Near-infrared light triggered antibacterial and antioxidant Ti-MXene bone implant material

Abstract

The invention relates to an antibacterial and antioxidant Ti-MXene bone implant material triggered by near-infrared light and a preparation method of the Ti-MXene bone implant material. The material is composed of a pure Ti substrate and a plurality of Ti3C2TX MXene coatings which are electrostatically self-adsorbed on the pure Ti substrate, and then is crosslinked and coated by gelatin. The multi-layer Ti3C2TX MXene is combined with the surface of a metal matrix, and has excellent biocompatibility and antibacterial and antioxidant effects. According to the coating, multiple layers of Ti < 3 > C < 2 > TX MXene are stripped from an MAX phase (Ti < 3 > Al < 2 >) through hydrochloric acid etching, then a Ti sheet is soaked in alkali liquor with dispersed MXene, and titanate and MXene are subjected to electrostatic self-bonding on the surface; and the combination is further enhanced through gelatin coating. The material can realize photo-thermal antibacterial ability under the irradiation of 808nm NIR with lower power, and has good antioxidant ability and osteoblast compatibility.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical materials, and in particular relates to a Ti-MXene bone implant material with near-infrared light-triggered antibacterial and antioxidant properties. Background Art

[0002] Bones are a vital part of the human connective tissue system. They not only provide mechanical stability for muscle attachment but also protect internal organs, playing an irreplaceable role in the body. Bone defects are common in clinical orthopedics, with causes ranging from mechanical damage to fractures. Consequently, the demand for developing functional implant metal materials for clinical applications is rapidly increasing.

[0003] Titanium and its alloys offer a promising material for bone implants due to their high strength-to-weight ratio, high elasticity, and excellent biocompatibility, preventing load transfer to bone. However, infections associated with conventional titanium alloy implants are increasingly recognized as a difficult global public health issue. Entering bacteria rapidly attach to the bioactive implant surface and form biofilms. Traditional antibiotic treatments are ineffective, leading to persistent and recurrent infections, tissue damage, and inflammatory responses. Consequently, bacterial biofilm formation and chronic inflammation are key pathological features of implant infections.

[0004] MXene, a novel class of transition metal carbides / nitrides / carbonitrides, is an emerging two-dimensional nanomaterial with an ultrathin structure and excellent physicochemical properties. In recent years, MXene has been used for rapid bacterial eradication via NIR-induced post-transmission thermodynamics (PTT) due to its large absorption area, strong absorption in the solar spectrum, and abundant free electron distribution. Due to its high photothermal conversion efficiency and high absorptivity in the near-infrared region, MXene has been explored and developed in biomedical applications due to its low toxicity, biodegradability, bioimaging, biosensing, and drug delivery. Furthermore, MXene can influence cell behavior in various ways, including cell adhesion, cell spreading, cell proliferation, cell migration, cell differentiation, and ultimately tissue repair.

[0005] The MAX phase (Ti3AlC2) was peeled off to form multilayer Ti3C2T by hydrochloric acid etching. XMXene, and then immersing the Ti sheet in an alkaline solution dispersed with MXene, the surface is electrostatically self-bonded between titanate and MXene, and then the bonding is further strengthened by gelatin coating, and the Ti-MXene bone implant material is prepared. The coating not only gives the Ti implant the ability to convert light into heat under near-infrared light conditions, but also has good photothermal antibacterial properties under 808nm near-infrared light irradiation, which can effectively inhibit the formation of bacterial biofilms. It also shows good biocompatibility and excellent antioxidant capacity. However, this concept has rarely been reported in the field of biomedical materials technology. In view of this, the present invention provides a Ti-MXene bone implant material with near-infrared light-triggered antibacterial and antioxidant properties. Summary of the Invention

[0006] This invention addresses the two main challenges of bacterial infection and chronic inflammation associated with titanium-based implants, a commonly used medical metal implant in orthopedic implants. By developing a near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material, the coating enhances the antibacterial and antioxidant properties of titanium-based implants, improving their biocompatibility. Furthermore, the coating's surface temperature rises from 25.3°C to 59.8°C upon 808nm NIR irradiation, demonstrating high photothermal conversion efficiency.

[0007] The MAX phase (Ti3AlC2) was peeled off to form multilayer Ti3C2T by hydrochloric acid etching. X MXene, then immersing the Ti sheet in an alkaline solution containing MXene, allows electrostatic self-bonding of titanate and MXene on the surface. This bonding is further strengthened by gelatin coating, resulting in a Ti-MXene bone implant material. This coating imparts excellent antibacterial properties to the implant, and the materials used are all non-toxic and have excellent antioxidant capacity. Overall, the implant can effectively reduce the risk of secondary infection after implantation in the human body and has good biocompatibility.

[0008] The present invention is specifically implemented through the following technical solutions:

[0009] 1. A near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material, characterized in that the bone implant material is composed of a pure Ti matrix and a multilayer Ti3C2T X The MXene coating is composed of a cross-linked gelatin coating. The coating is etched with hydrochloric acid to peel off the MAX phase (Ti3AlC2) to form a multilayer Ti3C2T X MXene, and then the Ti sheet is immersed in an alkaline solution dispersed with MXene, the surface is electrostatically self-bonded between titanate and MXene, and then further strengthened by gelatin coating. XThe bone implant material, which is bonded to the surface of a metal matrix, has stable photothermal conversion and antibacterial properties under 808nm near-infrared light irradiation, and exhibits good osteoblast biocompatibility and excellent antioxidant capacity. The method for preparing the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material comprises the following steps:

[0010] 1. Pretreatment: Using pure titanium as the substrate, polish each surface of the titanium sheet step by step with sandpaper of different mesh sizes (600#, 800#, 1000#) to make the surface smooth, and then use anhydrous ethanol and deionized water to ultrasonically clean the surface, and then dry it for later use;

[0011] 2. Preparation of multilayer Ti3C2TxMXene: A certain amount of MAX phase (Ti3AlC2) was slowly added to HF, and magnetic stirring was continued at a low speed. Then, the product was washed with deionized water and anhydrous ethanol three times each. The product was added to DMSO and magnetic stirring was continued. Then, the product was washed with deionized water and anhydrous ethanol three times each. The product was freeze-dried to obtain multilayer Ti3C2Tx MXene powder for use;

[0012] 3. Oscillation treatment: The multilayer Ti3C2Tx MXene powder obtained in step (2) is added to a potassium hydroxide solution and continuously oscillated at room temperature to obtain a MXene powder suspension with a smaller size;

[0013] 4. Ti sheet loaded with MXene: The Ti sheet obtained in step (1) was placed face up in a sample bottle, and then an equal amount of the MXene suspension obtained in step (3) was added. After a period of rest, the MXene was loaded on the Ti sheet by electrostatic self-adsorption, which was recorded as M.

[0014] 5. Gelatin coating: A gelatin solution of a certain concentration is prepared by heating in a water bath, and the M obtained in step (4) is placed in a well plate. An equal amount of gelatin solution is added to each well for soaking. The well plate is then taken out, washed with deionized water, and dried to obtain the near-infrared light-triggered antibacterial osteogenic bone implant material, which is denoted as M@G.

[0015] Furthermore, the mass of Ti3AlC2 in the step (2) is 4 to 10 g; and the concentration of hydrofluoric acid in the step (2) is 40 to 50%.

[0016] Furthermore, the oscillation speed in step (3) is 150-300 rpm and the oscillation time is 72-144 h.

[0017] Furthermore, the soaking time in step (4) is 8 to 12 hours.

[0018] Furthermore, the gelatin solution concentration in step (5) is 2 to 8 mg / ml; the water bath heating temperature in step (5) is 40 to 60° C., and the time is 10 to 25 minutes; and the soaking time in step (5) is 8 to 12 hours.

[0019] Beneficial effects

[0020] The beneficial effects of the present invention are:

[0021] (1) MXene's excellent near-infrared absorption ability improves the photothermal performance of the sample. Under near-infrared light irradiation, it can give the implant surface excellent antibacterial properties. This bone implant material has excellent antibacterial properties and has a good killing effect on Gram-positive bacteria (Staphylococcus aureus). It can give the implant surface excellent antibacterial properties, effectively inhibit the formation of bacterial biofilms, and reduce the risk of secondary wound infection.

[0022] (2) MXene has excellent biocompatibility and can effectively eliminate stress shielding after implantation into the human body. MXene itself has good antioxidant capacity and can remove reactive oxygen species produced by oxidative stress in tissues surrounding the implant, thereby reducing the inflammatory response of surrounding tissues in the early stage of implantation.

[0023] (3) The bone implant material has a simple structure, low cost, is easy to prepare, and has universal applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to make the purpose, technical solutions and beneficial effects of the present invention more clear, the present invention provides the following drawings for illustration:

[0025] Figure 1 This is a summary diagram of the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material in Example 1.

[0026] Figure 2 XRD images of multilayer MXene of titanium aluminum carbide and near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material in Example 1.

[0027] Figure 3 These are SEM images of the titanium material (Ti) after soaking in NaOH in Example 1 and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material (M@G).

[0028] Figure 4 The untreated titanium material (Ti) in Example 1 and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant materials (M, M@G) were exposed to near-infrared irradiation (λ = 808 nm, 0.6 W / cm 2 ) photothermal heating curve.

[0029] Figure 5 The antibacterial effects of the untreated titanium material (Ti) and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material (M, M@G) in Example 2 on Gram-positive bacteria (Staphylococcus aureus).

[0030] Figure 6 The biocompatibility of the untreated titanium material (Ti) and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material (M, M@G) in Example 2.

[0031] Figure 7 The overall antioxidant capacity of the untreated titanium material (Ti) and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material (M, M@G) in Example 2. DETAILED DESCRIPTION

[0032] Example 1

[0033] 6. Pretreatment: Using pure titanium as the substrate, polish each surface of the titanium sheet step by step with sandpaper of different mesh sizes (600#, 800#, 1000#) to make the surface smooth, and then use anhydrous ethanol and deionized water to ultrasonically clean the surface, and then dry it for later use;

[0034] 7. Preparation of multilayer Ti3C2Tx MXene: 5 g of MAX phase (Ti3AlC2) was slowly added to 40% HF with continuous magnetic stirring at low speed. The mixture was then washed three times with deionized water and three times with anhydrous ethanol. The product was then added to DMSO with continued magnetic stirring, and then washed three times with deionized water and three times with anhydrous ethanol. The product was freeze-dried to obtain multilayer Ti3C2Tx MXene powder for later use.

[0035] 8. Oscillation treatment: The multilayer Ti3C2Tx MXene powder obtained in step (2) was added to 8M potassium hydroxide solution and continuously oscillated at room temperature for 108 h to obtain a smaller MXene powder suspension;

[0036] 9. Ti sheet loaded with MXene: The Ti sheet obtained in step (1) was placed face up in a sample bottle, and then an equal amount of the MXene suspension obtained in step (3) was added. After standing for 12 hours, the MXene was loaded on the Ti sheet by electrostatic self-adsorption, which was recorded as M.

[0037] Coated gelatin: Heat to 50°C in a water bath for 20 minutes, prepare a 5 mg / mL gelatin solution, place the M obtained in step (4) in a well plate, add 1 mL of the gelatin solution to each well and soak for 12 hours, then take out, wash with deionized water, and dry to obtain the near-infrared light-triggered antibacterial osteogenic bone implant material, which is recorded as M@G.

[0038] Figure 1 This is a summary diagram of the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material in Example 1. Figure 2 XRD images of multilayer MXene of titanium aluminum carbide and near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material in Example 1. Figure 3 These are SEM images of the titanium material (Ti) after soaking in NaOH in Example 1 and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material (M@G). Figure 4 The untreated titanium material (Ti) in Example 1 and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant materials (M, M@G) were exposed to near-infrared irradiation (λ = 808 nm, 0.6 W / cm 2 ) photothermal heating curves, the temperature of the M and M@G groups increased significantly.

[0039] Example 2

[0040] Pretreatment: Using pure titanium as the substrate, the surfaces of the titanium sheet were polished step by step with sandpaper of different mesh sizes (600#, 800#, 1000#) to make the surface smooth, and the surface was ultrasonically cleaned with anhydrous ethanol and deionized water, and then dried for use;

[0041] Preparation of multilayer Ti3C2Tx MXene: 5 g of MAX phase (Ti3AlC2) was slowly added to 40% HF and continuously magnetically stirred at low speed. The mixture was then washed three times with deionized water and anhydrous ethanol. The product was added to DMSO and magnetically stirred again. The product was then washed three times with deionized water and anhydrous ethanol. The product was freeze-dried to obtain multilayer Ti3C2Tx MXene powder for later use.

[0042] Oscillation treatment: The multilayer Ti3C2Tx MXene powder obtained in step (2) was added to 8M potassium hydroxide solution and continuously oscillated at room temperature for 108 h to obtain a smaller MXene powder suspension;

[0043] Ti sheet loaded with MXene: The Ti sheet obtained in step (1) was placed face up in a sample bottle, and then an equal amount of the MXene suspension obtained in step (3) was added. After standing for 12 hours, MXene was loaded on the Ti sheet by electrostatic self-adsorption, which was recorded as M.

[0044] Coated gelatin: Heat to 50°C in a water bath for 20 minutes, prepare an 8 mg / mL gelatin solution, place the M obtained in step (4) in a well plate, add 1 mL of the gelatin solution to each well and soak for 12 hours, then take out, wash with deionized water, and dry to obtain the near-infrared light-triggered antibacterial osteogenic bone implant material, which is recorded as M@G.

[0045] Figure 5 The antibacterial effects of the untreated titanium material (Ti) and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant materials (M, M@G) in Example 2 on Gram-positive bacteria (Staphylococcus aureus) are shown. Without NIR irradiation, the Ti sample group had no inhibitory effect on Staphylococcus aureus. The antibacterial efficiency of M against Staphylococcus aureus reached 18.7%, and the antibacterial efficiency of M@G against Staphylococcus aureus reached 21.4%. Under NIR irradiation treatment (λ = 808 nm, 0.6 W / cm 2 ) The antibacterial efficiency of M against Staphylococcus aureus reached 99.2%, and the antibacterial efficiency of M against Staphylococcus aureus reached 100%. Figure 6 The biocompatibility of the untreated titanium material (Ti) and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material (M, M@G) in Example 2. Figure 7 The overall antioxidant capacity of the untreated titanium material (Ti) and the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material (M, M@G) in Example 2 is shown. The DPPH free radical scavenging rate of the Ti sheet is only 8.46%, which is much weaker than that of M and M@G. The scavenging rate of M@G is 74.1%.

[0046] Obviously, the above-mentioned Examples 1 and 2 of the present invention are merely examples for the purpose of clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will be able to make other variations or modifications based on the above description. It is not necessary and impossible to enumerate all embodiments here. However, these obvious variations or modifications derived from the spirit of the present invention remain within the scope of protection of the present invention.

Claims

1. A near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material, characterized in that: The bone implant material is composed of a pure Ti matrix and a multilayer Ti3C2T4 matrix adsorbed thereon by electrostatic self-adsorption. X The MXene coating is composed of a cross-linked gelatin coating. The coating is etched with hydrochloric acid to peel off the MAX phase (Ti3AlC2) to form a multilayer Ti3C2T X MXene, and then the Ti sheet is immersed in an alkaline solution dispersed with MXene, the surface is electrostatically self-bonded between titanate and MXene, and then further strengthened by gelatin coating. X The bone implant material, which is bonded to the surface of a metal matrix, has stable photothermal conversion and antibacterial properties under 808nm near-infrared light irradiation, and exhibits good osteoblast biocompatibility and excellent antioxidant capacity. The method for preparing the near-infrared light-triggered antibacterial and antioxidant Ti-MXene bone implant material comprises the following steps: (1) Pretreatment: Using pure titanium as the substrate, the surfaces of the titanium sheet were polished step by step with sandpaper of different mesh sizes (600#, 800#, 1000#) to make the surface smooth, and the surface was ultrasonically cleaned with anhydrous ethanol and deionized water, and then dried for use; (2) Preparation of multilayer Ti3C2Tx MXene: A certain amount of MAX phase (Ti3AlC2) was slowly added to HF, and magnetic stirring was continued at a low speed. Then, the product was washed with deionized water and anhydrous ethanol three times each. The product was added to DMSO and magnetic stirring was continued. Then, the product was washed with deionized water and anhydrous ethanol three times each. The product was freeze-dried to obtain multilayer Ti3C2Tx MXene powder for use; (3) Oscillation treatment: The multilayer Ti3C2Tx MXene powder obtained in step (2) is added to a potassium hydroxide solution and continuously oscillated at room temperature to obtain a MXene powder suspension with a smaller size; (4) Ti sheet loading MXene: The Ti sheet obtained in step (1) is placed face up in a sample bottle, and then an equal amount of the MXene suspension obtained in step (3) is added. After a period of rest, the MXene is loaded on the Ti sheet by electrostatic self-adsorption, which is recorded as M. (5) Gelatin coating: A gelatin solution of a certain concentration is prepared by heating in a water bath, and the M obtained in step (4) is placed in a well plate. An equal amount of gelatin solution is added to each well for soaking, and then the well is taken out, washed with deionized water, and dried to obtain the near-infrared light-triggered antibacterial osteogenic bone implant material, which is recorded as M@G.

2. The method for preparing the near-infrared light-triggered antibacterial osteogenic bone implant material according to claim 1, characterized in that: The mass of Ti3AlC2 in the step (2) is 4 to 10 g; the concentration of hydrofluoric acid in the step (2) is 40 to 50%.

3. The method for preparing the near-infrared light-triggered antibacterial osteogenic bone implant material according to claim 1, characterized in that: The concentration of potassium hydroxide in the step (3) is 2 to 8 M; the oscillation speed in the step (3) is 150 to 300 rpm, and the time is 72 to 144 hours.

4. The method for preparing the near-infrared light-triggered antibacterial osteogenic bone implant material according to claim 1, characterized in that: The soaking time in step (4) is 8 to 12 hours.

5. The method for preparing the near-infrared light-triggered antibacterial osteogenic bone implant material according to claim 1, characterized in that: The gelatin solution concentration in step (5) is 2-8 mg / ml; the water bath heating temperature in step (5) is 40-60° C. for 10-25 min; and the soaking time in step (5) is 8-12 h.

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