CN118044507A - Drug-carrying system and preparation method and application thereof - Google Patents
Drug-carrying system and preparation method and application thereof Download PDFInfo
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- CN118044507A CN118044507A CN202410453087.1A CN202410453087A CN118044507A CN 118044507 A CN118044507 A CN 118044507A CN 202410453087 A CN202410453087 A CN 202410453087A CN 118044507 A CN118044507 A CN 118044507A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000000575 pesticide Substances 0.000 claims abstract description 75
- 239000004480 active ingredient Substances 0.000 claims abstract description 63
- 239000002105 nanoparticle Substances 0.000 claims abstract description 52
- 239000011787 zinc oxide Substances 0.000 claims abstract description 52
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- 239000002096 quantum dot Substances 0.000 claims abstract description 40
- 239000003814 drug Substances 0.000 claims abstract description 19
- 229940079593 drug Drugs 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 73
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
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- 238000002390 rotary evaporation Methods 0.000 claims description 4
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 3
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- MUJOIMFVNIBMKC-UHFFFAOYSA-N fludioxonil Chemical compound C=12OC(F)(F)OC2=CC=CC=1C1=CNC=C1C#N MUJOIMFVNIBMKC-UHFFFAOYSA-N 0.000 claims description 3
- QTYCMDBMOLSEAM-UHFFFAOYSA-N ipconazole Chemical compound C1=NC=NN1CC1(O)C(C(C)C)CCC1CC1=CC=C(Cl)C=C1 QTYCMDBMOLSEAM-UHFFFAOYSA-N 0.000 claims description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a drug-carrying system, a preparation method and application thereof, and relates to the technical field of pesticides. The drug-carrying system comprises a pesticide active ingredient and a shell wrapping the pesticide active ingredient, wherein the shell comprises composite particles, and the composite particles comprise zinc oxide nano particles and quantum dots loaded on the surfaces of the zinc oxide nano particles. The drug-carrying system can control the release of the pesticide active ingredient, increase the duration of the effect, improve the stability of the pesticide active ingredient and improve the control effect. Meanwhile, the drug carrying system has the good characteristics of reducing the toxicity of the pesticide active ingredient, reducing the pollution of the pesticide active ingredient to the environment and the like. In addition, the composite particles have good antibacterial performance, and can play a synergistic bactericidal effect with pesticide active ingredients, so that the drug-carrying system is endowed with an enhanced bactericidal effect. In addition, zinc element required by crop growth is introduced into the zinc oxide nano particles while the function of the drug-carrying system is realized, so that the growth metabolism of crops is promoted.
Description
Technical Field
The invention relates to the technical field of pesticides, in particular to a drug-carrying system and a preparation method and application thereof.
Background
Pesticide formulations have an important impact on sustainable development of agriculture and ecological environment. However, the conventional pesticide formulation has low water dispersibility, high organic solvent content and serious environmental pollution. And the traditional pesticide preparation has the problems of short duration, multiple application times, low prevention effect and the like.
The pesticide formulation has very important significance for improving the pesticide effect and stabilizing the quality of the pesticide. The pesticide controlled release preparation provides a new solution for the pesticide application reduction and synergy problems of improving the pesticide duration, reducing the pesticide application times and the like, and the release performance of the pesticide controlled release preparation is closely related to the carrier material and the preparation technology thereof. Although sustained and controlled release preparations have been widely studied in recent decades, in many reports, the drug-carrying materials mostly have only one function, are developed around controlled release, have low application value, or can cause environmental pressure and other problems. The green and bioactive synergistic carrier is developed, so that the slow release system realizes the double functions of medicine and material, and the medicine carrying system plays a great role in application, and has important significance for pesticide application reduction and synergy. In order to meet the demand of sustainable development of agriculture, the development of a multifunctional drug-carrying system and a preparation method thereof has important research and practical values.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a drug-carrying system, a preparation method and application thereof, and aims to solve the problems of short duration, low prevention effect and the like of the existing pesticide preparation.
The technical scheme of the invention is as follows:
In a first aspect of the present invention, there is provided a drug delivery system, wherein the drug delivery system comprises a pesticide active ingredient and a shell encapsulating the pesticide active ingredient, the shell comprising composite particles comprising zinc oxide nanoparticles and quantum dots supported on the surfaces of the zinc oxide nanoparticles.
Optionally, the mass ratio of the pesticide active ingredient to the shell is (0.6-3.3): 1.
Optionally, the mass ratio of the zinc oxide nano particles to the quantum dots is (90-99.9): 0.1-10.
Optionally, the quantum dots include at least one of carbon quantum dots, nitrogen-doped carbon quantum dots, graphene quantum dots, nitrogen-doped graphene quantum dots, and carboxylated graphene quantum dots;
The pesticide active ingredient comprises at least one of pyraclostrobin, tebuconazole, ipconazole, cyhalothrin, fludioxonil, difenoconazole and trifluorecited in the claims.
In a second aspect, the present invention provides a method for preparing a drug delivery system according to the present invention as described above, comprising the steps of:
providing zinc oxide nanoparticles and a quantum dot dispersion;
Adding the zinc oxide nano particles into the quantum dot dispersion liquid, carrying out ultrasonic stirring, and then filtering and drying to obtain composite particles;
adding the composite particles into water, and then adding an alkali solution to adjust the pH value of the system to 9.3-10.6, so as to obtain a first mixed solution;
Adding the pesticide active ingredient into an organic solvent to obtain a second mixed solution;
Adding the second mixed solution into the first mixed solution, and shearing to obtain Pickering emulsion;
and performing rotary evaporation and freeze drying on the Pickering emulsion to obtain the drug carrying system.
Optionally, the organic solvent includes at least one of cyclohexane, toluene, acetone, and dichloromethane.
Optionally, in the step of adding the second mixed solution to the first mixed solution, the mass ratio of the composite particles in the first mixed solution to the pesticide active ingredients in the second mixed solution is 1 (0.6-3.3).
Optionally, the volume ratio of the first mixed solution to the second mixed solution is (2-15): 1.
Optionally, the rotation speed adopted by shearing is 8000-12000 rpm, and the time adopted by shearing is 2-20 min; the temperature adopted by the freeze drying is-45 to-86 ℃, and the time adopted by the freeze drying is 6-36 h.
In a third aspect, the present invention provides an application of the drug-carrying system according to the present invention or the drug-carrying system prepared by the preparation method according to the present invention in the field of plant disease and pest protection.
The beneficial effects are that: the pesticide carrying system is formed by wrapping pesticide active ingredients by a shell formed by composite particles, and the shell enables the pesticide carrying system to control the release of the pesticide active ingredients, increase the duration time, improve the stability of the pesticide active ingredients and improve the prevention effect, thereby effectively solving the problems of high release speed, short duration time, multiple application times, low prevention effect and the like of the active ingredients of the existing pesticide preparation. Meanwhile, the drug carrying system has the good characteristics of reducing the toxicity of the pesticide active ingredient, reducing the pollution of the pesticide active ingredient to the environment and the like. In addition, the zinc oxide nano particles in the composite particles have a bactericidal effect, and quantum dots (such as carbon quantum dots, nitrogen-doped carbon quantum dots, graphene quantum dots, nitrogen-doped graphene quantum dots, carboxylated graphene quantum dots and the like) also have a bactericidal effect, so that the composite particles have good antibacterial performance, can play a synergistic bactericidal effect with pesticide active ingredients, and further endow the drug-carrying system with an enhanced bactericidal effect. In addition, zinc element required by crop growth is introduced into the zinc oxide nano particles while the functions of the drug-carrying system are realized, so that the growth metabolism of crops is promoted.
Drawings
FIG. 1 is an optical microscope image of the drug delivery system prepared in example 1 of the present invention.
Detailed Description
The invention provides a drug-carrying system, a preparation method and application thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the design of nano pesticide controlled release formulations, the choice and performance of the carrier material is critical. The carrier material not only can effectively load active ingredients, but also can regulate and control the release of pesticide active ingredients through the physical and chemical properties of the carrier material, thereby endowing the carrier material with various properties. Based on the above, the embodiment of the invention provides a drug-carrying system (the nature of the drug-carrying system is also a drug-carrying microcapsule), wherein the drug-carrying system comprises a pesticide active ingredient and a shell for wrapping the pesticide active ingredient, the shell comprises composite particles, and the composite particles comprise zinc oxide nanoparticles and quantum dots loaded on the surfaces of the zinc oxide nanoparticles. The drug carrying system in the embodiment of the invention is formed by wrapping the pesticide active ingredient by the shell formed by the composite particles, and the shell enables the drug carrying system to control the release of the pesticide active ingredient, increase the duration time, improve the stability of the pesticide active ingredient, improve the prevention effect, and effectively solve the problems of high release speed, short duration time, multiple application times, low prevention effect and the like of the active ingredient of the existing pesticide preparation. Meanwhile, the drug carrying system has the good characteristics of reducing the toxicity of the pesticide active ingredient, reducing the pollution of the pesticide active ingredient to the environment and the like.
In addition, the zinc oxide nano particles in the composite particles have a bactericidal effect, and quantum dots (such as carbon quantum dots, nitrogen-doped carbon quantum dots, graphene quantum dots, nitrogen-doped graphene quantum dots, carboxylated graphene quantum dots and the like) also have a bactericidal effect, so that the composite particles have good antibacterial performance, can play a synergistic bactericidal effect with pesticide active ingredients, and further endow the drug-carrying system with an enhanced bactericidal effect. In addition, zinc element required by crop growth is introduced into the zinc oxide nano particles while the functions of the drug-carrying system are realized, so that the growth metabolism of crops is promoted.
In particular, in the embodiments of the present invention, zinc oxide (ZnO) nanoparticle has excellent antibacterial properties due to its nano-sized effect, high specific surface area and high surface activity, and is also a biosafety material having photo-oxidation and photo-catalysis effects on chemical and biological components. Various zinc oxide-based nanostructures have been applied in the biological field, ranging from cancer treatments to antibacterial products. The quantum dots (such as carbon quantum dots, nitrogen-doped carbon quantum dots, graphene quantum dots, nitrogen-doped graphene quantum dots, carboxylated graphene quantum dots and the like) have excellent biocompatibility and electronic performance, are simple and convenient to prepare, and are good candidates for improving the zinc oxide performance in the nanocomposite.
In some embodiments, the mass ratio of the pesticide active ingredient to the shell is (0.6-3.3): 1. For example, it may be 0.6:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, or 3.3:1, etc.
In some embodiments, the mass ratio of the zinc oxide nano particles to the quantum dots is (90-99.9): 0.1-10. For example, the mass ratio of the zinc oxide nanoparticle to the quantum dot may be 90:0.1, 90:2, 90:5, 90:10, 95:0.1, 95:2, 95:5, 95:10, 97:0.1, 97:2, 97:5, 97:10, 99.9:0.1, 99.9:2, 99.9:5, 99.9:10, or the like.
In some embodiments, the quantum dots include at least one of carbon quantum dots (i.e., pure carbon quantum dots that are undoped), nitrogen-doped carbon quantum dots, graphene quantum dots (i.e., pure graphene quantum dots that are undoped and functionalized), nitrogen-doped graphene quantum dots, and carboxylated graphene quantum dots, but are not limited thereto. The carbon quantum dots and the nitrogen-doped carbon quantum dots have excellent biocompatibility, solubility and stability. It consists of a hydrophobic carbon core and surface-rich hydrophilic functional groups (such as hydroxyl, carbonyl and carboxyl groups). The carbon quantum dots and the nitrogen-doped carbon quantum dots have good photodynamic sterilization effect on microorganisms under the irradiation of visible light, and can achieve the synergistic killing effect of photothermal and photodynamic. The graphene quantum dots, the nitrogen-doped graphene quantum dots and the carboxylated graphene quantum dots have good photo-thermal conversion efficiency, and can also generate Reactive Oxygen Species (ROS), and excessive ROS can damage cell membranes, proteins and DNA, so that cells are killed. Therefore, the quantum dots in the composite particles in the embodiment exist, so that the drug-carrying system can achieve the effect of synergetic killing cells by photo-thermal and photodynamic without loading a photosensitizer, and the drug-carrying system and the pesticide active ingredient in the drug-carrying system have synergetic effect.
In some embodiments, the pesticide active ingredient includes, but is not limited to, at least one of pyraclostrobin, tebuconazole, ipconazole, cyhalothrin, fludioxonil, difenoconazole, and triflumizole.
The embodiment of the invention also provides a preparation method of the drug carrying system, which is provided by the embodiment of the invention, and comprises the following steps:
s1, providing zinc oxide nano-particles and quantum dot dispersion liquid; adding the zinc oxide nano particles into the quantum dot dispersion liquid, carrying out ultrasonic stirring, and then filtering and drying to obtain composite particles;
S2, adding the composite particles into water, and then adding an alkali solution to adjust the pH value of a system to 9.3-10.6, so as to obtain a first mixed solution;
s3, adding the pesticide active ingredient into the organic solvent to obtain a second mixed solution;
s4, adding the second mixed solution into the first mixed solution, and shearing to obtain Pickering emulsion;
s5, performing rotary evaporation (removing organic solvent) and freeze drying (removing water) on the Pickering emulsion to obtain the drug-carrying system.
The invention prepares the drug carrying system by an emulsion template method, and prepares the oil-in-water type Pickering emulsion for solubilizing the pesticide active ingredient by taking the composite particles as a stabilizer.
Specifically, zinc oxide nano particles loaded with quantum dots are arranged on an oil-water interface to form an interface film to wrap oil drops containing pesticide active ingredients (the oil drops are composed of the pesticide active ingredients and an organic solvent), so that collision and combined aggregation among the oil drops are prevented, and the loading of the pesticide active ingredients is realized; meanwhile, the amphipathy of the quantum dot (the surface of the quantum dot contains abundant hydrophilic functional groups such as hydroxyl, carbonyl and carboxyl) further promotes the spontaneous migration of the composite particles to an oil-water interface, and the synergistic effect of the zinc oxide nano particles and the quantum dot effectively reduces the interfacial tension to form stable Pickering emulsion. Therefore, the composite particles are coated on the surfaces of the oil phase liquid drops to form a stable interface film, so that collision and coalescence among the oil drops containing the pesticide active ingredients are prevented, the oil drops containing the pesticide active ingredients are protected, and the stability of the oil-in-water pickering emulsion is improved. Further, after removing the organic solvent and water in the pickering emulsion, the stabilizer (i.e. the composite particles) is wrapped on the surface of the pesticide active ingredient, and the drug-carrying system is obtained.
In addition, the composite particles not only play a role in stabilizing the Pickering emulsion and solubilizing the pesticide active ingredient, but also have good antibacterial performance and play a role in synergistic sterilization with the pesticide active ingredient.
The preparation method provided by the embodiment of the invention is simple, the prepared pickering emulsion has stable performance and high pesticide active ingredient load, and the prepared drug-carrying system has high pesticide active ingredient load.
In the step S1, quantum dots in the composite particles are adsorbed on the surfaces of the zinc oxide nanoparticles. The quantum dots (such as carbon quantum dots, nitrogen-doped carbon quantum dots, graphene quantum dots, nitrogen-doped graphene quantum dots, carboxylated graphene quantum dots and the like) have larger specific surface area and rich oxygen-containing functional groups, have electronegativity, and the surfaces of the zinc oxide nanoparticles are positively charged, so that the quantum dots and the zinc oxide nanoparticles realize spontaneous assembly due to electrostatic attraction, and are adsorbed on the surfaces of the zinc oxide nanoparticles through static electricity. Meanwhile, due to the electrostatic attraction effect of the zinc oxide nanoparticle and the quantum dot, the dispersion of the quantum dot is facilitated, so that the zinc oxide nanoparticle and the quantum dot exist in a composite particle form, and the effect of the quantum dot can be fully exerted.
In some embodiments, the method of preparing zinc oxide nanoparticles includes the steps of:
And adding a sodium hydroxide solution into the zinc acetate solution, transferring the zinc acetate solution into a hydrothermal reaction kettle, and performing hydrothermal reaction for 4-12 hours (for example, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, and the like) at the temperature of 100-120 ℃ (for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃ and the like) to obtain the zinc oxide nanoparticles.
In some embodiments, the method of preparing the quantum dot dispersion includes the steps of:
and mixing the quantum dots with water, and performing ultrasonic treatment to obtain the quantum dot dispersion liquid.
In some embodiments, the quantum dots include at least one of carbon quantum dots (i.e., pure carbon quantum dots that are undoped), nitrogen-doped carbon quantum dots, graphene quantum dots (i.e., pure graphene quantum dots that are undoped and functionalized), nitrogen-doped graphene quantum dots, and carboxylated graphene quantum dots, but are not limited thereto. The carbon quantum dots and the nitrogen-doped carbon quantum dots have excellent biocompatibility, solubility and stability. The amphiphilic polymer consists of a hydrophobic carbon core and hydrophilic functional groups (such as hydroxyl, carbonyl and carboxyl) with rich surfaces, and the amphipathy can stabilize Pickering emulsion. In addition, the carbon quantum dots and the nitrogen-doped carbon quantum dots have good photodynamic sterilization effect on microorganisms under the action of illumination, and can achieve the synergistic killing effect of photo-heat and photodynamic. The graphene quantum dots, the nitrogen-doped graphene quantum dots and the carboxylated graphene quantum dots have good photo-thermal conversion efficiency, and can also generate Reactive Oxygen Species (ROS), and excessive ROS can damage cell membranes, proteins and DNA, so that cells are killed. Therefore, the quantum dots in the embodiment exist, so that the drug-carrying system can achieve the effect of synergetic killing cells by photo-thermal and photodynamic without loading a photosensitizer, and the drug-carrying system and the pesticide active ingredient in the drug-carrying system have synergetic effect.
In step S1, in some embodiments, the step of ultrasonic agitation is specifically:
Step A: ultrasonic treatment for 2s, stopping for 2s, repeating the process until the total time of ultrasonic treatment and stopping reaches 0.5-1 h,
And (B) step (B): stirring for 1-5 min;
step C: the steps a to B are repeated four times.
As an example, the step a specifically includes: the procedure was repeated 450 times with ultrasound for 2s and stopped for 2s, at which time the total time of ultrasound and stopping was 0.5h.
In this embodiment, the ultrasonic time is too long, which causes a temperature increase, which causes aggregation of the quantum dots, and affects the loading effect, so that the ultrasonic and stopping are performed at intervals. In addition, the ultrasonic wave is used together with stirring, so that the mixing of the quantum dots and the zinc oxide nano particles can be promoted, and a good loading effect is achieved.
In the step S2, an alkaline solution is added to adjust the pH value of the system to 9.3-10.6, so that the wettability of the composite particles is improved, the composite particles are better distributed on an oil-water interface, an interface film is formed to wrap oil drops, and collision and combination aggregation among the oil drops are prevented.
In step S3, the pesticidal active ingredient is described above, and will not be described here.
In some embodiments, the organic solvent includes, but is not limited to, at least one of cyclohexane, toluene, acetone, and methylene chloride.
In step S4, in some embodiments, in the step of adding the second mixed solution to the first mixed solution, the mass ratio of the composite particles in the first mixed solution to the pesticide active ingredient in the second mixed solution is 1 (0.6-3.3), for example, may be 1:0.6, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, or 1:3.3.
In some embodiments, the volume ratio of the first mixed solution to the second mixed solution is (2-15): 1, for example, may be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, or the like.
In some embodiments, the shear is performed at a rotational speed of 8000-12000 rpm (e.g., 8000rpm, 9000rpm, 10000rpm, 11000rpm, 12000rpm, etc.), and the shear is performed for a time of 2-20 min (e.g., 2min, 5min, 10min, 15min, 20min, etc.).
In the step S5, the temperature adopted for the freeze drying is-45 to-86 ℃ (for example, the temperature can be-45 ℃, -50 ℃, -55 ℃, -60 ℃, -65 ℃, -70 ℃, -75 ℃, -80 ℃, -85 ℃ or-86 ℃ and the like), and the time adopted for the freeze drying is 6-36 h (for example, the temperature can be 6h, 10h, 15h, 20h, 25h, 30h, 35h or 36h and the like).
The embodiment of the invention also provides application of the drug carrying system in the field of plant disease and insect pest protection.
The embodiment of the invention also provides application of the drug-carrying system prepared by the preparation method in the field of plant disease and insect pest protection. The pesticide active ingredient in the pesticide carrying system has high loading quantity and slow release effect, and can effectively prevent and treat plant diseases and insect pests.
In some embodiments, the steps of applying are specifically:
mixing a drug carrying system, an auxiliary agent and water to obtain a suspending agent;
the suspending agent is mixed with water, diluted and applied (may be sprayed specifically) on plants.
The invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a preparation method of a drug carrying system, which comprises the following steps:
(1) Preparation of Zinc oxide nanoparticles
Mixing zinc acetate with water to prepare zinc acetate solution with the concentration of 0.02 mol/L; sodium hydroxide was mixed with water to prepare a sodium hydroxide solution having a concentration of 0.2 mol/L.
And placing the zinc acetate solution on a magnetic stirrer, dropwise adding sodium hydroxide solution while stirring, adjusting the pH value of the system to 11, and fully stirring to obtain a mixed solution.
Transferring the mixed solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 10 hours at 110 ℃, naturally cooling to room temperature, and collecting precipitate.
Washing the precipitate with deionized water and absolute ethyl alcohol for 2 times respectively, drying in an oven at 55 ℃ for 6 hours, and grinding to obtain nano zinc oxide powder (namely zinc oxide nano particles).
(2) Preparation of carbon Quantum dots
Mixing 10g of urea, 10g of citric acid and 35mL of water, uniformly stirring, and then placing in a microwave oven, and obtaining a product after using 800W high fire for 12 min;
Adding water into the obtained product, ultrasonically stirring and dissolving, standing for 1h, taking the upper liquid, carrying out suction filtration, and freeze-drying at the temperature of 86 ℃ below zero to obtain the carbon quantum dot.
(3) Preparation of composite particles
Mixing the carbon quantum dots with water, and performing ultrasonic treatment at 700W for 30min to prepare a carbon quantum dot dispersion liquid with the concentration of 1 mg/mL.
Adding zinc oxide nano particles into the carbon quantum dot dispersion liquid, enabling the mass ratio of the zinc oxide nano particles to the carbon quantum dots to be 99:1, and then carrying out the following steps:
Step a: 2s of 700W ultrasonic treatment, stopping for 2s, repeating the process for 450 times until the total time of ultrasonic treatment and standing is 0.5h;
Step b: stirring for 5min;
Step c, repeating the steps a to b four times.
And then filtering, and drying the obtained product in an oven at 55 ℃ for 6 hours to obtain composite particles, wherein the composite particles comprise zinc oxide nano particles and carbon quantum dots loaded on the surfaces of the zinc oxide nano particles.
(4) Preparation of Pickering emulsion
Adding 0.1g of the composite particles into 50mL of deionized water, uniformly dispersing by ultrasonic, dropwise adding a sodium hydroxide solution with the concentration of 0.2mol/L into the solution, and regulating the pH of the system to 10 to obtain a first mixed solution (namely, water phase).
0.1G of pyraclostrobin is dissolved in 25mL of toluene and stirred uniformly to obtain a second mixed solution (namely an oil phase).
And adding the second mixed solution into the first mixed solution, and shearing at high speed for 20min by using a high-speed shearing dispersing emulsifying machine (IKA T18, namely German Ai Kashu developing type dispersing machine) at a rotating speed of 10000rpm to obtain the pickering emulsion with the pyraclostrobin solubilized.
(5) Preparation of drug-carrying System
And (3) taking the Pickering emulsion, rotationally evaporating to remove toluene, and freeze-drying at-86 ℃ to remove water to obtain a drug-carrying system, wherein an optical microscope diagram of the drug-carrying system is shown in figure 1 and comprises pyraclostrobin and a shell for wrapping the pyraclostrobin, and the shell comprises zinc oxide nanoparticles and carbon quantum dots loaded on the surfaces of the zinc oxide nanoparticles.
The drug-carrying system prepared in the example 1 is used for preventing and controlling the sheath blight of wheat, setting and comparing, and 3 wheat test fields (the wheat in which has the sheath blight) are tested and respectively marked as No. 1 wheat field, no. 2 wheat field and No. 3 wheat field, wherein the basic conditions of the 3 wheat test fields are consistent, and the drug application time and the investigation time are consistent. The disease states of wheat are investigated before the application, the disease indexes and average disease indexes of No. 1 wheat field, no. 2 wheat field and No. 3 wheat Tian Zhongxiao wheat are calculated, then the application is carried out, the growth condition of the wheat is observed after the application, the phenomenon of phytotoxicity is observed, the disease states of the wheat are investigated after 20 days of the application, and the disease indexes and average disease indexes are calculated.
The specific application method comprises the following steps:
According to mass percent, mixing 25% of the drug-carrying system prepared in the example 1, 0.2% of xanthan gum, 0.4% of an organosilicon defoamer, 1% of a silicon dioxide stabilizer, 4% of glycerol, 5% of a polycarboxylate dispersant and 64.4% of water to obtain a first suspending agent; mixing and diluting the first suspending agent and water according to the volume ratio of 1:1500 to obtain a first diluent; then spraying the first diluent on wheat Tian Shang No. 1, and enabling the amount of one suspending agent per 667m 2 wheat Tian Shangdi to be 60mL;
According to mass percentage, 25% of pyraclostrobin, 0.2% of xanthan gum, 0.4% of organic silicon defoamer, 1% of silicon dioxide stabilizer, 4% of glycerol, 5% of polycarboxylate dispersant and 64.4% of water are mixed to obtain a second suspending agent; mixing and diluting the second suspending agent and water according to the volume ratio of 1:1500 to obtain a second diluent; then spraying the second diluent on a No. 2 wheat field, wherein the dosage of two suspending agents per 667m 2 wheat Tian Shangdi is 60mL;
Meanwhile, no drug was applied to wheat field No. 3 and water was sprayed only as a blank Control (CK).
The results are shown in Table 1 below.
TABLE 1 control effect of wheat sheath blight
Note that: control effect = [ (control area disease index increase value-treatment area disease index increase value)/control area disease index increase value ] ×100%.
For example, the control effect of wheat in wheat field No. 1 is: [ (11.9-1.7) - (3.5-1.7) ]/(11.9-1.7) ×100% =82.4%. Therefore, the drug-carrying system provided by the embodiment has the effect of preventing and treating the sheath blight of wheat, and the wheat grows well.
Example 2
The embodiment provides a preparation method of a drug carrying system, which comprises the following steps:
(1) Preparation of Zinc oxide nanoparticles
The procedure for preparing zinc oxide nanoparticles was the same as in step (1) of example 1.
(2) Preparation of carbon Quantum dots
The procedure for preparing the carbon quantum dots was the same as in step (2) of example 1.
(3) Preparation of composite particles
The carbon quantum dots and water are mixed, and the mixture is subjected to 700W ultrasonic treatment for 30 min to prepare the carbon quantum dot dispersion liquid with the concentration of 1 mg/mL.
Adding zinc oxide nano particles into the carbon quantum dot dispersion liquid, enabling the mass ratio of the zinc oxide nano particles to the carbon quantum dots to be 95:5, and then carrying out the following steps:
Step a: 2s of 700W ultrasonic treatment, stopping 2s, repeating the process for 900 times until the total time of ultrasonic treatment and standing is 1h;
Step b: stirring for 5min;
Step c, repeating the steps a to b four times.
And then filtering, and drying the obtained product in an oven at 55 ℃ for 6 hours to obtain composite particles, wherein the composite particles comprise zinc oxide nano particles and carbon quantum dots loaded on the surfaces of the zinc oxide nano particles.
(4) Preparation of Pickering emulsion
Adding 0.1g of composite particles into 100mL of deionized water, uniformly dispersing by ultrasonic, adding a sodium hydroxide solution with the drop concentration of 0.2mol/L, and regulating the pH of the system to 10 to obtain a first mixed solution (namely, water phase).
0.1G of difenoconazole is dissolved in 25mL of cyclohexane and stirred uniformly to obtain a second mixed solution (namely an oil phase).
Adding the second mixed solution into the first mixed solution, and shearing at high speed for 20min by using a high-speed shearing dispersing emulsifying machine (IKA T18, namely German Ai Kashu developing type dispersing machine) at a rotating speed of 10000rpm to obtain Pickering emulsion;
(5) Preparation of drug-carrying System
And taking the Pickering emulsion, removing cyclohexane by rotary evaporation, and then freeze-drying at the temperature of-86 ℃ to remove water to obtain a drug carrying system.
In summary, the invention provides a drug-carrying system and a preparation method and application thereof, wherein the drug-carrying system is formed by wrapping pesticide active ingredients by a shell formed by composite particles, and the shell enables the drug-carrying system to control the release of the pesticide active ingredients, increase the duration time, improve the stability of the pesticide active ingredients and improve the prevention effect, thereby effectively solving the problems of high release speed, short duration time, multiple application times, low prevention effect and the like of the active ingredients of the existing pesticide preparation. Meanwhile, the drug carrying system has the good characteristics of reducing the toxicity of the pesticide active ingredient, reducing the pollution of the pesticide active ingredient to the environment and the like. In addition, the zinc oxide nano particles in the composite particles have a bactericidal effect, and the quantum dots also have a bactericidal effect, so that the composite particles have good antibacterial performance, can play a synergistic bactericidal effect with pesticide active ingredients, and further endow the drug-carrying system with an enhanced bactericidal effect. In addition, zinc element required by crop growth is introduced into the zinc oxide nano particles while the functions of the drug-carrying system are realized, so that the growth metabolism of crops is promoted.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. The drug-carrying system is characterized by comprising a pesticide active ingredient and a shell for wrapping the pesticide active ingredient, wherein the shell comprises composite particles, and the composite particles comprise zinc oxide nanoparticles and quantum dots loaded on the surfaces of the zinc oxide nanoparticles.
2. The drug delivery system of claim 1, wherein the mass ratio of the pesticide active ingredient to the shell is (0.6-3.3): 1.
3. The drug delivery system of claim 1, wherein the mass ratio of the zinc oxide nanoparticles to the quantum dots is (90-99.9): 0.1-10.
4. The drug delivery system of claim 1, wherein the quantum dots comprise at least one of carbon quantum dots, nitrogen-doped carbon quantum dots, graphene quantum dots, nitrogen-doped graphene quantum dots, and carboxylated graphene quantum dots;
The pesticide active ingredient comprises at least one of pyraclostrobin, tebuconazole, ipconazole, cyhalothrin, fludioxonil, difenoconazole and trifluorecited in the claims.
5. A method of preparing a drug delivery system according to claim 1, comprising the steps of:
providing zinc oxide nanoparticles and a quantum dot dispersion;
Adding the zinc oxide nano particles into the quantum dot dispersion liquid, carrying out ultrasonic stirring, and then filtering and drying to obtain composite particles;
adding the composite particles into water, and then adding an alkali solution to adjust the pH value of the system to 9.3-10.6, so as to obtain a first mixed solution;
Adding the pesticide active ingredient into an organic solvent to obtain a second mixed solution;
Adding the second mixed solution into the first mixed solution, and shearing to obtain Pickering emulsion;
and performing rotary evaporation and freeze drying on the Pickering emulsion to obtain the drug carrying system.
6. The method according to claim 5, wherein the organic solvent comprises at least one of cyclohexane, toluene, acetone, and methylene chloride.
7. The method according to claim 5, wherein in the step of adding the second mixed solution to the first mixed solution, the mass ratio of the composite particles in the first mixed solution to the pesticidal active ingredient in the second mixed solution is 1 (0.6-3.3).
8. The method according to claim 5, wherein the volume ratio of the first mixed solution to the second mixed solution is (2-15): 1.
9. The method according to claim 5, wherein the rotation speed for shearing is 8000-12000 rpm, and the time for shearing is 2-20 min;
The temperature adopted by the freeze drying is-45 to-86 ℃, and the time adopted by the freeze drying is 6-36 h.
10. Use of a drug delivery system according to any one of claims 1 to 4 or a drug delivery system prepared by a preparation method according to any one of claims 5 to 9 in the field of plant pest protection.
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