Bactericide containing carbendazim
The quaternized chitosan-carrageenan composite system was encapsulated and a nanoparticle bactericide was prepared, which solved the toxic problem caused by excessive use of cyperidine, and achieved efficient antibacterial effect on Fusarium oxyspora and Aspergillus parasiticum and environmentally friendly bactericide delivery.
Patent Information
- Application Number
- CN202510441115.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-09
- Publication Date
- 2025-07-11
AI Technical Summary
The toxicity problems caused by excessive use of existing pyrotinoid fungicides, especially the potential toxicity risks to plants and soils, and long-term use poses a threat to ecosystems.
The quaternized chitosan-carrageenan composite system is used to encapsulate the carbendazole to prepare nanoparticles that encapsulate the carbendazole. The targeting and controlled release of carbendazole is achieved through nano-encapsulation technology, reducing the use and improving bioavailability.
It significantly enhances the antibacterial activity against Fusarium oxysporus and Aspergillus parasitica, reduces the risk of toxicity to plants, improves the bioavailability and stability of bacterial agents, and reduces the negative impact on the environment.
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Figure BDA0005351078570000091 
Figure BDA0005351078570000092
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of fungicides, and particularly to a fungicide containing carbendazim. Background Art
[0002] Fungicides are used in agriculture to control plant diseases caused by fungi, which can significantly reduce the yield and quality of crops. Among them, Fusarium oxysporum and Aspergillus parasiticus are harmful fungal pathogens; Fusarium oxysporum invades plants through the roots, blocks the vascular system of plants, and causes plant wilt and death; Aspergillus parasiticus infects grains (such as corn, peanuts, cotton seeds, etc.) and nuts, resulting in food and feed contamination, posing a serious hazard to human and animal health, and may cause diseases such as liver cancer and immunosuppression. Continuous use of fungicides may pose potential risks to the ecosystem, especially if residues are present in agricultural products and soil. The negative impact of fungicides on soil organisms may also pose a potential threat to the long-term productivity of the soil. Due to the overuse of fungicides, adverse effects on microorganisms, soil, human and animal health have been reported.
[0003] As a broad-spectrum fungicide, carbendazim has been widely used to control the above-mentioned fungal pathogens. Subchronic exposure to a large amount of carbendazim has been shown to cause testicular changes, sperm production inhibition and embryotoxicity in animals. Its reproductive toxicity seems to be due to the inhibition of microtubule assembly and carbendazim-induced gene mutations.
[0004] Therefore, it is necessary to find alternative methods to reduce the amount of fungicides used and improve their effectiveness. Using nano-encapsulated pesticides can reduce phytotoxicity. Nano-capsules improve diffusion through the cuticle and allow slow and sustained release of the active ingredient when reaching the target site. Nano-encapsulation of agricultural chemicals using biocompatible polymers helps to achieve targeted and controlled release of fungicides. Summary of the Invention
[0005] The present invention provides a fungicide containing carbendazim, which can solve the poisoning problem caused by excessive use of carbendazim in the prior art.
[0006] A fungicide containing carbendazim comprises the following components in parts by weight:
[0007] Nanoparticles of quaternized chitosan-carrageenan encapsulated carbendazim: 10-20 parts;
[0008] Surfactant: 1-3 parts;
[0009] Thickener: 0.5-2 parts;
[0010] Preservative: 0.1-0.5 parts;
[0011] Solvent: 70-85 parts.
[0012] Furthermore, the quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles are prepared through the following steps:
[0013] S1. Mixed solution:
[0014] Under the condition of continuous stirring, the carbendazim solution, the carrageenan solution and the dioctyl sulfosuccinate solution are added dropwise into the quaternized chitosan solution, and stirring is continued for 3 - 5 h to obtain a mixed solution;
[0015] S2. Centrifugation and washing:
[0016] The mixed solution is centrifuged at 10000 rpm for 1 - 2 h to separate the nanoparticles, and the centrifuged precipitate is washed 2 - 3 times with deionized water to remove residual acetic acid and other unreacted substances, obtaining a precipitate;
[0017] S3. Freeze-drying:
[0018] The precipitate is freeze-dried using mannitol as a cryoprotectant to obtain the quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles.
[0019] Furthermore, the carbendazim solution in step S1 is prepared through the following steps:
[0020] The carbendazim powder is dissolved in acetic acid with a concentration of 3 wt% to obtain a carbendazim solution with a concentration of 5 wt%.
[0021] Furthermore, the carrageenan solution in step S1 is prepared through the following steps:
[0022] The carrageenan is dissolved in distilled water to obtain a carrageenan solution with a concentration of 0.15 wt%.
[0023] Furthermore, the dioctyl sulfosuccinate solution in step S1 is prepared through the following steps:
[0024] The dioctyl sulfosuccinate is dissolved in distilled water to obtain a dioctyl sulfosuccinate solution with a concentration of 0.5 wt%.
[0025] Furthermore, the quaternized chitosan solution in step S1 is prepared through the following steps:
[0026] The quaternized chitosan is dissolved in acetic acid with a concentration of 3 wt% to obtain a quaternized chitosan solution with a concentration of 0.5 wt%.
[0027] Furthermore, the quaternized chitosan is prepared through the following steps:
[0028] Dissolve chitosan in isopropanol and adjust the pH of the chitosan solution to 8 with 1M NaOH; add 2,3-epoxypropyltrimethylammonium chloride to the chitosan solution, stir and react at a constant temperature of 60 - 90 °C for 6 - 10 h, then filter, wash with absolute ethanol, and dry to obtain quaternized chitosan; the mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride is 1:3.
[0029] Furthermore, the volume ratio of the carbendazim solution, carrageenan solution, dioctyl sulfosuccinate solution, and quaternized chitosan solution is 10 - 15:20 - 30:5 - 10:100.
[0030] Furthermore, the surfactant is one of Tween 80 and sodium dodecyl sulfate; the thickener is one of xanthan gum and carboxymethyl cellulose; the preservative is one of sodium benzoate and potassium sorbate; the solvent is deionized water.
[0031] Furthermore, the carbendazim-containing fungicide is prepared by the following steps:
[0032] Add the surfactant and thickener to the solvent, stir until completely dissolved to obtain a solution; add the nanoparticles of quaternized chitosan-carrageenan encapsulated carbendazim to the above solution, stir until evenly dispersed; then add the preservative to the solution, stir until completely dissolved; ultrasonically treat the solution for 1 - 2 h and filter to obtain the fungicide.
[0033] The beneficial effects of the present invention:
[0034] (1) The present invention uses a chitosan-carrageenan composite system to encapsulate carbendazim, and prepares a fungicide containing nanoparticles of quaternized chitosan-carrageenan encapsulated carbendazim; the experimental results show that the fungicide exhibits significant antibacterial activity against Fusarium oxysporum and Aspergillus parasiticus, can effectively reduce the usage amount of the fungicide and improve its bioavailability, thereby reducing the toxicity risk to plants; chitosan, as an environmentally friendly biopolymer, has good biocompatibility and bioadhesion; carrageenan has natural antibacterial activity, can synergistically enhance the bactericidal effect, and can exhibit excellent stability in acidic environments and high-temperature conditions; the carbendazim drug delivery system based on chitosan-carrageenan can achieve efficient drug delivery and significantly enhance the bactericidal performance of the fungicide.
[0035] (2) The present invention prepares quaternized chitosan by quaternizing chitosan. Quaternized chitosan not only retains the biocompatibility and biodegradability of chitosan but also exhibits stronger antibacterial activity due to the introduction of quaternary ammonium groups. This modification significantly reduces the dosage of carbendazim and further reduces the potential toxicity to plants. In addition, the solubility of quaternized chitosan in water is significantly better than that of unmodified chitosan, which helps to improve the stability and bioavailability of the fungicide, thereby optimizing its performance in practical applications. Detailed Embodiments
[0036] The following describes in detail the specific embodiments of the present invention, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.
[0037] Example 1
[0038] This example provides a carbendazim-containing fungicide, including the following components in parts by weight:
[0039] Nanoparticles of carbendazim encapsulated by quaternized chitosan-carrageenan: 10 parts;
[0040] Surfactant sodium dodecyl sulfate: 1 part;
[0041] Thickener carboxymethyl cellulose: 0.5 part;
[0042] Preservative sodium benzoate: 0.1 part;
[0043] Deionized water: 70 parts.
[0044] The nanoparticles of carbendazim encapsulated by quaternized chitosan-carrageenan are prepared by the following steps:
[0045] S1. Mixed solution:
[0046] Under continuous stirring, the carbendazim solution, carrageenan solution, and dioctyl sulfosuccinate solution are added dropwise to the quaternized chitosan solution, and stirring is continued for 3 h to obtain a mixed solution. The volume ratio of the carbendazim solution, carrageenan solution, dioctyl sulfosuccinate solution, and quaternized chitosan solution is 10:20:5:100.
[0047] S2. Centrifugation and washing:
[0048] The mixed solution is centrifuged at 10,000 rpm for 2 h to separate the nanoparticles. The centrifuged precipitate is washed 3 times with deionized water to remove residual acetic acid and other unreacted substances, obtaining a precipitate.
[0049] S3. Freeze-drying:
[0050] The precipitate was freeze-dried using mannitol as a cryoprotectant to obtain nanoparticles of quaternized chitosan-carrageenan encapsulating carbendazim.
[0051] The carbendazim solution described in step S1 was prepared by the following steps:
[0052] The carbendazim powder was dissolved in acetic acid with a concentration of 3 wt% to obtain a carbendazim solution with a concentration of 5 wt%.
[0053] The carrageenan solution described in step S1 was prepared by the following steps:
[0054] The carrageenan was dissolved in distilled water to obtain a carrageenan solution with a concentration of 0.15 wt%.
[0055] The dioctyl sulfosuccinate solution described in step S1 was prepared by the following steps:
[0056] The dioctyl sulfosuccinate was dissolved in distilled water to obtain a dioctyl sulfosuccinate solution with a concentration of 0.5 wt%.
[0057] The quaternized chitosan solution described in step S1 was prepared by the following steps:
[0058] The quaternized chitosan was dissolved in acetic acid with a concentration of 3 wt% to obtain a quaternized chitosan solution with a concentration of 0.5 wt%;
[0059] The quaternized chitosan was prepared by the following steps:
[0060] Chitosan was dissolved in isopropanol, and the pH of the chitosan solution was adjusted to 8 with 1 M NaOH; 2,3-epoxypropyltrimethylammonium chloride was added to the chitosan solution, and the mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride was 1:3. After stirring and reacting at 80 °C for 8 h, it was filtered, washed with absolute ethanol, and dried to obtain quaternized chitosan.
[0061] The fungicide containing carbendazim was prepared by the following steps:
[0062] Surfactant sodium dodecyl sulfate and thickener carboxymethyl cellulose were added to deionized water, and stirred until completely dissolved to obtain a solution; the nanoparticles of quaternized chitosan-carrageenan encapsulating carbendazim were added to the above solution and stirred until evenly dispersed; then preservative sodium benzoate was added to the solution and stirred until completely dissolved; the solution was ultrasonically treated for 1 h and filtered to obtain the fungicide.
[0063] Example 2
[0064] In comparison with Example 1, this example is different in that the following part in "S1 mixed solution: Under the condition of continuous stirring, carbendazim solution, carrageenan solution and dioctyl sulfosuccinate solution are added dropwise into quaternized chitosan solution, and stirring is continued for 3 h to obtain a mixed solution; the volume ratio of carbendazim solution, carrageenan solution, dioctyl sulfosuccinate solution and quaternized chitosan solution is 10:20:5:100" is changed to "S1 mixed solution: Under the condition of continuous stirring, carbendazim solution, carrageenan solution and dioctyl sulfosuccinate solution are added dropwise into quaternized chitosan solution, and stirring is continued for 3 h to obtain a mixed solution; the volume ratio of carbendazim solution, carrageenan solution, dioctyl sulfosuccinate solution and quaternized chitosan solution is 12:25:7:100"; the remaining raw materials and the preparation process are the same as those in Example 1.
[0065] Example 3
[0066] In comparison with Example 1, this example is different in that the following part in "S1 mixed solution: Under the condition of continuous stirring, carbendazim solution, carrageenan solution and dioctyl sulfosuccinate solution are added dropwise into quaternized chitosan solution, and stirring is continued for 3 h to obtain a mixed solution; the volume ratio of carbendazim solution, carrageenan solution, dioctyl sulfosuccinate solution and quaternized chitosan solution is 10:20:5:100" is changed to "S1 mixed solution: Under the condition of continuous stirring, carbendazim solution, carrageenan solution and dioctyl sulfosuccinate solution are added dropwise into quaternized chitosan solution, and stirring is continued for 3 h to obtain a mixed solution; the volume ratio of carbendazim solution, carrageenan solution, dioctyl sulfosuccinate solution and quaternized chitosan solution is 15:30:10:100"; the remaining raw materials and the preparation process are the same as those in Example 1.
[0067] Example 4
[0068] In comparison with Example 3, this example is different in that the following part in "This example provides a carbendazim-containing bactericide, which includes the following components in parts by weight: quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles: 10 parts; surfactant sodium dodecyl sulfate: 1 part; thickener carboxymethyl cellulose: 0.5 part; preservative sodium benzoate: 0.1 part; deionized water: 70 parts" is changed to "This example provides a carbendazim-containing bactericide, which includes the following components in parts by weight: quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles: 15 parts; surfactant sodium dodecyl sulfate: 2 parts; thickener carboxymethyl cellulose: 1 part; preservative sodium benzoate: 0.3 part; deionized water: 80 parts."
[0069] Example 5
[0070] Compared with Example 3, this example is different in that the statement "This example provides a carbendazim-containing fungicide, comprising the following components in parts by weight: nanoparticles of quaternized chitosan-carrageenan encapsulating carbendazim: 10 parts; surfactant sodium dodecyl sulfate: 1 part; thickener carboxymethyl cellulose: 0.5 part; preservative sodium benzoate: 0.1 part; deionized water: 70 parts" is changed to "This example provides a carbendazim-containing fungicide, comprising the following components in parts by weight: nanoparticles of quaternized chitosan-carrageenan encapsulating carbendazim: 20 parts; surfactant sodium dodecyl sulfate: 3 parts; thickener carboxymethyl cellulose: 2 parts; preservative sodium benzoate: 0.5 part; deionized water: 85 parts."
[0071] Comparative Example 1
[0072] This comparative example provides a carbendazim-containing fungicide, comprising the following components in parts by weight:
[0073] Nanoparticles of chitosan-carrageenan encapsulating carbendazim: 10 parts;
[0074] Surfactant sodium dodecyl sulfate: 1 part;
[0075] Thickener carboxymethyl cellulose: 0.5 part;
[0076] Preservative sodium benzoate: 0.1 part;
[0077] Deionized water: 70 parts.
[0078] The nanoparticles of chitosan-carrageenan encapsulating carbendazim are prepared by the following steps:
[0079] S1. Mixed solution:
[0080] Under the condition of continuous stirring, the carbendazim solution, the carrageenan solution and the dioctyl sulfosuccinate solution are added dropwise into the chitosan solution, and stirring is continued for 3 h to obtain a mixed solution; the volume ratio of the carbendazim solution, the carrageenan solution, the dioctyl sulfosuccinate solution and the chitosan solution is 10:20:5:100;
[0081] S2. Centrifugation and washing:
[0082] The mixed solution is centrifuged at 10000 rpm for 2 h to separate the nanoparticles, and the centrifuged precipitate is washed 3 times with deionized water to remove residual acetic acid and other unreacted substances, obtaining a precipitate;
[0083] S3. Freeze-drying:
[0084] The precipitate is freeze-dried with mannitol as a cryoprotectant to obtain the nanoparticles of chitosan-carrageenan encapsulating carbendazim.
[0085] The carbendazim solution described in step S1 is prepared through the following steps:
[0086] Dissolve carbendazim powder in acetic acid with a concentration of 3 wt% to obtain a carbendazim solution with a concentration of 5 wt%.
[0087] The carrageenan solution described in step S1 is prepared through the following steps:
[0088] Dissolve carrageenan in distilled water to obtain a carrageenan solution with a concentration of 0.15 wt%.
[0089] The dioctyl sodium sulfosuccinate solution described in step S1 is prepared through the following steps:
[0090] Dissolve dioctyl sodium sulfosuccinate in distilled water to obtain a dioctyl sodium sulfosuccinate solution with a concentration of 0.5 wt%.
[0091] The chitosan solution described in step S1 is prepared through the following steps:
[0092] Dissolve chitosan in acetic acid with a concentration of 3 wt% to obtain a chitosan solution with a concentration of 0.5 wt%.
[0093] The carbendazim-containing fungicide is prepared through the following steps:
[0094] Add surfactant sodium dodecyl sulfate and thickener carboxymethyl cellulose to deionized water, stir until completely dissolved to obtain a solution; add the chitosan-carrageenan encapsulated carbendazim nanoparticles to the above solution, stir until evenly dispersed; then add preservative sodium benzoate to the solution, stir until completely dissolved; ultrasonically treat the solution for 1 h and filter to obtain the fungicide.
[0095] Comparative Example 2
[0096] This comparative example provides a carbendazim-containing fungicide, including the following components in parts by weight:
[0097] Carbendazim powder: 10 parts;
[0098] Surfactant sodium dodecyl sulfate: 1 part;
[0099] Thickener carboxymethyl cellulose: 0.5 part;
[0100] Preservative sodium benzoate: 0.1 part;
[0101] Deionized water: 70 parts.
[0102] The carbendazim-containing fungicide is prepared through the following steps:
[0103] Add the surfactant sodium dodecyl sulfate and the thickener carboxymethyl cellulose to deionized water, and stir until completely dissolved to obtain a solution; add carbendazim powder to the above solution and stir until evenly dispersed; then add the preservative sodium benzoate to the solution and stir until completely dissolved; ultrasonically treat the solution for 1 h and filter to obtain the bactericide.
[0104] Perform antibacterial tests on the bactericides of Examples 1 - 5 and Comparative Examples 1 - 2 using the agar diffusion method. The specific operation steps are as follows:
[0105] 1. Material preparation:
[0106] Culture medium: Prepare potato dextrose agar (PDA) medium.
[0107] Fungal culture: Culture Fusarium oxysporum and Aspergillus parasiticus on PDA medium for 7 days to obtain mature colonies.
[0108] 2. Prepare agar plates
[0109] Heat and melt the PDA medium, pour it into a sterile petri dish, and wait for it to solidify; on the solidified agar plate, use a sterile punch (with a diameter of 6 mm) to punch holes on the agar surface to form evenly distributed holes.
[0110] 3. Inoculate fungi
[0111] Cut a mycelium block with a diameter of about 6 mm from the edge of the fungal colony cultured for 7 days; inoculate the mycelium block at the central position of the agar plate.
[0112] 4. Add samples
[0113] Treatment group: Add the bactericide to the agar holes, and add 60 μL of the bactericide to each hole.
[0114] Control group: Add distilled water to the agar holes, and add 60 μL of distilled water to each hole.
[0115] 5. Incubate
[0116] Incubate the inoculated agar plates in an incubator at 25 °C; the incubation time is usually 7 days, and the growth of fungi is regularly observed during this period.
[0117] 6. Measure the inhibition zone
[0118] After the incubation is completed, measure the diameter of the inhibition zone around each hole; the inhibition zone refers to the transparent area where the growth of fungi is inhibited; use a vernier caliper or a ruler to measure the diameter of the inhibition zone and record the data.
[0119] 7. Calculate the inhibition rate
[0120]
[0121] The test results are shown in Table 1 below.
[0122] Table 1
[0123]
[0124] As can be seen from Table 1, the fungicides containing nanoparticles of quaternized chitosan-carrageenan encapsulating carbendazim in Examples 1-5 have excellent antibacterial effects against Fusarium oxysporum and Aspergillus parasiticus; compared with Example 1, in Comparative Example 1, the fungicide used contains nanoparticles of chitosan-carrageenan encapsulating carbendazim instead of nanoparticles of quaternized chitosan-carrageenan encapsulating carbendazim, and the antibacterial effect of the obtained fungicide is reduced; compared with Example 1, in Comparative Example 2, carbendazim is used as the fungicide, and the antibacterial effect is also lower, which is not conducive to reducing the dosage of the fungicide.
[0125] The above are only several specific embodiments of the present invention disclosed. However, the embodiments of the present invention are not limited thereto, and any changes that can be thought of by those skilled in the art should fall within the protection scope of the present invention.
Claims
1. A carbendazim-containing fungicide, characterized in that, It comprises the following components in parts by weight: Quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles: 10 - 20 parts; Surfactant: 1 - 3 parts; Thickener: 0.5 - 2 parts; Preservative: 0.1 - 0.5 parts; Solvent: 70 - 85 parts.
2. The fungicide containing carbendazim according to claim 1, characterized in that, The quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles are prepared by the following steps: S1. Mixed solution: Dropwise add the carbendazim solution, carrageenan solution and dioctyl sulfosuccinate solution into the quaternized chitosan solution, and stir for 3 - 5 h to obtain a mixed solution; S2. Centrifugation and washing: Centrifuge the mixed solution at 10000 - 12000 rpm for 1 - 2 h, and wash the centrifuged precipitate with deionized water 2 - 3 times to obtain a precipitate; S3. Freeze-drying: Freeze-dry the precipitate using mannitol as a cryoprotectant to obtain quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles.
3. A carbendazim-containing fungicide according to claim 2, wherein, The carbendazim solution described in step S1 is prepared by the following steps: Dissolve carbendazim powder in acetic acid with a concentration of 3 wt%, to obtain a carbendazim solution with a concentration of 5 wt%.
4. A carbendazim-containing fungicide according to claim 2, characterized in that, The carrageenan solution described in step S1 is prepared by the following steps: Dissolve carrageenan in distilled water to obtain a carrageenan solution with a concentration of 0.15 wt%.
5. The fungicide containing carbendazim according to claim 2, wherein The dioctyl sulfosuccinate solution described in step S1 is prepared by the following steps: Dissolve dioctyl sulfosuccinate in distilled water to obtain a dioctyl sulfosuccinate solution with a concentration of 0.5 wt%.
6. The fungicide containing carbendazim according to claim 2, wherein, The quaternized chitosan solution described in step S1 is prepared by the following steps: Dissolve quaternized chitosan in acetic acid with a concentration of 3 wt% to obtain a quaternized chitosan solution with a concentration of 0.5 wt%.
7. A carbendazim-containing fungicide according to claim 6, wherein The quaternized chitosan is prepared by the following steps: Dissolve chitosan in isopropanol, and adjust the pH of the chitosan solution to 8 with 1M NaOH; add 2,3-epoxypropyltrimethylammonium chloride to the chitosan solution, stir and react at a constant temperature of 60 - 90 °C for 6 - 10 h, then filter, wash with absolute ethanol and dry to obtain quaternized chitosan; the mass ratio of chitosan to 2,3-epoxypropyltrimethylammonium chloride is 1:
3.
8. A carbendazim-containing fungicide according to claim 2, characterized in that, The volume ratio of the carbendazim solution, carrageenan solution, dioctyl sulfosuccinate solution and quaternized chitosan solution described in step S1 is 10 - 15:20 - 30:5 - 10:
100.
9. A carbendazim-containing fungicide according to claim 1, characterized in that, The surfactant is one of Tween 80 and sodium dodecyl sulfate; the thickener is one of xanthan gum and carboxymethyl cellulose; the preservative is one of sodium benzoate and potassium sorbate; the solvent is deionized water.
10. A carbendazim-containing fungicide according to claim 1, characterized in that, It is prepared by the following steps: add the surfactant and thickener to the solvent, stir until completely dissolved to obtain a solution; add the quaternized chitosan-carrageenan encapsulated carbendazim nanoparticles to the above solution, stir until uniformly dispersed; then add the preservative to the solution, stir until completely dissolved; ultrasonically treat the solution for 1 - 2 h and filter to obtain a bactericide.