L-arginine functionalized TiO 2-x Method for preparing MXene composite nanomaterial and application thereof

Abstract

This invention relates to the field of biomedical antibacterial nanomaterials technology, specifically to an L-arginine-functionalized TiO2. 2‑x Preparation method and application of MXene composite nanomaterials. The preparation method of this invention includes: preparing Ti3C2T using the LiF / HCl in-situ etching method. x MXene dispersion; Ti3C2T x MXene is mixed with glycerol and then subjected to a hydrothermal reaction, forming TiO2 in situ on the MXene surface. 2‑x TiO 2‑x -MXene; further functionalization with L-arginine yields LA@TiO 2‑x -MXene composite nanomaterials. The materials of this invention exhibit excellent near-infrared photothermal response and ultrasonic response acoustic dynamic activity, and can generate NO and ONOO under ultrasonic stimulation. ‑ The materials of this invention can be used to prepare anti-MRSA antibacterial materials, anti-biofilm materials, antibacterial dressings, or antibacterial coatings for medical device surfaces, exhibiting synergistic antibacterial effects of photothermal, acoustic dynamic, and active nitrogen species.

Description

Technical Field

[0001] This invention relates to the field of biomedical antibacterial nanomaterials technology, and more specifically, to an L-arginine-functionalized TiO₂. 2-x -MXene composite nanomaterials, their preparation methods, and applications. Background Technology

[0002] Bacterial infections are a significant challenge in clinical medicine and public health. While the discovery and use of antibiotics have significantly reduced mortality rates associated with bacterial infections, the long-term and widespread use of antibiotics has led to increasingly prominent issues of bacterial resistance. The emergence of methicillin-resistant Staphylococcus aureus (MRSA) and other drug-resistant bacteria poses a serious challenge to traditional antibiotic treatment. Therefore, developing novel antimicrobial materials with multiple antimicrobial mechanisms that do not rely on traditional antibiotics has become an important research direction in the field of anti-infection.

[0003] Nanomaterials, due to their size effect, surface modifiability, and stimulus-responsive properties, show great potential in the field of antibacterial applications. By controlling the composition, structure, and surface functions of nanomaterials, they can be endowed with various functions such as photothermal, acoustic-dynamic, reactive oxygen species generation, and microenvironment regulation, thereby achieving effective inhibition or removal of bacteria and their biofilms. Among them, MXene materials have strong near-infrared absorption capacity and good photothermal conversion performance, showing promise for photothermal antibacterial applications. However, single MXene materials mainly rely on photothermal effects to exert their antibacterial effects, resulting in a relatively simple antibacterial mechanism, and their ability to remove bacteria and biofilms in complex infectious environments still needs improvement.

[0004] Titanium dioxide-based materials possess certain acoustic-dynamic activity, generating reactive oxygen species under ultrasonic stimulation, thereby causing oxidative damage to bacteria. Combining TiO2 with MXene holds promise for simultaneously introducing photothermal and acoustic-dynamic effects, constructing a multi-mode synergistic antibacterial system. However, existing TiO2 / MXene composites still suffer from challenges in preparation, including stringent reaction conditions, susceptibility to over-oxidation of MXene, and the difficulty in simultaneously achieving both acoustic-dynamic activity and photothermal performance. Therefore, the challenge lies in how to construct a TiO2 composite with good ultrasonic response activity while maintaining the photothermal properties of MXene. 2-x The MXene composite structure is a problem that needs to be solved for the further application of this type of antibacterial material.

[0005] In recent years, gaseous signaling molecules such as nitric oxide (NO) have been used in the design of novel antibacterial materials due to their strong diffusion and biomembrane penetration capabilities. NO can disrupt bacterial membrane structures, interfere with bacterial metabolism, and further react with reactive oxygen species to generate peroxynitrite (ONO). -L-arginine, as a precursor to NO production, possesses excellent biocompatibility and functionalization potential. Introducing it into a sonodynamically active nanoplatform holds promise for generating NO or related reactive nitrogen species under ultrasonic stimulation.

[0006] Based on this, a novel approach combining near-infrared photothermal response, ultrasonic acoustodynamic activity, and NO / ONOO ratio is constructed. - The ability to generate MXene-based composite nanomaterials is of great significance for improving the killing efficiency of drug-resistant bacteria and the removal effect of biofilms. Summary of the Invention

[0007] This invention provides an L-arginine-functionalized TiO2 2-x Preparation method of MXene composite nanomaterials to solve the existing TiO2 problem 2-x The preparation conditions for MXene composite materials are harsh, MXene is prone to over-oxidation, it is difficult to balance acoustic and photothermal properties, and the single antibacterial mechanism is insufficient to clear drug-resistant bacteria and biofilms.

[0008] According to one aspect of the present invention, an L-arginine-functionalized TiO2 is provided. 2-x The preparation method of MXene composite nanomaterials includes the following steps:

[0009] Step 1: Prepare Ti3C2T by in-situ etching with LiF / HCl x MXene;

[0010] Step 2: Perform hydrothermal treatment in a water-organic mixed solvent system to form TiO2 in situ on the MXene surface. 2-x TiO 2-x -MXene composite materials;

[0011] Step 3: Introduce L-arginine for functionalization modification to obtain LA@TiO 2-x -MXene composite nanomaterials.

[0012] Based on the above scheme, step 1 preferably includes:

[0013] Step 11: Place LiF in a 50mL polytetrafluoroethylene liner, add HCl and ultrapure water, dissolve at 30℃ for 10min, add MAX(Ti3AlC2) in multiple portions, then heat to 45℃, react for 72h and then remove.

[0014] Step 12: Centrifuge 3 times at 10000 rpm × 1 min using 1M HCl, then centrifuge with ultrapure water until the upper liquid turns black. Add 40 mL of ultrapure water to disperse the lower precipitate and vortex for 20 min.

[0015] Step 13: Transfer the liquid obtained in Step 12 to a glass bottle, purge with nitrogen for 15 min, sonicate for 30 min to separate the multiple layers of MXene, remove and centrifuge at 3000 rpm for 30 min to obtain Ti3C2T. x Dispersion.

[0016] Based on the above scheme, the preferred embodiment is that in step 11, the LiF is 1.60g, the HCl is 15mL, and in step 12, the ultrapure water is 5mL.

[0017] Based on the above scheme, step 2 preferably includes:

[0018] Step 21: Mix the Ti3C2Tx dispersion prepared in Step 1 with glycerol until homogeneous, then sonicate, transfer to the inner liner of the reactor, and use the reactor to carry out the hydrothermal reaction.

[0019] Step 22: After the reactor cools down, remove the mixture from the inner liner of the reactor and store it in a 4°C refrigerator. Take 1 mL of the mixture, add 3-4 mL of ethanol to precipitate the product, and centrifuge repeatedly at differential speed to separate excess glycerol and obtain TiO2. 2-x -MXene dispersion.

[0020] Based on the above scheme, step 21 preferably includes preparing 3 mL of 12 mg / mL Ti3C2Tx dispersion and mixing it evenly with an equal amount of glycerol; after mixing the Ti3C2Tx dispersion and an equal amount of glycerol evenly, sonicating for 5 min, and then transferring it into the inner liner of the reaction vessel.

[0021] Based on the above scheme, the preferred option is that the hydrothermal reaction temperature in the reactor in step 21 is 150℃ and the reaction time is 15h.

[0022] Based on the above scheme, step 3 specifically involves adding 1 mL of the hydrothermally obtained TiO2 dispersion to the bottom flask. 2-x LA@TiO2-x-MXene was added, followed by 2 mL of L-arginine solution with a concentration of 120 mg / mL and stirred for 1 h. After stirring, 6 mL of ultrapure water was added and the mixture was centrifuged multiple times at different speeds to obtain the LA@TiO2-x-MXene dispersion.

[0023] This invention also provides an L-arginine-functionalized TiO2 2-x The application of MXene composite nanomaterials, which possess near-infrared photothermal response properties and ultrasonic response acoustic dynamic activity, and are capable of generating NO and / or ONOO under ultrasonic stimulation.- Active species.

[0024] This invention also provides an L-arginine-functionalized TiO2 2-x -MXene composite nanomaterials are used to inhibit, disrupt, or remove MRSA biofilms.

[0025] This invention also provides an L-arginine-functionalized TiO2 2-x The application of MXene composite nanomaterials, under near-infrared light irradiation and / or ultrasonic stimulation, utilizes photothermal effects, acoustic dynamic effects, and NO and / or ONOO. - The synergistic effect of active species enhances the antibacterial effect.

[0026] A LA@TiO3 of the present invention 2-x The preparation method of MXene involves growing oxygen-deficient TiO on the MXene surface using an in-situ hydrothermal method. 2-x It retains the near-infrared photothermal conversion performance of MXene and endows it with ultrasonic response acoustic dynamic activity, thus realizing photothermal-acoustic dual-mode synergistic antibacterial activity.

[0027] Meanwhile, this invention introduces L-arginine as a NO precursor, which can controllably release NO under ultrasonic stimulation and ROS action. The NO reacts with ROS generated by acoustic dynamics to generate highly active ONOO. - This further enhanced the oxidative damage resistance and constructed a photothermal-acoustic dynamic NO / ONOO - Triple synergistic antibacterial mechanism.

[0028] The preparation method of this invention is mild, and the TiO₂ content can be adjusted by controlling the hydrothermal parameters. 2-x The concentration and morphology of oxygen defects were controlled, avoiding excessive oxidation of MXene and ensuring the structural stability and functional integrity of the composite material.

[0029] The composite nanomaterials of this invention have significant killing and removal effects on drug-resistant bacteria such as MRSA and their biofilms, and have important application value in the field of biomedical anti-infection. Attached Figure Description

[0030] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. In the drawings:

[0031] Figure 1 In Embodiment 1 of the present invention, MXene and TiO 2-x -MXene、LA@TiO2-x -Scanning transmission electron microscopy image of MXene nanomaterials.

[0032] Figure 2a The same concentrations of MXene and TiO2 were used in Example 1 of this invention. 2-x -MXene、LA@TiO 2-x -Graphic heating effect curve of MXene.

[0033] Figure 2b The TiO2 produced by the hydrothermal reaction in Example 1 of this invention 2-x -MXene UV-Redshift diagram.

[0034] Figure 3 In Embodiment 1 of the present invention, MXene and TiO 2-x -MXene、LA@TiO 2-x ESR spectra of singlet oxygen detection by MXene.

[0035] Figure 4a The TiO in Embodiment 1 of the present invention 2-x -MXene NO detection spectrum;

[0036] Figure 4b LA@TiO in Embodiment 1 of the present invention 2-x -MXene NO detection spectrum;

[0037] Figure 4c In Embodiment 1 of the present invention, MXene and TiO 2-x -MXene、LA@TiO 2-x -MXene's ONOO - Detection spectrum.

[0038] Figure 5 LA@TiO in Embodiment 1 of the present invention 2-x - MXene fibroblast cell survival rate diagram.

[0039] Figure 6a The MXene and TiO provided in Embodiment 1 of the present invention 2-x -MXene、LA@TiO 2-x - Plate inhibition experiment diagram of MXene nanomaterials against methicillin-resistant Staphylococcus aureus (MRSA);

[0040] Figure 6b The MXene and TiO provided in Embodiment 1 of the present invention 2-x -MXene、LA@TiO 2-x -Statistical chart of plate inhibition of MXene nanomaterials against methicillin-resistant Staphylococcus aureus (MRSA);

[0041] Figure 7a The MXene and TiO provided in Embodiment 1 of the present invention 2-x -MXene、LA@TiO 2-x Image of residual MRSA biofilm CV staining under the elimination effect of MXene nanomaterials;

[0042] Figure 7b The MXene and TiO provided in Embodiment 1 of the present invention 2-x -MXene、LA@TiO 2-x - Relative content of residual MRSA biofilm under the action of MXene nanomaterials. Detailed Implementation

[0043] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[0044] It should be understood that, when used in this specification and the appended claims, the term "comprising" indicates the presence of a descriptive feature, integral, step, operation, element, and / or component, but does not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components, and / or sets.

[0045] It should be understood that, unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing particular embodiments only and are not intended to limit the scope of the invention.

[0046] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0047] The following examples illustrate the sources of raw materials: Lithium fluoride (LiF) is sourced from Aladdin.

[0048] Hydrochloric acid (HCl) and anhydrous ethanol glycerol are traditional Chinese medicines.

[0049] MAX (Ti3AlC2) is produced by Shandong Xiyan.

[0050] L-arginine, p-aminobenzenesulfonic acid, and naphthylethylenediamine hydrochloride are the source materials.

[0051] Anticoagulated rabbit whole blood was purchased from Giant Rock Bio.

[0052] Crystal Violet (CV) was purchased from Seville Bio.

[0053] Example 1

[0054] A LA@TiO3 of the present invention 2-x The preparation method of MXene nanomaterials, with specific steps as follows:

[0055] (1) Preparation of MXene: 1.60g LiF was placed in a 50mL polytetrafluoroethylene liner, 15mL HCl and 5mL ultrapure water were added, and the mixture was dissolved at 30℃ for 10min. 1.0g MAX (Ti3AlC2) was added in several portions, and then the temperature was raised to 45℃. After reacting for 72h, the mixture was taken out and centrifuged at 10000rpm×1min. Then, it was centrifuged three times at the same speed with 1M HCl. Then, it was centrifuged again with ultrapure water until the upper liquid turned black. 40mL ultrapure water was added to disperse the lower precipitate and vortexed for 20min. Then, it was transferred to a glass bottle and nitrogen gas was purged for 15min. The mixture was sonicated for 30min to separate the multilayer MXene. The mixture was then taken out and centrifuged at 3000rpm×30min to obtain Ti3C2T x Dispersion.

[0056] (2) TiO 2-x Preparation of MXene: Prepare 3 mL of 12 mg / mL Ti3C2T x The dispersion was mixed thoroughly with an equal volume of glycerol and sonicated for 5 minutes. The mixture was then transferred to the inner liner of a reactor and subjected to a hydrothermal reaction at 150°C for 15 hours. After the reactor cooled, the mixture was removed from the inner liner and stored in a 4°C refrigerator. 1 mL of the mixture was taken and 3-4 mL of ethanol was added to precipitate the product. Excess glycerol was removed by repeated differential centrifugation to obtain TiO₂. 2-x -MXene dispersion.

[0057] (3) LA@TiO 2-x Preparation of MXene: Prepare a 120 mg / mL L-arginine aqueous solution. First, add 1 mL of the hydrothermal dispersion TiO2 to a round-bottom flask. 2-x MXene was then added, followed by 2 mL of the above L-arginine solution and stirred. After stirring for 1 hour, 6 mL of ultrapure water was added, and the mixture was centrifuged multiple times at differential speed to obtain LA@TiO. 2-x -MXene dispersion.

[0058] MXene and TiO from Example 1 2-x -MXene、LA@TiO 2-x The morphological observation of MXene under scanning transmission electron microscopy is performed as follows:

[0059] First, the prepared liquid samples of the three nanomaterials were ultrasonically dispersed into a uniform suspension. The powder solution was then placed on a copper mesh surface using a dropper method and dried. It was ensured that the powder sample was uniformly distributed on the copper mesh and free of contaminants. The copper mesh was gently blown with a bulb syringe to prevent any loose powder from falling off. A suitable field of view was then found under a scanning transmission electron microscope (STEM) for imaging. The STEM results are attached. Figure 1 As shown.

[0060] According to the appendix Figure 1 Scanning transmission electron microscopy (STEM) results show that, as can be seen from the figure, after hydrothermal treatment on MXene nanosheets, crystalline structures with morphologies of fine needles and round strips grow on their surface. This is due to the oxidation of MXene to produce TiO2. Before and after L-arginine loading, STEM analysis and comparison showed no significant changes in the appearance and morphology.

[0061] The same concentrations of MXene and TiO2 from Example 1 were used. 2-x -MXene、LA@TiO 2-x MXene was tested for its photothermal heating capability using the following method:

[0062] Prepare MXene and TiO2 at the same concentration 2-x -MXene、LA@TiO 2-x -MXene sample aqueous solution, using the same power 808nm (1.5W / cm) 2 The solution was irradiated with a laser, and the temperature was recorded every 10 seconds. The change in solution temperature with irradiation time was tested under the same laser power and material concentration.

[0063] like Figure 2a TiO3 of the three materials 2-x -MXene、LA@TiO 2-x The photothermal performance of MXene showed a temperature rise of 57.3℃, while that of MXene, exhibiting poorer photothermal performance, was 52.8℃. These experimental results indicate that the addition of L-arginine does not affect the photothermal performance of the material, and that MXene exhibits inferior photothermal performance under the same conditions. Figure 2b UV analysis of materials with the same concentration revealed that TiO2 was present after hydrothermal treatment. 2-x -MXene materials exhibit a significant UV-to-red shift, and TiO2 shows a similar shift after the UV-to-red shift. 2-x The highest absorption peak of MXene is similar to the emission wavelength of an 808nm laser, and its ability to absorb 808nm laser light is stronger than that of MXene, which is why it has better photothermal effects.

[0064] MXene and TiO from Example 1 2-x -MXene、LA@TiO 2-xMXene was used to perform acoustic-dynamic performance testing, and the testing method is as follows: ESR electron spin resonance detection ROS

[0065] Figure 3 The graph shows the ESR results of this invention, indicating that TiO2... 2-x -MXene、LA@TiO 2-x -MXene possesses the ability to generate singlet oxygen radicals under ultrasonic irradiation, LA@TiO 2-x -MXene has a weak ability to generate singlet oxygen radicals because some singlet oxygen radicals are converted into NO.

[0066] Take TiO from Example 1 2-x -MXene、LA@TiO 2-x MXene was tested for its NO performance; in an acidic aqueous solution, NO was oxidized by oxygen to NO2. - The p-aminobenzenesulfonic acid in Griess reagent reacts with NO2 - The diazonium salt formed by the diazotization reaction can be directly coupled with N-naphthylethylenediamine to form a purple dye. The absorbance of this dye at 540 nm can be detected by a UV-Vis spectrophotometer. By combining the standard curve obtained by reacting standard sodium nitrite samples of different concentrations with Griess reagent, the content of NO generated by the material during the ultrasonic process can be determined.

[0067] Figure 4a The TiO of the present invention 2-x -MXene generates NO performance test, Figure 4b The LA@TiO of the present invention 2-x -MXene NO production performance testing revealed arginine-modified LA@TiO₂ during the ultrasound process of an ultrasonic therapy device. 2-x The absorption value of MXene at 540 nm continuously increases, while TiO2... 2-x -MXene remained unchanged. This indicates that the ROS generated during the ultrasound process oxidized arginine to produce NO.

[0068] ONOO - LA-TiO2 is produced during the ultrasound process of the ultrasound therapy device. 2-x NO and O2 produced by MXene - The combined generation is a highly reactive free radical that reacts with lipids, proteins, and DNA, thus enhancing the acoustic dynamics of the material. For ONOO... - The nitration reaction is a characteristic reaction of this free radical, capable of adding a nitro group (-NO2) to the benzene ring of tyrosine, forming 3-nitrotyrosine. Therefore, this free radical can be detected by the nitration reaction in a test solution composed of NaHCO3 and tyrosine. A liquid fluorescence spectrometer (E) can be used to detect this free radical.x 313nm, E m The detection of 3-nitrotyrosine was performed at 406 nm, and the results are as follows: Figure 4c As shown. Only LA-TiO 2-x The MXene group exhibited a strong fluorescence peak under ultrasonic treatment, indicating that the material can produce ONOO. - Free radicals are produced, while other materials do not.

[0069] To further verify the biocompatibility of the material, mouse embryonic fibroblasts (3T3) were used as normal cells to test LA@TiO₂. 2-x - The cytotoxicity of MXene. All cells were cultured in a humidified incubator at 37°C with 5% CO2. Different concentrations of LA@TiO2 were used. 2-x 3T3 cells were incubated with MXene nanoparticle dispersion for 24 hours, and then cytotoxicity was determined by the MTT assay.

[0070] The test results are attached. Figure 5 As shown, the test results indicate that LA@TiO 2-x -MXene nanoparticles did not cause a significant decrease in 3T3 cell viability; the average cell survival rate remained above 90%, indicating that LA@TiO2... 2-x -MXene is non-toxic to healthy tissue cells and has good biocompatibility.

[0071] To test LA@TiO 2-x - The antibacterial function of MXene nanomaterials against MRSA bacteria. Figure 6a , 6b The antibacterial activity of the nanomaterial MRSA provided in Example 1 of this invention was investigated. The antibacterial performance was tested using the plate method. First, the components were divided into: PBS group, MXene group, and TiO2 group. 2-x -MXene group, LA@TiO 2-x -MXene group, the concentration of all materials was 40 μg / mL. The treatments for each group were: Control group, NIR group, US group, US+NIR group, and NIR+US group, with the NIR treatment power being 1 W / cm². 2 The processing time is 4 minutes, and the power processed by the US is 1 W / cm². 2 The incubation period was 6 minutes. Each group of bacterial suspensions was inoculated onto solid culture medium using the same method. The difference in colony counts on the solid culture medium after overnight incubation was calculated as the inhibition rate for each group. The experimental results are as follows: Figure 6aThe PBS group showed dense colony growth under all treatment conditions, with no bactericidal effect, verifying the reliability of the experimental system. The pure MXene group showed only a slight bactericidal effect under NIR treatment, indicating weak overall antibacterial ability. TiO2 2-x -MXene group: Significantly enhanced bactericidal effect under US and NIR stimulation, LA@TiO 2-x -MXene group: US and NIR treatments have shown significant bactericidal effects; under the combined treatment of US+NIR and NIR+US, the number of colonies is significantly reduced, especially in the NIR+US group, where the plates are almost colony-free, representing a sterilization rate of nearly 100%. Figure 6b For the quantitative results of colony counting, the survival rate was 100% during the Control treatment, indicating that none of the materials had antibacterial activity under normal conditions. For each drug group, the PBS group showed near 100% survival under all treatment conditions, indicating no bactericidal effect. The MXene group only exhibited inhibitory activity against NIR; the survival rate decreased to ~70% under NIR treatment, indicating limited bactericidal ability. TiO2 2-x -MXene: Survival rate of US or NIR treatment alone is approximately 40%-50%; survival rate further decreases to ~10%-20% after US+NIR and NIR+US combined treatment, significantly improving the bactericidal effect. LA@TiO 2-x -MXene group: NIR treatment survival rate versus TiO₂ 2-x -MXene consistency, lower bacterial survival rate during US treatment proves NO and ONOO - The antibacterial effect was excellent; the survival rate of US+NIR treatment decreased to ~10%, and the survival rate of NIR+US sequential treatment was about 0.2%, achieving near-complete sterilization. It was the material with the best antibacterial performance among all groups. For the US+NIR group and the NIR+US group, the NIR+US group performed better because the temperature generated by NIR laser irradiation increases bacterial permeability, resulting in a stronger ROS effect.

[0072] For LA@TiO 2-x The ability of MXene nanoparticles to eliminate MRSA biofilms was tested using the crystal violet method. The classic experiment of the crystal violet staining method for detecting bacterial biofilms is as follows: the deeper the blue / purple color, the more biofilm residue there is and the worse the anti-biofilm effect; the larger the white / transparent area, the more thoroughly the biofilm is removed and the better the anti-biofilm effect. Figure 7a , 7bImages and statistical graphs of residual MRSA biofilm CV staining after elimination of the lipopeptide nanoparticle formulation provided in Example 2 of this invention are shown. The materials were divided into: Control group, NIR group, US group, US+NIR group, and NIR+US group. Antibacterial experiments were then conducted. After the experiments, the samples were washed with PBS solution, and then the experiments were performed according to the prescribed crystal violet staining procedure. Figure 7b The absence of inhibition rate in the Control group indicates that none of the materials in each group have their own inhibitory effect. During US processing, the MXene group showed no effect, and the LA@TiO group... 2-x -MXene compared to TiO 2-x MXene exhibited a higher inhibition rate, indicating that this material has a stronger inhibitory effect on biofilm formation caused by NO production. After NIR+US treatment, the MXene group showed an effect of 22.1%, while TiO2 showed a lower effect. 2-x The effect of the MXene group was 76.3%, LA@TiO 2-x The effect of the -MXene group was 92.4%.

[0073] An L-arginine-functionalized TiO2 of the present invention 2-x The preparation method and application of MXene composite nanomaterials have the following advantages and beneficial effects:

[0074] (1) To address the problems of high reaction temperature, harsh solvent system, and easy over-oxidation of MXene in the preparation of existing TiO2 / Ti3C2 composite materials, this paper adopts a low-temperature hydrothermal strategy in a water-organic mixed solvent system to construct TiO2 / Ti3C2 composite materials. 2-x -MXene composite material. This strategy enables in-situ growth of TiO2 on the MXene surface and introduces oxygen vacancy structures through controlled oxidation. While maintaining the structural stability of MXene, it endows the material with good photothermal response and sonodynamic activity, laying the material foundation for the subsequent construction of multifunctional therapeutic systems.

[0075] (2) In the above TiO 2-x- Based on the MXene platform, L-arginine was further introduced for functionalization to construct LA@TiO2. 2-x -MXene multifunctional nanosystem. L-arginine, as a precursor to NO generation, can release NO under the action of ultrasound-induced reactive oxygen species, thereby introducing a gas therapy effect on the basis of photothermal therapy and sonodynamic therapy, and enhancing the material's ability to remove bacteria and biofilms.

[0076] A LA@TiO3 of the present invention 2-x The preparation method of MXene has the following advantages and beneficial effects:

[0077] (1) To address the problems of high reaction temperature, harsh solvent system, and easy over-oxidation of MXene in the preparation of existing TiO2 / Ti3C2 composite materials, this paper adopts a low-temperature hydrothermal strategy in a water-organic mixed solvent system to construct TiO2 / Ti3C2 composite materials. 2-x -MXene composite material. This strategy enables in-situ growth of TiO2 on the MXene surface and introduces oxygen vacancy structures through controlled oxidation. While maintaining the structural stability of MXene, it endows the material with good photothermal response and sonodynamic activity, laying the material foundation for the subsequent construction of multifunctional therapeutic systems.

[0078] (2) In the above TiO 2-x Based on the MXene platform, L-arginine was further introduced for functionalization to construct LA@TiO2. 2-x -MXene multifunctional nanosystem. L-arginine, as a precursor to NO generation, can release NO under the action of ultrasound-induced reactive oxygen species, thereby introducing a gas therapy effect on the basis of photothermal therapy and sonodynamic therapy, and enhancing the material's ability to remove bacteria and biofilms.

[0079] Finally, the method described in this application is merely a preferred embodiment and is not intended to limit the scope of protection of this invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this invention should be included within the scope of protection of this invention.

Claims

1. An L-arginine-functionalized TiO2 2-x The method for preparing MXene composite nanomaterials is characterized by... Includes the following steps: Step 1: Prepare Ti3C2T by in-situ etching with LiF / HCl x MXene; Step 2: Perform hydrothermal treatment in a water-organic mixed solvent system to form TiO2 in situ on the MXene surface. 2-x TiO 2-x -MXene composite materials; Step 3: Introduce L-arginine for functionalization modification to obtain LA@TiO 2-x -MXene composite nanomaterials.

2. The L-arginine-functionalized TiO2 as described in claim 1 2-x The method for preparing MXene composite nanomaterials is characterized by... Step 1 includes: Step 11: Place LiF in a 50mL polytetrafluoroethylene liner, add HCl and ultrapure water, dissolve at 30℃ for 10min, add MAX(Ti3AlC2) in multiple portions, then heat to 45℃, react for 72h and then remove. Step 12: Centrifuge 3 times at 10000 rpm × 1 min using 1M HCl, then centrifuge with ultrapure water until the upper liquid turns black. Add 40 mL of ultrapure water to disperse the lower precipitate and vortex for 20 min. Step 13: Transfer the liquid obtained in Step 12 to a glass bottle, purge with nitrogen for 15 min, sonicate for 30 min to separate the multiple layers of MXene, remove and centrifuge at 3000 rpm for 30 min to obtain Ti3C2T. x Dispersion.

3. The L-arginine-functionalized TiO2 as described in claim 2 2-x The method for preparing MXene composite nanomaterials is characterized by... In step 11, the amount of LiF is 1.60 g and the amount of HCl is 15 mL. In step 12, the amount of ultrapure water is 5 mL.

4. The L-arginine-functionalized TiO₂ as described in claim 1 2-x The method for preparing MXene composite nanomaterials is characterized by... Step 2 includes, Step 21, prepare the Ti3C2T in step 1. x After the dispersion is mixed evenly with glycerol, it is sonicated and then transferred into the inner liner of the reactor for hydrothermal reaction. Step 22: After the reactor cools down, remove the mixture from the inner liner of the reactor and store it in a 4°C refrigerator. Take 1 mL of the mixture, add 3-4 mL of ethanol to precipitate the product, and centrifuge repeatedly at differential speed to separate excess glycerol and obtain TiO2. 2-x -MXene dispersion.

5. An L-arginine-functionalized TiO2 as described in claim 4 2-x The method for preparing MXene composite nanomaterials is characterized by... Step 21 includes preparing 3 mL of 12 mg / mL Ti3C2T. x The dispersion was mixed thoroughly with an equal amount of glycerol.

6. The L-arginine-functionalized TiO₂ as described in claim 1 2-x The method for preparing MXene composite nanomaterials is characterized by... In step 21, the hydrothermal reaction in the reactor is carried out at a temperature of 150°C for 15 hours.

7. The L-arginine-functionalized TiO₂ as described in claim 1 2-x The method for preparing MXene composite nanomaterials is characterized by... Step 3 includes first adding the hydrothermally obtained TiO2 dispersion to a round-bottom flask. 2-x MXene was added to L-arginine solution and stirred; after stirring, 6 mL of ultrapure water was added and the mixture was centrifuged multiple times at differential speed to obtain LA@TiO₂. 2-x -MXene dispersion.

8. An L-arginine-functionalized TiO2 prepared by the method of claim 1 2-x The application of MXene composite nanomaterials is characterized by... The composite nanomaterials possess near-infrared photothermal response properties and ultrasonic response acoustic dynamic activity, and can generate NO and / or ONOO under ultrasonic stimulation. - Active species.

9. An L-arginine-functionalized TiO2 prepared by the method of claim 1 2-x -MXene composite nanomaterials are used to inhibit, disrupt, or remove MRSA biofilms.

10. An L-arginine-functionalized TiO2 prepared by the method of claim 1 2-x The application of MXene composite nanomaterials is characterized by... Under near-infrared light and / or ultrasound stimulation, through photothermal effect, acoustic dynamic effect, and NO and / or ONOO - The synergistic effect of active species enhances the antibacterial effect.

Images