Porous titanium-based implant with photo-thermal surface as well as preparation method and application of porous titanium-based implant

Abstract

The invention discloses a porous titanium-based implant with a photo-thermal surface and a preparation method and application of the porous titanium-based implant, and belongs to the technical field of biomedical materials. The preparation method comprises the steps that a porous titanium substrate is prepared through 3D printing, then flowing acid etching treatment and anodic oxidation treatment are conducted in sequence, then the porous titanium substrate is placed in photo-thermal coating dispersion liquid for reaction, cleaning and drying are conducted, and the porous titanium-based implant with the photo-thermal surface is obtained. The photo-thermal coating dispersion liquid is obtained by dispersing MXene-ZnO composite particles in a dopamine hydrochloride solution. The porous titanium-based implant provided by the invention can be rapidly heated to a proper temperature under the irradiation of near-infrared light, and has good antibacterial, anti-tumor and osteogenesis promoting properties and biocompatibility.

Description

Technical Field

[0001] The present invention relates to the technical field of biomedical materials, and in particular to a porous titanium-based implant with a photothermal surface, a preparation method thereof, and an application thereof. Background Art

[0002] The information disclosed in the background of the invention is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Osteosarcoma is a common primary malignant tumor in children and adolescents, and its clinical treatment has long faced multiple challenges. The current mainstream approach is centered around surgical resection, supplemented by postoperative chemotherapy and radiotherapy to eliminate residual lesions. However, this model has significant limitations: while chemotherapy and radiotherapy kill tumor cells, they also damage normal tissues and induce systemic toxic side effects. Furthermore, it is difficult to completely eliminate tiny residual lesions, leading to a higher risk of tumor recurrence. Furthermore, postoperative bone defects require the implantation of replacement materials to restore structural integrity, but bacterial infection around the implant can easily trigger an inflammatory response, hindering bone healing and even leading to implant failure.

[0004] In the field of implant materials, 3D-printed titanium and its alloys have become a common choice for bone defect repair due to their good mechanical properties and biocompatibility, but their clinical application is limited by insufficient surface functionality. Traditional titanium-based implants have weak bonding ability with host bone tissue and low bone integration efficiency, which affects long-term stability. At the same time, they lack active antibacterial and anti-tumor biological functions and cannot cope with the dual threats of postoperative infection and tumor recurrence. Although some studies have improved bioactivity through surface modification, such as introducing micro-nano structures or releasing antibacterial ions to enhance osteogenic and antibacterial effects, existing strategies are difficult to take into account multiple functional requirements - some coating materials have insufficient biocompatibility or cytotoxicity problems, and the rapid release of antibacterial ions leads to a lack of long-term effectiveness. Single-function designs cannot meet complex clinical scenarios.

[0005] Near-infrared light, as a noninvasive, deep-tissue penetrating physical manipulation method, offers unique advantages in tumor photothermal therapy. However, its clinical application faces the core challenge of precise temperature control. The effectiveness of photothermal therapy is highly dependent on local temperature regulation. Excessively high temperatures (above 50°C) can irreversibly damage surrounding normal cells (such as osteoblasts and vascular endothelial cells), triggering protein denaturation, increased inflammation, and tissue necrosis, disrupting the bone repair microenvironment. Low temperatures (below 40°C) fail to effectively induce tumor cell apoptosis, resulting in insufficient anti-tumor efficacy and may even stimulate tumor cells to develop heat resistance. Existing near-infrared photoresponsive materials struggle to achieve the synergistic balance of precise temperature control, efficient anti-tumor effects, and normal tissue protection. Furthermore, insufficient interfacial bonding strength between photothermal materials and the titanium substrate, poor long-term in vivo stability, and distribution uniformity that affects temperature field consistency further limit their application in bone implants. These challenges collectively hinder the clinical effectiveness of titanium-based implants in osteosarcoma treatment and bone defect repair. There is an urgent need to develop surface functionalization methods that combine precise temperature control with efficient antibacterial, anti-tumor, and osteogenic properties with excellent biocompatibility. Summary of the Invention

[0006] In view of this, the present invention provides a porous titanium-based implant with a photothermal surface, a preparation method and an application thereof. The porous titanium-based implant provided by the present invention can be rapidly heated to an appropriate temperature under the irradiation of near-infrared light, and has good antibacterial, anti-tumor, osteogenic properties and biocompatibility.

[0007] In a first aspect, the present invention provides a method for preparing a porous titanium-based implant having a photothermal surface, comprising the following steps: A porous titanium substrate is prepared by 3D printing, followed by flow acid etching and anodizing treatments. The substrate is then placed in a photothermal coating dispersion for reaction, washed, and dried to obtain a porous titanium-based implant with a photothermal surface. The preparation process of the photothermal coating dispersion comprises the following steps: ZnO nanoparticles are placed in an amino-containing silane coupling agent solution for reaction to obtain amino-ZnO nanoparticles; MXene is dispersed in a glutaraldehyde solution and stirred for reaction; then, the amino-ZnO nanoparticles are added and the reaction is continued with stirring to obtain MXene-ZnO composite particles; the MXene-ZnO composite particles are dispersed in a dopamine hydrochloride solution, and the concentration of the MXene-ZnO composite particles is controlled to be 0.05~0.12mg / mL to obtain a photothermal coating dispersion.

[0008] Preferably, the amino-containing silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane or N-cyclohexyl-3-aminopropyltrimethoxysilane; the volume fraction of the amino-containing silane coupling agent is 5-15%; the amount ratio of ZnO nanoparticles to silane coupling agent is 1g: (8-15)mL; the temperature for reacting the ZnO nanoparticles in the amino-containing silane coupling agent solution is 50-70°C, and the reaction time is 4-10h.

[0009] Preferably, the mass fraction of the glutaraldehyde solution is 0.5-5 wt %; the usage ratio of the MXene to the glutaraldehyde solution is 1 g: (8-25) mL; and in the step of dispersing the MXene in the glutaraldehyde solution and stirring the reaction, the stirring reaction temperature is 10-40° C., and the stirring reaction time is 0.5-5 h.

[0010] Preferably, in the step of adding the amino-ZnO nanoparticles and continuing the stirring reaction, the stirring reaction temperature is 10-40° C., and the stirring reaction time is 5-15 hours; the mass ratio of the MXene to the amino-ZnO nanoparticles is 1:(0.8-1.2).

[0011] Preferably, after the step of adding the amino-ZnO nanoparticles and continuing to stir the reaction, the step of adding a blocking reagent is further included, wherein the blocking reagent is selected from one or more of glycine, β-alanine, L-cysteine ​​or glucosamine; after adding the blocking reagent, stirring is continued for 20 to 60 minutes, and then centrifugation, washing, and drying are performed to obtain MXene-ZnO composite particles.

[0012] Preferably, in the dopamine hydrochloride solution, the concentration of dopamine hydrochloride is 1-5 mg / mL, the pH is 8.0-9.0, and the solvent is tris-hydrochloric acid buffer.

[0013] Preferably, the reaction temperature in the photothermal coating dispersion is 30-45° C. and the reaction time is 4-10 hours.

[0014] Preferably, the solution used for the flow acid etching treatment is a mixed solution of hydrofluoric acid and nitric acid, and the flow acid etching treatment time is 80~120s; the solution for the anodizing treatment is a glycerol aqueous solution containing ammonium fluoride, the anodizing treatment voltage is 20~30V, and the anodizing treatment time is 0.5~2h.

[0015] In a second aspect, the present invention provides a porous titanium-based implant having a photothermal surface prepared by the above preparation method.

[0016] In a third aspect, the present invention provides an application of the above-mentioned porous titanium-based implant with a photothermal surface, wherein the application is an application in preparing a bone tissue defect repair material.

[0017] Compared with the prior art, the present invention has achieved the following beneficial effects: (1) The present invention constructs a composite photothermal coating of MXene-ZnO composite particles and polydopamine on the surface of a 3D-printed porous titanium-based implant. Under irradiation with 2W, 808nm near-infrared light, the surface temperature can be rapidly increased and stably maintained at 42~45℃. This precise temperature control range can not only efficiently ablate tumor cells and kill surrounding bacteria, but also avoid thermal damage to normal tissues, effectively solving the clinical limitation of traditional single-function implants that cannot cope with postoperative infection and tumor recurrence at the same time.

[0018] (2) The micro-nanostructure and Zn in the coating of the porous titanium-based implant constructed by the present invention 2+ The synergistic effect can significantly enhance the osteogenic differentiation ability of mesenchymal stem cells. Combined with the biocompatibility and osteogenic activity of polydopamine and MXene, it effectively improves the low bone integration efficiency of traditional titanium-based implants. At the same time, with the help of the bonding effect of polydopamine on the porous titanium substrate, the coating effect on MXene-ZnO composite particles, and the covalent bonding between MXene and ZnO, the multiple structural stability of the implant coating is achieved.

[0019] (3) The present invention has the advantages of simple operation and controllable cost through the step-by-step construction process of flow acid etching, anodic oxidation and photothermal coating. The prepared coating material has both excellent photothermal conversion ability and biosafety, and solves the problems of low interface bonding strength, poor long-term stability, insufficient temperature control accuracy, and uneven temperature distribution of existing photothermal materials. It finally realizes the multifunctional synergy of "precise photothermal treatment-high-efficiency antibacterial-promoting bone repair", and provides an integrated solution for the repair of bone defects after osteosarcoma surgery. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The drawings, which constitute part of the present invention, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute undue limitations thereon. It is obvious that one of ordinary skill in the art could derive other drawings based on these drawings without inventive effort.

[0021] Figure 1 is a scanning electron microscope image of the MXene material prepared by the present invention; Figure 2 is an infrared spectrum of the MXene-ZnO composite particles prepared in Example 1 of the present invention; Figure 3is a scanning electron microscope image of the MXene-ZnO composite particles prepared in Example 1 of the present invention; Figure 4 1 is a scanning electron microscope image of AE-PZM-1 prepared in Example 1 of the present invention; wherein, a is a scanning electron microscope image at a magnification of 1000×, and b is a scanning electron microscope image at a magnification of 10000×; Figure 5 is a scanning electron microscope image of the AE-PM prepared in Comparative Example 2 of the present invention; Figure 6 1 is an infrared spectrum of AE-PZM-1 of Example 1 of the present invention, AE-PM of Comparative Example 2, and AE of Comparative Example 4; Figure 7 Graph showing changes in sample surface temperature over time for AE-PZM-1 of Example 1 of the present invention, AE-PM of Comparative Example 2, and AE of Comparative Example 4 under irradiation with near-infrared light (808 nm, 2 W); Figure 8 Graphs showing the expression of osteogenic genes in rat bone marrow mesenchymal stem cells on the surfaces of AE-PZM-1 of Example 1 of the present invention, AE-PM of Comparative Example 2, and AE of Comparative Example 4; wherein A is a graph showing the expression of the ALP gene, B is a graph showing the expression of the OCN gene, C is a graph showing the expression of the OPN gene, and D is a graph showing the expression of the Runx2 gene; E is a graph showing the expression of the BMP-2 gene, and F is a graph showing the expression of the COL-1 gene; in the graph, the relative expression levels are calculated based on the gene expression levels of Comparative Example 4 (set to 1), and in the graph, "*" represents P < 0.05, "**" represents P < 0.01, "***" represents P < 0.001, and "****" represents P < 0.0001; Figure 9 Graphs showing cell viability of osteosarcoma (HOS) cells cultured on the surfaces of AE-PZM-1 of Example 1 of the present invention, AE-PM of Comparative Example 2, and AE of Comparative Example 4, after irradiation with and without near-infrared light for 1, 2, and 3 days; wherein A represents no infrared light irradiation; B represents infrared light irradiation; in the graphs, "ns" represents no significant difference, "*" represents P < 0.05, "**" represents P < 0.01, and "****" represents P < 0.0001; Figure 10 OD values ​​at 450 nm of rat bone marrow mesenchymal stem cells on the surfaces of AE-PZM-1 of Example 1 of the present invention, AE-PM of Comparative Example 2, and AE of Comparative Example 4 after 1-3 days of proliferation; in the figure, "ns" represents no significant difference, "*" represents P < 0.05, "**" represents P < 0.01, and "****" represents P < 0.0001; Figure 11The OD values ​​at 450 nm of rat bone marrow mesenchymal stem cells on the surfaces of AE-PZM-3 of Comparative Example 5 and AE of Comparative Example 4 after 1-3 days of proliferation are shown in the figure; in the figure, "****" represents P < 0.0001; Figure 12 The Zn content of AE-PZM-1 of Example 1 of the present invention and AE-PDA-ZM of Comparative Example 6 was immersed in 1 mL of PBS buffer at 37°C. 2+ Release curve. DETAILED DESCRIPTION

[0022] It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0023] The present invention provides a method for preparing a porous titanium-based implant with a photothermal surface, comprising the following steps: A porous titanium substrate is prepared by 3D printing, followed by flow acid etching and anodizing treatments. The substrate is then placed in a photothermal coating dispersion for reaction, washed, and dried to obtain a porous titanium-based implant with a photothermal surface. The preparation process of the photothermal coating dispersion comprises the following steps: ZnO nanoparticles are placed in an amino-containing silane coupling agent solution for reaction to obtain amino-ZnO nanoparticles; MXene is dispersed in a glutaraldehyde solution and stirred for reaction; then, the amino-ZnO nanoparticles are added and the reaction is continued with stirring to obtain MXene-ZnO composite particles; the MXene-ZnO composite particles are dispersed in a dopamine hydrochloride solution, and the concentration of the MXene-ZnO composite particles is controlled to be 0.05~0.12mg / mL to obtain a photothermal coating dispersion.

[0024] This invention, through multi-step surface modification and functional coating construction, endows 3D-printed titanium-based implants with near-infrared light responsiveness, antibacterial properties, anti-tumor properties, and integrated osteogenesis. First, a porous titanium substrate is prepared using 3D printing technology. Its pore structure simulates the mechanical microenvironment of natural bone tissue, providing spatial support for bone cell growth. A subsequent flow acid etching treatment etches the titanium surface, removing the oxide layer and forming a micron-scale rough structure, improving surface wettability and mechanical anchoring with subsequent coatings. Anodizing treatment then forms a titanium dioxide film with a nanotubular structure on the titanium substrate surface. This micro-nano composite structure not only enhances protein adsorption and cell adhesion, but also serves as a transition layer between the coating and the substrate, improving interfacial bonding strength.

[0025] The preparation process of the photothermal coating dispersion achieves multi-component synergistic functionality through chemical modification. First, an amino-containing silane coupling agent is grafted onto the surface of ZnO nanoparticles via a hydrolysis-condensation reaction. The introduced amino groups (-NH2) provide active sites for subsequent crosslinking with MXene. Simultaneously, the organic chain of the silane coupling agent improves the dispersibility of ZnO and its compatibility with the organic coating. After the MXene is dispersed in a glutaraldehyde solution, its surface hydroxyl groups (-OH) or terminal groups react with the aldehyde groups (-CHO) of glutaraldehyde, functionalizing the MXene surface to an aldehyde-modified state. Subsequently, amino-modified ZnO nanoparticles are added. A Schiff base reaction between the aldehyde and amino groups (-CHO + -NH2 → -C=N-) results in covalent bonding between the MXene and ZnO, forming MXene-ZnO composite nanoparticles. This structure combines the excellent near-infrared photothermal conversion efficiency of MXene with the antibacterial and osteogenic properties of ZnO. After dispersing the MXene-ZnO composite particles in the dopamine hydrochloride solution, dopamine undergoes self-polymerization to form an adhesive polydopamine (PDA) coating. The coating forms hydrogen bonds with the titanium substrate surface through the phenolic hydroxyl groups in the molecule, and at the same time enhances the internal cohesion of the coating through the intermolecular π-π stacking effect. The dispersion of the MXene-ZnO composite particles is further stabilized through metal ion chelation, and the MXene-ZnO composite particles are firmly fixed to the titanium substrate surface. At the same time, the biocompatibility of polydopamine itself can promote cell adhesion and osteogenic differentiation, and its phenolic hydroxyl structure can enhance photothermal stability.

[0026] The present invention controls the concentration of MXene-ZnO composite particles in the dopamine hydrochloride solution to 0.05-0.12 mg / mL, more preferably 0.08-0.1 mg / mL, to adjust the coating thickness and photothermal performance, ensuring precise temperature control of 42-45°C under near-infrared light irradiation, which not only meets the temperature threshold required for tumor cell ablation and antibacterial treatment, but also avoids toxicity and thermal damage to normal tissues, thereby achieving the multifunctional synergy of "structural support-photothermal therapy-antibacterial-osseointegration".

[0027] In the present invention, the amino-containing silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, or N-cyclohexyl-3-aminopropyltrimethoxysilane. 3-aminopropyltriethoxysilane (APTES) is preferred. Amino-containing silane coupling agents contain both hydrolyzable alkoxy and amino groups in their molecular structure. The alkoxy groups hydrolyze in aqueous solution to form silanol (-Si-OH) groups, which can undergo a condensation reaction with hydroxyl (-OH) groups on the surface of ZnO nanoparticles to form Si-O-Zn bonds, achieving chemical grafting of the coupling agent onto the ZnO surface. The amino groups, as reactive functional groups, can subsequently undergo a Schiff base reaction with aldehyde groups on the MXene surface, thereby covalently linking the ZnO to the MXene.

[0028] In the present invention, the volume fraction of the amino-containing silane coupling agent is 5-15%, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., preferably within a range with any of the above values ​​as the upper or lower limit. The ratio of ZnO nanoparticles to amino-containing silane coupling agent is 1g: (8-15)mL, ensuring that the coupling agent molecules fully cover the ZnO surface. The ZnO nanoparticles are placed in the amino-containing silane coupling agent solution and the reaction temperature is 50-70°C, such as 50°C, 53°C, 58°C, 60°C, 65°C, 68°C, 70°C, etc., and the reaction time is 4-10 hours, such as 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, etc., to promote the hydrolysis and condensation of the silane coupling agent and the amination reaction on the ZnO surface. The present invention does not impose any particular limitation on the solvent of the amino-containing silane coupling agent solution. For example, it can be ethanol or a mixed solvent of ethanol and water. Acid can also be added to promote hydrolysis.

[0029] After the step of placing the mixture in a solution of an amino-containing silane coupling agent for reaction, the present invention further includes the steps of solid-liquid separation, washing, and drying. The solid-liquid separation can be carried out by centrifugation or filtration. The washing solvent is water or ethanol. The present invention does not impose any special restrictions on the drying method, and methods such as freeze drying, vacuum drying, and supercritical carbon dioxide drying can all be used. The present invention preferably adopts the vacuum drying method.

[0030] The present invention does not impose any special restrictions on the source of MXene. It can be purchased or homemade, and can be prepared according to common methods in the field. The present invention preferably uses LiF and HCl to etch MAX phase materials. MAX phase materials are a type of layered ternary compounds that have the excellent properties of both metals and ceramics. The chemical formula is usually expressed as M n+1 AX n(n = 1, 2, 3, etc.), where M is a transition metal, A is a main group element, and X is carbon, nitrogen, or boron. The present invention does not impose any particular restrictions on MAX phase materials; examples include Ti3AlC2, Ti2AlC, Nb2AlC, Ti3SiC2, and Ti4AlN3.

[0031] The mass fraction of the glutaraldehyde solution described herein is 0.5-5wt%. The ratio of the MXene to the glutaraldehyde solution is 1g: (8-25)mL, more preferably 1g: (10-20)mL. The surface of MXene is rich in groups such as hydroxyl (-OH) and carboxyl (-COOH), with which the aldehyde groups of glutaraldehyde can undergo nucleophilic addition reactions, functionalizing the MXene with the aldehyde groups via a "MXene-glutaraldehyde" intermediate. In the step of dispersing the MXene in the glutaraldehyde solution and stirring the reaction, the stirring reaction temperature is 10-40°C, for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, or 40°C, preferably at room temperature. The stirring reaction lasts for 0.5-5 hours, more preferably 0.5-2 hours.

[0032] In the step of adding the amino-modified ZnO nanoparticles and continuing the stirring reaction, the stirring reaction temperature is 10-40°C, for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, etc., preferably at room temperature. The stirring reaction time is 5-15 hours. Using glutaraldehyde as a crosslinker between MXene and ZnO offers the advantages of mild reaction conditions, short reaction time, and no need for additional catalysts or activators. Furthermore, the formed covalent bond (-C=N-) provides enhanced structural stability in the subsequent dopamine hydrochloride solution.

[0033] In the present invention, the mass ratio of MXene to amination-modified ZnO nanoparticles is 1:(0.8-1.2). This ratio ensures uniform dispersion of the amination-modified ZnO nanoparticles on the surface of the MXene sheet. Furthermore, this ratio allows for a balanced combination of the photothermal responsiveness of MXene and the antibacterial and osteogenic properties of ZnO.

[0034] In the present invention, after adding the amino-modified ZnO nanoparticles and continuing the stirring reaction, a blocking reagent is added. The blocking reagent is selected from one or more of glycine, β-alanine, L-cysteine, or glucosamine, with glycine being more preferred. After the Schiff base reaction, unreacted free aldehyde groups may remain in the system. Their high reactivity may lead to subsequent nonspecific binding with polydopamine or biological tissues, and even induce cytotoxicity. The amino groups (-NH2) in the blocking reagent can undergo a Schiff base reaction with the remaining aldehyde groups to form stable amide structures, thereby eliminating the potential risk of free aldehyde groups and improving the biocompatibility of the composite particles. After adding the blocking reagent, stirring is continued for 20-60 minutes, followed by centrifugation, washing, and drying to obtain the MXene-ZnO composite particles.

[0035] In the present invention, the dopamine hydrochloride solution has a concentration of 1 to 5 mg / mL, a pH of 8.0 to 9.0, and is prepared using a tris(hydroxymethylaminomethane)-hydrochloric acid buffer solution as the solvent. The weakly alkaline environment promotes the self-aggregation of dopamine molecules to form a polydopamine coating. This coating can tightly bind to the titanium substrate surface through hydrogen bonding or coordination. The polydopamine molecular chains can then wrap around the MXene-ZnO composite particles. Furthermore, the polydopamine's abundant phenolic hydroxyl and amino groups enhance biocompatibility, promoting cell adhesion and osteogenic differentiation.

[0036] In the present invention, the reaction temperature in the photothermal coating dispersion is 30-45°C, more preferably 30-40°C, and the reaction time is 4-10 hours. By controlling the polymerization process at the appropriate temperature and time, the polydopamine is fully coated with the MXene-ZnO composite particles, forming a continuous and stable coating on the titanium substrate surface. Excessive reaction time can also prevent the coating from becoming too thick or loose. This process is carried out under stirring to ensure the uniformity of the photothermal coating dispersion.

[0037] In the present invention, the flow acid etching process uses a mixed solution of hydrofluoric acid and nitric acid. The hydrofluoric acid etches the oxide layer (TiO2) on the titanium surface, forming micron-sized pits. The nitric acid acts as an oxidizing agent, inhibiting excessive hydrofluoric acid corrosion and regulating the etching rate. The flow acid etching process lasts for 80 to 120 seconds. The present invention imposes no particular limitations on the specific flow acid etching process; commonly used flow acid etching processes in the art can be used.

[0038] In the present invention, the solution of the anodizing treatment is a glycerol aqueous solution containing ammonium fluoride, more preferably, the concentration of the ammonium fluoride is controlled to be 0.2~0.4M; the volume ratio of glycerol to water in the glycerol aqueous solution is (0.5~5):1. The voltage of the anodizing treatment is 20~30V, and the time of the anodizing treatment is 0.5~2h. The present invention does not impose any special restrictions on the specific anodizing treatment method, and the anodizing treatment method commonly used in the art can be adopted. The present invention is preferably: the porous titanium substrate is connected to the positive electrode of a regulated power supply, the negative electrode is connected to a platinum sheet, the sample and the platinum electrode are placed in the glycerol aqueous solution containing ammonium fluoride, the power-on voltage is controlled to be 20~30V, and the power-on time is 0.5~2h.

[0039] The present invention does not impose any special restrictions on the specific 3D printing method, and the 3D printing method commonly used in the art can be used. The present invention preferably uses selective laser melting (SLM) technology to prepare a porous titanium substrate. The porosity of the porous titanium substrate is preferably 60-90%, and the pore size is 500-1000 μm, which is compatible with the pore size of cancellous bone (200-600 μm), providing a physical channel for bone cell migration and vascularization.

[0040] In the present invention, the material of the porous titanium substrate is pure titanium or Ti-6Al-4V alloy. Ti-6Al-4V alloy has both high strength and biocompatibility, while pure titanium is more corrosion-resistant. Both are suitable for different implantation environment requirements, and technicians in this field can make a choice according to actual needs.

[0041] The present invention also provides a porous titanium-based implant with a photothermal surface prepared by the above preparation method.

[0042] The present invention also provides an application of the porous titanium-based implant with a photothermal surface, wherein the application is an application in preparing a bone tissue defect repair material, more preferably an application in a bone tissue defect repair material after osteosarcoma surgery.

[0043] The technical solution of the present invention is further described below with reference to specific examples. The present invention has no particular restrictions on the sources of the reagents used in the following examples, and commercially available products known to those skilled in the art can be used. The room temperature mentioned in the following examples refers to 25±3°C.

[0044] In the following examples, PDA refers to polydopamine; OD value refers to optical density (OD), which is equivalent to absorbance; Trizol reagent refers to total RNA extraction reagent; and cDNA refers to complementary DNA.

[0045] In the following examples, the preparation method of MXene is as follows: LiF (1.6 g) is dispersed in 20 mL of 9 M HCl solution and stirred for 5 minutes to disperse the powder. After that, 1 g of Ti3AlC2 is slowly added, and the Al layer is etched at 35°C for 24 hours. The prepared acid dispersion is centrifuged at 3500 rpm for 5 minutes, and centrifuged 5 times until the precipitate is close to neutral. Then, the obtained precipitate is further centrifuged at 3500 rpm for 30 minutes to remove the unetched multilayer MXene and MAX. After the final suspension is centrifuged at 8000 rpm for 1 hour, the MXene material is prepared by vacuum freeze drying, and its scanning electron microscope image is shown as follows. Figure 1 Prepare as many times as desired.

[0046] In the following embodiments, a triply periodic minimal surface (TPMS) is a surface that extends infinitely periodically along three independent directions (e.g., the X, Y, and Z axes) in three-dimensional space. Its core characteristic is that the average curvature is zero everywhere. The TPMS structure highly matches the zero curvature characteristic of natural trabecular bone, and its connected channels promote bone cell ingrowth and angiogenesis.

[0047] Example 1 This embodiment provides a method for preparing a porous titanium-based implant with a photothermal surface.

[0048] (1) Preparation of amino-modified ZnO nanoparticles (ZnO-NH2): 3-Aminopropyltriethoxysilane (APTES) and ethanol were mixed in a volume ratio of 1:9, and a small amount of deionized water (the volume ratio of APTES to ethanol was 1:100) was added thereto. After stirring and mixing, ZnO nanoparticles were added. The mixture was stirred at 60°C for 6 hours and then centrifuged. The solid product was washed with ethanol and deionized water and vacuum dried to obtain amino ZnO nanoparticles (ZnO-NH2).

[0049] (2) Preparation of MXene-ZnO composite particles: 1 g of MXene material was dispersed in 10 mL of 1 wt% glutaraldehyde solution and stirred at room temperature for 1 hour. Then, 1 g of ZnO-NH2 nanoparticles was added. After stirring for 6 hours, 0.1 M glycine solution was added. The mixture was stirred for 30 minutes and centrifuged. The solid product was then washed with deionized water and anhydrous ethanol and vacuum dried to obtain MXene-ZnO composite particles. The infrared spectra of MXene-ZnO composite particles and MXene material are shown in Figure 2. Figure 2 As shown, for MXene materials, the Ti-C stretching vibration is at 857.92 cm -1This confirms the integrity of the core framework, and the OH stretching vibration (3312.26 cm -1 ) and Ti-O deformation mode (546.26 cm -1 ), indicating surface functionalization. For MXene-ZnO composite nanoparticles, in addition to the typical absorption peak of MXene, the vibration absorption peak of Zn-O (423.13 cm -1 ) confirmed the integration of ZnO, Schiff base vibration (C=N, 1605.47 cm -1 ) and CH stretching vibration (2924.09 cm -1 ) proved that covalent bonding occurred between MXene and ZnO, 1046.68 cm -1 The C—O bond is an acetal structure (COC) formed after MXene is cross-linked with glutaraldehyde. The scanning electron microscope image of MXene-ZnO composite particles is shown in Figure 2. Figure 3 As shown, it can be seen that ZnO nanoparticles are anchored within the layered structure of multilayer MXene nanosheets.

[0050] (3) Preparation of photothermal coating dispersion: Dopamine hydrochloride was dissolved in tris-hydrochloric acid (Tris-HCl) buffer at pH 8.5 to prepare a dopamine hydrochloride solution with a concentration of 2 mg / mL. MXene-ZnO composite particles were then added to control the concentration of the MXene-ZnO composite particles to 0.1 mg / mL. The mixture was stirred and dispersed to obtain a photothermal coating dispersion.

[0051] (4) Preparation of porous titanium-based implants with photothermal surface: A porous Ti-6Al-4V substrate with a size of 10×10×2 mm and a pore size of 700 μm and a porosity of 70% was prepared using selective laser melting (SLM) technology. 3 . 5mL of 2wt% hydrofluoric acid and 31mL of 20wt% nitric acid were evenly mixed to obtain a mixed acid solution, and the mixed acid solution was used to perform flow acid etching treatment on each surface of the porous Ti-6Al-4V substrate, with a total treatment time of 90s. Then, an anodizing treatment was performed for 1h in a propylene glycol aqueous solution containing 0.27M NH4F (propylene glycol: water = 1:1, v / v) at a DC voltage of 25V to construct a TiO2 nanotube array on the surface of the porous Ti-6Al-4V substrate. The porous Ti-6Al-4V substrate with the TiO2 nanotube array was immersed in the photothermal coating dispersion of step (3), stirred and reacted at 37°C for 6h, the reacted sample was removed, washed with deionized water, and vacuum dried at 37°C to obtain a porous titanium-based implant with a photothermal surface, which was denoted as AE-PZM-1. Its scanning electron microscope image is shown as follows. Figure 4 As shown, from Figure 4 As can be seen in a, the surface of the porous Ti-6Al-4V substrate is covered by the polydopamine-coated MXene-ZnO composite coating; Figure 4 In figure b, it can be clearly seen that there is a TiO2 nanotube array on the surface of the porous Ti-6Al-4V substrate, and the polydopamine-coated MXene-ZnO composite coating covers the TiO2 nanotube array.

[0052] Example 2 This embodiment provides a method for preparing a porous titanium-based implant with a photothermal surface.

[0053] (1) Preparation of amino-modified ZnO nanoparticles (ZnO-NH2): 3-Aminopropyltriethoxysilane (APTES) and ethanol were mixed in a volume ratio of 1:9, and a small amount of deionized water (the volume ratio of APTES to ethanol was 1:50) was added thereto. After stirring and mixing, ZnO nanoparticles were added. The mixture was stirred at 60°C for 6 hours and then centrifuged. The solid product was washed with ethanol and deionized water and vacuum dried to obtain amino ZnO nanoparticles (ZnO-NH2).

[0054] (2) Preparation of MXene-ZnO composite particles: 0.5 g of MXene material was dispersed in 10 mL of 1 wt% glutaraldehyde solution and stirred at room temperature for 1 hour. Then, 0.5 g of ZnO-NH2 nanoparticles were added. After stirring for 6 hours, 0.1 M glycine solution was added and stirring was continued for 30 minutes. The mixture was centrifuged and the solid product was washed with deionized water and anhydrous ethanol and vacuum dried to obtain MXene-ZnO composite particles.

[0055] (3) Preparation of photothermal coating dispersion: Dopamine hydrochloride was dissolved in tris-hydrochloric acid (Tris-HCl) buffer with a pH of 8.5 to prepare a dopamine hydrochloride solution with a concentration of 3 mg / mL. MXene-ZnO composite particles were then added to control the concentration of the MXene-ZnO composite particles to 0.1 mg / mL. The mixture was stirred and dispersed to obtain a photothermal coating dispersion.

[0056] (4) Preparation of porous titanium-based implants with photothermal surface: A porous Ti-6Al-4V substrate with a size of 10×10×2 mm and a pore size of 700 μm and a porosity of 70% was prepared using selective laser melting (SLM) technology. 3. 5mL of 2wt% hydrofluoric acid and 31mL of 20wt% nitric acid were mixed evenly to obtain a mixed acid solution, and the mixed acid solution was used to perform flow acid etching on each surface of the porous Ti-6Al-4V substrate, with a total treatment time of 90s. Then, an anodizing treatment was performed for 1h in a propylene glycol aqueous solution containing 0.27M NH4F (propylene glycol: water = 1:1, v / v) at a DC voltage of 25V to construct a TiO2 nanotube array on the surface of the porous Ti-6Al-4V substrate. The porous Ti-6Al-4V substrate with the TiO2 nanotube array was immersed in the photothermal coating dispersion of step (3), stirred and reacted at 37°C for 6h, the reacted sample was removed, washed with deionized water, and vacuum dried at 37°C to obtain a porous titanium-based implant with a photothermal surface, which was recorded as AE-PZM-2.

[0057] Comparative Example 1 Compared with Example 1, this comparative example is different in that no MXene-ZnO composite particles are added to the photothermal coating dispersion of this comparative example, and the other parameters and preparation methods remain unchanged. The obtained titanium-based implant is recorded as AE-PDA.

[0058] Comparative Example 2 The difference between this comparative example and Example 1 is that in the photothermal coating dispersion of this comparative example, MXene is used to replace the MXene-ZnO composite particles, and the other parameters and preparation methods remain unchanged. The obtained titanium-based implant is recorded as AE-PM, and its scanning electron microscope image is shown as follows: Figure 5 As shown, it can be seen that a layer of polydopamine-wrapped MXene coating is deposited on the surface.

[0059] Comparative Example 3 Compared with Example 1, this comparative example differs in that in the photothermal coating dispersion of this comparative example, ZnO nanoparticles are used to replace MXene-ZnO composite particles, and the other parameters and preparation methods remain unchanged. The obtained titanium-based implant is recorded as AE-PZ.

[0060] Comparative Example 4 Compared with Example 1, this comparative example is different in that the porous Ti-6Al-4V substrate for constructing the TiO2 nanotube array is not immersed in the photothermal coating dispersion in this comparative example, and only the porous Ti-6Al-4V substrate for constructing the TiO2 nanotube array is prepared, which is recorded as AE.

[0061] Comparative Example 5 The difference between this comparative example and Example 1 is that in step (3) of this comparative example, the concentration of MXene-ZnO composite particles is controlled to be 0.5 mg / mL, and the obtained titanium-based implant is recorded as AE-PZM-3.

[0062] Comparative Example 6 This comparative example differs from Example 1 in that no MXene-ZnO composite particles are added to the photothermal coating dispersion in this comparative example, and the MXene-ZnO composite particles are added dropwise to the PDA surface in the form of a dispersion. The specific preparation method is as follows: A porous Ti-6Al-4V substrate with a size of 10×10×2 mm and a pore size of 700 μm and a porosity of 70% was prepared using selective laser melting (SLM) technology. 3 A mixed acid solution (5 mL of 2 wt% hydrofluoric acid and 31 mL of 20 wt% nitric acid) was uniformly mixed to prepare a solution. Each surface of the porous Ti-6Al-4V substrate was subjected to flow acid etching using this solution for a total treatment time of 90 s. Subsequently, the substrate was anodized for 1 h in a glycerol solution containing 0.27 M NH₄F (glycerol:water = 1:1, v / v) at a DC voltage of 25 V to construct a TiO₂ nanotube array on the surface of the porous Ti-6Al-4V substrate. The porous Ti-6Al-4V substrate with the TiO₂ nanotube array was then immersed in a 2 mg / mL dopamine hydrochloride solution (in Tris-HCl buffer, pH = 8.5) and stirred at 37°C for 6 h to obtain a porous titanium-based implant coated with PDA. The MXene-ZnO composite particles were then dispersed in ethanol, and the concentration of the MXene-ZnO composite particles was controlled to be 0.1 mg / mL; then they were dropped onto the surface of a porous titanium-based implant coated with polydopamine (PDA), and dried to obtain a porous titanium-based implant with a photothermal surface, which was recorded as AE-PDA-ZM.

[0063] Test example 1. Infrared measurement The infrared spectra of AE-PZM-1 of Example 1, AE-PM of Comparative Example 2 and AE of Comparative Example 4 were measured. Figure 6 As shown, the AE of Comparative Example 4 is at 488.42 cm -1 The Ti-O bond absorption peak was detected at 2984.16 cm-1. -1 The -OH absorption peak appeared at 1073.94 cm -1 The CO absorption peak appeared at 1402.32 cm -1 (C=C), 1251.08 cm -1 (CN), 427.03 cm -1 The relevant absorption peak was detected at (Zn-O), indicating that the coating of nanoparticles and the connection of chemical bonds were effectively achieved.

[0064] 2. Photothermal conversion performance measurement: The surfaces of the porous titanium implants of Examples 1-2 and Comparative Examples 1-6 were irradiated with near-infrared light of 808 nm in wavelength and 2 W in power for 5 min, and the surface temperatures of the samples were detected. The surface temperature rise of the AE-PZM-1 of Example 1, the AE-PM of Comparative Example 2, and the AE sample of Comparative Example 4 is shown in FIG. Figure 7 As shown in the figure, the temperature change of the AE group is almost negligible, while the AE-PM and AE-PZM-1 groups quickly heated up from the ambient temperature (26°C) to around 43°C within 120 seconds.

[0065] Five random points on the surface of the porous titanium implants of Examples 1-2 and Comparative Examples 1-6 were irradiated with near-infrared light with a wavelength of 808 nm and a power of 2 W. The temperature was recorded after 5 minutes of irradiation, and the relative standard deviation (RSD) was calculated to determine the surface temperature uniformity.

[0066] The results are summarized in Table 1.

[0067] As shown in Table 1, when only polydopamine (PDA) was added to the surface, the temperature was only raised to approximately 37°C. Further addition of ZnO nanoparticles had no significant effect on the sample's surface photothermal performance. However, when MXene or MXene-ZnO composite particles were added to the surface coating, the sample's surface photothermal performance was significantly improved. When irradiated with near-infrared light, the surface temperature rose to approximately 43°C, providing conditions for photothermal therapy. The sample surface of Example 1 exhibited superior temperature uniformity compared to that of Comparative Example 6.

[0068] Table 1 Surface temperature of porous titanium implants of Examples 1-2 and Comparative Examples 1-6 after near-infrared light irradiation

[0069] 3. Expression of osteogenic-related genes in rat bone marrow mesenchymal stem cells: RT-qPCR (reverse transcription real-time quantitative polymerase chain reaction) was used to detect the expression of osteogenic genes in rat bone marrow mesenchymal stem cells. 5 The cells were inoculated at a density of 100 μg / mL onto the surface of AE-PZM-1 of Example 1, AE-PM of Comparative Example 2, and AE of Comparative Example 4. After culturing for 7 days, the cells were rinsed with PBS buffer and 600 μL of Trizol reagent was added to each well. Afterwards, the RNA was reverse transcribed into cDNA using a reverse transcription kit. The expression of six target genes (ALP, OCN, COL-I, BMP-2, OPN, and Runx2) and the internal reference gene GAPDH were tested. Gene expression was normalized according to the expression of GAPDH, and the test results are shown in Figure 2. Figure 8 As shown in A~F.

[0070] It can be seen that after 7 days, the expression of bone-related markers in the AE-PZM-1 group was significantly upregulated, and the levels of ALP, OCN, OPN, Runx2, COL-1, and BMP-2 increased by more than 90% compared with the AE group.

[0071] 4. Determination of antibacterial properties: The antibacterial rate of the sample surface was quantitatively determined by measuring the bacterial absorbance value on the surface of the porous titanium implants of Example 1 and Comparative Examples 1 to 6.

[0072] The test method is as follows: Bacteria (Escherichia coli and Staphylococcus aureus) are inoculated on the sample surface and incubated at 37°C for 24 hours. Afterwards, the bacteria are transferred to a new bacteria-free well, the surface is rinsed with sterile culture medium, and the original solution is diluted 10-fold. The diluted solution is then incubated at 37°C for 24 hours, and the absorbance of each well is measured at 600nm using a microplate reader. For the group receiving near-infrared light irradiation, near-infrared light with a wavelength of 808nm and a power of 2W is used for 10 minutes daily. The surface inhibition rate of each sample group is calculated according to the following formula: .

[0073] The test results are summarized in Table 2. As can be seen from Table 2, without near-infrared light irradiation, the PDA coating does not significantly improve the surface's antibacterial properties. While MXene exhibits some antibacterial activity, the antibacterial effect is primarily dependent on the ZnO nanoparticles. The higher the concentration of the MXene-ZnO composite particles, the higher the antibacterial rate. When near-infrared light treatment is added, the photothermal effects of polydopamine and MXene synergize with the antibacterial effect of ZnO, effectively enhancing the surface's antibacterial efficacy.

[0074] Table 2 Antibacterial rate of porous titanium implants in Example 1 and Comparative Examples 1 to 6

[0075] 5. Osteosarcoma cell viability assay: Osteosarcoma (HOS) cells were cultured at a rate of 5 × 10 4 The density of cells / mL was inoculated onto the surface of the AE-PZM-1 of Example 1, the AE-PM of Comparative Example 2, and the AE sample of Comparative Example 4 for cultivation. During the cultivation process, the photothermal culture group used near-infrared light with a wavelength of 808nm and a power of 2W to irradiate the sample for 10 minutes every day. After culturing for 1, 2, and 3 days, the sample was transferred to a new sample well, and 1mL of fresh culture medium and 100μL of CCK-8 solution were added to the sample well. After incubation at 37°C for 1h, 200μL of the solution was transferred to a 96-well plate, and the sample absorbance was detected using an enzyme reader to calculate the cell viability. The calculation formula for cell viability is: ; The experimental group refers to the culture group containing porous titanium implant samples, and the blank culture medium refers to the culture medium without porous titanium implant samples.

[0076] like Figure 9 As shown in Figure A, when no near-infrared light irradiation was performed, no significant difference was observed on day 1. By day 2, the cell viability of the AE-PZM-1 group decreased to 90.3%, and further decreased on day 3 (AE-PM: 91.7%; AE-PZM-1: 86.3%). Figure 9 As shown in Figure 3B, combined photothermal therapy significantly enhanced this antiproliferative effect, reducing cell viability to 83% (AE-PM) and 60.3% (AE-PZM-1) on day 2. By day 3, cell viability in the AE-PZM-1 group had significantly decreased to 29.3%.

[0077] 6. Cell proliferation test: Rat bone marrow mesenchymal stem cells were cultured at a rate of 2×10 4 The samples of AE-PZM-1 (Example 1), AE-PM (Comparative Example 2), AE (Comparative Example 4), and AE-PZM-3 (Comparative Example 5) were inoculated at a density of 100 μL / mL. After 1, 2, and 3 days of culture, the samples were transferred to new wells, and 1 mL of fresh culture medium and 100 μL of CCK-8 solution were added. After incubation at 37°C for 1 hour, 200 μL of the solution was transferred to a 96-well plate, and the absorbance (OD value) was measured at 450 nm using a microplate reader. The results are shown in Figure 2. Figure 10 and Figure 11 shown.

[0078] On day 1, no significant differences were observed between the groups. By day 2, the OD values ​​of the AE-PZM-1 and AE-PM groups were significantly higher than those of the AE group, with the AE-PZM-1 group showing the most pronounced proliferation enhancement (****P<0.0001). This proliferation advantage was further enhanced on day 3. No increase in absorbance was observed in AE-PZM-3 (Comparative Example 5) after culture, and its surface OD values ​​on days 2 and 3 were significantly lower than those of the AE group, indicating significantly increased toxicity to mesenchymal stem cells, leading to significant cell death.

[0079] 7. Zn 2+ Determination of sustained-release curve: In order to evaluate the Zn 2+ To determine the release of zinc ions, samples were immersed in 1 mL of PBS buffer at 37°C. The zinc ion concentration was quantitatively measured daily using inductively coupled plasma mass spectrometry (ICP-MS).

[0080] The results are as follows Figure 12 As shown in the figure, it can be seen that when MXene-ZnO composite particles are directly drop-coated on the PDA surface, Zn 2+ Release is rapid in solution, with over 60% released within 3 days and complete release within approximately 10 days. This rapid release is highly toxic to cells. However, after coating with polydopamine, the release rate was significantly slowed and the release period was significantly prolonged. By day 18, release was essentially complete, effectively matching the cell's osteogenic mineralization cycle (21 days) without significant toxicity.

[0081] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing a porous titanium-based implant with a photothermal surface, characterized in that: The steps include: A porous titanium substrate is prepared by 3D printing, followed by flow acid etching and anodizing treatments. The substrate is then placed in a photothermal coating dispersion for reaction, washed, and dried to obtain a porous titanium-based implant with a photothermal surface. The preparation process of the photothermal coating dispersion comprises the following steps: ZnO nanoparticles are placed in an amino-containing silane coupling agent solution for reaction to obtain amino-ZnO nanoparticles; MXene is dispersed in a glutaraldehyde solution and stirred for reaction; then, the amino-ZnO nanoparticles are added and the reaction is continued with stirring to obtain MXene-ZnO composite particles; the MXene-ZnO composite particles are dispersed in a dopamine hydrochloride solution, and the concentration of the MXene-ZnO composite particles is controlled to be 0.05~0.12mg / mL to obtain a photothermal coating dispersion.

2. The preparation method according to claim 1, wherein The amino-containing silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, or N-cyclohexyl-3-aminopropyltrimethoxysilane; the volume fraction of the amino-containing silane coupling agent is 5-15%; the amount ratio of ZnO nanoparticles to the amino-containing silane coupling agent is 1g: (8-15)mL; the ZnO nanoparticles are placed in the amino-containing silane coupling agent solution, and the reaction temperature is 50-70°C, and the reaction time is 4-10h.

3. The preparation method according to claim 1, wherein The mass fraction of the glutaraldehyde solution is 0.5-5 wt %; the usage ratio of the MXene to the glutaraldehyde solution is 1 g: (8-25) mL; and in the step of dispersing the MXene in the glutaraldehyde solution and stirring the reaction, the stirring reaction temperature is 10-40° C., and the stirring reaction time is 0.5-5 h.

4. The preparation method according to claim 1, wherein In the step of adding the amino-ZnO nanoparticles and continuing the stirring reaction, the stirring reaction temperature is 10-40° C., and the stirring reaction time is 5-15 hours; the mass ratio of the MXene to the amino-ZnO nanoparticles is 1:(0.8-1.2).

5. The preparation method according to claim 1, wherein After the step of adding the amino-ZnO nanoparticles and continuing to stir the reaction, the step also includes adding a blocking reagent, wherein the blocking reagent is selected from one or more of glycine, β-alanine, L-cysteine ​​or glucosamine; after adding the blocking reagent, stirring is continued for 20 to 60 minutes, and then centrifugation, washing, and drying are performed to obtain MXene-ZnO composite particles.

6. The preparation method according to claim 1, wherein In the dopamine hydrochloride solution, the concentration of dopamine hydrochloride is 1-5 mg / mL, the pH is 8.0-9.0, and the solvent is tris(hydroxymethylaminomethane)-hydrochloric acid buffer solution.

7. The preparation method according to claim 1, wherein The reaction temperature in the photothermal coating dispersion is 30-45° C. and the reaction time is 4-10 hours.

8. The preparation method according to claim 1, wherein The solution used in the flow acid etching treatment is a mixed solution of hydrofluoric acid and nitric acid, and the flow acid etching treatment time is 80-120 seconds; the solution used in the anodizing treatment is a glycerol aqueous solution containing ammonium fluoride, the anodizing treatment voltage is 20-30V, and the anodizing treatment time is 0.5-2 hours.

9. A porous titanium-based implant with a photothermal surface obtained by the preparation method according to any one of claims 1 to 8.

10. The use of the porous titanium-based implant with a photothermal surface according to claim 9, characterized in that: The application is in the preparation of bone tissue defect repair materials.

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