Preparation method of hollow manganese-based prussian blue nanocage and fungal disease prevention and treatment thereof

Abstract

The application belongs to the technical field of antifungal agent preparation, and particularly relates to a preparation method of hollow manganese-based Prussian blue nanocage and fungal disease prevention and treatment. The raw materials of the hollow manganese-based Prussian blue nanocage include manganese salt, potassium ferricyanide and polyvinylpyrrolidone, the molar ratio of the polyvinylpyrrolidone, potassium ferricyanide and manganese salt is 0.1-0.8:2-6:0.2-1, the average particle size of the hollow manganese-based Prussian blue nanocage is 440-460 nm, and the shape of the hollow manganese-based Prussian blue nanocage is a hollow three-dimensional shape in the middle. The synthesized hollow manganese-based Prussian blue nanocage can rapidly disintegrate and release a large amount of manganese ions, greatly inhibit the infection ability of pathogenic bacteria, improve the stress resistance of plants, has a wide application prospect, has high biocompatibility, can realize high-efficiency bacteriostatic efficiency, and ensures the safety of crops.

Description

Technical Field

[0001] The invention belongs to the technical field of antifungal agent preparation, and particularly relates to a preparation method of a hollow manganese-based Prussian blue nanocage and fungal disease prevention and treatment thereof. Background Art

[0002] With the continuous advancement of science and technology and the intensification of environmental problems, the shortcomings of traditional pesticides have gradually become apparent. In recent years, nanotechnology has achieved breakthrough research progress in plant pest and disease control, laying the foundation for nanotechnology to become a powerful tool for efficient production and sustainable development in modern agriculture. Nano-antimicrobial materials are a new class of materials with antibacterial properties. Due to the high specific surface area and high reactivity of the antimicrobial agents in these materials, they significantly enhance their overall antimicrobial efficacy, minimizing the growth and reproduction of microorganisms including bacteria, fungi, yeasts, algae, and viruses. Products made with these antimicrobial materials exhibit hygienic and self-cleaning properties, effectively preventing the spread of bacteria. Among the various metal and oxide nanoparticles, silver nanoparticles have the greatest antimicrobial efficacy and are the most extensively studied. Numerous researchers have demonstrated that silver nanoparticles have effective inhibitory effects against bacteria, viruses, and fungi, particularly against antibiotic-resistant strains. Gold is one of the most chemically stable elements, but nanoparticles exhibit unique physical and chemical properties. When gold particles are sufficiently small, quantum size effects occur, causing the gold nanoparticles to transform into insulators and forming standing electron waves between different energy levels. If the energy level gap exceeds a certain range and single-electron transitions occur, they exhibit unique optical and electronic properties, with potential applications in transistors, light-controlled switches, and sensors. Most metal nanomaterials offer improved safety and are currently widely used in the biomedical field for rapid testing, disease diagnosis, and treatment. Modification of metal nanoparticles with functional molecules can combat multidrug resistance in bacteria, exhibiting excellent antibacterial activity and promising antibacterial development prospects.

[0003] Although Prussian blue nanomaterials have made great progress in biomedicine, they are still not widely used in agricultural production and antibacterial fields. At present, the main measure for preventing and treating fungal diseases is to spray chemical pesticides. Although chemical pesticides are quick to take effect, the long-term and large-scale use of chemical pesticides leads to the increasing resistance of crops to multiple fungicides year by year, and causes problems such as pesticide residues and ecological pollution. Chinese invention patent application CN113498781A provides an application of nano manganese dioxide in preventing and treating rice bacterial blight. The invention fully mixes nano manganese dioxide particles with water to form a nano pesticide preparation in the form of a suspension. The nano pesticide preparation is evenly sprayed on rice leaves, which has a significant effect on inhibiting bacterial blight infection. The nano pesticide preparation can also play the role of fertilizer to promote plant growth, but the method is complicated to operate and has a high preparation cost, which needs further improvement. Therefore, there is an urgent need to develop an antifungal nano material with good control effect, low cost, simple and effective, and environmentally friendly. Summary of the Invention

[0004] In view of the problems existing in the prior art, the present invention provides a preparation method of a hollow manganese-based Prussian blue nanocage and fungal disease prevention and treatment thereof.

[0005] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A hollow manganese-based Prussian blue nanocage, characterized in that the raw materials of the hollow manganese-based Prussian blue nanocage include manganese salt, potassium ferrocyanide and polyvinyl pyrrolidone, and the molar ratio of polyvinyl pyrrolidone, potassium ferrocyanide and manganese salt is 0.1-0.8:2-6:0.2-1.

[0007] Preferably, the molar ratio of polyvinyl pyrrolidone, potassium ferrocyanide and manganese salt is 0.4-0.5:3-4:0.2-0.5.

[0008] Preferably, the average particle size of the hollow manganese-based Prussian blue nanocage is 440-460 nm, and the shape of the hollow manganese-based Prussian blue nanocage is a three-dimensional shape with a hollow center.

[0009] Preferably, the manganese salt is selected from any one of manganese chloride, manganese sulfate and manganese oxide.

[0010] The present invention also provides a method for preparing the hollow manganese-based Prussian blue nanocage, which is characterized by dissolving polyvinyl pyrrolidone, potassium ferrocyanide and manganese salt in a hydrochloric acid solution and reacting to obtain the nanocage.

[0011] Preferably, the acid solution is selected from hydrochloric acid or nitric acid, and the concentration of the acid solution is 0.01-0.05M.

[0012] Preferably, the reaction temperature is 70-90° C., and the reaction time is 12-48 h.

[0013] Preferably, stirring is performed before the reaction, and washing, centrifugation and drying are performed after the reaction.

[0014] Preferably, the stirring speed is 600-650 r / min, and the stirring time is 15-30 min.

[0015] Preferably, the washing is water washing, alcohol is added during the centrifugation, the washing and centrifugation are performed 3-5 times, and the drying is freeze-drying.

[0016] The present invention also provides a suspension of the hollow manganese-based Prussian blue nanocage, characterized in that the raw materials of the suspension include hollow manganese-based Prussian blue nanocage, a wetting agent, a dispersant, an antifreeze agent, a defoaming agent and a grinding aid.

[0017] Preferably, calculated based on the total mass of the suspending agent, the content of the hollow manganese-based Prussian blue nanocage is 30-40wt%, the content of the wetting agent is 1-2wt%, the content of the dispersant is 2-5wt%, the content of the antifreeze agent is 3-6wt%, the content of the defoaming agent is 0.1-1wt%, the content of the grinding aid is 0.1-2wt%, and the balance is water.

[0018] Preferably, the wetting agent is selected from any one of NS-500LQ, 1015, GY-D09 and GY-D1285, the antifreeze agent is selected from any one of ethylene glycol, propylene glycol and triethanolamine, the grinding aid is selected from any one of magnesium aluminum silicate, titanium dioxide and white carbon black, the dispersant is selected from any one of Triton X-102, Tween-80 and Tween-20, and the defoaming agent is selected from any one of FoamStar ST 2410AG, ethylenediamine PO-EO block polyether and sodium lauryl sulfate K-12.

[0019] The present invention also provides a method for preparing the hollow manganese-based Prussian blue nanocage suspension, comprising the following steps:

[0020] (1) First, mix the wetting agent, dispersant, antifreeze agent, grinding aid and water to obtain solution A;

[0021] (2) The hollow manganese-based Prussian blue nanocages, the defoaming agent and the solution A are mixed and ground to obtain the product.

[0022] Preferably, the mixing speed in step (2) is 1500-2800 rpm, the mixing time is 20-60 min, and the grinding uses 0.2-0.4 mm zirconium beads.

[0023] The present invention also provides the use of the hollow manganese-based Prussian blue nanocage and its suspension in the preparation of a drug for inhibiting fungal infection.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The manganese-doped hollow-surfaced Prussian blue nanocages synthesized in the present invention can rapidly disintegrate and release a large amount of manganese ions, greatly inhibiting the infection ability of pathogenic bacteria and improving the stress resistance of plants, and have broad application prospects.

[0026] (2) The present invention also provides a method for preparing and implementing a hollow manganese-based Prussian blue nanocage suspension that is simple, low-cost, has high antibacterial efficiency, and has high biocompatibility.

[0027] (3) The present invention can achieve high antibacterial efficiency while ensuring the safety of crops, providing a promising and environmentally friendly technology for the antibacterial effect of nanomaterials, and also providing new technical support for the creation of high-efficiency nanomaterial preparations. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a scanning electron microscope image of the hollow manganese-based Prussian blue nanocage prepared in Example 1.

[0029] Figure 2 This is a transmission electron microscope image of the hollow manganese-based Prussian blue nanocage prepared in Example 1.

[0030] Figure 3 Microscope observation pictures (20 times and 40 times) of the hollow manganese-based Prussian blue nanocage suspension prepared in Example 1.

[0031] Figure 4 This is the EDS spectrum of the hollow manganese-based Prussian blue nanocage prepared in Example 1.

[0032] Figure 5 This is a scanning electron microscope mapping image of the hollow manganese-based Prussian blue nanocage prepared in Example 1.

[0033] Figure 6 This is a particle size diagram of the hollow manganese-based Prussian blue nanocages prepared in Example 1.

[0034] Figure 7 Mn 2+ Content standard curve.

[0035] Figure 8 The Mn of the hollow manganese-based Prussian blue nanocage suspension prepared in Example 3 2+ Release amount.

[0036] Figure 9The bacteriostatic effect of the hollow manganese-based Prussian blue nanocage suspension prepared in Example 1 on wheat scab and tomato gray mold.

[0037] Figure 10 The leaf incidence of tomato gray mold by the hollow manganese-based Prussian blue nanocage suspension prepared in Example 1. DETAILED DESCRIPTION

[0038] It is worth mentioning that the raw materials used in the present application are all ordinary commercially available products.

[0039] Example 1

[0040] A preparation method of a hollow manganese-based Prussian blue nanocage and a suspension thereof.

[0041] (1) Preparation method of manganese-doped Prussian blue nanocage: 0.045 mmol of polyvinylpyrrolidone, 0.4 mmol of potassium ferricyanide, and 50 mg of manganese chloride powder were added to 40 mL of deionized water containing 0.01 mol of HCl, stirred at 600 r / min at room temperature for 30 min, and then placed in a face-centered hollow drying box at 80℃ for 24 h. The product after reaction was washed with deionized water, then alcohol was added and centrifuged, repeated three times, and freeze-dried to obtain the hollow manganese-based Prussian blue nanocage.

[0042] (2) Preparation method of manganese-doped Prussian blue nanocage suspension: 1% of wetting agent NS-500LQ, 2% of dispersing agent Tween 80, and 5% of antifreeze agent ethylene glycol were dissolved in the total mass of the suspension to obtain a mixed solution A; 30% of manganese-doped Prussian blue hollow manganese-based Prussian blue nanocage, 0.5% of defoaming agent FoamStar ST 2410 AG, and the mixed solution A were mixed, and homogenized and dispersed at 2800 rpm for 20 min to obtain a mixed solution B, which was ground with 0.2 mm zirconium beads to obtain the hollow manganese-based Prussian blue nanocage suspension.

[0043] wherein, Figure 3 The microscope observation chart (20 times, 40 times) of the hollow manganese-based Prussian blue nanocage suspension prepared in this example.

[0044] Example 2

[0045] A preparation method of a hollow manganese-based Prussian blue nanocage and a suspension thereof.

[0046] (1) Preparation method of hollow manganese-based Prussian blue nanocages: 0.055 mmol polyvinyl pyrrolidone, 0.35 mmol potassium ferrocyanide and 40 mg manganese acetate powder were added to 40 mL deionized water containing 0.01 mol HNO3, stirred at 600 r / min at room temperature for 20 min, placed in a dough-shaped hollow drying oven at 70°C for 48 h, and the reaction product was washed with deionized water, then added with alcohol and centrifuged, repeated five times, and freeze-dried to obtain hollow manganese-based Prussian blue nanocages.

[0047] (2) Preparation method of hollow manganese-based Prussian blue nanocage suspension: Based on the total mass of the suspension, 2% of wetting agent GY-D09 and 5% of dispersant Triton X-102 were dissolved in 3% of antifreeze agent triethanolamine, and then mixed with 0.1% of grinding aid magnesium aluminum silicate and the balance of water to obtain mixed solution A; 40% of hollow manganese-based Prussian blue nanocages, 0.1% of defoaming agent sodium lauryl sulfate K-12 and mixed solution A were mixed and homogenized at 1500 rpm for 60 minutes to obtain mixed solution B, which was ground with 0.4 mm zirconium beads to obtain hollow manganese-based Prussian blue nanocage suspension.

[0048] Example 3

[0049] A method for preparing a hollow manganese-based Prussian blue nanocage and a suspension thereof.

[0050] (1) Preparation method of hollow manganese-based Prussian blue nanocages: 0.050 mmol polyvinyl pyrrolidone, 0.42 mmol potassium ferrocyanide and 40 mg manganese sulfate powder were added to 40 mL deionized water containing 0.05 mol HCl, stirred at 650 r / min at room temperature for 15 min, placed in a dough-shaped hollow drying oven at 90°C for 12 h, and the reaction product was washed with deionized water, then added with alcohol and centrifuged, repeated three times, and freeze-dried to obtain Prussian blue hollow manganese-based Prussian blue nanocages.

[0051] (2) Preparation method of hollow manganese-based Prussian blue nanocage suspension: based on the total mass of the suspension, 1% of wetting agent GY-D1285 and 2.5% of dispersant Tween 20 were dissolved in 6% of antifreeze agent propylene glycol, and then mixed with 2% of grinding aid titanium dioxide and the balance of water to obtain mixed solution A; 35% of hollow manganese-based Prussian blue nanocages, 1% of defoaming agent ethylenediamine PO-EO block polyether and mixed solution A were mixed, homogenized and dispersed at 2800 rpm for 20 minutes to obtain mixed solution B, which was ground with 0.2 mm zirconium beads to obtain hollow manganese-based Prussian blue nanocage suspension.

[0052] Comparative Example 1

[0053] A method for preparing a zinc-doped Prussian blue nanocage and a suspension thereof.

[0054] (1) Preparation method of zinc-doped Prussian blue nanocages: 0.045 mmol polyvinyl pyrrolidone, 0.4 mmol potassium ferrocyanide and 50 mg zinc chloride powder were added to 40 mL deionized water containing 0.01 mol HCl, stirred at 600 r / min at room temperature for 30 min, placed in a hollow drying oven at 80°C for 24 h, and the reaction product was washed with deionized water, then added with alcohol and centrifuged, repeated three times, and freeze-dried to obtain zinc-doped Prussian blue nanocages.

[0055] (2) Preparation method of zinc-doped Prussian blue nanocage suspension: Based on the total mass of the suspension, 1% of wetting agent NS-500LQ and 2% of dispersant Tween 80 were dissolved in 5% of antifreeze agent ethylene glycol, and then mixed with 1% of grinding aid white carbon black and the balance of water to obtain mixed solution A; 30% of zinc-doped Prussian blue nanocages and 0.5% of defoaming agent FoamStar ST 2410 AG were mixed with mixed solution A, and homogenized and dispersed at 2800 rpm for 20 minutes to obtain mixed solution B, which was ground with 0.2 mm zirconium beads to obtain zinc-doped Prussian blue nanocage suspension.

[0056] Comparative Example 2

[0057] A method for preparing a hollow manganese-based Prussian blue nanocage and a suspension thereof.

[0058] (1) Preparation method of hollow manganese-based Prussian blue nanocages: 0.045 mmol polyvinyl pyrrolidone, 0.4 mmol potassium ferrocyanide and 50 mg manganese chloride powder were added to 40 mL deionized water containing 0.01 mol HCl, stirred at 600 r / min at room temperature for 30 min, placed in a dough-shaped hollow drying oven at 150°C for 24 h, and the reaction product was washed with deionized water, then added with alcohol and centrifuged, repeated three times, and freeze-dried to obtain hollow manganese-based Prussian blue nanocages.

[0059] (2) Preparation method of hollow manganese-based Prussian blue nanocage suspension: Based on the total mass of the suspension, 1% of wetting agent NS-500LQ and 2% of dispersant Tween 80 were dissolved in 5% of antifreeze agent ethylene glycol, and then mixed with 1% of grinding aid white carbon black and the balance of water to obtain mixed solution A; 30% of hollow manganese-based Prussian blue nanocages, 0.5% of defoaming agent FoamStar ST 2410 AG and mixed solution A were mixed and homogenized at 2800 rpm for 20 minutes to obtain mixed solution B, which was ground with 0.2 mm zirconium beads to obtain hollow manganese-based Prussian blue nanocage suspension.

[0060] Comparative Example 3

[0061] A method for preparing a hollow manganese-based Prussian blue nanocage and a suspension thereof.

[0062] (1) Preparation method of hollow manganese-based Prussian blue nanocages: 0.045 mmol polyvinyl pyrrolidone, 4 mmol potassium ferrocyanide and 50 mg manganese chloride powder were added to 40 mL deionized water containing 0.01 mol HCl, stirred at 600 r / min at room temperature for 30 min, placed in a hollow drying oven at 80°C for 24 h, and the reaction product was washed with deionized water, then added with alcohol and centrifuged, repeated three times, and freeze-dried to obtain hollow manganese-based Prussian blue nanocages.

[0063] (2) Preparation method of hollow manganese-based Prussian blue nanocage suspension: Based on the total mass of the suspension, 1% of wetting agent NS-500LQ and 2% of dispersant Tween 80 were dissolved in 5% of antifreeze agent ethylene glycol, and then mixed with 1% of grinding aid white carbon black and the balance of water to obtain mixed solution A; 30% of hollow manganese-based Prussian blue nanocages, 0.5% of defoaming agent FoamStar ST 2410 AG and mixed solution A were mixed and homogenized at 2800 rpm for 20 minutes to obtain mixed solution B, which was ground with 0.2 mm zirconium beads to obtain hollow manganese-based Prussian blue nanocage suspension.

[0064] from Figure 1 、 2 The scanning electron microscope and transmission electron microscope images of the hollow manganese-based Prussian blue nanocage prepared in Example 1 show that the manganese-doped Prussian blue nanocage forms a hollow shape in the middle. Figure 4 、 5 The EDS spectrum and mapping diagram of the hollow manganese-based Prussian blue nanocage prepared in Example 1 show that the manganese-doped Prussian blue nanocage contains Fe and Mn elements, proving that manganese ions have been successfully doped into Prussian blue, indicating that the manganese-based Prussian blue nanocage of the present invention was successfully prepared. Figure 6 The particle size diagram of the hollow manganese-based Prussian blue nanocages prepared in Example 1 shows that the average particle size of the hollow manganese-based Prussian blue nanocages is 440-460 nm.

[0065] Test 1

[0066] (1) Experimental methods

[0067] The hollow manganese-based Prussian blue nanocage suspension prepared in Example 3 was dissolved and dispersed in water. 5 mL of sample solution was taken on the first, second, and third days, and 3 mL of aqua regia was added. The solution was digested for 3 days. The digested solution was diluted 4 times and filtered through a 0.22 μm organic filter. The ions in the sample were analyzed by ICP spectrometer, and their relative intensities were measured. The Mn content of each sample was calculated based on the known standard curve. 2+ Content. Among them, Mn 2+ The standard curve of content is shown in Figure 2. Figure 7As shown in Example 3, the Mn of the hollow manganese-based Prussian blue nanocage suspension was prepared. 2+ Release amount chart Figure 8 shown.

[0068] (2) Data Analysis

[0069] Figure 8 It can be clearly seen that a large amount of manganese ions are released on the first, second and third days, which can give the hollow manganese-based Prussian blue nanocages excellent antibacterial activity.

[0070] Test 2

[0071] (1) Experimental methods

[0072] Laboratory-stored strains of Gibberella oxysporum, Botrytis cinerea, Colletotrichum jujuba, and Brassica rapa were aseptically transferred to potato dextrose agar (PDA) and cultured continuously in an incubator (T = 25 ± 2°C, L / D = 12h / 12h). The strains were inoculated 3-5 days before the experiment. Aseptically, a culture of Rhizoctonia solani (Rice Sheath Blight) (grown to approximately two-thirds of the plate) was punched from the outer edge of the colony using a 5mm borer sterilized with an alcohol burner and cooled to room temperature. Under sterile conditions, the nanocage suspensions prepared in Examples 1-3 and Comparative Examples 1-3 were added, wherein the concentrations of the hollow manganese-based Prussian blue nanocage suspension in Example 1 were 10, 20, 50, and 100 mg / mL, respectively. After the drug-containing culture medium solidified, the inoculation needle, which had been sterilized with an alcohol lamp and cooled to room temperature, gently picked up the bacterial cake with the mycelium side facing down and gently placed it in the center of the solidified culture medium. One piece was inoculated into each dish, and the dishes were sealed, marked, and placed in an incubator. After 48 hours, the diameter of each colony was measured using the cross-cross method, and the EC was calculated using the colony diameter method. 50 , take the average, and calculate the antibacterial rate according to the formula. Example 1 The antibacterial effect of the hollow manganese-based Prussian blue nanocage suspension on wheat scab and tomato gray mold is as follows Figure 9 shown.

[0073] DPS software was used for data statistical analysis. The logarithm of fungicide concentration was taken as X value and the corresponding mycelium inhibition growth rate value was taken as Y value for linear regression. The virulence regression equation and the virulence EC value of the agent to the target pathogen were obtained. 50 value.

[0074] The mycelial inhibition growth rate was calculated as follows:

[0075]

[0076] (2) Data Analysis

[0077] according to Figure 9Calculate the EC of 20 mg / L hollow manganese-based Prussian blue nanocage suspension prepared in Example 1 against wheat gibberella and tomato gray mold. 50 The concentrations of the hollow manganese-based Prussian blue nanocage suspension were 55 and 64 mg / L, respectively, indicating that the hollow manganese-based Prussian blue nanocage suspension had good antibacterial activity.

[0078] The mycelial growth inhibition rates of the nanocage suspensions prepared in Examples 1-3 and Comparative Examples 1-3 are shown in Table 1.

[0079] Table 1

[0080]

[0081]

[0082] Test 3

[0083] (1) Experimental methods

[0084] After cutting leaves of similar size from 4-week-old tomato plants, they were immersed in 70% alcohol for 10 seconds on an ultra-clean workbench, rinsed three times with sterile water, and then immersed in 2% sodium hypochlorite for 10 minutes for disinfection. The treated leaves were placed flat on agar medium and pressed with sterilized wet cotton at both ends. Afterwards, three wounds were evenly scratched on the leaf vein with a sterile needle. Each wound was inoculated with 10 μL of fungus, with an OD of 0. 600 = 0.1, and on the second day of inoculation with gray mold, 1 mL of the hollow manganese-based Prussian blue nanocage suspension prepared in Example 1 was sprayed, wherein the concentrations of the hollow manganese-based Prussian blue nanocage suspension were 10, 20, 50, and 100 mg / L, respectively. Afterwards, the changes in the leaf wounds were observed and recorded, and the incidence rate was calculated. The effect of the hollow manganese-based Prussian blue nanocage suspension prepared in Example 1 on the incidence rate of gray mold on tomato leaves is shown in Figure 1. Figure 10 shown.

[0085] Calculate the incidence rate as shown below:

[0086]

[0087] (2) Data Analysis

[0088] Figure 10 It can be seen that as the concentration of hollow manganese-based Prussian blue nanocage suspension increases, the incidence of leaf disease gradually decreases.

[0089] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A hollow manganese-based Prussian blue nanocage, characterized in that: The raw materials of the hollow manganese-based Prussian blue nanocage include manganese salt, potassium ferrocyanide and polyvinyl pyrrolidone, and the molar ratio of polyvinyl pyrrolidone, potassium ferrocyanide and manganese salt is 0.1-0.8:2-6:0.2-1; The preparation method of the hollow manganese-based Prussian blue nanocage is as follows: polyvinyl pyrrolidone, potassium ferrocyanide and manganese salt are dissolved in an acid solution and reacted to obtain the hollow manganese-based Prussian blue nanocage. The reaction temperature is 70-90° C. and the reaction time is 12-48 h.

2. The hollow manganese-based Prussian blue nanocage according to claim 1, characterized in that The manganese salt is selected from any one of manganese chloride, manganese sulfate, manganese acetate and manganese oxide, and the molar ratio of the polyvinyl pyrrolidone, potassium ferrocyanide and manganese salt is 0.4-0.5:3-4:0.2-0.

5.

3. The hollow manganese-based Prussian blue nanocage according to claim 1, characterized in that The average particle size of the hollow manganese-based Prussian blue nanocage is 440-460 nm, and the appearance of the hollow manganese-based Prussian blue nanocage is a three-dimensional hollow shape.

4. A method for preparing the hollow manganese-based Prussian blue nanocage according to any one of claims 1 to 3, characterized in that: Dissolve polyvinyl pyrrolidone, potassium ferrocyanide and manganese salt in acid solution and react to obtain the product.

5. The preparation method according to claim 4, characterized in that The acid solution is selected from hydrochloric acid or nitric acid, the concentration of the acid solution is 0.01-0.05 M, the reaction temperature is 70-90° C., the reaction time is 12-48 h, stirring is performed before the reaction, and washing, centrifugation and drying are performed after the reaction.

6. The preparation method according to claim 5, characterized in that The stirring speed is 600-650 r / min, the stirring time is 15-30 min, the washing is water washing, alcohol is added during the centrifugation, the washing and centrifugation are both performed 3-5 times, and the drying is freeze-drying.

7. A hollow manganese-based Prussian blue nanocage suspension, characterized in that: The raw materials of the suspending agent include: the hollow manganese-based Prussian blue nanocage according to any one of claims 1 to 3, a wetting agent, a dispersant, an antifreeze agent, a defoaming agent and a grinding aid.

8. The suspending agent according to claim 7, characterized in that Based on the total mass of the suspending agent, the content of the hollow manganese-based Prussian blue nanocage is 30-40wt%, the content of the wetting agent is 1-2wt%, the content of the dispersant is 2-5wt%, the content of the antifreeze agent is 3-6wt%, the content of the defoaming agent is 0.1-1wt%, the content of the grinding aid is 0.1-2wt%, and the balance is water.

9. The suspending agent according to claim 7, characterized in that The wetting agent is selected from any one of NS-500LQ, 1015, GY-D09 and GY-D1285, the dispersant is selected from any one of Triton X-102, Tween-80 and Tween-20, the antifreeze is selected from any one of ethylene glycol, propylene glycol and triethanolamine, the defoaming agent is selected from any one of FoamStarST 2410 AG, ethylenediamine PO-EO block polyether and sodium lauryl sulfate K-12, and the grinding aid is selected from any one of magnesium aluminum silicate, titanium dioxide and white carbon black.

10. A method for preparing a suspension concentrate according to any one of claims 7 to 9, characterized in that: The steps include: (1) First, mix the wetting agent, dispersant, antifreeze agent, grinding aid and water to obtain solution A; (2) Then, the hollow manganese-based Prussian blue nanocages, defoaming agent and solution A are mixed and ground to obtain the product.

11. The preparation method according to claim 10, characterized in that: The mixing speed in step (2) is 1500-2800 rpm, the time is 20-60 min, and the grinding uses 0.2-0.4 mm zirconium beads.

12. Use of the hollow manganese-based Prussian blue nanocage according to any one of claims 1 to 3, or the hollow manganese-based Prussian blue nanocage prepared by the preparation method according to any one of claims 4 to 6, or the suspension concentrate according to any one of claims 7 to 9, or the suspension concentrate prepared by the preparation method according to any one of claims 10 to 11 in preparing a drug for inhibiting fungal infection.

Images