CN113016791A - Preparation method of avermectin-loaded mesoporous silica nanoparticle controlled release agent - Google Patents
Preparation method of avermectin-loaded mesoporous silica nanoparticle controlled release agent Download PDFInfo
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- CN113016791A CN113016791A CN202110326270.1A CN202110326270A CN113016791A CN 113016791 A CN113016791 A CN 113016791A CN 202110326270 A CN202110326270 A CN 202110326270A CN 113016791 A CN113016791 A CN 113016791A
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- avermectin
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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
- A01N25/08—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 solids as carriers or diluents
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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
- 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
Abstract
The invention relates to a preparation method of an avermectin-loaded mesoporous silica nanoparticle controlled release agent in the technical field of pesticides, which comprises the following specific steps: step (1): dissolving a template agent in deionized water to obtain a water phase; step (2): dissolving abamectin in an organic solvent to obtain an oil phase; and (3): and (3) mixing the water phase in the step (1) with the oil phase in the step (2), then adding a silicon source and alkali liquor, uniformly stirring, aging at room temperature for 6-8h, carrying out centrifugal separation to obtain solid nanoparticles, washing with deionized water for 3-4 times, and carrying out freeze drying to obtain the abamectin-loaded mesoporous silica nanoparticle controlled release agent. The preparation method of the controlled release agent is simple, the period is short, the wall material preparation and the drug loading are carried out synchronously, the production cost is low, the preparation stability is high, the biological activity is excellent, the preparation method is safe to people and livestock, and the preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent is environment-friendly.
Description
Technical Field
The invention relates to the technical field of pesticides, in particular to a preparation method of an avermectin-loaded mesoporous silica nanoparticle controlled release agent, and belongs to the technical field of pesticides.
Background
At present, the development strategy of the pesticide formulation in China is to develop a new pesticide formulation suitable for the national conditions of China by starting from a sustainable development strategy and referring to the advanced experience in China. At present, pesticide formulations are developed in the direction of water-based, granular, controlled release, functionalization and labor saving, and a plurality of high-efficiency, safe and economic new pesticide formulations are being developed and applied and gradually replace the traditional old pesticide formulations. The pesticide dosage forms develop in the following directions:
(1) water-based formulations such as emulsion in water and suspending agent are gradually replacing missible oil and wettable powder;
(2) the water dispersible granule is one of the dosage forms with good development prospect in the future;
(3) the controlled release agent with comprehensive functions becomes the mastership in the pesticide formulation.
The traditional pesticide controlled release agent has the defects of the traditional pesticide controlled release agent, for example, most wall materials of the controlled release agent are synthetic high polymer materials, and can pollute the environment during synthesis, and most of the controlled release agents have poor biodegradability and are easy to pollute the environment; the controlled release carrier prepared by using a high molecular method has larger particles which are generally more than micron-sized, so that the controlled release carrier is not uniform enough in distribution and easy to fall off when being applied, and the aims of protecting the environment and reducing the pesticide dosage cannot be achieved. In addition, the traditional preparation method of the controlled release carrier is complicated, the preparation of wall materials and the drug loading cannot be synchronously carried out, the period is long, and the industrial large-scale production is not facilitated. Therefore, a simple and efficient method for preparing a pesticide controlled-release agent is required.
Disclosure of Invention
Aiming at the problems of preparation and use of the pesticide controlled release agent taking a high molecular organic material as a wall material in the prior art, the invention provides the preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent, which has the advantages of simple preparation method, short period, synchronous wall material preparation and drug loading, low production cost, high preparation stability, excellent biological activity, safety to people and livestock and environmental friendliness.
The invention aims to realize the preparation method of the mesoporous silica nanoparticle controlled release agent loaded with the abamectin, which is characterized by comprising the following steps:
step (1): dissolving a template agent in deionized water to obtain a water phase;
step (2): dissolving abamectin in an organic solvent to obtain an oil phase;
and (3): and (3) mixing the water phase in the step (1) with the oil phase in the step (2), then adding a silicon source and alkali liquor, uniformly stirring, aging at room temperature for 6-8h, carrying out centrifugal separation to obtain solid nanoparticles, washing with deionized water for 3-4 times, and carrying out freeze drying to obtain the abamectin-loaded mesoporous silica nanoparticle controlled release agent.
The preparation method of the mesoporous silica nanoparticle avermectin-loaded controlled release agent has the advantages of few raw material formula varieties, simple synthesis conditions, environmental friendliness and arrangement of preparation processes, and in the process of synthesizing the mesoporous silica nanoparticle avermectin-loaded controlled release agent, the preparation process of the wall material serving as the silica nanoparticle is synchronously realized with the avermectin drug loading process, so that the release period of the avermectin can be effectively prolonged, and the prevention and treatment period of the drug is prolonged; meanwhile, due to the protection effect of the mesoporous silica carrier, the decomposition rate of the abamectin under natural conditions is greatly reduced, so that the effective insecticidal time of the abamectin in the field can be kept, the pesticide effect can be fully exerted, the pesticide can be prevented from running off into the environment, the utilization rate of the pesticide is improved, and the greening process of the pesticide is realized.
Furthermore, the controlled release agent has the particle size of 100-400 nm and the specific surface area of more than 30 m2And/g, the mass ratio of the abamectin to the controlled release agent is 20-50%.
Further, the mass ratio of the template agent to the abamectin to the silicon source is 1: (0.1-0.3): (0.5-2).
Further, in the step (1), the template agent is one or a combination of cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium chloride aqueous solution, and the mass concentration of the solution is 5-13%.
Further, in the step (2), the mass volume concentration of the abamectin and the organic solvent is 1.0-6.0 g/100 mL, and the organic solvent is one or more than one of methanol, ethanol and isopropanol in any ratio.
Further, in the step (3), the silicon source is one or a combination of tetraethoxysilane and trimethoxy silane, and the concentration ratio of the silicon source to the alkali liquor is as follows: (0.5-1): 1.
further, the alkali liquor is ammonia water, sodium hydroxide or potassium hydroxide, the concentration of the solution is 0.5 mol/L, and the pH value is adjusted to 8-9.
In the step (3), the stirring temperature is 20-35 ℃, and the stirring speed is 100-600 rpm.
Drawings
FIG. 1 is a chemical structural formula diagram of avermectin used in the invention.
FIG. 2 is an electron microscope scanning image of the controlled release agent of mesoporous silica nanoparticle loaded avermectin of the present invention.
Fig. 3 is a schematic diagram showing the comparison of the anti-photodegradation capabilities of the mesoporous silica nanoparticle-loaded avermectin controlled-release agent and the original avermectin drug.
Fig. 4 is a schematic diagram of a toxicity experiment of the mesoporous silica nanoparticle avermectin-loaded controlled release agent on cells.
Fig. 5 is a degradation diagram of abamectin and the mesoporous silica nanoparticles loaded with abamectin prepared in example 2 under natural light.
Fig. 6 is a schematic diagram of cytotoxicity of Abamectin-loaded mesoporous silica nanoparticles (abemactin @ MSNs), monodisperse silica Microspheres (MSNs), Abamectin emulsifiable concentrate (abemactin EC) and Abamectin water emulsion (abemactin EW) after treatment of a549 cells for 2 hours and 24 hours.
Detailed Description
The chemical structural formula of the abamectin used in the following examples is shown in figure 1.
Example 1
The preparation process of the mesoporous silica nanoparticle avermectin-loaded controlled release agent of the embodiment is as follows:
(1) dissolving 1 g of hexadecyl trimethyl ammonium bromide in 80 mL of deionized water to obtain a water phase for later use;
(2) dissolving 0.3 g of abamectin in 50 mL of ethanol to obtain an oil phase for later use;
(3) adding the water phase obtained in the step (1) into the oil phase obtained in the step (2), mixing, adding 1 mL of ethyl orthosilicate and 0.5 mL of 0.5 mol/L ammonia water, adjusting the pH value to 8, stirring and mixing to obtain microemulsion, magnetically stirring at the room temperature (30 ℃) at the rotating speed of 200 rpm for 6 hours to obtain abamectin-loaded nanoparticle emulsion, centrifuging to obtain solid particles, washing the solid particles with deionized water for 3 times, and freeze-drying to obtain the abamectin-loaded mesoporous silica nanoparticles.
Example 2:
the preparation process of the mesoporous silica nanoparticle avermectin-loaded controlled release agent of the embodiment is as follows:
(1) dissolving 0.5 g of hexadecyl trimethyl ammonium chloride in 90 mL of deionized water to obtain a water phase for later use;
(2) dissolving 0.1 g of abamectin in 40 mL of methanol to obtain an oil phase for later use;
(3) adding the water phase obtained in the step (1) into the oil phase obtained in the step (2), mixing, adding 1 mL of trimethoxy silane and 0.5 mol/L of ammonia water 1 m L, adjusting the pH to 9, stirring and mixing to obtain a microemulsion, magnetically stirring at the room temperature (20 ℃) at the rotating speed of 150 rpm for 6 hours to obtain an abamectin-loaded nanoparticle emulsion, centrifuging to obtain solid particles, washing the solid particles with deionized water for 4 times, and freeze-drying to obtain the abamectin-loaded mesoporous silica nanoparticles.
Example 3:
the preparation process of the mesoporous silica nanoparticle avermectin-loaded controlled release agent of the embodiment is as follows:
(1) dissolving 0.8 g of hexadecyl trimethyl ammonium bromide in 70 mL of deionized water to obtain a water phase for later use;
(2) dissolving 0.2 g of abamectin in 50 mL of ethanol to obtain an oil phase for later use;
(3) adding the water phase obtained in the step (1) into the oil phase obtained in the step (2), adding 0.8 mL of ethyl orthosilicate and 1 mL of ammonia water with the concentration of 0.5 mol/L, adjusting the pH to 8, stirring and mixing to obtain microemulsion, magnetically stirring the microemulsion at room temperature (25 ℃) at the rotating speed of 100 rpm for 6 hours to obtain avermectin-loaded nanoparticle emulsion, centrifuging to obtain solid particles, washing the solid particles with deionized water for 3 times, and freeze-drying to obtain the avermectin-loaded mesoporous silica nanoparticles.
Example 4
The preparation process of the mesoporous silica nanoparticle avermectin-loaded controlled release agent of the embodiment is as follows:
(1) dissolving 0.6 g of hexadecyl trimethyl ammonium bromide in 100 mL of deionized water to obtain a water phase for later use;
(2) dissolving 0.1 g of abamectin in 50 mL of isopropanol to obtain an oil phase for later use;
(3) adding the water phase obtained in the step (1) into the oil phase obtained in the step (2), adding 0.8 mL of trimethoxy silane and 1 mL of sodium hydroxide solution with the concentration of 0.5 mol/L, adjusting the pH value to 8, stirring and mixing to obtain microemulsion, magnetically stirring at the room temperature of 30 ℃ and the rotating speed of 500 rpm for 6 hours to obtain avermectin-loaded nanoparticle emulsion, centrifuging to obtain solid particles, washing the solid particles with deionized water for 4 times, and freeze-drying to obtain the avermectin-loaded mesoporous silica nanoparticles.
Example 5
The preparation process of the mesoporous silica nanoparticle avermectin-loaded controlled release agent of the embodiment is as follows:
(1) dissolving 0.5 g of hexadecyl trimethyl ammonium chloride in 70 mL of deionized water to obtain a water phase for later use;
(2) dissolving 0.05 g of abamectin in 50 mL of methanol to obtain an oil phase for later use;
(3) adding the water phase obtained in the step (1) into the oil phase obtained in the step (2), adding 0.5 mL of ethyl orthosilicate and 0.5 mL of potassium hydroxide solution with the concentration of 0.5 mol/L, adjusting the pH value to 8, stirring and mixing to obtain microemulsion, magnetically stirring the microemulsion at the room temperature of 25 ℃ at the rotating speed of 600 rpm for 6 hours to obtain avermectin-loaded nanoparticle emulsion, centrifuging to obtain solid particles, washing the solid particles with deionized water for 3 times, and freeze-drying to obtain the avermectin-loaded mesoporous silica nanoparticles.
Example 6
The preparation process of the mesoporous silica nanoparticle avermectin-loaded controlled release agent of the embodiment is as follows:
(1) dissolving 0.9 g of hexadecyl trimethyl ammonium chloride in 100 mL of deionized water to obtain a water phase for later use;
(2) dissolving 0.25 g of abamectin in 50 mL of ethanol to obtain an oil phase for later use;
(3) adding the water phase obtained in the step (1) into the oil phase obtained in the step (2), adding 0.5 mL of trimethoxy silane and 0.8 mL of potassium hydroxide solution with the concentration of 0.5 mol/L, adjusting the pH value to 9, stirring and mixing to obtain microemulsion, magnetically stirring the microemulsion at room temperature (25 ℃) at the rotating speed of 400 rpm for 6 hours to obtain avermectin-loaded nanoparticle emulsion, centrifuging to obtain solid particles, washing the solid particles with deionized water for 3-4 times, and freeze-drying to obtain the avermectin-loaded mesoporous silica nanoparticles.
Examples of Performance tests
Fig. 2 is an electron microscope scanning image of the avermectin-loaded mesoporous silica nanoparticles prepared in example 1, which shows that the microspheres of the nanoparticles are regular in shape, uniform in size and uniform in dispersion.
In addition, the specific surface area of the mesoporous silica nanoparticle loaded with the avermectin in example 1 is measured and compared with that of the blank silica nano. The procedure for measuring the specific surface area was determined by a Micromeritics ASAP 2460 analyzer (Micromeritics Instrument Corporation, USA) at a temperature of 77K. Using BET (brunauer-e)mmet-teller) model linear regression calculated the surface area and pore size distribution of the samples and Barrett-Joyner-halenda (bjh) method. As shown in fig. 3, the left graph is a nitrogen adsorption curve of the blank mesoporous silica, and the right graph is a nitrogen adsorption curve of the mesoporous silica loaded with avermectin. By N2The porosity of the blank silicon dioxide microspheres and the mesoporous silicon dioxide loaded with the abamectin is determined by adsorption-desorption analysis, and when the relative pressure is 0.2-0.3, a hysteresis loop exists, which indicates that the mesoporous characteristics have IV-type isotherms and the pore diameter uniformity is large. However, the shape of the nitrogen adsorption curve of the mesoporous silica loaded with the avermectin is obviously changed, and the nitrogen adsorption capacity is weakened to cause mesoporous characteristics due to the loading of the avermectin in pores. Furthermore, we have determined that the BET surface area of the monodisperse silica is 52 m2(ii)/g, pore diameter 9.97 nm. After loading the abamectin, the specific surface area and the pore diameter are respectively reduced to 36 m2G and 6.70 nm. The specific surface area and the pore space of the mesoporous silica nano particle loaded with the avermectin are obviously smaller than those of the blank mesoporous silica, and the further demonstration that the avermectin is loaded into the blank mesoporous silica is provided.
As shown in fig. 4, which is a graph for analyzing the release performance of the avermectin microcapsule prepared from the avermectin-loaded mesoporous silica nanoparticles prepared in example 2 of the present invention and the existing polymeric capsule wall material, it can be seen from fig. 4 that the avermectin-loaded mesoporous silica nanoparticles of the present invention have a longer sustained release performance compared to the avermectin microcapsule prepared from the existing polymeric capsule wall material: when the release time is 15 days, the accumulative release rate of the avermectin microcapsule of the polymer capsule wall material reaches nearly 80 percent, while the accumulative release rate of the mesoporous silica nanoparticle loaded with the avermectin is only 60 percent, and the release is stopped after 30 days of release, which shows that the avermectin microcapsule prepared by the method and the wall material has better slow release performance.
The anti-photodegradation performance of the avermectin-loaded mesoporous silica nanoparticle prepared in example 2 is further illustrated.
As is known to all, under natural conditions, the abamectin is easy to photolyze, and the formula for reducing the photodegradation resistance of the abamectin is the key for realizing the drug property of the long-acting release of the abamectin and improving the utilization efficiency of the abamectin. Fig. 5 shows the degradation of abamectin and the abamectin-loaded mesoporous silica nanoparticles prepared in example 2 under natural light. As a result: the decomposition rate of the abamectin technical reaches 42.7 percent after five days, and only 10.9 percent of the abamectin in the mesoporous silicon dioxide nano particles loaded with the abamectin is decomposed at the moment; after 9 days, the decomposition rate of the abamectin technical is 58.6%. However, only less than 16% of the avermectins in the avermectin-loaded mesoporous silica nanoparticles are decomposed. This means that the formulation is more than doubled in retarding the abamectin degradation rate. Therefore, the mesoporous silica nanoparticles loaded with the avermectins prepared by the method have a strong protective effect on the avermectins, and the mesoporous silica nanoparticles loaded with the avermectins have good photodegradation shielding performance.
In the process of pesticide application, the pesticide can enter the body of a pesticide application person, so that the physical health and safety of the pesticide application person are threatened. Therefore, the proliferation of human lung cells is one of the important ways to evaluate the cytotoxicity of abamectin. Therefore, cytotoxicity of the mesoporous silica nanoparticles (Abamectin @ MSNs), monodisperse silica Microspheres (MSNs), Abamectin emulsifiable concentrate (Abamectin EC) and Abamectin aqueous emulsion (Abamectin EW) loaded with Abamectin, which are prepared in example 3, on A549 cells after 2 hours and 24 hours of treatment is detected by an MTT method. As shown in FIG. 6, wherein Control is a blank Control. After 2 hours of treatment, the cell survival rates of the cells treated by the avermectin missible oil and the cells treated by the avermectin water emulsion are respectively 80.2 percent and 73.6 percent. After 2 hours, the cell viability of the Abamectin @ MSNs and the MSNs after treatment at the same concentration was as high as 89.7% and 96.9%, respectively. After 24 hours, cell viability was maintained at 71.6% and 91.9% for treatment with Abamectin @ MSNs and MSNs, but showed lower values for cell viability after treatment with Abamectin EC and Abamectin EW (39.0% and 19.8%, respectively). The result shows that the killing effect of the abamectin on cells is particularly obvious, but the toxicity to A549 cells is obviously reduced after the abamectin is encapsulated by the mesoporous silica nano particles, and the threat of the traditional abamectin dosage form to the health and safety of the drug administration personnel is greatly reduced.
Claims (8)
1. A preparation method of an avermectin-loaded mesoporous silica nanoparticle controlled release agent is characterized by comprising the following steps:
step (1): dissolving a template agent in deionized water to obtain a water phase;
step (2): dissolving abamectin in an organic solvent to obtain an oil phase;
and (3): and (3) mixing the water phase in the step (1) with the oil phase in the step (2), then adding a silicon source and alkali liquor, uniformly stirring, aging at room temperature for 6-8h, carrying out centrifugal separation to obtain solid nanoparticles, washing with deionized water for 3-4 times, and carrying out freeze drying to obtain the abamectin-loaded mesoporous silica nanoparticle controlled release agent.
2. The preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent according to claim 1, wherein the controlled release agent has a particle size of 100-400 nm and a specific surface area of more than 30 m2And/g, the mass ratio of the abamectin to the controlled release agent is 20-50%.
3. The preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent according to claim 1, wherein the mass ratio of the template agent to the avermectin to the silicon source is 1: (0.1-0.3): (0.5-2).
4. The preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent according to claim 1, wherein in the step (1), the template agent is one or a combination of cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium chloride aqueous solution, and the mass concentration of the solution is 5-13%.
5. The preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent according to claim 1, wherein in the step (2), the mass volume concentration of the avermectin and the organic solvent is 1.0-6.0 g/100 mL, and the organic solvent is one or more than one of methanol, ethanol and isopropanol in any ratio.
6. The preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled-release agent according to claim 1, wherein in the step (3), the silicon source is one or a combination of tetraethoxysilane and trimethoxy silane, and the concentration ratio of the silicon source to the alkali liquor is as follows: (0.5-1): 1.
7. the preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent according to claim 6, wherein in the step (3), the alkali solution is ammonia water, sodium hydroxide or potassium hydroxide, the concentration of the alkali solution is 0.5 mol/L, and the pH value of the mixed solution is adjusted to 8-9 after the alkali solution is added.
8. The preparation method of the avermectin-loaded mesoporous silica nanoparticle controlled release agent according to claim 6, wherein in the step (3), the stirring temperature is 20-35 ℃, and the stirring speed is 100-600 rpm.
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Cited By (2)
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| CN114027296A (en) * | 2021-11-10 | 2022-02-11 | 山东农业大学 | Nano pesticide preparation for preventing and controlling pine wood nematode and its vector insect |
| CN114097774A (en) * | 2021-11-20 | 2022-03-01 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of mesoporous silica nano double-layer microsphere controlled release agent |
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| CN114097774A (en) * | 2021-11-20 | 2022-03-01 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of mesoporous silica nano double-layer microsphere controlled release agent |
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