Metal-organic framework, preparation method and application thereof in photodynamic sterilization
By using liquid anodic glow discharge technology to assist in the synthesis of Sc-TCPP MOF materials, the problems of complex preparation of metal-organic framework materials and insufficient traditional photosensitizers have been solved, achieving a highly efficient photodynamic sterilization effect, which is suitable for bacterial inactivation.
Patent Information
- Application Number
- CN202411165855.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-23
- Publication Date
- 2026-01-27
- Estimated Expiration
- 2044-08-23
AI Technical Summary
Existing methods for preparing metal-organic framework materials have problems such as cumbersome operation, high energy consumption, long synthesis time, and large reagent consumption. Furthermore, traditional photosensitizers have problems such as self-aggregation quenching, poor photostability, limited penetration depth, and photodamage to normal tissues in photodynamic therapy.
Metal-organic framework (MOF) materials were synthesized using liquid anodic glow discharge technology. Micro-plasma treatment was used to accelerate the deprotonation of organic linkers, promoting the formation of the MOF. Transition metals were introduced into the porphyrin ring to prepare Sc-TCPP MOF materials for photodynamic sterilization.
It achieves efficient sterilization under low dose, low irradiance and low light exposure time, with a sterilization rate of 99%, avoiding complex and cumbersome post-modification processes, improving photocatalytic oxidation ability, and the material has broad light absorption in the visible light region, making it suitable for multi-wavelength light irradiation.
Smart Images
Figure CN118955933B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of biomedical technology, specifically to a metal-organic framework material, its preparation method, and its application in photodynamic sterilization. Background Technology
[0002] Pathogenic microorganisms such as bacteria and viruses pose a persistent threat to human health. Consuming spoiled food or water contaminated with pathogens can lead to short-term illnesses (such as diarrhea and headaches) and sometimes even cancer; therefore, controlling the growth of these pathogens is extremely important. Currently, antibiotics are widely used in the pharmaceutical and livestock industries; however, overuse of antibiotics can lead to antibiotic resistance in pathogens, significantly impacting sterilization and disease treatment. Therefore, developing non-pharmaceutical-based antimicrobial agents or strategies is crucial.
[0003] In recent years, photodynamic therapy (PDT) has attracted much attention in the medical and environmental fields due to its advantages such as high efficiency, broad-spectrum antibacterial activity, and lack of drug resistance. During the treatment, photosensitizers (PS) are excited by light and generate reactive oxygen species (ROS) through intersystem crossing (ISC). These include singlet oxygen, which is the most effective sterilizer. 1 O2). However, existing traditional photosensitizers still have many shortcomings. For example, 1) their structures generally contain conjugated π-electron macrocycles, which are prone to self-aggregation quenching, resulting in poor photostability and severely affecting their photocatalytic ability as photosensitizers, leading to poor therapeutic effects; 2) some photosensitizers require short-wavelength light for excitation, but the penetration depth of these short-wavelength light sources is limited, making it inconvenient to treat deep tissue lesions; 3) to solve the difficulty of PS penetrating into the cell membrane, functional groups or cationic groups are introduced into the PS structure, which requires complex synthesis methods and cumbersome operation steps; 4) the generation of ROS by traditional photosensitizers depends on the excitation time, intensity, and concentration of the light source, but high concentrations, excessively long irradiation times, and intensities inevitably cause a certain degree of photodamage to normal tissues. Therefore, there is an urgent need to develop a bactericidal strategy that is simple to synthesize, can work within the phototherapy window (650-800 nm), has a short irradiation time, low intensity, and high efficiency.
[0004] Porphyrins and their derivatives are a class of photosensitive organic molecules with a wide optical absorption range in the visible light region. Adding porphyrins as structural units to metal-organic frameworks (MOFs) can solve the self-aggregation problem and maximize the photophysical properties of ROS generation. Furthermore, introducing certain transition metals into the porphyrin ring can enhance the ISC process, thereby improving photocatalytic activity. However, existing MOF materials based on porphyrin-based organic molecules as ligands (such as the PCN series) are prone to rapid electron-hole recombination, requiring combination with other functional materials to form heterostructured photocatalysts that promote photoelectron charge transfer. This necessitates multi-step synthesis strategies and complex post-modification and / or post-doping methods, which suffer from drawbacks such as cumbersome operation, high energy consumption, long synthesis time, and large reagent consumption. Therefore, there is an urgent need to develop a green, simple, rapid, and low-energy-consumption method for MOF synthesis to achieve efficient sterilization. Summary of the Invention
[0005] One of the objectives of this invention is to provide a method for preparing metal-organic framework materials, which addresses the drawbacks of existing metal-organic framework material preparation methods, such as cumbersome operation, high energy consumption, long synthesis time, and large reagent consumption, due to the multi-step synthesis strategy and complex post-modification and / or post-doping methods.
[0006] This invention is achieved through the following technical solution: a method for preparing a metal-organic framework material, comprising: dissolving 4-tetra(4-carboxyphenyl)porphyrin in N,N-dimethylformamide to obtain solution A; dissolving scandium chloride hexahydrate in ultrapure water to obtain solution B; the molar ratio of solution A to solution B is 1:1; mixing the prepared solutions A and B and ultrasonically treating them for 2 min to ensure thorough mixing and obtain a mixed solution; subjecting the mixed solution to micro-plasma treatment for 45-60 min; and centrifuging the micro-plasma-treated mixed solution to obtain a solid metal-organic framework.
[0007] Furthermore, the preparation method may also include washing and precipitating the metal-organic framework solid, freeze-drying the precipitate in a vacuum freeze dryer, and then adding ultrapure water to the freeze-dried precipitate to prepare a 0.5 mg / mL solution, which is then stored at 0–4 °C.
[0008] Furthermore, the washing of the precipitate includes washing the precipitate three times with N,N-dimethylformamide and ethanol.
[0009] Furthermore, the freeze-drying time is 12-24 hours.
[0010] Furthermore, the plasma treatment may include: immersing a platinum electrode as the anode completely in the mixed solution; placing a hollow stainless steel tube 3-5 mm above the surface of the mixed solution, and blowing argon gas into the liquid surface from the bottom of the hollow stainless steel tube at a rate of 100 mL / min; using a plasma discharge module, applying a 7V input voltage to form a micro-plasma between the mixed solution and the bottom of the stainless steel tube, and continuously discharging for 45-60 min.
[0011] Furthermore, the centrifugation process includes a centrifuge speed of 10,000 to 12,000 rpm and a centrifugation time of 20 to 30 minutes.
[0012] Another aspect of the present invention provides a metal-organic framework material. The metal-organic framework material is prepared according to the method described above.
[0013] Finally, this invention provides an application of metal-organic framework materials in photodynamic sterilization. Metal-organic framework materials are prepared using the method described above and then used for photodynamic sterilization.
[0014] Furthermore, in photodynamic sterilization, the amount of metal-organic framework material added is 5~20 μg / mL.
[0015] Furthermore, the irradiation wavelength is 420~660 nm, and the irradiation intensity is 12 mW / cm². 2 The irradiation time is 10 minutes.
[0016] Furthermore, it kills pathogenic bacteria such as Escherichia coli and Staphylococcus aureus.
[0017] Furthermore, photodynamic sterilization has a kill rate of 99-100% for pathogenic bacteria.
[0018] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0019] 1. This invention utilizes liquid anolyte glow discharge technology to provide a large number of high-energy electrons during the discharge process, promoting the rapid deprotonation of organic linkers and thus accelerating the formation of metal-organic framework (MOF) materials. Compared with traditional metal-organic framework (MOF) synthesis methods such as solvothermal method, microwave-assisted synthesis method, and etching method, this technology has advantages such as small size, low energy consumption, simplicity and speed, and green reagents.
[0020] 2. This invention also accelerates the process of metal entering the porphyrin ring during liquid anodic glow discharge (SAGD), promotes the formation of multi-site metal-organic framework (MOF) materials, and significantly improves the photocatalytic oxidation ability based on the special properties of scandium (Sc), thereby avoiding the complex and cumbersome post-modification process. The synthesis of scandium metal-organic frameworks assisted by liquid anodic glow discharge (SAGD) micro-plasma technology has the advantages of simple operation, fast synthesis speed and low energy consumption.
[0021] 3. This invention utilizes the synthesized high-porphyrin metallized Sc-TCPP MOF in photodynamic sterilization, achieving sterilization at extremely low doses (5~10 μg / mL) and low irradiance (12 mW / cm²). 2 It can perform photocatalytic sterilization with low light exposure time (10 min) and a sterilization rate of over 99%. Furthermore, due to the wide ultraviolet absorption of MOF in the visible light region, it can inactivate bacteria to a certain extent under multiple wavelengths of light. Attached Figure Description
[0022] The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and form part of this application, do not constitute a limitation thereof. In the drawings:
[0023] Figure 1 This is a flowchart of a method according to an exemplary embodiment 1 of the present invention.
[0024] Figure 2 This is a schematic diagram of the synthesis of scandium metal-organic framework by micro-plasma treatment in Embodiment 1 of the present invention.
[0025] Figure 3 This is a scanning electron microscope image of the scandium metal-organic framework (Sc-TCPP MOF) in Example 1 of the present invention.
[0026] Figure 4 This is a transmission electron microscope image of the scandium metal-organic framework (Sc-TCPP MOF) in Example 1 of the present invention.
[0027] Figure 5 This is the EPR spectrum of singlet oxygen generated by photoexcitation of scandium metal-organic framework under neutral conditions in Example 2 of the present invention.
[0028] Figure 6 This is a photograph of a Staphylococcus aureus agar plate treated with scandium metal-organic framework solution in Example 2 of the present invention.
[0029] Figure 7 The survival rate of Staphylococcus aureus obtained after treatment with scandium metal-organic framework solution in Example 2 of this invention is statistically analyzed.
[0030] Figure 8 This is a photograph of an Escherichia coli agar plate treated with scandium metal organic framework solution in Example 2 of the present invention.
[0031] Figure 9 The survival rate of Escherichia coli obtained statistically after treatment with scandium metal-organic framework solution in Example 2 of this invention.
[0032] Figure 10 These are photographs of Staphylococcus aureus agar plates treated with scandium metal-organic framework solutions at different wavelengths in Example 3 of the present invention.
[0033] Figure 11 The survival rate of Staphylococcus aureus treated with scandium metal-organic framework solution at different wavelengths in Example 3 of the present invention is shown. Detailed Implementation
[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.
[0035] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail. The terms “comprising,” “including,” “having,” “containing,” etc., as used herein are open-ended and mean including but not limited to. Unless the context clearly indicates otherwise, the expressions “a” and “an” as used herein include plural references. For example, reference to “a cell” includes a plurality of such cells and equivalents known to those skilled in the art, etc. The term “about” as used herein indicates a range of ±20% of the following numerical value. In some embodiments, the term “about” indicates a range of ±10% of the following numerical value. In some embodiments, the term “about” indicates a range of ±5% of the following numerical value.
[0036] Exemplary Example 1
[0037] Figure 1 A flowchart of the method of this exemplary embodiment is shown. This exemplary embodiment provides a method for preparing a metal-organic framework material. Specifically, it includes the following steps:
[0038] Step 1: Dissolve methyl-tetra(4-carboxyphenyl)porphyrin in N,N-dimethylformamide to prepare solution A.
[0039] Specifically, 87.5 mg of TCPP was dissolved in 17 mL of DMF.
[0040] Step 2: Dissolve scandium chloride hexahydrate in ultrapure water to prepare solution B.
[0041] Specifically, 28.7 mg of scandium chloride hexahydrate was dissolved in 3 mL of ultrapure water.
[0042] Step 3: Mix the prepared solutions A and B, and then sonicate to ensure thorough mixing and obtain a mixed solution. The molar ratio of the two solutions after thorough mixing is 1:1.
[0043] Specifically, the ultrasonic treatment time is 2 minutes and the ultrasonic frequency is 40 Hz.
[0044] Step 4: Perform micro-plasma treatment on the mixed solution for 45-60 minutes.
[0045] Specifically, micro-plasma processing can include:
[0046] The platinum electrode, acting as the anode, is fully immersed in the mixed solution.
[0047] Place the hollow stainless steel tube 3-5 mm above the surface of the mixed solution, and blow argon gas into the liquid surface from the bottom of the hollow stainless steel tube at a rate of 100 mL / min.
[0048] Using a plasma discharge module, a 7V input voltage is applied to create micro-plasma between the mixed solution and the bottom of the stainless steel tube, and the discharge continues for 45-60 minutes.
[0049] Step 5: Centrifuge the mixed solution after micro-plasma treatment to obtain a metal-organic framework solid.
[0050] Specifically, in the centrifugation process, the centrifuge speed is 10,000~12,000 rpm and the centrifugation time is 20~30 min.
[0051] Step 6: Wash the solid metal-organic framework to precipitate, freeze-dry the precipitate in a vacuum freeze dryer, add ultrapure water to the freeze-dried precipitate to prepare a 0.5 mg / mL solution, and store it at 0~4 ℃.
[0052] Specifically, the metal-organic framework solid was washed three times with dimethylformamide and ethanol, and then precipitated and freeze-dried for 12-24 hours.
[0053] Exemplary Example 2
[0054] This embodiment describes the application of a metal-organic framework material in photodynamic sterilization. The metal-organic framework solution prepared according to the steps in Exemplary Embodiment 1 is added to a diluted bacterial suspension at an amount of 5-20 μg / mL.
[0055] Then, irradiate with a wavelength of 420~660 nm and an irradiation intensity of 12 mW / cm2 for 10 min.
[0056] Specifically, the bacterial suspension was prepared by placing Escherichia coli and Staphylococcus aureus separately in 2.5% LB liquid medium and incubating them on a shaking incubator at 37°C for 12 h.
[0057] To better understand the metal-organic framework material, its preparation method, and its application in photodynamic sterilization provided in this exemplary embodiment, the following description, in conjunction with the accompanying drawings and embodiments, further clarifies the content of this method.
[0058] Example 1
[0059] In this embodiment, 2,6,6-tetramethylpiperidine (TEMP) and scandium chloride hexahydrate were purchased from Aladdin Biochemical Technology Co., Ltd. (Shanghai, China); N,N-dimethylformamide (DMF), ethanol, hydrochloric acid and tris(hydroxymethyl)aminomethane (Tris) were purchased from Chengdu Kelon Chemical Co., Ltd. (Chengdu, China); and tetra(4-carboxyphenyl)porphyrin (TCPP) was purchased from Maclean Biotechnology Co., Ltd. (Shanghai, China).
[0060] The steps for synthesizing metal-organic framework solutions include:
[0061] Weigh 87.5 mg of TCPP and dissolve it completely in 17 mL of DMF solution to obtain solution A.
[0062] 28.7 mg of scandium chloride hexahydrate was weighed and completely dissolved in 3 mL of ultrapure water to obtain solution B.
[0063] Solution A and solution B were mixed in a 50 mL glass reactor for micro-plasma treatment.
[0064] Specifically, the micro-plasma treatment involves placing a hollow stainless steel tube about 3 mm above the surface of the mixed solution, blowing argon gas into the liquid surface from the bottom of the stainless steel tube at a rate of 100 mL / min, and immersing a platinum electrode as the anode completely in the solution.
[0065] Using the DP-GB 15 kV-ignition type (China, Guangao Electronics) as the plasma discharge module, micro-plasma can be formed between the solution and the bottom of the stainless steel tube after applying an input voltage of 7V.
[0066] After continuous discharge for 45 min, centrifugation at 10000 rpm for 20 min was performed to obtain the precipitate, which is the metal-organic framework.
[0067] The precipitate was washed three times with N,N-dimethylformamide (DMF) and ethanol to remove residual medium-tetra(4-carboxyphenyl)porphyrin (TCPP) and scandium ions (Sc). 3+ ).
[0068] Finally, the washed precipitate was dried in a vacuum freeze dryer for 12 h, and the freeze-dried precipitate was added to ultrapure water to prepare a 0.5 mg / mL metal-organic framework solution, which was then stored in a refrigerator at 0-4 ℃ for later use.
[0069] Figure 2 This diagram illustrates the microplasma treatment process for synthesizing scandium metal-organic frameworks in this embodiment. As can be seen from the diagram,
[0070] The schematic diagram illustrates the synthesis of scandium (Sc) metal-organic frameworks (Sc-TCPP MOFs) via micro-plasma treatment. The continuous introduction of argon gas into the system provides a sufficient non-oxidizing atmosphere and blows a large amount of active material generated by the micro-plasma at the gas-liquid interface to the liquid surface. The abundant high-energy electrons generated in the solution deprotonate the organic linker (TCPP), promoting the binding of Sc to TCPP and thus accelerating MOF formation. Simultaneously, micro-plasma treatment not only promotes the growth of the MOF crystal structure but also accelerates the incorporation of Sc into the porphyrin ring of TCPP, ultimately achieving the preparation of multi-site, porphyrin-metallized scandium metal-organic frameworks (Sc-TCPP MOFs).
[0071] Figure 3 A scanning electron microscope image of the scandium metal-organic framework (Sc-TCPP MOF) fabricated using the steps described in this embodiment is shown. Figure 4 A transmission electron microscope image of the scandium metal-organic framework (Sc-TCPP MOF) fabricated using the steps described in this embodiment is shown. As can be seen from the image, the scandium metal-organic framework synthesized through microplasma treatment exhibits a cubic configuration.
[0072] As can be seen from this embodiment, with the development of micro-plasma technology, its progress in assisted synthesis of functional nanomaterials is rapid. Among them, liquid anodic glow discharge (SAGD) technology provides a large number of high-energy electrons during the discharge process, promoting rapid deprotonation of organic linkers and thus accelerating MOF formation. Compared with traditional MOF synthesis methods such as solvothermal methods, microwave-assisted synthesis, and etching methods, this technology has advantages such as small size, low energy consumption, simplicity, speed, and green reagents. Furthermore, this method can accelerate the process of metal entering the porphyrin ring, promoting the formation of multi-site MOFs, and significantly improving photocatalytic oxidation capacity based on the special properties of Sc. This greatly avoids complex and cumbersome post-modification processes. Moreover, Sc exists in two chemical forms in MOFs: as a metal node in the framework structure and coordinated with N atoms in the porphyrin ring. The multiple metal sites significantly improve the photosensitivity of MOFs, thus demonstrating its good effect in photodynamic sterilization.
[0073] Example 2
[0074] The metal-organic framework solution used in this embodiment was prepared according to the method described in Example 1.
[0075] In this embodiment, experiments on Escherichia coli and Staphylococcus aureus are conducted to verify the application of metal-organic frameworks in photodynamic sterilization.
[0076] First, the generation of singlet oxygen under photoexcitation in the prepared scandium metal-organic framework under neutral conditions was examined. This was achieved through the following steps:
[0077] First, prepare the buffer solution by weighing 0.4846 g of Tris solid into 50 mL of ultrapure water, gradually adding 50 times the amount of hydrochloric acid diluent, stirring until homogeneous, and reading the pH value of the solution using a pH meter. Repeat this process until the pH of the solution stabilizes at 7.0. A 100 mmol / L Tris-HCl buffer solution with pH=7 is prepared and collected for later use.
[0078] TEMP is used in aqueous solution as 1 O2 capture agent: Add 10 μL TEMP to a 200 μL mixture of MOF (10 μg / mL) and buffer (Tris-HCl, pH=7).
[0079] Subsequently, the light was irradiated with a 420 nm LED (3 V, 3 W) for 15 s, 60 s, 120 s, and 180 s, respectively. Immediately after the irradiation, the light was placed in an EPR spectrometer to detect reactive oxygen species and their yields. The results are as follows: Figure 5 As shown, Figure 5The EPR spectrum of singlet oxygen produced by photoexcitation of a scandium metal-organic framework under neutral conditions is shown. The figure shows that the production of singlet oxygen increases with increasing illumination time. Singlet oxygen (… 1 O2 (oxygen 2) possesses strong oxidizing properties and can be used for sterilization. As a highly reactive reactive oxygen species (ROS), it can react with unsaturated fatty acids in cell membranes, leading to lipid peroxidation, which in turn damages the integrity and function of cell membranes. It can also oxidize amino acid residues in proteins, especially sulfur-containing amino acids, causing protein denaturation and enzyme inactivation. Singlet oxygen generated through photodynamic processes can effectively kill pathogenic bacteria.
[0080] In summary, the scandium metal-organic framework prepared by this invention has bactericidal effects. The following experiments will further illustrate the bactericidal effect of the scandium metal-organic framework on common Escherichia coli and Staphylococcus aureus.
[0081] First, prepare the culture medium for culturing Escherichia coli and Staphylococcus aureus:
[0082] Weigh 5 g of LB broth into 200 mL of ultrapure water and stir until dissolved to obtain liquid culture medium.
[0083] Weigh 25 g of LB broth into 1000 mL of ultrapure water, add 15 g of agar powder, and stir and dissolve evenly in a 60°C water bath to obtain a solid culture medium.
[0084] The culture medium was then placed in an autoclave and sterilized at 121 °C for 20 min.
[0085] After preparing the culture medium, Escherichia coli and Staphylococcus aureus were placed in 2.5% LB liquid medium and incubated on a shaking incubator at 37°C for 12 h.
[0086] Then, the bacterial suspension was diluted to 10. 6 The scandium metal organic framework solution was mixed with different volumes of scandium metal organic framework solution. Specifically, the final concentrations of scandium metal organic framework solution for treating Staphylococcus aureus were 5, 10, and 20 μg / mL; the final concentrations of scandium metal organic framework solution for treating Escherichia coli were 1, 5, and 10 μg / mL.
[0087] Then use an LED light with a wavelength of 420 nm (12 mW / cm²). 2 ) for 10 minutes.
[0088] Next, 60 μL of the treated bacterial solution was dispersed on an LB broth plate containing 1.5% agar and 2.5% broth, and then spread evenly on the plate using a glass spreader sterilized with an alcohol lamp.
[0089] Finally, incubate at 37°C for 24 hours.
[0090] The procedure for the blank control group is similar to the steps described above, except that sterile water is used instead of MOF stock solution.
[0091] Figure 6 A photograph of a Staphylococcus aureus agar plate treated with scandium-organic framework solution is shown in this embodiment. Figure 7 The survival rate of Staphylococcus aureus obtained after treatment with scandium metal organic framework solution in this embodiment is shown.
[0092] Figure 8 This image shows a photograph of an E. coli agar plate treated with a scandium-organic framework solution in this embodiment. Figure 9 The survival rate of Escherichia coli after treatment with scandium metal-organic framework solution in this embodiment is shown.
[0093] As can be seen from the above figure, scandium metal-organic framework solution, when used as a bactericide in photodynamic sterilization, has a good killing effect on Staphylococcus aureus and Escherichia coli.
[0094] As can be seen from this embodiment, Sc-TCPP MOF can achieve operation at extremely low doses (5 μg / mL) and low irradiance (12 mW / cm²). 2 It achieves highly efficient photocatalytic sterilization under low light exposure time (10 min), with a sterilization rate of over 90%. Furthermore, the porphyrin-metallized metal-organic framework synthesized through micro-plasma technology can significantly enhance the antibacterial activity (the sterilization effect of 5 μg / mL metal-organic framework can reach 60% within 10 min under no light exposure).
[0095] Example 3
[0096] This embodiment illustrates the effect of scandium metal-organic framework on the photodynamic bactericidal effect of Staphylococcus aureus under different wavelengths of light.
[0097] The scandium-organic framework solution used in this embodiment was prepared according to the steps described in Example 1. The cultivation and inactivation steps for Staphylococcus aureus in this embodiment are the same as those in Example 2. The difference lies in the final concentration of the scandium-organic framework solution used to treat Staphylococcus aureus, which is 5 μg / mL, and the wavelength of light used.
[0098] Specifically, during the irradiation process, the irradiation intensity was kept constant at 12 mW / cm². 2 The illumination time was 10 minutes, and light was applied at wavelengths of 420nm, 470nm, 570nm, and 660nm respectively. The final results are as follows. Figure 10 As shown, Figure 10 The images shown here are photographs of Staphylococcus aureus agar plates treated with scandium-organic framework solutions at different wavelengths in this embodiment. Figure 11 The figure shows the bacterial survival rates of Staphylococcus aureus treated with scandium-organic framework solutions at different wavelengths in this embodiment. As can be seen from the figure, irradiation with 420nm wavelength light has a good killing effect on Staphylococcus aureus.
[0099] As can be seen from this embodiment, the scandium metal-organic framework material itself has a wide ultraviolet absorption in the visible light region, which can achieve a certain degree of inactivation of bacteria under multiple wavelengths of light, and still has a good bactericidal effect at a relatively long wavelength of 660 nm.
[0100] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. The application of a metal-organic framework material in photodynamic sterilization, characterized in that, The metal-organic framework material is prepared by the following method: Solution A was prepared by dissolving 4-tetra(4-carboxyphenyl)porphyrin in N,N-dimethylformamide; Solution B was prepared by dissolving scandium chloride hexahydrate in ultrapure water. The prepared solutions A and B were mixed and then subjected to ultrasonic treatment to ensure thorough mixing of the two solutions and to obtain a mixed solution. The ultrasonic treatment time was 2 min and the ultrasonic frequency was 40 kHz. The mixed solution was subjected to micro-plasma treatment for 45-60 minutes. Centrifugation was performed on the mixed solution after micro-plasma treatment to obtain a metal-organic framework solid. The metal-organic framework solid was washed and precipitated, and the precipitate was freeze-dried in a vacuum freeze dryer. The freeze-dried precipitate was then mixed with ultrapure water to prepare a 0.5 mg / mL solution, which was stored at 0–4 °C. The washing precipitate includes precipitating after washing three times with dimethylformamide and ethanol; The freeze-drying time is 12-24 hours; The micro-plasma processing includes: The platinum electrode, acting as the anode, is completely immersed in the mixed solution. Place the hollow stainless steel tube 3-5 mm above the surface of the mixed solution, and blow argon gas into the liquid surface from the bottom of the hollow stainless steel tube at a rate of 100 mL / min. Using a plasma discharge module, a 7V input voltage is applied to form micro-plasma between the mixed solution and the bottom of the stainless steel tube, and the discharge continues for 45~60 minutes. The centrifugation process includes a centrifuge speed of 10,000 to 12,000 rpm and a centrifugation time of 20 to 30 minutes. The prepared metal-organic framework material was used for photodynamic sterilization.
2. The application of the metal-organic framework material according to claim 1 in photodynamic sterilization, characterized in that, In the photodynamic sterilization process, the amount of metal-organic framework material added is 5~20 μg / mL.
3. The application of the metal-organic framework material according to claim 1 in photodynamic sterilization, characterized in that, In the photodynamic sterilization process, the irradiation wavelength is 420~660 nm and the irradiation intensity is 12 mW / cm². 2 The irradiation time is 10 minutes.