A black talc-loaded manganese oxide antibacterial material and preparation method thereof

Abstract

The present invention relates to the technical field of antibacterial materials, and in particular to an antibacterial material comprising black talc and manganese oxide, and a preparation method thereof. The antibacterial material comprising black talc and manganese oxide loaded on its surface, wherein the manganese oxide comprises Mn3O4 and MnOOH. The antibacterial material is obtained by loading manganese oxide on the surface of the black talc using potassium permanganate, urea, and hexadecyltrimethylammonium bromide as raw materials and employing a hydrothermal reaction in-situ synthesis method. The present invention utilizes the unique layered structure of black talc and synthesizes manganese oxide on the surface of the black talc using a liquid phase in-situ synthesis method. The crystal phase and morphology of the manganese oxide are controlled by adding black talc and regulating the synthesis temperature. This material not only improves the stability of the manganese oxide, reduces aggregation, and exhibits high antibacterial properties, but also enhances its biocompatibility, exhibits low cytotoxicity and low hemolytic properties, and is suitable for various biomedical applications.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial materials, and in particular to an antibacterial material of black talc loaded with manganese oxide and a preparation method thereof. Background Art

[0002] Although metal oxide antibacterial materials exhibit good antibacterial properties, there are still many problems that need to be solved in practical applications. First, many metal oxides tend to aggregate in solution. This aggregation phenomenon not only reduces their effective surface area, but may also lead to a significant decrease in antibacterial activity. For example, zinc oxide nanoparticles tend to form aggregates in water, which limits the performance of their antibacterial properties. Secondly, the synthesis process of metal oxides is usually complicated and has strict requirements on operating conditions. This not only increases production costs, but also limits their promotion in large-scale applications. For example, although the commonly used sol-gel method can obtain materials with higher purity, due to its complex process, it often leads to insufficient uniformity of the material, thereby affecting the antibacterial effect. Biocompatibility is also an important issue. Some metal oxides may induce toxic reactions in the body, leading to cell damage or inflammatory reactions, limiting their application in biomedical materials.

[0003] Currently, researchers have developed a variety of techniques for preparing antimicrobial metal oxide materials, primarily including chemical precipitation, sol-gel, hydrothermal, and solid-phase synthesis. Each of these techniques has its advantages and disadvantages. For example, chemical precipitation is widely used due to its simplicity and low cost, but it can easily lead to aggregation and uneven material properties. Sol-gel methods can achieve relatively uniform particle distribution, but their complex process and high sensitivity to temperature and humidity often result in insufficient homogeneity, which in turn affects antimicrobial efficacy. Hydrothermal synthesis, under high temperature and pressure conditions, can produce high-purity and high-crystallinity metal oxides, but this requires high equipment investment and has limited applicability. While solid-phase synthesis can improve material stability, it often requires a long time and high energy consumption. To address these issues, researchers have also attempted to combine metal oxides with other materials to form novel composite materials. For example, combining metal oxides with polymers, carbon materials, and other materials to form composites can further enhance antimicrobial properties and environmental adaptability. Modulating the particle size, morphology, and surface modification of metal oxides can also significantly improve their antimicrobial efficacy. However, the preparation process of composite materials is often complicated, and interactions at the material interface may lead to unstable performance.

[0004] In summary, although existing metal oxide antimicrobial material technology has made certain progress, it still has significant limitations. First, many metal oxides aggregate in practical applications, resulting in the inability to fully exert their antimicrobial effects. Second, the synthesis process is complex and involves multiple steps, which increases production costs and time. At the same time, biocompatibility and safety issues are gradually receiving attention, and some metal oxides may have potential toxic effects on organisms. Therefore, it is particularly important to develop a new type of antimicrobial material that can not only improve antimicrobial properties but also have good biocompatibility. Summary of the Invention

[0005] The present invention aims to address the above-mentioned deficiencies in the prior art and to provide a black talc-loaded manganese oxide antibacterial material and its preparation method. The material not only has excellent antibacterial properties but also improves biocompatibility, making it suitable for use in the medical and biomaterial fields.

[0006] The invention discloses a black talc-loaded manganese oxide antibacterial material, comprising black talc and manganese oxide loaded on the surface of the black talc, wherein the manganese oxide comprises Mn3O4 and MnOOH.

[0007] The present invention provides a method for preparing the above-mentioned black talc-loaded manganese oxide antibacterial material, which uses potassium permanganate, urea and cetyltrimethylammonium bromide as raw materials, adopts a hydrothermal reaction in-situ synthesis method, and loads manganese oxide on the surface of the black talc to obtain the antibacterial material.

[0008] Furthermore, the temperature of the hydrothermal reaction is 150-190°C.

[0009] Furthermore, the purity of the black talc is 70-85%.

[0010] Furthermore, black talc is dissolved in a certain amount of KMnO4 and urea solution, and then CTAB is added to the mixed solution and stirred in a water bath, and a hydrothermal reaction is carried out at 150-190°C. After the reaction is completed, it is filtered, dried and cooled to room temperature, and then taken out and fully ground to obtain a powdered sample, namely the antibacterial material.

[0011] Furthermore, the mass ratio of black talc to KMnO4 is 0.4-0.8.

[0012] Further, the mixture was stirred in a water bath at 60-80°C for 30 min.

[0013] Further, drying at 60-80°C and cooling to room temperature.

[0014] This invention utilizes the unique layered structure of black talc to synthesize manganese oxide on the black talc surface using a liquid-phase in-situ synthesis method. The addition of black talc and controlled synthesis temperature control the crystal phase and morphology of the manganese oxide. High temperatures and the addition of talc facilitate the conversion of Mn3O4 to MnOOH. This not only improves the stability of the manganese oxide, reduces aggregation, and enhances its antibacterial properties, but also enhances its biocompatibility, resulting in low cytotoxicity and low hemolytic activity, making it suitable for various biomedical applications.

[0015] The preparation method of the present invention is simple, easy to realize large-scale production, and has good market application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 XRD patterns of samples prepared in Examples 1-3 and Comparative Examples 1-3;

[0017] Figure 2 XPS graphs of samples prepared in Examples 1-3 and Comparative Examples 1-3;

[0018] Figure 3 The SEM images of Examples 1-3 and Comparative Examples 1-3 are shown;

[0019] Figure 4 TEM of Examples 1-3 and Comparative Examples 1-3;

[0020] Figure 5-10 Statistical graphs of the antibacterial performance test and biosafety test results of Comparative Examples 1-3 and Examples 1-3;

[0021] Figure 11 This is the SEM imaging of Example 3 (M / T-190) and bacteria. DETAILED DESCRIPTION

[0022] The following are specific embodiments of the present invention and the accompanying drawings to further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0023] Example 1

[0024] In this example, M / T-150 was prepared. 0.79g of KMnO4 and 0.075g of urea were added to 20mL of deionized water. 0.225g of CTAB was then dissolved, and 0.5g of black talc was added. The mixture was heated in a 60°C waterbath for 30 minutes. After removal, the mixture was transferred to a hydrothermal reactor and hydrothermalized at 150°C. After completion of the reaction, the mixture was filtered, oven-dried at 60-80°C, cooled to room temperature, and thoroughly ground to obtain a powdered sample. This yielded M / T-150.

[0025] Example 2

[0026] In this example, M / T-170 was prepared. 0.79g of KMnO4 and 0.075g of urea were added to 20mL of deionized water. 0.225g of CTAB was then dissolved, and 0.5g of black talc was added. The mixture was heated in a 60°C waterbath for 30 minutes. After removal, the mixture was transferred to a hydrothermal reactor and hydrothermalized at 170°C. After completion of the reaction, the mixture was filtered, oven-dried at 60-80°C, cooled to room temperature, and thoroughly ground to obtain a powdered sample. This yielded M / T-170.

[0027] Example 3

[0028] In this example, M / T-190 was prepared. 0.79g of KMnO4 and 0.075g of urea were added to 20mL of deionized water. 0.225g of CTAB was then dissolved, and 0.5g of black talc was added. The mixture was heated in a 60°C waterbath for 30 minutes. After removal, the mixture was transferred to a hydrothermal reactor and hydrothermalized at 190°C. After completion of the reaction, the mixture was filtered, oven-dried at 60-80°C, cooled to room temperature, and thoroughly ground to obtain a powdered sample. This resulted in M / T-190.

[0029] Comparative Example 1

[0030] In this comparative example, M-150 was prepared. 0.79g of KMnO4 and 0.075g of urea were added to 20mL of deionized water, followed by the addition of 0.225g of CTAB to dissolve the mixture. The mixture was then placed in a 60°C waterbath and heated for 30 minutes. The mixture was then transferred to a hydrothermal reactor and hydrothermalized at 150°C. After the reaction, the mixture was filtered, oven-dried at 60-80°C, cooled to room temperature, and thoroughly ground to obtain a powdered sample. This yielded M-150.

[0031] Comparative Example 2

[0032] In this comparative example, M-170 was prepared. 0.79g of KMnO4 and 0.075g of urea were added to 20mL of deionized water, followed by the addition of 0.225g of CTAB to dissolve the mixture. The mixture was then placed in a 60°C waterbath and heated for 30 minutes. The mixture was then transferred to a hydrothermal reactor and hydrothermalized at 170°C. After the reaction, the mixture was filtered, oven-dried at 60-80°C, cooled to room temperature, and thoroughly ground to obtain a powdered sample. This yielded M-170.

[0033] Comparative Example 3

[0034] In this comparative example, M-190 was prepared. 0.79g of KMnO4 and 0.075g of urea were added to 20mL of deionized water, followed by the addition of 0.225g of CTAB to dissolve the mixture. The mixture was then placed in a 60°C waterbath and heated for 30 minutes. The mixture was then transferred to a hydrothermal reactor and hydrothermalized at 190°C. After the reaction, the mixture was filtered, oven-dried at 60-80°C, cooled to room temperature, and thoroughly ground to obtain a powdered sample. This yielded M-190.

[0035] Antibacterial activity test: Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were grown in 5 ml of Luria-Bertani (LB) broth at 37°C for 4 hours. The bacterial culture was then diluted to 10 4 to 10 5 times, making its concentration about 10 6 CFU / mL. Different concentrations of antimicrobial materials (M-150, M-170, M-190, M / T-150, M / T-170, M / T-190) were added to the bacterial suspension, and their antimicrobial efficacy was evaluated using the plate count technique. The bacterial growth inhibition rate was determined by comparing the colony counts of the test samples with those of the control group.

[0036] Biosafety Testing: 1. Cytotoxicity: The cytotoxicity of the composite material on BJ cells was determined using a direct contact method. BJ cells were cultured in 1640 medium supplemented with 10% fetal bovine serum and 1% penicillin / streptomycin in a 5% CO2 atmosphere at 37°C for three days. The samples were then incubated in 96-well plates for 24 hours. After incubation, 100 μL of CCK-8 (Cell Proliferation and Toxicity Assay Kit) reagent was added to each well and incubated at 37°C for an additional hour. Absorbance at 450 nm was measured using a plate reader to calculate cell viability. 2. Hemolysis: Fresh rabbit blood treated with anticoagulant was washed with phosphate buffered saline to prepare a 5% erythrocyte suspension. Equal amounts of 500 μL of the composite material solution were mixed with the same amount of erythrocyte suspension and incubated at 37°C for one hour. Phosphate buffered saline and water were used as negative and positive controls, respectively. After centrifugation, the supernatant was collected and absorbance was measured at 545 nm using a microplate reader to calculate the hemolysis rate.

[0037] The results of antibacterial performance test and biosafety test are shown in Table 1 and Figure 5-10 shown.

[0038] Table 1. Biological properties of Examples and Comparative Examples

[0039]

[0040] As can be seen from the above table, the antibacterial properties of the M / T-150 material prepared in Example 1 at a concentration of 0.50 mg / mL are 88.67% (E. coli) and 82.56% (S. aureus); the cell survival rate at a concentration of 0.025 mg / mL is 59.29%; and the hemolysis rate at a concentration of 0.10 mg / mL is 18.12%.

[0041] The antibacterial properties of the M / T-170 material prepared in Example 2 at a concentration of 0.50 mg / mL were 94.85% (E. coli) and 94.05% (S. aureus); the cell survival rate at a concentration of 0.025 mg / mL was 68.80%; and the hemolysis rate at a concentration of 0.10 mg / mL was 19.03%.

[0042] The antibacterial properties of the M / T-190 material prepared in Example 3 at a concentration of 0.50 mg / mL were 96.56% (E. coli) and 99.45% (S. aureus); the cell survival rate at a concentration of 0.025 mg / mL was 84.13%; and the hemolysis rate at a concentration of 0.10 mg / mL was 1.79%.

[0043] The antibacterial properties of the M-150 material prepared in Comparative Example 1 at a concentration of 0.50 mg / mL were 95.36% (E. coli) and 93.21% (S. aureus); the cell survival rate at a concentration of 0.025 mg / mL was 41.87%; and the hemolysis rate at a concentration of 0.10 mg / mL was 95.61%.

[0044] The antibacterial properties of the M-170 material prepared in Comparative Example 2 at a concentration of 0.50 mg / mL were 81.21% (E. coli) and 84.69% (S. aureus); the cell survival rate at a concentration of 0.025 mg / mL was 48.08%; and the hemolysis rate at a concentration of 0.10 mg / mL was 111.52%.

[0045] The antibacterial properties of the M-190 material prepared in Comparative Example 3 at a concentration of 0.50 mg / mL were 95.92% (E. coli) and 93.05% (S. aureus); the cell survival rate at a concentration of 0.025 mg / mL was 58.92%; and the hemolysis rate at a concentration of 0.10 mg / mL was 55.58%.

[0046] Figure 1 These are XRD patterns of samples prepared in Examples 1-3 and Comparative Examples 1-3. The Mn oxides in the Examples and Comparative Examples are mixtures of Mn3O4 and MnOOH.

[0047] Figure 2XPS analysis of samples prepared in Examples 1-3 and Comparative Examples 1-3 shows the Mn valence distribution in the XPS analysis of the Examples and Comparative Examples. The addition of black talc increases the content of high-valence Mn(IV). At the same synthesis temperature, the addition of black talc increases the content of higher-valence Mn(IV), indicating that black talc regulates the formation of MnOOH and Mn3O4, affecting the Mn valence distribution.

[0048] Figure 3 The SEM images of Examples 1-3 and Comparative Examples 1-3 show that MnOx alone exhibits a rod-like morphology, and the higher the temperature, the larger the rods. The addition of black talc causes the rod-like MnOx to be converted into irregular nanoparticles. M / T-150 is a smaller nanowire, M / T-170 is a mixture of nanorods and nanoparticles, and M / T-190 is the most significant, with most of the particles being irregular nanoparticles.

[0049] Figure 4 TEM morphology and crystal phase analysis of Examples 1-3 and Comparative Examples 1-3. The primary crystalline phase observed for M-150 is Mn3O4, while the primary crystalline phase observed for M-170 and M-190 is Mn3O4, with a mixed crystalline phase of Mn3O4 and MnOOH observed. The primary crystalline phase observed for M / T-150 and M / T-170 is Mn3O4, while the primary crystalline phase observed for M / T-190 is MnOOH. The addition of black talc stabilizes the MnOOH crystalline phase at 190 degrees Celsius.

[0050] Figure 5 Statistical chart of biological performance and antibacterial performance of comparative example 1; the biological performance of comparative example 1 (M-150) is high in antibacterial effect, with each concentration being higher than 95%; the cell survival rate is low, all lower than 75%, and the hemolysis rate is high, all higher than 5%.

[0051] Figure 6 Statistical chart of biological performance and antibacterial performance of comparative example 2; the biological performance of comparative example 2 (M-170) is high in antibacterial effect, with each concentration being higher than 95%; the cell survival rate is low, all lower than 75%, and the hemolysis rate is high, all higher than 5%.

[0052] Figure 7 Statistical chart of biological performance and antibacterial performance of comparative example 3; the biological performance of comparative example 3 (M-190) is high in antibacterial effect, with each concentration being higher than 95%; the cell survival rate is low, being lower than 75% when the concentration is higher than 0.025, and the hemolysis rate is high, being higher than 5% when the concentration is higher than 0.10.

[0053] Figure 8Statistical graphs of the biological properties and antibacterial properties of Example 1; the biological properties of Example 1 (M / T-150) show that the antibacterial effect is average, exceeding 95% when the concentration is lower than 0.5; the cell survival rate is average, falling below 75% when the concentration is higher than 0.025; the hemolysis rate is high, exceeding 5% when the concentration is higher than 0.10.

[0054] Figure 9 Statistical chart of biological performance and antibacterial performance of Example 2; the biological performance of Example 2 (M / T-170) is high, the antibacterial effect is higher than 95%; the cell survival rate is average, lower than 80% when the concentration is higher than 0.050, and the hemolysis rate is high, higher than 5% when the concentration is higher than 0.10.

[0055] Figure 10 Statistical chart of biological performance and antibacterial performance of Example 3; Example 3 (M / T-190) has high biological performance and antibacterial effect, both higher than 95%; high cell survival rate, both higher than 75%, good hemolysis rate, both higher than 5% when the concentration is higher than 0.20.

[0056] Figure 11 SEM imaging of Example 3 (M / T-190) and bacteria. The bacterial morphology was deformed after the addition of M / T-190.

[0057] Any matters not mentioned above shall be subject to the existing technology.

[0058] Although some specific embodiments of the present invention have been described in detail through examples, those skilled in the art should understand that the above examples are for illustration only and are not intended to limit the scope of the present invention. Those skilled in the art of the present invention may make various modifications or additions to the described specific embodiments or replace them in similar ways, but they will not deviate from the direction of the present invention or exceed the scope defined by the appended claims. Those skilled in the art should understand that any modifications, equivalent replacements, improvements, etc. made to the above embodiments based on the technical essence of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an antibacterial material of black talc-loaded manganese oxide, characterized in that: The antibacterial material includes black talc and manganese oxide loaded on its surface, wherein the manganese oxide includes Mn3O4 and MnOOH; The preparation steps are as follows: The antibacterial material is obtained by using potassium permanganate, urea and cetyltrimethylammonium bromide as raw materials and adopting a hydrothermal reaction in-situ synthesis method to load manganese oxide on the surface of black talc; The temperature of the hydrothermal reaction is 150-190 °C.

2. The preparation method according to claim 1, wherein: The purity of black talc is 70-85%.

3. The preparation method according to claim 1, wherein: Black talc is dissolved in a certain amount of KMnO4 and urea solution, and then CTAB is added to the mixed solution and stirred in a water bath. A hydrothermal reaction is carried out at 150-190°C. After the reaction is completed, it is filtered, dried and cooled to room temperature, and then taken out and fully ground to obtain a powdered sample, namely the antibacterial material.

4. The preparation method according to claim 3, wherein: The mass ratio of black talc to KMnO4 is 0.4-0.

8.

5. The preparation method according to claim 3, wherein: Stir in a 60-80°C water bath for 30 min.

6. The preparation method according to claim 3, wherein: Dry at 60-80℃ and cool to room temperature.

7. An antibacterial material of black talc loaded with manganese oxide prepared by the preparation method according to any one of claims 1 to 6.

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