CN116584480A - Preparation method and application of metal organic framework nano pesticide controlled release agent - Google Patents
Preparation method and application of metal organic framework nano pesticide controlled release agent Download PDFInfo
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- CN116584480A CN116584480A CN202310468821.7A CN202310468821A CN116584480A CN 116584480 A CN116584480 A CN 116584480A CN 202310468821 A CN202310468821 A CN 202310468821A CN 116584480 A CN116584480 A CN 116584480A
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- pesticide
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- controlled release
- release agent
- metal
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- 238000013270 controlled release Methods 0.000 title claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 81
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
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- 229920001661 Chitosan Polymers 0.000 claims abstract description 51
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 35
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- 239000002086 nanomaterial Substances 0.000 claims abstract description 20
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- 239000013110 organic ligand Substances 0.000 claims description 22
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 12
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- HVCDAMXLLUJLQZ-UHFFFAOYSA-N 4-[3,6,8-tris(4-carboxyphenyl)pyren-1-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C1=CC=C23)=CC(C=4C=CC(=CC=4)C(O)=O)=C(C=C4)C1=C2C4=C(C=1C=CC(=CC=1)C(O)=O)C=C3C1=CC=C(C(O)=O)C=C1 HVCDAMXLLUJLQZ-UHFFFAOYSA-N 0.000 claims description 6
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- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 5
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- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 43
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Classifications
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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
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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
- A01N25/22—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 ingredients stabilising the active ingredients
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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
- A01N25/30—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
- 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
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Abstract
The invention belongs to the field of pesticide preparations, and in particular relates to a preparation method and application of a metal organic framework nano pesticide controlled release agent, which comprises the following steps: dispersing a nano-sized MOF material with larger mesopores in an organic solvent, adding a pesticide active ingredient, filling the pesticide active ingredient into a pore canal of the MOF nano material, and carrying out centrifugal separation to obtain a drug-loaded MOF nano material; dispersing the obtained product in an aqueous solution containing lignosulfonate, stirring, and centrifugally separating to obtain a lignosulfonate-encapsulated MOF nano pesticide controlled release agent; dispersing the obtained product in an aqueous solution containing chitosan, stirring, centrifuging, separating, washing and drying to obtain the target product lignin sulfonate and chitosan double-encapsulated MOF nano pesticide controlled release agent. The invention is suitable for large-size pesticide molecules, and has the characteristics of simple preparation, low cost, high pesticide loading capacity, resistance to pesticide ultraviolet degradation and the like.
Description
Technical Field
The invention belongs to the field of pesticide preparations, and in particular relates to a preparation method and application of a metal organic framework nano pesticide controlled release agent.
Background
Grain safety and food safety are basic guarantees for human life and healthy life. Only if the crop yield of the existing cultivated land area is continuously improved, the requirements of food and agricultural products with continuously increased global population can be met. As long as crops exist, harmful organisms (such as pathogens, pests and the like) exist, and pesticides are needed for prevention and control. The use of pesticides plays an irreplaceable role in improving crop and agricultural product yield. However, due to pesticide spray droplet drift, crop leaf surface liquid medicine roll-off, rain wash, ultraviolet photolysis and the like, the actual utilization rate of the target organism to the traditional pesticide preparation is lower than 0.1%. In order to cope with extremely low pesticide utilization, it is necessary to control pests with excessive amounts of pesticides, which inevitably results in ecological environmental pollution, pesticide residues in agricultural products, and ultimately poses serious threat to human public health. The off-target loss of pesticides is a key problem of extremely low use efficiency of traditional pesticide preparations. In order to reduce the pesticide dosage and improve the pesticide effect, the water-based nano pesticide controlled release agent with small size and high specific surface area is expected to solve the key problems of the traditional pesticide preparation. The nano pesticide is a pesticide preparation product created by utilizing nano materials and a preparation technology to effectively and efficiently combine raw medicines, carriers and auxiliary agents. In 2019, the International Union of Pure and Applied Chemistry (IUPAC) first released ten new technologies of chemistry that change the world annually, nano pesticides were first. The water-based nano pesticide preparation can obviously improve the apparent dispersity of the pesticide in water, increase the deposition and retention of the pesticide on the leaf surfaces of crops, realize the controlled release of the pesticide, improve the bioavailability of the pesticide and reduce the dosage of the pesticide.
In recent years, nanofarmers based on Metal Organic Frameworks (MOFs)Drugs have attracted great attention. MOFs are a porous crystalline material formed by coordination of metal ions/metal oxygen clusters and various organic ligands. Currently, MOF nano pesticide research works are mainly based on two widely used MOF materials (e.g., ZIF-8 and UIO-66). ZIF-8 (made of Zn) 2+ Coordinated with 2-methylimidazole) has a cage of 1.16 nm, connected by a small window of 0.34 nm. Due to the small window aperture of ZIF-8, pesticide molecules cannot be loaded in the synthetic ZIF-8 material. Pesticide molecules can only be mixed in the ZIF-8 material in the presence of pesticide active ingredients in the process of preparing the ZIF-8 by a one-pot method. UiO-66 (made of Zr IV Oxygen clusters and terephthalic acid) have 1.1 nm octahedral cages and 0.8 nm tetrahedral cages in a ratio of 1:2, connected by triangular windows of 0.6 nm. The small size of the cage and triangular window makes it difficult to load pesticide molecules into the smaller micropores of UiO-66, where the pesticide molecules are mainly adsorbed on the surface of the UiO-66 material. These research systems do not fully utilize the pore structure of MOF materials, and in addition, it is difficult to prepare intelligent controlled release nano pesticides by using similar MOF materials such as ZIF-8 and UiO-66. By selecting a porous material with large pores<2 nm) or mesoporous (2-50 nm), good biocompatibility, high thermal, mechanical and chemical stability, which are capable of loading pesticide molecules in large micropores or mesopores and then encapsulating the surfaces thereof to prepare the MOF nano pesticide controlled release agent.
Avermectin (AVM) is a biological pesticide produced by fermentation of Streptomyces griseus in Streptomyces griseus, and interferes with neurophysiologic activity, paralysis and killing of pests by stimulating release of gamma-aminobutyric acid and the like which have an inhibitory effect on nerve conduction of arthropods. However, avermectin having a 16-membered macrolide structure has the disadvantages of poor water solubility, easiness in ultraviolet degradation and the like, so that the insecticidal effect of the avermectin is affected. The emamectin benzoate is a novel efficient semisynthetic antibiotic pesticide synthesized from avermectin, and the action mechanism of the emamectin benzoate is basically the same as that of the avermectin. The emamectin benzoate has the characteristics of super-high efficiency, low toxicity, low residue, no public hazard and the like, has been widely applied to the control of various pests on crops such as vegetables, fruit trees, tobacco, tea, cotton, soybeans and the like, has insecticidal activity improved by 3 orders of magnitude compared with abamectin, and has no harm to beneficial insects in the process of controlling the pests. However, emamectin benzoate still has the disadvantages of poor water solubility and susceptibility to ultraviolet light degradation. The beta-cypermethrin is a broad-spectrum pesticide, is not systemic, but has the effects of contact killing and stomach toxicity, and damages the nervous system function of pests through interaction with sodium channels of the pests. Because the avermectin and the emamectin benzoate belong to biological pesticides, the insecticidal process is slow, and for crops with a large number of insect pests, the avermectin or the emamectin benzoate and the beta-cypermethrin are compounded for use, so that the quick-acting property is good, the insecticidal effect is wider, the price is low, and the lasting period is long. Pyraclostrobin is a broad-spectrum bactericide, and can finally lead to cell death by inhibiting mitochondrial respiration, and has the advantages of protection, treatment, permeation, systemic conductivity and rain wash resistance, longer duration and wider application range. Besides the direct action on pathogenic bacteria, pyraclostrobin can also improve the absorption of crops on nitrogen, so that the rapid growth of crops is promoted, the yield of crops is improved, and the aim of high yield of crops is fulfilled. It is worth pointing out that avermectin, emamectin benzoate, beta-cypermethrin and pyraclostrobin all have relatively large molecular sizes, and only large mesoporous MOF nano-carriers can be effectively loaded into the pore canal to prepare the nano-preparation, so that the problems of large mesoporous MOF surface encapsulation and early pesticide leakage are brought at the same time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method and application of the metal organic framework nano pesticide controlled release agent which are particularly suitable for large-size pesticide molecules, simple in preparation, low in cost, high in pesticide loading capacity, resistant to pesticide ultraviolet degradation and capable of promoting pesticide application reduction and efficiency enhancement.
In order to solve the technical problems, the invention is realized as follows:
the preparation method of the metal organic framework nano pesticide controlled release agent comprises the following steps:
step 1: dispersing the metal organic frame nano material in an organic solvent A, adding a pesticide active ingredient, stirring at room temperature, filling the pesticide active ingredient into a pore canal of the metal organic frame nano material, and centrifugally separating to obtain the drug-loaded metal organic frame nano material;
step 2: dispersing the drug-loaded metal organic framework nano material obtained in the step 1 in an aqueous solution containing lignosulfonate, stirring at room temperature, and centrifugally separating to obtain a lignosulfonate-encapsulated metal organic framework nano pesticide controlled release agent;
step 3: dispersing the lignosulfonate encapsulated metal organic framework nano pesticide obtained in the step 2 in an aqueous solution containing chitosan, stirring at room temperature, centrifuging, separating, washing and drying to obtain the target product lignosulfonate and chitosan double encapsulated metal organic framework nano pesticide controlled release agent.
Further, the metal organic framework nano material in the step 1 is PCN-777 nano particles or NU-1000 nano particles.
Further, the preparation method of the PCN-777 nano-particles comprises the following steps: zrOCl 2 ·8H 2 O and organic ligand 2,4, 6-tri (4' -carboxyphenyl) -1,3, 5-triazine are dissolved in an organic solvent B according to the mol ratio of 10-2:1, trifluoroacetic acid with the molar equivalent of 10-55 of the organic ligand is added, the mixture is uniformly mixed, the mixture is placed in a reaction kettle for reaction at the temperature of 110-160 ℃ for 5-24 h, cooled to room temperature, centrifugally separated, washed by an organic solvent B and an organic solvent A respectively, and dried to obtain PCN-777 nano particles.
Further, the preparation method of the NU-1000 nano particles comprises the following steps: zrCl is added to 4 Dissolving organic ligand 1,3,6, 8-tetra (4' -carboxyphenyl) pyrene in an organic solvent B according to the molar ratio of 20-5:1, adding 1000-4000 molar equivalents of acetic acid of the organic ligand, adding water according to the volume ratio of acetic acid to water of 5:0-3, uniformly mixing, placing in a reaction kettle, reacting at 70-120 ℃ for 0.3-3 h, cooling to room temperature, centrifugally separating, respectively carrying out solvent exchange by using the organic solvent B and the organic solvent A, and drying to obtain NU-1000 nano particles。
Further, the organic solvent A is at least one of ethanol and acetone.
Further, the organic solvent B is at least one of dimethylformamide or diethylformamide.
Further, the pesticide active ingredient is one or a mixture of more than two of abamectin, emamectin benzoate, beta-cypermethrin and pyraclostrobin.
Further, the mass ratio of the metal organic framework nano material to the pesticide active ingredient in the step 1 is 1:0.5-10; the concentration of the pesticide active ingredient in the organic solvent A is 4-100 g/L.
Further, the lignosulfonate is at least one of sodium lignosulfonate or calcium lignosulfonate; the mass ratio of the lignosulfonate to the chitosan is 1:0-5; the mass ratio of the metal organic framework nano material to the lignosulfonate is 1:0.2-5.
The product obtained by the preparation method of the metal organic framework nano pesticide controlled release agent is applied to pesticide control, and the pesticide release is controlled by environmental factors; the environmental factor is one or the combination of more than two of pH value, laccase, phosphate and phytic acid.
The invention discloses a preparation method and a pesticide controlled release method of a MOF nano pesticide controlled release agent which are particularly suitable for large-size pesticide molecules, simple in preparation, low in cost, high in pesticide loading capacity and resistant to pesticide ultraviolet degradation. Highly stable zeolite type mesoporous PCN-777 (from Zr IV Oxygen cluster and 2,4, 6-tris (4' -carboxyphenyl) -1,3, 5-triazine coordinated with 3.5 nm of the larger mesogen Kong Long, NU-1000 (from Zr) IV Oxygen cluster and 1,3,6, 8-tetra (4' -carboxyphenyl) pyrene coordinate to form a large mesoporous cage with 3 nm. The MOF material with larger mesopores can be loaded with pesticide molecules with larger size to prepare nano pesticide controlled release agent, prevent pesticide ultraviolet degradation, improve the prevention and control effect on target organisms and reduce the toxicity on non-target organisms. To date, there is no material for PCN-777 as a drugThere is no report on NU-1000 materials as pesticide nanocarriers. Lignin is a natural polymer, one of the components constituting the plant cell wall, and its content is inferior to cellulose and chitin. The molecular structure of lignin has active groups such as aryl, phenolic hydroxyl, alcoholic hydroxyl, carbonyl, conjugated double bond and the like. The use of lignin is mostly utilized in the form of lignin sulfonate. Sodium lignin sulfonate and calcium lignin sulfonate are nontoxic, soluble in water, strong in dispersing ability, low in cost and environment-friendly. By strong complexation (MOF surface coordinates unsaturated Zr IV Phenolic hydroxyl groups of sites and lignosulfonate), electrostatic action (positive charges on the surface of MOF and sulfonate anions of lignosulfonate), and the like, and the lignosulfonate is encapsulated on the surface of drug-loaded PCN-777 or NU-1000 nano particles, so that the lignosulfonate encapsulated MOF nano pesticide controlled release agent is prepared. Further, through electrostatic action and hydrogen bonding action between chitosan and lignosulfonate, chitosan is encapsulated on the surfaces of lignosulfonate encapsulated drug-loaded MOF nano-particles, so that the lignosulfonate and chitosan double-encapsulated MOF nano-pesticide controlled release agent is prepared, and the double-encapsulation can obtain better pesticide encapsulation performance and prevent pesticide from leaking in advance. The organic ligand and the lignosulfonate of the MOF nanomaterial have obvious absorption to ultraviolet light and can resist ultraviolet degradation of pesticides loaded in the MOF pore canal. According to the characteristics of plant diseases and insect pests, the properties of lignosulfonate, the properties of MOF materials and the physiological environment of crops, the invention discloses a few stimulus-responsive pesticide control release methods: pH (crops, pathogens, pests), laccase (polyphenol oxidase; cell wall of plants, pathogens, pests), phosphate (plants), phytic acid (inositol hexaphosphate; plants). The preparation method of the MOF nano pesticide controlled release agent is particularly suitable for large-size pesticide molecules (including the pesticide molecules with the small-size Yu Jiekong pore canal), has the advantages of simple preparation, low cost, high pesticide loading capacity, resistance to pesticide ultraviolet degradation and the like, promotes pesticide application reduction and synergy, and solves the key problems faced by the traditional pesticide preparation.
Compared with the prior art, the invention has the following beneficial effects:
1. PCN-777 has a larger mesoporous Kong Long of 3.5 nm and NU-1000 has a larger mesoporous cage of 3 nm. The MOF nano-materials with larger mesopores are particularly suitable for loading pesticide molecules (abamectin, emamectin benzoate, high-efficiency cypermethrin, pyraclostrobin and the like) with larger sizes, and the MOF nano-pesticide controlled release agent is prepared, so that the prevention and control effects on target organisms are improved, the toxicity on non-target organisms is reduced, and the purpose of pesticide decrement and synergy is achieved.
2. Phenolic hydroxyl of lignosulfonate coordinates unsaturated Zr with MOF surface IV The strong multiple coordination action between sites, the electrostatic action between sulfonate ions of lignosulfonate and the surface of MOF with positive charges and the like, so that the lignosulfonate is firmly encapsulated on the surface of PCN-777 or NU-1000 nano particles carrying medicines, and the prepared lignosulfonate encapsulated MOF nano pesticide controlled release agent can realize the pesticide controlled release purpose. Further, the MOF nano pesticide controlled release agent double-encapsulated by lignosulfonate and chitosan is prepared, so that better pesticide encapsulation performance can be obtained, the pesticide is prevented from leaking in advance, and the pesticide controlled release application is met. Both lignosulfonate and chitosan are natural polymers, and are nontoxic, low in cost and environment-friendly.
3. The pesticide loading rate in the MOF nano pesticide controlled release agent double-encapsulated by lignosulfonate and chitosan is 25 percent (mass percent), and the pesticide loading rate is high, so that the MOF nano pesticide controlled release dosage form with low concentration can achieve the effect of preventing and controlling plant diseases and insect pests, reduce the production cost of users, and also reduce the difficulty of the dosage form in the aspects of preparation, spraying and the like.
4. The organic ligand and the lignosulfonate of the MOF nano material have obvious absorption to ultraviolet light, can resist the ultraviolet light degradation of pesticides loaded in MOF pore channels, and improve the effective utilization rate of pesticides.
5. According to the characteristics of plant diseases and insect pests, the properties of lignosulfonate, the properties of MOF materials and the physiological environment of crops, the invention discloses a few stimulus-responsive pesticide control release methods: pH (acidity, alkalinity), laccase, phosphate and phytic acid, the pesticide controlled release application of the MOF nano pesticide controlled release agent is realized, the prevention and control effects on target organisms are improved, and simultaneously the toxicity on non-target organisms is reduced.
6. The preparation method of the MOF nano pesticide controlled release agent is particularly suitable for large-size pesticide molecules, has the advantages of simplicity in preparation, low cost, high pesticide loading capacity, resistance to pesticide ultraviolet degradation and the like, promotes pesticide application reduction and synergy, and solves the key problems faced by the traditional pesticide preparation.
Drawings
FIG. 1 shows the preparation of the organic ligand 2,4, 6-tris (4' -carboxyphenyl) -1,3, 5-triazine (H) of PCN-777 3 TATB).
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of PCN-777 nanoparticle (a) prepared in example 1 and abamectin PCN-777 nanoparticle controlled release agent (b) double-encapsulated with sodium lignin sulfonate and chitosan prepared in example 4.
Fig. 3 is an X-ray diffraction (XRD) pattern of PCN-777 nano-particles prepared in example 1, avermectin-loaded PCN-777 nano-particles prepared in example 3, and sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent prepared in example 4.
FIG. 4 is a graph showing the particle size distribution of Dynamic Light Scattering (DLS) of PCN-777 nanoparticles prepared in example 1, and of the double-encapsulated abamectin PCN-777 nanoparticles prepared in example 4, and of the chitosan-lignin-sulfonate controlled-release agent.
Fig. 5 is a zeta pattern of PCN-777 nanoparticles prepared in example 1, avermectin-loaded PCN-777 nanoparticles prepared in example 3, sodium lignosulfonate-encapsulated avermectin PCN-777 nano pesticide controlled release agent prepared in example 3, and sodium lignosulfonate-chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent prepared in example 4.
Fig. 6 is a graph of a nitrogen adsorption and desorption isothermal curve (a) and a corresponding pore size distribution (b) of the PCN-777 nanoparticle prepared in example 1, the avermectin-loaded PCN-777 nanoparticle prepared in example 3, the sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent prepared in example 4.
Fig. 7 is a thermogravimetric analysis (GTA) curve of the PCN-777 nanoparticle prepared in example 1, the avermectin loaded PCN-777 nanoparticle prepared in example 3, and the sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nanoparticle controlled release agent prepared in example 4.
FIG. 8 shows sodium lignin sulfonate, chitosan, avermectin, organic ligand (H) 3 TATB), PCN-777 nano particles prepared in example 1, sodium lignin sulfonate and chitosan double-encapsulated abamectin PCN-777 nano pesticide controlled release agent prepared in example 4.
Fig. 9 is an ultraviolet degradation curve of avermectin active ingredient of the avermectin PCN-777 nano pesticide controlled release agent double-encapsulated by sodium lignin sulfonate and chitosan prepared in example 4 (example 9).
FIGS. 10 a-d are graphs showing pesticide control release curves of pH value (acidic, alkaline), laccase, phosphate and Phytic Acid (PA) stimulus responses of the sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nanometer pesticide control release agent prepared in example 4 (example 10).
FIG. 11 shows the chemical structure of the organic ligand 1,3,6, 8-tetrakis (4' -carboxyphenyl) pyrene for preparing NU-1000.
FIG. 12 is a Scanning Electron Microscope (SEM) photograph of NU-1000 nanoparticles prepared according to example 2.
FIG. 13 is an X-ray diffraction (XRD) pattern of NU-1000 nanoparticles prepared in example 2.
FIG. 14 is a zeta potential (zeta) plot of NU-1000 nanoparticles prepared in example 2.
FIG. 15 is a graph showing the adsorption and desorption isotherm curve (a) and the corresponding pore size distribution (b) of NU-1000 nanoparticles prepared in example 2.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described with reference to specific embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. These examples should be construed as merely illustrative of the present invention and not limiting the scope of the present invention. All other embodiments obtained after various changes or modifications to the invention based on the technical solutions and embodiments of the invention are also within the scope of the claims of the invention after reading the description of the invention.
Example 1: preparation of PCN-777 nanoparticles
ZrOCl 2 ·8H 2 O (360 mg) and the organic ligand 2,4, 6-tris (4' -carboxyphenyl) -1,3, 5-triazine (90 mg) were dissolved in dimethylformamide 12 mL, and 0.4 mL trifluoroacetic acid (equivalent to 26 molar equivalents of the organic ligand) was added thereto and mixed uniformly by ultrasonic treatment for 10 minutes. The resulting mixed solution was placed in a stainless steel reaction kettle of polytetrafluoroethylene substrate and reacted at 140 ℃ for 12 h. After the reaction, cooling to room temperature, centrifugally separating, washing with dimethylformamide and acetone for several times respectively, and drying to obtain white PCN-777 nano particles.
Example 2: preparation of NU-1000 nanoparticles
ZrCl is added to 4 (8 mg) and the organic ligand 1,3,6, 8-tetra (4' -carboxyphenyl) pyrene (2 mg) are dissolved in 2 mL dimethylformamide, 0.4 mL acetic acid (equivalent to 2330 molar equivalents of the organic ligand) is added, then 0.2 mL water is added, and the mixture is uniformly mixed by ultrasonic treatment for 15 minutes. The resulting mixed solution was placed in a stainless steel reaction vessel of polytetrafluoroethylene substrate and reacted at 90 ℃ for 1 h. After the reaction is finished, cooling to room temperature, centrifugally separating, respectively carrying out solvent exchange for several times by using dimethylformamide and ethanol, and drying to obtain the yellow NU-1000 nano particles.
Example 3: preparation of sodium lignin sulfonate encapsulated avermectin PCN-777 nano pesticide controlled release agent
The synthesized PCN-777 nanoparticle (140, mg) was dispersed in 25, mL acetone or ethanol, 500mg of abamectin active ingredient was added, and the mixed solution was stirred at room temperature in the dark for 24, h. And (3) centrifugally separating to obtain the PCN-777 nano particles loaded with the avermectin. Subsequently, the drug loaded PCN-777 nanoparticles were immediately dispersed in 25 mL aqueous solution containing sodium lignin sulfonate (6 mg/mL), and the mixed solution was stirred at room temperature in the dark for 24 h. And then centrifuging to remove unbound sodium lignin sulfonate, and freeze-drying to obtain the sodium lignin sulfonate encapsulated avermectin PCN-777 nanometer pesticide controlled release agent.
Example 4: preparation of avermectin PCN-777 nano pesticide controlled release agent double-encapsulated by sodium lignin sulfonate and chitosan
The sodium lignin sulfonate encapsulated avermectin PCN-777M nano pesticide controlled release agent obtained in the example 3 is immediately dispersed in 25 mL chitosan-containing aqueous solution (6 mg/mL) without drying treatment, and the mixed solution is stirred at room temperature for 15 min. And then centrifuging, separating and washing to remove unbound chitosan, and freeze-drying to obtain the avermectin PCN-777 nano pesticide controlled release agent double-encapsulated by sodium lignin sulfonate and chitosan.
Example 5: preparation of sodium lignin sulfonate and chitosan double-encapsulated emamectin benzoate PCN-777 nano pesticide controlled release agent
The preparation method was the same as in example 3 and example 4, except that the emamectin benzoate active ingredient was substituted for the avermectin active ingredient.
Example 6: preparation of sodium lignin sulfonate and chitosan double-encapsulated emamectin benzoate and beta-cypermethrin compounded PCN-777 nano pesticide controlled release agent
The preparation was the same as in example 5, except that emamectin benzoate and beta-cypermethrin (mass ratio 9:1) were used instead of pure emamectin benzoate.
Example 7: preparation of calcium lignosulfonate and chitosan double-encapsulated pyraclostrobin PCN-777 nano pesticide controlled release agent
The preparation method was the same as in example 3 and example 4 except that pyraclostrobin active ingredient was used instead of abamectin active ingredient and calcium lignosulfonate was used instead of sodium lignosulfonate.
Example 8: preparation of sodium lignin sulfonate and chitosan double-encapsulated abamectin NU-1000 nanometer pesticide controlled release agent
The preparation was the same as in example 3 and example 4, except that NU-1000 nanoparticles were used instead of PCN-777 nanoparticles.
Example 9: ultraviolet degradation of sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent
200 The mg sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent is dispersed in 10 mL water. Uniformly ultrasonic-treating 1 mL nm pesticide dispersion liquid, spreading on the surface of each culture dish with the diameter of 6 cm, and naturally airing in dark place. Then, the petri dish on which the nano pesticide controlled release agent was spread was placed at a distance of 254 nm ultraviolet lamp (36W) 20 cm for irradiation. After the ultraviolet light irradiates for different time, the culture dish spreading the nano pesticide controlled release agent is taken out in sequence, the undegraded avermectin is washed and extracted by acetone, and the determination is carried out by high performance liquid chromatography.
Example 10: pesticide controlled release of nano pesticide controlled release agent
Multiple portions of the sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent (30 mg) prepared in example 4 are weighed, respectively dispersed in 2 mL aqueous solutions containing ethanol (ethanol/water, 1:4, v/v) and 0.1% Tween-80, packaged in different dialysis bags (MWCO, 8000), and then respectively placed in 148 mL aqueous solutions containing ethanol (ethanol/water, 1:4, v/v) and 0.1% Tween-80 at different pH values (pH 5.0, pH 7.0 and pH 9.0), laccase at different contents (0.8 and 1.5U/mL, pH 5.0), phosphate at different concentrations (1 and 3 mM, pH 7.0) and phytic acid at different concentrations (1 and 3 mM, pH 7.0). And taking out 1 mL to release the sample solution at different intervals, adding an equal volume of corresponding fresh solution to keep the total volume unchanged, and measuring the content of the released pesticide active ingredient by using high performance liquid chromatography. The pesticide released is ultimately expressed in terms of the cumulative pesticide release rate.
FIG. 1 is a chemical structure of an organic ligand 2,4, 6-tris (4' -carboxyphenyl) -1,3, 5-triazine for the preparation of PCN-777.
The scanning electron micrograph of FIG. 2 shows that the PCN-777 nanoparticle prepared in example 1 has a polyhedral shape and an average size of about 250nm; the sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent (AVM@PCN-777@SL/CS) prepared in the example 4 keeps a polyhedral shape and has an average size of about 250 nm.
The X-ray diffraction (XRD) pattern of the PCN-777 nanoparticle prepared in example 1 of FIG. 3 is well matched with the theoretical XRD pattern, and the structure of the obtained nanoparticle is proved to be PCN-777; after pesticide loading, sodium lignin sulfonate and chitosan encapsulation, the MOF structure of avermectin-loaded PCN-777 nano-particles (AVM@PCN-777) prepared in example 3 and avermectin PCN-777 nano-pesticide controlled release agent (AVM@PCN-777@SL/CS) double-encapsulated by sodium lignin sulfonate and chitosan prepared in example 4 remained unchanged, but these amorphous phase substances were introduced, resulting in gradual decrease of the corresponding XRD diffraction peak intensity.
The particle size distribution of dynamic light scattering in fig. 4 shows that the average hydration diameter of the PCN-777 nano-particle prepared in example 1 is 271 nm, and the average hydration diameter of the sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano-pesticide controlled release agent prepared in example 4 is 308 nm, which illustrates the encapsulation of sodium lignin sulfonate and chitosan on the surface of the PCN-777 nano-particle.
FIG. 5 shows the zeta potential of the PCN-777 nanoparticle prepared in example 1 to be 30.9. 30.9 mV, indicating the presence of coordinated unsaturated Zr on the surface of the PCN-777 nanoparticle IV A site; the abamectin loaded PCN-777 nanoparticle prepared in example 3 has an electromotive force of 14.5 mV, indicating the loading of pesticides; the electromotive potential of the avermectin PCN-777 nano pesticide controlled release agent (AVM@PCN-777@SL) encapsulated by sodium lignin sulfonate prepared in the embodiment 3 is-21.4 mV, which shows that the sodium lignin sulfonate is encapsulated on the surface of the pesticide-carrying PCN-777 nano particle; the electromotive force of the abamectin PCN-777 nano pesticide controlled release agent double-encapsulated by the sodium lignin sulfonate and the chitosan prepared in the example 4 is 29.9 mV, which indicates that the chitosan is further encapsulated on the surface of the PCN-777 nano particles encapsulated by the sodium lignin sulfonate and carrying the pesticide.
The results of the nitrogen adsorption and desorption isothermal curves of FIG. 6 show that PCBET specific surface area of N-777 nanoparticle was 725 m 2 Per gram, BET specific surface areas of avermectin-loaded PCN-777 nano particles, sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent are respectively reduced to 26 and 19 m 2 And/g, illustrating that the loading of the pesticide, the encapsulation of sodium lignin sulfonate and chitosan results in the filling and plugging of PCN-777 mesoporous channels. The corresponding pore size distribution plot shows that PCN-777 nanoparticles exhibit larger mesopores of about 3nm, with the BJH method measuring pore size (about 3 nm) being less than 3.5 nm medium Kong Long for the PCN-777 crystal structure; the mesoporous pore canal of the avermectin PCN-777 nano-pesticide controlled release agent which is loaded with the avermectin and double-encapsulated by the avermectin PCN-777 nano-particles, the sodium lignin sulfonate and the chitosan is filled and plugged.
The thermogravimetric analysis of FIG. 7 shows that the weight loss of PCN-777 nanoparticles is less than the weight loss of theoretical decomposition, indicating the presence of coordinated unsaturated Zr for PCN-777 nanoparticles IV A site; the weight loss of the avermectin-loaded PCN-777 nano-particle, sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent illustrates the loading of pesticide and the encapsulation of sodium lignin sulfonate and chitosan. The high performance liquid chromatography is used for measuring that the drug loading rate of the pesticide in the double-encapsulated MOF nano pesticide controlled release agent is 25 percent (mass percent), and the pesticide loading rate is high, so that the low-concentration MOF nano pesticide controlled release agent can achieve the effect of preventing and controlling plant diseases and insect pests, reduce the production cost of users, and reduce the difficulty of the agent in the aspects of preparation, spraying and the like.
FIG. 8 is a sodium lignin sulfonate, chitosan, avermectin, organic ligand H 3 Ultraviolet visible absorption spectrum diagram of TATB, PCN-777 nano-particle, sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nano pesticide controlled release agent. The sodium lignin sulfonate and the organic ligand have strong absorption to ultraviolet light, and obviously, the PCN-777 nano particles and the MOF nano pesticide controlled release agent have strong absorption to ultraviolet light, so that the loaded avermectin can be protected from being degraded by ultraviolet light of sunlight.
Fig. 9 is an ultraviolet degradation curve of avermectin for avermectin PCN-777 nm pesticide controlled release agent double encapsulated with sodium lignin sulfonate and chitosan (example 9). When the 72 h part is irradiated by ultraviolet light, only 6.6% of the avermectin raw material is not degraded by ultraviolet light, and 53.0% of the avermectin active ingredients in the MOF nano pesticide controlled release agent are still reserved, so that the ultraviolet light degradation resistance is improved by 8 times.
Fig. 10 a-d are graphs of pesticide controlled release of sodium lignin sulfonate and chitosan double-encapsulated avermectin PCN-777 nm prepared in example 4 in advance under the condition of no stimulus and pesticide controlled release of acid, alkaline, phosphate and Phytic Acid (PA) stimulus response (example 10). In an aqueous solution containing ethanol (ethanol/water, 1:4, v/v) and 0.1% tween-80, the double encapsulated avermectin PCN-777 nm pesticide controlled release agent showed a lower pesticide early release (pH 7.0) with a 96 h pesticide cumulative release rate of only 9.2% without any irritation (fig. 10 a); under the acidic (pH 5.0) condition, the cumulative release rate of 96 h pesticides is 18.9%, compared with the cumulative release rate of 96 h pesticides of the sodium lignin sulfonate encapsulated avermectin PCN-777 nano pesticide controlled release agent prepared in example 3, which is 21.8% of the pesticide released in advance (pH 7.0), the double-encapsulated MOF nano pesticide controlled release agent is mainly chitosan encapsulation under the acidic condition, the sodium lignin sulfonate encapsulation is not affected, and the pesticide release rate is lower; under alkaline (pH 9.0) conditions, the 96 h pesticide cumulative release rate is 52.5%, and mainly PCN-777 structure is partially destroyed, so that the pesticide is released. At pH5.0, where laccase activity was maximal, 0.8 and 1.5U/mL laccase resulted in a 72 h cumulative pesticide release rate increase from 18.3% to 44.9% and 57.8%, respectively, for the doubly encapsulated MOF nano pesticide controlled release agent (FIG. 10 b). The cumulative pesticide release rates of 96 h for the 1 and 3 mM phosphates were 35.8% and 53.7%, respectively, in the presence of phosphate (fig. 10 c). The cumulative pesticide release rates of 96 h for 1 and 3 mM phytic acid in the presence of phytic acid were 44.5% and 61.6%, respectively (fig. 10 d).
FIG. 11 shows the chemical structure of the organic ligand 1,3,6, 8-tetrakis (4' -carboxyphenyl) pyrene for preparing NU-1000.
FIG. 12 is a scanning electron micrograph of NU-1000 nanoparticles prepared in example 2, exhibiting a football-like shape with an average major axis dimension of about 110 nm.
FIG. 13 shows that the XRD pattern of the NU-1000 nanoparticle prepared in example 2 matches the theoretical XRD pattern, confirming that the prepared nanoparticle is NU-1000.
FIG. 14 shows that the zeta potential of the NU-1000 nanoparticles prepared in example 2 is 28.9 mV, indicating the presence of coordinated unsaturated Zr on the surface of the NU-1000 nanoparticles IV The sites are favorable for the coordination encapsulation of lignosulfonate on the surfaces of the NU-1000 nano particles carrying the medicine.
FIG. 15 is a graph showing the adsorption and desorption isotherm of nitrogen and the pore size distribution of NU-1000 nanoparticles prepared in example 2, the BET specific surface area of NU-1000 nanoparticles being 1302 m 2 The mesoporous size (about 2.3 nm) measured by the BJH method is smaller than 3nm mesoporous cages of NU-1000 crystal structure, and pesticide molecules with larger molecular size can be loaded into NU-1000 mesoporous channels.
The above-described embodiments are only preferred embodiments of the present invention and are not intended to limit the present invention. It is noted that various modifications and variations of the present invention are possible to those skilled in the art. Any modification, equivalent replacement, improvement, etc., including loading of other pesticidal active ingredients for preparing the MOF nano pesticide controlled release agent, should be included in the scope of protection of the present invention, while remaining within the spirit and principle of the present invention.
Claims (10)
1. The preparation method of the metal organic framework nano pesticide controlled release agent is characterized by comprising the following steps of:
step 1: dispersing the metal organic frame nano material in an organic solvent A, adding a pesticide active ingredient, stirring at room temperature, filling the pesticide active ingredient into a pore canal of the metal organic frame nano material, and centrifugally separating to obtain the drug-loaded metal organic frame nano material;
step 2: dispersing the drug-loaded metal organic framework nano material obtained in the step 1 in an aqueous solution containing lignosulfonate, stirring at room temperature, and centrifugally separating to obtain a lignosulfonate-encapsulated metal organic framework nano pesticide controlled release agent;
step 3: dispersing the lignosulfonate encapsulated metal organic framework nano pesticide obtained in the step 2 in an aqueous solution containing chitosan, stirring at room temperature, centrifuging, separating, washing and drying to obtain the target product lignosulfonate and chitosan double encapsulated metal organic framework nano pesticide controlled release agent.
2. The method for preparing the metal-organic framework nano pesticide controlled release agent according to claim 1, which is characterized in that: the metal organic framework nano material in the step 1 is PCN-777 nano particles or NU-1000 nano particles.
3. The method for preparing the metal-organic framework nano pesticide controlled release agent as set forth in claim 2, which is characterized in that: the preparation method of the PCN-777 nano-particles comprises the following steps: zrOCl 2 ·8H 2 O and organic ligand 2,4, 6-tri (4' -carboxyphenyl) -1,3, 5-triazine are dissolved in an organic solvent B according to the mol ratio of 10-2:1, trifluoroacetic acid with the molar equivalent of 10-55 of the organic ligand is added, the mixture is uniformly mixed, the mixture is placed in a reaction kettle for reaction at the temperature of 110-160 ℃ for 5-24 h, cooled to room temperature, centrifugally separated, washed by an organic solvent B and an organic solvent A respectively, and dried to obtain PCN-777 nano particles.
4. The method for preparing the metal-organic framework nano pesticide controlled release agent as set forth in claim 2, which is characterized in that: the preparation method of the NU-1000 nano particles comprises the following steps: zrCl is added to 4 And the organic ligand 1,3,6, 8-tetra (4' -carboxyphenyl) pyrene is dissolved in an organic solvent B according to the mol ratio of 20-5:1, 1000-4000 mol equivalent of acetic acid of the organic ligand is added, water is added according to the volume ratio of acetic acid to water of 5:0-3, the mixture is uniformly mixed, the mixture is placed in a reaction kettle, the reaction is carried out at 70-120 ℃ for 0.3-3 h, the mixture is cooled to room temperature, centrifugal separation is carried out, the organic solvent B and the organic solvent A are respectively used for carrying out solvent exchange, and NU-1000 nano particles are obtained after drying.
5. The method for preparing the metal-organic framework nano pesticide controlled release agent as set forth in claim 1, which is characterized in that: the organic solvent A is at least one of ethanol and acetone.
6. The method for preparing the metal-organic framework nano pesticide controlled release agent according to claim 3 or 4, which is characterized in that: the organic solvent B is at least one of dimethylformamide or diethylformamide.
7. The method for preparing the metal-organic framework nano pesticide controlled release agent as set forth in claim 1, which is characterized in that: the pesticide active ingredient is one or a mixture of more than two of abamectin, emamectin benzoate, beta-cypermethrin and pyraclostrobin.
8. The method for preparing the nano pesticide controlled release agent with the metal-organic framework according to claim 1, wherein the mass ratio of the nano material with the metal-organic framework to the pesticide active ingredient in the step 1 is 1:0.5-10; the concentration of the pesticide active ingredient in the organic solvent A is 4-100 g/L.
9. The method for preparing the nano pesticide controlled release agent for the metal organic framework according to claim 1, wherein the lignosulfonate is at least one of sodium lignosulfonate or calcium lignosulfonate; the mass ratio of the lignosulfonate to the chitosan is 1:0-5; the mass ratio of the metal organic framework nano material to the lignosulfonate is 1:0.2-5.
10. The use of the product of the method for preparing a metal-organic framework nano pesticide controlled release agent according to any one of claims 1 to 5 in pesticide control, characterized in that the pesticide release is controlled by environmental factors; the environmental factor is one or the combination of more than two of pH value, laccase, phosphate and phytic acid.
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