and GO@Cu2O NPs formed a relatively uniform coating on its surface through PDA; the water contact angle measurement results show that ( Figure 3 c, Figure 3 e), coating grafting can enhance the hydrophilicity of the ZrO2 surface; photothermal performance test results show ( Figure 3 The ZrO2-PDA-GO@Cu2O surface exhibits significant heating capacity under near-infrared laser-assisted conditions, suggesting that this composite coating imparts excellent photothermal conversion performance and good photothermal stability to the zirconia material.

[0045] 2. Biosafety evaluation and antibacterial performance evaluation (1) CCK-8 cell viability: The cell compatibility of GO@Cu2O NPs and ZrO2-PDA-GO@Cu2O was detected, such as Figure 4 As shown in a~d, at a certain concentration (≤250 μg / mL), GO@Cu2O NPs showed no significant cytotoxicity to hBMSCs, while the ZrO2-PDA-GO@Cu2O surface also showed significant cytotoxicity to hBMSCs, demonstrating that the material has good biocompatibility.

[0046] (2) Hemolysis test: to verify the blood compatibility of GO@Cu2O NPs; such as Figure 4As shown in e~f, GO@Cu2O NPs did not exhibit significant cytotoxicity at the experimental concentrations, demonstrating that the material possesses good biocompatibility.

[0047] (3) Evaluation of antibacterial properties: Verify the antibacterial properties of GO@Cu2O NPs and ZrO2-PDA-GO@Cu2O surfaces, as well as the biofilm formation and removal performance of mature biofilms on the ZrO2-PDA-GO@Cu2O surface. For example... Figure 5 As shown in figures a through e, GO@Cu2O NPs exhibit certain antibacterial properties, and these properties gradually increase with increasing material concentration. Furthermore, with the assistance of near-infrared laser, their antibacterial properties are further enhanced. Figure 5 As shown in f~h, the ZrO2-PDA-GO@Cu2O surface possesses certain antibacterial capabilities, and its antibacterial performance is further enhanced with the assistance of near-infrared laser. Figure 5 As shown in i~k, the ZrO2-PDA-GO@Cu2O surface has a certain inhibitory effect on the formation of biofilms, and with the assistance of near-infrared laser, it has a certain removal effect on mature biofilms.

[0048] 3. Study on the promotion of osteogenic differentiation of hBMSCs on ZrO2-PDA-GO@Cu2O surface (1) In vitro osteogenic performance testing: RT-qPCR, alizarin red staining and quantitative detection, immunofluorescence technology; such as Figure 6 As shown in a~e, the ZrO2-PDA-GO@Cu2O surface did not exhibit significant cytotoxicity during osteogenic induction, and it did have a certain impact on the expression of osteogenic-related genes, thus enhancing the osteogenic properties of the ZrO2 surface. Figure 6 As shown in f~h, the modification with PDA and GO@Cu2O coatings enhanced the calcium nodule formation ability of the ZrO2 surface. This was demonstrated by immunofluorescence results ( Figure 6 i~k) further verified the osteogenic properties of the GO@Cu2O coating.

[0049] (2) In vivo osteogenic performance testing and biosafety performance assessment: femoral defect model, Micro-CT technology, H&E staining. For example... Figure 7 As shown, the ZrO2-PDA-GO@Cu2O surface has a certain promoting effect on the repair of femoral bone defects in rats, and does not cause significant adverse effects on rats during the culture process.

[0050] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a PDA-GO@Cu2O composite functional coating on a zirconia surface, characterized in that, The method includes the following steps: (1) Mix the GO aqueous dispersion with 0.1 M CuSO4 solution and react at 300 rpm for 10 min; add PEG-600 solution to reaction product 1 and stir well, add 0.05 M ascorbic acid solution and 0.1 M NaOH solution and stir well. After the solution turns black, continue stirring for 30 min, let stand, and centrifuge, wash and dry the obtained reaction product 2 to obtain GO@Cu2ONPs; (2) After grinding, washing and drying, ZrO2 was positioned on the side wall of a beaker. Dopamine was added to a pH=8.5, 0.1 mM Tris·HCl solution. The resulting mixed solution was added to the beaker and the liquid level was submerged in ZrO2. The reaction was carried out at room temperature and 500 rpm for 3 h. The reaction product 3 on the side wall of the beaker was washed with pure water to obtain ZrO2-PDA. (3) Add 500 μg / mL GO@Cu2O NPs aqueous solution to the above beaker and make the liquid level cover ZrO2-PDA. React at room temperature and 500 rpm for 3 h. Wash the reaction product 4 on the side wall of the beaker with pure water to obtain zirconia implant ZrO2-PDA-GO@Cu2O.

2. The method as described in claim 1, characterized in that, In step (1), in reaction product 1, the mass-to-volume ratio of GO to CuSO4 solution in the GO aqueous dispersion is 1 g: 50 mL.

3. The method as described in claim 1, characterized in that, In step (2), the volume ratio of reaction product 1, PEG-600 solution, ascorbic acid solution and 0.1 M NaOH solution is 1:1:1:

1.

4. The method as described in claim 1, characterized in that, In step (1), the centrifugal washing is performed by washing with deionized water and anhydrous ethanol in sequence, followed by centrifugation, in order to remove unreacted substances and impurities.

5. The method as described in claim 1, characterized in that, In step (2), the mass-to-volume ratio of dopamine to Tris·HCl solution is 0.8 g: 400 mL.

6. The method as described in claim 1, characterized in that, In step (2), the polishing, washing and drying are specifically as follows: polishing with 100#, 200#, 400# and 1000# silicon carbide sandpaper in sequence to ensure a smooth surface, followed by ultrasonic cleaning with acetone, anhydrous ethanol and deionized water for 10 min in sequence to remove the debris attached to the surface, and then placing it in an oven to dry.

7. The method as described in claim 1, characterized in that, In step (3), the washing process involves washing three times with ultrapure water to remove impurities.

8. The PDA-GO@Cu2O composite functional coating on the zirconia surface prepared by any one of claims 1 to 7.

9. The application of the zirconia surface PDA-GO@Cu2O composite functional coating of claim 8 in the preparation of surface modification materials for dental zirconia implants.

Images