Mxene-based photothermal coupling composite film for bone repair and preparation method thereof

Abstract

This invention belongs to the field of biological engineering technology, specifically relating to an MXene-based photothermal coupling composite film for bone repair and its preparation method; comprising MXene, type I collagen, and gelatin solution, obtained by sequential bridging and cross-linking with FeCl3 solution; wherein the mass ratio of MXene to type I collagen is (3-9):(1-7), and gelatin accounts for 3.6%-10.4% of the final composite material mass; the preparation method includes: ultrasonically dispersing MXene and mixing it with gelatin solution, then compounding it with type I collagen solution, vacuum filtering and drying to form a matrix film, and finally cross-linking it by impregnation with FeCl3 solution; this film has mechanical properties matching natural bone tissue, good biocompatibility, and high-efficiency photothermal conversion capability under near-infrared light irradiation, and is suitable for bone defect repair and photothermal synergistic therapy.

Description

Technical Field

[0001] This invention relates to the field of biological engineering technology, and in particular to MXene-based photothermal coupling composite films for bone repair and their preparation methods. Background Technology

[0002] Artificial bone substitutes have attracted widespread attention due to their advantages such as wide availability, highly customizable shape and size, mass production capability, and lack of immune rejection risk. Among them, titanium-based metal materials are widely used as artificial bone substitutes because of their bone-like tissue structure, high mechanical properties, and excellent biocompatibility. However, they suffer from problems such as low bioactivity, lack of bone induction capacity, limited bone regeneration effect, and poor corrosion resistance. In particular, titanium easily dissolves into the body after corrosion, hindering bone healing and exacerbating the release of inflammatory cytokines, leading to chronic inflammation and implant loosening. In addition, the mechanical strength of titanium-based metal materials is mismatched with that of bone tissue, resulting in insufficient mechanical properties and difficulty in withstanding high loads, which limits their widespread application in bone defect repair.

[0003] In recent years, titanium carbide MXene (Ti3C2T) has been used in research and development. x As a novel titanium-based two-dimensional nanomaterial, MXene (Ti3C2T) exhibits excellent mechanical strength, chemical stability, biocompatibility, and photothermal conversion properties, showing broad application prospects in biomedical fields such as biosensing, drug delivery, tumor therapy, and tissue engineering. For example, Zhang et al. discovered that MXene (Ti3C2T)... x After implantation into subcutaneous and cranial defects in rats, the composite membrane exhibited good biocompatibility, osteoinductive properties, and bone regeneration activity, without significant inflammation or toxic side effects. It was able to promote osteogenic differentiation of pre-osteoblasts in the early stages. Furthermore, MXene exhibits strong absorption properties in the near-infrared region, efficiently converting light energy into heat energy. This wavelength of light has good penetrability into biological tissues, allowing its photothermal effect to reach deep tissue layers. Appropriate photothermal stimulation not only exerts antibacterial effects but also directly promotes the metabolic activity of osteoblasts, accelerating bone repair. Therefore, the key problem this invention aims to solve is how to combine MXene with bone repair materials, optimizing its mechanical properties and compatibility with bone tissue, and further synergistically utilizing its photothermal effect to enhance bone regeneration capacity. Summary of the Invention

[0004] The purpose of this invention is to provide an MXene-based photothermal coupling composite film for bone repair and its preparation method. This film is achieved through a specific composite of MXene, type I collagen, and gelatin, and Fe... 3+ Cross-linking was used to construct an organic-inorganic hybrid material that combines excellent mechanical properties, bioactivity, and efficient near-infrared photothermal response, which can be used for bone defect repair and to achieve photothermal synergistic therapy. This solves the problems mentioned in the background art.

[0005] The technical solution adopted in this invention is as follows: an MXene-based photothermal coupling composite film for bone repair, comprising MXene, type I collagen and gelatin solution, is prepared by sequential bridging and crosslinking treatment with FeCl3 solution; the mass ratio of MXene to type I collagen is (3-9):(1-7), and gelatin accounts for 3.6%-10.4% of the mass of the final composite material.

[0006] Preferably, the MXene is a two-dimensional layered material Ti3C2T. X .

[0007] Preferably, the mass ratio of MXene to type I collagen is 6:4 (i.e., 3:2). At this ratio, the reinforcing effect of MXene and the binding effect of type I collagen and gelatin achieve the best synergistic balance, resulting in the optimal overall performance of the composite film.

[0008] Furthermore, a method for preparing an MXene-based photothermal coupling composite film for bone repair is proposed, comprising the following steps:

[0009] (1) Preparation of MXene dispersion: MXene was dispersed in water by ultrasonication at 100W for 20 minutes to obtain a 25mg / ml MXene suspension;

[0010] (2) Preparation of MXene / gelatin premix: Mix 8 mg / ml gelatin with the 25 mg / ml MXene suspension obtained in step (1) at a volume ratio of (0.9-2.6):(2.1-6.4), stir magnetically at 300-500 rpm for 30-60 min, mix evenly and then sonicate to obtain a 20 mg / ml MXene / gelatin solution;

[0011] (3) Preparation of composite slurry: The 20 mg / ml MXene / gelatin solution obtained in step (2) and the 20 mg / ml type I collagen solution are mixed at a volume ratio of (3-9):(1-7), and magnetically stirred at 300-500 rpm for 30-60 min to obtain a composite slurry with rheological shear thinning behavior.

[0012] (4) Primary film formation: The composite slurry obtained in step (3) is vacuum filtered for 40 minutes and then dried for 15 minutes to obtain the primary film;

[0013] (5) Post-crosslinking treatment: The nascent film obtained in step (4) is soaked in 10 mg / ml FeCl3 solution at room temperature for 30 minutes, then rinsed with deionized water 3 times for 5 minutes each time, and finally dried at room temperature (temperature 20-25℃, humidity 30%-50%RH) to obtain the MXene-based composite film material.

[0014] The beneficial effects of the present invention are as follows: (1) The present invention uses a "sequential bridging" process to sequentially combine MXene, gelatin solution and type I collagen, and then uses Fe 3+ Ionic crosslinking constructs a stable organic-inorganic multi-level network structure, giving the film strong toughness and tear resistance.

[0015] (2) The mechanical properties of the film, such as hardness and elastic modulus, are highly matched with those of natural bone tissue, which can provide effective and durable mechanical support for bone defect areas.

[0016] (3) The film exhibits efficient photothermal conversion capability under 808nm near-infrared laser irradiation and can be rapidly heated to above 60℃. This photothermal effect can not only be used for controllable thermotherapy, but also synergistically promote osteoblast activity.

[0017] (4) The membrane retains the inherent biocompatibility of type I collagen, which can effectively promote the adhesion and regeneration of osteoblasts.

[0018] (5) The preparation method described is mild, has controllable parameters and good repeatability. The performance of the thin film can be effectively controlled by adjusting the proportion of solid components and process conditions, making it suitable for widespread application. Attached Figure Description

[0019] Figure 1 This is an appearance diagram of the photothermal coupling MXene-based composite thin film material of the present invention.

[0020] Figure 2 This is a hardness diagram of the photothermal coupling MXene-based composite thin film material of the present invention.

[0021] Figure 3 This is a diagram showing the elastic modulus of the photothermal coupling MXene-based composite thin film material of this invention.

[0022] Figure 4 This is a load-displacement curve of the photothermal coupling MXene-based composite thin film material of the present invention.

[0023] Figure 5 This is the temperature change curve of the photothermal coupled MXene-based composite thin film material of the present invention under 808nm laser irradiation.

[0024] Figure 6 This is an infrared thermal image of the photothermal coupled MXene-based composite thin film material of the present invention under 808nm laser irradiation.

[0025] Figure 7 The photothermal coupled MXene-based composite thin film material of the present invention is shown in the SEM image. Figure 1 .

[0026] Figure 8The photothermal coupled MXene-based composite thin film material of the present invention is shown in the SEM image. Figure 2 .

[0027] Figure 9 The photothermal coupled MXene-based composite thin film material of the present invention is shown in the SEM image. Figure 3 .

[0028] Figure 10 The photothermal coupled MXene-based composite thin film material of the present invention is shown in the SEM image. Figure 4 . Detailed Implementation

[0029] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and preferred embodiments.

[0030] Example 1: MXene was dispersed in water by sonication at 100W for 20 minutes to obtain a 25 mg / ml MXene suspension. 1.7 ml of 8 mg / ml gelatin and the above 4.3 ml of 25 mg / ml MXene suspension were magnetically stirred at 300-500 rpm for 30-60 minutes. After uniform mixing, the mixture was sonicated to obtain a 20 mg / ml MXene / gelatin solution.

[0031] The above 6 ml of 20 mg / ml MXene / gelatin solution and 4 ml of 20 mg / ml type I collagen solution were magnetically stirred at 300-500 rpm for 30-60 min to obtain a composite slurry with rheological shear thinning behavior.

[0032] 10 ml of composite slurry was vacuum filtered for 40 minutes and then dried for 15 minutes to obtain a nascent film. The nascent film was then immersed in 10 ml of a 10 mg / ml FeCl3 solution at room temperature for 30 minutes, followed by rinsing three times with deionized water (to remove residual ferric chloride solution from the surface), 5 minutes each time. Finally, it was dried at room temperature to obtain the MXene-based composite film material with photothermal coupling function (e.g., ...) of this embodiment. Figure 8 (As shown). The mass ratio of MXene to type I collagen is 6:4 (i.e., 3:2). MXene accounts for 53.5% of the weight of the final composite material, gelatin accounts for 6.8% of the weight of the final composite material, and type I collagen accounts for 39.7% of the weight of the final composite material.

[0033] Comparative Example 1: The only difference between Comparative Example 1 and Example 1 is that MXene is not added. The remaining preparation steps and process parameters are exactly the same as in Example 1, yielding a pure collagen-gelatin composite film (e.g., ...). Figure 10 (As shown).

[0034] Comparative Example 2: The only difference between Comparative Example 2 and Example 1 is that type I collagen and gelatin are not added; only MXene is added. The remaining preparation steps and process parameters are exactly the same as in Example 1, resulting in a pure MXene film.

[0035] Example 2: MXene was dispersed in water by ultrasonication at 100W for 20 minutes to obtain a 25 mg / ml MXene suspension. 0.9 ml of 8 mg / ml gelatin and the above 2.1 ml of the 25 mg / ml MXene suspension were magnetically stirred at 300-500 rpm for 30-60 minutes. After uniform mixing, the mixture was ultrasonically vibrated to obtain a 20 mg / ml MXene / gelatin solution.

[0036] The above 3 ml of 20 mg / ml MXene / gelatin solution and 7 ml of 20 mg / ml type I collagen solution were magnetically stirred at 300-500 rpm for 30-60 min to obtain a composite slurry with rheological shear thinning behavior.

[0037] 10 ml of composite slurry was vacuum filtered for 40 minutes and then dried for 15 minutes to obtain a nascent film. The nascent film was then immersed in 10 ml of a 10 mg / ml FeCl3 solution at room temperature for 30 minutes, rinsed three times with deionized water for 5 minutes each time, and finally dried at room temperature to obtain the MXene-based composite film material with photothermal coupling function (e.g., ...) of this embodiment. Figure 7 (As shown). The mass ratio of MXene to type I collagen is 3:7. MXene accounts for 26.3% of the weight of the final composite material, gelatin accounts for 3.6% of the weight of the final composite material, and type I collagen accounts for 70.1% of the weight of the final composite material.

[0038] Example 3: MXene was dispersed in water by ultrasonication at 100W for 20 minutes to obtain a 25 mg / ml MXene suspension. 2.6 ml of 8 mg / ml gelatin and the above 6.4 ml of the 25 mg / ml MXene suspension were magnetically stirred at 300-500 rpm for 30-60 minutes. After uniform mixing, the mixture was ultrasonically vibrated to obtain a 20 mg / ml MXene / gelatin solution.

[0039] The above 9 ml of 20 mg / ml MXene / gelatin solution and 1 ml of 20 mg / ml type I collagen solution were magnetically stirred at 300-500 rpm for 30-60 min to obtain a composite slurry with rheological shear thinning behavior.

[0040] 10 ml of the composite slurry was vacuum filtered for 40 minutes and then dried for 15 minutes to obtain the nascent film. The nascent film was then immersed in 10 ml of a 10 mg / ml FeCl3 solution at room temperature for 30 minutes, rinsed three times with deionized water for 5 minutes each time, and finally dried at room temperature to obtain the MXene-based composite film material with photothermal coupling function in this embodiment (e.g., ...). Figure 9 (As shown). The mass ratio of MXene to type I collagen is 9:1. MXene accounts for 79.7% of the weight of the final composite material, gelatin accounts for 10.4% of the weight of the final composite material, and type I collagen accounts for 9.9% of the weight of the final composite material.

[0041] Example Performance Testing and Result Analysis

[0042] 1. Selection of the optimal implementation method

[0043] By comparing the mechanical properties of Examples 1, 2, and 3, it was found that the mechanical properties of the composite material first increased and then decreased with the increase of MXene content. When the mass ratio of MXene to type I collagen was 3:7, the content of biopolymers (type I collagen + gelatin) was high, and the reinforcing effect of the MXene sheets was not fully utilized, resulting in insufficient overall film strength. When the mass ratio was increased to 6:4, the rigid reinforcing effect of MXene and the flexible bonding effect of biopolymers reached the best balance, and the mechanical properties reached their peak. At the same time, the photothermal properties could meet the requirements of most application scenarios. When the mass ratio was further increased to 9:1, the content of biopolymers was too low, and it was impossible to effectively bond the MXene sheets, resulting in a large number of pores and defects inside the film. The mechanical strength was significantly reduced, and the problem of easy oxidation of pure MXene films gradually became prominent. Therefore, this application uses Example 1 as the optimal embodiment for discussion.

[0044] 2. Microstructure characterization

[0045] like Figure 1 As shown, Figure 8 As shown, the photothermal coupled MXene-based composite thin film material prepared in Embodiment 1 of the present invention has a smooth surface, and the MXene sheet structure, type I collagen, and gelatin are evenly distributed without obvious agglomeration. The overall structure of the film is complete and dense, which lays the foundation for its excellent mechanical and photothermal properties.

[0046] 3. Mechanical property testing

[0047] Hardness test: such as Figure 2 As shown, the composite film prepared in Example 1 has a significantly higher hardness than that of Example 2, Example 3, Control Example 1, and Control Example 2.

[0048] Elastic modulus test: such as Figure 3As shown, the composite film prepared in Example 1 has a better elastic modulus than the other groups, exhibiting better resistance to deformation.

[0049] Mechanical strength test: such as Figure 4 As shown, the composite film prepared in Example 1 has the highest mechanical strength, verifying that MXene and type I collagen have the best synergistic enhancement effect at a mass ratio of 6:4.

[0050] 4. Photothermal performance test

[0051] like Figure 5 and Figure 6 As shown, the photothermal coupled MXene-based composite thin film material prepared in Embodiment 1 of the present invention can rapidly rise to over 60°C within 30 seconds under 808nm laser irradiation, exhibiting a fast heating rate and high maximum temperature, demonstrating excellent photothermal conversion efficiency and photothermal response performance, and can meet the temperature and response speed requirements of application scenarios such as photothermal therapy and photothermal drive.

[0052] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. MXene-based photothermal coupling composite film for bone repair, characterized in that, It consists of MXene, type I collagen and gelatin solution, which are prepared by sequential bridging and ion crosslinking with FeCl3 solution; wherein the mass ratio of MXene to type I collagen is (3-9):(1-7), and gelatin accounts for 3.6%-10.4% of the mass of the final composite material.

2. The MXene-based photothermal coupling composite film for bone repair according to claim 1, characterized in that, The MXene is a two-dimensional layered material Ti3C2T X .

3. The MXene-based photothermal coupling composite film for bone repair according to claim 1, characterized in that, The mass ratio of MXene to type I collagen is 6:

4.

4. The MXene-based photothermal coupling composite film for bone repair according to claim 1, wherein, The composite film exhibits rheological shear thinning behavior.

5. A method for preparing the MXene-based photothermal coupling composite film for bone repair according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Preparation of MXene dispersion: MXene was dispersed in water by ultrasonication at 100W for 20 minutes to obtain a 25mg / ml MXene suspension; (2) Preparation of MXene / gelatin premix: 8mg / ml gelatin solution was mixed with the 25mg / ml MXene suspension obtained in step (1) at a volume ratio of (0.9-2.6):(2.1-6.4), and after magnetic stirring and uniform mixing, ultrasonic vibration was performed to obtain a 20mg / ml MXene / gelatin solution; (3) Preparation of composite slurry: The 20mg / ml MXene / gelatin solution obtained in step (2) was mixed with 20mg / ml Type I collagen solution was mixed at a volume ratio of (3-9):(1-7) and magnetically stirred to obtain a composite slurry with rheological shear thinning behavior; (4) Primary film forming: the composite slurry obtained in step (3) was vacuum filtered for 40 minutes and then dried for 15 minutes to obtain a primary film; (5) Post-crosslinking treatment: the primary film obtained in step (4) was soaked in 10 mg / ml FeCl3 solution at room temperature for 30 minutes, then rinsed with deionized water, and finally dried at room temperature to obtain the MXene-based composite film material.

6. The production method according to claim 5, wherein In step (2), the magnetic stirring speed is 300-500 rpm and the duration is 30-60 min.

7. The preparation method according to claim 5, characterized in that, In step (3), the magnetic stirring speed is 300-500 rpm and the duration is 30-60 min.

8. The preparation method according to claim 5, characterized in that, In step (5), the rinsing with deionized water is performed 3 times, each time for 5 minutes.

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