Pesticide composition for improving quality and increasing yield and preparation method thereof

Abstract

The invention relates to the technical field of pesticides, and particularly discloses a quality-improving and yield-increasing pesticide composition and a preparation method thereof. The quality-improving and yield-increasing pesticide composition is composed of a drug-loading core and an intelligent response shell wrapping the drug-loading core, the drug-loading core is metal-doped hollow carbon microspheres loaded with pesticide active ingredients, and the intelligent response shell is a cyclodextrin-adipic dihydrazide cross-linked network formed through host-guest interaction and dynamic covalent bonding. According to the invention, the acid sensitivity of hydrazone bonds and the enzyme sensitivity of cyclodextrin skeletons are utilized to construct a dual-signal response controlled release mechanism, so that pesticide is ensured to be released in an explosive manner only in a dual environment in which low pH and specific enzyme exist at a pathogenic bacterium infection point at the same time, and'mistaken release 'caused by environmental fluctuation is greatly avoided; the composition has multiple functions of high drug loading capacity, synergistic sterilization, nutrition supplement and the like, and the raw materials are biodegradable and environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of pesticide technology, and in particular to a pesticide composition for improving quality and increasing yield, and its preparation method. Background Technology

[0002] Pesticides are a crucial means of ensuring agricultural production. They are typically processed into pesticide compositions—formulations made from pesticide active ingredients, carriers, and adjuvants through specific processes, which can be used directly or after dilution, such as wettable powders, suspensions, and emulsifiable concentrates. However, the release of active ingredients in these traditional formulations is often uncontrollable and rapid, easily degraded by environmental factors such as light, rain, and microorganisms, resulting in low utilization rates and short durations of effectiveness. This not only increases application costs and labor intensity but also causes serious environmental pollution and food safety risks. Currently, some environmentally responsive pesticides have been developed, such as pH-responsive or enzyme-responsive pesticides. However, most are still limited to a single response mechanism, exhibiting significant limitations in practical applications; their targeting precision is insufficient: the microenvironment of plant leaves or rhizosphere is complex and variable. Non-pathogen-related factors (such as acid rain, fertilizers, or plant secretions) may cause pH fluctuations, leading to pH-responsive "false releases"; similarly, enzymes secreted by non-target microorganisms in the environment can interfere with the specificity of enzyme responses, resulting in pesticide "false releases," making true precision application impossible. This single-signal triggering mechanism easily leads to pesticide release in non-target areas, causing waste and increasing environmental risks. Furthermore, these pH or enzyme responses typically only have loading and release functions, lacking value-added functions such as synergistic fungicide action and plant nutrient supplementation. Therefore, developing an intelligent pesticide delivery system that integrates multiple responses, synergistic treatment, and environmental friendliness is of great significance for achieving green and sustainable agricultural development.

[0003] Therefore, this invention is proposed to solve the above-mentioned technical problems. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a smart pesticide composition and its preparation method that can simultaneously respond to both pH and enzyme signals and have synergistic therapeutic functions, including the following steps: To achieve the above objectives, the present invention adopts the following technical solution: A pesticide composition for improving quality and increasing yield, the pesticide composition comprising a drug-loaded core and a smart responsive shell surrounding the drug-loaded core, wherein the drug-loaded core is a metal-doped hollow carbon microsphere loaded with pesticide active ingredients; the smart responsive shell surrounding the drug-loaded core is a cyclodextrin-adipic acid dihydrazide crosslinked network formed through host-guest interaction and dynamic covalent bonding, and the mass ratio of the drug-loaded core to the smart responsive shell is (0.8~1.2):1.

[0005] In this invention, the intelligent response shell is a cyclodextrin-adipate dihydrazide crosslinked network encapsulating the drug-carrying core. This network is constructed through host-guest interactions (the alkane chain of adipate dihydrazide embeds into the hydrophobic cavity of cyclodextrin) and dynamic covalent bonding (the hydrazide group of adipate dihydrazide forms a hydrazone bond with the aldehyde group of cyclodextrin), exhibiting a distinct double-layer core-shell structure. The mass ratio of the intelligent response shell to the drug-carrying core is (0.8–1.2):1, preferably 1:1. The formed hydrazone bonds and β-1,4-glycosidic bonds can respond to organic acids secreted by plant pathogens during plant infection and enzymes targeting β-1,4-glycosidic bonds, thereby achieving precise pesticide release and reducing pesticide loss in the environment.

[0006] Furthermore, the metal-doped hollow carbon microspheres are carbon microspheres co-doped with copper and manganese.

[0007] Furthermore, the active pesticide ingredient is selected from one or more of thifluzamide, tebuconazole, carbendazim, difenoconazole, or pyraclostrobin.

[0008] The present invention also provides a method for preparing a pesticide composition for improving quality and increasing yield, comprising the following steps: (1) Preparation of metal-doped hollow carbon microsphere cores; (2) The metal-doped hollow carbon microsphere core obtained in step (1) is subjected to surface oxidation activation to obtain oxidized carbon microspheres; (3) Load the active pesticide ingredient into the oxidized carbon microspheres described in step (2) to obtain the drug-loaded core. (4) The drug-loaded core, aldehyde-modified β-cyclodextrin and adipic acid dihydrazide are mixed in an aqueous phase and subjected to a one-pot self-assembly reaction to form a cyclodextrin-adipic acid dihydrazide crosslinking network on the surface of the drug-loaded core, thereby obtaining the quality-improving and yield-enhancing pesticide composition.

[0009] Furthermore, the preparation method of the metal-doped hollow carbon microspheres in step (1) includes the following steps: a) Dissolve dopamine hydrochloride, surfactant, and histidine in a mixed solvent of water and ethanol to form a precursor solution; b) Add copper salt and manganese salt to the precursor solution described in step a) to obtain solution I; c) Add an organic pore-expanding agent and an alkali to solution I described in step b) and carry out a hydrothermal polymerization reaction to obtain metal-doped precursor microspheres; d) The precursor microspheres obtained in step c) are subjected to high-temperature carbonization under an inert atmosphere to obtain the metal-doped hollow carbon microspheres.

[0010] Further, in step a), the mass ratio of dopamine hydrochloride, surfactant, and histidine is 1:0.05:0.05, the ratio of dopamine hydrochloride to the mixed solvent to the liquid is 1:50 (g / mL), the volume ratio of water to ethanol in the mixed solvent is 1:1, and the surfactant is one of Pluronic F127 and P123.

[0011] This invention achieves highly uniform doping of metal ions in a carbon matrix by utilizing the synergistic coordination of dopamine hydrochloride and histidine. Dopamine hydrochloride functions as both a carbon-nitrogen precursor and a dominant coordinating agent: it not only constructs the basic framework of hollow porous carbon microspheres through high-temperature carbonization, but also forms stable coordination intermediates with transition metal ions through catechol and amino functional groups in its molecule. Simultaneously, the imidazole group on the histidine side chain, with its strong specific coordination ability towards metal ions, acts as a key synergistic coordinating component, forming a multiple coordination network with dopamine hydrochloride. This effectively prevents hydrolysis, segregation, or aggregation of metal ions during hydrothermal and carbonization processes, ultimately ensuring that metals such as copper and manganese are uniformly and stably doped into the carbon microspheres at the atomic or nanoscale.

[0012] Further, in step b), the copper salt includes one or more of copper nitrate trihydrate, copper chloride, copper sulfate, and copper acetate; the manganese salt includes one or more of manganese nitrate tetrahydrate, manganese chloride, manganese sulfate, and manganese acetate. Further, in step b), the mass ratio of the copper salt (Cu²⁺) to dopamine hydrochloride is 0.002:1, and the mass ratio of the manganese salt (Mn²⁺) to dopamine hydrochloride is 0.005:1.

[0013] Further, in step c), the organic pore-expanding agent is diethyl ether, the alkali is any one of ammonia, sodium hydroxide, and potassium hydroxide, the concentration of the alkali is 0.5 mol / L, and the volume ratio of solution I, organic pore-expanding agent, and alkali is 50:1:2.

[0014] Further, in step c), the hydrothermal polymerization reaction temperature is 50~60℃, and the reaction time is 1~1.5 hours.

[0015] Further, in step d), the calcination inert atmosphere is either nitrogen or argon; the calcination temperature is 400–600°C; the calcination time is 2 hours; and the heating rate is 3°C / min.

[0016] Furthermore, the surface oxidation activation described in step (2) is performed by reflux treatment with a 2 mol / L dilute nitric acid solution at 60°C for 0.5 hours.

[0017] In this invention, the surface oxidation activation of carbon microspheres is to introduce carboxyl groups on the surface of carbon microspheres, which can react with the hydrazide group of adipic acid dihydrazide to form a strong amide bond, thus firmly fixing the entire smart response shell to the surface of carbon microspheres through covalent bonds, making it less likely to fall off the surface of carbon microspheres when diluted, sprayed or washed by rain.

[0018] Furthermore, the preparation method of the aldehyde-modified β-cyclodextrin includes: dissolving β-cyclodextrin in water, adding sodium periodate for oxidation reaction, dialysis purification after the reaction is completed, and freeze-drying to obtain aldehyde-modified β-cyclodextrin.

[0019] The beneficial effects of this invention are: The pesticide composition for improving quality and increasing yield provided by this invention relies on a smart shell with stable hydrazone bonds (pH response) and cyclodextrin skeleton (enzyme response). Under a single stimulus (acid only or enzyme only), the carrier shell is only partially damaged, resulting in slow and incomplete pesticide release. However, when dual signals coexist, the breaking of hydrazone bonds (destruction of chemical cross-linking) and the enzymatic hydrolysis of the cyclodextrin skeleton (destruction of the physical skeleton) produce a synergistic disintegration effect. This design ensures that the pesticide is released explosively and precisely only when both acid and specific enzyme signals are present at the pathogen infection site. This minimizes the risk of "false release" caused by environmental fluctuations (such as pH fluctuations caused by acid rain or fertilizers, or enzymes secreted by non-target microorganisms), significantly improving pesticide utilization, reducing environmental risks, and delaying the development of pesticide resistance.

[0020] This invention's pesticide composition for improving quality and increasing yield integrates multiple functions such as high loading capacity, synergistic treatment, and nutritional supplementation. The hollow carbon microsphere core not only provides ample space for pesticide loading, but its robust carbon walls also effectively protect the internal active pesticide ingredients from degradation by environmental factors such as sunlight and rain, thus extending the duration of effectiveness. Its carbon skeleton and doped copper / manganese elements endow the carrier with synergistic bactericidal ability of photothermal therapy and chemikinetic therapy; in addition, the copper, manganese and nitrogen elements introduced after the carrier degrades achieve the unity of plant protection and nutrient enhancement, promote crop growth and metabolism, and achieve the effect of improving quality and increasing yield.

[0021] The main raw materials of the quality-improving and yield-increasing pesticide composition in this invention, such as dopamine, β-cyclodextrin, and adipic acid dihydrazide, all have good biodegradability and biocompatibility. Their final decomposition products in the environment are water, carbon dioxide, and inorganic salts, with no risk of persistent residues. Attached Figure Description

[0022] Figure 1 The graphs show the response effects of Example 1 at pH 5.5, cellulase, pH 5.5, and cellulase, respectively. Detailed Implementation

[0023] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Example 1

[0024] 1. The preparation of the drug-loaded core shall be carried out in the following steps: (1) Preparation of metal-doped hollow carbon microspheres a) Dopamine hydrochloride, surfactant (Pluronic F127) and histidine are dissolved in a mixed solvent of water and ethanol, wherein the mass ratio of dopamine hydrochloride:surfactant:histidine is 1:0.05:0.05, the feed-to-liquid ratio of dopamine hydrochloride to the mixed solvent is 1:50 (g / mL), and the volume ratio of water to alcohol is 1:1, to form a precursor solution; b) Add copper nitrate trihydrate and manganese nitrate tetrahydrate to the precursor solution in step a), wherein the mass ratio of copper nitrate trihydrate (Cu²⁺) to dopamine hydrochloride is 0.002:1, and the mass ratio of manganese nitrate tetrahydrate (Mn) is... 2 Based on the mass ratio of its content to that of dopamine hydrochloride, the mass ratio is 0.005:1, resulting in solution I; c) Add diethyl ether and ammonia to solution I from step b), wherein the concentration of ammonia is 0.5 mol / L, and the volume ratio of solution I, diethyl ether, and alkali is 50:1:2. Perform a hydrothermal polymerization reaction at 50°C. The reaction time is 1 hour, yielding metal-doped polymer precursor microspheres. d) Under a nitrogen atmosphere, the precursor microspheres obtained in step c) were subjected to high-temperature carbonization at a carbonization calcination temperature of 400℃, a calcination time of 2 hours, and a heating rate of 3℃ / min to obtain metal-doped hollow carbon microspheres.

[0025] Oxidation activation of the surface of metal-doped hollow carbon microspheres The metal-doped hollow carbon microspheres prepared in (1) above were dispersed in a 2 mol / L dilute nitric acid solution at a material-to-liquid ratio of 1:5 (g / mL) and refluxed at 60°C for 0.5 hours to obtain oxidized carbon microspheres.

[0026] Preparation of drug delivery core The carbon oxide microspheres prepared in (2) above and carbendazim were dispersed in ethyl acetate at a mass ratio of 1:0.6, wherein the material-to-liquid ratio of carbendazim to ethyl acetate was 1:10. The mixture was stirred at room temperature for 6 hours, filtered and dried to obtain the drug-loaded core.

[0027] The preparation of aldehyde-modified β-cyclodextrin is carried out according to the following steps: Step A: Add β-cyclodextrin to 100 mL of deionized water at a material-to-liquid ratio of 1:15 (g / mL), stir gently until the β-cyclodextrin is completely dissolved, and slowly adjust the pH of the system to 3.0 with 0.1 mol / L HCl solution to obtain solution A; Step B: Weigh out sodium periodate with a mass ratio of 0.2:1 to β-cyclodextrin in Step A, and add it to deionized water with a material-to-liquid ratio of 1:30 (g / mL) to obtain solution B; Step C: Using a constant pressure dropping funnel, add solution B dropwise to solution A. After the addition is complete, stir the reaction for 3 hours.

[0028] Step D: Transfer all the reaction solution to a pretreated dialysis bag and dialyze with a large amount of deionized water, changing the water every 6-8 hours. Continue dialysis for 60 hours until no white precipitate (iodate ion detection) is found in the dialysate when tested with 1% nitric acid-acidified AgNO3 solution. Step E: After freeze-drying the solution, aldehyde-modified β-cyclodextrin solid is obtained. The preparation of responsive pesticide compositions is carried out according to the following steps: S1: The above-mentioned drug-loaded core and aldehyde-modified β-cyclodextrin were dispersed in water at a mass ratio of 2:1, and the material-to-liquid ratio of the drug-loaded core to water was 0.005:1 (g / mL). S2: Disperse adipic acid dihydrazide in water at a material-to-liquid ratio of 0.005:1 (g / mL), and the mass ratio of adipic acid dihydrazide to β-cyclodextrin in step S1 is 1:1; S3: Quickly add the solution obtained from S1 to S2, let it stand at 50°C for 2 hours, centrifuge, wash with water, and then dry in a 50°C forced-air drying oven to obtain the quality-enhancing and yield-increasing pesticide composition.

[0029] Comparative Example 1 Compared with Example 1, the only difference is that in "3. Preparation of responsive pesticide composition", the aldehyde-modified β-cyclodextrin is replaced with an equal amount of β-cyclodextrin, while the other steps and conditions remain the same.

[0030] Comparative Example 2 Compared with Example 1, the only difference is that the preparation of "1. Preparation of drug-loaded core, and (2) oxidation activation of surface of metal-doped hollow carbon microspheres" is not performed, while the other steps and conditions remain the same.

[0031] Comparative Example 3 Compared with Example 1, the only difference is that in the preparation method of "1. Preparation of drug-loaded core, (1) Preparation of metal-doped hollow carbon microspheres", dopamine hydrochloride is replaced with an equal amount of phenolic resin, and the other steps and conditions are kept the same.

[0032] Test case The performance of the carbendazim-containing pesticide compositions prepared in Example 1 and Comparative Examples 1-3 were tested respectively. 1. Testing of drug loading effect The specific testing method is as follows: Drug loading effect: High performance liquid chromatography (HPLC) was used with a C18 column and a mobile phase of methanol-water solution with a volume ratio of 7:3. The detection wavelength was 280 nm. The adsorption capacity of carbon microspheres and the actual drug loading rate of the quality improvement and yield enhancement composition were calculated by standard curve method.

[0033] Adsorption capacity (mg / g) = (Total amount of carbendazim added - Amount of carbendazim in ethyl acetate) / Total amount of carbon microspheres Pesticide loading rate (%) = (Total amount of carbendazim in the pesticide composition / Total amount of pesticide composition) * 100% The experimental results are shown in Table 1: Table 1 Group Adsorption capacity of carbon microspheres (mg / g) Drug loading rate (%) Example 1 556 17.5 Comparative Example 1 552 15.4 Comparative Example 2 549 14.3 Comparative Example 3 156 5 As shown in Table 1, the carbon microspheres prepared in this invention have a high loading capacity for carbendazim, which is much higher than the high values ​​reported in the current literature. The carbon microspheres in this invention, as a carrier for carbendazim, have the characteristics of being inexpensive, easy to obtain, and having a high pesticide loading capacity.

[0034] 2. Response effect test 2.1 pH response performance test (single acidic stimulus) Test method: Equal masses (4g) of the carbendazim-containing pesticide compositions prepared in Example 1 and Comparative Examples 1-3 were placed in pretreated dialysis bags. 50mL of pH 5.5 phosphate buffer was used as the release medium. The beakers were placed on a magnetic stirrer at 37℃ and shaken at 100rpm. 0.2mL of the sustained-release solution was collected at 1h, 2h, 4h, 8h, 12h, 24h, and 48h, respectively. The pesticide concentration was determined by HPLC, and the cumulative release was calculated. The results are shown in Table 2 and... Figure 1 .

[0035] Table 2 Group Example 1 Release amount (mg) Comparative Example 1 Release Amount (mg) Comparative Example 2 Release Amount (mg) Comparative Example 3 Release Amount (mg) 1h 15 50 60 5 2h 33 100 150 10 4h 72 250 300 25 8h 105 300 350 55 12h 135 350 400 70 24h 155 380 450 75 48h 175 390 500 80 2.2 Enzyme response performance test (single enzyme stimulation) Equal masses (4 g) of the carbendazim-containing pesticide compositions prepared in Example 1 and Comparative Examples 1-3 were placed in pretreated dialysis bags. 50 mL of pH 7.0 phosphate buffer containing 1 mg / mL plant cellulase was used as the release medium. The beakers were placed on a magnetic stirrer at 37°C and shaken at 100 rpm. 40 mL of the slow-release solution was collected at 1 h, 2 h, 4 h, 8 h, 12 h, 24 h, and 48 h, respectively. The pesticide concentration was determined by HPLC, and the cumulative release was calculated. The results are shown in Table 3. Figure 1 .

[0036] Table 3 Group Example 1 Release amount (mg) Comparative Example 1 Release Amount (mg) Comparative Example 2 Release Amount (mg) Comparative Example 3 Release Amount (mg) 1h 20 65 54 8 2h 40 108 153 13 4h 76 279 288 28 8h 107 350 346 54 12h 142 403 421 69 24h 161 534 492 89 48h 189 568 523 103 2.3 Equal masses (4 g) of the carbendazim-containing pesticide compositions prepared in Example 1 and Comparative Examples 1-3 were placed in pretreated dialysis bags. 50 mL of pH 5.5 phosphate buffer containing 1 mg / mL plant cellulase was used as the release medium. The beaker was placed on a magnetic stirrer at 37°C and shaken at 100 rpm. 40 mL of the slow-release solution was collected at 1 h, 2 h, 4 h, 8 h, 12 h, 24 h, and 48 h, respectively. The pesticide concentration was determined by HPLC, and the cumulative release was calculated. The results are shown in Table 4. Figure 1 .

[0037] Table 4 Group Example 1 Release amount (mg) Comparative Example 1 Release Amount (mg) Comparative Example 2 Release Amount (mg) Comparative Example 3 Release Amount (mg) 1h 50 67 65 45 2h 102 105 193 98 4h 174 279 325 151 8h 280 345 465 162 12h 460 394 503 170 24h 585 531 523 171 48h 621 565 543 174 From Tables 2-4 and Figure 1 As shown, under single stimulation (pH=5.5 only or containing only cellulase), the pesticide release of the quality-improving and yield-increasing pesticide composition prepared in Example 1 was significantly lower than that under dual stimulation (pH=5.5 + cellulase) within 48 hours. Particularly under dual stimulation, Example 1 exhibited explosive release within 12 hours, far exceeding the release under any single stimulation condition. This fully demonstrates that the intelligent response shell designed in this invention produces a synergistic disintegration effect when both acidic and enzymatic signals are present simultaneously, thereby achieving rapid and precise pesticide release and effectively solving the problem of "false release" easily caused by single-response mechanisms.

[0038] In contrast, comparative examples showed that Comparative Example 1, by replacing aldehyde-based β-cyclodextrin with ordinary β-cyclodextrin, failed to form a dynamically covalently bonded cross-linked network, resulting in insufficient shell stability and a high release rate under a single stimulus. Comparative Example 2, by not performing surface oxidation activation on the carbon microspheres, resulted in a weak bond between the intelligent response shell and the drug-carrying core, leading to easy detachment and uncontrolled pesticide release. Comparative Example 3, by replacing dopamine hydrochloride with phenolic resin, disrupted the uniform doping system of metal ions, significantly reducing the drug loading capacity and responsiveness of the carbon microspheres, ultimately failing to achieve both efficient drug loading and effective signal response release.

[0039] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A pesticide composition for improving quality and increasing yield, characterized in that, The pesticide composition comprises a drug-loaded core and a smart responsive shell encapsulating the drug-loaded core. The drug-loaded core is a metal-doped hollow carbon microsphere loaded with pesticide active ingredients. The smart responsive shell is a cyclodextrin-adipic acid dihydrazide crosslinking network formed through host-guest interactions and dynamic covalent bonding. The mass ratio of the drug-loaded core to the smart responsive shell is (0.8~1.2):

1.

2. The quality-improving and yield-increasing pesticide composition according to claim 1, characterized in that, The metal-doped hollow carbon microspheres are carbon microspheres co-doped with copper and manganese.

3. The quality-improving and yield-increasing pesticide composition according to claim 1, characterized in that, The active ingredient of the pesticide is selected from one or more of thifluzamide, tebuconazole, carbendazim, difenoconazole, or pyraclostrobin.

4. A method for preparing the quality-improving and yield-increasing pesticide composition as described in any one of claims 1-3, characterized in that, Includes the following steps: (1) Preparation of metal-doped hollow carbon microspheres; (2) The metal-doped hollow carbon microspheres obtained in step (1) are subjected to surface oxidation activation to obtain oxidized carbon microspheres; (3) Load the active pesticide ingredient into the oxidized carbon microspheres described in step (2) to obtain the drug-loaded core. (4) The drug-loaded core, aldehyde-modified β-cyclodextrin and adipic acid dihydrazide are mixed in an aqueous phase and subjected to a one-pot self-assembly reaction to form a cyclodextrin-adipic acid dihydrazide crosslinking network on the surface of the drug-loaded core, thereby obtaining the quality-improving and yield-enhancing pesticide composition.

5. The method according to claim 4, characterized in that, The preparation method of the metal-doped hollow carbon microspheres in step (1) includes: a) Dissolve dopamine hydrochloride, surfactant, and histidine in a mixed solvent of water and ethanol to form a precursor solution; b) Add the copper salt and manganese salt to the precursor solution described in step a) to obtain solution I; c) Add an organic pore-expanding agent and an alkali to solution I described in step b) and carry out a hydrothermal polymerization reaction to obtain metal-doped polymer precursor microspheres; d) The precursor microspheres obtained in step c) are subjected to high-temperature carbonization under an inert atmosphere to obtain the metal-doped hollow carbon microspheres.

6. The method according to claim 5, characterized in that, In step a), the mass ratio of dopamine hydrochloride, surfactant and histidine is 1:0.05:0.05, the ratio of dopamine hydrochloride to the mixed solvent to the liquid is 1:50 (g / mL), the volume ratio of water and ethanol in the mixed solvent is 1:1, and the surfactant is one of Pluronic F127 and P123.

7. The method according to claim 5, characterized in that, In step b), the mass ratio of the copper salt (Cu²⁺) to dopamine hydrochloride is 0.002:1, and the mass ratio of the manganese salt (Mn²⁺) to dopamine hydrochloride is 0.005:

1.

8. The method according to claim 5, characterized in that, Step c), the organic pore-expanding agent is diethyl ether, the alkali is any one of ammonia, sodium hydroxide, and potassium hydroxide, the concentration of the alkali is 0.5 mol / L, and the volume ratio of solution I, organic pore-expanding agent and alkali is 50:1:

2.

9. The method according to claim 4, characterized in that, The surface oxidation activation described in step (2) involves reflux treatment with a 2 mol / L dilute nitric acid solution at 60°C for 0.5 hours.

10. The method according to claim 4, characterized in that, The method for preparing aldehyde-modified β-cyclodextrin includes: dissolving β-cyclodextrin in water, adding sodium periodate for oxidation reaction, dialysis purification after the reaction is completed, and freeze-drying to obtain aldehyde-modified β-cyclodextrin.

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