CN113243366A - Compound nanogel sustained release agent and preparation method and application thereof - Google Patents
Compound nanogel sustained release agent and preparation method and application thereof Download PDFInfo
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- CN113243366A CN113243366A CN202110549983.4A CN202110549983A CN113243366A CN 113243366 A CN113243366 A CN 113243366A CN 202110549983 A CN202110549983 A CN 202110549983A CN 113243366 A CN113243366 A CN 113243366A
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- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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Abstract
The invention relates to the field of agricultural prevention and control, in particular to a compound nanogel sustained-release agent and a preparation method and application thereof. The invention provides a compound nanogel sustained release agent containing bronopol, a synergist, a carrier material and a cross-linking agent, wherein the synergist comprises one or more of zhongshengmycin, amino-oligosaccharin, zinc thiazole and copper hydroxide. The invention prepares the nano gel sustained-release agent by compounding the bronopol and the synergist, has obvious control effect on plant bacterial diseases such as plant bacterial wilt, bacterial angular leaf spot, canker and soft rot, and the compound nano gel sustained-release agent has small particle size, stable cold and hot storage physicochemical properties, good water dispersibility, no adhesion of particles, no increase of particle size, less than 5% of decomposition rate, long lasting period, good safety, difficult generation of drug resistance, small dosage and simultaneously has the effects of increasing yield and synergism.
Description
Technical Field
The invention relates to the field of agricultural prevention and control, in particular to a compound nanogel sustained-release agent and a preparation method and application thereof.
Background
Bacterial diseases are a disease caused by bacterial infestation of plants. In recent years, the diseases are serious, such as tomato bacterial wilt, ginger bacterial wilt, Chinese cabbage soft rot, cucumber bacterial angular leaf spot, rice bacterial leaf blight, corn stalk rot, wheat glume, citrus canker and the like. At present, the main domestic prevention and treatment method is pesticide prevention and treatment, but the types of effective prevention and treatment agents are lack, and meanwhile, the drug resistance of bacteria is enhanced year by using the same agents for a long time, so that the effect duration is short and the drug effect is poor; therefore, the difficulty of chemical prevention is increased continuously; and the problems of environmental pollution, increase of pesticide cost for farmers and the like caused by excessive use of pesticides are not beneficial to sustainable development of agriculture.
Disclosure of Invention
In order to solve the problems, the invention provides a compound nanogel sustained-release agent and a preparation method and application thereof. The pesticide is prepared into the nano pesticide preparation, so that the potential application of the nano technology in the protection and transmission of the medicine is fully utilized, and new power is provided for sustainable agricultural development; the compound nano gel sustained release agent can effectively prevent and treat bacterial diseases and has the advantages of long lasting period, good drug effect, low cost and no environmental pollution.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a compound nanogel sustained-release agent which comprises the following raw materials in percentage by mass: 1 to 70 percent of active ingredients, 0.5 to 90 percent of carrier materials, 0.1 to 20 percent of cross-linking agents and 0.1 to 10 percent of surface active agents; the effective components comprise bronopol and a synergist; the synergist comprises one or more of zhongshengmycin, amino-oligosaccharin, zinc thiazole and copper hydroxide; the mass ratio of the bronopol to the synergist is (1-80): (1-80).
Preferably, the feed comprises the following raw materials in percentage by mass: 1 to 50 percent of active ingredients, 25 to 85 percent of carrier materials, 1 to 17 percent of cross-linking agents and 0.2 to 10 percent of surface active agents.
Preferably, the mass ratio of the bronopol to the synergist is (1-40): (1-40).
Preferably, the mass ratio of the bronopol to the synergist is (1-20): (1-20).
Preferably, the surfactant comprises a water-soluble surfactant; the water-soluble surfactant comprises one or a mixture of a plurality of polycarboxylate, quaternary ammonium salt, polyoxyethylene ether phosphate, styryl phenol polyoxyethylene ether phosphate, sulfonate, polyvinyl alcohol, carboxylate and polyoxyethylene polyoxypropylene segmented copolymer; the carrier material comprises sodium alginate; the crosslinking agent comprises anhydrous copper sulfate.
The invention provides a preparation method of the compound nanogel sustained release agent, which comprises the following steps:
mixing bronopol, a synergist, a carrier material, a surfactant and water to obtain a first mixed solution; adding the first mixed solution into an oil phase under a high-speed shearing condition to obtain a second mixed solution; the mass ratio of the oil phase to the first mixed solution is (1.5-20) to 1; and dropwise adding a cross-linking agent into the second mixed solution to obtain the compound nanogel sustained-release agent.
Preferably, the oil phase comprises one or more of cyclohexane, isopropanol, rapeseed oil, xylene, methyl oleate, 200# solvent oil and methyl esterified soybean oil.
Preferably, the dropping speed is 30-60 drops/min.
The invention provides an application of the compound nanogel slow-release agent or the compound nanogel slow-release agent prepared by the preparation method in preventing and treating plant bacterial diseases.
Preferably, the bacterial diseases include bacterial wilt, angular leaf spot, brown spot, basal rot, canker, soft rot, stem rot and bacterial blight.
The invention provides a method for preventing and treating plant bacterial diseases, which comprises spraying, drip irrigation, root irrigation, broadcast application, hole application or seed dressing of the compound nano gel sustained-release agent or the sustained-release agent prepared by the preparation method.
Has the advantages that: the invention provides a compound nanogel sustained release agent containing bronopol, a synergist, a carrier material and a cross-linking agent, wherein the synergist comprises one or more of zhongshengmycin, amino-oligosaccharin, zinc thiazole and copper hydroxide, and the mass ratio of the bronopol to the synergist is (1-80): (1-80). The invention prepares the nano gel slow release agent by compounding the bronopol and the synergist, has obvious control effect on plant bacterial diseases such as plant bacterial wilt, bacterial angular leaf spot, canker and soft rot, has small particle size, stable physicochemical properties of cold and hot storage (0 ℃, 7d, 54 ℃, 14d), good dispersibility in water, no adhesion of particles, no increase of particle size, less than 5 percent of decomposition rate, long lasting period, good safety, difficult generation of drug resistance, little dosage, good suspension stability, good drug effect and convenient use, and can also play the effects of increasing production and efficiency and delaying drug resistance.
Moreover, the invention provides a preparation method of the compound nanogel sustained-release agent, and the preparation method is simple, energy-saving, pollution-free in raw material preparation, energy-saving, environment-friendly, less in environmental hazard and good in application prospect.
Detailed Description
The substances according to the invention, if not specifically required, are all commercially available to the person skilled in the art.
The invention provides a compound nanogel sustained-release agent which comprises the following raw materials in percentage by mass: 1 to 70 percent of active ingredients, 0.5 to 90 percent of carrier materials, 0.1 to 20 percent of cross-linking agents and 0.1 to 10 percent of surface active agents; the effective components comprise bronopol and a synergist; the synergist comprises one or more of zhongshengmycin, amino-oligosaccharin, zinc thiazole and copper hydroxide; the mass ratio of the bronopol to the synergist is (1-80): (1-80).
The raw materials of the compound nanogel sustained release agent preferably comprise the following raw materials in percentage by mass: 1 to 50 percent of active ingredients, 25 to 85 percent of carrier materials, 1 to 17 percent of cross-linking agents and 0.2 to 10 percent of surface active agents; more preferably, the active ingredient is 15 to 30 percent, the carrier material is 55 to 70 percent, the cross-linking agent is 5 to 10 percent, and the surfactant is 5 to 10 percent.
The mass ratio of the bronopol to the synergist is preferably (1-40): (1-40), more preferably (1-20): (1-20), most preferably (1-4): (1-2).
In the present invention, the surfactant preferably includes a water-soluble surfactant; the water-soluble surfactant preferably comprises one or a mixture of a plurality of polycarboxylate, quaternary ammonium salt, polyoxyethylene ether phosphate, styrylphenol polyoxyethylene ether phosphate, sulfonate, polyvinyl alcohol, carboxylate and polyoxyethylene polyoxypropylene segmented copolymer; the sulfonate preferably comprises sodium dodecyl sulfate; the quaternary ammonium salt comprises dodecyl trimethyl ammonium bromide; the polyoxyethylene polyoxypropylene block copolymer preferably comprises an EO-PO block copolymer; the carboxylate is preferably sodium polyacrylate; the carrier material preferably comprises sodium alginate; the crosslinking agent preferably comprises anhydrous copper sulfate.
The bronopol can achieve the effect of preventing and treating bacteria by being matched with the zhongshengmycin, the amino-oligosaccharin, the zinc thiazole and/or the copper hydroxide; sodium alginate is a carrier material for preparing the compound nanogel sustained release agent, and can increase the sustained release effect of the agent; the surfactant can disperse the effective components in the preparation process; copper sulfate is used as a cross-linking agent, copper ions and uniformly dispersed sodium alginate are utilized to form three-dimensional reticular gel through cross-linking, the content of the copper ions in the compound nano gel sustained release agent is increased, and the sustained release effect of the agent is improved; after the compound nano gel sustained release agent is applied, copper ions are slowly released, so that the compound nano gel sustained release agent has a sterilization effect and can further improve the drug effect.
The invention provides a preparation method of the compound nanogel sustained release agent, which comprises the following steps:
mixing bronopol, a synergist, a carrier material, a surfactant and water to obtain a first mixed solution; adding the first mixed solution into an oil phase under a high-speed shearing condition to obtain a second mixed solution; the mass ratio of the oil phase to the first mixed solution is (1.5-20) to 1; and dropwise adding a cross-linking agent into the second mixed solution to obtain the compound nanogel sustained-release agent.
Mixing bronopol, a synergist, a carrier material, a surfactant and water to obtain a first mixed solution; adding the first mixed solution into an oil phase under a high-speed shearing condition to obtain a second mixed solution; the mass ratio of the oil phase to the first mixed solution is (1.5-20): 1, more preferably (2-19): 1, still more preferably (5-17): 1, and most preferably (7-15): 1; and dropwise adding a cross-linking agent into the second mixed solution to obtain the compound nanogel sustained-release agent.
In the invention, when the synergist preferably comprises zhongshengmycin and/or amino-oligosaccharin, the mass ratio of the bronopol to the synergist to the carrier material to the surfactant to the water is preferably (1-30): (0.1-20): (10-200): (1-10): (100-1000), more preferably (1-16): (0.5-10): (10-90): (2-5): (100-500); the water is preferably distilled water. The mixing method is not limited in any way, and can be a method known to those skilled in the art.
The invention firstly dissolves bronopol, water-soluble zhongshengmycin and/or amino-oligosaccharin, a carrier material and a surfactant in water to be used as a first mixed solution, the first mixed solution is added into an oil phase to be subjected to high-speed shearing to prepare a second mixed solution, then a cross-linking agent solution is added into the second mixed solution, the second mixed solution is stirred uniformly and is subjected to ultrasonic treatment to disperse the second mixed solution into nano particles, and the cross-linking agent and the carrier material in the second mixed solution are utilized to form three-dimensional network gel through cross-linking to wrap effective components in the three-dimensional network gel.
The shearing speed is preferably 8000-20000 rpm, more preferably 8000-19000 rpm; the shearing time is preferably 1-5 min, and more preferably 1-4 min; the shearing temperature is preferably 5-50 ℃, and more preferably 20-35 ℃.
In the present invention, the oil phase preferably comprises one or more of cyclohexane, isopropanol, rapeseed oil, xylene, methyl oleate, 200# solvent oil and methyl esterified soybean oil.
In the invention, the concentration of the cross-linking agent is preferably 0.5-3 m/L, and more preferably 1.5 m/L.
After the cross-linking agent is dripped into the second mixed solution, the invention preferably further comprises the steps of carrying out ultrasonic treatment, centrifugation and drying on the obtained mixed solution to obtain the compound nanogel sustained-release agent. The dripping speed is preferably 30-60 drops/min, and more preferably 30-50 drops/min. The dispersing mode of the invention is preferably ultrasonic dispersing; the ultrasonic dispersion time is preferably 0.5-2 h, more preferably 0.5-1.6 h, and most preferably 0.5-1.3 h; the centrifugation frequency is preferably 3 times, so that the compound nanogel sustained release agent with higher purity is obtained; the rotation speed of the centrifugation is preferably 10000 rpm; the time of the centrifugation is preferably 10 min; washing the centrifuged precipitate with preferably equal amount of isopropanol after each centrifugation; the drying time is preferably 24 hours; the temperature of the drying is preferably 25 ℃; the ultrasonic time is preferably 0.5-3 h, and more preferably 0.5-2 h; the frequency of the ultrasonic wave is preferably 15-25 KHz, and more preferably 20-25 KHz. The oil phase and the solvent (water) of the first mixed solution in the formula are completely discarded through centrifugation and drying, so that the prepared finished product of the compound nano gel sustained-release agent does not comprise the first mixed solution solvent and the oil phase.
In the present invention, when the synergist preferably comprises zinc thiazole and/or copper hydroxide, the present invention preferably mixes bronopol, synergist, surfactant and carrier material with water to obtain a first mixed solution (dispersed phase); adding the first mixed solution into an oil phase under a high-speed shearing condition to obtain a second mixed solution; and (3) dropwise adding a cross-linking agent into the second mixed solution (W/O type multi-phase dispersion liquid) to obtain the compound nanogel sustained-release agent.
The method is simple, energy-saving, pollution-free raw material preparation, energy-saving and environment-friendly, has little harm to the environment, and has good application prospect.
In the invention, the mass ratio of the bronopol, the synergist, the carrier material, the surfactant and the water is preferably (1-30): (0.1-20): (10-200): (1-10): (100-1000), more preferably (1-16): (0.5-10): (10-90): (2-5): (100-500); the water is preferably distilled water. The mixing method is not limited in any way, and can be a method known to those skilled in the art.
After the bronopol, the synergist, the surfactant and the carrier material are mixed with water, preferably, wet grinding and filtering are carried out on the mixed solution obtained by mixing in sequence; in the present invention, the wet grinding is preferably performed in a grinding cylinder; the wet grinding mode is preferably circulating grinding; during grinding, the mass ratio of the grinding beads to the mixed solution is (1-3) to 1, and the mass ratio of the grinding beads to the mixed solution is more preferably 2 to 1; the grinding balls are preferably zirconium beads; the particle size of the zirconium beads is preferably 1.8 mm; the rotation speed of the wet grinding is preferably 2000-25000 rpm, more preferably 3000-23000 rpm, further preferably 5000-20000 rpm, and most preferably 6000-19000 rpm; the wet grinding time is preferably 3-4 h, and more preferably 3.2-3.8 h; the particle size of the grinding solution obtained after wet grinding is preferably less than 400 nm; the filtration is preferably carried out using a 0.45 μm microfiltration membrane.
The rotating speed of the shearing is preferably 8000-20000 rpm, more preferably 8000-19000 rpm, and most preferably 15000 rpm; the shearing time is preferably 1-5 min, more preferably 2-4 min, and most preferably 3 min; the shearing temperature is preferably 5-50 ℃, and more preferably 20-35 ℃.
In the invention, the concentration of the cross-linking agent is preferably 0.5-3 m/L, and more preferably 1.5 m/L.
After the cross-linking agent is dripped into the second mixed solution, the invention preferably further comprises the steps of carrying out ultrasonic treatment, centrifugation and drying on the obtained mixed solution to obtain the compound nanogel sustained-release agent. The mode of ultrasound in the invention is preferably ultrasonic dispersion; the ultrasonic time is preferably 0.5-3 h, and more preferably 1-2 h; the frequency of the ultrasonic wave is preferably 5-25 KHz, and more preferably 20-25 KHz; the centrifugation frequency is preferably 3 times, so that the compound nanogel sustained release agent with higher purity is obtained; the rotation speed of the centrifugation is preferably 10000 rpm; the time of the centrifugation is preferably 10 min; washing the centrifuged precipitate with preferably equal amount of isopropanol after each centrifugation; the drying time is preferably 24 hours; the temperature of the drying is preferably 25 ℃. According to the invention, the oil phase and the first mixed solution solvent in the formula are completely discarded through centrifugation and drying, so that the prepared finished product of the compound nano gel sustained-release agent does not comprise the water and the oil phase in the first mixed solvent.
The compound nano gel sustained-release agent is prepared into a nano pesticide preparation by wrapping, coupling, embedding and the like the pesticide by adopting a high-molecular nano material, so that the potential application of a nanotechnology in the protection and transmission of the pesticide is fully utilized, new power is provided for sustainable agricultural development, and the compound nano gel sustained-release agent can effectively prevent and treat bacterial diseases; therefore, the compound nanogel sustained-release agent can be used for preventing and treating plant bacterial diseases.
The invention provides the application of the compound nanogel sustained-release agent or the sustained-release agent prepared by the preparation method in preventing and treating plant bacterial diseases. In the present invention, the bacterial diseases preferably include bacterial wilt, angular leaf spot, brown spot, basal rot, canker, soft rot, stem rot and bacterial blight; the plant preferably comprises ginger, Chinese cabbage, rice, orange, cotton, strawberry, potato, soybean, eggplant, tomato, wheat, tobacco, cucumber, konjak, gourd, corn, rice, etc. The effect of the compound nano-gel slow-release agent is verified by adopting a toxicity test and a field test, and the result shows that the compound nano-gel slow-release agent has longer lasting period which is more than 90 days compared with a single agent sold in the market and a compound nano-gel slow-release agent prepared by using calcium chloride as a cross-linking agent, is safe to crops, reduces the dosage of the agent and reduces the cost.
The invention provides a method for preventing and treating plant bacterial diseases, which comprises spraying, drip irrigation, root irrigation, broadcast application, hole application or seed dressing, wherein the compound nano gel sustained-release agent or the sustained-release agent prepared by the preparation method is adopted; the application amount of the method is preferably 2-50 g a.i./mu, and more preferably 15-50 g a.i./mu.
In order to further illustrate the present invention, the following examples are provided to describe in detail a built nanogel sustained release agent, a preparation method and applications thereof, but they should not be construed as limiting the scope of the present invention.
Example 1
The raw materials of the compound nanogel sustained release agent (1.2% bronopol and zhongshengmycin compound nanogel sustained release agent) are shown in table 1, wherein the mass ratio of the bronopol to the zhongshengmycin is 2: 1.
TABLE 11.2% bronopol-Zhongshengmycin Complex nanogel sustained-release agent component
| Components | Dosage of |
| Bronopol (in terms of effective component) | 0.1g |
| Zhongshengmycin (calculated according to effective component) | 0.05g |
| Sodium alginate (carrier material) | 9g |
| Anhydrous copper sulfate (crosslinking agent) | 1g |
| Sodium dodecyl sulfate (sulfonate surfactant) | 0.5g |
| Oleic acid methyl ester (oil phase) | 90g |
| Distilled water (first mixed solution solvent) | 30g |
a. Respectively weighing bronopol, zhongshengmycin, sodium alginate and sodium dodecyl sulfate, adding the bronopol, zhongshengmycin, sodium alginate and sodium dodecyl sulfate into distilled water, and uniformly stirring the mixture to obtain a first mixed solution, wherein the mass ratio of the bronopol to the zhongshengmycin to the sodium alginate to the sodium dodecyl sulfate to the distilled water is 0.1: 0.05: 9: 0.5: 30, i.e. 1:0.5:90:5: 300;
b. slowly dropping the first mixed solution prepared in the step (a) into methyl oleate under the high-speed shearing of 8000rpm at 20 ℃, and shearing for 1min to obtain W/O microemulsion (second mixed solution); the mass ratio of the oil phase to the first mixed solution is 18:7.93, i.e. 2.2: 1;
c. adding water into anhydrous copper sulfate to prepare a copper sulfate aqueous solution with the concentration of 1.5m/L, dropwise adding into the W/O microemulsion in the step (b) at the dropping speed of 30 drops/min, uniformly stirring, and then performing ultrasonic treatment for 0.5h at the frequency of 20KHz to form a uniformly dispersed nano suspension.
d. And (c) placing the nano suspension in the step (c) in a high-speed centrifuge, centrifuging at 10000rpm for 10min, discarding the supernatant, adding equivalent isopropanol to clean the centrifugal precipitate, centrifuging at 10000rpm for 10min again, repeating the operation for three times, and then vacuum-drying the centrifugal precipitate at 25 ℃ for 24h to obtain the compound nano gel sustained-release agent, namely the 1.2% bronopol and zhongshengmycin compound nano gel sustained-release agent.
The oil phase and the first mixed solution solvent in the formula are completely discarded through the step (d), so that the finished product of the prepared bronopol nanogel sustained release agent does not comprise the first mixed solution solvent and the oil phase.
The particle diameter, surface Zate potential and particle dispersion coefficient of the 1.2% bronopol/zhongshengmycin complex nanogel sustained release agent prepared in the embodiment are measured as follows: adding 10mg of the prepared nanogel sustained release agent into 100mL of absolute ethyl alcohol, performing ultrasonic treatment until a sample is completely dispersed, and measuring by using a Laser Particle Analyzer (LPA) (ZS90, Markov Co., England);
and (3) measuring the drug loading capacity: weighing 0.1g of sample, dispersing in 10mL of 0.1M sodium citrate solution, and determining the contents of bronopol and zhongshengmycin by high performance liquid chromatography after the sample is completely dissolved;
and (3) measuring the heat storage stability: heat storage stability measurements were carried out according to GB/T19136-2003;
and (3) low-temperature stability determination: low temperature stability measurements were performed according to GB/T19137;
and (3) suspension rate determination: 1g of the sample is taken and placed in 50ml of distilled water, the mixture is stirred evenly and then transferred into a clean test tube, and the stability of the suspension is observed every other week. The Sedimentation volume ratio (F) was calculated by observing the mixture continuously for a certain period of time. The specific method comprises the following steps: the suspension was put in a measuring cylinder and mixed, the total volume V0 of the suspension was measured, and after leaving for 10 weeks, the volume Vu of the sediment was observed when the sedimentation surface was not changed, and the sedimentation volume ratio F was set to be Vu/V0 × 100%, formula i.
The results are shown in Table 2.
Table 21.2% bronopol-Zhongshengmycin Complex nanogel sustained Release agent quality technical index
| Test item/test method | Test results |
| Total effective component content (%) | Bronopol: 0.83; zhongshengmycin: 0.42 |
| Average particle diameter (nm) | 96 |
| Surface Zate potential (mV) | -20.5 |
| Coefficient of particle dispersion | 0.065 |
| Volume ratio of sedimentation | 0.99 |
| Stability at Low temperature | Qualified |
| Stability in Heat storage | Qualification rate and decomposition rate<5％ |
As can be seen from Table 2, the composite nanogel sustained release agent with small particles, good dispersity and stable physicochemical properties can be obtained in the embodiment.
Example 2
The raw materials of the compound nanogel sustained release agent (25% of bronopol and amino-oligosaccharin compound nanogel sustained release agent) are shown in table 3, wherein the mass ratio of bronopol to amino-oligosaccharin is 4: 1.
Component of table 325% bronopol-amino-oligosaccharin compounded nanogel sustained release agent
The preparation was carried out according to the preparation method of example 1, wherein the emulsification shear rate was 10000rpm, the emulsification time was 2min, and sonication was carried out for 1h, and the other operations were the same as example 1, wherein the ratio of the oil phase to the first mixed solution was 150:56.8, i.e., 2.641: 1.
The oil phase and the first mixed solution solvent in the formula are completely discarded through the step (d), so that the finished product of the prepared bronopol nanogel sustained release agent does not comprise the first mixed solution solvent and the oil phase.
The indexes are detected according to the method described in the example 1, and the quality technical indexes of the 25% bronopol-amino-oligosaccharin nano-gel sustained-release agent prepared in the example 2 are shown in the table 4.
Quality technical index of 425% bronopol-amino-oligosaccharin nano gel sustained release agent
| Test item/test method | Test results |
| Total effective component content (%) | Bronopol: 5.04; amino-oligosaccharin: 20.16 |
| Average particle diameter (nm) | 90 |
| Surface Zate potential (mV) | -22.5 |
| Coefficient of particle dispersion | 0.074 |
| Volume ratio of sedimentation | 0.98 |
| Stability at Low temperature | Qualified |
| Stability in Heat storage | Qualification rate and decomposition rate<5％ |
As shown in Table 4, the composite nanogel sustained release agent with small particles, good dispersity and stable physicochemical property can be obtained in the embodiment.
Example 3
The raw materials of the compound nanogel sustained release agent (44% of bronopol and zinc thiazole compound nanogel sustained release agent) are shown in table 5, wherein the mass ratio of bronopol to zinc thiazole is 1: 1.
Component of table 544% bronopol-thiazole zinc compound nanogel sustained release agent
a. Respectively weighing bronopol, zinc thiazole, sodium alginate, sodium polyacrylate and polyvinyl alcohol, adding into distilled water, and stirring; transferring to a grinding cylinder, and carrying out wet grinding by using a grinding machine (grinding beads: zirconium beads, the mass ratio of the grinding beads to the mixed solution obtained by mixing is 2:1, the particle size is 1.8mm, the rotating speed is 10000rpm, the grinding mode is a circulating grinding mode, grinding is carried out for 3h, filtering is carried out by adopting a 0.45-micron microporous filter membrane, filtrate is taken, and the filtrate is taken as a disperse phase (first mixed solution), wherein the mass ratio of the bronopol, the zinc thiazole, the sodium alginate, the sodium polyacrylate, the polyvinyl alcohol and the distilled water is 0.7: 0.7: 1: 0.15: 0.15: 30, namely 7:7:10:1.5:1.5: 300.
b. Slowly dropping the dispersed phase prepared in the step (a) into a mixed solution of dimethylbenzene and 200# solvent oil under the high-speed shearing of 15000rpm at 25 ℃, and shearing for 3min to obtain a W/O type multi-phase dispersion liquid (a second mixed solution); the mass ratio of the oil phase to the dispersed phase (first mixed solution) was 30:12.7, i.e., 2.36: 1;
c. adding water into anhydrous copper sulfate to prepare a copper sulfate aqueous solution with the concentration of 1.5m/L, dropwise adding the anhydrous copper sulfate aqueous solution into the W/O type multi-phase dispersion liquid (second mixed solution) in the step (b) at the dropping speed of 60 drops/min, uniformly stirring, and performing ultrasonic treatment for 1.5 hours at the ultrasonic frequency of 25KHz to form a uniformly dispersed nano suspension.
d. And (c) placing the nano suspension in the step (c) into a high-speed centrifuge, centrifuging at 10000rpm for 10min, discarding the supernatant, adding equivalent isopropanol to clean the centrifugal precipitate, centrifuging at 10000rpm for 10min again, repeating the operation for three times, and then vacuum-drying the centrifugal precipitate at 25 ℃ for 24h to obtain the 44% bronopol-thiazole zinc nano gel sustained-release agent.
The oil phase and the dispersed phase (first mixed solution) solvent in the formula are completely discarded through the step (d), so that the finished product of the bronopol nanogel sustained-release agent does not comprise the dispersed phase (first mixed solution) solvent and the oil phase.
The indexes are detected according to the method described in the example 1, and the quality technical indexes of the 44% bronopol thiazole zinc nanogel sustained release agent prepared in the example 3 are shown in the table 6.
Quality technical index of 644% bronopol and thiazole zinc compound nanogel slow-release agent
| Test item/test method | Test results |
| Total effective component content (%) | Bronopol: 22.05; zinc thiazole: 22.05 |
| Average particle diameter (nm) | 356 |
| Surface Zate potential (mV) | -19.0 |
| Coefficient of particle dispersion | 0.113 |
| Volume ratio of sedimentation | 0.99 |
| Stability at Low temperature | Qualified |
| Stability in Heat storage | Qualification rate and decomposition rate<5％ |
As can be seen from the experimental data shown in table 6, the present example can obtain a nanogel sustained release agent with small particles, good dispersion degree and stable physicochemical properties.
Example 4
39% bronopol and copper hydroxide compounded nanogel sustained-release agent
The raw materials of the compound nanogel sustained release agent (39% of bronopol and copper hydroxide compound nanogel sustained release agent) are shown in table 7, wherein the mass ratio of bronopol to copper hydroxide is 1.5:1.
TABLE 739% Brornitrol/cupric hydroxide compounded nanogel slow-release agent
The preparation was carried out with reference to the preparation method of example 3, in which the wet milling time was 4 hours, the emulsification shear rate was 20000rpm, emulsification was 5min, and sonication was carried out for 2 hours, and the other operations were the same as example 3, in which the ratio of the oil phase to the first mixed solution was 130:25.2, i.e., 5.16: 1.
The oil phase and the first mixed solution solvent in the formula are completely discarded through the step (d), so that the finished product of the prepared bronopol nanogel sustained release agent does not comprise the first mixed solution solvent and the oil phase.
The indexes are detected according to the method described in the example 1, and the quality technical indexes of the 39% bronopol-copper hydroxide nanogel sustained release agent prepared in the example 4 are shown in the table 8.
TABLE 839% bronopol-cupric hydroxide compounded nanogel sustained-release agent quality technical index
| Test item/test method | Test results |
| Total effective component content (%) | Bronopol: 23.22; copper hydroxide: 15.48 |
| Average particle diameter (nm) | 234 |
| Surface Zate potential (mV) | -22.5 |
| Coefficient of particle dispersion | 0.074 |
| Volume ratio of sedimentation | 0.98 |
| Stability at Low temperature | Qualified |
| Stability in Heat storage | Qualification rate and decomposition rate<5％ |
As can be seen from the experimental data recorded in Table 8, the compound nanogel sustained release agent with small particles, good dispersity and stable physicochemical properties can be obtained in the embodiment.
Application example 1
The toxicity and the synergistic effect of the compound nanogel sustained release agent are measured by adopting a method of combining indoor toxicity measurement and field test.
Firstly, determining the Synergistic Ratio (SR) of two medicaments compounded according to a certain proportion by indoor toxicity measurement, wherein the SR is less than 0.5 for antagonism, the SR is more than or equal to 0.5 and less than or equal to 1.5 for addition, and the SR is more than 1.5 for synergism, and then carrying out field test on the basis.
The method for measuring indoor toxicity comprises the following steps: adding appropriate amount of medicinal liquid into cooled NB culture medium according to experimental design concentration, setting 4 times of treatment, diluting the strain grown on NA culture medium to 1 × 10 with sterilized water7And (3) inoculating 100uL of bacterial liquid into each treatment culture medium of the suspension with the spore concentration/mL, and shaking at the temperature of 28-30 ℃ (120 r/min).
The turbidity of each treatment was measured before the start of the incubation, and when the control treatment reached the logarithmic phase, the turbidity of each treatment was measured and recorded. And (4) calculating the bacterial growth inhibition rate according to a calculation formula shown in formula II according to the investigation data.
Carrying out regression analysis on the logarithm value and the control effect rate value of the concentration of the medicament by using SPSS (Spassmex Sublimata), and counting EC (effective dose) of each treatment50And calculating the EC of each agent therefrom50The value is obtained. Meanwhile, the combined Synergistic Ratio (SR) of the two medicaments in different proportions is calculated according to the Wadley method, the antagonism is achieved when the SR is less than 0.5, the addition effect is achieved when the SR is more than or equal to 0.5 and less than or equal to 1.5, and the synergism is achieved when the SR is more than 1.5. The calculation formula is shown as formula III and formula IV: SR ═ EC50(theoretical value)/EC50(observed value), formula III, EC50(theoretical value) ═ (a + b)/[ (a/(EC of A)50) + (EC of B/B50)]Formula iv, wherein: a. b is the proportion of active ingredient A, B in the composition, A is bronopol, B is selected from one of zhongshengmycin, amino-oligosaccharin, zinc thiazole and copper hydroxide.
1.1, test germs: pseudomonas solanacearum (Pseudomonas solanacearum SHBCC D10937, Shanghai treasure Biotech center); and (3) experimental design: the effective inhibition concentration range of the bronopol and hexaconazole and the mixture of the bronopol and hexaconazole in different proportions is determined by a preliminary test. The virulence determination results are shown in table 9.
TABLE 9 analysis of toxicity test results of bronopol and zhongshengmycin compounded nanogel sustained-release preparation on pseudomonas solanacearum
From table 9, it can be seen that the ratio SR of bronopol to zhongshengmycin is greater than 1.5 for pseudomonas solanacearum at (1: 80) - (80: 1), which indicates that both exhibit synergy when mixed in the range of (1: 80) - (80: 1), and that when bronopol and zhongshengmycin are at (1: 10) - (10: 1), the synergy is more prominent, the synergy ratio is more than 2.0, and particularly, the ratio SR of bronopol to zhongshengmycin is 4: when 1, the synergistic ratio is the largest, and the synergistic effect is the most obvious.
1.2, test germs: soft rot of carrot (firming carrot SHBCC D72647, Shanghai treasure center for biotechnology); and (3) experimental design: the effective inhibition concentration range of the bronopol and the amino-oligosaccharide raw pesticide and the mixture of the bronopol and the amino-oligosaccharide raw pesticide in different proportions is determined through a preliminary test. The virulence assay results are shown in table 10.
TABLE 10 analysis of virulence determination results of the combination of bronopol and amino-oligosaccharin on Roughtonia carotovora
As can be seen from Table 10, the synergistic ratio SR of bronopol to amino-oligosaccharide is greater than 1.5 when the ratio of bronopol to amino-oligosaccharide is (1: 80) - (80: 1), which indicates that both show synergistic effect when mixed in the range of (1: 80) - (80: 1), and when the ratio of bronopol to amino-oligosaccharide is (1: 40) - (20: 1), the synergistic effect is more prominent, the synergistic ratio is more than 2.13, especially when the ratio of bronopol to amino-oligosaccharide is 1:2, the synergistic ratio is the greatest, and the synergistic effect is the most significant.
1.3, test germs: pseudomonas solanacearum (Pseudomonas solanacearum SHBCC D10937, Shanghai treasure Biotech center); and (3) experimental design: the effective inhibition concentration range of the bronopol and the zinc thiazole raw drug and the mixture of the bronopol and the zinc thiazole raw drug with different proportions is determined by a preliminary test. The virulence assay results are shown in table 11.
TABLE 11 analysis of virulence determination results of pseudomonas solanacearum by combining bronopol and zinc thiazole
From table 11, it is known that the ratio SR of bronopol to zinc thiazole is greater than 1.5 for pseudomonas solanacearum at (1: 80) - (80: 1), which indicates that both exhibit synergy when mixed in the range of (1: 80) - (80: 1), and that the synergy is more prominent when the ratio SR of bronopol to zinc thiazole is (1: 40) - (30: 1), and the synergy ratio SR is more prominent when the ratio SR is 1: 80) - (80: 1, especially when the ratio SR is 1: when 1, the synergistic ratio is the largest, and the synergistic effect is the most obvious.
1.4, test germs: soft rot of carrot (firming carrot SHBCC D72647, Shanghai treasure center for biotechnology); and (3) experimental design: the effective inhibition concentration range of the bronopol and the copper hydroxide raw medicines and the mixture of the bronopol and the copper hydroxide raw medicines with different proportions is determined through a preliminary test. The virulence assay results are shown in table 12.
TABLE 12 analysis of virulence determination results of the combination of bronopol and cupric hydroxide on carrot Roxiphobacillus carotovorus
From table 12, it is known that the synergistic ratio SR of bronopol to copper hydroxide is greater than 1.5 when the ratio of bronopol to copper hydroxide is (1: 80) - (80: 1), which indicates that both exhibit synergistic effects when mixed in the range of (1: 80) - (80: 1), and that when the ratio of bronopol to amino-oligosaccharide is (1: 40) - (40: 1), the synergistic effects are more prominent, the synergistic ratio is more than 2.12, and particularly, the ratio of bronopol to zhongshengmycin is 3: and 2, the synergistic ratio is maximum, and the synergistic effect is most obvious.
Application example 2
2.1, selecting plots planted with tomatoes all year round and having serious tomato bacterial wilt, and carrying out 17 treatments in total, wherein the dosage of the compound nano gel sustained-release agent prepared in the example 1 in the treatment 1 is 30g a.i./mu; treatment 2 is the compound nanogel sustained-release agent prepared in example 1, and the dosage is 15g a.i./mu; treatment 3 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 30g a.i./mu; treatment 4 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 15g a.i./mu; treatment 5 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 30g a.i./mu; treatment 6 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 15g a.i./mu; treatment 7 is the compound nanogel sustained-release agent prepared in example 4, and the dosage is 30g a.i./mu; treatment 8 is the compound nanogel sustained-release agent prepared in example 4, and the dosage is 15g a.i./mu; treatment 9 is reference agent 1 (1.2% bronopol/zhongshengmycin complex nanogel sustained release agent prepared by replacing anhydrous copper sulfate with calcium chloride of the same mass, and the other components and the preparation process are the same as those in example 1), and the dosage is 30g a.i./mu; the treatment 10 is a reference medicament 1, and the dosage is 15g a.i./mu; treatment 11 was reference agent 2 (the amount of bronopol used in example 1 was changed to 0.135g, the amount of zhongshengmycin used was changed to 0.015g, and other conditions were not changed), and the amount of bronopol used was 30g a.i./mu; the treatment 12 is a reference medicament 2, and the dosage is 15g a.i./mu; the treatment 13 is 20% of bronopol wettable powder sold in the market, and the dosage is 30g a.i./mu; the treatment 14 is 3% zhongshengmycin wettable powder, and the dosage is 30g a.i./mu; treating 15% of amino-oligosaccharin aqueous solution with the dosage of 30g a.i./mu; the treatment 16 is 77% copper hydroxide wettable powder, and the dosage is 30g a.i./mu; the treatment 17 is 1.2% bronopol/zhongshengmycin wettable powder (the effective component ratio is consistent with that in example 1) prepared by a conventional preparation method and conventional additives in the field, and the specific method is to uniformly mix the bronopol, zhongshengmycin, a dispersing agent, a wetting agent and a filler in a mixing cylinder, wherein the bronopol (calculated by the effective components) is 0.83%, the zhongshengmycin (calculated by the effective components) is 0.42%, the dispersing agent is alkyl benzene sulfonate, the using amount is 5%, the wetting agent is sodium dodecyl sulfate, the using amount is 3%, the filler is white carbon black, the complement is 100%, the mixture is uniformly mixed after being crushed by a jet mill, and the using amount is 30g a.i./mu.
Each treatment was repeated 4 times, and random arrangement was used to periodically sample, investigate the control effect on tomato bacterial wilt at different periods, and measure the tomato yield at harvest, the results are shown in Table 13. All the treatments are diluted by the same water amount and then applied by adopting a drip irrigation mode.
TABLE 13 efficacy test of the compound nanogel sustained-release agent with different components for preventing and treating tomato bacterial wilt
The results in table 13 show that the compound nanogel sustained-release agents prepared in examples 1 to 4 have significantly higher control effects on tomato bacterial wilt than commercially available agents, 1.2% bronopol-zhongshengmycin wettable powder and reference agents, show significant synergistic effects, maintain higher control effects for 90 days after application, and have more significant yield-increasing effects, when the dosages are the same and low. And the safety is better without causing phytotoxicity in the test period. Therefore, the compound nanogel slow-release agent prepared by the invention has the advantages of small dosage, long lasting period and slow-release yield-increase synergistic effect, thereby reducing the production cost and the generation of drug resistance. In addition, compared with reference medicament 1, the nano-gel sustained release preparation prepared by adopting anhydrous copper sulfate to replace the conventionally used calcium chloride can effectively improve the control effect and the tomato yield. As can be seen from reference agent 2, when the ratio of bronopol to zhongshengmycin is greater than 80:1, the drug effect and yield increase rate are significantly reduced.
2.2, selecting plots planted with cucumbers all year round and having serious cucumber bacterial angular leaf spot, and treating 17 plots to obtain the compound nano gel sustained-release agent prepared in the example 1 in the treatment step 1, wherein the dosage is 40g a.i./mu; the treatment 2 is the compound nanogel sustained-release agent prepared in the example 1, and the dosage is 20g a.i./mu; treatment 3 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 40g a.i./mu; treatment 4 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 20g a.i./mu; treatment 5 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 40g a.i./mu; treatment 6 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 20g a.i./mu; treatment 7 is the compound nanogel sustained-release agent prepared in example 4, and the dosage is 40g a.i./mu; treatment 8 is the compound nanogel sustained-release agent prepared in example 4, and the dosage is 20g a.i./mu; treatment 9 is reference medicament 1 (25% bronopol-amino-oligosaccharin compound nanogel sustained release agent prepared by replacing anhydrous copper sulfate with calcium chloride of the same mass, and other components and preparation processes are the same as those in example 2), and the dosage is 40g a.i./mu; the treatment 10 is a reference medicament 1, and the dosage is 20g a.i./mu; treatment 11 was reference agent 2 (the dosage of bronopol in example 2 was changed to 0.3g, the dosage of oligosaccharins was changed to 1.7g, and other conditions were not changed), and the dosage was 40g a.i./mu; the treatment 12 is a reference medicament 2, and the dosage is 20g a.i./mu; the treatment 13 is 20% of bronopol wettable powder sold in the market, and the dosage is 40g a.i./mu; the treatment 14 is 3% zhongshengmycin wettable powder, and the dosage is 40g a.i./mu; treating 15% amino-oligosaccharin aqueous solution with dosage of 40g a.i./mu; the treatment 16 is 77% copper hydroxide wettable powder, and the dosage is 40g a.i./mu; the treatment 17 is 25% bronopol-amino-oligosaccharin wettable powder (the effective component ratio is consistent with the example 2) prepared by a conventional preparation method and conventional additives in the field, and the specific method is to uniformly mix bronopol, amino-oligosaccharin, a dispersing agent, a wetting agent and a filler in a mixing cylinder, wherein the bronopol is 5.04%, the amino-oligosaccharin is 20.16%, the dispersing agent is sodium naphthalenesulfonic acid-formaldehyde condensate, the using amount is 3%, the wetting agent is alkyl naphthalenesulfonate, the using amount is 3%, the filler is kaolin, the balance is complemented, the mixture is pulverized by a jet mill and then uniformly mixed, and the specific using amount is 40g a.i./mu. Each treatment was repeated 4 times, and random arrangement was used, samples were periodically taken, the control of cucumber bacterial angular leaf spot at different times was investigated, and the cucumber yield at harvest was determined, and the results are shown in Table 14. All the treatments are diluted by the same water amount and then applied by root irrigation.
TABLE 14 efficacy test of compound nanogel sustained-release agent with different components for preventing and treating cucumber bacterial angular leaf spot
The experimental data recorded in table 14 show that the bronopol complex nanogel sustained release agents prepared in examples 1 to 4 have significantly higher control effects on cucumber bacterial angular leaf spot than the commercially available agents at the same dosage and low dosage, have 25% bronopol and zhongshengmycin soluble solutions and reference agents, show significant synergistic effects, maintain higher control effects for 90 days after application, and have more significant yield increasing effects. The safety is better because no phytotoxicity is generated during the test period; therefore, the compound nanogel slow-release agent prepared by the invention has the advantages of small dosage, long lasting period and yield increase and synergism, thereby reducing the production cost and the generation of drug resistance. In addition, compared with the reference medicament 1, the nano-gel sustained release preparation prepared by adopting anhydrous copper sulfate to replace the conventionally used calcium chloride can effectively improve the control effect and the cucumber yield. As can be seen from reference agent 2, when the ratio of bronopol to amino-oligosaccharide is less than 1:80, the drug effect and yield increase are significantly reduced.
2.3, selecting a plot with corn planted all year round and severe corn stem rot, and treating 15 plots to obtain the compound nano gel sustained-release agent prepared in the example 1 in the step 1, wherein the dosage is 50g a.i./mu; treatment 2 is the compound nanogel sustained-release agent prepared in example 1, and the dosage is 25g a.i./mu; treatment 3 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 50g a.i./mu; treatment 4 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 25g a.i./mu; treatment 5 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 50g a.i./mu; treatment 6 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 25g a.i./mu; treatment 7 is the compound nanogel sustained-release agent prepared in example 4, and the dosage is 50g a.i./mu; treatment 8 is the compound nanogel sustained release agent prepared in example 4, and the dosage is 25g a.i./mu; treatment 9 is reference medicament 1 (44% bronopol-amino-oligosaccharin compound nanogel sustained release agent prepared by replacing anhydrous copper sulfate with calcium chloride of the same mass, and other components and preparation processes are the same as those in example 3), and the dosage is 50g a.i./mu; the treatment 10 is a reference medicament 1, and the dosage is 25g a.i./mu; the treatment 11 is 20% of bronopol wettable powder sold in the market, and the dosage is 50g a.i./mu; the treatment 12 is 3% Zhongshengmycin wettable powder, and the dosage is 50g a.i./mu; treating 13% amino-oligosaccharin aqueous solution with dosage of 50g a.i./mu; the treatment 14 is 77% copper hydroxide wettable powder and the dosage is 50 ga.i./mu; the treatment 15 is 44% bronopol-thiazole zinc suspending agent (the effective component ratio is consistent with the example 3) prepared by adopting the conventional preparation method and the conventional auxiliary agent in the field, and the specific method is to use dispersing agent, wetting agent, defoaming agent, thickening agent (optionally added) and antifreeze agent (optionally added), wherein the bronopol is 22.05%, the thiazole zinc is 22.05%, the dispersing agent is alkylphenol ethoxylate, the dosage is 5%, the wetting agent is sodium dodecyl benzene sulfonate, the dosage is 2%, the organic silicon defoaming agent is 0.2%, the thickening agent is Arabic gum 1% and the antifreeze agent is propylene glycol 3%. Uniformly mixing the materials through high-speed shearing, adding bronopol and zinc thiazole, and ball-milling the materials in a ball mill for 2-3 hours to ensure that the particle diameters of the particles are all below 5 mu m, and supplementing the balance of deionized water, wherein the dosage is 50g a.i./mu. Each treatment was repeated 4 times, and random sampling was performed periodically to investigate the control of corn stalk rot at different times and to determine the corn yield at harvest, the results of which are shown in Table 15. All the treatments are diluted by the same amount of water and then applied in a spraying mode.
TABLE 15 efficacy test of compound nanogel sustained-release agent with different components for preventing and treating corn stalk rot
The results in table 15 show that the compound nanogel sustained-release agents prepared in examples 1 to 4 have significantly higher control effects on corn stalk rot than commercially available agents, namely 44% bronopol-thiazole zinc suspending agent and reference agent, show significant synergistic effects, maintain higher control effects for 90 days after application, and have more significant yield increasing effects, when the dosages are the same and low. The safety is better because no phytotoxicity is generated during the test period; therefore, the bronopol compound nanogel sustained release agent prepared by the invention has the advantages of small dosage, long lasting period and yield increase and synergy, thereby reducing the production cost and reducing the generation of drug resistance. In addition, compared with the reference medicament 1, the nano-gel sustained release agent prepared by adopting anhydrous copper sulfate to replace the conventionally used calcium chloride can effectively improve the control effect and the corn yield.
2.4, selecting a plot with rice planted all year round and severe bacterial leaf blight of rice, and treating 15 plots to obtain the compound nanogel sustained release agent prepared in the example 1 in the step 1, wherein the dosage is 45g a.i./mu; treatment 2 is the compound nanogel sustained-release agent prepared in example 1, and the dosage is 22.5g a.i./mu; treatment 3 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 45g a.i./mu; treatment 4 is the compound nanogel sustained-release agent prepared in example 2, and the dosage is 22.5g a.i./mu; treatment 5 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 45g a.i./mu; treatment 6 is the compound nanogel sustained-release agent prepared in example 3, and the dosage is 22.5g a.i./mu; treatment 7 is the compound nanogel sustained-release agent prepared in example 4, and the dosage is 45g a.i./mu; treatment 8 is the compound nanogel sustained-release agent prepared in example 4, and the dosage is 22.5g a.i./mu; treatment 9 is reference agent 1 (other components and preparation process of 39% bronopol-copper hydroxide compound nanogel sustained release agent prepared by replacing anhydrous copper sulfate with calcium chloride of the same mass are the same as those in example 4), and the dosage is 45g a.i./mu; the treatment 10 is a reference medicament 1, and the dosage is 22.5g a.i./mu; the treatment 11 is 20% of bronopol wettable powder sold in the market, and the dosage is 45g a.i./mu; the treatment amount is 12% of zhongshengmycin wettable powder, and the dosage is 45g a.i./mu; treating 13% amino-oligosaccharin aqueous solution with dosage of 45g a.i./mu; the treatment 14 is 77% copper hydroxide wettable powder, and the dosage is 45g a.i./mu; the treatment 15 is 39% bronopol-copper hydroxide wettable powder (the effective component ratio is the same as that in example 4) prepared by a conventional preparation method and a conventional auxiliary agent in the field, and the specific method is to uniformly mix bronopol, copper hydroxide, a dispersing agent, a wetting agent and a filler in a mixing cylinder, wherein the bronopol is 23.22%, the copper hydroxide is 15.48%, the dispersing agent is sodium lignosulfonate with the dosage of 6%, the wetting agent is sodium lauryl sulfate with the dosage of 4%, and the carrier is attapulgite with the balance. The components are crushed by a jet mill and then uniformly mixed, and the dosage is 45g a.i./mu. All the treatments are diluted by the same water amount and then applied by root irrigation.
Each treatment was repeated 4 times, and random arrangement was used to periodically sample and investigate the control effect on bacterial blight of rice at different periods, and the rice yield at harvest was determined, and the results are shown in Table 16.
TABLE 16 Effect test of compounded nanogel sustained-release agent with different components on preventing and treating bacterial leaf blight of rice
The results in table 16 show that the compound nanogel sustained-release agents prepared in examples 1 to 4 have significantly higher control effects on bacterial leaf blight of rice than commercially available agents, namely 39% bronopol-copper hydroxide wettable powder and reference agents, and show significant synergistic effects, and the compound nanogel sustained-release agents still have higher control effects after being applied for 90 days, and have more significant yield-increasing effects. The safety is better because no phytotoxicity is generated during the test period; therefore, the compound nanogel slow-release agent prepared by the invention has the advantages of small dosage, long lasting period and yield increase and synergism, thereby reducing the production cost and the generation of drug resistance. In addition, compared with a reference medicament, the nano gel sustained release agent prepared by adopting anhydrous copper sulfate to replace the conventionally used calcium chloride can effectively improve the control effect and the rice yield.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The compound nanogel sustained release agent is characterized by comprising the following raw materials in percentage by mass: 1 to 70 percent of active ingredients, 0.5 to 90 percent of carrier materials, 0.1 to 20 percent of cross-linking agents and 0.1 to 10 percent of surface active agents; the effective components comprise bronopol and a synergist; the synergist comprises one or more of zhongshengmycin, amino-oligosaccharin, zinc thiazole and copper hydroxide; the mass ratio of the bronopol to the synergist is (1-80): (1-80).
2. The compound nanogel sustained-release agent according to claim 1 is characterized by comprising the following raw materials in percentage by mass: 1 to 50 percent of active ingredients, 25 to 85 percent of carrier materials, 1 to 17 percent of cross-linking agents and 0.2 to 10 percent of surface active agents; the mass ratio of the bronopol to the synergist is (1-40): (1-40).
3. The compound nanogel sustained-release agent according to claim 1, wherein the mass ratio of the bronopol to the synergist is (1-20): (1-20).
4. The compound nanogel sustained-release agent according to any one of claims 1 to 3, wherein the surfactant comprises a water-soluble surfactant; the water-soluble surfactant comprises one or a mixture of a plurality of polycarboxylate, quaternary ammonium salt, polyoxyethylene ether phosphate, styryl phenol polyoxyethylene ether phosphate, sulfonate, polyvinyl alcohol, carboxylate and polyoxyethylene polyoxypropylene segmented copolymer; the carrier material comprises sodium alginate; the crosslinking agent comprises anhydrous copper sulfate.
5. The preparation method of the compound nanogel sustained-release agent as defined in any one of claims 1 to 4, which is characterized by comprising the following steps:
mixing bronopol, a synergist, a carrier material, a surfactant and water to obtain a first mixed solution;
adding the first mixed solution into an oil phase under a high-speed shearing condition to obtain a second mixed solution; the mass ratio of the oil phase to the first mixed solution is (1.5-20) to 1;
and dropwise adding a cross-linking agent into the second mixed solution to obtain the compound nanogel sustained-release agent.
6. The method of claim 5, wherein the oil phase comprises one or more of cyclohexane, isopropanol, rapeseed oil, xylene, methyl oleate, 200# solvent oil and methyl esterified soybean oil.
7. The production method according to claim 5, wherein the dropping speed is 30 to 60 drops/min.
8. The application of the compound nanogel slow-release agent of any one of claims 1 to 4 or the compound nanogel slow-release agent prepared by the preparation method of any one of claims 5 to 7 in preventing and treating plant bacterial diseases.
9. The use according to claim 8, characterized in that said bacterial diseases comprise bacterial wilt, angular leaf spot, brown spot, basal rot, canker, soft rot, stem rot and bacterial blight.
10. A method for preventing and treating plant bacterial diseases, which is characterized by comprising spraying, drip irrigation, root irrigation, broadcast application, hole application or seed dressing of the compound nanogel sustained-release agent of any one of claims 1 to 4 or the sustained-release agent prepared by the preparation method of any one of claims 5 to 7.
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| CN114868739A (en) * | 2022-04-25 | 2022-08-09 | 江苏省农业科学院 | Special auxiliary agent for improving prevention and treatment effects of root irrigation and pesticide application, and preparation method and use method thereof |
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