CN113678825A - Anti-scour biological insecticide and preparation method thereof - Google Patents

Anti-scour biological insecticide and preparation method thereof Download PDF

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Publication number
CN113678825A
CN113678825A CN202110913399.2A CN202110913399A CN113678825A CN 113678825 A CN113678825 A CN 113678825A CN 202110913399 A CN202110913399 A CN 202110913399A CN 113678825 A CN113678825 A CN 113678825A
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solution
mixed solution
cmc
gelatin
emulsion
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陈宏伟
章卓琳
杨树锫
庞秋雯
刘思琪
蒋晟
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Suzhou University of Science and Technology
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    • A—HUMAN NECESSITIES
    • 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
    • A01N25/26—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 in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • 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
    • A01N25/30—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
    • A—HUMAN NECESSITIES
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A—HUMAN NECESSITIES
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Toxicology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Natural Medicines & Medicinal Plants (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to the field of biological pesticides, and discloses an anti-scour biological pesticide which is of a microsphere structure and comprises: a plant source pesticide is taken as a core material of an insecticidal effective substance; coating a core material, wherein gelatin and CMC are used as wall materials of the raw materials; and a polymer which is modified on the surface of the wall material and has high leaf surface affinity, wherein the polymer is catechol-modified polyvinyl alcohol. In addition, the invention also discloses a preparation method of the biological pesticide. The anti-scour biological insecticide disclosed by the invention has high leaf surface hanging and retaining capacity and anti-scour capacity, can improve the utilization rate of pesticide, and is beneficial to solving the problem of pesticide residue.

Description

Anti-scour biological insecticide and preparation method thereof
Technical Field
The invention relates to the field of biopesticides, and in particular relates to an anti-scour biological insecticide and a preparation method thereof.
Background
The pesticide is an important agricultural production data, is widely applied to prevention and control of diseases, insects and pests in agricultural and forestry production activities, and plays an important role in guaranteeing agricultural production safety, agricultural product quality safety and ecological environment safety. In recent years, the usage amount of pesticides is increased year by year, and although the usage amount of pesticides ensures the grain yield to a certain extent and reduces economic loss, the use amount of pesticides is too high, so that a plurality of new problems are brought to human life, such as overproof pesticide residues, serious environmental pollution, ecological balance damage and the like.
The biological pesticide achieves the purpose of preventing and treating plant diseases and insect pests by utilizing a biological living body or a pure natural active component generated by the biological living body, and does not generate the problems of chemical residue and environmental pollution. The plant-derived green pesticide is an active substance with insect-resisting and bacteriostatic effects prepared by extracting roots, stems, leaves, flowers, fruits, seeds and the like of plants or by utilizing secondary metabolites thereof. Compared with chemical pesticides, the pesticide has the advantages of good environmental compatibility, no enrichment and pollution, safety to people and livestock, difficulty in generating drug resistance by diseases and pests, high safety and good selectivity, can be decomposed into nontoxic substances in the nature, and is a development direction of future pesticides.
In addition, the problem of environmental pollution can be solved from the other side by the leaf surface retention of the pesticide, the longer the pesticide is retained on the leaf surface, the longer the pesticide plays a role, on one hand, the pesticide application frequency can be reduced, on the other hand, the pesticide retention time is increased, the situation that the pesticide is flushed into the soil by rainwater and the like when the pesticide is not used can be avoided, and the environment is improved by pesticide residues in the soil.
Based on the two points, the invention provides the anti-scouring biological insecticide and the preparation method thereof, which can effectively improve the utilization rate of the pesticide and avoid the problem of pesticide residue in the land.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an anti-scouring biological insecticide and a preparation method thereof, which can improve the retention capacity and the anti-rain scouring type of the insecticide on plant leaves, improve the utilization rate of pesticides and solve the problem of chemical residue.
To achieve the above objects and other advantages in accordance with the present invention, a first object of the present invention is to provide a scour-resistant biopesticide in a microsphere structure comprising: a plant source pesticide is taken as a core material of an insecticidal effective substance;
coating a core material, wherein gelatin and CMC are used as wall materials of the raw materials;
and a polymer with high leaf surface affinity, which is modified by catechol-modified polyvinyl alcohol, is modified on the surface of the wall material.
Preferably, the botanical pesticide is one or more of azadirachtin, rotenone, pyrethrin and capsaicin.
Preferably, the mass ratio of the core material to the wall material in the microsphere is 1: 0.5-3.
Preferably, the mass ratio of the gelatin to the CMC is 7-11: 1.
Preferably, the mass ratio of polymer to microspheres is 1: 20.
The second purpose of the invention is to provide a preparation method of the anti-scour biopesticide, which comprises the following steps:
extracting plant source pesticide active substances in plants by a supercritical fluid extraction method;
respectively dissolving a certain amount of gelatin and CMC in distilled water to form a gelatin solution and a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution;
adding the extracted plant source pesticide active substance into the mixed solution and reacting to form a first emulsion;
coagulating the first emulsion to form a second emulsion by adjusting the pH to acidity and adjusting the stirring temperature and speed;
adjusting the pH of the second emulsion to be neutral, and curing the second emulsion to form a microsphere dispersion under the condition of adding glutaminase;
and (3) carrying out precipitation, washing, suction filtration and freeze drying on the microsphere dispersion liquid to obtain the plant source microspheres.
Adding a certain amount of plant source microspheres, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide for ultrasonic dispersion, and then magnetically stirring to prepare a pre-modification mixed solution;
dispersing polymer catechol modified polyvinyl alcohol in a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, heating until the polymer catechol modified polyvinyl alcohol is completely dissolved, and cooling to room temperature; dropwise adding the obtained solution into the pre-modified mixed solution, magnetically stirring at normal temperature, and then heating to 50 ℃ for a period of time to continue reaction;
and cooling the mixed solution after reaction to room temperature, respectively centrifuging and washing by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological pesticide.
Preferably, the catechol-modified polyvinyl alcohol is prepared by the following steps:
a1, dispersing PVA-210 in dimethylphenylene, continuously magnetically stirring until the solid is completely dissolved, and cooling to room temperature;
a2, adding 3, 4-dihydroxybenzaldehyde and p-methylbenzenesulfonic acid into the solution obtained in the step A1, and magnetically stirring and reacting in an anaerobic environment;
a3: cooling the solution obtained in the step A2 to room temperature, slowly adding the solution into acetone under magnetic stirring, and carrying out suction filtration and separation under reduced pressure to obtain light brown flaky precipitates;
a4: re-dispersing the precipitate obtained in the step A3 in dimethyl sulfoxide, continuously magnetically stirring until the precipitate is completely dissolved, cooling to room temperature, and repeating the operation in the step A3 until a white flaky precipitate is finally obtained;
and A5, performing Soxhlet extraction on the white flaky precipitate finally obtained in the step A4 by using dichloromethane under the protection of nitrogen, and finally obtaining the fibrous polymer catechol-modified polyvinyl alcohol.
Preferably, the preparation method of the anti-scour biological insecticide comprises the following specific steps:
extracting plant source pesticide active substances in plants by a supercritical fluid extraction method;
respectively adding a certain amount of gelatin and CMC (carboxy methyl cellulose) into distilled water to dissolve the gelatin and the CMC to form a gelatin solution and a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution, wherein the mass concentration of the gelatin and the CMC in the mixed solution is 0.5-2%;
adding the extracted plant source pesticide active substance into the mixed solution, and emulsifying for 2-3 min in a tissue mixer at the rotating speed of 8000-12000 r/min to form a first emulsion;
adjusting the pH value to 4.5-5 by using a 10% acetic acid solution, adjusting the stirring temperature to 35-50 ℃, and adjusting the stirring speed to 300-500 r/min to enable the first emulsion to be coagulated to form a second emulsion;
adjusting the pH of the second emulsion to be neutral by using a 10% sodium hydroxide solution, and curing the second emulsion to form a microsphere dispersion under the condition of adding glutaminase, wherein the mass percentage of the added glutaminase in the total reaction system is 0.5-1.5%, the stirring speed of 100-200 r/min is required to be kept during curing, and the curing time is 4-5 h;
and (3) carrying out precipitation, washing, suction filtration and freeze drying on the microsphere dispersion liquid to obtain the plant source microspheres.
Adding a certain amount of plant source microspheres, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into 60mL of a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide for ultrasonic dispersion, and magnetically stirring for 0.5-1 h to prepare a pre-modification mixed solution;
dispersing polymer catechol modified polyvinyl alcohol in 10mL of mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, heating to 90 ℃ for complete dissolution, and cooling to room temperature; dropwise adding the obtained solution into the pre-modified mixed solution, magnetically stirring at normal temperature for 24 hours, then heating to 50 ℃, and continuing to react for 3 hours;
and cooling the mixed solution after reaction to room temperature, separately centrifuging and washing twice by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological insecticide.
Preferably, the added plant source microspheres, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine are 2g to 3g, 0.2g to 0.4g and 0.1g to 0.2g respectively in mass; the mass of the added catechol-modified polyvinyl alcohol is 0.1 g-0.15 g.
Preferably, the volume ratio of the N, N-dimethylformamide to the dimethyl sulfoxide in the mixed solution of the N, N-dimethylformamide and the dimethyl sulfoxide is 2: 1.
Compared with the prior art, the invention has the beneficial effects that:
in addition, the microspheres are modified with polymers with high foliage affinity on the surfaces of the microspheres, so that the hanging capacity of the insecticide on the foliage of plants can be improved, and the insecticide is prevented from being washed by rainwater. In conclusion, the pesticide improves the utilization rate of pesticide and reduces the pesticide residue in soil.
Detailed Description
In order to understand the present invention, the following examples are given to further illustrate the present invention. The following description is only a preferred embodiment of the present invention, and is only for the purpose of describing the present invention, and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The anti-scour biological insecticide provided by the invention is prepared by the following method:
s1 extracting plant-derived pesticide active substances from plants by supercritical fluid extraction, wherein the plant-derived pesticide is specifically extracted from neem seed, rotenone from derris root, pyrethrin from pyrethrum flower, and capsaicin from capsicum.
The invention uses supercritical fluid extraction method to extract plant source pesticide active substance in plant. The supercritical fluid extraction method has some characteristics of rectification and liquid-liquid extraction, and adopts low-temperature CO2Is an extractant, effectively prevents the oxidation and the dissipation of heat-sensitive substances; in addition, the device can extract substances which have high boiling points, low volatility and are easy to pyrolyze at the temperature below the boiling point; in addition, no organic solvent is used in the whole supercritical fluid extraction process, so that the extract has no residual solvent, and the harm to human body and environmental pollution in the extraction process are prevented.
S2, adding a certain amount of gelatin and CMC into distilled water respectively to dissolve the gelatin and the CMC to form a gelatin solution and a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution, wherein the mass concentration of the gelatin and the CMC in the mixed solution is 0.5-2%; wherein the mass ratio of the gelatin to the CMC is 7-11: 1 during mixing.
And S3, adding the extracted plant source pesticide active substances into the mixed solution, and emulsifying the mixed solution in a tissue mixer at the rotating speed of 8000-12000 r/min for 2-3 min to form a first emulsion, wherein the mass ratio of the total mass of the gelatin and the CMC to the plant source pesticide active substances is 7-11: 1.
S4, adjusting the pH to 4.5-5 by using a 10% acetic acid solution, adjusting the stirring temperature to 35-50 ℃, and stirring at a speed of 300-500 r/min to coagulate the first emulsion to form a second emulsion;
s5, adjusting the pH of the second emulsion to be neutral by using a 10% sodium hydroxide solution, and adding glutaminase to solidify the second emulsion to form microsphere dispersion liquid, wherein the mass percentage of the added glutaminase in the total reaction system is 0.5-1.5%, the stirring speed of 100-200 r/min needs to be kept during solidification, and the solidification time is 4-5 h;
and S6, washing the microsphere dispersion liquid by precipitation, carrying out suction filtration, and then carrying out freeze drying to obtain the plant source microspheres.
S7, adding 2g to 3g of plant source microspheres, 0.2g to 0.3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.1g to 0.2g of 4-dimethylaminopyridine into 40mL of mixed solution of N, N-dimethylformamide and 20mL of dimethyl sulfoxide for ultrasonic dispersion, and then magnetically stirring for 0.5h to 1h to prepare pre-modified mixed solution;
s8, dispersing 0.1g to 0.15g of polymer catechol modified polyvinyl alcohol in 6mL of mixed solution of N, N-dimethylformamide and 4mL of dimethyl sulfoxide, heating to 90 ℃ for complete dissolution, and cooling to room temperature; dropwise adding the obtained solution into the pre-modified mixed solution, magnetically stirring at normal temperature for 24 hours, then heating to 50 ℃, and continuing to react for 3 hours;
and S9, cooling the mixed solution after reaction to room temperature, separately centrifuging and washing twice by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological pesticide.
In this process, the polymer catechol-modified polyvinyl alcohol was prepared as follows:
a1, dispersing 2.5g of PVA-210 in 80mL of dimethylphenylene, continuously magnetically stirring at 85 ℃ until the solid is completely dissolved, and cooling to room temperature;
a2 to the solution obtained in the step A1 were added 2.5g of 3, 4-dihydroxybenzaldehyde and p-0.75 g of toluenesulfonic acid, and the mixture was magnetically stirred and reacted at 85 ℃ for 12 hours in an anaerobic atmosphere from which oxygen in the system was taken out by purging with nitrogen for 15 min.
A3: cooling the solution obtained in the step A2 to room temperature, slowly adding the solution into 400mL of acetone under magnetic stirring, and carrying out suction filtration and separation under reduced pressure to obtain light brown flaky precipitates;
a4: re-dispersing the precipitate obtained in the step A3 in 50mL of dimethyl sulfoxide, magnetically stirring at 85 ℃ until the precipitate is completely dissolved, cooling to room temperature, and repeating the operation in the step A3 until a white flaky precipitate is finally obtained;
and A5, performing Soxhlet extraction on the white flaky precipitate finally obtained in the step A4 by using dichloromethane under the protection of nitrogen, wherein the purification time is 48 hours, and finally obtaining the fibrous polymer catechol modified polyvinyl alcohol.
The invention uses plant pesticide as core material, which has good insecticidal effect, such as capsaicin has excellent treatment effect on controlling cabbage aphid and cabbage caterpillar, pyrethrin has toxic killing effect on various insects such as mosquito, fly, bugle and cockroach, azadirachtin has multiple effects of food refusal, avoidance, growth regulation and sterilization on insects, and rotenone has excellent insecticidal effect on cabbage butterfly larva, diamond back moth and aphid. And the pure natural botanical pesticide has the advantages of no pollution and no material.
In addition, the wall material of the pesticide is selected from gelatin and CMC, which are natural materials, and the pesticide has the advantages of no pollution and no environmental burden. The pesticide has a microcapsule connection structure, on one hand, the volume of the microcapsule structure is larger than that of common plant source pesticides, and once the microcapsule structure is reserved on plant leaves, the hanging and holding capacity of the microcapsule structure on the leaves is superior to that of the common plant source pesticides, so that the utilization efficiency of the pesticides can be improved, the application times of the pesticides are reduced, the pesticide residue in soil is avoided, and the soil quality is reduced. On the other hand, the microcapsule structure can provide a protective environment for effective insecticidal substances, can avoid the influence of sunlight, rainwater and the like on the properties of the plant-source pesticide to a certain extent, and ensures the insecticidal effect of the pesticide.
Most importantly, the surface of the microsphere pesticide is modified with a polymer with high leaf surface affinity, so that the suspension capacity and the anti-scouring capacity of the pesticide on the leaf surfaces of plants can be greatly improved; through this kind of modification method, make the insecticide can stay on the blade, can effectively avoid the rainwater to the influence of insecticide, promoted the utilization ratio of insecticide, in addition, the promotion of insecticide utilization ratio can reduce the number of times of giving medicine to the poor free of charge, has reduced cost of labor and pesticide cost, and in the past, can reduce pesticide residue, has avoided the pesticide to the change of soil property after flowing into soil, keeps the original ecology of soil, finally realizes the purpose of environmental protection.
The advantages of the scour resistant biopesticide are illustrated herein by the following examples which are set forth in greater detail and by the test of pesticidal effectiveness of the examples and comparative examples.
Example 1
S11: extracting nimbin from nim seed by supercritical fluid extraction.
S12, dissolving 14g of gelatin in 2800mL of distilled water to form a gelatin solution, dissolving 2g of CMC in 400mL of distilled water to form a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution.
S13 adding 32g of extracted azadirachtin into the mixed solution and emulsifying in a tissue mixer at 8000r/min for 2min to form a first emulsion.
S14, adjusting the pH to 4.5 by using 10% acetic acid solution, adjusting the stirring temperature to 35 ℃, the stirring speed to 300r/min and the stirring time to 40min, and coagulating the first emulsion to form a second emulsion;
and S15, adjusting the pH of the second emulsion to be neutral by using a 10% sodium hydroxide solution, and adding glutaminase to solidify the second emulsion to form a microsphere dispersion, wherein the mass percentage of the added glutaminase in the total reaction system is 0.5%, the stirring speed of 100r/min is required to be kept during solidification, and the solidification time is 4 h.
And S16, washing the microsphere dispersion liquid by precipitation, carrying out suction filtration, and then carrying out freeze drying to obtain the plant source microspheres.
S17, adding 2g of plant source microspheres, 0.2g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.1g of 4-dimethylaminopyridine into a mixed solution of 40mL of N, N-dimethylformamide and 20mL of dimethyl sulfoxide for ultrasonic dispersion, and then magnetically stirring for 0.5h to prepare a pre-modification mixed solution.
S18, dispersing 0.1g of polymer catechol-modified polyvinyl alcohol in 6mL of mixed solution of N, N-dimethylformamide and 4mL of dimethyl sulfoxide, heating to 90 ℃ for complete dissolution, and cooling to room temperature; the obtained solution is dripped into the pre-modified mixed solution, magnetically stirred for 24 hours at normal temperature, and then heated to 50 ℃ to continue the reaction for 3 hours. The polymer catechol-modified polyvinyl alcohol has been described in the above embodiments.
And S19, cooling the mixed solution after reaction to room temperature, separately centrifuging and washing twice by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological pesticide.
Example 2
S21: extracting rotenone from the roots of derris by supercritical fluid extraction.
And S22, dissolving 20g of gelatin in 2000mL of distilled water to form a gelatin solution, dissolving 2g of CMC in 200mL of distilled water to form a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution.
S23, adding 22g of extracted rotenone into the mixed solution and emulsifying in a tissue mixer at 10000r/min for 2.5min to form a first emulsion.
S24, adjusting the pH to 4.7 by using 10% acetic acid solution, adjusting the stirring temperature to 45 ℃, the stirring speed to 400r/min and the stirring time to 40min, and coagulating the first emulsion to form a second emulsion;
and S25, adjusting the pH of the second emulsion to be neutral by using a 10% sodium hydroxide solution, and adding glutaminase to solidify the second emulsion to form a microsphere dispersion, wherein the mass percentage of the added glutaminase in the total reaction system is 1%, the stirring speed of 150r/min is required to be kept during solidification, and the solidification time is 4.5 h.
And S26, washing the microsphere dispersion liquid by precipitation, carrying out suction filtration, and then carrying out freeze drying to obtain the plant source microspheres.
S27, adding 2.5g of plant source microspheres, 0.25g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.15g of 4-dimethylaminopyridine into 40mL of mixed solution of N, N-dimethylformamide and 20mL of dimethyl sulfoxide for ultrasonic dispersion, and then magnetically stirring for 0.75h to prepare pre-modification mixed solution;
s28, dispersing 0.13g of polymer catechol-modified polyvinyl alcohol in 6mL of mixed solution of N, N-dimethylformamide and 4mL of dimethyl sulfoxide, heating to 90 ℃ for complete dissolution, and cooling to room temperature; dropwise adding the obtained solution into the pre-modified mixed solution, magnetically stirring at normal temperature for 24 hours, then heating to 50 ℃, and continuing to react for 3 hours; the polymer catechol-modified polyvinyl alcohol has been described in the above embodiments.
And S29, cooling the mixed solution after reaction to room temperature, separately centrifuging and washing twice by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological pesticide.
Example 3
S31: supercritical fluid extraction is adopted to extract pyrethrin in the pyrethrum flower and capsaicin in the pepper.
And S32, dissolving 22g of gelatin in 1100mL of distilled water to form a gelatin solution, dissolving 2g of CMC in 100mL of distilled water to form a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution.
S33, adding 22g of pyrethrin and 10g of capsaicin into the mixed solution, and emulsifying for 3min in a tissue mixer at 12000r/min to form a first emulsion.
S34, adjusting the pH to 5 by using 10% acetic acid solution, adjusting the stirring temperature to 50 ℃, the stirring speed to 500r/min and the stirring time to 40min, and coagulating the first emulsion to form a second emulsion;
and S35, adjusting the pH of the second emulsion to be neutral by using a 10% sodium hydroxide solution, and adding glutaminase to solidify the second emulsion to form a microsphere dispersion, wherein the mass percentage of the added glutaminase in the total reaction system is 1.5%, the stirring speed of 200r/min is required to be kept during solidification, and the solidification time is 5 h.
And S36, washing the microsphere dispersion liquid by precipitation, carrying out suction filtration, and then carrying out freeze drying to obtain the plant source microspheres.
S37, adding 3g of plant source microspheres, 0.3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.2g of 4-dimethylaminopyridine into a mixed solution of 40mL of N, N-dimethylformamide and 20mL of dimethyl sulfoxide for ultrasonic dispersion, and magnetically stirring for 1h to prepare a pre-modification mixed solution;
s38, dispersing 0.15g of polymer catechol-modified polyvinyl alcohol in 6mL of mixed solution of N, N-dimethylformamide and 4mL of dimethyl sulfoxide, heating to 90 ℃ for complete dissolution, and cooling to room temperature; dropwise adding the obtained solution into the pre-modified mixed solution, magnetically stirring at normal temperature for 24 hours, then heating to 50 ℃, and continuing to react for 3 hours; the polymer catechol-modified polyvinyl alcohol has been described in the above embodiments.
And S39, cooling the mixed solution after reaction to room temperature, separately centrifuging and washing twice by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological pesticide.
And (3) testing the insect killing and expelling effect:
the insect killing and expelling effect is characterized by applying a certain amount of insecticide in a plant with diseases and insect pests, the quality of the applied insecticide is determined by controlling the quality of capsaicin to be equal, the number of dead insects in 7 days and 30 days is tested, and in 15 days, the rainwater is simulated to flush the plant once.
The death rate (%) < dead insect number/total insect number x 100%
Comparative example 1 is no pesticide application, comparative example 2 is a conventional plant-derived pesticide capsaicin applied in an amount equal to the mass of capsaicin applied in the examples, and comparative example 3 is plant-derived microspheres without surface modification.
Figure BDA0003204510770000091
Figure BDA0003204510770000101
It is apparent from comparative examples and comparative example 1 that the insecticide has excellent insecticidal effects, the insecticidal efficiency of the insecticide is 50.63% in seven days and 81.4% in 30 days, which are respectively improved by 40.93% and 71.7% compared with the blank control group. Through the comparative example and the comparative example 2, it can be found that although the insecticidal effect of the insecticide is basically equal to that of a common botanical insecticide in the initial stage, the insecticide still has good insecticidal effect in the later stage, particularly after a simulated rain day, and the preparation of the insecticide into microspheres can improve the hanging and retaining capacity of the insecticide to a certain extent, and the microsphere structure can achieve the purpose of slow release and improve the lasting effect of the insecticide. Compared with the comparative example 3, the embodiment of the insecticidal effect in 30 days is obviously superior to the comparative example, which proves that the polymer with high leaf surface affinity is modified on the surface of the insecticide microsphere to effectively improve the hanging and retaining capacity of the insecticide and improve the anti-scouring capacity.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, whereby the invention is not limited to the details given, without departing from the general concept defined by the claims and the scope of equivalents.

Claims (10)

1. An anti-scour biopesticide in a microsphere configuration, comprising: a plant source pesticide is taken as a core material of an insecticidal effective substance;
coating a core material, wherein gelatin and CMC are used as wall materials of the raw materials;
and a polymer with high leaf surface affinity modified on the surface of the wall material, wherein the polymer is catechol-modified polyvinyl alcohol; the insecticide is adhered to the surface of the leaf blade through excellent adhesion, and the function of resisting rain wash of the insecticide is achieved.
2. The scouring resistant biopesticide of claim 1, wherein the botanical pesticide is one or more of azadirachtin, rotenone, pyrethrin, capsaicin.
3. The scouring-resistant biopesticide according to claim 1, wherein the mass ratio of the core material to the wall material in the microspheres is 1: 0.5-3.
4. The scouring-resistant biopesticide of claim 1, wherein the mass ratio of gelatin to CMC is 7-11: 1.
5. The scour resistant biopesticide of claim 1, wherein the mass ratio of the polymer to the microspheres is 1: 20.
6. A method for preparing an anti-scour biopesticide according to any one of claims 1 to 5, comprising the steps of:
extracting plant source pesticide active substances in plants by a supercritical fluid extraction method;
respectively adding a certain amount of gelatin and CMC (carboxy methyl cellulose) into distilled water to dissolve the gelatin and the CMC to form a gelatin solution and a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution;
adding the extracted plant source pesticide active substance into the mixed solution and reacting to form a first emulsion;
coagulating the first emulsion to form a second emulsion by adjusting the pH to acidity and adjusting the stirring temperature and speed;
adjusting the pH of the second emulsion to be neutral, and adding glutaminase to solidify the second emulsion to form microsphere dispersion;
and (3) carrying out precipitation, washing, suction filtration and freeze drying on the microsphere dispersion to obtain the plant source microspheres.
Adding a certain amount of plant source microspheres, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide for ultrasonic dispersion, and then magnetically stirring to prepare a pre-modification mixed solution;
dispersing polymer catechol modified polyvinyl alcohol in a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, heating until the polymer catechol modified polyvinyl alcohol is completely dissolved, and cooling to room temperature; dropwise adding the obtained solution into the pre-modified mixed solution, magnetically stirring at normal temperature, and then heating to 50 ℃ for a period of time to continue reaction;
and cooling the mixed solution after reaction to room temperature, respectively centrifuging and washing by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological pesticide.
7. The scour resistant biopesticide of claim 6, wherein the catechol-modified polyvinyl alcohol is prepared by the steps of:
a1, dispersing PVA-210 in dimethylphenylene, continuously magnetically stirring until the solid is completely dissolved, and cooling to room temperature;
a2, adding 3, 4-dihydroxybenzaldehyde and p-methylbenzenesulfonic acid into the solution obtained in the step A1, and magnetically stirring and reacting in an anaerobic environment;
a3: cooling the solution obtained in the step A2 to room temperature, slowly adding the solution into acetone under magnetic stirring, and carrying out suction filtration and separation under reduced pressure to obtain light brown flaky precipitates;
a4: re-dispersing the precipitate obtained in the step A3 in dimethyl sulfoxide, continuously magnetically stirring until the precipitate is completely dissolved, cooling to room temperature, and repeating the operation in the step A3 until a white flaky precipitate is finally obtained;
and A5, performing Soxhlet extraction on the white flaky precipitate finally obtained in the step A4 by using dichloromethane under the protection of nitrogen, and finally obtaining the fibrous polymer catechol-modified polyvinyl alcohol.
8. The scour-resistant biopesticide of claim 6, wherein the preparation method comprises the steps of:
extracting plant source pesticide active substances in plants by a supercritical fluid extraction method;
respectively adding a certain amount of gelatin and CMC (carboxy methyl cellulose) into distilled water to dissolve the gelatin and the CMC to form a gelatin solution and a CMC solution, and mixing the gelatin solution and the CMC solution to form a mixed solution, wherein the mass concentration of the gelatin and the CMC in the mixed solution is 0.5-2%;
adding the extracted plant source pesticide active substance into the mixed solution, and emulsifying for 2-3 min in a tissue mixer at the rotating speed of 8000-12000 r/min to form a first emulsion;
adjusting the pH to 4.5-5 by using a 10% acetic acid solution, adjusting the stirring temperature to 35-50 ℃, and adjusting the stirring speed to 300-500 r/min to enable the first emulsion to be coagulated to form a second emulsion;
adjusting the pH of the second emulsion to be neutral by using a 10% sodium hydroxide solution, and curing the second emulsion to form a microsphere dispersion under the condition of adding glutaminase, wherein the mass percentage of the added glutaminase in a total reaction system is 0.5-1.5%, the stirring speed of 100-200 r/min needs to be kept during curing, and the required curing time is 4-5 h;
and (3) carrying out precipitation, washing, suction filtration and freeze drying on the microsphere dispersion to obtain the plant source microspheres.
Adding a certain amount of plant source microspheres, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine into 60mL of a mixed solution of N, N-dimethylformamide and dimethyl sulfoxide for ultrasonic dispersion, and magnetically stirring for 0.5-1 h to prepare a pre-modification mixed solution;
dispersing polymer catechol modified polyvinyl alcohol in 10mL of mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, heating to 90 ℃ for complete dissolution, and cooling to room temperature; dropwise adding the obtained solution into the pre-modified mixed solution, magnetically stirring at normal temperature for 24 hours, then heating to 50 ℃, and continuing to react for 3 hours;
and cooling the mixed solution after reaction to room temperature, separately centrifuging and washing twice by adopting ethanol and water, and freeze-drying to obtain the anti-scouring biological insecticide.
9. The scouring resistant biopesticide of claim 6, wherein the added amounts of the plant-derived microspheres, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride and 4-dimethylaminopyridine are 2g to 3g, 0.2g to 0.4g and 0.1g to 0.2g, respectively; the mass of the catechol-modified polyvinyl alcohol is 0.1 g-0.15 g.
10. The scour resistant biopesticide of claim 6, wherein the volume ratio of N, N-dimethylformamide to dimethyl sulfoxide in the mixed solution of N, N-dimethylformamide and dimethyl sulfoxide is 2: 1.
CN202110913399.2A 2021-08-10 2021-08-10 Anti-scour biological insecticide and preparation method thereof Withdrawn CN113678825A (en)

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