Preparation method and application of bovine serum albumin modified gold platinum-niobium carbide nano-enzyme composite material
By preparing bovine serum albumin-modified gold-platinum-niobium carbide nanozyme composite materials, the shortcomings of traditional chemotherapy drugs have been overcome, achieving efficient cascade catalysis and near-infrared photothermal therapy in the tumor microenvironment, providing multimodal imaging diagnosis, and enhancing the specificity and safety of chemotherapy.
Patent Information
- Application Number
- CN202511185545.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-22
- Publication Date
- 2025-11-28
AI Technical Summary
Traditional chemotherapy drugs suffer from a lack of specificity, cytotoxicity, short half-life, poor solubility, and a tendency to induce multidrug resistance. In addition, chemodynamic therapy alone is inefficient and has limited anti-tumor efficacy.
A gold-platinum-niobium carbide nanozyme composite material modified with bovine serum albumin was prepared. By loading gold and platinum nanoparticles onto niobium carbide nanosheets and modifying them with bovine serum albumin, a nanozyme composite material with multiple enzyme activities was formed for multimodal imaging diagnosis and cascade chemotherapy of tumors.
It achieves highly efficient cascade catalytic reactions in the tumor microenvironment, enhances the efficacy of chemodynamic therapy, synergizes with near-infrared photothermal therapy, provides multimodal imaging diagnosis, and improves the specificity and safety of treatment.
Smart Images
Figure CN121015874A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of nanoenzyme composite material preparation technology, specifically to a method for preparing and applying a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material. Background Technology
[0002] Cancer is currently the leading cause of death. Common cancer treatments include surgical resection, chemotherapy, radiotherapy, and biotherapy. Surgery is currently the most effective way to remove malignant solid tumors, while chemotherapy is widely used in cancer treatment due to its simplicity and convenience. However, chemotherapy faces challenges such as lack of specificity, cytotoxicity, short half-life, poor solubility, and the development of multidrug resistance and stem cell-like growth. Therefore, exploring a nanomaterial that is both effective in diagnosis and treatment, and is highly efficient and safe, has become a research hotspot in cancer diagnosis and treatment, and also has significant clinical application value.
[0003] The tumor microenvironment, the environment in which tumor cells arise and survive, is characterized by high H2O2 content, hypoxia, and low pH. Chemodynamic therapy involves nanomaterials activating the Fenton / Fenton-like reaction within the tumor microenvironment, generating ROS and killing tumor cells, while simultaneously producing O2 at the tumor site where there is no tissue depth limitation. Starvation therapy consumes glucose, a functional substance essential for tumor survival in the tumor microenvironment, achieving an anti-tumor effect; this process also generates H2O2, providing raw materials for chemodynamic therapy. Near-infrared photothermal therapy (PTT) is a treatment strategy that utilizes nanomaterials as photothermal agents to absorb the energy of near-infrared light and convert it into heat energy, ablating lesions at high temperatures in the local tumor area. Compared to traditional photothermal therapy, near-infrared photothermal therapy has advantages in its penetrability, allowing it to penetrate skin, tissue, and blood effectively; nanomaterials, as photothermal agents, have excellent photothermal conversion properties, efficiently converting low energy input into heat energy; and it can effectively enhance the efficacy of other treatments while achieving photothermal therapy.
[0004] Nanozymes, as a class of nanomaterials possessing natural enzyme activity, have advantages such as low cost, high stability, simple preparation, long lifespan, and tunable activity. By mimicking natural enzymes, they can catalyze reactions in physiological environments or in vivo, improve the tumor microenvironment, and achieve chemodynamic therapy of tumors by generating ROS. However, due to the less-than-ideal concentration of H2O2 in the tumor microenvironment, the effect of simple chemodynamic therapy is not ideal. Therefore, it is necessary to explore a method to enhance its chemodynamic therapeutic effect and simultaneously exert a synergistic anti-tumor effect.
[0005] In summary, traditional chemotherapy drugs suffer from a lack of specificity, cytotoxicity, short half-life, poor solubility, and a tendency to induce multidrug resistance. In addition, chemodynamic therapy alone is inefficient and lacks a single anti-tumor approach. Summary of the Invention
[0006] The purpose of this invention is to address the problems of traditional chemotherapy drugs, such as lack of specificity, cytotoxicity, short half-life, poor solubility, and easy development of multidrug resistance, as well as the low efficiency of simple chemodynamic therapy and the limited range of anti-tumor methods. The invention provides a method for preparing and applying a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material.
[0007] A method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material, comprising the following steps:
[0008] First, niobium aluminum carbide powder is sequentially etched and stripped, and then ultrasonically treated to obtain a niobium carbide nanosheet solution. The niobium carbide nanosheets in the solution have a size of 50-150 nm and a thickness of 1-3 nm. Gold nanoparticles and platinum nanoparticles are loaded onto the surface of the niobium carbide nanosheets under bovine serum albumin modification to obtain a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material.
[0009] Application of a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material, wherein the bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material is used in the preparation of multimodal imaging diagnostic drugs for tumors, as well as photothermal therapy and cascade chemotherapy drugs.
[0010] The beneficial effects of this invention are:
[0011] This invention discloses a method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material. By loading tightly bound, in-situ grown bovine serum albumin-modified ultrafine nanoparticles onto niobium carbide nanosheets, this method achieves good biocompatibility and can be used as a nanocomposite material for combining tumor chemodynamic therapy with starvation therapy to realize a cascade reaction and synergistically enhance near-infrared photothermal therapy, thereby improving the efficacy of chemotherapy. This invention enriches the types of nanocomposite materials based on MXene for synergistic and enhanced near-infrared photothermal therapy of tumors with nanoenzyme cascade catalytic therapy.
[0012] Since gold and platinum, as elements with high atomic numbers, possess excellent X-ray attenuation properties, and niobium carbide nanosheets have high near-infrared photothermal absorption rates, niobium carbide nanosheets loaded with gold and platinum nanoparticles are expected to become ideal contrast agents for tumor computed tomography (CT) and photoacoustic imaging (PAI).
[0013] Bovine serum albumin (BSA) serves as a protective agent and stabilizer in the synthesis of noble metal nanoparticles, primarily through the abundance of negatively charged carboxyl groups (-COO) on its surface. - ) and phosphate groups (-PO3) 2- It binds to positively charged metal ions through electrostatic interactions and also functions by forming stable coordination bonds with metal ions through the imidazole and thiol functional groups contained in BSA. It controls the particle size of in-situ synthesized gold-platinum nanoparticles to 2-3 nm and loads them onto the surface of high specific surface area MXene sheets. This overcomes the disadvantages of single noble metals being prone to aggregation and deposition when used as nanozymes, while retaining multiple activities of noble metal nanozymes such as glucose oxidase, catalase (CAT), and peroxidase (POD), thus improving the catalytic performance and biocompatibility of noble metal nanoparticles. This composite nanomaterial decomposes H2O2 in the tumor microenvironment through its peroxidase-like (POD) activity, producing •OH, which has a killing effect on tumor cells. It also decomposes H2O2 to produce O2 through its catalase-like (CAT) activity, improving the hypoxic conditions in the tumor microenvironment. Furthermore, through its glucose oxidase-like (GOx) activity, it consumes the energy supplied by tumor cells to supply glucose and produces H2O2, thereby achieving efficient and cascaded catalysis of the enzyme, realizing a cyclical catalytic reaction that continuously provides O2 and •OH and consumes glucose in the tumor microenvironment.
[0014] Small-sized niobium carbide nanosheets, used as substrates for nanoenzyme composites, not only possess high surface area but also exhibit excellent photothermal and photoelectric properties. Niobium carbide nanosheets loaded with small-sized gold-platinum nanoparticles can also be applied to NIR-induced tumor thermal ablation therapy; among them, Nb2CT... x As a plasmon polaron, BSA-AuPt / Nb2CT under laser irradiation x Electrons on the surface are excited from the stable state to the plasma state, thereby reducing charge transfer resistance. This excellent photothermal and photoelectric properties enhance the enzyme-like catalytic performance of noble metal nanocomposites.
[0015] In summary, this invention rationally grows ultra-small gold and platinum nanoparticles in situ on small-sized niobium carbide nanosheets with bovine serum albumin modification. This not only plays a diagnostic role in tumors but also enhances the catalytic ability of enzymes, enabling enzymes to achieve cascade catalytic therapy in conjunction with starvation and photothermal therapy, ultimately achieving efficient and safe anti-tumor treatment.
[0016] This invention addresses the issues of low sensitivity and specificity of radiotherapy and chemotherapy, as well as the insufficient tumor-killing ability of single photothermal therapy or chemodynamic therapy. It explores a method that combines chemodynamic therapy and starvation therapy to achieve a cascaded chemical reaction. Simultaneously, under the synergistic effect of near-infrared photothermal therapy, it enhances the efficacy of chemodynamic therapy. As a highly efficient and safe nanomaterial, it enables the development of more individualized and precise treatment plans for cancer patients.
[0017] This invention provides a method for preparing and applying a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material. Attached Figure Description
[0018] Figure 1 This shows a scanning electron microscope (SEM) image of the etched multilayer niobium carbide nanosheets obtained in Example 1.
[0019] Figure 2 This indicates that the etching product niobium carbide (Nb2CT) obtained in Example 1 x X-ray diffraction (XRD) spectra of ) and its precursor niobium aluminum carbide powder (Nb2AlC);
[0020] Figure 3 This refers to the small-sized Nb2CT obtained in Example 1. x Transmission electron microscopy (TEM) image of nanosheets;
[0021] Figure 4 This refers to the Nb2CT obtained in Example 1. x Three-dimensional morphology of nanosheets using atomic force microscopy (AFM);
[0022] Figure 5 This indicates that BSA-AuPt / Nb2CT in Example 1 x Transmission electron microscopy (TEM) image of nanozyme composite material;
[0023] Figure 6 In Example 1, BSA-AuPt / Nb2CT is used. x High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images and corresponding elemental mapping diagrams of nanofilm composite materials;
[0024] Figure 7 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x Composite nanomaterials, Nb2CT x Fourier transform infrared (FT-IR) spectra of nanosheets and BSA;
[0025] Figure 8 This refers to the BSA-AuPt / Nb2CT obtained in Example 1.x Nyquist plots of electrochemical impedance spectroscopy (EIC) of composite nanomaterials with and without laser irradiation;
[0026] Figure 9 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x Photocurrent diagram of composite nanomaterials under laser irradiation;
[0027] Figure 10 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x A graph showing the O2 content in a CAT-like reactive system of composite nanomaterials under and without laser irradiation;
[0028] Figure 11 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x The POD-like activity of the composite nanomaterial with and without laser irradiation, and the UV-Vis absorption spectrum of the colorimetric agent TMB at 652 nm.
[0029] Figure 12 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x GOx activity of composite nanomaterials, glucose content detected by DNS colorimetric method;
[0030] Figure 13 This refers to the multilayer Nb2CT obtained in Example 1. x Nanosheets, monolayer or few-layer Nb2CT x Nanosheets and BSA-AuPt / Nb2CT x Stability of composite nanomaterials in different solutions. Detailed Implementation
[0031] Specific Implementation Method 1: This implementation method describes a method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material, which is carried out according to the following steps:
[0032] First, niobium aluminum carbide powder is sequentially etched and stripped, and then ultrasonically treated to obtain a niobium carbide nanosheet solution. The niobium carbide nanosheets in the solution have a size of 50-150 nm and a thickness of 1-3 nm. Gold nanoparticles and platinum nanoparticles are loaded onto the surface of the niobium carbide nanosheets under bovine serum albumin modification to obtain a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material.
[0033] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the specific steps for etching the niobium aluminum carbide powder are as follows:
[0034] Niobium aluminum carbide powder was added to a hydrofluoric acid solution and magnetically stirred at 23-25°C for 48-120 h. The solution was then washed alternately with deionized water and anhydrous ethanol until the pH value of the solution was 6-7, thus obtaining etched niobium carbide nanosheets.
[0035] The other steps are the same as in Specific Implementation Method 1.
[0036] Specific Implementation Method 3: The difference between this implementation method and Specific Implementation Method 1 or 2 is that the mass ratio of the niobium aluminum carbide powder to the volume of the hydrofluoric acid solution is (0.5~1) g: 10 mL, the mass concentration of the hydrofluoric acid solution is 30~50%, and the particle size of the niobium aluminum carbide powder is 300~500 mesh.
[0037] The other steps are the same as in Specific Implementation Method 1 or 2.
[0038] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One through Three in that the specific steps for peeling off the etched niobium carbide nanosheets are as follows:
[0039] The etched niobium carbide nanosheets were added to a tetrapropylammonium hydroxide solution and magnetically stirred at 23-25°C for 48-72 h. The solution was then washed alternately with deionized water and anhydrous ethanol until the pH value was 6-7, thus obtaining the exfoliated niobium carbide nanosheet solution.
[0040] The other steps are the same as those in Specific Implementation Methods One to Three.
[0041] Specific Implementation Method 5: The difference between this implementation method and Specific Implementation Methods 1 to 4 is that the mass ratio of the etched niobium carbide nanosheets to the volume of the tetrapropylammonium hydroxide solution is (0.5~1.5) g: (5~10) mL, and the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide solution is 20~25%.
[0042] The other steps are the same as those in Specific Implementation Methods One through Four.
[0043] Specific Implementation Method Six: The difference between this implementation method and Specific Implementation Methods One through Five is that the specific steps for ultrasonic treatment of the exfoliated niobium carbide nanosheet solution are as follows:
[0044] Under ice bath conditions, the exfoliated niobium carbide nanosheet solution was ultrasonically treated for 0.5–1 h to obtain a niobium carbide nanosheet solution; the mass concentration of the niobium carbide nanosheet solution was 10–15 mg / mL.
[0045] The other steps are the same as those in Specific Implementation Methods 1 to 5.
[0046] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One through Six in that the specific steps for loading gold nanoparticles and platinum nanoparticles onto the surface of niobium carbide nanosheets under bovine serum albumin modification are as follows:
[0047] Chloroauric acid solution, chloroplatinic acid solution, and bovine serum albumin solution were mixed with niobium carbide nanosheet solution and stirred at 23-25℃ for 0.5-4 h to obtain solution A; then sodium borohydride solution at 0-5℃ was added, and stirring was continued for 3-5 min. The mixture was then collected by centrifugation and finally washed to obtain bovine serum albumin modified gold-platinum-niobium carbide nanoenzyme composite material.
[0048] The other steps are the same as those in Specific Implementation Methods 1 to 6.
[0049] Specific Implementation Method Eight: The difference between this implementation method and Specific Implementation Methods One to Seven is that the volume ratio of the chloroauric acid solution, chloroplatinic acid solution, bovine serum albumin solution and niobium carbide nanosheet solution is (500~600):(480~600):(40~80):10000, and the molar concentration of the chloroauric acid solution and chloroplatinic acid solution is 3~5mM.
[0050] The other steps are the same as those in Specific Implementation Methods 1 to 7.
[0051] Specific Implementation Method Nine: The difference between this implementation method and Specific Implementation Methods One to Eight is that the volume ratio of the sodium borohydride solution to solution A is (0.5~1):10, and the molar concentration of the sodium borohydride solution is 4~5mM.
[0052] The other steps are the same as those in Specific Implementation Methods 1 to 8.
[0053] Specific Implementation Method Ten: The difference between this implementation method and Specific Implementation Methods One to Nine is that: the application of a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material, wherein the bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material is used in the preparation of multimodal imaging diagnostic drugs for tumors, as well as photothermal therapy and cascade chemotherapy drugs.
[0054] The other steps are the same as those in Specific Implementation Methods 1 to 9.
[0055] The beneficial effects of the present invention are verified using the following embodiments:
[0056] Example 1: A method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material, comprising the following steps:
[0057] Step S1: Niobium aluminum carbide is etched.
[0058] 1 g of niobium aluminum carbide powder was added slowly in portions to 10 mL of hydrofluoric acid solution and magnetically stirred at 25 °C for 96 h. Then, the solution was washed alternately with deionized water and anhydrous ethanol until the pH value of the solution was 6-7 to obtain etched niobium carbide nanosheets.
[0059] The hydrofluoric acid solution has a mass concentration of 40%, and the niobium aluminum carbide powder has a particle size of 400 mesh.
[0060] Step S2: The etched multilayer niobium carbide is stripped.
[0061] 1 g of etched niobium carbide nanosheets were added to 10 mL of tetrapropylammonium hydroxide (TPAOH) solution and magnetically stirred at 25 °C for 72 h. The solution was washed alternately with deionized water and anhydrous ethanol until the pH value of the solution was 6-7, thus obtaining a single-layer or few-layer niobium carbide nanosheet solution after exfoliation.
[0062] The mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide solution is 25%.
[0063] Step S3: The monolayer or few-layer niobium carbide solution after intercalation treatment is subjected to ultrasonic treatment;
[0064] Under ice bath conditions, the exfoliated monolayer or few-layer niobium carbide nanosheet solution was ultrasonically treated for 1 h to obtain a small-sized monolayer or few-layer niobium carbide nanosheet solution; wherein the size of the niobium carbide nanosheet was 100 nm and the thickness was 1.5 nm.
[0065] The mass concentration of the niobium carbide nanosheet solution was 15 mg / mL;
[0066] Step S4: The specific steps for in-situ growth of gold and platinum nanoparticles on niobium carbide nanosheets by electrostatic adsorption under the modification of bovine serum albumin are as follows;
[0067] 580 μL of chloroauric acid solution, 600 μL of chloroplatinic acid solution, and 40 μL of bovine serum albumin solution were mixed with 10 mL of small-sized monolayer or few-layer niobium carbide nanosheet solution and stirred at 25 °C for 2 h to obtain solution A. Then, 1 mL of freshly prepared sodium borohydride solution at 5 °C was added, and the mixture was stirred vigorously for 4 min. The mixture was then collected by centrifugation and finally washed to obtain the bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material (BSA-AuPt / Nb2CT). x (The gold and platinum micro-nano particles are approximately 2 nm in size.)
[0068] The molar concentrations of chloroauric acid solution and chloroplatinic acid solution were both 4 mM; the molar concentration of sodium borohydride solution was 4.72 mM.
[0069] Figure 1This shows a scanning electron microscope (SEM) image of the etched multilayer niobium carbide nanosheets obtained in Example 1; as shown. Figure 1 As shown, the niobium aluminum carbide exhibits an accordion-like structure after etching.
[0070] Figure 2 This indicates that the etching product niobium carbide (Nb2CT) obtained in Example 1 x X-ray diffraction (XRD) spectra of ) and its precursor, niobium aluminum carbide powder (Nb2AlC); such as Figure 2 As shown, the original niobium aluminum carbide powder exhibits significant diffraction peaks on the (002), (004), (100), (101), (103), (104), (106), and (107) crystal planes; after hydrofluoric acid etching, Nb2CT x The (002) characteristic peak becomes significantly broadened and shifts to a lower angle, while the intensity of the characteristic peak of niobium aluminum carbide decreases significantly and eventually disappears with the etching process. These changes are similar to those of Nb2CT. x The typical layered structure characteristics are consistent with those of MAX, confirming the successful conversion of MAX phase to MXene.
[0071] Figure 3 This refers to the small-sized Nb2CT obtained in Example 1. x Transmission electron microscopy (TEM) images of nanosheets; such as Figure 3 As shown, Nb2CT after intercalation-ultrasound processing x The structure exhibits a single or few layers and is small in size, around 100nm, confirming the successful implementation of an efficient exfoliation process.
[0072] Figure 4 This refers to the Nb2CT obtained in Example 1. x Three-dimensional morphology of nanosheets using atomic force microscopy (AFM); such as Figure 4 As shown, after the intercalation-ultrasonic exfoliation process, the nanosheet thickness is 1-2 nm, which is consistent with the typical thickness range of monolayer / few-layer MXene, further verifying the precise control of the exfoliation process over the layered structure.
[0073] Figure 5 This indicates that BSA-AuPt / Nb2CT in Example 1 x Transmission electron microscopy (TEM) images of nanozyme composite materials; such as Figure 5 As shown, the BSA-modified AuPt nanoparticles exhibit a monodisperse state with a uniform particle size of approximately 2 nm, and are present in Nb2CT. x The nanosheets are uniformly distributed on the surface, and this structure effectively exposes catalytic active sites, laying the foundation for enhanced enzyme-like activity.
[0074] Figure 6 In Example 1, BSA-AuPt / Nb2CT is used. xHigh-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images and corresponding elemental mappings of nanofilm composite materials; such as Figure 6 As shown, ultrafine AuPt nanoparticles in Nb2CT x The nanosheets exhibit a uniform monodisperse state, and the surface scan results of Nb, Au, and Pt elements further confirm their spatial distribution consistency. This structure effectively ensures the full exposure of the catalytic active interface and the efficiency of electron transfer.
[0075] Figure 7 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x Composite nanomaterials, Nb2CT x Fourier transform infrared (FT-IR) spectra of nanosheets and BSA; such as Figure 7 As shown, in BSA-AuPt / Nb2CT x The spectral lines include 1650-1660 cm⁻¹ -1 and 1540-1550 cm -1 The presence of characteristic peaks belonging to the amide I band (C=O stretching vibration) and amide II band (NH bending vibration) of BSA confirms that BSA is stably anchored to AuPt / Nb2CT. x The interface provides biocompatibility to the complex and inhibits nanoparticle aggregation.
[0076] Figure 8 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x Nyquist plots of electrochemical impedance spectroscopy (EIS) of composite nanomaterials with and without laser irradiation; such as Figure 8 As shown, the semi-circular radius of the composite nanomaterial irradiated by laser is smaller than that of the unirradiated composite nanomaterial, indicating that under laser irradiation, electrons on the composite nanomaterial are excited from the stable state to the plasma state, thereby reducing the charge transfer resistance.
[0077] Figure 9 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x Photocurrent diagram of composite nanomaterials under laser irradiation; such as Figure 9 As shown, the composite nanomaterial exhibits a significant photocurrent under laser irradiation. These results are for BSA-AuPt / Nb2CT. x This provides a theoretical basis for enhancing enzyme activity.
[0078] Figure 10 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x A graph showing the O2 content in a CAT-like reactive system of composite nanomaterials under and without laser irradiation; as shown. Figure 10As shown, the reaction system was placed in an aqueous environment, containing hydrogen peroxide, BSA-AuPt / Nb2CT. x Under the same concentration conditions in the reaction system, and with laser irradiation, the BSA-AuPt / Nb2CT composite nanomaterials... x The CAT-like activity is stronger.
[0079] Figure 11 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x The composite nanomaterial exhibits POD-like activity with and without laser irradiation; the UV-Vis absorption spectrum of the colorimetric reagent TMB at 652 nm is shown. Figure 11 As shown, the reaction system was placed in an aqueous environment, containing hydrogen peroxide, TMB, and BSA-AuPt / Nb2CT. x Under the same concentration conditions in the reaction system, and with laser irradiation, the BSA-AuPt / Nb2CT composite nanomaterials... x The POD-like activity is stronger.
[0080] Figure 12 This refers to the BSA-AuPt / Nb2CT obtained in Example 1. x GOx activity of composite nanomaterials, glucose content detection using DNS colorimetric method; (e.g.) Figure 12 As shown, under 37℃ water bath conditions, the consumption of glucose in the reaction system was detected using DNS reagent. The results showed that with the increase of the concentration of the composite nanozyme material, glucose consumption increased after 24 hours, and the remaining glucose in the reaction system decreased significantly, indicating that it can effectively consume glucose in the reaction system, demonstrating that BSA-AuPt / Nb2CT... x Composite nanomaterials can effectively consume glucose.
[0081] Figure 13 This refers to the multilayer Nb2CT obtained in Example 1. x Nanosheets, monolayer or few-layer Nb2CT x Nanosheets and BSA-AuPt / Nb2CT x The stability of composite nanomaterials in different solutions; such as Figure 13 As shown, from left to right, each group of solvents consists of water, PBS, and saline, respectively; and each bottle contains multilayer Nb2CT. x Single-layer or few-layer Nb2CT x and BSA-AuPt / Nb2CT x This shows that the three substances are relatively stable in water, but sedimentation begins to occur in PBS and Saline over time. Nb2CT xAfter modification with BSA, the nanosheets still showed good dispersibility in PBS and Saline solutions after 24 hours, with no obvious precipitation, indicating that BSA can significantly improve the physical stability of the nanosheets.
Claims
1. A method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material, characterized in that: The preparation method is carried out according to the following steps: First, niobium aluminum carbide powder is sequentially etched and stripped, and then ultrasonically treated to obtain a niobium carbide nanosheet solution. The niobium carbide nanosheets in the solution have a size of 50~150 nm and a thickness of 1~3 nm. Gold nanoparticles and platinum nanoparticles are loaded onto the surface of the niobium carbide nanosheets under bovine serum albumin modification to obtain a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material.
2. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 1, characterized in that: The specific steps for etching niobium aluminum carbide powder are as follows: Niobium aluminum carbide powder was added to a hydrofluoric acid solution and magnetically stirred at 23-25°C for 48-120 h. The solution was then washed alternately with deionized water and anhydrous ethanol until the pH value of the solution was 6-7, thus obtaining etched niobium carbide nanosheets.
3. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 2, characterized in that: The mass ratio of the niobium aluminum carbide powder to the volume of the hydrofluoric acid solution is (0.5~1) g: 10 mL, the mass concentration of the hydrofluoric acid solution is 30~50%, and the particle size of the niobium aluminum carbide powder is 300~500 mesh.
4. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 1, characterized in that: The specific steps for peeling off the etched niobium carbide nanosheets are as follows: The etched niobium carbide nanosheets were added to a tetrapropylammonium hydroxide solution and magnetically stirred at 23-25°C for 48-72 hours. The solution was then washed alternately with deionized water and anhydrous ethanol until the pH value reached 6-7, thus obtaining the exfoliated niobium carbide nanosheet solution.
5. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 4, characterized in that: The ratio of the mass of the etched niobium carbide nanosheets to the volume of the tetrapropylammonium hydroxide solution is (0.5~1.5) g : (5~10) mL, and the mass fraction of tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide solution is 20~25%.
6. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 1, characterized in that: The specific steps for ultrasonic treatment of the exfoliated niobium carbide nanosheet solution are as follows: Under ice bath conditions, the exfoliated niobium carbide nanosheet solution was ultrasonically treated for 0.5–1 h to obtain a niobium carbide nanosheet solution; the mass concentration of the niobium carbide nanosheet solution was 10–15 mg / mL.
7. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 1, characterized in that: The specific steps for loading gold nanoparticles and platinum nanoparticles onto the surface of niobium carbide nanosheets with bovine serum albumin modification are as follows: Chloroauric acid solution, chloroplatinic acid solution, and bovine serum albumin solution were mixed with niobium carbide nanosheet solution and stirred at 23-25℃ for 0.5-4 h to obtain solution A; then sodium borohydride solution at 0-5℃ was added, and stirring was continued for 3-5 min. The mixture was then collected by centrifugation and finally washed to obtain bovine serum albumin modified gold-platinum-niobium carbide nanoenzyme composite material.
8. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 7, characterized in that: The volume ratio of the chloroauric acid solution, chloroplatinic acid solution, bovine serum albumin solution and niobium carbide nanosheet solution is (500~600):(480~600):(40~80):10000, and the molar concentration of the chloroauric acid solution and chloroplatinic acid solution is 3~5mM.
9. The method for preparing a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material according to claim 7, characterized in that: The volume ratio of the sodium borohydride solution to solution A is (0.5~1):10, and the molar concentration of the sodium borohydride solution is 4~5 mM.
10. The application of a bovine serum albumin-modified gold-platinum-niobium carbide nanoenzyme composite material prepared by the method according to any one of claims 1-9, characterized in that: The bovine serum albumin-modified gold-platinum-niobium carbide nanozyme composite material is used in the preparation of multimodal imaging diagnostic drugs for tumors, as well as photothermal therapy and cascade chemotherapy drugs.