Sea urchin-like antibacterial piezoelectric copper zinc oxide and preparation method and application thereof

Abstract

The application discloses a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide and a preparation method and application thereof, and belongs to the field of biological medical materials. The preparation of the copper-zinc oxide comprises the following steps: (1) weighing Cu 2+ and Zn 2+ containing compound raw materials, dissolving the raw materials in deionized water, and preparing a mixed solution after dispersion; (2) adding the mixed solution obtained in the step (1) into deionized water containing DMSO, stirring and uniformly mixing, and preparing a solution containing Cu 2+ and Zn 2+ ; (3) adding an alkali source into the solution obtained in the step (2), heating and reacting, centrifugally collecting a precipitate, and obtaining the copper-zinc oxide after washing. The copper-zinc particles are subjected to thermal hydrolysis under the action of the organic solvent DMSO under an alkaline condition, and the copper-zinc oxide with a sea urchin-shaped structure is generated; and the oxide exhibits excellent piezoelectric antibacterial performance under stirring at room temperature.

Description

Technical Field

[0001] This invention belongs to the field of biomedical materials, specifically relating to a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide, its preparation method, and its application. Background Technology

[0002] Antimicrobial resistance is one of the top ten public health threats facing the world in recent years, such as the emergence of drug-resistant bacteria due to antibiotic overuse. Zinc oxide (ZnO), due to its good stability, low price, abundant resources, and excellent antibacterial properties at low concentrations, has become a hot topic in inorganic antibacterial agent research. In recent years, ZnO has also shown promise in catalysis, antibacterial activity, and dye degradation due to its unique piezoelectric properties. By utilizing mild energy from the environment and releasing electrons under controlled stimulation, it catalyzes redox reactions of substrates (such as water and tissue oxygen), generating a series of reactive oxygen species (ROS) radicals (such as hydroxyl radicals and superoxide anions). This is one of the most promising pathways for ZnO to exert its antibacterial properties. Therefore, focusing on the development of high-performance piezoelectric zinc oxide complexes has significant practical value and major clinical application prospects for further improving ROS levels and achieving highly efficient antibacterial activity.

[0003] Although metal doping is an effective way to enhance the piezoelectric properties of ZnO, and previous studies have shown that copper doping can significantly improve the piezoelectric catalytic performance of ZnO, current research indicates that the crystal morphology of ZnO needs improvement, and the specific surface area of ​​the current material structure is relatively small, resulting in certain defects in its photocatalytic or piezoelectric properties.

[0004] Therefore, developing materials with high specific surface area and high effective exposed area is one of the potential ways to maximize piezoelectric performance and construct highly efficient ROS-level antibacterial materials. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, one of the objectives of this invention is to provide a method for preparing sea urchin-shaped antibacterial piezoelectric copper-zinc oxide. This invention utilizes copper doping and further control of material morphology to develop materials with high specific surface area and high exposed effective area, thereby achieving dual-effect piezoelectric properties to effectively increase ROS, and thus constructing highly efficient antibacterial drugs.

[0006] The second objective of this invention is to provide a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide prepared according to the above method.

[0007] The third objective of this invention is to provide the application of the sea urchin-shaped antibacterial piezoelectric copper-zinc oxide prepared according to the above method in the preparation of antibacterial drugs.

[0008] One of the objectives of this invention is achieved through the following technical solution:

[0009] A method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide includes the following steps:

[0010] (1) Weigh out the amount containing Cu 2+ and containing Zn 2+ The compound raw material is dissolved in deionized water and dispersed to obtain a mixed solution;

[0011] (2) Add the mixed solution obtained in step (1) to deionized water containing DMSO, stir and mix evenly to obtain a solution containing Cu. 2+ and Zn 2+ The solution;

[0012] (3) Add an alkaline source to the solution obtained in step (2), heat to react, centrifuge to collect the precipitate, and wash to obtain the final product.

[0013] Further, the Cu-containing step (1) 2+ The compound raw material is any one of copper chloride, copper nitrate, and copper acetate, wherein the Zn-containing... 2+ The raw materials for the compound are any one of zinc chloride, zinc nitrate, and zinc acetate dihydrate.

[0014] Further, the Cu described in step (2) 2+ With Zn 2+ The molar ratio of Zn in the solution is 1:9. 2+ The final molar concentration is 1.0 mmol / L-12.0 mmol / L.

[0015] Further, in step (2), the volume ratio of DMSO to deionized water in the deionized water containing DMSO is (0.45-2):9.

[0016] Furthermore, the alkali source in step (3) includes any one of NH3·H2O, NaOH, and KOH solution.

[0017] Furthermore, the final concentration of hydroxide ions in the solution obtained in step (2) of the alkaline source in step (3) is 4.0-48.0 mmol / L.

[0018] Furthermore, the heating reaction temperature in step (3) is 50-90℃, and the heating reaction time is 3-12h.

[0019] The second objective of this invention is achieved by the following technical solution:

[0020] Sea urchin-like antibacterial piezoelectric copper-zinc oxide was prepared by the above method.

[0021] The third objective of this invention is achieved by the following technical solution:

[0022] This invention relates to the application of the sea urchin-shaped antibacterial piezoelectric copper-zinc oxide prepared by the above method in the preparation of antibacterial drugs.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] 1. The copper-zinc oxide prepared by this invention has a sea urchin-like morphology, which expands the specific surface area and exposed effective area of ​​the copper-zinc oxide, thereby improving the piezoelectric properties of the copper-zinc oxide material. This invention demonstrates through experimental data that oscillation can induce the piezoelectric effect of ZnO / CuO, achieving efficient ROS generation. Furthermore, this copper-zinc oxide exhibits highly efficient antibacterial properties even at a concentration of only 40 ng / mL. Attached Figure Description

[0025] Figure 1 This is a TEM image of the copper-zinc oxide prepared in Example 1 of the present invention;

[0026] Figure 2 XPS image of the urchin-shaped copper-zinc oxide prepared in Example 1 of this invention;

[0027] Figure 3 This is a graph showing the detection results of piezoelectric reactive oxygen species generated by the sea urchin-shaped copper-zinc oxide prepared in Example 1 of this invention.

[0028] Figure 4 The images show the antibacterial test results of the sea urchin-shaped copper-zinc oxide prepared in Example 1 of this invention after being induced by different treatment methods. From left to right, the images show the antibacterial results of the copper-zinc oxide after shaking culture for 0h, 8h, 16h and 24h, and static culture for 24h. Detailed Implementation

[0029] The present invention will now be further described in conjunction with the accompanying drawings and specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0030] Example 1

[0031] Accurately weigh 13 mg of zinc acetate dihydrate and 1.3 mg of copper acetate, dissolve them in 1 mL of deionized water, and ultrasonically disperse them evenly. Then, add the mixture to 20 mL of deionized water containing 1 mL of DMSO, ultrasonically disperse it evenly, and stir (600 rpm) for 1 h. Subsequently, add 25 μL of ammonia solution (1 mol / L), heat the mixture at 60 °C for 4 h, and centrifuge and wash to obtain a light brown solid powder, which is copper zinc oxide.

[0032] Example 2

[0033] Accurately weigh zinc chloride (2.86 mg) and copper chloride (0.31 mg), dissolve them in 1 mL of deionized water, and ultrasonically disperse them evenly. Then, add 20 mL of deionized water containing 2 mL of DMSO, ultrasonically disperse the mixture evenly, and stir (600 rpm) for 1 h. Subsequently, add 84 μL of pre-prepared NaOH aqueous solution (1 mol / L), heat the mixture at 50 °C for 12 h, and centrifuge and wash to obtain the target copper-zinc oxide.

[0034] Example 3

[0035] Accurately weigh zinc nitrate (47.75 mg) and copper nitrate (5.25 mg), dissolve them in 1 mL of deionized water, and ultrasonically disperse them evenly. Then, add 20 mL of deionized water containing 3.64 mL of DMSO, ultrasonically disperse the mixture evenly, and stir (600 rpm) for 1 h. Subsequently, add 1.05 mL of pre-prepared KOH aqueous solution (1 mol / L), heat the mixture at 90 °C for 3 h, and centrifuge and wash to obtain the target copper-zinc oxide.

[0036] Experimental Example 1

[0037] The morphology of the copper-zinc oxide obtained in Example 1 was characterized by transmission electron microscopy (TEM), and the results are as follows: Figure 1 As shown.

[0038] like Figure 1 As shown, the copper-zinc oxide prepared by this invention exhibits a uniform sea urchin-like morphology, with needle-like aggregates uniformly dispersed on the surface of nanoparticles. This result provides the possibility of increasing the specific surface area and exposed effective area of ​​the copper-zinc oxide to enhance its piezoelectric properties.

[0039] Experimental Example 2

[0040] The electronic structure of the elements in the urchin-like copper-zinc oxide obtained in Example 1 was determined using X-ray photoelectron spectroscopy (XPS), and the results are as follows: Figure 2 As shown.

[0041] Figure 2 XPS analysis of the prepared urchin-like copper-zinc oxide showed that Zn2p peaks could be separated into Zn2p peaks. 3 / 2 (1022.31eV) and Zn2p 1 / 2 (1045.42 eV) indicates that Zn is mainly composed of Zn 2+ It exists in form. Simultaneously, Cu2p exhibits Cu2p... 3 / 2 (935.42eV) and Cu2p 1 / 2 (955.34eV) and Cu 2+ The specific accompanying peaks (Sat. 943.21 eV and 963.19 eV) indicate that Cu also exists in the divalent Cu form. 2+The form exists within the composite. Furthermore, the O1s spectrum exhibits metal-O and -OH peaks at 530.75 eV and 531.77 eV, respectively. These results confirm that the copper-zinc oxide prepared in Example 1 is a ZnO / CuO nanocomposite.

[0042] Experimental Example 3

[0043] To investigate the piezoelectric properties of the urchin-like copper-zinc oxide obtained in Example 1 and the resulting reactive oxygen species (ROS) levels, magnetic stirring at room temperature and TMB (3,3',5,5'-tetramethylphenyldiamine) were used for testing and verification. The specific steps are as follows: First, PBS buffer solution (pH=5), 0.2 mol / L H2O2 solution, 1 mg / mL TMB solution, and 3.4 mg / mL copper-zinc oxide solution were prepared, respectively. TMB, as a chromogenic agent, reacts with ROS and produces a significant color change. 1500 μL of PBS, 200 μL of H2O2 solution, 200 μL of TMB solution, and 500 μL of copper-zinc oxide solution were mixed together, and then stirred at 150 rpm at room temperature to promote effective reaction. The solutions were analyzed using UV absorption spectroscopy at 15 min, 30 min, 45 min, 60 min, 90 min, and 120 min of reaction. The results of the TMB UV absorption change curve induced by copper-zinc oxide are shown below. Figure 3 As shown.

[0044] like Figure 3 The UV absorption curves of the urchin-shaped copper-zinc oxide obtained by stirring at room temperature for different times to induce TMB oxidation show that the UV absorption peak intensity of the TMB dimer at 635 nm increases significantly with increasing stirring time. This indicates that TMB reacts with ROS to generate a substance with significant UV absorption characteristics, resulting in a gradual increase in the UV absorption peak intensity of the solution. This phenomenon demonstrates that the copper-zinc oxide exhibits a piezoelectric effect during stirring, thereby inducing ROS formation. Therefore, the above results not only verify the piezoelectric properties of the copper-zinc oxide obtained in Example 1 but also reveal its great potential in ROS formation.

[0045] Test Example 4

[0046] To comprehensively evaluate the antibacterial properties of the sea urchin-shaped copper-zinc oxide obtained in Example 1, methicillin-resistant Staphylococcus aureus (MRSA), a highly drug-resistant strain, was used as the test strain for antibacterial performance testing. The sea urchin-shaped copper-zinc oxide obtained in Example 1 was divided into two groups: a static culture group and a shaking and stirring group. In the static culture group, 200 μL of a 40 ng / mL copper-zinc oxide PBS solution (pH = 7.4) was mixed with 1800 μL of a 1×10⁻⁶ ppm solution. 5A CFU / mL bacterial (MRSA) suspension was mixed and then incubated at 37°C for 24 hours. After incubation, 100 μL of the mixture was spread onto the surface of an agar medium, which was then incubated at 37°C for another 16 hours. The number of colonies on the surface was observed. In the vibrating stirring group (piezoelectric group), 200 μL of a 40 ng / mL copper zinc oxide PBS (pH = 7.4) solution was mixed with 1800 μL of a 1×10⁻⁶ CFU / mL PBS solution. 5 A mixture of CFU / mL MRSA bacteria was incubated at 37°C in a shaker at 150 rpm for 8 h, 16 h, and 24 h. After each incubation period, 100 μL of the mixture was spread onto an agar medium and incubated at 37°C for another 16 h before observing the number of colonies on the surface. Finally, macroscopic images obtained from the two experiments were used to evaluate the antibacterial and piezoelectric effects of copper-zinc oxide under static and vibratory stirring conditions.

[0047] Figure 4 The figures show the results of bacterial plating experiments on the sea urchin-shaped copper-zinc oxide prepared in Example 1 after induction by different treatment methods. It can be clearly observed from the figures that the antibacterial performance of the copper-zinc oxide significantly increases with increasing shaking time. This result fully demonstrates that the copper-zinc oxide prepared in this invention possesses excellent piezoelectric antibacterial properties. Compared to the static culture group, the results of the vibration-stirring group show that the antibacterial performance of the copper-zinc oxide is more pronounced after 24 hours of vibration incubation. This indicates that vibration can induce piezoelectric behavior in the copper-zinc oxide, thereby generating more ROS and achieving highly efficient antibacterial activity. Therefore, the above results prove that by inducing piezoelectric behavior in copper-zinc oxide through vibration, highly efficient ROS generation can be achieved, thus achieving highly efficient antibacterial activity. More importantly, even at a copper-zinc oxide concentration of only 40 ng / mL, the copper-zinc oxide prepared in Example 1 exhibits extremely high antibacterial performance. This result not only further corroborates the rationality and advancement of the design of this invention but also fully demonstrates that the highly efficient, low-concentration antibacterial performance of the copper-zinc oxide material obtained in this invention makes it a promising candidate for application in the biomedical field.

[0048] In summary, the copper-zinc oxide prepared by this invention exhibits a sea urchin-like structure, which expands the specific surface area and effective exposed area of ​​the copper-zinc oxide, enhancing the piezoelectric properties of the material and achieving efficient ROS generation and a significant improvement in antibacterial performance. This discovery not only enriches the research content of piezoelectric antibacterial materials but also provides new ideas and directions for constructing highly efficient antibacterial materials.

[0049] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide, characterized in that, Includes the following steps: (1) Weigh out the amount containing Cu 2+ and containing Zn 2+ The compound raw material is dissolved in deionized water and dispersed to obtain a mixed solution; (2) Add the mixed solution obtained in step (1) to deionized water containing DMSO, stir and mix evenly to obtain a solution containing Cu. 2+ and Zn 2+ The solution; (3) Add an alkaline source to the solution obtained in step (2), heat to react, centrifuge to collect the precipitate, and wash to obtain the final product.

2. The method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide according to claim 1, characterized in that, Step (1) contains Cu 2+ The compound raw material is any one of copper chloride, copper nitrate, and copper acetate, wherein the Zn-containing... 2+ The raw materials for the compound are any one of zinc chloride, zinc nitrate, and zinc acetate dihydrate.

3. The method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide according to claim 2, characterized in that, Step (2) Cu 2+ With Zn 2+ The molar ratio of Zn in the solution is 1:

9. 2+ The final molar concentration is 1.0 mmol / L-12.0 mmol / L.

4. The method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide according to claim 1, characterized in that, In step (2), the volume ratio of DMSO to deionized water in the deionized water containing DMSO is (0.45-2):

9.

5. The method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide according to claim 1, characterized in that, The alkaline source in step (3) includes any one of NH3·H2O, NaOH, and KOH solution.

6. The method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide according to claim 1, characterized in that, The final concentration of hydroxide ions in the solution obtained in step (2) of the alkaline source in step (3) is 4.0-48.0 mmol / L.

7. The method for preparing a sea urchin-shaped antibacterial piezoelectric copper-zinc oxide according to claim 1, characterized in that, The heating reaction temperature in step (3) is 50-90℃, and the heating reaction time is 3-12h.

8. A sea urchin-shaped antibacterial piezoelectric copper-zinc oxide, characterized in that, Prepared by the method according to any one of claims 1-7.

9. The application of the sea urchin-shaped antibacterial piezoelectric copper-zinc oxide according to claim 8 in the preparation of antibacterial drugs.

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