Yellow-blue discoloration hemocyanin mancozeb compound bactericide and preparation method thereof

Abstract

The invention discloses a yellow-blue discoloration hemocyanin mancozeb compound bactericide and a preparation method thereof, and belongs to the technical field of pesticide preparation, the yellow-blue discoloration hemocyanin mancozeb compound bactericide comprises, by mass, 30%-80% of mancozeb, 0.0001%-1% of hemocyanin, 2%-8% of supramolecular carriers and 4%-65% of auxiliaries, the compound bactericide is yellow, and the compound bactericide becomes blue when making contact with water. The mancozeb and the hemocyanin are inlaid through the supramolecular carrier, efficient synergy of the biological protein and the chemical bactericide is achieved, same-effect prevention and treatment are achieved under the condition that the dosage of the mancozeb is reduced, and poison to the environment is reduced; the stability of biological protein is improved, and the lasting period of the compound bactericide is prolonged; multi-stage targeted delivery is realized, so that the permeability of the bactericide to crop leaf surfaces is improved, and meanwhile, the drug resistance risk of crops to the bactericide is also reduced; meanwhile, the specific oxygenation discoloration characteristic of the hemocyanin is utilized, so that the drug effect of the sterilization component is visually monitored.

Description

Technical Field

[0001] The present application relates to the technical field of pesticide preparation, and in particular to a yellow-blue color-changing hemocyanin mancozeb compound fungicide and a preparation method thereof. Background Art

[0002] As a broad-spectrum protective fungicide, mancozeb has long had the following problems: ① Continuous use of a single dose leads to a rapid increase in pathogen resistance; ② Mancozeb is environmentally toxic, especially to aquatic organisms; ③ When used in the field, the effective period of mancozeb is ≤15 days, and the short effective period requires frequent application. Summary of the invention

[0003] The embodiment of the present application provides a yellow-blue color-changing hemocyanin-mancozeb compound fungicide and a preparation method thereof, which comprises an active ingredient composed of hemocyanin and mancozeb through the synergistic effect of metal coordination, and utilizes a supramolecular carrier as a carrier to improve stability, thereby effectively preventing and treating plant fungal and bacterial diseases, significantly reducing the dosage of mancozeb and the risk of drug resistance, and utilizing the unique oxygenation color-changing property of hemocyanin to realize visual monitoring of the efficacy of the fungicidal ingredient.

[0004] In the first aspect, the present application provides a yellow-blue color-changing hemocyanin mancozeb compound fungicide, whose components, by mass percentage, include 30%-80% mancozeb, 0.0001%-1% hemocyanin, 2%-8% supramolecular carrier and 4%-65% adjuvant. The compound fungicide is yellow and turns blue when in contact with water.

[0005] The present application uses hemocyanin and mancozeb as active substances to work synergistically with supramolecular carriers. Mancozeb can inhibit thiol metabolism and hemocyanin can destroy the membrane structure of pathogens, thereby achieving multi-target effects. The dual mechanism reduces the resistance mutation rate of crops to compound fungicides; at the same time, it can also induce an increase in the expression of the PR-1 gene, activate the immune system of crops, and greatly increase the systemic resistance time; the manganese ions in mancozeb and the copper ions in hemocyanin form coordination bonds to increase the penetration of the compound fungicide through the cell membrane, and at the same time, the unique oxygenation color change characteristics of hemocyanin are used to achieve visual monitoring of the efficacy of the fungicide ingredients; hexamine is used as a stabilizer to reduce catalytic oxidation and extend the shelf life of the compound fungicide.

[0006] In some of the embodiments, the auxiliary agent components include, by mass percentage, 1%-15% of a dispersant, 1%-15% of a wetting agent, 1%-25% of an anti-caking agent, and 1%-10% of hexamethylenetetramine.

[0007] In some embodiments, the supramolecular carrier comprises at least one of β-cyclodextrin, hydroxypropyl-β-cyclodextrin, sulfobutyl ether-β-cyclodextrin, and γ-cyclodextrin.

[0008] In some embodiments, the dispersant comprises at least one of calcium lignin sulfonate, sodium lignin sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylates, and alkyl naphthalene sulfonates.

[0009] In some embodiments, the wetting agent comprises at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium hexadecyl sulfate, and sodium α-olefin sulfonate.

[0010] In some embodiments, the anti-caking agent comprises at least one of silicon dioxide, talc, diatomaceous earth, and metal stearate.

[0011] In some of the embodiments, the compound fungicide is a wettable powder, and the particle size D90 of the compound fungicide is ≤10 μm, the water content is ≤2%, and the suspension rate is ≥85%.

[0012] In addition, the present application also proposes a method for preparing a yellow-blue color-changing hemocyanin-mancozeb compound fungicide, comprising: dissolving 0.0001%-1% hemocyanin and 2%-8% supramolecular carrier in a pH buffer solution to form an inclusion complex, and then mixing 30%-80% mancozeb, 4%-65% adjuvant and the inclusion complex.

[0013] Based on the preparation method of the yellow-blue color-changing hemocyanin and mancozeb compound fungicide in the examples of the present application, supramolecular embedding technology is used to simultaneously embed metal ions and biomacromolecules with supramolecular carriers, so that hemocyanin and mancozeb act synergistically, thereby achieving disease microenvironment-triggered targeted delivery and breaking through the wax layer barrier based on the yellow-blue color-changing hemocyanin and mancozeb compound fungicide while maintaining protein activity.

[0014] In some embodiments, the molar ratio of hemocyanin to the supramolecular carrier is 1:1-1:3.

[0015] In some embodiments, hemocyanin and the supramolecular carrier are dissolved in a pH buffer solution and then subjected to ultrasonic treatment to form an inclusion complex, wherein the frequency of the ultrasonic treatment is 30-50 kHz and the time is 20-40 min.

[0016] In some embodiments, the pH value of the pH buffer solution is 5-8.

[0017] Based on the yellow-blue color-changing hemocyanin mancozeb compound fungicide and its preparation method in the embodiment of the present application, mancozeb and hemocyanin are embedded by supramolecular carriers, so as to achieve efficient synergy between biological protein and chemical fungicide, achieve the same control effect while reducing the dosage of mancozeb, and reduce the toxicity to the environment; improve the stability of biological protein and increase the effective period of compound fungicide; utilize the metal coordination and pH / light responsive release between mancozeb and hemocyanin to achieve multi-level targeted delivery, so as to improve the penetration rate of compound fungicide to crop leaves and reduce the sensitivity of crops to compound fungicide. The risk of fungicide resistance; the surface of hemocyanin and mancozeb structure has positive charge, which can combine more tightly with the opposite charge on the surface of crops, making the compound fungicide more adsorbable on the surface of crops and more resistant to rain erosion. In the process of spraying the compound fungicide, the positive charge is released to automatically capture charged pathogens in the environment, kill pathogens in the air, and cut off the transmission path; at the same time, the unique oxygenation color change property of hemocyanin is used to observe whether the compound fungicide changes from yellow to blue by contacting the compound fungicide with water, so as to judge whether the hemocyanin in the compound fungicide is inactivated, and the Cu in the hemocyanin 2+ Active center and mancozeb Mn 2+ Whether coordination bonds are formed to achieve synergistic effect, and realize visual monitoring of the efficacy of bactericidal ingredients. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical solution and advantages of the present application more clear, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application and are not used to limit the present application.

[0019] Traditional fungicides in the existing technology have the disadvantages of short-lasting effect, high toxicity and easy to develop drug resistance, while biological fungicides have the technical problems of poor stability and poor targeting.

[0020] In order to solve the above technical problems, the present application proposes a yellow-blue color-changing hemocyanin mancozeb compound fungicide, whose components, by mass percentage, include 30%-80% mancozeb, 0.0001%-1% hemocyanin, 2%-8% supramolecular carrier and 4%-65% adjuvant. The compound fungicide is yellow and turns blue when in contact with water.

[0021] This application uses hemocyanin and mancozeb as active substances and supramolecular carriers to work synergistically. Mancozeb can inhibit thiol metabolism and hemocyanin can destroy the membrane structure of pathogens, achieving multi-target effects. The dual mechanism reduces the resistance mutation rate of crops to compound fungicides; at the same time, it can also induce the increase of PR-1 gene expression, activate the immune system of crops, and greatly increase the systemic resistance time; the manganese ions in mancozeb and the copper ions in hemocyanin form coordination bonds to increase the penetration of compound fungicides to cell membranes; compound fungicides have two major functions: first, during the spraying process of compound fungicides, positive charges are released to automatically capture negatively charged pathogens in the environment, kill pathogens in the air, and cut off the airborne transmission pathway. Second, the surface of the compound fungicide structure carries a positive charge, which can be more tightly combined with the opposite charge on the surface of the crop to form a dense drug film, so that the drug film of the compound fungicide has stronger adsorption on the crop surface, is more resistant to rain erosion, and has a longer lasting effect.

[0022] Specifically, by contacting the compound fungicide with water and observing whether the compound fungicide changes from yellow to blue, it can be judged whether the hemocyanin in the compound fungicide is inactivated, and the Cu in the hemocyanin 2+ Active center and mancozeb Mn 2+ Whether coordination bonds are formed to achieve synergistic effect, and realize visual monitoring of the efficacy of bactericidal ingredients.

[0023] Specifically, hexamethylenetetramine acts as a stabilizer to reduce catalytic oxidation and extend the shelf life of compound fungicides.

[0024] In some of the embodiments, the auxiliary agent components include, by mass percentage, 1%-15% of a dispersant, 1%-15% of a wetting agent, 1%-25% of an anti-caking agent, and 1%-10% of hexamethylenetetramine.

[0025] In some embodiments, the supramolecular carrier comprises at least one of β-cyclodextrin, hydroxypropyl-β-cyclodextrin, sulfobutyl ether-β-cyclodextrin, and γ-cyclodextrin.

[0026] Based on the above embodiments, the apparent solubility of mancozeb is improved by embedding the hydrophobic segments of the supramolecular carrier, and the contact angle is reduced by the hydrogen bond network formed by the hydroxyl groups on the outer edge of the supramolecular carrier, thereby further increasing the solubility of the compound fungicide; the Tm of hemocyanin after being embedded in the supramolecular carrier is improved, and the cavity of the supramolecular carrier can also isolate oxygen to reduce the decomposition rate of hemocyanin; the supramolecular carrier can fuse with plant wax to form a microtubule channel, thereby improving the permeability of the compound fungicide; the supramolecular carrier can be protonated in the pH range of the diseased area to improve the release rate of the compound fungicide to the target area.

[0027] In some embodiments, the dispersant comprises at least one of calcium lignin sulfonate, sodium lignin sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylates, and alkyl naphthalene sulfonates.

[0028] Based on the above embodiments, the dispersant can prevent the aggregation of active ingredient particles, reduce sedimentation and agglomeration, and ensure that the compound fungicide forms a stable suspension in water when used.

[0029] In some embodiments, the wetting agent comprises at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium hexadecyl sulfate, and sodium α-olefin sulfonate.

[0030] Based on the above embodiments, the wetting agent plays a role in reducing surface tension and increasing spreadability in the compound fungicide, which can make the compound fungicide powder quickly wet and penetrate into water, and can also increase the coverage of the compound fungicide on the target surface.

[0031] In some embodiments, the anti-caking agent comprises at least one of silicon dioxide, talc, diatomaceous earth, and metal stearate.

[0032] Based on the above embodiment, the anti-caking agent prevents the wettable powder compound fungicide from absorbing moisture and agglomerating, and reduces physical degradation caused by environmental changes during storage.

[0033] In some of the embodiments, the compound fungicide is a wettable powder, and the particle size D90 of the compound fungicide is ≤10 μm, the water content is ≤2%, and the suspension rate is ≥85%.

[0034] Based on the above embodiments, at this particle size, the effect of gravity is smaller, and it is easier to be better wrapped by the adjuvant, and at the same time, the suspension rate of the compound fungicide is also higher. The high suspension rate makes the compound fungicide more uniform in the diluent; the compound fungicide reacts with yellow-blue color when entering water to form a small molecule state, the specific surface area is increased, the spread on the crop surface is more uniform, the protection is more comprehensive, the dosage is reduced, the efficacy and safety are improved, and the lasting effect is prolonged.

[0035] In addition, the present application also proposes a method for preparing a yellow-blue color-changing hemocyanin-mancozeb compound fungicide, comprising: dissolving 0.0001%-1% hemocyanin and 2%-8% supramolecular carrier in a pH buffer solution to form an inclusion complex, and then mixing 30%-80% mancozeb, 4%-65% adjuvant and the inclusion complex.

[0036] Based on the preparation method of the yellow-blue color-changing hemocyanin and mancozeb compound fungicide in the examples of the present application, supramolecular embedding technology is used to simultaneously embed metal ions and biomacromolecules with supramolecular carriers, so that hemocyanin and mancozeb act synergistically, thereby achieving disease microenvironment-triggered targeted delivery and breaking through the wax layer barrier based on the yellow-blue color-changing hemocyanin and mancozeb compound fungicide while maintaining protein activity.

[0037] In some embodiments, the molar ratio of hemocyanin to the supramolecular carrier is 1:1-1:3.

[0038] Based on the above embodiments, the optimal embedding effect of the supramolecular carrier on hemocyanin can be achieved within this molar ratio range.

[0039] In some embodiments, hemocyanin and the supramolecular carrier are dissolved in a pH buffer solution and then subjected to ultrasonic treatment to form an inclusion complex, wherein the frequency of the ultrasonic treatment is 30-50 kHz and the time is 20-40 min.

[0040] Based on the above embodiments, the supramolecular embedding process is promoted by ultrasonic treatment with a specific frequency and time, so that hemocyanin and the supramolecular carrier are better embedded.

[0041] In some embodiments, the pH value of the pH buffer solution is 5-8.

[0042] Based on the above embodiment, the pH of the compound bactericide is maintained in the active range of hemocyanin by using a pH buffer solution with a pH value of 5-8 to prevent the denaturation and inactivation of hemocyanin.

[0043] The present application is further described by the following examples: Example 1 The composition of the yellow-blue color-changing hemocyanin mancozeb compound fungicide in this embodiment includes, by mass percentage, 80% mancozeb, 1% hemocyanin, 8% hydroxypropyl-β-cyclodextrin, 5% sodium lignin sulfonate, 1% sodium lauryl sulfate, 3.9 parts of nano-silicon dioxide, and 6% hexamethylenetetramine.

[0044] The preparation process of the yellow-blue color-changing hemocyanin mancozeb compound fungicide in this embodiment is as follows: hemocyanin and hydroxypropyl-β-cyclodextrin are dissolved in a phosphate buffer solution with a pH of 6.8, and subjected to 40KHz ultrasonic treatment for 30 minutes to form an inclusion complex, and then mancozeb, an auxiliary agent and the inclusion complex are mixed in a jet mill until D90≤10μm to obtain a finished product.

[0045] Example 2 The composition of the yellow-blue color-changing hemocyanin mancozeb compound fungicide in this embodiment includes, by mass percentage, 30% mancozeb, 0.0001% hemocyanin, 2% hydroxypropyl-β-cyclodextrin, 11% sodium lignin sulfonate, 15% sodium lauryl sulfate, 25% nano-silicon dioxide, and 10% hexamethylenetetramine.

[0046] The preparation process of the yellow-blue color-changing hemocyanin mancozeb compound fungicide in this embodiment is the same as that in Example 1.

[0047] Example 3 The composition of the yellow-blue color-changing hemocyanin mancozeb compound fungicide in this embodiment includes, by mass percentage, 50% mancozeb, 0.05% hemocyanin, 4.95% hydroxypropyl-β-cyclodextrin, 10% sodium lignin sulfonate, 10% sodium lauryl sulfate, 20% nano-silicon dioxide, and 5% hexamethylenetetramine.

[0048] The preparation process of the yellow-blue color-changing hemocyanin mancozeb compound fungicide in this embodiment is the same as that in Example 1.

[0049] The yellow-blue color-changing hemocyanin mancozeb compound fungicide prepared in the above embodiment was selected to test persimmon hemocyanin and citrus black spot disease, and the test process and test results are shown as follows: Persimmon leaf hemp disease test agent: the yellow-blue color-changing hemocyanin mancozeb compound fungicide prepared in Examples 1, 2 and 3, and mancozeb single agent (80% dosage).

[0050] Test method: Select persimmon orchards in Gongcheng, Guangxi, where the incidence of hemp leaf disease is ≥30% for more than 2 consecutive years. The varieties are moon persimmons, the age of the trees is 5-10 years, the spacing between plants and rows is consistent, and the terrain is flat and the soil fertility is uniform. There are no other persimmon varieties or highly susceptible crops within 100 meters around the test site. The area of ​​the plot is 30-50 square meters (about 10 persimmon trees). The following experimental design is carried out to verify its control effect on persimmon hemp leaf disease: Treatment 1: Blank control Treatment 2: 80% mancozeb single dose 750 times Treatment 3: Yellow-blue color-changing hemocyanin and mancozeb compound fungicide 750 times Treatment 4: Yellow-blue color-changing hemocyanin and mancozeb compound fungicide 500 times Treatment 5: Yellow-blue color-changing hemocyanin and mancozeb compound fungicide 300 times Survey and data processing: (1) Disease classification standards - Grade 0: No lesions.

[0051] - Level 1: The lesion area accounts for ≤5% of the leaf area.

[0052] - Level 3: The lesion area accounts for 6%-25% of the leaf area.

[0053] - Level 5: The lesion area accounts for 26%-50% of the leaf area.

[0054] - Level 7: The lesion area accounts for 51%-75% of the leaf area.

[0055] - Level 9: The lesion area accounts for >75% of the leaf area or the leaves are dead.

[0056] - Isolation measures: Set up a 1-2 meter isolation zone between cells to prevent the drift of the agent.

[0057] After application: the control effect was investigated on the 30th day.

[0058] - Sampling method: 5 persimmon trees were randomly selected from each plot, and 2 mature leaves were taken from each tree in the 5 directions of east, south, west, north and center, for a total of 10 leaves / plant and 50 leaves / plot.

[0059] - Record content: Record the number, area and severity of lesions on each leaf and calculate the disease index.

[0060] (2) Calculation of drug efficacy - Disease index:

[0061] Among them: the disease index is a comprehensive indicator that takes into account the incidence and severity, and is used to quantify the occurrence of plant diseases; the number of diseased leaves (fruits) at each level is the number of diseased plants within the disease grading standard of that level; the relative level value is the level of the diseased plant in the disease grading standard; the total number of plants surveyed is the total number of all plants surveyed.

[0062] - Control effect:

[0063] Among them: relative control effect is a quantitative indicator to measure the effect of pesticides or other control measures on disease control. By comparing the difference in disease index between the treatment group and the control group, the effectiveness of the control measures is reflected in the form of percentage; the CK disease index is the disease index of the blank control group; the treatment disease index is the disease index of the treatment group treated with fungicides.

[0064] Example 1 The control effect of the yellow-blue color-changing hemocyanin mancozeb compound fungicide on persimmon leaf disease is shown in the following table: Table 1. The control effect of the compound fungicide in Example 1 on persimmon leaf disease

[0065] Example 2 The control effect of the yellow-blue color-changing hemocyanin mancozeb compound fungicide on persimmon leaf disease is shown in the following table: Table 2. The control effect of the composite fungicide in Example 2 on persimmon leaf disease

[0066] Example 3 The control effect of the yellow-blue color-changing hemocyanin mancozeb compound fungicide on persimmon leaf disease is shown in the following table: Table 3. The control effect of the composite fungicide in Example 3 on persimmon leaf disease

[0067] Test results: From the control effects of treatment 2 and treatment 3 in each example, it can be seen that the control effect of the compound fungicide prepared according to the present application on persimmon hemp leaf disease is better than that of a single agent of mancozeb (80% dosage), which indicates that the control effect of the compound fungicide can be greatly improved by utilizing the synergistic effect of hemocyanin and mancozeb and embedding them with supramolecular carriers.

[0068] The mancozeb contents of the compound fungicide in Examples 1, 2 and 3 are 80%, 30% and 50%, respectively. The mancozeb content of the compound fungicide in Example 1 is equal to that of the single agent of mancozeb (80% dosage), while the mancozeb contents in the compound fungicides in Examples 2 and 3 are lower than the single agent of mancozeb (80% dosage) used. However, from the comparison of the control effects of Treatment 2 and Treatment 3 in each embodiment, we can find that the present application achieves the same or even better control effect with the same or reduced dosage of mancozeb, and reduces the toxic effect of the compound fungicide on the environment.

[0069] Citrus black spot disease test agent: the yellow-blue color-changing hemocyanin mancozeb compound fungicide prepared in Examples 1, 2 and 3, and mancozeb single agent (80% dosage).

[0070] Test method: Based on the citrus planted in the test field where black spot disease was seriously occurred in Guangxi in previous years, the following experimental design was carried out according to GB / T17980.103-2004 "Guidelines for Field Efficacy Tests of Pesticides (II) Part 103: Control of Citrus Canker by Fungicides" to verify its control effect on citrus black spot disease: Treatment 1: Blank control Treatment 2: 80% mancozeb single dose 750 times Treatment 3: Yellow-blue color-changing hemocyanin and mancozeb compound fungicide 750 times Treatment 4: Yellow-blue color-changing hemocyanin and mancozeb compound fungicide 500 times Treatment 5: Yellow-blue color-changing hemocyanin and mancozeb compound fungicide 300 times The plots of experimental agent, control agent and blank control were randomly arranged, and the plot area was 3 mature fruit trees.

[0071] (1) Survey methods Two plants were surveyed in each plot, and samples were taken from five points of each plant, including east, west, south, north and center. Ten fruits and all leaves on two tips were surveyed at each point. Leaf (fruit) grading method; Level 1: Each leaf (fruit) has 1 to 5 spots; Level 3: There are 6 to 10 spots on each leaf (fruit); Level 5: There are 11-15 lesions on each leaf (fruit); Level 7: There are 16-20 lesions on each leaf (fruit); Level 9: There are more than 21 spots on each leaf (fruit).

[0072] Investigate the disease base before applying the pesticide, and investigate the prevention and control effect 30 days after applying the pesticide.

[0073] (2) Calculation method of drug efficacy - Disease index:

[0074] Among them: the disease index is a comprehensive indicator that takes into account the incidence and severity, and is used to quantify the occurrence of plant diseases; the number of diseased leaves (fruits) at each level is the number of diseased plants within the disease grading standard of that level; the relative level value is the level of the diseased plant in the disease grading standard; the total number of plants surveyed is the total number of all plants surveyed.

[0075] - Control effect:

[0076] Among them: relative control effect is a quantitative indicator to measure the effect of pesticides or other control measures on disease control. By comparing the difference in disease index between the treatment group and the control group, the effectiveness of the control measures is reflected in the form of percentage; the CK disease index is the disease index of the blank control group; the treatment disease index is the disease index of the treatment group treated with fungicides.

[0077] Example 1 The control effect of the yellow-blue color-changing hemocyanin mancozeb compound fungicide on citrus black spot disease is shown in the following table: Table 4. Table of control effects of the compound fungicide in Example 1 on citrus black spot disease

[0078] Example 2 The control effect of the yellow-blue color-changing hemocyanin mancozeb compound fungicide on citrus black spot disease is shown in the following table: Table 5. Control effect of the compound fungicide in Example 2 on citrus black spot disease

[0079] Example 3 The control effect of the yellow-blue color-changing hemocyanin mancozeb compound fungicide on citrus black spot disease is shown in the following table: Table 6. Table of control effects of the compound fungicide in Example 3 on citrus black spot disease

[0080] Test results: From the control effects of treatment 2 and treatment 3 in each example, it can be seen that the compound fungicide prepared according to the present application has better control effect on citrus black spot disease than the single agent of mancozeb (80% dosage), and the control effect of the compound fungicide with a lower mancozeb content in Examples 2 and 3 on citrus black spot disease is also better than the single agent of mancozeb (80% dosage).

[0081] In summary, the yellow-blue color-changing hemocyanin mancozeb compound fungicide provided in the present application has excellent control effects on persimmon leaf blight and citrus black spot disease, especially compared with the high-content mancozeb fungicide that is toxic to the environment. The present application embeds mancozeb and hemocyanin through supramolecular carriers, realizes the efficient synergy of biological protein and chemical fungicide, achieves the same or even better control effect while greatly reducing the amount of mancozeb used, and realizes the purpose of green and non-toxic environmental protection.

[0082] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A yellow-blue color-changing hemocyanin mancozeb compound fungicide, characterized in that: The components thereof include, by mass percentage, 30%-80% of mancozeb, 0.0001%-1% of hemocyanin, 2%-8% of supramolecular carrier and 4%-65% of auxiliary agent. The compound fungicide is yellow in color and turns blue when in contact with water.

2. A yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 1, characterized in that: The auxiliary agent components include, by mass percentage, 1%-15% of a dispersant, 1%-15% of a wetting agent, 1%-25% of an anti-caking agent, and 1%-10% of hexamethylenetetramine.

3. A yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 1, characterized in that: The supramolecular carrier comprises at least one of β-cyclodextrin, hydroxypropyl-β-cyclodextrin, sulfobutyl ether-β-cyclodextrin and γ-cyclodextrin.

4. A yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 2, characterized in that: The dispersant comprises at least one of calcium lignin sulfonate, sodium lignin sulfonate, naphthalene sulfonate formaldehyde condensate, polycarboxylates, and alkyl naphthalene sulfonate.

5. A yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 2, characterized in that: The wetting agent comprises at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium hexadecyl sulfate and sodium α-olefin sulfonate.

6. A yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 2, characterized in that: The anti-caking agent comprises at least one of silicon dioxide, talc, diatomaceous earth and metal stearate.

7. The method for preparing the yellow-blue color-changing hemocyanin mancozeb compound fungicide according to any one of claims 1 to 6, characterized in that: include: 0.0001%-1% hemocyanin and 2%-8% supramolecular carrier are dissolved in a pH buffer solution to form an inclusion compound, and then 30%-80% mancozeb, 4%-65% adjuvant and the inclusion compound are mixed.

8. The method for preparing a yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 7, characterized in that: The molar ratio of the hemocyanin to the supramolecular carrier is 1:1-1:

3.

9. The method for preparing a yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 7, characterized in that: The hemocyanin and the supramolecular carrier are dissolved in the pH buffer solution and then subjected to ultrasonic treatment to form the inclusion complex. The frequency of the ultrasonic treatment is 30-50 kHz and the time is 20-40 minutes.

10. The method for preparing a yellow-blue color-changing hemocyanin mancozeb compound fungicide according to claim 7, characterized in that: The pH value of the pH buffer solution is 5-8.

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