Bodipy-modified molybdenum carbide nanosheet, and preparation method and application thereof

CN116549634BActive Publication Date: 2026-08-21HEFEI UNIV
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Patent Information

Application Number
CN202310286688.3
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2023-03-21
Publication Date
2026-08-21
Estimated Expiration
2043-03-21

AI Technical Summary

Technical Problem

抗生素作为抗菌杀菌的特效药,是治疗细菌感染的主要手段,但是在抗生素作为抗菌药的频繁使用过程中,许多细菌的耐药性不断上升,对未来抗生素治疗构成巨大威胁

Benefits of technology

[0017]本发明首先通过合理的制备工艺制备了一种新型MXene材料二维碳化钼(Mo2CTx),其作为光热剂具有较高的光热转化效率,在浓度相对较低的情况下具有较好的杀菌效果。当二维碳化钼(Mo2CTx)浓度为100μg·mL-1时便能在NIR(808nm,1.5W·cm-2)光照下使温度升高,细菌可以在短时间内被灭活,杀菌率可以达到99%以上。同时,本发明在该二维碳化钼(Mo2CTx)的基础上通过氟硼荧进行修饰,进一步提高了杀菌效果。氟硼荧修饰后的碳化钼(BODIPY-Mo2CTx)在浓度为75μg·mL-1时杀菌率基本达到99%,杀菌性能提高幅度明显。

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Abstract

The application relates to a kind of fluorine boron fluorescent modified molybdenum carbide nanosheet and its preparation method and application, belong to the technical field of functional nanomaterial preparation.First, from carbon gallium molybdenum selectively etching gallium layer to prepare molybdenum carbide, then 2,4-dimethyl pyrrole and p-nitrobenzaldehyde are used as raw materials, and fluorine boron fluorescent containing amino is obtained by oxidation, coordination, reduction, finally molybdenum carbide and fluorine boron fluorescent are combined by interface electric charge attraction to obtain fluorine boron fluorescent modified molybdenum carbide BODIPY-Mo2CT with sheet structure, sheet thickness is 1.5-3nm, facing diameter is 0.5-2mu m x It can release small-molecule organic fluorine boron fluorescent on the basis of photothermal heat destruction of cell structure, and generate singlet oxygen under illumination to further kill bacteria to improve the overall sterilization efficiency, and the photothermal effect makes the temperature around nanosheet increase, so as to improve the dispersion degree of fluorine boron fluorescent, and further improve the sterilization efficiency.
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Description

Technical Field

[0001] This invention belongs to the field of functional nanomaterial preparation technology, specifically relating to a fluorine-boron-fluorescent modified molybdenum carbide nanosheet, its preparation method, and its application. Background Technology

[0002] As is well known, bacteria are widely distributed in the environment and possess strong adaptability and survival capabilities even in harsh conditions. Bacteria are also pathogens of many diseases, and bacterial diseases can be transmitted between different populations through various means, such as contact, respiration, and insect bites, exhibiting high infectivity and posing a significant threat to society. Antibiotics, as highly effective antibacterial agents, are the primary means of treating bacterial infections. However, with the frequent use of antibiotics, antibiotic resistance in many bacteria is constantly increasing, posing a significant threat to future antibiotic treatment. Therefore, exploring antibiotic-free treatments for bacterial diseases is of great importance.

[0003] In recent years, with the rapid development of nanotechnology, novel nanoplatforms for treating bacterial diseases have been extensively studied. Nanomaterials possess unique physical and chemical properties and can be optimized according to different needs, attracting widespread attention in combating bacterial infections and even biofilm infections. Compared to traditional antibacterial agents (antibiotics), antibacterial strategies based on nanomaterials, such as photodynamic therapy (PDT), sonodynamic therapy, chemodynamic therapy (CDT), photothermal therapy (PTT), and magnetolysis, have been proposed and applied in antibacterial treatment. Among them, photodynamic therapy and photothermal therapy utilize photosensitizers or photothermal agents to accumulate at the affected site and kill bacteria by local laser irradiation (such as ultraviolet or near-infrared light). Near-infrared light (NIR) has high spatial controllability and penetrating power, and causes less damage to the human body. Due to its non-emission, lack of drug resistance, and excellent biocompatibility, photothermal therapy has greater potential in antibacterial effects. It relies on photothermal agents (PTA) to convert NIR into heat energy. The generated heat can not only be transferred to the cell membrane, causing bacterial death by disrupting the cell membrane structure and denaturing proteins, but also inhibit the formation of bacterial cell membranes. Furthermore, PTA does not lead to drug resistance. For example, Chinese patent CN 107441489 A discloses a composite photothermal antibacterial agent of antimicrobial peptide-modified gold nanorods, which kills bacteria through the antimicrobial effect of the antimicrobial peptide itself and the photothermal effect generated under near-infrared light irradiation. Chinese patent CN 114940734 A reports a dual-cationic covalent organic framework complex, its preparation method, and its application, preparing a DC-COF with a special structure and composition possessing photothermal activity, which can be used as a selective photothermal agent for local sterilization.

[0004] This invention attempts to prepare two-dimensional sheet Mo2CT modified with fluorine-boron-fluorescence. xNanosheets (BODIPY-Mo2CT) x We plan to apply it to photothermal / photodynamic synergistic antibacterial therapy, hoping to leverage its excellent bactericidal properties. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a fluorine-boron-fluorescent modified molybdenum carbide nanosheet, its preparation method and application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] This invention proposes a fluorine-boron-fluorescent modified molybdenum carbide nanosheet BODIPY-Mo2CT x Composed of fluorine boron fluorescent (BODIPY) and two-dimensional molybdenum carbide (Mo2CT) x They are bonded together by interfacial charge attraction, have a sheet-like structure, a sheet thickness of 1.5-3 nm, and an facing diameter of 0.5-2 μm.

[0008] This invention proposes a method for preparing fluorinated boron fluorescently modified molybdenum carbide nanosheets. First, molybdenum carbide is obtained by selectively etching a gallium layer from gallium molybdenum carbon. Then, using 2,4-dimethylpyrrole and p-nitrobenzaldehyde as raw materials, fluorinated boron fluorescently containing amino groups is obtained through oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone, coordination with boron trifluoride diethyl ether, and reduction with a reducing agent. Finally, molybdenum carbide and fluorinated boron fluorescently are bonded together through interfacial charge attraction to obtain fluorinated boron fluorescently modified molybdenum carbide BODIPY-Mo2CT. x .

[0009] As a preferred embodiment of the present invention, the preparation method steps are as follows:

[0010] 1) First, molybdenum carbide precipitate is prepared by etching the gallium atom layer in molybdenum carbide with hydrochloric acid solution. Then, the molybdenum carbide precipitate is dispersed in water, sonicated and centrifuged to remove the precipitate. The supernatant is then taken to obtain a molybdenum carbide nanosheet suspension.

[0011] 2) Using 2,4-dimethylpyrrole and p-nitrobenzaldehyde as raw materials, 2,3-dichloro-5,6-dicyano-p-benzoquinone was oxidized, boron trifluoride diethyl ether was coordinated, and a reducing agent was used to reduce the fluorine boron fluorescent solution to obtain an amino-containing fluorine boron fluorescent solution; then the obtained fluorine boron fluorescent solution was dissolved in ethanol and the pH was adjusted to 1-3 to obtain a transparent fluorine boron fluorescent solution.

[0012] 3) Add the fluorine-boron fluorescent solution obtained in step 2) to the molybdenum carbide nanosheet suspension obtained in step 1) at a mass ratio of fluorine-boron fluorescent to molybdenum carbide of 1:0.5-1. The resulting nanoparticle precipitate is fluorine-boron fluorescent modified molybdenum carbide BODIPY-Mo2CT. x .

[0013] As a further preferred technical solution of the present invention, in the preparation method, the specific steps of step 1) for preparing the molybdenum carbide nanosheet suspension are as follows:

[0014] First, 200 mg of molybdenum carbide (MoC) and 20 mL of hydrochloric acid were thoroughly mixed and placed in a sealed reaction vessel. The mixture was reacted at 120-140 °C for 120-168 h. After the reaction, the mixture was repeatedly centrifuged, washed, and then freeze-dried to obtain a solid powder. 100 mg of the powder was placed in a 25% aqueous solution of tetramethylammonium hydroxide, stirred and mixed, washed with deionized water, and then dispersed in deionized water. The mixture was sonicated at 0-10 °C for 1 h, centrifuged, and the supernatant was collected and freeze-dried to obtain layered molybdenum carbide powder. 0.2 g of the molybdenum carbide powder was dispersed in 50 mL of deionized water and sonicated at 0-10 °C for 1 h. The precipitate was then removed by centrifugation, and the supernatant was collected to obtain a suspension of molybdenum carbide nanosheets.

[0015] As a further preferred technical solution of the present invention, in the preparation method, step 2) of preparing the fluoroboron fluorescent solution is as follows: 2.9g of 2,4-dimethylpyrrole and 1.8g of p-nitrobenzaldehyde are dissolved in tetrahydrofuran, protected by nitrogen gas, and 1-3mL of trifluoroacetic acid is added. The mixture is reacted at 25-30℃ for 12-18h, and then 2.8g of... 2,3-Dichloro-5,6-dicyanobenzoquinone was reacted at 25-30℃ for 4-6 h. Then, 70-80 mL of triethylamine and 75-85 mL of boron trifluoride ether were added at 0-5℃, and the reaction was continued at 25-30℃ for 10-12 h. After extraction with dichloromethane and water, the organic phase was dried with anhydrous sodium sulfate, filtered to remove the drying agent, and the organic solvent was removed by rotary evaporation. Separation was performed by column chromatography, followed by the addition of 90-120 mL of anhydrous ethanol, 1-5 mL of hydrazine hydrate, and 0.1-0.5 g of palladium on carbon. The reaction was continued at 90-100℃ for 2-4 h. Finally, after purification and drying, amino-containing fluoroboronfluoride was obtained. 0.2 g of fluoroboronfluoride was dissolved in 20-50 mL of ethanol, and the pH of the solution was adjusted to 1-3 with hydrochloric acid to obtain a transparent fluoroboronfluoride solution.

[0016] As a further preferred technical solution of the present invention, in the preparation method, in step 3), 20 mL of the fluorine-boron fluorescent solution obtained in step 2) is added dropwise to 20 mL of the molybdenum carbide nanosheet suspension obtained in step 1), and the mixture is stirred for 15-30 min. After the reaction is completed, the product obtained after repeated centrifugation, washing, and drying is the fluorine-boron fluorescent modified molybdenum carbide nanosheet BODIPY-Mo2CT. x .

[0017] This invention first prepares a novel MXene material, two-dimensional molybdenum carbide (Mo2CT), through a rational preparation process. x As a photothermal agent, it has high photothermal conversion efficiency and good bactericidal effect at relatively low concentrations. When two-dimensional molybdenum carbide (Mo2CT) is used...x The concentration is 100 μg·mL -1 It can be achieved in NIR (808nm, 1.5W·cm) at that time. -2 Under light, the temperature rises, and bacteria can be inactivated in a short time, achieving a sterilization rate of over 99%. Simultaneously, this invention utilizes the two-dimensional molybdenum carbide (Mo2CT)... x Based on the existing molybdenum carbide (BODIPY-Mo2CT), the bactericidal effect was further improved by modification with fluorinated boronfluoride. x At a concentration of 75 μg·mL -1 The sterilization rate reaches approximately 99%, and the sterilization performance is significantly improved.

[0018] Compared with the prior art, the superior effects of the present invention are as follows:

[0019] 1) The fluorine-boron-fluorescence modified molybdenum carbide nanosheets of the present invention are formed by the attraction and bonding of fluorine-boron-fluorescence and two-dimensional molybdenum carbide through interfacial charge. This does not damage the surface structure of molybdenum carbide, can maintain the original morphology and structure of molybdenum carbide nanosheets, and has a large specific surface area, with a sheet thickness of about 1.5-3 nm and a face diameter of about 0.5-2 μm.

[0020] 2) The fluorine-boron-fluorescent modified molybdenum carbide nanosheets of the present invention have good biocompatibility, high biodegradability in vivo, and are biodegradable. The near-infrared light used has spatial controllability and strong penetrating ability, and causes very little damage to the human body.

[0021] 3) The fluorine-boron-fluorine modified molybdenum carbide nanosheets of the present invention can release small molecule organic fluorine-boron-fluorine on the basis of photothermal destruction of cell structure, and generate singlet oxygen under light to further kill bacteria, thereby improving the overall bactericidal efficiency. At the same time, the photothermal effect increases the temperature around the nanosheets, thereby improving the dispersion of fluorine-boron-fluorine and thus improving the bactericidal efficiency. Attached Figure Description

[0022] Figure 1 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x Scanning electron microscope image (a) and transmission electron microscope image (b).

[0023] Figure 2 Fluoroboron fluorescent compounds prepared in Example 1 1 H NMR spectrum.

[0024] Figure 3 Molybdenum carbide (Mo2Ga2C) raw material and exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x ), fluorine-boron-fluorescent modified molybdenum carbide (BODIPY-Mo2CT)x X-ray diffraction pattern (XRD) of .

[0025] Figure 4 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x ), fluorine-boron-fluorescent modified molybdenum carbide (BODIPY-Mo2CT) x X-ray photoelectron spectroscopy (XPS) of .

[0026] Figure 5 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x Atomic force microscopy (AFM) images and precise measurement data of its morphology, size, and thickness.

[0027] Figure 6 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x Infrared photothermal imaging and data graphs showing temperature changes over time in an aqueous solution.

[0028] Figure 7 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x ), fluorine-boron-fluorescent modified molybdenum carbide (BODIPY-Mo2CT) x The bactericidal effect of the bacteria was shown in the images obtained by plate counting (a: Escherichia coli; b: Staphylococcus aureus). Detailed Implementation

[0029] The following detailed description, in conjunction with embodiments and accompanying drawings, further illustrates the fluorine-boron-fluorescent modified molybdenum carbide nanosheets of the present invention, their preparation method, and their applications.

[0030] Example 1

[0031] 1) Take 200 mg of molybdenum gallium carbon (Mo₂C) and 20 mL of 10 mol / L hydrochloric acid, mix thoroughly, and place in a sealed reaction vessel. React at 140 °C for 140 h. After the reaction is complete, cool to room temperature. After the reaction is complete, repeatedly centrifuge and wash until the pH reaches 7. Then wash three times with anhydrous ethanol and freeze-dry for one day. Take the powder and mix it in a 25% aqueous solution of tetramethylammonium hydroxide (30 mL solution per 100 mg). Stir for 3 hours, wash twice with deionized water, disperse in deionized water, sonicate at 0 °C for 1 h, centrifuge (3000 r / min, 20 min), and freeze-dry the supernatant to obtain sheet-like Mo₂CT. x powder.

[0032] 2) Take 0.2g of the molybdenum carbide precipitate obtained in step 1), disperse it in 50mL of deionized water, sonicate it at 0℃ for 1h with an ultrasonic power of 300W, and then centrifuge it at 3000r / min to remove the precipitate. Take the supernatant to obtain the molybdenum carbide nanosheet suspension.

[0033] 3) Dissolve 2.9 g of 2,4-dimethylpyrrole and 1.8 g of p-nitrobenzaldehyde in 200 mL of tetrahydrofuran, purge with nitrogen for protection, add 1 mL of trifluoroacetic acid, and react at 25 °C for 12 h. Then add 2.8 g of 2,3-dichloro-5,6-dicyanobenzoquinone, and continue the reaction at 25 °C for 4 h. Add 70 mL of triethylamine and 75 mL of boron trifluoride diethyl ether at 0 °C, and react at 25 °C for 10 h. After extraction with dichloromethane and water, dry the organic phase with anhydrous sodium sulfate, filter to remove the drying agent, remove the organic solvent by rotary evaporation, separate by column chromatography, and then add 90 mL of anhydrous ethanol, 1 mL of hydrazine hydrate and 0.1 g of palladium on carbon, and react at 90 °C for 2 h. Finally, after purification and drying, obtain amino-containing fluoroboron fluorescent powder.

[0034] 4) Take 0.2g of the fluorine boron fluorescent obtained in step 3), dissolve it in 50mL of ethanol, add hydrochloric acid to adjust the pH of the solution to 1, and obtain a transparent solution.

[0035] 5) Take 20 mL of the fluorine-boron fluorescent solution obtained in step 4) and add it dropwise to 20 mL of the molybdenum carbide nanosheet suspension obtained in step 2). Stir the mixture at 600 r / min for 30 min. After the reaction is complete, the product obtained after repeated centrifugation, washing, and drying is the fluorine-boron fluorescent modified molybdenum carbide nanosheet BODIPY-Mo2CT. x .

[0036] Figure 1 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x Scanning electron microscope (a) and transmission electron microscope (b) images of the image. Figure 1 As can be seen, the two-dimensional molybdenum carbide sheets are semi-transparent, indicating that molybdenum carbide has been effectively exfoliated into single-layer or few-layer nanosheets with a diameter of approximately 0.5-2 μm.

[0037] Figure 2 The amino-containing fluoroboron fluorescent compound prepared in Example 1 1 H NMR spectrum. From Figure 2 As can be seen, the doublets at chemical shifts of 6.98 and 6.77 are both benzene ring hydrogens, the singlet at chemical shift of 5.96 is pyrrole hydrogen, the singlet at chemical shift of 3.84 is amino hydrogen, and the singlets at chemical shifts of 2.54 and 1.48 are both methyl hydrogens.

[0038] Figure 3Molybdenum carbide (Mo2Ga2C) raw material and exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x ), fluorine-boron-fluorescent modified molybdenum carbide (BODIPY-Mo2CT) x X-ray diffraction (XRD) pattern of ) . From Figure 3 As can be seen from this, compared with Mo2Ga2C raw materials, the stripped Mo2CT... x They exhibit completely different structural characteristics. The main peaks of Mo2Ga2C are located at 9.89°, 34.18°, 37.4°, 39.94°, 42.58°, 49.52°, 53.5°, and 61.1°, corresponding to (002), (100), (103), (008), (105), (107), (108), and (110) diffractions, respectively. After etching, the (002) diffraction peak of Mo2Ga2C shifted from 9.89° to around 7°. Furthermore, the diffraction peaks of Mo2Ga2C almost completely disappeared in the 2θ range of 30-45°, indicating that the Ga layer in Mo2Ga2C was successfully etched away. In addition, compared with Mo2CT... x Compared to BODIPY-Mo2CT x (002) The intensity of the diffraction peaks decreased significantly, indicating that Mo2CT x The highly ordered arrangement was disrupted by the introduction of BODIPY, resulting in a decrease in crystallinity.

[0039] Figure 4 Molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x ) and fluorine-boron-fluorescent modified molybdenum carbide (BODIPY-Mo2CT) x XPS curve. From Figure 4 It can be seen from BODIPY-Mo2CT x An additional peak for F element was observed at the 685 eV position. F element is unique to BODIPY, indicating that BODIPY-Mo2CT... x Preparation successful.

[0040] Figure 5 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x Atomic force microscopy (AFM) images and precise measurement data of its morphology, size, and thickness. From Figure 5 The molybdenum carbide nanosheets (Mo2CT) can be seen in the image. x It has a sheet-like structure with a sheet thickness of 1.5-3 nm.

[0041] Figure 6 The exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x Infrared photothermal imaging and time-temperature variation data of the image dispersed in an aqueous solution. Figure 6 As can be seen from this, Mo2CT x It exhibits significant photothermal properties.

[0042] Example 2

[0043] 1) Take 200 mg of molybdenum gallium carbon (Mo₂C) and 20 mL of 10 mol / L hydrochloric acid, mix thoroughly, and place in a sealed reaction vessel. React at 130 °C for 135 h. After the reaction is complete, cool to room temperature, and after the reaction is finished, repeatedly centrifuge and wash until the pH reaches 7. Then wash three times with anhydrous ethanol and freeze-dry for one day. Take the powder and mix it in a 25% aqueous solution of tetramethylammonium hydroxide (30 mL solution per 100 mg). Stir for 3 hours, wash twice with deionized water, disperse in deionized water, sonicate at 5 °C for 1 h, centrifuge (3000 r / min, 20 min), and freeze-dry the supernatant to obtain sheet-like Mo₂CT. x powder.

[0044] 2) Take 0.2g of the molybdenum carbide precipitate obtained in step 1), disperse it in 50mL of deionized water, sonicate it at 0℃ for 1h with an ultrasonic power of 300W, and then centrifuge it at 3000r / min to remove the precipitate. Take the supernatant to obtain the molybdenum carbide nanosheet suspension.

[0045] 3) Dissolve 2.9 g of 2,4-dimethylpyrrole and 1.8 g of p-nitrobenzaldehyde in 190 mL of tetrahydrofuran, purge with nitrogen for protection, add 2 mL of trifluoroacetic acid, and react at 28 °C for 16 h. Then add 2.8 g of 2,3-dichloro-5,6-dicyanobenzoquinone, and continue the reaction at 28 °C for 5 h. Add 75 mL of triethylamine and 80 mL of boron trifluoride ether at 1 °C, and react at 28 °C for 11 h. After extraction with dichloromethane and water, dry the organic phase with anhydrous sodium sulfate, filter to remove the drying agent, remove the organic solvent by rotary evaporation, separate by column chromatography, and then add 100 mL of anhydrous ethanol, 2 mL of hydrazine hydrate and 0.2 g of palladium on carbon, and react at 95 °C for 3 h. Finally, after purification and drying, obtain amino-containing fluoroboron fluorescent powder.

[0046] 4) Take 0.2g of the fluorine boron fluorescent obtained in step 3), dissolve it in 50mL of ethanol, add hydrochloric acid to adjust the pH of the solution to 1, and obtain a transparent solution.

[0047] 5) Take 20 mL of the fluorine-boron fluorescent solution obtained in step 4) and add it dropwise to 20 mL of the molybdenum carbide nanosheet suspension obtained in step 2). Stir the mixture at 600 r / min for 30 min. After the reaction is complete, the product obtained after repeated centrifugation, washing, and drying is the fluorine-boron fluorescent modified molybdenum carbide nanosheet BODIPY-Mo2CT. x .

[0048] Example 3

[0049] Take the exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x ), fluorine-boron-fluorescent modified molybdenum carbide (BODIPY-Mo2CT) x The bacteria were dispersed in the broth used for culturing the bacteria at concentrations of 25, 50, 75, and 100 μg·mL. -1 At 1.5 W·cm -2 Irradiate with an 808nm laser for 5 minutes, incubate at 37℃ for 4 hours, dilute with phosphate buffer 10000 times, take 100μL of the diluted suspension and spread it on Luria Bertani solid medium, incubate at 37℃ for 12 hours, calculate the colony count, and calculate the sterilization rate accordingly.

[0050] Table 1

[0051]

[0052] Table 1 shows the levels of Escherichia coli and Staphylococcus aureus on the photothermal agent Mo2CT. x (M) and BODIPY-Mo2CT x (BM) Different concentration treatments (0, 25, 50, 70 and 100 μg·mL) -1 With or without NIR irradiation (L, 1.5 W·cm) -2 The survival rate of bacteria in different groups after MXene treatment was determined by plate counting method (5 min).

[0053] Exfoliated molybdenum carbide nanosheets (Mo2CT) prepared in Example 1 x ), fluorine-boron-fluorescent modified molybdenum carbide (BODIPY-Mo2CT) x The bactericidal effect of ) is shown in the image using the plate count method, as follows: Figure 7 As shown. The results indicate that Mo2CT x The photothermal sterilization performance increases with increasing concentration, especially at a concentration of 50 μg·mL⁻¹. -1 At the same time, there was a significant difference in sterilization efficiency. As can be seen from the bacterial survival rates in Table 1, the modified molybdenum carbide nanosheets showed a significantly improved sterilization rate compared to the unmodified titanium carbide nanosheets, especially at a concentration of 100 μg·mL⁻¹. -1 At that time, after continuous irradiation for 5 minutes, the inactivation rate reached approximately 100%. Mo2CT x At sufficient concentrations, the photothermal effect is sufficiently good for antibacterial activity. In a comparative study of two types of bacteria, it was found that the photothermal bactericidal effect was stronger against Escherichia coli than against Staphylococcus aureus. This is due to the difference in cell wall composition between Gram-negative and Gram-positive bacteria.

[0054] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing fluorine-boron-fluorescent modified molybdenum carbide nanosheets, characterized in that, First, molybdenum carbide was prepared by selectively etching a gallium layer from gallium molybdenum carbide. Then, using 2,4-dimethylpyrrole and p-nitrobenzaldehyde as raw materials, fluoroboronium containing amino groups was obtained through oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone, coordination with boron trifluoride diethyl ether, and reduction with a reducing agent. Finally, molybdenum carbide and fluoroboronium were bonded together through interfacial charge attraction to prepare fluoroboronium-modified molybdenum carbide BODIPY-Mo2CT. x The specific steps are as follows: 1) First, molybdenum carbide precipitate is prepared by etching gallium atom layers in molybdenum carbide with hydrochloric acid solution. Then, the molybdenum carbide precipitate is dispersed in water, sonicated and centrifuged to remove the precipitate. The supernatant is then taken to obtain a molybdenum carbide nanosheet suspension. 2) Using 2,4-dimethylpyrrole and p-nitrobenzaldehyde as raw materials, 2,3-dichloro-5,6-dicyano-p-benzoquinone was oxidized, boron trifluoride diethyl ether was coordinated, and a reducing agent was used to reduce the fluorine boron fluorescent solution to obtain an amino-containing fluorine boron fluorescent solution; then the obtained fluorine boron fluorescent solution was dissolved in ethanol and the pH was adjusted to 1-3 to obtain a transparent fluorine boron fluorescent solution. 3) Add the fluorine-boron fluorescent solution obtained in step 2) to the molybdenum carbide nanosheet suspension obtained in step 1) at a mass ratio of fluorine-boron fluorescent to molybdenum carbide of 1:0.5-1. The resulting nanoparticle precipitate is fluorine-boron fluorescent modified molybdenum carbide BODIPY-Mo2CT. x It is composed of fluorine boron fluorescent (BODIPY) and two-dimensional molybdenum carbide (Mo2CT). x They are bonded together by interfacial charge attraction, have a sheet-like structure, a sheet thickness of 1.5-3 nm, and an facing diameter of 0.5-2 μm.

2. The method as described in claim 1, characterized in that, The specific steps are as follows: Step 1): First, mix 200 mg of molybdenum gallium carbide (MoCarb) with 20 mL of hydrochloric acid and place the mixture in a sealed reactor. React at 120-140 °C for 120-168 h. After the reaction, repeatedly centrifuge and wash the mixture, then freeze-dry to obtain a solid powder. Take 100 mg of the powder and place it in a 25% aqueous solution of tetramethylammonium hydroxide. Stir and mix the powder, wash it with deionized water, disperse it in deionized water, and sonicate it at 0-10 °C for 1 h. Centrifuge the powder, collect the supernatant, and freeze-dry it to obtain layered molybdenum carbide powder. Take 0.2 g of the molybdenum carbide powder and disperse it in 50 mL of deionized water. Sonicate it at 0-10 °C for 1 h, then centrifuge to remove the precipitate and collect the supernatant to obtain a molybdenum carbide nanosheet suspension. Step 2): Dissolve 2.9 g of 2,4-dimethylpyrrole and 1.8 g of p-nitrobenzaldehyde in tetrahydrofuran, purge with nitrogen for protection, add 1-3 mL of trifluoroacetic acid, and react at 25-30 °C for 12-18 h. Then add 2.8 g of... 2,3-Dichloro-5,6-dicyanobenzoquinone was reacted at 25-30℃ for 4-6 h. Then, 70-80 mL of triethylamine and 75-85 mL of boron trifluoride ether were added at 0-5℃, and the reaction was continued at 25-30℃ for 10-12 h. After extraction with dichloromethane and water, the organic phase was dried with anhydrous sodium sulfate, filtered to remove the drying agent, and the organic solvent was removed by rotary evaporation. Separation was performed by column chromatography, followed by the addition of 90-120 mL of anhydrous ethanol, 1-5 mL of hydrazine hydrate, and 0.1-0.5 g of palladium on carbon. The reaction was continued at 90-100℃ for 2-4 h. Finally, after purification and drying, amino-containing fluoroboronfluoride was obtained. 0.2 g of fluoroboronfluoride was dissolved in 20-50 mL of ethanol, and the pH of the solution was adjusted to 1-3 with hydrochloric acid to obtain a transparent fluoroboronfluoride solution. Step 3): Add 20 mL of the fluorine-boron fluorescent solution obtained in Step 2) dropwise to 20 mL of the molybdenum carbide nanosheet suspension obtained in Step 1), stir and react for 15-30 min. After the reaction is complete, the product obtained after repeated centrifugation, washing, and drying is the fluorine-boron fluorescent modified molybdenum carbide nanosheet BODIPY-Mo2CT. x .

3. The application of fluorine-boron-fluorescent modified molybdenum carbide nanosheets prepared by the method described in claim 1 or 2 in the preparation of photosensitive agents or photothermal agents for photosterilization.

Citation Information

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