CN113717011A - Preparation method of pH/protease dual-response integrated pesticide-fertilizer - Google Patents
Preparation method of pH/protease dual-response integrated pesticide-fertilizer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C21/00—Methods of fertilising, sowing or planting
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/50—Surfactants; Emulsifiers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
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- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Health & Medical Sciences (AREA)
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- Plant Pathology (AREA)
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Abstract
The invention relates to the technical field of agricultural fertilizer and pesticide integration, in particular to a construction method of a pH/protease dual-response integrated pesticide fertilizer. The Metal Organic Framework (MOF) is used as a pesticide carrier, metal ions contained in the MOF can be used as micronutrient elements required by crops, the MOF carrying the pesticide is subjected to post-synthesis modification, and a hydrophobic polymer is wrapped on the outer layer of the MOF through polymerization, so that the slow release performance of the pesticide and the fertilizer is enhanced. The hydrophobic natural polymer is further wrapped, so that the pesticide and metal salt ions can be further loaded to improve the content of the pesticide and the fertilizer, and finally the integrated pesticide-fertilizer is prepared. The prepared integrated pesticide-fertilizer has high drug loading rate, good biological safety, excellent pH responsiveness and protease responsiveness, and can effectively kill pests and promote the growth of crops.
Description
Technical Field
The invention relates to the technical field of agricultural fertilizer and pesticide integration, in particular to a preparation method of a pH/protease dual-response integrated pesticide fertilizer.
Background
The rapidly growing world population places higher demands on food. The application of pesticide and fertilizer can increase crop yield and relieve the demand of grain in the aspect of yield, but has a plurality of outstanding problems of large dosage, low utilization rate and the like. According to statistics, millions of tons of pesticides and fertilizers are wasted due to leaching, evaporation, photolysis, chemical decomposition, biotransformation and the like every year in China, so that the ecological environment is seriously damaged, the food safety is threatened to a certain extent, and certain physiological toxicity exists on animals and human beings. Therefore, the utilization rate of the pesticide and the fertilizer is improved, and the direction and the target for reducing the harm of the pesticide and the fertilizer to human health and ecological environment are achieved.
The advent of slow release pesticides and fertilizers has greatly alleviated their use and safety issues. The slow release pesticide and fertilizer take a certain material as a carrier, the pesticide and fertilizer are loaded through chemical or physical action, and then the release rate and the release period of the pesticide and fertilizer are controlled under various mechanisms, so that the pesticide and fertilizer are ensured to stay in an action window, and the utilization rate of the pesticide and fertilizer is further improved. However, most of the existing slow-release pesticides and fertilizers are realized by mechanisms such as diffusion, osmotic pressure and the like, and the ideal controlled-release performance cannot be achieved. In addition, the pesticide and the fertilizer are used independently, so that the labor force is increased, and the production cost is increased. Therefore, the development of an integrated pesticide fertilizer with stimulation response becomes a trend of sustainable agricultural development, the precise release of pesticides and fertilizers is regulated and controlled through the external environment, and meanwhile, pest control and plant nutrition supply are realized.
Therefore, a preparation method of the pH/protease dual-response integrated pesticide-fertilizer is provided.
Disclosure of Invention
The invention aims to provide a preparation method of a pH/protease dual-response integrated pesticide-fertilizer. The prepared integrated pesticide-fertilizer has high drug loading rate, good biological safety, excellent pH responsiveness and protease responsiveness, and can effectively kill pests and promote the growth of crops.
The technical scheme adopted by the invention is as follows:
a preparation method of a pH/protease dual-response integrated pesticide fertilizer takes a Metal Organic Framework (MOF) as a pesticide carrier, metal ions contained in the MOF can be used as trace nutrient elements required by crops, the pH response release of the pesticide and the fertilizer is realized by the acid-base sensitivity of the MOF, then, the MOF carrying the pesticide is subjected to synthesis modification, and a hydrophobic polymer is wrapped on the outer layer of the MOF through polymerization to enhance the slow release performance of the pesticide and the fertilizer. The hydrophobic natural polymer is further wrapped, pesticide and metal salt ions can be further loaded to improve the content of the pesticide and the fertilizer, and protease in the pesticide and the fertilizer is released in a protease responsive manner through hydrolysis of protease in the pest body on the hydrophobic natural polymer. The integrated pesticide fertilizer prepared finally in the invention realizes the controllable release of pesticide and fertilizer through pH and protease, is expected to improve the utilization rate of pesticide and fertilizer and reduce the pollution to the environment.
Specifically, the preparation method of the pH/protease dual-response integrated pesticide-fertilizer comprises the following steps:
1) preparation of drug-loaded MOF
Slowly dripping the mixed aqueous solution of the pesticide and the metal salt into the mixed aqueous solution of the organic ligand and the surfactant, stirring for 0.8-1.2 min, standing for 1.6-2.4 h at room temperature, centrifuging, washing and drying to obtain the medicine-carrying MOF nano particles. Wherein the volume ratio of the mixed aqueous solution of the pesticide and the metal salt to the mixed aqueous solution of the organic ligand and the surfactant is 1: 0.8-1.2, and the mass usage ratio of the pesticide, the metal salt, the organic ligand and the surfactant is 1: 0.8-1.2: 2.9-4.5: 0.0024-0.0036.
2) Preparation of the ligands
Dispersing histamine dihydrochloride and triethylamine in an organic solvent under an ice bath condition, fully protecting with nitrogen, dropwise adding alpha-bromo isobutyryl bromide into the dispersion system, returning to room temperature for reacting overnight, quenching with 10% potassium hydroxide aqueous solution, extracting to obtain an organic phase, drying with anhydrous magnesium sulfate, carrying out vacuum filtration, and carrying out rotary evaporation to obtain the ligand. Wherein the concentration of the histamine dihydrochloride is 8-12 mg/mL, and the volume ratio of the triethylamine, the organic solvent, the alpha-bromoisobutyryl bromide and the 10% potassium hydroxide aqueous solution is 1: 26.4-39.6: 0.21-0.32: 26.4-39.6.
3) Post-synthetic modification of drug-loaded MOF
Carrying out ultrasonic treatment on the drug-loaded MOF (11.2-16.8 mg/mL) obtained in the step 1) in an organic solvent, adding the ligand obtained in the step 2) into the dispersion system, continuing ultrasonic dispersion for 4-6 min, stirring for 8-12 h at 80-120 ℃, centrifuging, washing and drying to obtain the modified drug-loaded MOF. Wherein the mass usage ratio of the medicine-carrying MOF to the ligand is 1: 0.90-1.35.
4) Preparation of modified drug-loaded MOF of hydrophobic polymer coating
Ultrasonically dispersing the modified drug loaded MOF (22.2-33.3 mg/mL) obtained in the step 3) in anhydrous methanol, sequentially adding a monomer, a catalyst and a ligand, sealing a reaction bottle, fully protecting with nitrogen, and injecting 0.8-1.2 mL of anhydrous methanol solution (13.6-20.4 mg/mL) of a reducing agent into the reaction bottle. Reacting at 28-42 ℃ for 8-12 h, centrifuging, washing with anhydrous methanol and toluene in sequence, and drying to obtain the modified drug-loaded MOF coated by the hydrophobic polymer. Wherein the molar ratio of the monomer, the initiator, the catalyst, the ligand and the reducing agent is 1: 0.0010-0.0015: 0.00024-0.00036: 0.0056-0.0084.
5) Preparation of modified drug-loaded MOF with double-layer coating
Dispersing the modified drug-loaded MOF (26.6-39.9 mg/mL) of the hydrophobic polymer coating obtained in the step 4) and a mixture of dissolved metal salt, hydrophobic natural polymer and pesticide respectively by using an ethanol aqueous solution containing 0.1% of surfactant, dropwise adding the dispersed modified drug-loaded MOF of the hydrophobic polymer coating into the mixed solution of the three after ultrasonic treatment, and stirring for 8-12 min at 20-30 ℃. And finally, carrying out centrifugation, washing and vacuum drying to obtain the modified medicine-carrying MOF with the double-layer coating, namely the integrated medicine fertilizer. Wherein the volume ratio of the required ethanol water solution is 1: 0.8-1.2, and the mass ratio of the modified drug-loaded MOF, the metal salt, the hydrophobic natural high-molecular compound and the pesticide of the hydrophobic polymer coating is 1: 0.48-0.72: 0.8-1.2: 0.72-1.08.
The organic ligand in the step 1) is 2-methylimidazole, and the pesticide, the metal salt and the surfactant in the step and the step 5) are dinotefuran, zinc acetate dihydrate and hexadecyl trimethyl ammonium bromide respectively.
The organic solvent in the step 2) is trichloromethane, and the organic solvent in the step 3) is n-butanol.
And 4) the monomer, the catalyst, the ligand and the reducing agent in the step 4) are methyl methacrylate, copper chloride, pentamethyldiethylenetriamine and ascorbic acid respectively.
The concentration of the ethanol aqueous solution in the step 5) is 85 percent.
The hydrophobic polymer and the hydrophobic natural polymer are polymethyl methacrylate and zein respectively.
The pH/protease dual-response integrated pesticide-fertilizer prepared by the method can be widely applied to the sustainable agricultural fields of crop pest control, nutrition supply and the like.
The invention has the following beneficial effects:
the integrated pesticide fertilizer disclosed by the invention has the advantages that good slow release performance is ensured, meanwhile, the controllable release of pesticide and fertilizer can be realized through the stimulation of pH and protease, particularly, when crops suffer from insect damage, the protease in an insect body can decompose the zein on the outer layer, and the accurate targeted release of pesticide is realized.
The integrated pesticide fertilizer disclosed by the invention fully utilizes the high specific surface area of the MOF and is combined with the double-shell layer, so that the pesticide loading is high and can reach 16.19% at most, the release in soil can reach more than 32 days, and the development of the MOF in the field of agricultural chemistry is promoted by the excellent slow-release performance.
The integrated pesticide fertilizer can be applied to soil to prevent and treat soil insects, and the internal pesticide is protected by the multi-shell layer, so that the washing resistance of the integrated pesticide fertilizer to underground runoff can be enhanced, and the prevention and treatment effect of the pesticide to the insects is improved.
The integrated pesticide fertilizer can also be sprayed on the leaf surface to prevent and control the pests on the leaf surface, the surface of the pesticide fertilizer is electropositive, the deposition of the pesticide fertilizer on electronegative leaves is facilitated, the pesticide in the pesticide fertilizer is protected by multiple shells, the ultraviolet resistance of the pesticide fertilizer is improved, and the effective period of the pesticide is prolonged.
The content of zinc ions in the integrated pesticide fertilizer can reach 21.13%, and the growth of crops such as corn and the like can be effectively promoted.
The integrated pesticide fertilizer has high biological safety to non-target organisms.
Drawings
Fig. 1 shows the release rate (a) of the pesticide in the integrated pesticide fertilizer under different pH conditions and the release rate (b) of the pesticide in the presence or absence of protease under the condition of pH 7.
FIG. 2 shows the release rates of the fertilizer in the integrated fertilizer under different pH conditions (a) and the release rates of the fertilizer under the condition of pH 7 in the presence or absence of protease (b).
FIG. 3 is a comparison graph of the lethality of the integrated insecticide-fertilizer and pure pesticide to pests, wherein (a) is the first-time insecticidal efficiency, and (b) is the second-time insecticidal efficiency.
FIG. 4 is a statistical analysis of height, root length, wet weight and dry weight of corn plants after 35 days of cultivation with integrated insecticide fertilizer.
Detailed Description
The present invention will be described in more detail by the following examples, which should be construed as being merely illustrative of preferred embodiments of the present invention and not limitative of the remainder of the disclosure.
Example 1
Preparation of drug-loaded MOF
11.165g of 2-methylimidazole and 9.109mg of hexadecyl trimethyl ammonium bromide are added into a round bottom flask, 3.0g of dinotefuran and 3.0g of zinc acetate dihydrate are added into another round bottom flask, and are dissolved by 50mL of deionized water respectively, the dissolved dinotefuran and zinc acetate dihydrate solution are slowly added into the mixed solution of the 2-methylimidazole and the hexadecyl trimethyl ammonium bromide in a dropwise manner, the mixture is stirred for 1min, the mixture is stood at room temperature for 2h and then centrifuged (12000rpm,10min), and the precipitate is fully washed by the deionized water to obtain the MOF drug-loaded nanoparticles.
Example 2
Preparation of the ligands
After dispersing 2.0g of histamine dihydrochloride and 6.043mL of triethylamine in 200mL of chloroform under ice bath and sufficiently protecting with nitrogen, 1.62mL of α -bromoisobutyryl bromide was slowly added dropwise to the above dispersion, the temperature was returned to room temperature, and the reaction was carried out overnight. After the reaction is finished, the reaction system is quenched in 200mL of 10% potassium hydroxide aqueous solution, an organic phase is extracted, dried by anhydrous magnesium sulfate, subjected to vacuum filtration, and rotary evaporated to obtain the ligand.
Example 3
Post-synthetic modification of drug-loaded MOF
And (2) carrying out ultrasonic treatment on 0.28g of the drug-loaded MOF obtained in the example 1 in 20mL of n-butanol for 30min, then adding 0.315g of the ligand obtained in the example 2 into the dispersion system for ultrasonic dispersion for 5min, stirring in an oil bath at 100 ℃ for 10h, after the reaction is finished, centrifuging (1000rpm,10min) and washing with distilled water for three times, and drying to obtain the modified drug-loaded MOF.
Example 4
Preparation of modified drug-loaded MOF (Metal organic framework) of polymethyl methacrylate (PMMA) envelope
100mg of the modified drug loaded MOF obtained in example 3 is ultrasonically dispersed in absolute methanol for 30min, 1.44mL of purified methyl methacrylate, 0.7mg of copper chloride and 0.9mL of pentamethyldiethylenetriamine are sequentially added into the modified drug loaded MOF, then a reaction bottle is sealed, and after nitrogen protection is carried out for 30min, 1mL of an absolute methanol solution (17mg/mL) of ascorbic acid is slowly injected into the reaction bottle. And (3) continuously protecting the mixture with nitrogen for 10min, reacting at the temperature of 35 ℃ for 10h, centrifuging (1000rpm for 10min), washing the obtained precipitate with anhydrous methanol to remove unreacted monomers, washing away free polymers with toluene, and drying to obtain the modified drug-loaded MOF coated with the polymethyl methacrylate.
Example 5
Preparation of modified drug-loaded MOF with double-layer coating
Respectively dispersing and dissolving 200mg of the modified drug-loaded MOF of the polymethyl methacrylate coating film obtained in the embodiment 4, 180mg of dinotefuran, 120mg of zinc acetate dihydrate and 200mg of zein by using 6mL of 85% ethanol aqueous solution containing 0.1% of hexadecyl trimethyl ammonium bromide, dropwise adding the dispersed modified drug-loaded MOF of the polymethyl methacrylate coating film into the mixed solution of the three, stirring for 10min at 25 ℃, and finally centrifuging (1000rpm,10min), washing and drying to obtain the modified MOF drug-loaded double-layer coating film, namely the integrated drug fertilizer.
The beneficial effects of the present invention are further illustrated by the following experimental examples:
fig. 1 shows the release rate of dinotefuran in the integrated fertilizer under different pH conditions (a) and the release rate of dinotefuran in the presence or absence of protease under the pH of 7 (b), and as shown in the figure, the release rates of dinotefuran reach 76.5% and 54.9% after 120h in phosphate buffer solutions with pH of 5.0 and 7.0, respectively, which indicates that the release rate of dinotefuran in the integrated fertilizer has good slow release performance and shows obvious responsiveness to pH, while the release rate of dinotefuran after 120h after adding protease in phosphate buffer solution with pH of 7 is 66.4% and is about 1.2 times under the condition of no protease, which indicates that the release rate of dinotefuran in the integrated fertilizer also shows obvious responsiveness to protease.
Fig. 2 shows the release rate (a) of zinc ions in the integrated fertilizer under different pH conditions and the release rate (b) in the presence or absence of protease under pH 7. As shown in the figure, the release rates of zinc ions in phosphate buffer solutions with pH 5.0 and 7.0 after 120h were 18.6% and 3.6%, respectively, and after protease was added to phosphate buffer solution with pH 7, the release rate of zinc ions after 120h was 6.1%, indicating that the release of zinc ions showed significant responsiveness to both pH and protease.
The release process of dinotefuran and zinc ions is explained as follows: under the action of protease, the zein at the outermost layer is hydrolyzed, firstly, dinotefuran and zinc ions loaded in the coating layer are released, the polymethyl methacrylate exposed at the outer layer is tightly coated on the surface of the MOF, the water is slowed down to enter the MOF pore passage, the MOF is dissociated along with the prolonging of time, and the dinotefuran and the zinc ions in the MOF are gradually released. Under acidic conditions, large amounts of H+Enrichment at the surface of the MOF allows the MOF to dissociate more quickly, allowing the internal dinotefuran and zinc ions to be released more quickly, exhibiting a clear pH response. The pesticide and the fertilizer can be accurately released by regulating and controlling the pH and the protease, the utilization efficiency of the pesticide and the fertilizer is improved, and the negative influence on the environment is reduced.
FIG. 3 is a comparison graph of the lethality of the pure pesticide and the integrated pesticide fertilizer to pests, wherein (a) is the primary pesticidal efficiency, and (b) is the secondary pesticidal efficiency. As shown in the figure, after 48 hours, the primary pest killing rate of the pure pesticide and the integrated pesticide fertilizer is 100 percent and 96.6 percent respectively, and the pest killing rate of the integrated pesticide fertilizer is slightly lower than that of the pure pesticide, because a certain time is needed for releasing the pesticide in the integrated pesticide fertilizer. And then, the substrate containing the pure pesticide and the integrated pesticide fertilizer is washed by deionized water in the primary insecticidal stage, the pests are put in the substrate again after the substrate is dried, and after 72 hours, the secondary insecticidal rates of the pure pesticide and the integrated pesticide fertilizer to the pests are respectively 63.3% and 96.6%, so that the enhancement of the washing capacity of the pesticide in the integrated pesticide fertilizer to the underground runoff is demonstrated, the effective period of the pesticide is prolonged, and the utilization rate of the pesticide is improved. The above results directly demonstrate that the present invention can be effectively used for pest management.
FIG. 4 is a statistical analysis of height, root length, wet weight and dry weight of corn plants after 35 days of cultivation with integrated insecticide fertilizer. As shown in the figure, the height, root length, wet weight and dry weight of the corn plant are respectively increased by 18.44%, 3.84%, 20.12% and 29.69% compared with the blank group after the corn plant is cultured for 35 days by using the integrated pesticide fertilizer, and the data show that the invention can effectively promote the growth of crops.
The integrated pesticide fertilizer constructed by the invention can accurately regulate and control the release of pesticide and fertilizer through pH and protease, improves the utilization rate of pesticide and fertilizer, prolongs the effective period, fully exerts the characteristics of pesticide effect and lasting fertilizer effect, not only can effectively prevent and control pests, but also can provide trace nutrient elements for crops and promote the growth of crops. The invention can reduce the times of spraying and fertilizing in the aspect of crop management, saves labor, time and labor and has wide application prospect in the field of sustainable agriculture.
Claims (9)
1. A preparation method of a pH/protease dual-response integrated pesticide-fertilizer comprises the following steps:
1) preparation of drug-loaded MOF
Slowly dripping a mixed aqueous solution of pesticide and metal salt into a mixed aqueous solution of organic ligand and surfactant, stirring for 0.8-1.2 min, standing for 1.6-2.4 h at room temperature, centrifuging, washing and drying to obtain medicine-carrying MOF nanoparticles; wherein the volume ratio of the mixed aqueous solution of the pesticide and the metal salt to the mixed aqueous solution of the organic ligand and the surfactant is 1: 0.8-1.2, and the mass usage ratio of the pesticide, the metal salt, the organic ligand and the surfactant is 1: 0.8-1.2: 2.9-4.5: 0.0024-0.0036;
2) preparation of the ligands
Dispersing histamine dihydrochloride and triethylamine in an organic solvent under an ice bath condition, fully protecting with nitrogen, dropwise adding alpha-bromo isobutyryl bromide into the dispersion system, recovering to room temperature for reaction overnight, quenching with 10% potassium hydroxide aqueous solution for reaction, extracting to obtain an organic phase, drying with anhydrous magnesium sulfate, performing vacuum filtration, and performing rotary evaporation to obtain a ligand; wherein the concentration of the histamine dihydrochloride is 8-12 mg/mL, and the volume ratio of the triethylamine, the organic solvent, the alpha-bromoisobutyryl bromide and the 10% potassium hydroxide aqueous solution is 1: 26.4-39.6: 0.21-0.32: 26.4-39.6;
3) post-synthetic modification of drug-loaded MOF
Carrying out ultrasonic treatment on the drug-loaded MOF (11.2-16.8 mg/mL) obtained in the step 1) in an organic solvent, adding the ligand obtained in the step 2) into the dispersion system, continuing ultrasonic dispersion for 4-6 min, stirring for 8-12 h at 80-120 ℃, centrifuging, washing and drying to obtain the modified drug-loaded MOF; wherein the mass usage ratio of the medicine-carrying MOF to the ligand is 1: 0.90-1.35;
4) preparation of modified drug-loaded MOF of hydrophobic polymer coating
Ultrasonically dispersing the modified drug loaded MOF (22.2-33.3 mg/mL) obtained in the step 3) in anhydrous methanol, sequentially adding a monomer, a catalyst and a ligand, sealing a reaction bottle, fully protecting with nitrogen, injecting 0.8-1.2 mL of an anhydrous methanol solution (13.6-20.4 mg/mL) of a reducing agent into the reaction bottle, reacting at 28-42 ℃ for 8-12 h, centrifuging, sequentially washing with anhydrous methanol and toluene, and drying to obtain the modified drug loaded MOF wrapped by a hydrophobic polymer; wherein the molar usage ratio of the monomer, the initiator, the catalyst, the ligand and the reducing agent is 1: 0.0010-0.0015: 0.00024-0.00036: 0.0056-0.0084;
5) preparation of modified drug-loaded MOF with double-layer coating
Dispersing the modified drug-loaded MOF (26.6-39.9 mg/mL) of the hydrophobic polymer coating obtained in the step 4) and a mixture of dissolved metal salt, a hydrophobic natural polymer and a pesticide by using an ethanol aqueous solution containing 0.1% of a surfactant, performing ultrasonic treatment, dropwise adding the modified drug-loaded MOF of the dispersed hydrophobic polymer coating into the mixed solution of the three, stirring for 8-12 min at 20-30 ℃, and finally performing centrifugation, washing and vacuum drying to obtain the modified drug-loaded MOF of the double-layer coating, namely the integrated drug fertilizer; wherein the volume ratio of the required ethanol water solution is 1: 0.8-1.2, and the mass ratio of the modified drug-loaded MOF, the metal salt, the hydrophobic natural high-molecular compound and the pesticide of the hydrophobic polymer coating is 1: 0.48-0.72: 0.8-1.2: 0.72-1.08.
2. The preparation method of the pH/protease dual-response integrated pesticide-fertilizer of claim 1, characterized by comprising the following steps: the organic ligand and the surfactant are respectively 2-methylimidazole and hexadecyl trimethyl ammonium bromide, and the pesticide and the metal salt are respectively dinotefuran and zinc acetate dihydrate.
3. The preparation method of the pH/protease dual-response integrated pesticide-fertilizer of claim 1, characterized by comprising the following steps: the organic solvent in the step 2) is trichloromethane, and the organic solvent in the step 3) is n-butanol.
4. The preparation method of the pH/protease dual-response integrated pesticide-fertilizer of claim 1, characterized by comprising the following steps: the monomer, the catalyst, the ligand and the reducing agent are methyl methacrylate, copper chloride, pentamethyldiethylenetriamine and ascorbic acid respectively.
5. The preparation method of the pH/protease dual-response integrated pesticide-fertilizer of claim 1, characterized by comprising the following steps: the concentration of the ethanol aqueous solution is 85%.
6. The preparation method of the pH/protease dual-response integrated pesticide-fertilizer of claim 1, characterized by comprising the following steps: the hydrophobic polymer and the hydrophobic natural polymer are polymethyl methacrylate and zein respectively.
7. A preparation method of a pH/protease dual-response integrated pesticide-fertilizer is characterized by comprising the following steps: prepared by the process of any one of claims 1 to 6.
8. The preparation method of the pH/protease dual-response integrated pesticide-fertilizer of claim 1, characterized by comprising the following steps: the pesticide loading was 16.19%.
9. The pH/protease dual-response integrated pesticide-fertilizer of claim 7 can be widely applied to the sustainable agricultural fields of crop pest control, nutrition supply and the like.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115843809A (en) * | 2022-12-29 | 2023-03-28 | 福建农林大学 | Climate response type nano herbicide and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115843809A (en) * | 2022-12-29 | 2023-03-28 | 福建农林大学 | Climate response type nano herbicide and preparation method thereof |
| CN115843809B (en) * | 2022-12-29 | 2023-09-08 | 福建农林大学 | Weather-responsive nano herbicide and preparation method thereof |
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