Ti3C2Tx / CS coating material and preparation method thereof

Abstract

The invention discloses a Ti3C2Tx / CS coating material and a preparation method thereof.The preparation method comprises the steps that LiF and an HCl solution are mixed to form an etching solution, Ti3AlC2 powder is added into the etching solution, a reaction is conducted at the preset temperature, and sediment is generated; collecting generated precipitates through the steps of centrifugal treatment and washing, and carrying out ultrasonic treatment and freeze drying to obtain an MXene solid; the preparation method comprises the following steps: dissolving an MXene solid in double distilled water, mixing an MXene solution with a chitosan solution to form a Ti3C2Tx / CS composite solution, taking a titanium sheet as a substrate material, and pretreating the titanium sheet to introduce amino groups; and the surface of the pretreated titanium sheet is coated with the Ti3C2Tx / CS composite solution through a spin coating technology, so that the Ti3C2Tx / CS coating is formed. The problem that an existing implant surface treatment technology does not have antibacterial activity is solved, and the combining capacity of the implant and soft and hard tissues is further improved.

Description

Technical Field

[0001] This application relates to the technical field of composite material preparation, and particularly to a Ti3C2T x / CS coating material and its preparation method. Background Art

[0002] Dental implant is an advanced dental restoration technology aimed at restoring the function and aesthetics of missing or damaged teeth through artificial implantation. The core lies in implanting an implant made of a highly biocompatible material (usually titanium alloy) into the alveolar bone of the patient through surgery. After a period of healing, the implant forms a stable bone-bond with the surrounding alveolar bone, and then a abutment and a crown are installed on it to simulate the structure and function of natural teeth. The success of dental implants depends not only on the bonding of hard tissues but also on the close bonding of soft tissues with the superstructure of the implant. This bonding ensures the stability of dental implants in the oral cavity and the normal functioning of their functions, and also provides an important soft tissue barrier for oral health.

[0003] Currently, the development of dental implant technology has been relatively mature, especially in the selection, design, and surface treatment of implant materials. The surface treatment technology of implants has been significantly improved, such as sandblasting, acid etching, anodization, etc. These technologies can increase the surface roughness of implants, which is beneficial to cell attachment and growth, thus accelerating the process of bone bonding. On the other hand, in order to improve the bonding of soft tissues with implant abutments, researchers have begun to explore the application of coating technology on the abutment surface to further improve the stability of dental implants and the oral health level of patients.

[0004] Although the existing technology has made significant progress in the field of dental implants, there are still some deficiencies. Titanium implants themselves do not have antibacterial activity, and it is difficult to completely eradicate the subgingival plaque after its formation, which may lead to peri-implantitis. The bonding ability of titanium metal with surrounding soft tissues is limited, which may weaken the soft tissue seal and increase the risk of plaque invasion and inflammation.

[0005] Therefore, how to solve the problem of the lack of antibacterial activity in the existing implant surface treatment technology to further improve the bonding ability of implants with hard and soft tissues is still an urgent problem to be solved in the current field of dental implants. Summary of the Invention

[0006] In the embodiments of this application, by providing a Ti3C2Tx / CS coating material and its preparation method, the problem of the lack of antibacterial activity in the existing implant surface treatment technology is solved to further improve the bonding ability of implants with hard and soft tissues.

[0007] In the first aspect, the embodiments of this application provide a Ti3C2T xPreparation method of / CS coating material, comprising: mixing LiF and HCl solution to form an etching solution, adding Ti3AlC2 powder into the etching solution, reacting at a preset temperature to generate a precipitate; collecting the generated precipitate through centrifugation and washing steps, and obtaining MXene solid through ultrasonic treatment and freeze-drying; dissolving the MXene solid in double-distilled water, mixing the MXene solution with chitosan solution to form Ti3C2T x / CS composite solution, using a titanium sheet as the substrate material, pre-treating the titanium sheet to introduce amino groups; coating the Ti3C2T x / CS composite solution on the surface of the pre-treated titanium sheet by spin coating technology to form Ti3C2T x / CS coating.

[0008] Further, the step of mixing LiF and HCl solution to form an etching solution, adding Ti3AlC2 powder into the etching solution, and reacting at a preset temperature to generate a precipitate includes: in a PTFE beaker, mixing LiF and 9M HCl solution at a ratio of 1:2 to form a mixed solution; using a stirrer to stir the mixed solution at a constant 40°C for 15 minutes until LiF is completely dissolved in the HCl solution to form an etching solution; adding 2g of Ti3AlC2 powder into the etching solution, placing the PTFE beaker in a 40°C constant temperature water bath, and maintaining this temperature for reaction for 48 hours to ensure that the Al atomic layer in the Ti3AlC2 powder is fully etched by the etching solution to generate a precipitate.

[0009] Further, the step of collecting the generated precipitate through centrifugation and washing steps, and obtaining MXene solid through ultrasonic treatment and freeze-drying includes: centrifuging the content in the PTFE beaker at a set centrifugation speed of 3500 rpm to collect the precipitate; washing the precipitate with deionized water multiple times, and centrifuging after each washing until the pH value of the supernatant is higher than 6 to ensure removal of residual etching solution and impurities; redispersing the washed precipitate in deionized water and performing ultrasonic treatment for 30 minutes to promote the exfoliation and dispersion of the precipitate; performing centrifugation again at a centrifugation speed of 3500 rpm to collect the exfoliated precipitate; wherein, the exfoliated precipitate is a MXene nanosheet dispersion; freeze-drying the MXene nanosheet dispersion to remove moisture and obtain MXene solid.

[0010] Further, the step of dissolving the MXene solid in double-distilled water, mixing the MXene solution with chitosan solution to form Ti3C2T xThe Ti3C2Tx / CS composite solution includes: dissolving chitosan and 2% acetic acid solution in a ratio of 0.5:19.5 to obtain a chitosan solution with a mass fraction of 2.5 wt%; dissolving the MXene solution and double-distilled water in a ratio of 1:2000, and performing ultrasonic treatment for 20 minutes to obtain a well-dispersed Ti3C2Tx solution with a concentration of 0.05 wt%. x The well-dispersed Ti3C2Tx x solution is added dropwise into the chitosan solution according to preset different percentages to form a Ti3C2Tx x / CS composite solution.

[0011] Further, the pretreatment of the titanium sheet to introduce amino groups includes: successively polishing the surface of the titanium sheet with sandpapers of different mesh numbers; after polishing, performing plasma treatment on the surface of the titanium sheet to introduce amino groups.

[0012] Further, the Ti3C2Tx x / CS composite solution is coated on the surface of the pretreated titanium sheet by spin coating technology to form a Ti3C2Tx x / CS coating, including: adding glutaraldehyde as a crosslinking agent into the Ti3C2Tx x / CS composite solution to react with the amino groups introduced during the pretreatment of the titanium sheet surface and the amino groups in chitosan to form a crosslinked structure; using spin coating technology to coat the Ti3C2Tx x / CS composite solution containing the crosslinking agent on the surface of the pretreated titanium sheet; after coating, placing the titanium sheet at room temperature for crosslinking for 1 h and performing drying treatment to form a Ti3C2Tx x / CS coating.

[0013] In a second aspect, an embodiment of the present application provides a Ti3C2Tx x / CS coating material, and the Ti3C2Tx x / CS coating material is obtained by the preparation method described in any one of claims 1 to 6.

[0014] One or more technical solutions provided in the embodiments of the present application have at least the following technical effects:

[0015] An embodiment of the present application provides a preparation method of a Ti3C2Tx x / CS coating material. By introducing MXene (Ti3C2Tx x) The material, and this coating exhibits strong antibacterial activity. MXene, as a new type of two-dimensional material, has unique physical and chemical properties and can effectively inhibit the growth and reproduction of bacteria, thus significantly reducing the risk of peri-implantitis. Chitosan (CS), as a natural polymer material, has good biocompatibility and biodegradability. Combining it with the MXene solution to form a composite coating not only maintains the antibacterial performance of MXene but also further enhances the binding ability of the coating to the surrounding soft tissues, promoting the healing and regeneration of soft tissues. By means of spin coating technology, the Ti3C2T x / CS composite solution was uniformly coated on the surface of the pretreated titanium sheet, forming a stable and dense coating. This coating not only has good adhesion and durability but also can effectively prevent the attachment and invasion of dental plaque, providing strong guarantee for the long-term stability of dental implants and oral health. The preparation method of this application is relatively simple and easy to operate, without the need for complex equipment and cumbersome steps. By controlling the reasonable raw material ratio and process parameters, the Ti3C2T x / CS coating material with excellent performance can be efficiently prepared, providing strong support for the further development and application of dental implant technology. In summary, the preparation method of the Ti3C2T x / CS coating material provided by this application has the advantages of significant antibacterial performance, good biocompatibility, enhanced coating stability, and simplified preparation process, etc., solving the problem that the existing implant surface treatment technology does not have antibacterial activity, so as to further improve the binding ability of the implant to hard and soft tissues. Brief Description of the Drawings

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required to be used in the description of the embodiments of the present application or the prior art. Obviously, the drawings in the following description are some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained according to these drawings.

[0017] Figure 1 It is a flowchart of a preparation method of a Ti3C2T x / CS coating material provided by an embodiment of the present application;

[0018] Figure 2 It is a schematic diagram of the material preparation process and surface morphology provided by an embodiment of the present application;

[0019] Figure 3 It is a schematic diagram of the XRD and infrared characterizations of the material provided by an embodiment of the present application;

[0020] Figure 4Schematic diagram of the antibacterial experiment on the material surface provided by the embodiment of the present application;

[0021] Figure 5 Schematic diagram of the cell viability obtained through the cell proliferation experiment provided by the embodiment of the present application;

[0022] Figure 6 Schematic diagram of the cell spreading obtained through the cell adhesion experiment provided by the embodiment of the present application;

[0023] Figure 7 Schematic diagram of the inflammatory gene expression obtained through the anti-inflammatory ability test provided by the embodiment of the present application. Detailed implementation manners

[0024] Now, various exemplary implementation manners of the present application will be described in detail. This detailed description should not be considered as a limitation of the present application, but should be understood as a more detailed description of certain aspects, characteristics, and implementation schemes of the present application.

[0025] It should be understood that the terms described in the present application are only for describing specific implementation manners and are not used to limit the present application. Additionally, for the numerical ranges in the present application, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present application. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0026] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present application pertains. Although the present application only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present application. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0027] Without departing from the scope or spirit of the present application, various improvements and changes can be made to the specific implementation manners of the present application specification, which are obvious to those skilled in the art. Other implementation manners obtained from the specification of the present application are obvious to those skilled in the art. The specification and embodiments of the present application are only exemplary.

[0028] Regarding the terms "comprising", "including", "having", "containing", etc. used herein, they are all open-ended terms, meaning including but not limited to.

[0029] The embodiment of the present application provides a kind of Ti3C2T xPreparation method of / CS coating material, as follows Figure 1 shown, this method includes steps S101 to S104. Among them, Figure 1 This is only an execution order shown in the embodiments of this application, and does not represent the only execution order of a preparation method of Ti3C2T x / CS coating material. Under the condition that the final result can be achieved, Figure 1 the steps shown can be executed in parallel or reversed.

[0030] S101: Mix LiF and HCl solution to form an etching solution, add Ti3AlC2 powder into the etching solution, and react at a preset temperature to generate a precipitate.

[0031] Specifically, mix LiF and HCl solution to form an etching solution, add Ti3AlC2 powder into the etching solution, and react at a preset temperature to generate a precipitate, including: In a PTFE beaker, mix LiF and 9M HCl solution in a ratio of 1:2 to form a mixed solution. It can be 2g of LiF mixed with 40ML of 9M HCl solution, or 3g of LiF mixed with 60ML of 9M HCl solution. Use a stirrer to stir the mixed solution at a constant 40°C for 15 minutes until LiF is completely dissolved in the HCl solution to form an etching solution. That is, the preset temperature can be 40°C. Add 2g of Ti3AlC2 powder into the etching solution, place the PTFE beaker in a 40°C constant temperature water bath, and keep this temperature for reaction for 48 hours to ensure that the Al atomic layer in the Ti3AlC2 powder is fully etched by the etching solution to generate a precipitate.

[0032] It should be noted that the precipitate in this application is Ti3C2T x precipitate. LiF and HCl play a key role as etching agents. Their selective etching effect enables the Al atomic layer to be effectively removed, while the Ti3C2 layered structure is retained, and a Ti3C2T x shown) precipitate with specific surface functional groups is formed. x precipitate.

[0033] S102: Collect the generated precipitate through centrifugation and washing steps, and obtain MXene solid through ultrasonic treatment and freeze-drying.

[0034] Specifically, the generated precipitate is collected through centrifugation and washing steps, and the MXene solid is obtained through ultrasonic treatment and freeze-drying, including: centrifuging the contents in a PTFE beaker at a centrifugation speed of 3500 rpm to collect the precipitate. The precipitate is washed multiple times with deionized water, and centrifugation is performed after each wash until the pH value of the supernatant is higher than 6 to ensure the removal of residual etching solution and impurities. The washed precipitate is redispersed in deionized water and ultrasonicated for 30 minutes to promote the exfoliation and dispersion of the precipitate. Centrifugation is performed again at a centrifugation speed of 3500 rpm to collect the exfoliated precipitate. Among them, the exfoliated precipitate is a MXene nanosheet dispersion. The MXene nanosheet dispersion is freeze-dried to remove moisture and obtain the MXene solid.

[0035] Further, after centrifugation, a black precipitate is obtained. To ensure the removal of residual etching solution and impurities, the precipitate is washed multiple times with deionized water. After each wash, centrifugation is performed to separate the washed precipitate and the supernatant. This washing process continues until the pH value of the supernatant is higher than 6 to ensure the complete removal of residual etching solution and impurities. Next, the washed precipitate is redispersed in deionized water. To promote the exfoliation and dispersion of the precipitate, ultrasonication is performed for 30 minutes. Ultrasonication helps to break the agglomerated structure in the precipitate and form a more uniform dispersion. After ultrasonication, centrifugation is performed again at a centrifugation speed of 3500 rpm. The purpose of this step is to collect the exfoliated precipitate, namely the MXene nanosheet dispersion. The exfoliated precipitate now exists in the form of single-layer or multi-layer Ti3C2T x MXene nanosheets. Finally, the MXene nanosheet dispersion is freeze-dried. The purpose of freeze-drying is to remove the moisture in the dispersion, thereby obtaining the MXene solid.

[0036] It should be noted that the Ti3C2T x MXene material used in this application, as a leading material among two-dimensional transition metal carbides, not only inherits the excellent properties common to the MXene family, such as excellent electrical conductivity, outstanding mechanical flexibility, and high functionalization potential, but also exhibits unique advantages in antibacterial performance and promoting soft tissue regeneration. Ti3C2T x MXene exhibits high antibacterial activity against a variety of bacteria, including but not limited to Gram-negative Escherichia coli and Gram-positive Bacillus subtilis. Compared with traditional antibacterial materials such as graphene oxide (GO), Ti3C2T xIt is superior in antibacterial efficiency, which provides strong support for the prevention and treatment of peri-implantitis. Its antibacterial mechanism involves interaction with the bacterial cell membrane, leading to bacterial structural damage and cell death, thus effectively inhibiting the formation and spread of dental plaque. Ti3C2T x MXene not only has antibacterial properties but also can significantly promote soft tissue regeneration. Research shows that this material can stimulate the proliferation and migration of fibroblasts, which are key processes in soft tissue repair and regeneration. By promoting granulation tissue growth, angiogenesis, collagen deposition, and re-epithelialization, Ti3C2T x accelerates the healing process of infected wounds and provides strong biological support for the soft tissue recovery after dental implant surgery. In the regulation of periodontal tissue inflammation, Ti3C2T x MXene shows the potential to reduce the release of pro-inflammatory cytokines, which helps to reduce the inflammatory response and damage degree of periodontal tissue. Ti3C2T x The combination of Ti3C2T

[0037] S103: Dissolve MXene solid in double-distilled water, mix the MXene solution with the chitosan solution to form a Ti3C2T x / CS composite solution. Use titanium sheets as the substrate material and pretreat the titanium sheets to introduce amino groups.

[0038] Specifically, dissolve MXene solid in double-distilled water, mix the MXene solution with the chitosan solution to form a Ti3C2T x / CS composite solution, including: Dissolve chitosan and 2% acetic acid solution in a ratio of 0.5:19.5 to obtain a chitosan solution with a mass fraction of 2.5 wt%. Dissolve the MXene solution and double-distilled water in a ratio of 1:2000 and perform ultrasonic treatment for 20 minutes to obtain a well-dispersed Ti3C2T x solution with a concentration of 0.05 wt%. Add the well-dispersed Ti3C2T x solution dropwise into the chitosan solution according to different preset percentages to form a Ti3C2T x / CS composite solution.

[0039] Specifically, 0.5 g of chitosan can be dissolved in 19.5 mL of 2% acetic acid solution to obtain a chitosan solution with a mass fraction of 2.5 wt%. Dissolve 0.01 g of MXene solid in 20 mL of double-distilled water and perform ultrasonic treatment for 20 minutes to obtain a well-dispersed Ti3C2T xSolution. According to preset different percentages (0.5 wt% / 1 wt% / 2 wt%), the dispersed Ti3C2T x solution was added dropwise into the chitosan solution to form Ti3C2T x / CS composite solution.

[0040] The titanium sheet was pretreated to introduce amino groups, including: using sandpapers with different mesh numbers to polish the surface of the titanium sheet step by step. After the polishing was completed, the surface of the titanium sheet was subjected to plasma treatment to introduce amino groups.

[0041] Specifically, sandpapers with 220 mesh, 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 1500 mesh and 2000 mesh were used to polish the surface of the titanium sheet step by step. This step was aimed at ensuring the flatness and cleanliness of the titanium sheet surface. After the polishing was completed, the surface of the titanium sheet was subjected to plasma treatment to successfully introduce amino functional groups on its surface.

[0042] S104: Coating the Ti3C2T x / CS composite solution on the surface of the pretreated titanium sheet by spin coating technology to form Ti3C2T x / CS coating.

[0043] Specifically, coating the Ti3C2T x / CS composite solution on the surface of the pretreated titanium sheet by spin coating technology to form Ti3C2T x / CS coating, including: adding glutaraldehyde as a crosslinking agent into the Ti3C2T x / CS composite solution to react with the amino groups introduced during the pretreatment of the titanium sheet surface and the amino groups in chitosan to form a crosslinked structure. Using spin coating technology to coat the Ti3C2T x / CS composite solution containing the crosslinking agent on the surface of the pretreated titanium sheet. After the coating was completed, the titanium sheet was placed at room temperature for crosslinking for 1 h and then dried to form Ti3C2T x / CS coating.

[0044] Furthermore, glutaraldehyde can react with the amino groups introduced during the pretreatment of the titanium sheet surface and the amino groups in chitosan to form a stable crosslinked structure, thereby enhancing the adhesion and mechanical properties of the coating. Using spin coating technology to coat the Ti3C2T xThe Ti3C2T / CS composite solution was evenly coated on the surface of the pretreated titanium sheet. The spin-coating technique evenly spreads the solution by rapidly rotating the titanium sheet, forming a thin and uniform coating under the action of centrifugal force. After the coating is completed, the titanium sheet is crosslinked at room temperature for 1 h. During this process, glutaraldehyde reacts with amino groups to form a stable crosslinked network. Subsequently, the titanium sheet is dried to remove the moisture and solvent in the coating, making the coating stronger and more stable. After the above steps, a uniform, dense, and strongly adherent Ti3C2T x / CS coating was finally formed on the surface of the titanium sheet. This coating combines the advantages of MXene and chitosan and has excellent biocompatibility.

[0045] The technical solutions of this application will be further described below in conjunction with specific embodiments.

[0046] It can be understood that all the raw materials used in the embodiments of this application can be obtained through commercial purchase.

[0047] Example 1: Control group - 0% Ti3C2T x Preparation of CS coating.

[0048] Objective: To prepare a pure chitosan (CS) coating without Ti3C2T x as the control group for the experiment.

[0049] The steps are as follows. 1. Dissolve 0.5 g of chitosan in 19.5 mL of 2% acetic acid solution to prepare a chitosan solution with a mass fraction of 2.5 wt%. Ensure that the chitosan is completely dissolved and the solution is uniformly transparent. 2. Pour the prepared chitosan solution into a clean petri dish, and use a spatula or glass rod to evenly spread the solution on the bottom of the petri dish. Avoid generating bubbles and ensure that the film layer is uniform. 3. Place the spread chitosan solution at room temperature for natural drying, or use a vacuum drying oven to accelerate the drying process. After drying, a pure chitosan film, i.e., the CS coating, is obtained. The CS coating prepared in this example will be used as the control group for all experiments on Ti3C2T x / CS coatings for comparison and analysis of the influence of the addition of Ti3C2T x on the film properties.

[0050] Example 2: Preparation of Ti3C2T x / CS coating.

[0051] Objective: To prepare a chitosan composite film containing a certain proportion of Ti3C2T x and study its properties.

[0052] The steps are as follows. 1. According to the steps of S102, prepare MXene solid, dissolve the MXene solid in double-distilled water, and perform ultrasonic treatment for 20 minutes to obtain well-dispersed Ti3C2Tx Solution. 2. The same as step 1 in Example 1, prepare a chitosan solution with a mass fraction of 2.5 wt%. 3. According to different preset percentages, add the dispersed Ti3C2T x solution dropwise into the chitosan solution, stirring while adding to ensure uniform mixing to form Ti3C2T x / CS composite solution. 4. Pour the prepared Ti3C2T x / CS composite solution into a clean petri dish and spread it evenly using a spatula or glass rod. Avoid generating bubbles and ensure a uniform film layer. 4. Add glutaraldehyde as a cross-linking agent to the Ti3C2T x / CS composite solution and let it stand at room temperature for cross-linking for 1 h. 5. Place the cross-linked composite film at room temperature for natural drying, or use a vacuum drying oven to accelerate the drying process. After drying, obtain the Ti3C2T x / CS coating.

[0053] Figure 2 Schematic diagrams of the material preparation process and surface morphology provided in the embodiments of this application. Figure 2 In (a) is the diagram of the mechanically polished titanium sheet and the plasma-treated titanium sheet. As can be seen from Figure 2 , after plasma treatment of the titanium sheet, due to the rich amino groups on the surface of the titanium sheet, it has good hydrophilicity. Figure 2 In (b) is the schematic diagram of the CS coating and the Ti3C2T x / CS coating. It can be seen that Ti3C2T x can be evenly dispersed in CS. Figure 2 In (c) are the scanning electron microscope pictures of the titanium sheet, the CS coating and the Ti3C2T x / CS coating.

[0054] Figure 3 Schematic diagrams of the XRD and infrared characterizations of the materials provided in the embodiments of this application. Figure 3 In (a) is the schematic diagram of the XRD of the material. Figure 3 In (a) is the Fourier transform infrared spectrum characterization of the material. The functional groups of CS include: 1027 cm - -1 represents C-OH of primary alcohol, 1644 cm - -1 is the stretching vibration peak of amide, 3339 cm - -1 is the stretching vibration of amino group. 3781 cm - -1 represents the out-of-plane vibration of the -OH functional group, 1986 cm - -1 represents the stretching vibration of C=O, 2327 cm -1 represents the cumulative double bond region of O=C=O. Since the surface of MXene materials is usually functionalized with negatively charged groups (such as =O, -OH, and -F) during synthesis, the results of FTIR spectra are slightly different from those reported in previous literature, mainly because their peak intensities are lower. Figure 3 In (b) of Figure 3 is the X-ray diffraction (XRD) characterization of the material. In the Ti3C2T x / CS coating, the characteristic peaks and overlapping peaks of CS and Ti3C2T x appear simultaneously. As shown in (b) of Figure 3 , the characteristic peak at 6.6° corresponds to the (002) crystal plane of the Ti3C2T x material, and there is no characteristic peak (2θ = 39°) of Al atoms in the precursor material Ti3AlC2 in the XRD results, indicating that Ti3C2T x has high purity.

[0055] Figure 4 This is a schematic diagram of the antibacterial experiment on the material surface provided by the embodiment of this application. Figure 4 In (a) of Figure 4 is a schematic diagram of the antibacterial performance of the titanium sheet. Figure 4 In (b) of Figure 4 is a schematic diagram of the antibacterial performance of the CS coating. Figure 4 In (c) of Figure 4 is a schematic diagram of the antibacterial performance of the Ti3C2T x / CS coating. The experimental steps of the antibacterial experiment on the material surface are as follows. Place the sterilized titanium plate and the coated titanium plate with a diameter of 15 mm (CS coating and Ti3C2T x / CS coating) at the bottom of a 24-well plate in sequence. Add 10 μL of the bacterial suspension to each plate and spread it evenly on the surface of the sample. Use a near-infrared light source (wavelength 808 nm, power density 100 mW / cm 2 ​)Irradiate the sample for 5 minutes. This step is to simulate the light conditions that may be used in actual applications and evaluate the effect of light on the antibacterial performance of the coating. After irradiation, wash the sample surface with 1 mL PBS to remove unattached bacteria. Transfer the washing solution to a sterile container and use a vortex oscillator to mix it thoroughly to collect the bacteria attached to the sample surface. Take 10 μL of the eluate and place it on a sterile solidified nutrient agar plate. Use a sterile spatula to spread the dilution evenly on the surface of the culture medium. Invert the plate and incubate it in an incubator for 24 hours. After the time point is reached, count the colonies on the plate and record the corresponding dilution factor. The number of colonies reflects the survival of bacteria on the sample surface, thereby enabling the evaluation of the antibacterial performance of the sample. The experimental results are analyzed as follows. Titanium sheet (control group): The titanium sheet, as the control group, the number of colonies on its surface will reflect the survival of bacteria without coating protection. CS-coated titanium plate: By comparing the number of colonies on the CS-coated titanium plate with that of the titanium sheet control group, the antibacterial performance of the CS coating can be evaluated. If the number of colonies on the CS-coated titanium plate is significantly reduced, it indicates that the CS coating has an antibacterial effect. Ti3C2T x / CS-coated titanium plate: Similarly, by comparing the number of colonies on the Ti3C2T x / CS-coated titanium plate with those on the CS-coated titanium plate and the titanium sheet control group, the antibacterial performance of the Ti3C2T x / CS coating can be evaluated. If the number of colonies on the Ti3C2T x / CS-coated titanium plate is further reduced, it indicates that the Ti3C2T x / CS coating has more excellent antibacterial performance.

[0056] Figure 5 This is a schematic diagram of cell viability obtained through cell proliferation experiments provided by the embodiments of this application. The experimental steps of the cell proliferation experiment are as follows. Digest HGF-1 cells with 0.25% trypsin to separate them from the culture dish or flask wall. Add serum to neutralize trypsin and stop the digestion process. Centrifuge the cell suspension, discard the supernatant, and remove trypsin and serum. Re-add the culture medium and pipette to resuspend the cells. Use a cell counting chamber to count the number of cells. Dilute the cell suspension with culture medium as needed to achieve an appropriate cell density. Inoculate the diluted cell suspension onto the materials to be tested. Ensure that the cells are evenly distributed on the materials. The materials to be tested are 0% Ti3C2T x / CS coating, 0.5% Ti3C2T x / CS coating, 1% Ti3C2T x / CS coating, and 2% Ti3C2T x / CS coating. At the set time points (24 hours, 48 hours, 72 hours), serum-free medium containing 10% CCK-8 reagent was added to each sample. Incubate at 37 °C for 2 hours to allow the CCK-8 reagent to fully react with the cells. Measure the absorbance of the supernatant at a wavelength of 450 nm to reflect cell viability. By comparing the absorbance values at different time points (24h, 48h, 72h), the proliferation of cells on different materials can be evaluated. The higher the absorbance value, the more cells and the stronger the cell viability. By comparing the absorbance values on different materials, the effect of different materials on the proliferation of HGF-1 cells can be evaluated. Through Figure 5 The experimental results show that after culturing for 24, 48, and 72 hours, the number of cells in all experimental groups gradually increased with time. Among them, the cell viability of the Ti3C2T x / chitosan composite coating group was higher than that of the pure chitosan group (CS group) after culturing for 24, 48, and 72 hours. As the content of Ti3C2T x increased, the OD value also increased, indicating a significant increase in the number of cells (p < 0.05). This shows that the Ti3C2T x / chitosan coating material is more conducive to the growth of fibroblasts than the pure chitosan coating material. In addition, our experimental results also show that the optimal concentration of Ti3C2T x is 2%.

[0057] Figure 6 This is a schematic diagram of cell spreading obtained through the cell adhesion experiment provided by the embodiment of the present application. Figure 6 In (a) is a schematic diagram of cell spreading on the CS coating. Figure 6 In (b) is a schematic diagram of cell spreading on the Ti3C2T x / CS coating. The experimental steps of the cell adhesion experiment are as follows. Seed HGF-1 cells on the CS coating and Ti3C2T x / CS coating materials. Discard the cell culture medium, wash the cells with PBS to remove non-adherent cells and culture medium components. Add 2.5% glutaraldehyde and fix overnight at 4 °C. Glutaraldehyde can crosslink the proteins in the cells to keep the cell morphology stable for subsequent observation. Discard the fixative and dehydrate step by step with different concentrations of alcohol. The gradient dehydration steps include 50%, 70%, 80%, 90%, and 100% alcohol, and each concentration is dehydrated for 10 minutes. The dehydration process can remove the water in the cells and tissues to prevent the formation of ice crystals during subsequent processing, thus maintaining the integrity of the cell morphology. Air-dry the dehydrated cell and material specimens for observation under a scanning electron microscope. The scanning electron microscope can produce high-resolution images to show the spreading morphology and adhesion of cells on the material surface. By comparing Figure 6In (a) and (b), it can be observed that the CS coating and the Ti3C2T x / CS coating's effect on the adhesion morphology of HGF-1 cells. On the CS coating, the cells showed a certain spreading morphology, but the specific morphology depends on the nature of the coating and the cell type. On the Ti3C2T x / CS coating, the cells exhibited better spreading and adhesion abilities because this coating combines the properties of Ti3C2T x and CS, providing a more suitable surface environment for cell growth.

[0058] Figure 7 This is a schematic diagram of the inflammatory gene expression obtained through the anti-inflammatory ability test provided by the embodiment of this application. The anti-inflammatory ability test steps are as follows. Collect RNA samples from the cells in the well plate. Use the SPARKeasy cell RNA kit to isolate and purify RNA according to the instructions. Use TaKaRa's PrimeScript RT Reagent kit to reverse transcribe the extracted RNA into cDNA. Prepare the PCR reaction system: 12.5 μL of TIANGEN Taq PCR MasterMix, 1 μL of cDNA, 2 μL of primers, and 9.5 μL of enzyme-free water. Table 1 shows the primer sequences used. Mix the above reagents, pre-denature at 95 °C for 3 minutes in a PCR amplifier, and then repeat the following steps 30 cycles: denature at 95 °C for 30 seconds, anneal at 63 °C for 30 seconds, and synthesize at 72 °C for 30 seconds; after the cycle ends, incubate at 72 °C for 10 minutes to end the reaction. Deposit the PCR product into the gel wells and perform electrophoresis in the -2PLUS electrophoresis system, and stain the DNA in the gel with Gel-Red DNA dye. Use the Gel Doc 2000 system to visualize and photograph the bands after electrophoresis, and compare the effects of different materials on the inflammatory gene expression according to the brightness and position of the bands. The stronger the band brightness, the higher the inflammatory gene expression level; the weaker the band brightness, the lower the inflammatory gene expression level. Select marker genes such as IL-6, IL-1β, and TNF-α for gene expression analysis. The semi-quantitative RT-PCR results showed that the expression of pro-inflammatory marker genes was up-regulated in RAW264.7 cells stimulated by LPS. However, on the surface of the Mxene / CS material, compared with the surfaces of pure titanium (Ti) and chitosan (CS), the expressions of IL-6, IL-1β, and TNF-α showed a downward trend, indicating that the Mxenen / CS material has an obvious anti-inflammatory effect in vitro.

[0059] Table 1

[0060]

[0061] In this application, the surface of a titanium sheet is treated by plasma technology to form amino groups. Then, glutaraldehyde is used as a crosslinking agent to carry out a crosslinking reaction between the amino groups on the surface of the titanium sheet and the amino groups of chitosan. This crosslinking process can enhance the mechanical properties and adhesion properties of the coating material, making it stronger and less likely to fall off. This application aims to utilize the excellent properties of Ti3C2T x Mxene and chitosan (CS) to construct a new type of coating material. Ti3C2T x and chitosan both have good antibacterial properties, biocompatibility, and anti-inflammatory properties. More importantly, when these two materials are combined, their properties can complement each other, thus forming a Ti3C2T x / CS coating material with excellent physical and chemical properties, antibacterial properties, and anti-inflammatory effects. This coating material has broad application prospects in the biomedical field.

[0062] Although this application provides method operation steps as described in the embodiments or flowcharts, more or fewer operation steps may be included based on routine or non-creative labor. The step sequence listed in this embodiment is only one way among the execution sequences of numerous steps and does not represent the only execution sequence.

[0063] The above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit this application; although this application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of this application.

Claims

1. A preparation method of a Ti3C2T x / CS coating material, characterized in that Comprising: Mix LiF and HCl solution to form an etching solution, add Ti3AlC2 powder into the etching solution, and react at a preset temperature to generate a precipitate; Collect the generated precipitate through centrifugation and washing steps, and obtain MXene solid through ultrasonic treatment and freeze-drying; Dissolve the MXene solid in double-distilled water, mix the MXene solution with the chitosan solution to form a Ti3C2T x / CS composite solution, use a titanium sheet as the substrate material, and pretreat the titanium sheet to introduce amino groups; The Ti3C2T x / CS composite solution was spin-coated on the surface of the pretreated titanium sheet to form a Ti3C2T x / CS coating.

2. The preparation method of the Ti3C2T x / CS coating material, characterized in that, The mixing of LiF and HCl solution to form an etching solution, adding Ti3AlC2 powder into the etching solution, and reacting at a preset temperature to generate a precipitate includes: In a PTFE beaker, mix LiF and 9M HCl solution in a ratio of 1:2 to form a mixed solution; Use a stirrer to stir the mixed solution at a constant 40 °C for 15 minutes until LiF is completely dissolved in the HCl solution to form an etching solution; Add 2 g of Ti3AlC2 powder into the etching solution, place the PTFE beaker in a constant temperature water bath at 40 °C, and maintain this temperature for reaction for 48 hours to ensure that the Al atomic layer in the Ti3AlC2 powder is fully etched by the etching solution to generate a precipitate.

3. The preparation method of the Ti3C2T x / CS coating material, characterized in that The collecting of the generated precipitate through centrifugation and washing steps, and obtaining MXene solid through ultrasonic treatment and freeze-drying includes: Centrifuge the content in the PTFE beaker with a set centrifugation speed of 3500 rpm to collect the precipitate; Wash the precipitate with deionized water multiple times, and perform centrifugation after each wash until the pH value of the supernatant is higher than 6 to ensure the removal of residual etching solution and impurities; Redisperse the washed precipitate in deionized water and perform ultrasonic treatment for 30 minutes to promote the exfoliation and dispersion of the precipitate; Perform centrifugation again at a centrifugation speed of 3500 rpm to collect the exfoliated precipitate; wherein, the exfoliated precipitate is a MXene nanosheet dispersion; Freeze-dry the MXene nanosheet dispersion to remove moisture and obtain MXene solid.

4. The preparation method of the Ti3C2T x / CS coating material, characterized in that, Dissolve the MXene solid in double-distilled water, mix the MXene solution with the chitosan solution to form a Ti3C2T x / CS composite solution, including: Dissolve chitosan and 2% acetic acid solution in a ratio of 0.5:19.5 to obtain a chitosan solution with a mass fraction of 2.5 wt%; Dissolve the MXene solution and double-distilled water in a ratio of 1:2000, and perform ultrasonic treatment for 20 minutes to obtain a well-dispersed Ti3C2T solution with a concentration of 0.05 wt%. x solution; According to different preset percentages, the well-dispersed Ti3C2T x solution was added dropwise to the chitosan solution to form a Ti3C2T x / CS composite solution.

5. The preparation method of the Ti3C2T x / CS coating material, characterized in that The pretreatment of the titanium sheet to introduce amino groups includes: Gradually polish the surface of the titanium sheet with sandpapers of different mesh numbers; After polishing, perform plasma treatment on the surface of the titanium sheet to introduce amino groups.

6. The preparation method of the Ti3C2T x / CS coating material, characterized in that, The Ti3C2T x / CS composite solution is coated on the surface of the pretreated titanium sheet by spin coating technology to form a Ti3C2T x / CS coating, Comprising: In the Ti3C2T x / CS composite solution, glutaraldehyde is added as a crosslinking agent to react with the amino groups introduced during the surface pretreatment of the titanium sheet and the amino groups in chitosan to form a crosslinked structure; The Ti3C2T x / CS composite solution containing a cross-linking agent was spin-coated on the surface of the pretreated titanium sheet; After coating, the titanium sheet was crosslinked at room temperature for 1 h and dried to form the Ti3C2T x / CS coating.

7. A Ti3C2T x / CS coating material, characterized in that Ti3C2T x The / CS coating material is obtained by the preparation method described in any one of claims 1 to 6.

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