Preparation method and application of high-efficiency antibacterial and anticorrosive titanium implant / mxene-based functionalized surface

Abstract

The application discloses a kind of efficient antibacterial antiseptic titanium implant / MXene-based functional surface preparation method, the method includes the following steps: one, MXene-based multifunctional nanohybrid material preparation;Two, titanium implant surface pretreatment;Three, dense film preparation;Four, functional surface preparation.The application is deposited by two-dimensional MXene nanosheet and nanohybrid material of metal oxide on the surface of titanium implant after chemical pretreatment, form functional surface with corrosion resistance, antibacterial and near-infrared light response performance, not only improve the corrosion resistance of titanium implant surface coating, and under near-infrared light irradiation, effectively inhibit bacterial growth by generating local thermal effect, give titanium implant excellent antibacterial performance, MXene-based multifunctional nanohybrid material and the preparation method of titanium implant / MXene-based functional surface show broad application prospect in biomedical coating and titanium implant functionalization application.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of biomedical coatings, and particularly relates to a high-efficiency antibacterial and anticorrosive titanium implant / MXene-based functional surface preparation method and application. BACKGROUND

[0002] Titanium implants are widely used in many fields, including orthopedics (artificial joint replacement, internal fixation of fractures), oral medicine (dental implants), plastic surgery (skull repair), etc., due to their good mechanical properties, mechanical properties, and biocompatibility. With excellent performance in bearing high load, avoiding biological rejection, and long-term stability, it provides reliable protection for functional repair and treatment support for patients.

[0003] However, titanium implants lack intrinsic antibacterial properties, and even comprehensive disinfection and aseptic operation during surgery cannot avoid postoperative infection caused by bacterial biofilm formation. To avoid complications and secondary surgery induced by infection, titanium implants need to be endowed with good antibacterial properties. Secondly, titanium alloys are generally considered to have high biocompatibility and corrosion resistance, because titanium can form a TiO2 passivation film after contact with oxygen, which acts as a physical barrier between corrosive substances in the body and titanium metal. However, after the titanium implant is implanted into the human body, due to the presence of a large number of corrosive ions and corrosive microenvironments in the body fluid environment, once the TiO2 passivation film is damaged, corrosion will occur due to the formation of corrosion potential and the combined effects of various chemical and biological factors in the body. Acidic substances produced by bacterial metabolism in the biofilm also cause local acidic environment of titanium implant. These factors will accelerate the local corrosion of the surface of the titanium implant, showing typical pitting corrosion and mechanical factor-assisted crevice corrosion. Oxidation layer damage not only causes serious damage to the surface structure of the implant, degradation of mechanical properties, implant fracture and loosening, and other problems, resulting in implant failure; dissolution of alloying elements in titanium alloy and release of Al, V and Ni ions into the surrounding tissue and body fluid will also have toxic side effects on the human body, causing inflammation. Therefore, the current situation of inflammation and implant failure caused by postoperative infection, corrosion damage, and release of toxic ions of titanium implants seriously threatens the safety of patients' lives and becomes a bottleneck problem affecting the long-term service and sustainable development of titanium implants.

[0004] Nanometer structure coating and film can be prepared on the surface of titanium and alloy by surface modification technology, which can effectively improve the surface performance of titanium implant. Among them, MXene, as a new type of two-dimensional nanomaterial similar to graphene oxide, has shown great potential in the field of regenerative medicine and tissue engineering due to its excellent photothermal properties, rich surface terminals, high hydrophilicity, chemical stability, and antibacterial activity, becoming one of the most potential materials for implant surface functionalization. Studies have shown that MXene has multiple antibacterial modes, including the synergistic effect of chemical and physical factors: as a photothermal material, it can effectively kill bacteria by generating local heat under light; as a nanometer knife, its sharp edge and direct physical contact with the surface of the bacterial membrane can destroy the cell structure of the bacteria and cause the bacteria to release cytoplasm; as a reactive oxygen species (ROS) generator, it can generate different types of ROS to cause bacterial death.

[0005] In the patent with application number 202410118173.7, a ROS-responsive micro-nano structure titanium implant nanocoating is disclosed, which is obtained by self-assembly of a thioether ketone dopamine molecular coating on the surface of a micro-nano structure implant and macrophage-targeted functionalized Nb2C MXene nanosheets. It solves the problem of periprosthetic osteolysis faced by orthopedic prosthetic implants, and the preparation method is simple and the material is easy to obtain.

[0006] In the patent with application number 202310247531.X, a MXene / metal nanoparticle multifunctional coating composite material is disclosed. The prepared MXene-based multifunctional coating composite material does not damage the surface structure of the substrate, retains the mechanical properties of the substrate, and has strong bonding force between the substrate and the functional layer.

[0007] In the patent with application number 202211043605.X, a preparation method of MXene@cuttlefish juice melanin composite with photothermal synergistic antibacterial performance is disclosed. The composite formed by uniformly distributing or wrapping cuttlefish juice melanin on the surface or inside of MXene nanosheets can effectively cut the bacterial cell wall due to the high photothermal performance and sharp edges of MXene, achieving bactericidal effect. Moreover, using the abundant, low-cost, and environmentally friendly biomass cuttlefish juice melanin as a template, the inherent aggregation and stacking problems of MXene are improved, and the biocompatibility of the composite is enhanced; MXene@cuttlefish juice melanin composite has excellent photothermal and mechanical antibacterial performance, and has wide application prospects in the fields of broad-spectrum antibacterial, tumor inhibition, and catalysis.

[0008] A MXene-ZnO nanohybrid material is disclosed in patent application No. 202210356362.9. The MXene-ZnO nanohybrid material is synthesized by low-temperature water bath, has excellent synergistic antibacterial effect, and is further simply blended with polydimethylsiloxane, dispersed in solvents such as dichloromethane and ethyl acetate, and finally sprayed on substrates such as cotton and fiber paper to obtain a hydrophobic antibacterial material with excellent antibacterial effect, rapid sterilization by light-heat synergistic effect, self-cleaning, and reusability.

[0009] It can be seen that the rich functional groups on the surface of MXenes also enable new properties to be imparted to MXenes by hybridizing them with other materials or improving their own properties, ultimately resulting in enhanced antibacterial properties through the provision of synergistic effects, which makes MXene nanosheets have the potential to develop functional surfaces of titanium implants. However, current researches mainly focus on optimizing the design by utilizing the excellent antibacterial properties of MXene nanomaterials, without fully considering the corrosion problem of titanium implants in complex body fluid environments.

[0010] Therefore, it is necessary to design a method for modifying the surface of a titanium implant, taking into account both corrosion prevention and antibacterial applications. SUMMARY

[0011] The technical problem to be solved by the present application is to provide a high-efficiency antibacterial and anticorrosive titanium implant / MXene-based functional surface preparation method to overcome the shortcomings of the prior art. The method prepares a dense film by smoothing the titanium implant, alkalizing treatment, and immersion in a silane coupling agent solution or a biologically inspired adhesive solution, and deposits a MXene-based multifunctional nanohybrid material obtained by hybridizing two-dimensional MXene nanosheets with metal oxides to obtain a titanium implant / MXene-based functional surface, which not only improves the corrosion resistance of the dense film on the surface of the titanium implant, but also effectively inhibits bacterial growth by generating a local thermal effect under near-infrared light irradiation, thereby imparting excellent antibacterial properties.

[0012] To solve the above technical problems, the technical solution adopted by the present application is as follows: a high-efficiency antibacterial and anticorrosive titanium implant / MXene-based functional surface preparation method, characterized in that the method comprises the following steps:

[0013] Step one, MXene-based multifunctional nanohybrid material preparation: add anhydrous ethanol to the aqueous solution of two-dimensional MXene and stir at room temperature to obtain a MXene dispersion, then add metal oxide nanomaterials to the MXene dispersion and stir at room temperature to obtain a mixed solution, and then perform hydrothermal reaction and centrifugation on the mixed solution to obtain a MXene-based multifunctional nanohybrid material;

[0014] Step two, surface pretreatment of titanium implant: the titanium implant is sequentially subjected to smoothing treatment and alkalization treatment to obtain a surface pretreated titanium implant;

[0015] Step three, preparation of a dense film on the surface of the titanium implant: the surface pretreated titanium implant obtained in step two is immersed in a silane coupling agent solution or a bio-inspired adhesive solution to form a dense film with a three-dimensional network structure on the surface of the titanium implant, thereby obtaining a titanium implant with a dense film on the surface;

[0016] Step four, preparation of a titanium implant / MXene-based functionalized surface: the MXene-based multifunctional nanohybrid material prepared in step one is deposited on the surface of the titanium implant with a dense film obtained in step three to obtain a titanium implant / MXene-based functionalized surface.

[0017] The present application improves the stability of MXene nanosheets by dispersing them and then hybridizing them with metal oxide nanomaterials, and covalently bonds them, which not only improves the stability of MXene nanosheets, but also significantly improves the antibacterial performance and corrosion resistance of the MXene-based multifunctional nanohybrid material through the synergistic effect provided by hybridization. The titanium implant is smoothed through smoothing treatment, which facilitates subsequent alkalization treatment and the preparation of a dense film. The alkalization treatment introduces hydroxyl radicals onto the surface of the titanium implant, which enhances the adhesion of the dense film. The surface pretreated titanium implant is immersed in a silane coupling agent solution or a bio-inspired adhesive solution to prepare a dense film on the surface of the surface pretreated titanium implant, which introduces a transition layer and improves the adhesion of the MXene-based multifunctional nanohybrid material on the surface of the titanium implant, facilitating the subsequent deposition of the MXene-based multifunctional nanohybrid material. The titanium implant / MXene-based functionalized surface with photothermal synergistic antibacterial performance and corrosion resistance is constructed by depositing the MXene-based multifunctional nanohybrid material on the titanium implant. The MXene-based functionalized surface not only improves the corrosion resistance of the coating on the surface of the titanium implant, but also effectively inhibits bacterial growth by generating a local thermal effect under near-infrared light irradiation, thereby imparting excellent antibacterial performance to the titanium implant.

[0018] The preparation method of the high-efficiency antibacterial and anticorrosive titanium implant / MXene-based functionalized surface has the characteristics that the volume ratio of water to anhydrous ethanol in the MXene dispersion liquid in step one is 1-4:1, the stirring at room temperature after adding the anhydrous ethanol is 0.5h-3h, the mass ratio of the metal oxide nanomaterial to the MXene in the mixed solution is 1:1-4, the stirring at room temperature after adding the metal oxide nanomaterial is 2h-5h, the hydrothermal reaction is carried out in a high-pressure reaction kettle lined with polytetrafluoroethylene, the process of the hydrothermal reaction and centrifugation is that after heating to 100 DEG C and keeping for 4h-8h, the obtained product is centrifuged at a speed of 3500rpm-5000rpm, then the supernatant is poured out, the precipitate is washed with deionized water and anhydrous ethanol and then centrifuged at a speed of 3500rpm-5000rpm, and the process of washing and centrifuging is repeated for 3-5 times to obtain a paste-shaped homogeneous black solution, i.e., the MXene-based multifunctional nanohybrid material. The MXene is uniformly dispersed in the MXene dispersion liquid by controlling the parameters of the MXene dispersion, the covalent bond combination of the MXene nanosheet and the metal oxide nanomaterial and the integrity of the MXene sheet structure are ensured by controlling the parameters of the hydrothermal reaction, the dispersibility and stability of the MXene nanosheet are improved, and the MXene-based multifunctional nanohybrid material is endowed with enhanced antibacterial performance and corrosion resistance by the synergistic effect provided by the hybridization with the metal oxide.

[0019] The preparation method of the high-efficiency antibacterial and anticorrosive titanium implant / MXene-based functionalized surface has the characteristics that the metal oxide nanomaterial in step one is iron oxide (Fe2O3), zinc oxide (ZnO), titanium dioxide (TiO)2, or zirconium oxide (ZrO2) nanoparticles; the MXene is Ti3C2T x MXene, Mo2CT x MXene or Nb2CT x MXene. The specific components of the metal oxide nanomaterial and the MXene are controlled to adapt to different working conditions.

[0020] The preparation method of the high-efficiency antibacterial and antiseptic titanium implant / MXene-based functionalized surface has the characteristics that, in the step two, the smoothing process is as follows: the titanium implant is ultrasonically treated in a metal cleaning agent for 20-60 minutes, then ultrasonically treated in anhydrous ethanol for 20-60 minutes, then washed with deionized water and dried, then dry-ground with 400-2000# sandpaper, wet-ground with 3000# sandpaper under water flow until the surface has no obvious scratches and grooves and the surface color is grayish white, and finally sequentially ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 10-30 minutes and dried.

[0021] The preparation method of the high-efficiency antibacterial and antiseptic titanium implant / MXene-based functionalized surface has the characteristics that, in the step two, the alkali treatment is plasma electrolytic oxidation alkali treatment, electrochemical alkali treatment or alkali immersion; the process of the plasma electrolytic oxidation alkali treatment is as follows: the titanium implant after the smoothing treatment is immersed in a stainless steel container containing a solution of 10-20 g / L NaAlO2 and 1.5-2 g / L Na3PO4·12H2O, then a direct current power source is used, the titanium implant after the smoothing treatment is used as the anode, the electrolytic solution is used as the cathode, and electrolysis is carried out under the conditions of a voltage of 200-500 V, a frequency of 500 Hz and a duty cycle of 5-20% for 5-10 minutes, then the titanium implant is taken out, washed with deionized water and dried; the process of the electrochemical alkali treatment is as follows: the titanium implant after the smoothing treatment is placed in an electrolyte of 0.1-1 mol / L NaOH, the titanium implant is used as the working electrode, a platinum electrode is used as the counter electrode, and a saturated calomel electrode is used as the reference electrode to form a three-electrode system, and the treatment is carried out under the condition of a voltage of 1-10 V for 10-30 minutes, then the titanium implant is taken out, washed with deionized water and dried; the alkali immersion method comprises the following steps: the titanium implant after the smoothing treatment is placed in a reaction kettle containing a solution of 5-10 mol / L NaOH, then hydrothermally treated at 100℃ for 12-24 hours, then taken out and washed with deionized water and dried after cooling to room temperature. By using the plasma electrolytic oxidation alkali treatment, the electrochemical alkali treatment or the alkali immersion method, the surface roughness of the titanium implant is increased, a dense oxide layer is formed, the hydrophilicity is increased, and hydroxyl radicals (-OH) are incorporated into the surface, so that the subsequent dense film can be better attached to the surface of the titanium implant.

[0022] The method for preparing the high-efficiency antibacterial and antiseptic titanium implant / MXene-based functional surface has the characteristics that the process of the immersion in the silane coupling agent solution in step three is that: the solution composed of 5-10% of the silane coupling agent, 85-90% of the anhydrous ethanol and the rest of the deionized water is slowly stirred for 1 hour for complete hydrolysis, then the surface pretreated titanium implant obtained in step two is immersed in the solution after the hydrolysis for 1-2 hours, and then vacuum drying is performed at 80-100 DEG C for 1-2 hours; the silane coupling agent is one of 3-aminopropyl triethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560), gamma-methacryloxypropyltrimethoxysilane (KH570) and N-(beta-aminoethyl)-gamma-aminopropyltrimeth(eth)oxysilane (KH792). The process of the immersion in the silane coupling agent solution is controlled to form a dense film, i.e. a transition layer, on the surface of the titanium implant, which facilitates the subsequent deposition of the MXene-based multifunctional nanohybrid material on the surface of the titanium implant.

[0023] The method for preparing the high-efficiency antibacterial and antiseptic titanium implant / MXene-based functional surface has the characteristics that the process of the immersion in the biological inspired adhesive solution in step three is that: the surface pretreated titanium implant is immersed in a container containing 50 mL of the biological inspired adhesive solution, then the container is placed in a water bath shaker with a shaking radius of 3 cm and a rate of 30-60 rpm / min, and is immersed for 12-48 hours in the dark at 25 DEG C under shaking, and then is ultrasonically vibrated for 10-30 minutes and is dried in a vacuum drying box at 40-50 DEG C. The process of the immersion in the biological inspired adhesive solution is controlled to form a dense film, i.e. a transition layer, on the surface of the titanium implant, which facilitates the subsequent coating of the MXene-based multifunctional nanohybrid material on the surface of the titanium implant.

[0024] The method for preparing the high-efficiency antibacterial and antiseptic titanium implant / MXene-based functional surface has the characteristics that the biological inspired adhesive solution is prepared by the following process: 0.0788 g of tris(hydroxymethyl)aminomethane hydrochloride is dissolved in deionized water, then the volume is adjusted to 50 mL in a volumetric flask to obtain a 1 mmol / L Tris buffer solution, then the Tris buffer solution is transferred to a beaker, 0.1000 g of the adhesive is added and uniformly mixed, then stirring is continued, and the pH value is adjusted to 8.5 with the Tris buffer solution to obtain the biological inspired adhesive solution; the adhesive is one or more than two of a dopamine hydrochloride solution, a chitosan quaternary ammonium salt solution or a tannic acid solution. The biological inspired adhesive in the application refers to a biomimetic wet-state biological adhesive inspired by mussels and barnacles, i.e. an adhesive derived from natural resources, also called a biological adhesive, which provides an alkaline environment for the spontaneous polymerization of the adhesive by adjusting the pH value to 8.5.

[0025] The preparation method of the high-efficiency antibacterial and anticorrosive titanium implant / MXene functional surface has the characteristics that the deposition in step four is immersion deposition or drop deposition; the immersion deposition process is as follows: the MXene-based multifunctional nanohybrid material prepared in step one is diluted with anhydrous ethanol to obtain a diluent with a concentration of 0.2 mg / mL to 2 mg / mL, then the titanium implant with a dense film on the surface is immersed in the diluent for 30 min, then taken out and dried in air for 2 min, and the immersion and drying are repeated three times, and then dried at 37 DEG C under a vacuum condition of 25 kPa for 4 h to 8 h; the drop deposition process is as follows: the MXene-based multifunctional nanohybrid material prepared in step one is diluted with anhydrous ethanol to obtain a diluent with a concentration of 0.2 mg / mL to 2 mg / mL, then the diluent is dropped on the surface of the titanium implant with a dense film on the surface at a dosage of 0.5 μL / mm 2 2 2 μL / mmThe titanium implant with a dense film on the surface is dropped, and then dried at 37 DEG C under a vacuum condition of 25 kPa for 4 h to 8 h. The present application controls the deposition process to prepare a uniform MXene-based multifunctional nanohybrid material layer on the surface of the titanium implant.

[0026] In addition, the present application also provides an application of the high-efficiency antibacterial and anticorrosive titanium implant / MXene functional surface, which has the characteristics that the preparation method of the MXene-based multifunctional nanohybrid material and the titanium implant / MXene functional surface is applied to the surface modification of biomedical coatings and titanium implants. The present application applies the preparation method of the MXene-based multifunctional nanohybrid material and the titanium implant / MXene functional surface to the surface modification of biomedical coatings and titanium implants, solves the problems of inflammatory reactions and implant failure caused by postoperative infection, corrosion damage and release of toxic and side ions of the titanium implant, and improves the antibacterial behavior and corrosion behavior of the titanium implant.

[0027] Compared with the prior art, the present application has the following advantages:

[0028] 1. This invention improves the adhesion of MXene-based multifunctional nanohybrid materials to the surface of titanium implants by smoothing, alkalizing, and impregnating the implant with a silane coupling agent solution or a bio-inspired adhesive solution to form a dense film, i.e., introducing a transition layer. Furthermore, by preparing MXene-based multifunctional nanohybrid materials by hybridizing two-dimensional MXene nanosheets with metal oxides and then depositing them, a functional surface with photothermal synergistic antibacterial and anti-corrosion properties is constructed, resulting in a titanium implant / MXene-based functionalized surface. The MXene-based multifunctional nanohybrid materials not only improve the corrosion resistance of the titanium implant surface coating but also effectively inhibit bacterial growth under near-infrared light irradiation through localized thermal effects, endowing the titanium implant with excellent antibacterial properties and demonstrating broad application prospects in the functionalization of titanium implants.

[0029] 2. Electrochemical experiments on the titanium implant / MXene-based functionalized surface of the present invention show that it has excellent corrosion resistance, providing a corrosion resistance value Z. f＝0.01Hz This represents an improvement of two orders of magnitude compared to titanium implants with a dense thin film on the surface.

[0030] 3. The titanium implant / MXene functionalized surface of the present invention has excellent near-infrared photothermal properties. When irradiated with near-infrared light (1.5W) for 10 minutes, a local thermal effect is generated, and the temperature of the functional surface can reach nearly 72°C, which can significantly destroy the integrity of the bacterial membrane. However, the titanium metal surface is only 30°C. When the temperature is cooled to room temperature, the functional surface remains intact without cracking or peeling. The photothermal properties give the titanium implant / MXene functionalized surface excellent antibacterial ability, with an inhibition rate of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0031] 4. The titanium implant / MXene-based functionalized surface of the present invention has a simple, effective and low-cost preparation method and process, providing a new option for the surface modification of titanium implants.

[0032] 5. This invention applies the preparation method of titanium implant / MXene-based functionalized surface to the surface modification of titanium implants, and applies MXene-based multifunctional nano-hybrid materials to biomedical coatings, which solves the problems of inflammatory reactions and implantation failure caused by postoperative infection, corrosion damage and release of toxic byproduct ions in titanium implants, and improves the antibacterial and corrosion behavior of titanium implants.

[0033] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0034] Figure 1 This is a TEM image of MXene used in step one of Embodiment 1 of the present invention.

[0035] Figure 2 TEM image of ZnO used in step one of Example 1 of the present application.

[0036] Figure 3 TEM image of MXene / ZnO multifunctional nanohybrid material obtained in step one of Example 1 of the present application.

[0037] Figure 4 Zeta potential image of MXene and ZnO used in step one and MXene / ZnO multifunctional nanohybrid material obtained in step one of Example 1 of the present application.

[0038] Figure 5 Surface optical morphology image and water contact angle test image of titanium implant used in step two, titanium implant with dense film on the surface obtained in step three, Ti / MXene@ZnO functionalized surface obtained in step four and Ti / MXene functionalized surface obtained by depositing MXene directly on the titanium implant of Example 1 of the present application.

[0039] Figure 6 Photothermal heating curve of titanium implant used in step two, titanium implant with dense film on the surface obtained in step three, Ti / MXene@ZnO functionalized surface obtained in step four and Ti / MXene functionalized surface obtained by depositing MXene directly on the titanium implant under near-infrared light irradiation at a wavelength of 808 nm and a power of 1.5 W of Example 1 of the present application.

[0040] Figure 7 Flat plate antibacterial experiment results of titanium implant used in step two, titanium implant with dense film on the surface obtained in step three, Ti / MXene@ZnO functionalized surface obtained in step four and Ti / MXene functional surface obtained by depositing MXene directly on the titanium implant of Example 1 of the present application.

[0041] Figure 8 Electrochemical impedance spectrum Bode plot of titanium implant used in step two, titanium implant with dense film on the surface obtained in step three, Ti / MXene@ZnO functionalized surface obtained in step four and Ti / MXene functional surface obtained by depositing MXene directly on the titanium implant of Example 1 of the present application. DETAILED DESCRIPTION

[0042] Example 1

[0043] This example includes the following steps:

[0044] Step one, preparation of MXene-based multifunctional nanohybrid material: 30 mL of anhydrous ethanol was added to the aqueous solution of MXene with a concentration of 10 mg / mL, and stirred at room temperature for 3 h to obtain a MXene dispersion solution, then 0.4 g of zinc oxide quantum dots was added to the MXene dispersion solution and stirred at room temperature for 3 h to obtain a mixed solution, then the mixed solution was loaded into a high-pressure reaction kettle lined with polytetrafluoroethylene, heated to 100℃ and hydrothermal for 4 h, cooled to room temperature, the obtained product was centrifuged at a speed of 4000 rpm, then the supernatant was poured out, the precipitate was washed with deionized water and anhydrous ethanol and centrifuged at a speed of 4000 rpm, and the process of washing and centrifuging was repeated 4 times to obtain a paste-like homogeneous black solution, namely MXene-based multifunctional nanohybrid material; x MXene dispersion solution was obtained by adding 30 mL of anhydrous ethanol to the aqueous solution of MXene with a concentration of 10 mg / mL and stirring at room temperature for 3 h, then 0.4 g of zinc oxide quantum dots was added to the MXene dispersion solution and stirred at room temperature for 3 h to obtain a mixed solution, then the mixed solution was loaded into a high-pressure reaction kettle lined with polytetrafluoroethylene, heated to 100℃ and hydrothermal for 4 h, cooled to room temperature, the obtained product was centrifuged at a speed of 4000 rpm, then the supernatant was poured out, the precipitate was washed with deionized water and anhydrous ethanol and centrifuged at a speed of 4000 rpm, and the process of washing and centrifuging was repeated 4 times to obtain a paste-like homogeneous black solution, namely MXene-based multifunctional nanohybrid material;

[0045] Step two, surface pretreatment of titanium implant: titanium with a diameter of 10 mm and a height of 3 mm was used as a titanium implant and ultrasonically cleaned in a metal cleaning agent for 30 min, then ultrasonically cleaned in anhydrous ethanol for 30 min, then rinsed with deionized water and dried, then dry ground with 400#, 800#, 1000#, 1500# and 2000# sandpaper in sequence, wet ground with 3000# sandpaper under water flow until there were no obvious scratches and grooves on the surface and the surface color was grayish white, finally ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 20 min in sequence and dried, to obtain a smooth treated titanium implant, then the smooth treated titanium implant was placed in a reaction kettle containing 10 mol / L NaOH solution, then hydrothermal treated at 100℃ for 12 h, then taken out after cooling to room temperature, rinsed with deionized water and dried at 60℃, to obtain a surface pretreated titanium implant;

[0046] Step three, preparation of dense film on the surface of titanium implant: the surface pretreated titanium implant obtained in step two was immersed in a container containing 50 mL of bio-inspired adhesive solution, then the container was placed in a water bath shaker with a shaking radius of 3 cm and a shaking rate of 50 rpm / min, and soaked at 25℃ in the dark for 24 h, then ultrasonically agitated for 15 min, and then dried in a vacuum drying oven at 45℃, to obtain a titanium implant with a dense film on the surface; the bio-inspired adhesive solution was prepared as follows: 0.0788 g of tris-hydroxymethyl aminomethane hydrochloride (Tris-HCl, chemical formula NH2C(CH2OH)3·HCl) was dissolved in 30 mL of deionized water, then transferred to a volumetric flask and made up to 50 mL to obtain a 1 mmol / L Tris buffer solution, then the Tris buffer solution was transferred to a beaker, 0.1000 g of dopamine hydrochloride was added and mixed uniformly, then continuously stirred, and the pH value was adjusted to 8.5 with the Tris buffer solution to obtain a bio-inspired adhesive solution;

[0047] Step four, titanium implant / MXene-based functionalized surface preparation: the MXene-based multifunctional nanohybrid material prepared in step one was diluted with anhydrous ethanol to obtain a diluent with a concentration of 1 mg / mL, and then the diluent was added to the surface of the titanium implant with a diameter of 10 mm in step two at a dosage of 2 μL / mm 2 The titanium implant surface with a diameter of 10 mm and a dense film obtained in step three was dripped, and then dried at 37℃ under a vacuum condition of 25 kPa for 6 h to obtain a Ti / MXene@ZnO functionalized surface.

[0048] It was detected that when the MXene-based multifunctional nanohybrid material prepared in the embodiment was applied to the surface modification and biomedical coating of a titanium implant, the Ti / MXene@ZnO functionalized surface constructed had an excellent photothermal antibacterial performance and a significant anticorrosion performance due to the local thermal effect generated under near-infrared light irradiation.

[0049] The metal oxide nanomaterial in step one of the embodiment can also be iron oxide nanoparticles, titanium dioxide nanoparticles, and zirconium oxide nanoparticles.

[0050] The MXene in step one of the embodiment can also be Mo2CT x The MXene or Nb2CT x MXene.

[0051] In step two of the embodiment, the smooth titanium implant can also be placed in a reaction kettle with a NaOH solution with a concentration of 5 mol / L, and then hydrothermally treated at 100℃ for 24 h, or placed in a reaction kettle with a NaOH solution with a concentration of 8 mol / L, and then hydrothermally treated at 100℃ for 18 h.

[0052] In step three of the embodiment, the surface pretreated titanium implant obtained in step two can be immersed in a container containing 50 mL of a bio-inspired adhesive solution, and then the container is placed in a water bath shaker with a shaking radius of 3 cm and a rate of 30 rpm / min, and soaked at 25℃ in the dark and under shaking conditions for 48 h, and then ultrasonically oscillated for 10 min, and then dried in a vacuum drying box at 50℃, or the surface pretreated titanium implant obtained in step two can be immersed in a container containing 50 mL of a bio-inspired adhesive solution, and then the container is placed in a water bath shaker with a shaking radius of 3 cm and a rate of 60 rpm / min, and soaked at 25℃ in the dark and under shaking conditions for 12 h, and then ultrasonically oscillated for 30 min, and then dried in a vacuum drying box at 40℃.

[0053] The adhesive in step three of the embodiment can also be one or more than two of dopamine hydrochloride, chitosan quaternary ammonium salt, or tannic acid solution.

[0054] Figure 1 Transmission electron microscopy (TEM) image of MXene used in step one of this example, Figure 2 TEM image of ZnO used in step one of this example, Figure 3 TEM image of MXene / ZnO multifunctional nanohybrid material obtained in step one of this example, from Figures 1-3 As can be seen from the TEM image, the ZnO nanoparticles in the MXene / ZnO multifunctional nanohybrid material are uniformly distributed on the surface of the MXene nanosheets to form a typical sheet-dot structure nanocomposite.

[0055] Figure 4 Zeta potential images of MXene and ZnO used in step one of this example and the MXene / ZnO multifunctional nanohybrid material obtained in step one, from Figure 4 As can be seen from the TEM image, the MXene@ZnO multifunctional nanohybrid material prepared by hydrothermal reaction reduces the Zeta potential of the MXene nanosheet and improves the stability of the MXene nanosheet.

[0056] Figure 5 Surface optical morphology images and water contact angle test images of the titanium implant used in step two, the titanium implant with a dense film on the surface obtained in step three, the Ti / MXene@ZnO functional surface obtained in step four, and the Ti / MXene functional surface obtained by directly depositing MXene on the titanium implant, Figure 5 The titanium implant is denoted as Ti, the titanium implant with a dense film on the surface is denoted as Ti-PDA, and the Ti / MXene functional surface obtained by directly depositing MXene on the titanium implant is denoted as Ti / MXene, from Figure 5 As can be seen from the TEM image, the surface of the Ti-PDA forms a dense and uniform three-dimensional network structure, which improves the adhesion of the MXene-based multifunctional nanohybrid material on the surface of the titanium implant with a dense film. A crack-free Ti / MXene@ZnO functional surface is formed on the surface of the titanium implant by the dripping method. The functional surface has increased hydrophilicity, which is conducive to the adhesion and direct contact of bacterial cells, so that the MXene-based multifunctional nanohybrid material exhibits improved antibacterial effect.

[0057] Figure 6 Photothermal warming curve of the titanium implant used in step two of this example, the titanium implant with a dense film on the surface obtained in step three, the Ti / MXene@ZnO functional surface obtained in step four, and the Ti / MXene functional surface obtained by directly depositing MXene on the titanium implant under near-infrared light irradiation at a wavelength of 808 nm and a power of 1.5 W, Figure 6Ti implant is recorded as Ti, the titanium implant with dense film on the surface is recorded as Ti-PDA, Ti / MXene functional surface obtained by directly depositing MXene on the titanium implant is recorded as Ti / MXene, the surfaces of Ti, Ti-PDA, Ti / MXene and Ti / MXene@ZnO in the 24-well plate are irradiated by using a near-infrared light (NIR) emitter (808 nm, 1.5 W), the temperature of the centrifuge tube and the functional surface are monitored in real time by using a thermal imager, the temperature is recorded every 30 s, and the recording is continued for 10 min, from Figure 6 As can be seen from Table 1, under the irradiation of near-infrared light with a wavelength of 808 nm and a power of 1.5 W, the Ti / MXene and Ti / MXene@ZnO functional surfaces have excellent photothermal conversion efficiency compared with Ti-PDA and Ti, especially the Ti / MXene@ZnO functional surface, the temperature can reach nearly 74℃ after the irradiation of near-infrared light for 10 min, while the temperature of the titanium implant surface is only 30℃.

[0058] The titanium implant used in step two, the titanium implant with dense film on the surface obtained in step three, the Ti / MXene@ZnO functional surface obtained in step four and the Ti / MXene functional surface obtained by directly depositing MXene on the titanium implant are subjected to the functional surface photothermal sterilization plate colony counting experiment, as shown in Table 2. Figure 7 , Figure 7 Ti implant is recorded as Ti, the titanium implant with dense film on the surface is recorded as Ti-PDA, Ti / MXene functional surface obtained by directly depositing MXene on the titanium implant is recorded as Ti / MXene, the sample needs to be irradiated by the ultraviolet lamp for 30 min on the front and back surfaces respectively before the plate colony counting experiment, the sample is placed in the 24-well plate, 1 mL of bacterial suspension of E. coli and S. aureus with a concentration of 1x10 6 CFU / ml is added into each well, the Ti, Ti-PDA, Ti / MXene and Ti / MXene@ZnO are irradiated by using a near-infrared light (NIR) emitter (808 nm, 1.5 W) for 10 min; after the sample subjected to the photothermal treatment is cultured in the 37℃ constant temperature incubator for 6 h, the bacterial suspension in the 24-well plate is diluted 100 times by using PBS solution and then subjected to the plate coating experiment, and then cultured in the 37℃ constant temperature incubator overnight; the colonies in the plate are observed, photographed and counted (CFU), and the bacteriostatic rate is calculated, the bacteriostatic rate (%) = (CFU of the control group-CFU of the experimental group) / CFU of the control group, wherein the control group is the sample without near-infrared light irradiation and the sample with near-infrared light irradiation, which are respectively marked as -NIR and +NIR, from Figure 7It can be seen that the Ti / MXene@ZnO functionalized surface, due to its superior photothermal conversion efficiency, exhibits excellent photothermal sterilization effects, significantly disrupting the integrity of bacterial membranes, and achieving an inhibition rate of nearly 100% against Escherichia coli and Staphylococcus aureus.

[0059] Figure 8 To utilize an electrochemical workstation and a three-electrode testing system (reference electrode: saturated AgCl / KCl; auxiliary electrode: platinum sheet, length × width × 2 cm; working electrode: working area 0.785 cm²), a three-electrode system was developed. 2 Bode plots of the sample were obtained by electrochemical impedance spectroscopy (EIS). The horizontal axis represents the logarithm of the frequency, the left vertical axis represents the corresponding impedance value, and the right vertical axis represents the corresponding phase angle. The electrolyte solution and test conditions used were simulated body fluid SBF (37℃, 7.4, 200mL). The EIS measurements were performed under non-polarized conditions, with a sinusoidal potential excitation frequency range of 100kHz to 10mHz and an amplitude of 10mV. The titanium implant is denoted as Ti, the titanium implant with a dense thin film on its surface is denoted as Ti-PDA, and the Ti / MXene functionalized surface obtained by directly depositing MXene on the titanium implant is denoted as Ti / MXene. Figure 8 As can be seen, the Ti / MXene@ZnO functional surface exhibits the best corrosion resistance, providing a corrosion resistance value Z. f＝0.01Hz Compared to Ti / MXene functional surfaces, it is an order of magnitude higher, and compared to Ti-PDA, it is two orders of magnitude higher.

[0060] Example 2

[0061] This embodiment includes the following steps:

[0062] Step 1: Preparation of MXene-based multifunctional nanohybrid materials: In 40 mL of two-dimensional monolayer Ti3C2T with a concentration of 10 mg / mL... x 40 mL of anhydrous ethanol was added to an aqueous solution of MXene and stirred at room temperature for 0.5 h to obtain an MXene dispersion. Then, 0.1 g of nano-zinc oxide quantum dots were added to the MXene dispersion and stirred at room temperature for 5 h to obtain a mixed solution. The mixed solution was then placed in a high-pressure reactor lined with polytetrafluoroethylene and heated to 60 °C and hydrothermally heated for 8 h. After cooling to room temperature, the obtained product was centrifuged at 3500 rpm. The supernatant was then decanted, and the precipitate was washed with deionized water and anhydrous ethanol and centrifuged at 3500 rpm. The washing and centrifugation process was repeated 3 times to obtain a paste-like homogeneous black solution, which is the MXene-based multifunctional nano-hybrid material.

[0063] Step two, titanium implant surface pretreatment: titanium pieces with length x width x height of 10 mm x 10 mm x 3 mm were used as titanium implants and ultrasonically cleaned in a metal cleaner for 20 min, then ultrasonically cleaned in anhydrous ethanol for 20 min, then rinsed with deionized water and dried, then dry ground with 400#, 800#, 1000#, 1500# and 2000# sandpaper, wet ground with 3000# sandpaper under water flow until there were no obvious scratches and grooves on the surface and the surface color was grayish white, and finally ultrasonically cleaned with acetone, anhydrous ethanol and deionized water for 30 min and dried, to obtain smooth treated titanium implants. The smooth treated titanium implants were immersed in a stainless steel container containing a solution of 15 g / L NaAlO2 and 1.6 g / L Na3PO4·12H2O, then a direct current power source was used, with the smooth treated titanium implants as the anode and the electrolytic solution as the cathode, under the conditions of a voltage of 400 V, a frequency of 500 Hz and a duty cycle of 20%, electrolysis was carried out for 8 min, then the titanium implants were taken out, rinsed with deionized water and dried at 60℃, to obtain the surface pretreated titanium implants;

[0064] Step three, titanium implant surface dense film preparation: a solution of 5% silane coupling agent, 90% anhydrous ethanol and the balance deionized water was slowly stirred for 1 h for complete hydrolysis, then the surface pretreated titanium implants obtained in step two were immersed in the hydrolyzed solution for 1.5 h, and then vacuum dried at 90℃ for 1.5 h, to obtain titanium implants with a dense film on the surface; the silane coupling agent was 3-aminopropyl triethoxysilane (KH550);

[0065] Step four, titanium implant / MXene-based functionalized surface preparation: the MXene-based multifunctional nanohybrid material prepared in step one was diluted with anhydrous ethanol to obtain a dilution solution with a concentration of 1.0 mg / mL, then the titanium implants with a dense film on the surface were immersed in the dilution solution for 30 min, then taken out and dried in air for 2 min, and the immersion and drying were repeated three times, and then dried at 37℃ under a vacuum of 25 kPa for 6 h, to obtain a Ti / MXene@ZnO functionalized surface.

[0066] It was detected that when the MXene-based multifunctional nanohybrid material prepared in this embodiment was applied to the surface modification and biomedical coating of titanium implants, the Ti / MXene@ZnO functionalized surface constructed had excellent photothermal antibacterial performance and significant anticorrosion performance due to the local thermal effect produced under near-infrared light irradiation.

[0067] In step two of this embodiment, the smoothed titanium implant can also be immersed in a stainless steel container containing 10 g / L NaAlO2 and 2 g / L Na3PO4·12H2O solution, and then electrolyzed for 5 min using a DC power supply with the smoothed titanium implant as the anode and the electrolytic solution as the cathode at a voltage of 500 V, a frequency of 500 Hz, and a duty cycle of 5%. Alternatively, the smoothed titanium implant can be immersed in a stainless steel container containing 20 g / L NaAlO2 and 1.5 g / L Na3PO4·12H2O solution, and then electrolyzed for 10 min using a DC power supply with the smoothed titanium implant as the anode and the electrolytic solution as the cathode at a voltage of 200 V, a frequency of 500 Hz, and a duty cycle of 15%.

[0068] In step four of this embodiment, the MXene-based multifunctional nano-hybrid material prepared in step one can be diluted with anhydrous ethanol to obtain a diluent with a concentration of 2 mg / mL. Then, the titanium implant with a dense film on its surface is immersed in the diluent for 30 min, then removed and dried in air for 2 min. This process of immersion and drying is repeated three times. Finally, it is dried at 37°C and 25 kPa vacuum for 8 h. Alternatively, the MXene-based multifunctional nano-hybrid material prepared in step one can be diluted with anhydrous ethanol to obtain a diluent with a concentration of 0.2 mg / mL. Then, the titanium implant with a dense film on its surface is immersed in the diluent for 30 min, then removed and dried in air for 2 min. This process of immersion and drying is repeated three times. Finally, it is dried at 37°C and 25 kPa vacuum for 4 h.

[0069] Example 3

[0070] This embodiment includes the following steps:

[0071] Step 1: Preparation of MXene-based multifunctional nanohybrid materials: In 50 mL of two-dimensional monolayer Ti3C2T with a concentration of 10 mg / mL... x 12.5 mL of anhydrous ethanol was added to an aqueous solution of MXene and stirred at room temperature for 2 h to obtain an MXene dispersion. Then, 0.3 g of titanium dioxide nanoparticles were added to the MXene dispersion and stirred at room temperature for 2 h to obtain a mixed solution. The mixed solution was then placed in a high-pressure reactor lined with polytetrafluoroethylene and heated to 80 °C for 6 h hydrothermally. After cooling to room temperature, the obtained product was centrifuged at 5000 rpm. The supernatant was then decanted, and the precipitate was washed with deionized water and anhydrous ethanol and centrifuged at 5000 rpm. The washing and centrifugation process was repeated 5 times to obtain a paste-like homogeneous black solution, which is the MXene-based nano-hybrid material.

[0072] Step two, surface pretreatment of titanium implant: titanium pieces with length x width x height of 10 mm x 10 mm x 3 mm as titanium implants are ultrasonically cleaned in a metal cleaning agent for 60 min, and then ultrasonically cleaned in anhydrous ethanol for 60 min. Then, the titanium implants are rinsed with deionized water and dried. Subsequently, the titanium implants are dry ground using sandpaper with grits of 400#, 800#, 1000#, 1500# and 2000# in sequence. The titanium implants are wet ground using sandpaper with a grit of 3000# under water flow until there are no obvious scratches and grooves on the surface and the surface color is grayish white. Finally, the titanium implants are ultrasonically cleaned with acetone, anhydrous ethanol and deionized water in sequence for 10 min and dried to obtain smooth titanium implants. The smooth titanium implants are placed in an electrolyte with 0.1 mol / L NaOH. The titanium implant is used as a working electrode, a platinum electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode to form a three-electrode system. The titanium implant is treated at a voltage of 10 V for 30 min. Subsequently, the titanium implant is taken out, rinsed with deionized water and dried to obtain a surface pretreated titanium implant.

[0073] Step three, preparation of a dense film on the surface of the titanium implant: a solution composed of 10% silane coupling agent, 85% anhydrous ethanol and the balance deionized water is slowly stirred for 1 h for complete hydrolysis. Then, the surface pretreated titanium implant obtained in step two is immersed in the solution, soaked for 1 h and vacuum dried at 100°C for 1 h to obtain a titanium implant with a dense film on the surface; the silane coupling agent is γ-glycidoxypropyltrimethoxysilane (KH560).

[0074] Step four, preparation of a titanium implant / MXene-based functionalized surface: the MXene-based nanohybrid material prepared in step one is diluted with anhydrous ethanol to obtain a diluent with a concentration of 2 mg / mL. Then, the diluent is applied to the surface of the titanium implant with a use amount of 0.5 μL / mm 2 The surface of the titanium implant with a dense film obtained in step three is dripped, and then dried at 37°C under a vacuum of 25 kPa for 4 h to obtain a Ti / MXene@TiO2 functionalized surface.

[0075] It is detected that when the MXene-based multifunctional nanohybrid material prepared in the embodiment is applied to the surface modification and biomedical coating of a titanium implant, the Ti / MXene@TiO2 functionalized surface constructed has an excellent photothermal antibacterial performance and a significant anticorrosion performance due to the local thermal effect generated under near-infrared light irradiation.

[0076] In step two of the embodiment, the smooth titanium implant can also be placed in an electrolyte with 1 mol / L NaOH. The titanium implant is used as a working electrode, a platinum electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode to form a three-electrode system. The titanium implant is treated at a voltage of 1 V for 10 min.

[0077] The solution composed of 8% silane coupling agent, 86% anhydrous ethanol and the rest deionized water is slowly stirred for 1h for sufficient hydrolysis in step three of the embodiment, then the surface pretreated titanium implant obtained in step two is immersed in the solution for 2h, and then vacuum dried at 80°C for 2h to obtain the titanium implant with dense film on the surface; the silane coupling agent can also be one of 3-aminopropyl triethoxysilane (KH550), γ-methacryloyloxypropyl trimethoxysilane (KH570) and N-(β-aminoethyl)-γ-aminopropyl trimeth(eth)oxysilane (KH792).

[0078] The MXene-based nanohybrid material prepared in step one is diluted with anhydrous ethanol to obtain a diluent with a concentration of 0.2mg / mL in step four of the embodiment, then the diluent is added to the surface of the titanium implant with dense film on the surface obtained in step three at a dosage of 3μL / mm 2 The surface of the titanium implant with dense film on the surface obtained in step three is dripped, and then dried at 37°C under a vacuum condition of 25kPa for 8h.

[0079] The above is only a preferred embodiment of the present application, and does not limit the present application. Any simple modification, change and equivalent change made according to the technical essence of the present application to the above embodiment are still within the protection scope of the technical solution of the present application.

Claims

1. A method for the preparation of high efficiency antibacterial and antifouling titanium implant / MXene-based functionalized surface, characterized by, The method comprises the following steps: Step one, preparation of MXene-based multifunctional nanohybrid material: adding anhydrous ethanol into the aqueous solution of two-dimensional MXene and stirring at room temperature to obtain a MXene dispersion, then adding metal oxide nanomaterial into the MXene dispersion and stirring at room temperature to obtain a mixed solution, and then performing hydrothermal reaction and centrifugation on the mixed solution to obtain the MXene-based multifunctional nanohybrid material; the metal oxide nanomaterial is iron oxide (Fe2O3), zinc oxide (ZnO), titanium dioxide (TiO2) or zirconium oxide (ZrO2) nanoparticles; Step two, surface pretreatment of titanium implant: sequentially performing smoothing treatment and alkalization treatment on the titanium implant to obtain a surface pretreated titanium implant; Step three, preparation of dense film on the surface of titanium implant: immersing the surface pretreated titanium implant obtained in step two in a silane coupling agent solution or a bio-inspired adhesive solution to form a dense film with a three-dimensional network structure on the surface of the titanium implant, thereby obtaining a titanium implant with a dense film on the surface; Step four, preparation of titanium implant / MXene-based functionalized surface: depositing the MXene-based multifunctional nanohybrid material prepared in step one on the surface of the titanium implant with a dense film obtained in step three to obtain a titanium implant / MXene-based functionalized surface.

2. The method according to claim 1, wherein, In step one, the volume ratio of water to anhydrous ethanol in the MXene dispersion is 1-4:1, the stirring at room temperature after adding anhydrous ethanol is performed for 0.5-3 hours, the mass ratio of metal oxide nanomaterial to MXene in the mixed solution is 1:1-4, the stirring at room temperature after adding metal oxide nanomaterial is performed for 2-5 hours, the hydrothermal reaction is performed in a high-pressure reaction kettle lined with polytetrafluoroethylene, and the process of hydrothermal reaction and centrifugation is as follows: heating to 60-100°C and keeping the temperature for 4-8 hours, then cooling to room temperature, centrifuging the obtained product at a speed of 3500-5000 rpm, then pouring the supernatant, washing the precipitate with deionized water and anhydrous ethanol, and then centrifuging at a speed of 3500-5000 rpm, and repeating the washing and centrifuging process for 3-5 times to obtain a paste-shaped homogeneous black solution, i.e. the MXene-based multifunctional nanohybrid material.

3. The method of claim 1, wherein the method is characterized by, The MXene in step one is Ti3C2T x MXene, Mo2CT x MXene or Nb2CT x MXene.

4. The method of claim 1, wherein the method is characterized by, In step two, the process of smoothing treatment is as follows: ultrasonically treating the titanium implant in a metal cleaning agent for 20-60 minutes, then ultrasonically treating the titanium implant in anhydrous ethanol for 20-60 minutes, then rinsing with deionized water and drying, then performing dry grinding with 400-2000# sandpaper, wet grinding with 3000# sandpaper under water flow until there are no obvious scratch grooves on the surface and the surface color is grayish white, and finally ultrasonically cleaning with acetone, anhydrous ethanol and deionized water for 10-30 minutes and drying.

5. The method of claim 1, wherein the method is characterized by, The alkali treatment in step two is a plasma electrolytic oxidation alkali treatment method, an electrochemical alkali treatment method or an alkali immersion method; the process of the plasma electrolytic oxidation alkali treatment method is as follows: after the smooth treatment of the titanium implant, the titanium implant is immersed in a stainless steel container containing a solution of 10 g / L-20 g / L NaAlO2 and 1.5 g / L-2 g / L Na3PO4·12H2O, then a direct current power source is used, the smooth treated titanium implant is used as an anode, and the electrolytic solution is used as a cathode, and electrolysis is carried out under the conditions of a voltage of 200 V-500 V, a frequency of 500 Hz and a duty cycle of 5%-20% for 5 min-10 min, and then the titanium implant is taken out, washed with deionized water and dried; the process of the electrochemical alkali treatment method is as follows: after the smooth treatment of the titanium implant, the titanium implant is placed in an electrolyte containing 0.1-1 mol / L NaOH, the titanium implant is used as a working electrode, a platinum electrode is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode to form a three-electrode system, and the titanium implant is treated under the condition of a voltage of 1-10 V for 10-30 min, and then the titanium implant is taken out, washed with deionized water and dried; the alkali immersion method comprises the following steps: after the smooth treatment of the titanium implant, the titanium implant is placed in a reaction kettle containing a solution of 5 mol / L-10 mol / L NaOH, and then the titanium implant is hydrothermally treated at 100 ℃ for 12 h-24 h, and then the titanium implant is taken out after cooling to room temperature, washed with deionized water and dried.

6. The method of claim 1, wherein the method is characterized by, The process of the immersion in the silane coupling agent solution in step three is as follows: a solution of 5%-10% silane coupling agent, 85%-90% anhydrous ethanol and the balance deionized water is slowly stirred for 1 h for complete hydrolysis, and then the surface pretreated titanium implant obtained in step two is immersed in the hydrolyzed solution for 1 h-2 h, and then vacuum drying is carried out at 80 ℃-100 ℃ for 1 h-2 h; the silane coupling agent is one of 3-aminopropyltriethoxysilane (KH550), γ-glycidoxypropyltrimethoxysilane (KH560), γ-methacryloyloxypropyltrimethoxysilane (KH570) and N-(β-aminoethyl)-γ-aminopropyltrimethoxy (ethoxy) silane (KH792).

7. The method of claim 1, wherein the method is characterized by, The process of the immersion in the bio-inspired adhesive solution in step three is as follows: the surface pretreated titanium implant is immersed in a container containing 50 mL of a bio-inspired adhesive solution, and then the container is placed in a water bath shaker with a shaking radius of 3 cm and a rate of 30 rpm-60 rpm, and the container is immersed in the water bath shaker under the conditions of 25 ℃, light shielding and shaking for 12 h-48 h, and then ultrasonic oscillation is carried out for 10 min-30 min, and then the container is placed in a vacuum drying box for drying at 40 ℃-50 ℃.

8. The method of claim 1, wherein the method is characterized by, The bio-inspired adhesive solution is prepared by the following process: 0.0788 g of tris(hydroxymethyl)aminomethane hydrochloride is dissolved in deionized water, and then the volume is adjusted to 50 mL in a volumetric flask to obtain a 1 mmol / L Tris buffer solution, then the Tris buffer solution is transferred to a beaker, 0.1000 g of an adhesive is mixed uniformly, then stirring is continued, and the pH value is adjusted to 8.5 with the Tris buffer solution to obtain a bio-inspired adhesive solution; the adhesive is one or more than two of dopamine hydrochloride, chitosan quaternary ammonium salt or tannic acid solution.

9. The method of claim 1, wherein the method is characterized by, The deposition in step four is immersion deposition or drop deposition; the process of the immersion deposition is that the MXene-based multifunctional nanohybrid material prepared in step one is diluted with anhydrous ethanol to obtain a diluent with a concentration of 0.2 mg / mL to 2 mg / mL, then the titanium implant with a dense film on the surface is immersed in the diluent for 30 min, then taken out and dried in air for 2 min, and the immersion and drying are repeated three times, and then dried at 37 DEG C under a vacuum condition of 25 kPa for 4 h to 8 h; the process of the drop deposition is that the MXene-based multifunctional nanohybrid material prepared in step one is diluted with anhydrous ethanol to obtain a diluent with a concentration of 0.2 mg / mL to 2 mg / mL, then the diluent is dropped on the surface of the titanium implant with a dense film on the surface at a dosage of 0.5 μL / mm 2 ~3 μL / mm 2 The drop deposition is performed on the surface of the titanium implant with a dense film on the surface, and then dried at 37 DEG C under a vacuum condition of 25 kPa for 4 h to 8 h.

10. Use of the method for the preparation of high-efficiency antibacterial and antifouling titanium implant / MXene-based functionalized surfaces according to any one of claims 1-9, characterized in that, The preparation method of the MXene-based multifunctional nano-hybrid material and titanium implant / MXene-based functional surface is applied to the surface modification of biomedical coatings and titanium implants.

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