Nanozyme and preparation method thereof, agricultural preparation and application thereof

Abstract

The present application relates to a nanozyme, a preparation method thereof, an agricultural formulation and its application. The raw materials for the preparation are as follows, calculated by weight: 1 to 6 parts of a metal salt; 0.5 to 4 parts of a surfactant; 1 to 1.04 parts of an acidic reagent; the metal salt comprises one or more of an iron salt, a manganese salt, a calcium salt, a zinc salt and a copper salt; the metal-organic framework material of the nanozyme is Prussian blue. The raw materials for the preparation of the nanozyme include specific components with a specific ratio, wherein the metal salt provides the active center and structural basis of the nanozyme, that is, the presence of metal ions can provide an active center, giving the nanozyme catalytic activity, similar to the catalytic effect of metal ions at the active site in natural enzymes; the surfactant controls the size and dispersibility of the nanozyme, and the acidic reagent adjusts the reaction conditions. The three cooperate with each other to provide a guarantee for the successful preparation and performance optimization of the nanozyme.

Description

Technical Field

[0001] The present application relates to the field of nanomaterial technology, and in particular to a nanoenzyme and a preparation method thereof, an agricultural formulation and its application. Background Art

[0002] Nanozymes, as environmentally friendly catalytic materials, are nanosized and possess enzymatic reaction kinetics and specificity similar to natural enzymes, making them widely applicable in biology, medicine, and other fields. In agriculture, nanozymes possess strong environmental tolerance and micro-fertilizer effects, making them particularly suitable for large-scale industrial production. However, despite the broad application prospects of nanozymes in agriculture, integrated fertilizer and drug production technologies based on nanozymes have not yet been widely adopted.

[0003] Seed coatings are widely used in agricultural production. By coating seeds, they provide essential nutrients and effectively control pests and diseases, playing a vital role in promoting healthy crop growth and increasing crop yields. However, traditional seed coatings often contain high concentrations of pesticides, which can easily cause phytotoxicity to seeds, affecting germination rates and seedling growth. Furthermore, traditional seed coatings have a short shelf life, low pesticide utilization rates, and may introduce toxic warning dyes, which are not only detrimental to the ecological environment but also make it difficult to meet the needs of green and sustainable agricultural development.

[0004] Therefore, there is an urgent need for products and technologies that can solve the problems of pesticide damage and abiotic stress caused by traditional seed dressing agents, improve the effective utilization rate of pesticides, and promote the healthy growth of seeds. Summary of the Invention

[0005] Based on this, the present application provides a nanozyme that can effectively degrade free radicals produced by pesticide stress and reduce their toxic effects on biological systems. When used as a seed coating material, it can not only reduce the risk of phytotoxicity of traditional pesticides on seeds, but also significantly improve the germination rate of seeds and the growth quality of seedlings; and accordingly provides a nanozyme and its preparation method, agricultural preparation and its application.

[0006] The specific technical solutions are as follows:

[0007] The first aspect of the present application provides a nanozyme comprising the following raw materials, calculated by weight:

[0008] 1 to 6 parts of metal salt;

[0009] 0.5 to 4 parts of surfactant;

[0010] 1 part to 1.04 parts of acidic reagent;

[0011] The metal salt includes one or more of iron salt, manganese salt, calcium salt, zinc salt and copper salt; the metal organic framework material of the nanozyme is Prussian blue.

[0012] In some embodiments, the surfactant includes tea seed cake extract;

[0013] The acidic agent includes citric acid.

[0014] On the other hand, the present application also provides a method for preparing a nanozyme, comprising the following steps:

[0015] The above-mentioned raw materials for preparing nanozymes are mixed, reacted and dried to prepare nanozymes.

[0016] In some embodiments, the stirring speed of the mixing is 500 r / min to 700 r / min, and the mixing time is 10 min to 30 min;

[0017] The reaction temperature is 60°C to 80°C, and the reaction time is 24h to 48h;

[0018] The drying method includes one or more of vacuum drying and freeze drying.

[0019] On the other hand, the present application also provides an agricultural preparation, which includes the above-mentioned nanozyme.

[0020] In some embodiments, the agricultural formulation includes a seed coating agent, and the nanozyme accounts for 5% to 9% by weight of the seed coating agent;

[0021] The seed coating agent comprises the following components in parts by weight:

[0022] 2 to 10 parts of pesticide;

[0023] 5 to 9 parts of the above-mentioned nanozyme;

[0024] 1.5 to 3 parts thickener;

[0025] 0.75 to 1.5 parts of bio-based polymer;

[0026] 0.1 to 0.5 parts of organic acid;

[0027] 3 to 5 parts of organic nitrogen compound;

[0028] 0.5~1.5 parts of mineral materials;

[0029] 0.1~0.3 parts of film-forming agent.

[0030] In some embodiments, the organic acid comprises one or more of salicylic acid, citric acid, ascorbic acid, and tartaric acid.

[0031] In some embodiments, the mineral material includes one or more of attapulgite, diatomaceous earth, bentonite, and sepiolite.

[0032] On the other hand, the present application also provides the use of the above agricultural formulation in improving the germination rate of seeds and the growth quality of seedlings.

[0033] In some embodiments, the seeds include one or more of soybean, wheat, corn, rapeseed, peanut, cotton, cucumber, tomato and carrot.

[0034] The raw materials for preparing the nanozyme of the present application include specific components with a specific ratio relationship, wherein the metal salt provides the active center and structural basis of the nanozyme, that is, the presence of metal ions can provide an active center, giving the nanozyme catalytic activity, similar to the catalytic effect of metal ions in the active site in natural enzymes; the surfactant controls the size and dispersibility of the nanozyme, the acidic reagent adjusts the reaction conditions, and the three cooperate with each other to provide a guarantee for the successful preparation and performance optimization of the nanozyme. Each component acts in coordination with a specific ratio relationship, and the nanomaterial modified by the surfactant has good water solubility and can be stably present in the form of a high concentration of colloid. When subsequently applied to seedling cultivation, it has the effect of promoting growth, enhancing stress resistance, increasing yield and improving quality of crops. In addition, the nanozyme itself has a bright blue color, so it can replace the highly toxic organic dyes commonly used in seed dressing agents on the market in a green way. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is an optical microscope image of the agricultural preparation in Example 1;

[0036] Figure 2 This is a digital image of the agricultural formulation in Example 1;

[0037] Figure 3 This is the phenotype diagram of the agricultural formulation in Example 1;

[0038] Figure 4 This is a bar graph showing the effect of the agricultural formulation on soybean germination rate in Example 1;

[0039] Figure 5 This is a diagram showing the effect of the agricultural formulation on soybean germination in Example 1;

[0040] Figure 6 This is a bar graph showing the effect of the agricultural formulation on soybean sprout length in Example 1;

[0041] Figure 7 This is a digital image showing the effect of the agricultural formulation on soybean growth promotion in Example 1;

[0042] Figure 8 The effect of the agricultural formulation in Example 1 on soybean plant height;

[0043] Figure 9 The effect of the agricultural formulation in Example 1 on the root length of soybean plants;

[0044] Figure 10 The effect of the agricultural formulation in Example 1 on the fresh weight of soybean plants;

[0045] Figure 11 This is a digital image showing the effect of the agricultural formulation in Example 1 on the resistance of soybean plants to salt stress;

[0046] Figure 12 This is a bar graph showing the effect of the agricultural formulation in Example 1 on the chlorophyll content of soybean plants subjected to salt stress. DETAILED DESCRIPTION

[0047] To facilitate understanding of the present application, the present application will be described more fully below, with preferred embodiments of the present application provided. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, the purpose of providing these embodiments is to provide a more thorough and comprehensive understanding of the disclosure of the present application.

[0048] The following is a detailed description of the implementation of this application in conjunction with some implementation methods and examples. This example is implemented based on the technical solution of this application, and provides a detailed implementation method and specific operation process, but the scope of protection of this application is not limited to the following examples.

[0049] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application pertains. The terms used herein in the specification of this application are for the purpose of describing specific embodiments only and are not intended to limit this application.

[0050] the term

[0051] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0052] In this application, "a plurality of" or "a plurality of" refers to a number greater than or equal to 2 unless otherwise specified. For example, "one or more" means one or more than or equal to two.

[0053] In this application, "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be understood as limiting the scope of protection of this application.

[0054] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0055] In this application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values within the numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two numerical endpoints. Unless otherwise specified, when a numerical interval refers only to integers within the numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed herein should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. "Numerical interval" allows for a broad range of numerical interval types including percentage intervals, ratio intervals, and ratio intervals.

[0056] In this application, unless otherwise specified, temperature parameters may be either constant temperature or fluctuating within a certain temperature range. It should be understood that constant temperature processing allows for temperature fluctuations within the precision range of instrument control. Fluctuations within ranges such as ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are permitted.

[0057] In this application, when referring to a range of units, if only the right endpoint is followed by the unit, it means that the units of the left and right endpoints are the same. For example, 2h~5h means that the units of the left endpoint "2" and the right endpoint "5" are both hours.

[0058] Nanozymes, environmentally friendly catalytic materials with nanometer-scale sizes and enzymatic reaction kinetics and specificity similar to those of natural enzymes, have broad applications in biology, medicine, and other fields. In agriculture, nanozymes, through integrated pesticide-fertilizer seed coating technology, have the potential to address the problems of pesticide damage and abiotic stress caused by traditional seed coatings, improve pesticide utilization, and promote healthy seed growth. First, nanozymes can significantly enhance the nutrient absorption efficiency of plant roots. Applying nanozymes to plant roots can enhance the plant's ability to absorb nutrients from the soil, thereby increasing plant growth and yield. Second, nanozymes improve seed tolerance to pesticides by catalyzing reactive oxygen species, thereby alleviating the severity of seed damage. Furthermore, nanozymes can help improve plant stress tolerance. Plants are vulnerable to environmental stresses such as drought, extreme temperatures, salinity, and heavy metals. Nanozymes enhance plant resistance by regulating metabolic pathways and signal transduction pathways, enabling them to better adapt to adverse environmental conditions. The potential applications of nanozymes in promoting crop growth and increasing yields have brought new breakthroughs in the high-quality production of agricultural products. More importantly, nanozymes have many advantages. Their preparation process is simple, their chemical properties are stable, their catalytic reactions have good repeatability, and they have strong environmental tolerance and micro-fertilizer effects, making them particularly suitable for large-scale industrial production.

[0059] Furthermore, seed coatings utilize film-forming materials such as bio-based polymers and thickeners, which self-assemble through organic acid crosslinking to form a three-dimensional network structure called a "biofilm hydrogel." This biofilm is highly sensitive to environmental changes and responds to stimuli (such as pH, temperature, humidity, and salinity) by swelling and shrinking in volume. This intelligently controls the release rate of pesticides and fertilizers, improving their utilization while also conserving water and enhancing soil quality. However, conventional nano seed coatings and their preparation methods offer only advantages at the nanoscale. Their components suffer from poor biodegradability, the environmental pollution caused by small-molecule surfactants, and relatively limited functionality.

[0060] Based on this, one embodiment of the present application provides a nanozyme, wherein the raw materials for preparing the nanozyme include, by weight:

[0061] 1 to 6 parts of metal salt;

[0062] 0.5 to 4 parts of surfactant;

[0063] 1 part to 1.04 parts of an acidic reagent; the metal salt includes one or more of iron salts, manganese salts, calcium salts, zinc salts and copper salts; the metal organic framework material of the nanozyme is Prussian blue.

[0064] The research results clearly demonstrate that, as a typical metal-organic framework (MOF) material, the crystal structure of Prussian blue nanoparticles provides them with a stable skeleton, enabling them to maintain stable catalytic activity under various environmental conditions. Furthermore, their surface has been carefully chemically modified to effectively bind to target molecules (such as superoxide anions, hydrogen peroxide, and hydroxyl radicals), accelerating their decomposition or conversion. These nanoparticles possess excellent antioxidant enzyme activity (primarily exhibiting superoxide dismutase- and catalase-like properties, as well as scavenging hydroxyl radicals). This property helps improve crop resistance to abiotic stress. Furthermore, the metal elements doped into Prussian blue-derived nanozymes promote growth, enhance stress resistance, increase yield, and improve crop quality. Manganese, among other elements, acts as an activator of various enzymes in plants, participating in photosynthesis and respiration, regulating ion balance within plants, and enhancing their adaptability to environmental stresses such as drought and salinity. Zinc is essential for plant growth and development, participating in crop photosynthesis, respiration, nitrogen metabolism, hormone synthesis, and plant growth. Zinc promotes photosynthesis, facilitates organic matter accumulation, and increases crop yield and stress tolerance. Copper participates in plant photosynthesis and respiration, catalyzing redox reactions, promoting carbohydrate and protein metabolism and synthesis, improving chlorophyll stability, and enhancing plant resistance to cold and drought. Iron is an essential trace element for plant growth and development, primarily promoting chlorophyll synthesis, participating in respiration, regulating plant growth and development, and improving stress tolerance. Iron ions catalyze chlorophyll synthesis, giving leaves their green color, participate in oxygen transport and release, and catalyze the activity of various enzymes. Calcium is an essential trace element for some lower and higher plants. In higher plants, calcium serves as a metal cofactor in urease, making it crucial for nitrogen metabolism. Calcium also regulates the activity of other enzymes, promoting normal plant growth and development.

[0065] In some embodiments, the surfactant includes tea seed cake extract.

[0066] In some embodiments, the acidic agent includes citric acid.

[0067] The raw materials for preparing the nanozyme of the present application include specific components with a specific ratio relationship, wherein the metal salt provides the active center and structural basis of the nanozyme, that is, the presence of metal ions can provide an active center, giving the nanozyme catalytic activity, similar to the catalytic effect of metal ions in the active site in natural enzymes; the surfactant controls the size and dispersibility of the nanozyme, the acidic reagent adjusts the reaction conditions, and the three cooperate with each other to provide a guarantee for the successful preparation and performance optimization of the nanozyme. The various components act in coordination with each other through a specific ratio relationship, and the nanomaterial modified by the surfactant has good water solubility and can be stably present in the form of a high concentration colloid. When subsequently applied to seedling cultivation, it has the effect of promoting growth, enhancing stress resistance, increasing yield and improving quality of crops.

[0068] One embodiment of the present application provides a method for preparing a nanozyme, comprising the following steps: mixing, reacting and drying the above-mentioned raw materials for preparing the nanozyme to prepare the nanozyme.

[0069] In some embodiments, the stirring speed of the mixing is 500 r / min to 700 r / min, and the mixing time is 10 min to 30 min.

[0070] In some embodiments, the reaction temperature is 60° C. to 80° C., and the reaction time is 24 h to 48 h.

[0071] In some embodiments, the drying method includes one or more of vacuum drying and freeze drying.

[0072] The preparation method of the above-mentioned nanozyme of the present application has a simple process and low cost. Using the nanozyme as a seed coating material can not only reduce the risk of phytotoxicity of traditional pesticides on seeds, but also significantly improve the germination rate of seeds and the growth quality of seedlings.

[0073] One embodiment of the present application provides an agricultural preparation, which includes the above-mentioned nanozyme.

[0074] In some embodiments, the agricultural preparation includes a seed coating agent, and the nanozyme accounts for 5% to 9% of the weight of the seed coating agent.

[0075] In some embodiments, the seed coating agent comprises the following components in parts by weight:

[0076] 2 to 10 parts of pesticide;

[0077] 5 to 9 parts of nanozyme;

[0078] 1.5 to 3 parts thickener;

[0079] 0.75 to 1.5 parts of bio-based polymer;

[0080] 0.1 to 0.5 parts of organic acid;

[0081] 3 to 5 parts of organic nitrogen compound;

[0082] 0.5~1.5 parts of mineral materials;

[0083] 0.1~0.3 parts of film-forming agent.

[0084] The above-mentioned seed coating agent combines the nanozymes of the present application with pesticides, thickeners, bio-based polymers, organic acids, organic nitrogen compounds, mineral materials and film-forming agents. By controlling the specific ratios of each preparation raw material, the components act synergistically, which promotes the addition of nanozymes. It can not only achieve green and efficient disease prevention and control, but also provide nutrients for crops, promote crop growth and enhance their stress resistance, so that the seed coating agent has significant economic and ecological benefits, and has broad application prospects in the field of modern agriculture.

[0085] It should be noted that the range of "2 parts to 10 parts" for pesticides refers to the minimum and maximum values within the range, as well as every value between these minimum and maximum values. Specific examples include, but are not limited to, the point values in the Examples and the following point values: 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts; or a range consisting of any two of these values, including, for example, 3 parts to 10 parts.

[0086] The nanozyme value range of "5 parts to 9 parts" refers to the minimum and maximum values within the range of 5 parts to 9 parts, as well as every value between the minimum and maximum values. Specific examples include, but are not limited to, the point values in the Examples and the following point values: 5 parts, 6 parts, 7 parts, 8 parts, 9 parts; or a range consisting of any two of these values, including, for example, 6 parts to 9 parts.

[0087] The range of the thickener is "1.5 to 3 parts", which means the minimum and maximum values of the range of 1.5 to 3 parts, as well as every value between the minimum and maximum values. Specific examples include, but are not limited to, the values in the embodiments and the following values: 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts, 3.0 parts; or a range consisting of any two of these values, including, for example, 2 to 3 parts.

[0088] The range of "0.75 to 1.5 parts" for bio-based polymers refers to the minimum and maximum values within the range of 0.75 to 1.5 parts, as well as every value between these minimum and maximum values. Specific examples include, but are not limited to, the values in the Examples and the following values: 0.75, 0.85, 0.95, 1.05, 1.15, 1.25, 1.35, 1.45, or 1.5 parts; or a range consisting of any two of these values, including, for example, 1 to 1.5 parts.

[0089] The range of "0.1 to 0.5 parts" for the organic acid content refers to the minimum and maximum values within the range of 0.1 to 0.5 parts, as well as any values between these minimum and maximum values. Specific examples include, but are not limited to, the values in the Examples and the following values: 0.1, 0.2, 0.3, 0.4, and 0.5 parts; or a range consisting of any two of these values, including, for example, 0.1 to 0.4 parts.

[0090] The range of "3 parts to 5 parts" for the organic nitrogen compound is "3 parts to 5 parts," which means the minimum and maximum values within the range of 3 parts to 5 parts, as well as every value between the minimum and maximum values. Specific examples include, but are not limited to, the values in the embodiments and the following values: 3.0 parts, 3.1 parts, 3.2 parts, 3.3 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.7 parts, 3.8 parts, 3.9 parts, 4.0 parts, 4.1 parts, 4.2 parts, 4.3 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.7 parts, 4.8 parts, 4.9 parts, 5.0 parts; or a range consisting of any two of these values, including, for example, 3 parts to 4.5 parts.

[0091] The range of "0.1 to 0.3 parts" for the film-forming agent refers to a minimum and maximum value within the range of 0.1 to 0.3 parts, as well as any value between these minimum and maximum values. Specific examples include, but are not limited to, the values in the Examples and the following values: 0.1, 0.2, and 0.3 parts; or a range consisting of any two of these values, including, for example, 0.1 to 0.2 parts.

[0092] In some embodiments, the following components are included in parts by weight:

[0093] 5 to 10 parts of pesticide;

[0094] 5 to 9 parts of nanozyme;

[0095] 1.5 to 2 parts thickener;

[0096] 0.75 to 1 part of bio-based polymer;

[0097] 0.1 to 0.25 parts of organic acid;

[0098] 3 to 5 parts of organic nitrogen compound;

[0099] 0.5~1 part of mineral material;

[0100] 0.1~0.3 parts of film-forming agent.

[0101] By further controlling the components of the seed coating agent within the above-mentioned ratio range, the risk of traditional pesticide damage to seeds is lower, and the seed germination rate and seedling growth quality are better.

[0102] In some embodiments, the pesticide comprises one or more of a fungicide and an insecticide.

[0103] In some embodiments, the fungicide comprises one or more of pyraclostrobin, iprodione, boscalid and prothioconazole.

[0104] In some embodiments, the insecticide comprises one or more of cyhalothrin, emamectin benzoate, clothianidin and thiamethoxam.

[0105] In some embodiments, the thickener includes one or more of guar gum, pectin, gelatin and starch.

[0106] In some embodiments, the bio-based polymer includes one or more of γ-polyglutamic acid, polylactic acid, polyhydroxyalkanoate, and chitin.

[0107] In some embodiments, the organic acid comprises one or more of salicylic acid, citric acid, ascorbic acid and tartaric acid.

[0108] In some embodiments, the organic nitrogen compound includes one or more of urea, amino acid, polyacrylamide and formamide.

[0109] In some embodiments, the mineral material includes one or more of attapulgite, diatomaceous earth, bentonite and sepiolite.

[0110] In some embodiments, the film-forming agent includes one or more of polyvinyl alcohol, polyacrylate, chitosan, sodium carboxymethyl cellulose, silicate, natural plant oil, ethyl cellulose, sodium alginate, polyacrylic acid, starch and lignin.

[0111] One embodiment of the present application further provides a method for preparing the above-mentioned seed coating agent, comprising the following steps: mixing the components of the above-mentioned seed coating agent to obtain the seed coating agent.

[0112] One embodiment of the present application further provides a use of the above-mentioned agricultural formulation in improving the germination rate of seeds and the growth quality of seedlings.

[0113] In some embodiments, the seeds include one or more of soybean, wheat, corn, rapeseed, peanut, cotton, cucumber, tomato and carrot.

[0114] The agricultural preparation of the present application has many advantages, such as improving the efficacy of medicine and fertilizer, enhancing the disease resistance and stress resistance of seeds, reducing the use of pesticides and chemical fertilizers, improving the soil environment, improving the quality of agricultural products, and environmental protection advantages through the efficient catalytic effect of nanozymes and the synergistic effect of medicines and fertilizers. It effectively promotes crop growth and enhances the stress resistance of crops, making the agricultural preparation have significant economic and ecological benefits, and has broad application prospects in the field of modern agriculture.

[0115] In order to make the purpose, technical solutions and advantages of this application more concise and clear, this application is illustrated with the following specific examples, but this application is by no means limited to these examples. The embodiments described below are only preferred embodiments of this application and can be used to describe this application. They should not be understood as limiting the scope of this application. It should be pointed out that any modifications, equivalent replacements and improvements made within the spirit and principles of this application should be included in the scope of protection of this application.

[0116] In order to better illustrate the present application, the present application is further described below with reference to the examples. The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents and materials used in the following examples are all commercially available unless otherwise specified.

[0117] Example 1

[0118] (1) Preparation of Prussian blue derivative nanozymes: Nanozymes are composed of metal salts, surfactants, and acidic reagents. The specific method is as follows: 1 part of surfactant (tea seed cake extract), 1 part of acidic reagent (citric acid), 2 parts of iron salt (potassium ferrocyanide), and 0.9 parts each of manganese salt, zinc salt, copper salt, and calcium salt (specifically manganese chloride, zinc nitrate, copper chloride, and calcium chloride) are added to 50 mL of deionized water containing 0.02 parts of acidic reagent, stirred at 600 r / min for 10 minutes at room temperature, placed in a vacuum drying oven at 80°C for 20 hours, washed with deionized water, then added with anhydrous ethanol and centrifuged, repeated three times, and freeze-dried to obtain nanozyme powder. Please refer to Table 1 for details.

[0119] (2) Preparation of seed coating agent: According to the weight parts, 10 parts of chlorpyrifos and 0.1 parts of salicylic acid were mixed and ground until the particle size of more than 80% was 80nm-100nm. 3 parts of urea and 0.5 parts of attapulgite were added and mixed evenly. Finally, 1.5 parts of guar gum, 0.75 parts of γ-polyglutamic acid, 5 parts of nanozyme, and 0.3 parts of film-forming agent (specifically starch) were added and stirred evenly to obtain the seed coating agent.

[0120] (3) Preparation of biofilm-based seed coating: Soybean seeds were immersed in the above-mentioned seed coating agent for 1 minute, taken out and dried to obtain seeds with a coating.

[0121] Examples 2 to 6

[0122] The preparation methods of the seed coating agents in Examples 2 to 6 are basically the same as those in Example 1, except that the components of the seed coating agents are different. For details, see Tables 1 and 2.

[0123] Other steps and conditions are the same as those in Example 1.

[0124] Example 7

[0125] The preparation methods for the seed coating agent in Example 7 are essentially the same as those in Example 1, differing in the ratio of the raw materials used to prepare the nanozymes, specifically the proportions of the metal salts. In Example 7, 1 part of iron salt (specifically, potassium ferrocyanide) and 0.1 part each of manganese salt, zinc salt, copper salt, and calcium salt (specifically, manganese chloride, zinc nitrate, copper chloride, and calcium chloride) were used. See Tables 1 and 2 for details.

[0126] Other steps and conditions are the same as those in Example 1.

[0127] Example 8

[0128] The preparation methods for the seed coating agent in Example 8 and Example 1 are essentially the same, differing in the ratio of the raw materials used to prepare the nanozymes, specifically the proportions of the metal salts. In Example 8, 2 parts of iron salt (specifically, potassium ferrocyanide) and 0.3 parts each of manganese salt, zinc salt, copper salt, and calcium salt (specifically, manganese chloride, zinc nitrate, copper chloride, and calcium chloride) were used. See Tables 1 and 2 for details.

[0129] Other steps and conditions are the same as those in Example 1.

[0130] Comparative Example 1

[0131] The preparation method of the seed coating agent in Comparative Example 1 is basically the same as that in Example 1. The difference is that the ratio of the raw materials for preparing the nanozyme is different, specifically the ratio of the acidic reagent is different, which is 0.005 parts of citric acid in Comparative Example 1. See Table 1 to Table 2 for details.

[0132] Other steps and conditions are the same as those in Example 1.

[0133] Comparative Example 2

[0134] The preparation methods of the seed coating agents in Comparative Example 2 and Example 1 are basically the same, except that the components of the seed coating agents are different and nanozymes are not introduced. See Table 2 for details.

[0135] Other steps and conditions are the same as those in Example 1.

[0136] Comparative Example 3

[0137] The preparation methods of the seed coating agents in Comparative Example 3 and Example 1 are basically the same, except that the components of the seed coating agents are different, specifically the content of organic acid (salicylic acid). Comparative Example 3 contains 0.6 parts of salicylic acid. See Tables 1 and 2 for details.

[0138] Other steps and conditions are the same as those in Example 1.

[0139] Table 1

[0140]

[0141] Table 2

[0142]

[0143] test:

[0144] 1. Film forming time detection of different formulas

[0145] (1) Experimental methods

[0146] When a good suspension seed coating agent is applied to seeds, the solution quickly solidifies into a film on the seed surface, forming a protective barrier against pests and diseases. Film-forming properties are a key indicator during the application of suspension seed coating agents. Testing method: Weigh 50g of seeds (accurate to 1g) into a Petri dish. Use a syringe to draw up 1g of the sample and inject it into the dish. Cover and invert the dish for 5 minutes. Open the lid and spread the coated seeds flat to allow the film to form. Gently move the seeds with a glass rod and observe the seed surface. If the seed coating agent solidifies and forms a film on all surfaces, the film-forming property is acceptable. Record the film-forming time for each formulation.

[0147] (2) Data Analysis

[0148] The test results are shown in Table 3. It can be clearly seen that the formulation of Example 1 has a fast film-forming property.

[0149] Table 3

[0150]

[0151] 2. Coating uniformity test of different formulas

[0152] (1) Experimental methods

[0153] Randomly select 100 coated seeds with qualified film-forming properties from the coated seeds prepared with different formulas and place them in 25 stoppered centrifuge tubes (4 seeds in each centrifuge tube). Use a pipette to accurately add 2.0-5.0 mL of ethanol solution (to ensure the absorbance is within the linear range), cover, soak for 1 hour, shake and extract for 15 minutes, and let it stand or centrifuge to obtain a clear solution. Using the ethanol solution as a reference, measure the absorbance A at the maximum absorption wavelength of the extract. Arrange the 25 measured absorbance data from small to large, and calculate the average absorbance value A. Coating uniformity X (%) = n / 25 100%, where n is the number of centrifuge tubes with absorbance A measured in the range of 0.7A~1.3A; 25 is the total number of centrifuge tubes.

[0154] (2) Data Analysis

[0155] The test results are shown in Table 4. It can be clearly seen that the coating effect of the formula in Example 1 is the most uniform.

[0156] Table 4

[0157]

[0158] 3. Shedding rate test of different formulas

[0159] (1) Experimental methods

[0160] Weigh 10g (accurate to 0.02g) of two portions of coated seeds to be tested for film-forming properties and place them separately in conical flasks. Accurately add 100mL of ethanol to one portion, stopper it and place it in an ultrasonic cleaner to oscillate for 10 minutes to fully dissolve the seed coating agent on the surface of the seeds. Take it out and let it stand for 10 minutes. Take 5mL of the solution and place it in a 50mL volumetric flask. Dilute it to the scale with ethanol and shake it well to obtain solution A. Place the other portion of coated seeds in an oscillator, oscillate for 10 minutes, then carefully place the seeds in another conical flask and treat them according to the method of solution A to obtain solution B. Use ethanol as a reference and measure its absorbance at the maximum absorption wavelength of the solution. Shedding rate after coating X(%) = (A0m1-A1m0) / A0m1 100%, where m0 is the mass of the coated seeds weighed for solution A, g; m1 is the mass of the coated seeds weighed for solution B, g; A0 is the absorbance of solution A; A1 is the absorbance A of solution B.

[0161] (2) Data Analysis

[0162] The test results are shown in Table 5, which clearly shows that the formulation of Example 1 has excellent anti-shedding performance.

[0163] Table 5

[0164]

[0165] 4. Detection of soybean pesticide damage by different formulations

[0166] (1) Experimental methods

[0167] The coated seeds of the Examples and Comparative Examples were placed in 9 cm Petri dishes, 10 seeds per dish, with three replicates for each treatment group. The culture was maintained at 60% humidity, and the germination rate was calculated after three days. Uncoated seeds served as a blank control.

[0168] (2) Data Analysis

[0169] The test results are shown in Table 6, which clearly shows that the formulation in Example 1 did not cause any phytotoxicity to soybeans.

[0170] Table 6

[0171]

[0172] 5. Test of the effect of different formulas on soybean root rot prevention and control

[0173] (1) Experimental methods

[0174] Prepare the fungus soil of Pythium aphanidermatum and put it into pots, then coat the seeds (such as Figure 3 ) were sown in pots, with 10 seeds per pot. Four pots were set up for each treatment group. After the seeds emerged and grew to the three-leaf stage, the pots were turned over to investigate the incidence and disease level of the plants, and the control efficacy was calculated. Uncoated seeds were used as a blank control.

[0175] (2) Data Analysis

[0176] The test results are shown in Table 7, which clearly shows that the formulation of Example 1 has excellent soybean root rot prevention and control effects.

[0177] Table 7

[0178]

[0179] 6. Effect of Seed Coating Agent on Soybean Germination Rate and Bud Length in Example 1

[0180] (1) Experimental methods

[0181] The coated seeds prepared in Example 1 were placed on filter paper, 25 seeds per group, for a total of 3 groups, with uncoated seeds serving as a blank control. The humidity was maintained at 60%-90%, and after 3 days, the germination rate and bud length were calculated.

[0182] (2) Data Analysis

[0183] The test results are as follows Figure 4 and Figure 5As shown in the figure, it can be clearly seen that seed coating has no adverse effect on soybean germination, and the germination rate is not much different, but the effect of promoting seed bud growth is obvious (such as Figure 6 ).

[0184] 7. Effect of Seed Coating Agent on Soybean Growth in Example 1

[0185] (1) Experimental methods

[0186] The coated seeds were sown in the soil, and the control group was uncoated seeds. The potted plants were placed in a light incubator for cultivation. After one week, the root length, plant height and fresh weight of each plant were observed and recorded.

[0187] (2) Data Analysis

[0188] The test results are as follows Figure 7 As shown in FIG, it can be seen that the seed coating agent of Example 1 has a promoting effect on soybean growth, which is specifically manifested in the promotion of root length, plant height and fresh weight (such as Figure 8 、 Figure 9 、 Figure 10 ).

[0189] 8. Example 1: Effect of Seed Coating Agent on Plant Salt Stress Resistance

[0190] (1) Experimental methods

[0191] Coated seeds were sown in soil, while a control group consisted of uncoated seeds. The plants were then potted in a light incubator. One group of coated and uncoated seeds were treated with a 0.1% NaCl solution to simulate salt stress. After one week, the growth of each plant was observed and recorded, and the chlorophyll content of its leaves was measured.

[0192] (2) Data Analysis

[0193] The test results are as follows Figure 11 As shown in the figure, it can be seen that the seed coating agent of Example 1 has a promoting effect on the salt stress resistance of soybeans, and the chlorophyll content is also higher than that of uncoated seeds (such as Figure 12 ).

[0194] From the above Tables 3 to 7 and Figures 1 to 12 The results show that, Figure 1 This is an optical microscope image of the agricultural preparation in Example 1; Figure 2 This is a digital image of the agricultural formulation in Example 1; Figure 3 This is the phenotype diagram of the agricultural formulation in Example 1; Figure 4 This is a bar graph showing the effect of the agricultural formulation on soybean germination rate in Example 1; Figure 5 This is a diagram showing the effect of the agricultural formulation on soybean germination in Example 1; Figure 6 This is a bar graph showing the effect of the agricultural formulation on soybean sprout length in Example 1; Figure 7 This is a digital image showing the effect of the agricultural formulation on soybean growth promotion in Example 1; Figure 8 The effect of the agricultural formulation in Example 1 on soybean plant height; Figure 9 The effect of the agricultural formulation in Example 1 on the root length of soybean plants; Figure 10 The effect of the agricultural formulation in Example 1 on the fresh weight of soybean plants; Figure 11 This is a digital image showing the effect of the agricultural formulation in Example 1 on the resistance of soybean plants to salt stress; Figure 12This is a bar graph showing the effects of the agricultural formulations in Example 1 on chlorophyll content in soybean plants after salt stress. The agricultural formulations described above have the following effects: 1. Solving the problem of pesticide damage: Nanozymes, as active oxygen catalytic materials, have the advantages of high efficiency, low toxicity, and repeatable catalysis. They can effectively degrade free radicals produced by pesticide stress and reduce their toxic effects on biological systems. In the agricultural field, the application of nanozymes can not only reduce the risk of pesticide damage to seeds caused by traditional pesticides, but also significantly improve seed germination rate and seedling growth quality. This technology provides a safer and more environmentally friendly solution for agricultural production, helping to increase crop yield and quality. 2. Promoting crop growth: Through the application of nanotechnology, drug and fertilizer ingredients can be more effectively attached to the seed surface, forming a durable protective layer that continuously inhibits the invasion and spread of pests and diseases while providing necessary nutrient support. Due to their small size and large specific surface area, nanozymes can more efficiently contact the seed surface, significantly improving the utilization rate of drug and fertilizer efficacy. In addition, the in situ catalytic oxygen production properties of nanozymes provide sufficient oxygen for rhizosphere microorganisms, further promoting the healthy growth of crops. This innovative technology provides more efficient and environmentally friendly solutions for agricultural production, increasing crop yields. 3. Enhanced seed disease resistance: Nanozyme coatings effectively protect plants by directly destroying pathogens or enhancing the plant's own immune system (for example, by boosting antioxidant enzyme activity). This technology can significantly improve seed disease resistance, reducing the risk of crop pests and diseases, thereby improving crop yield and quality. Nanozyme coatings offer an efficient and sustainable solution for plant disease control and have broad application prospects. 4. Enhanced stress resistance: The pesticide components in the seed coating effectively control pests and diseases. Simultaneously, the introduction of nanozymes enables them to exert multiple enzyme-like activities, efficiently catalyzing reactive oxygen species and further enhancing crop stress resistance, both against biotic and abiotic stresses. The unique structure of nanozymes can also enhance crop adaptability to adverse environments, providing a more comprehensive defense mechanism. This technology not only improves crop stress resistance but also reduces the threat of pests and diseases, achieving synergistic effects between pesticides and fertilizers, and optimizing agricultural production results. 5. Reduce the amount of pesticides used: Nanozymes, due to their high specific surface area and porosity, help to achieve the sustained release effect of pesticide active ingredients, thereby significantly improving the utilization rate of pesticides. At the same time, nanozymes can improve the dispersibility and stability of pesticides, enhance their solubility and mobility in the soil, and promote the effective use of pesticides by plants. Through this mechanism, not only the amount of pesticides used is reduced, but also the risk of environmental pollution is reduced, achieving the goal of more environmentally friendly and efficient agricultural production. 6. Improve the yield and quality of agricultural products: The agricultural preparations of the embodiments of the present application significantly improve the yield and quality of crops by promoting crop growth and enhancing stress resistance. In addition, since the amount of pesticides used is effectively reduced, the safety of agricultural products is improved, thereby enhancing their market competitiveness.This innovative technology not only optimizes agricultural production efficiency but also provides strong support for sustainable agricultural development. 7. Environmental and cost advantages: Nanoenzyme coating technology offers environmental advantages by reducing pesticide loss and volatilization, thereby reducing environmental pollution. Furthermore, this technology can improve the environmental behavior and biosafety of pesticides, enhancing the ecological safety of chemical pest control. The raw materials for this seed coating are widely available, the preparation process is simple, and it can be easily scaled up.

[0195] In summary, through the efficient catalytic action of nanozymes and the synergistic effect of pesticides and fertilizers, agricultural formulations offer numerous advantages, including improving the efficacy of pesticides and fertilizers, enhancing seed disease resistance and stress tolerance, reducing pesticide and fertilizer usage, improving the soil environment, and enhancing the quality of agricultural products, as well as environmental benefits. By effectively promoting crop growth and enhancing crop resistance, these formulations offer significant economic and ecological benefits, and hold broad application prospects in modern agriculture.

[0196] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0197] The above-described embodiments merely represent several implementation methods of the present application. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that a person of ordinary skill in the art may make various modifications and improvements without departing from the spirit of the present application, and these modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present patent application shall be determined by the appended claims.

Claims

1. An agricultural preparation selected from a seed coating agent, characterized in that: The agricultural formulation comprises the following components in parts by weight: 5 to 10 parts of pesticide; 5 to 9 parts of nanozyme; 1.5 to 3 parts thickener; 0.75 to 1.5 parts of bio-based polymer; 0.1 to 0.5 parts of organic acid; 3 to 5 parts of organic nitrogen compound; 0.5~1.5 parts of mineral materials; 0.1~0.3 parts of film-forming agent; The pesticide is selected from fludioxonil; the organic acid is selected from salicylic acid; the mineral material is selected from attapulgite; the thickener is selected from guar gum; and the organic nitrogen compound is selected from urea; The bio-based polymer is selected from γ-polyglutamic acid; the film-forming agent is selected from starch; The raw materials for preparing the nanozyme include, by weight: 3.2 to 5.6 parts of metal salt; 0.5 to 4 parts of surfactant; 1 part to 1.02 parts of acidic reagent; The metal salt includes potassium ferrocyanide, manganese chloride, zinc nitrate, copper chloride and calcium chloride; the surfactant is selected from tea seed cake extract; and the acidic agent is selected from citric acid.

2. An agricultural formulation according to claim 1, characterized in that The preparation method of the nanozyme comprises the following steps: The raw materials for preparing the nanozyme are mixed, reacted and dried to prepare the nanozyme.

3. An agricultural formulation according to claim 2, characterized in that The mixing speed is 500r / min~700r / min, and the mixing time is 10min~30min; The reaction temperature is 60°C to 80°C, and the reaction time is 24h to 48h; The drying method includes one or more of vacuum drying and freeze drying.

4. Use of the agricultural formulation according to any one of claims 1 to 3 for improving the germination rate of seeds and the growth quality of seedlings.

5. A use according to claim 4, characterized in that The seeds include one or more of soybean, wheat, corn, rapeseed, peanut, cotton, cucumber, tomato and carrot.

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