A nano antibacterial material with adjustable biological function and its preparation method

Abstract

The present invention is a nano antibacterial material with adjustable biological function and its preparation method. The nano antibacterial material is copper-silver co-doped K2Ti6O 13 Nanomaterial, wherein the doping amount of copper and silver is controlled in the molar percentage of (Cu+Ag) / Ti within the range of 0.5% to 3.0%, wherein the molar percentage of Cu / Ti is 0.1-2% and the molar percentage of Ag / Ti is 0.05-1.0%; the radial size of the one-dimensional nanostructure is 5nm to 200nm. The material can be controlled by adjusting the copper and silver doping amount according to its application requirements. 13 The biological functional properties of nano antibacterial materials. In addition to being used in industrial antibacterial products, the present invention can also be used in biomedical products because it has high antibacterial activity while also having excellent biocompatibility and biosafety.

Description

Technical Field

[0001] The technical solution of the present invention relates to the technical field of nano-antibacterial materials and provides a nano-antibacterial biomaterial, namely, by introducing copper ions and silver ions into the potassium titanate lattice, the synergistic effect of copper ions and silver ions is used to achieve the regulation of the antibacterial, biocompatibility, biosafety and other biological functions of the potassium titanate nanomaterial. Specifically, it is a potassium hexatitanate nano-antibacterial material with adjustable biological functions and a preparation method thereof. Background Art

[0002] Viruses and bacteria are ubiquitous. Many infections during the treatment of clinical diseases and major epidemic diseases are caused by the rapid spread and infection of related bacteria or viruses. Nano-antimicrobial materials, as a new type of antimicrobial agent, can cause physical and biochemical damage to bacteria or viruses through various pathways due to their unique physicochemical properties, thereby reducing the risk of inducing bacterial resistance. Therefore, nano-antimicrobial materials are widely in demand in daily necessities, environmental purification products, environmentally friendly green building materials and medical products. It is well known that silver, copper, zinc nanoparticles or their ions have broad-spectrum antimicrobial properties and strong antimicrobial effects and have been widely used in antimicrobial materials. However, the widespread use of these nanoparticles has led to a series of problems, such as environmental pollution and human toxicity. To address these problems, researchers have fixed metal nanoparticles or ions on the surface or pores of some carriers. On the one hand, this can achieve the slow release of antimicrobial particles or ions, and on the other hand, it can also give other materials good antimicrobial functions. Common carrier materials are divided into organic materials and inorganic materials. Organic materials have poor chemical stability and heat resistance, and easy degradation and aging are their fatal shortcomings. Inorganic materials have the advantages of excellent chemical stability, corrosion resistance, wear resistance, heat resistance, biocompatibility and catalytic activity. Therefore, loading silver, copper, zinc nanoparticles or ions with broad-spectrum antibacterial effects into nano-inorganic materials to give them antibacterial functions has become a major research direction. How to achieve uniform loading and continuous slow release of antibacterial particles or ions such as silver, copper, and zinc, and ensure their environmental safety and biosafety are the keys to their application, especially in antibacterial products that are closely related to human health. Potassium hexatitanate (K2Ti6O 13 Nanomaterials are inorganic materials with excellent physical and chemical properties, such as high specific surface area and chemical stability, good hydrophilicity, photoelectric properties, acid and alkali corrosion resistance, heat insulation performance, cell compatibility, and photocatalytic antibacterial activity under ultraviolet light excitation. The authorized invention patent (CN 201310043954.6) applied for by our research group in the early work disclosed a nanoribbon K2Ti6O 13 The preparation method adopts sol-gel method and hydrothermal reaction method to prepare nano-belt K2Ti6O 13 The invention is characterized in that the prepared K2Ti6O13 It is nanoribbon-shaped, has a large aspect ratio, high purity and good quality. Its limitation is that the prepared K2Ti6O 13 Single morphology and poor antibacterial properties. 13 The antibacterial function of nanomaterials was studied by Zhang Weiwei's master's thesis in our group. The sol-gel method and hydrothermal reaction method were used to prepare K2Ti6O doped with silver, copper or zinc. 13 Nanomaterials, the preparation method involved in this study is to add silver nitrate, copper nitrate, or zinc nitrate during the preparation of TiO2 precursor by sol-gel method to dope silver, copper or zinc ions into TiO2 lattice to replace some titanium ions, and then finally synthesize silver, copper or zinc single doped K2Ti6O through hydrothermal reaction. 13 Nanowires, due to the incorporation of silver, copper or zinc into K2Ti6O 13 The silver, copper and zinc antibacterial ions are present in the K2Ti6O 13 The problem of uniform distribution of the antibacterial metal ions on the nanowires was solved, and the sustained and slow release of antibacterial metal ions was achieved. The disadvantage of this study is that it only focuses on the visible light photocatalytic performance and antibacterial properties of the material, without considering the biocompatibility and biosafety of the material. The prepared material does not have the adjustability of biological functions, and the prepared copper or zinc ion single doped K2Ti6O 13 Nanowires have poor antibacterial activity against Staphylococcus aureus. Studies have shown that silver has the highest antibacterial activity, followed by copper, with zinc having the weakest antibacterial effect. Both copper and zinc are essential trace elements for the human body. The safe concentration of copper ions in the human body is much higher than that of silver ions, and its biosafety is higher than that of silver ions, due to its wide adjustable range. However, the adjustable range of zinc ions is narrower. Summary of the Invention

[0003] The present invention aims to address the shortcomings of current technologies by providing a nano-antibacterial material with adjustable biofunctionality and its preparation method. This material uses a titanium-containing compound, a copper-containing compound, and a silver-containing compound as reactants to prepare copper-silver co-doped TiO2 nanoparticles via a sol-gel method. The initial size of the TiO2 precursor is controlled by calcining at low or medium temperatures according to application requirements. This precursor is then mixed with a potassium hydroxide solution of a certain concentration and subjected to a hydrothermal reaction to synthesize copper-silver co-doped K2Ti6O 13 Nanomaterials, and by adjusting the doping amount of copper and silver to achieve the controllability of its biological functional properties. Therefore, the copper and silver co-doped K2Ti6O 13 Nanomaterials can flexibly adjust the copper and silver doping levels according to application requirements to highlight certain biological functional characteristics, thereby being applied to antibacterial industrial products in multiple industries. They can also be used in biomedical products while ensuring high antibacterial activity while having excellent biocompatibility and biosafety.

[0004] The technical solution of the present invention is:

[0005] A nano antibacterial material with adjustable biological function, the nano antibacterial material is copper-silver co-doped K2Ti6O 13 Nanomaterial, wherein the doping amount of copper and silver is controlled in the range of 0.5% to 3.0% according to the molar percentage of (Cu+Ag) / Ti, wherein the molar percentage of Cu / Ti is 0.1% to 2% and the molar percentage of Ag / Ti is 0.05% to 1.0%;

[0006] The radial size of its one-dimensional nanostructure is 5nm to 200nm;

[0007] The material can be tuned by adjusting the copper and silver doping amount according to its application requirements. 13 Biofunctional properties of nano-antibacterial materials;

[0008] The biological functional properties are antimicrobial activity, biocompatibility or biosafety;

[0009] The method for preparing the nano antibacterial material with adjustable biological function comprises the following steps:

[0010] 1) Preparation of copper-silver co-doped TiO2 nanopowder by sol-gel method:

[0011] Using butyl titanate, anhydrous ethanol, hydrated copper nitrate (Cu(NO3)2·XH2O), silver nitrate (AgNO3), nitric acid, and sodium polyacrylate as raw materials (i.e., butyl titanate as the titanium source, anhydrous ethanol as the solvent, Cu(NO3)2·XH2O providing copper ions, and AgNO3 providing silver ions);

[0012] A sodium polyacrylate aqueous solution, dilute nitric acid, and deionized water were mixed and magnetically stirred to prepare solution A;

[0013] Meanwhile, butyl titanate and anhydrous ethanol were mixed and dissolved, and then Cu(NO3)2·XH2O and AgNO3 were added to the above solution by molar percentage, and magnetic stirring was performed to prepare solution B;

[0014] Solution A and solution B are then mixed, sealed and magnetically stirred at room temperature for 0.5 to 5 hours. The generated white precipitate is filtered and dried to obtain a copper-silver co-doped TiO2 nanopowder. The nanopowder is granular with a particle size of 5 nm to 12 nm. The powder is calcined at 350 to 650° C. for 0.5 to 6 hours to obtain a copper-silver co-doped TiO2 nanopowder. At this time, the nanopowder is still granular with a particle size of 10 nm to 200 nm.

[0015] Wherein, in the preparation of solution A, the volume ratio is sodium polyacrylate aqueous solution: dilute nitric acid: deionized water = 1:1-5:25-100;

[0016] In the preparation of solution B, the volume ratio of butyl titanate to anhydrous ethanol is 1:0.5-1.5; the molar ratio of Cu(NO3)2·XH2O and AgNO3 to butyl titanate is (Cu+Ag) / Ti=0.5%-3%; Cu / Ti=0.1-2%, Ag / Ti=0.05-1.0%;

[0017] Solution A and solution B are mixed in a volume ratio of solution A:solution B = 3-10:1;

[0018] The method also includes the following steps: calcining the obtained copper-silver co-doped TiO2 nanopowder, adding the obtained powder into Tween 80 ethanol solution for ultrasonic dispersion, filtering and drying; the ultrasonic dispersion time is 5 to 20 minutes.

[0019] 2) Hydrothermal reaction: The copper-silver co-doped TiO2 nanopowder prepared in step 1) is added to a potassium hydroxide solution (as a potassium source), mixed by magnetic stirring, poured into a sealed reactor, and reacted at 100° C. to 200° C. for 6 to 48 hours; then cooled to room temperature in the furnace;

[0020] 3) Cleaning and drying: The hydrothermal reaction product of step 2) was washed with deionized water, filtered until the pH value was 7±0.5, and then dried to obtain copper-silver co-doped K2Ti6O 13 Nanomaterials.

[0021] Step 1) The concentration of the dilute nitric acid is 0.5-5% by mass; the mass percentage of the sodium polyacrylate aqueous solution is 1-10%;

[0022] Step 1) In the Tween 80 ethanol solution, the volume ratio is Tween 80: anhydrous ethanol = 0.5-10%.

[0023] Step 2) The concentration of the potassium hydroxide solution is 5 to 12 mol / L; 0.1 to 5 g of copper-silver co-doped TiO2 nanopowder is added to every 100 mL of potassium hydroxide solution;

[0024] Step 3) The drying temperature is 60° C. to 100° C., and the drying time is 6 h to 24 h.

[0025] The essential features of the present invention are:

[0026] At present, many nano-antibacterial products have limitations such as biosafety issues or product performance degradation in pursuit of high antibacterial activity, such as biosafety issues caused by excessive addition of antibacterial ions (copper, zinc, silver ions, etc.), nanotoxicity issues of nanomaterials themselves, and excessive addition of antibacterial materials in applied products causing degradation of other product performance.

[0027] For example, the existing pure K2Ti6O 13Nanomaterials, which must be excited by ultraviolet light to have antibacterial function, are then silver, copper or zinc single doped K2Ti6O 13 Nanomaterials have enhanced visible light photocatalytic antibacterial effect and have synergistic antibacterial function of antibacterial ions and photocatalytic antibacterial. However, copper or zinc single doped K2Ti6O 13 The nanomaterials have poor antibacterial effect on Staphylococcus aureus, while silver-doped K2Ti6O 13 Nanomaterials have obvious antibacterial effects, but the cost of silver is higher than that of copper and zinc, and its biocompatibility is worse than that of copper and zinc.

[0028] The present invention obtains copper-silver co-doped K2Ti6O 13 Nanomaterials. This material has a higher doping rate than copper-doped K2Ti6O when the total doping amount is the same. 13 The antibacterial properties of the nanomaterials were significantly improved, and compared with the silver-doped K2Ti6O 13 The antibacterial properties of the nanomaterials are comparable, indicating that copper can be used to replace part of the silver, which not only reduces the preparation cost but also improves the biocompatibility and biosafety of the materials. The synthesized copper-silver co-doped K2Ti6O 13 Nanomaterials have antibacterial and biocompatible regulatory functions, realizing the controllability of biological functions.

[0029] In the preparation method, the copper-silver co-doped TiO2 precursor is improved in the sol-gel method. The amount of sodium polyacrylate is increased to improve the dispersibility of the prepared precursor. Two materials (silver nitrate and copper nitrate) are added during the preparation process to change the composition of the material. A calcination process is added to control the initial size of the precursor to achieve the copper-silver co-doped material K2Ti6O 13 The morphology (aspect ratio) of the nanomaterial is controllable, and in order to prevent the precursor from melting and sticking during the calcination process, the copper-silver co-doped TiO2 precursor after calcination needs to be ultrasonically dispersed in Tween 80 ethanol solution before being used for hydrothermal reaction. This preparation method overcomes the melt adhesion problem of potassium titanate nanomaterials synthesized by the currently commonly used sintering method or molten salt method, and overcomes the shortcomings of the microwave reaction heating method such as the demanding equipment requirements. The preparation method has the advantages of simple process, mild synthesis conditions, and K2Ti6O 13 Features such as controllable shape.

[0030] The beneficial effects of the present invention are as follows:

[0031] 1. K2Ti6O selected by the present invention 13 It has excellent chemical stability, heat insulation, acid and alkali corrosion resistance, hydrophilicity and environmental friendliness, and is suitable as a carrier material for nano antibacterial materials. Copper and silver ions with broad-spectrum antibacterial effects can be prepared by combining sol-gel and hydrothermal synthesis to replace part of the titanium ions into K2Ti6O13 In the crystal lattice, the copper ions and silver ions can be evenly distributed on the carrier material, and the copper ions and silver ions can be slowly released, thereby realizing the long-lasting antibacterial function of the material.

[0032] 2. Copper ions are essential trace elements for the human body. Their safe dosage concentration in the human body is much higher than that of silver ions. Therefore, their biosafety is higher than that of silver ions. Copper ions also have the functional property of inducing osteogenesis. Silver ions have higher antibacterial activity than copper ions. The present invention fully considers the biosafety of the nano antibacterial material and controls the (Cu+Ag) / Ti doping molar percentage to 0.5% to 3%, wherein the doping amount of Cu is controlled to Cu / Ti=0.1-2 mol%, and the doping amount of Ag is controlled to Ag / Ti=0.05-1.0 mol%. The copper-silver co-doped K2Ti6O prepared by the present invention is 13 Nanomaterials can change their corresponding biological functional properties (such as antibacterial activity, biocompatibility, biosafety, etc.) by adjusting the doping amount of copper and silver according to application requirements, achieving K2Ti6O 13 Regulatable biological functions of nanomaterials.

[0033] 3. Nanotoxicity of nanomaterials is mainly manifested in that nanoparticles enter the human circulatory system through skin contact, respiratory system, or ingestion, and then enter the cells through endocytosis or osmosis, thereby destroying the cell structure and function and inducing pathological reactions. 13 Nanomaterials have one-dimensional nanostructures and are much less likely to enter cells than nanoparticles, thereby reducing the risk of the materials damaging the internal structure and function of cells and greatly reducing the nanotoxicity of the materials.

[0034] 4. Copper-silver co-doped K2Ti6O prepared by the present invention 13 Due to the controllable biological functions of nanomaterials, they can be used in a variety of industrial antibacterial products as well as in biomedical antibacterial products in the biomedical industry.

[0035] 5. The present invention adopts a preparation method combining sol-gel and hydrothermal synthesis to prepare copper-silver co-doped K2Ti6O 13 Nanomaterials, the preparation method is simple, the synthesis conditions are mild, the synthesized K2Ti6O 13 The prepared copper-silver co-doped K2Ti6O 13 It overcomes the melt adhesion problem of potassium titanate nanomaterials synthesized by the currently commonly used sintering method or molten salt method, and overcomes the problem of the microwave reaction heating method having strict equipment requirements. The raw materials used are low in cost and suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 The copper-silver co-doped K2Ti6O obtained in Example 1 13 XRD patterns of one-dimensional nanomaterials;

[0037] Figure 2 The copper-silver co-doped K2Ti6O obtained in Example 1 13 SEM morphology of one-dimensional nanomaterials;

[0038] Figure 3 The copper-silver co-doped K2Ti6O obtained in Example 1 13 The antibacterial rate of nanomaterials against Staphylococcus aureus (Gram-positive bacteria) and Escherichia coli (Gram-negative bacteria);

[0039] Figure 4 The copper-silver co-doped K2Ti6O obtained in Example 1 13 Cell proliferation rate after 24 h of co-culture of nanomaterials and fibroblasts;

[0040] Figure 5 The copper-silver co-doped K2Ti6O obtained in Example 2 13 XRD patterns of one-dimensional nanomaterials;

[0041] Figure 6 The copper-silver co-doped K2Ti6O obtained in Example 2 13 SEM morphology of one-dimensional nanomaterials;

[0042] Figure 7 The copper-silver co-doped K2Ti6O obtained in Example 2 13 The antibacterial rate of nanomaterials against Staphylococcus aureus (Gram-positive bacteria) and Escherichia coli (Gram-negative bacteria);

[0043] Figure 8 The copper-silver co-doped K2Ti6O obtained in Example 2 13 Cell proliferation rate after 24 h of co-culture of nanomaterials and fibroblasts;

[0044] Figure 9 The copper-silver co-doped K2Ti6O obtained in Example 3 13 XRD patterns of one-dimensional nanomaterials;

[0045] Figure 10 The copper-silver co-doped K2Ti6O obtained in Example 3 13 SEM morphology of one-dimensional nanomaterials. DETAILED DESCRIPTION

[0046] The present invention will be described in further detail below in conjunction with specific examples. The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0047] Example 1

[0048] 1) Preparation of copper-silver co-doped TiO2 nanopowder by sol-gel method:

[0049] A solution A was prepared by mixing a 5% by mass aqueous solution of sodium polyacrylate, a 2% by mass dilute nitric acid, and deionized water in a volume ratio of 1:2.5:75, and stirring the mixture magnetically.

[0050] Weigh butyl titanate, Cu(NO₃)₂·XH₂O, and AgNO₃, with a (Cu+Ag) / Ti molar ratio of 1 mol%, and copper and silver doping ratios of Cu / Ti = 0.5 mol% and Ag / Ti = 0.5 mol%, respectively. Dissolve butyl titanate and anhydrous ethanol in equal volumes. Then, add Cu(NO₃)₂·XH₂O and AgNO₃ to the mixture and stir magnetically to prepare Solution B.

[0051] Solution A and solution B were then mixed in a volume ratio of 5:1, sealed and magnetically stirred at room temperature for 2 hours, and the generated white precipitate was filtered and dried to obtain copper-silver co-doped TiO2 nanopowder.

[0052] 2) Hydrothermal reaction: 1 g of the copper-silver co-doped TiO2 nanopowder prepared in step 1) was added to 100 mL of a 10 mol / L potassium hydroxide solution. After mixing by magnetic stirring, the mixture was poured into a sealed reactor and reacted at 150°C for 12 h, followed by cooling to room temperature.

[0053] 3) Cleaning and drying: The hydrothermal reaction product of step 2) was washed with deionized water for several times and filtered until the pH value was 7±0.5, and then dried at 80°C for 12h to obtain copper-silver co-doped K2Ti6O 13 Nanomaterials are one-dimensional nanostructures with radial dimensions of 5nm to 12nm and a large aspect ratio. Figure 1-Figure 2 .

[0054] Antibacterial experiment: According to the national standard of the People's Republic of China "GB / T 21510-2008 Test method for antibacterial properties of nano-inorganic materials", the copper-silver co-doped K2Ti6O 13The antibacterial activity of the nano antibacterial material was tested against the experimental strains of Staphylococcus aureus (S. aureus, ATCC25923, Gram-positive bacteria) and Escherichia coli (E. coli, ATCC25922, Gram-negative bacteria). The results showed that when the experimental doses of the antibacterial material were 100 μg / mL, 500 μg / mL and 1000 μg / mL, the antibacterial rates of the material against Staphylococcus aureus were 99.7%, 100% and 100%, respectively, and the antibacterial rates against Escherichia coli were all 100%. Figure 3 The experimental dose of the nano-inorganic antibacterial material prepared by the present invention is much lower than the experimental dose (5000 μg / mL) in the "GB / T21510-2008 Test Method for Antibacterial Performance of Nano-inorganic Materials". It can achieve high antibacterial activity against the test strains at an experimental dose of 100 μg / mL.

[0055] Cytotoxicity evaluation experiment: The prepared copper and silver were co-doped with K2Ti6O 13 After the nano-antibacterial material was co-cultured with fibroblasts for 24 hours, the cytotoxicity of the material was evaluated. The results showed that when the experimental doses of the antibacterial material were 100μg / mL, 500μg / mL L and 1000μg / mL, the cell proliferation rates were (159.9±5.4)%, (135.2±8.1)% and (94.4±4.5)%, respectively. According to the cytotoxicity grade classification of "GB / T16886.5-2003 / ISO10993-5:1999 Biological Evaluation of Medical Devices Part 5: In Vitro Cytotoxicity Test", it can be seen that the cytotoxicity grades of the material at the three experimental doses were 0, 0 and 1, respectively, showing no cytotoxicity. It can be seen that the material has good antibacterial properties while also having excellent cell compatibility and biosafety. Figure 4 .

[0056] Example 2

[0057] 1) Preparation of copper-silver co-doped TiO2 nanopowder by sol-gel method:

[0058] The prepared 6% sodium polyacrylate aqueous solution, 3% dilute nitric acid and deionized water were mixed in a volume ratio of 1:3:80 and magnetically stirred to prepare solution A;

[0059] According to the molar percentage of (Cu+Ag) / Ti being 1.0 mol%, wherein the doping amounts of copper and silver are Cu / Ti=0.9 mol% and Ag / Ti=0.1 mol%, respectively, butyl titanate, Cu(NO3)2·XH2O, and AgNO3 are weighed, butyl titanate and anhydrous ethanol are first mixed and dissolved in an equal volume ratio, and then Cu(NO3)2·XH2O and AgNO3 are added to the above mixture and magnetically stirred to prepare solution B;

[0060] Solution A and solution B were then mixed in a volume ratio of 5.5:1, sealed and magnetically stirred at room temperature for 3 hours, and the generated white precipitate was filtered and dried to obtain copper-silver co-doped TiO2 nanopowder.

[0061] 2) Hydrothermal reaction: 2.5 g of the copper-silver co-doped TiO2 nanopowder prepared in step 1) was added to 100 mL of a 12 mol / L potassium hydroxide solution. After magnetic stirring, the mixture was poured into a sealed reactor and reacted at 180°C for 24 h. The mixture was then cooled to room temperature.

[0062] 3) Cleaning and drying: The hydrothermal reaction product of step 2) was washed with deionized water for several times and filtered until the pH value was 7±0.5, and then dried at 90°C for 10 h to obtain copper-silver co-doped K2Ti6O 13 Nanomaterials are one-dimensional nanostructures with radial dimensions of 5nm to 12nm and a large aspect ratio. Figure 5-Figure 6 .

[0063] Antibacterial experiment: According to the national standard of the People's Republic of China "GB / T 21510-2008 Test method for antibacterial properties of nano-inorganic materials", the copper-silver co-doped K2Ti6O 13 The antibacterial activity of the nano antibacterial material was tested against the test strains of Staphylococcus aureus (S. aureus, ATCC25923, Gram-positive bacteria) and Escherichia coli (E. coli, ATCC25922, Gram-negative bacteria). The results showed that when the experimental doses of the antibacterial material were 100 μg / mL, 500 μg / mL and 1000 μg / mL, the antibacterial rates of the material against Staphylococcus aureus were 99.2%, 100% and 100%, respectively, and the antibacterial rates against Escherichia coli were all 100%. Figure 7 The experimental dose of the nano-inorganic antibacterial material prepared by the present invention is much lower than the experimental dose (5000 μg / mL) in the "GB / T21510-2008 Test Method for Antibacterial Performance of Nano-inorganic Materials". It can achieve high antibacterial activity against the test strains at an experimental dose of 100 μg / mL.

[0064] Cytotoxicity evaluation experiment: The prepared copper and silver were co-doped with K2Ti6O 13After the nano-antibacterial material was co-cultured with fibroblasts for 24 hours, the cytotoxicity of the material was evaluated. The results showed that when the experimental doses of the antibacterial material were 100μg / mL, 500μg / mL L and 1000μg / mL, the relative cell proliferation rates were (157.6±5.4)%, (132.9±6.1)% and (98.7±4.4)%, respectively. According to the cytotoxicity classification of "GB / T16886.5-2003 / ISO10993-5:1999 Biological evaluation of medical devices Part 5: In vitro cytotoxicity test", the cytotoxicity levels of the material at the three experimental doses were 0, 0 and 1, respectively, indicating no cytotoxicity. The material also demonstrated excellent antibacterial activity, excellent cell compatibility and biosafety. Figure 8 Compared with Example 1, the silver ion doping amount in the material is reduced while the copper ion doping amount is increased. It can be seen that under the synergistic effect of copper and silver ions, the high antibacterial activity of the material can be maintained while the cell compatibility of the material can be guaranteed, demonstrating the copper-silver co-doped K2Ti6O 13 The controllability of the biological functions of nanomaterials.

[0065] Example 3

[0066] 1) Preparation of copper-silver co-doped TiO2 nanopowder by sol-gel method:

[0067] A solution A was prepared by mixing a 4% by mass aqueous solution of sodium polyacrylate, a 2% by mass dilute nitric acid, and deionized water in a volume ratio of 1:2:60 and magnetically stirring the mixture.

[0068] According to the (Cu+Ag) / Ti molar percentage of 1.5 mol%, wherein the doping amounts of copper and silver are Cu / Ti = 1.4 mol% and Ag / Ti = 0.1 mol%, respectively, butyl titanate, Cu(NO3)2·XH2O and AgNO3 are weighed, butyl titanate and anhydrous ethanol are first mixed and dissolved in a volume ratio of 1:1.2, and then Cu(NO3)2·XH2O and AgNO3 are added to the above mixture and magnetically stirred to prepare solution B;

[0069] Solution A and Solution B were then mixed in a 4:1 volume ratio, sealed, and magnetically stirred at room temperature for 1.5 hours. The resulting white precipitate was filtered to obtain copper-silver co-doped TiO2 nanopowder. This powder was calcined at 450°C for 3 hours to obtain copper-silver co-doped TiO2 nanopowder. This nanopowder was then placed in a 5% by volume Tween 80 ethanol solution, sealed, and ultrasonically dispersed for 10 minutes before filtration and drying.

[0070] 2) Hydrothermal reaction: 1 g of the copper-silver co-doped TiO2 nanopowder prepared in step 1) was added to 100 mL of 8 mol / L potassium hydroxide solution. After magnetic stirring, the mixture was poured into a sealed reactor and hydrothermally reacted at 180°C for 10 h, followed by cooling to room temperature.

[0071] 3) Cleaning and drying: The hydrothermal reaction product of step 2) was washed with deionized water for several times and filtered until the pH value was 7±0.5, and then dried at 60°C for 20h to obtain copper-silver co-doped K2Ti6O 13 Nanomaterials, which are one-dimensional nanorod structures, have radial dimensions of 20nm to 50nm and relatively small aspect ratios. Figure 9-10 .

[0072] Comparison of copper and silver co-doped K2Ti6O under different process conditions 13 From the morphological changes of the nanomaterials (SEM morphologies of the materials in Examples 1, 2 and 3), it can be seen that the preparation method can achieve controllable preparation of material morphology.

[0073] From the above examples, it can be seen that the material obtained by the present invention can be controlled by adjusting the copper and silver doping amount of K2Ti6O 13 Biofunctional properties of nano-antibacterial materials;

[0074] If the material is used in industrial antibacterial products, such as antibacterial ceramics, coatings and other environmentally friendly building materials, since there is no direct contact with human tissue, the requirements for biocompatibility and biosafety are reduced, and only antibacterial properties are pursued, then the doping amount of Ag and Cu can be appropriately increased;

[0075] If this material is used as a filler or reinforcement for antibacterial composite materials such as polymers and metals, the amount of addition directly affects the comprehensive mechanical properties of the material. It is not possible to add more of this material just to ensure its antibacterial properties. Then, the antibacterial properties can be ensured by increasing the doping amount of Ag and Cu. This ensures both the antibacterial properties of the composite material and its comprehensive mechanical properties.

[0076] If the material is used in biomedical antibacterial agents or antibacterial products, its antibacterial properties, biocompatibility and biosafety can be well controlled by adjusting the doping amounts of Cu and Ag, thereby achieving adjustable biological functions.

[0077] Matters not covered by the present invention are known technologies.

Claims

1. A nano antibacterial material with adjustable biological function, characterized by The nano antibacterial material is copper-silver co-doped K2Ti6O 13 A nanomaterial wherein the doping amounts of copper and silver are controlled within a range of 0.5% to 3.0% by molar percentage of (Cu+Ag) / Ti, wherein the molar percentage of Cu / Ti is 0.1% to 2% and the molar percentage of Ag / Ti is 0.05% to 1.0%; and wherein the radial dimension of the one-dimensional nanostructure is 5 nm to 200 nm; The material can be tuned by adjusting the copper and silver doping amount according to its application requirements. 13 Biofunctional properties of nano-antibacterial materials; the biofunctional properties are antibacterial activity, biocompatibility or biosafety; The method for preparing the nano antibacterial material with adjustable biological function comprises the following steps: 1) Preparation of copper-silver co-doped TiO2 nanopowder by sol-gel method: A sodium polyacrylate aqueous solution, dilute nitric acid, and deionized water were mixed and magnetically stirred to prepare solution A; Meanwhile, butyl titanate and anhydrous ethanol were mixed and dissolved, and then hydrated copper nitrate and silver nitrate were added to the above solution by molar percentage, and magnetic stirring was performed to prepare solution B; Then, solution A and solution B are mixed, sealed and magnetically stirred at room temperature for 0.5 to 5 hours, and the generated white precipitate is filtered and dried to obtain copper-silver co-doped TiO2 nanopowder; the nanopowder is calcined at 350 to 650°C for 0.5 to 6 hours to obtain copper-silver co-doped TiO2 nanopowder; Wherein, in the preparation of solution A, the volume ratio of sodium polyacrylate aqueous solution: dilute nitric acid: deionized water = 1:1~5:25~100; In the preparation of solution B, the volume ratio of butyl titanate to anhydrous ethanol is 1:0.5-1.5; the molar ratio of hydrated copper nitrate and silver nitrate to butyl titanate is (Cu+Ag) / Ti = 0.5%-3%; Cu / Ti = 0.1-2%, Ag / Ti = 0.05-1.0%; Solution A and solution B are mixed in a volume ratio of solution A: solution B = 3~10:1; 2) Hydrothermal reaction: The copper-silver co-doped TiO2 nanopowder prepared in step 1) is added to a potassium hydroxide solution and mixed by magnetic stirring. The mixture is poured into a sealed reactor and reacted at 100°C to 200°C for 6 to 48 hours. The mixture is then cooled to room temperature in the reactor. 0.1 to 5 g of the copper-silver co-doped TiO2 nanopowder is added per 100 mL of the potassium hydroxide solution. 3) Cleaning and drying: The hydrothermal reaction product of step 2) was washed with deionized water, filtered until the pH value was 7±0.5, and then dried to obtain copper-silver co-doped K2Ti6O 13 Nanomaterials; Step 1) The concentration of the dilute nitric acid is 0.5-5% by mass; the mass percentage of the sodium polyacrylate aqueous solution is 1-10%; The particle size of the copper-silver co-doped TiO2 nanoparticle powder is 5 to 12 nm; the particle size of the copper-silver co-doped TiO2 nanoparticle powder after calcination is 10 nm to 200 nm; The preparation method also includes the following steps: the obtained copper-silver co-doped TiO2 nanopowder is calcined, then added to a Tween 80 ethanol solution for ultrasonic dispersion, and then filtered and dried; the ultrasonic dispersion time is 5 to 20 minutes; the volume ratio of the Tween 80 ethanol solution is Tween 80: anhydrous ethanol = 0.5 to 10%.

2. The nano antibacterial material with adjustable biological function as claimed in claim 1, characterized in that: In step 2) of the preparation method, the concentration of the potassium hydroxide solution is 5 to 12 mol / L.

3. The nano antibacterial material with adjustable biological function as claimed in claim 1, characterized in that: In step 3) of the preparation method, the drying temperature is 60° C. to 100° C., and the drying time is 6 h to 24 h.

Images