CN115885989A - Slow-release pyrethroid nanoparticle and preparation method and application thereof - Google Patents
Slow-release pyrethroid nanoparticle and preparation method and application thereof Download PDFInfo
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- CN115885989A CN115885989A CN202211286150.4A CN202211286150A CN115885989A CN 115885989 A CN115885989 A CN 115885989A CN 202211286150 A CN202211286150 A CN 202211286150A CN 115885989 A CN115885989 A CN 115885989A
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- 239000002728 pyrethroid Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- 239000003814 drug Substances 0.000 claims abstract description 31
- 229940079593 drug Drugs 0.000 claims abstract description 27
- 238000011068 loading method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000011148 porous material Substances 0.000 claims description 37
- KAATUXNTWXVJKI-NSHGMRRFSA-N (1R)-cis-(alphaS)-cypermethrin Chemical compound CC1(C)[C@@H](C=C(Cl)Cl)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-NSHGMRRFSA-N 0.000 claims description 34
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- 238000000034 method Methods 0.000 claims description 12
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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 description 5
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- ZXQYGBMAQZUVMI-RDDWSQKMSA-N (1S)-cis-(alphaR)-cyhalothrin Chemical compound CC1(C)[C@H](\C=C(/Cl)C(F)(F)F)[C@@H]1C(=O)O[C@@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-RDDWSQKMSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the technical field of pesticides, and discloses a slow-release pyrethroid nanoparticle as well as a preparation method and application thereof. The pyrethroid pesticide is loaded by the hollow mesoporous silica, so that the pyrethroid pesticide has higher drug loading capacity, the release performance of the pyrethroid pesticide can be adjusted, the pyrethroid pesticide is quickly released in the early stage, pyrethroid pesticide molecules are continuously and slowly released in the later stage, the lasting period can reach more than 30 days, the insect control effect is obvious, and the application range and the period of the pyrethroid quick-release pesticide are expanded.
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a preparation method and application of a slow-release pyrethroid nanoparticle.
Background
Pesticides play an indispensable role in pest control. However, the pesticide has high toxicity, most of the pesticides have short duration and strong quick action, and have strong toxic and harmful effects on organisms. Therefore, the effect of prolonging the lasting period of the pesticide is important. Pyrethroid insecticides are originally discovered from the natural plant pyrethrum, and are artificially synthesized, and have the characteristics of high efficiency, broad spectrum, low toxicity, low residue and the like. The pyrethroid insecticide is mainly contact insecticide, has quick insecticidal effect and good effect, and generally has short lasting period. Under the influence of temperature, sunshine and other environment, the effective period of cypermethrin is about 5 days in spring and summer and less than 7 days in autumn and winter. Therefore, the effective period of the pyrethroid insecticide is prolonged, the insecticidal effect is improved, and the pyrethroid insecticide has particularly important significance for preventing and controlling agricultural pests.
With the development of nanotechnology, nanomaterials are used in the fields of medical treatment, construction, catalysts, and the like, and research in the field of controlled release of pesticides is getting more and more popular. The nanometer material has wide application prospect in the controlled release field, has better stability, realizes the slow release of effective components, and has no toxic and harmful effects on biosafety. The mesoporous silica nano-particles have the advantages of larger specific surface area and pore volume, adjustable pore diameter, high stability, easy functional modification and the like, so that the mesoporous silica nano-particles have higher molecular adsorption force and better safety to organisms. The mesoporous channel can change the crystalline state of the drug into the amorphous state, stably load the drug and regulate the pore size to control the drug delivery. The morphology and performance of mesoporous silica nanoparticles are directly related to the preparation raw materials and the preparation method. For example, patent CN105329905A adopts zeolite imidazolate framework nano-particles as a moldAdding a cationic surfactant and a silicon source into the plate, reacting under an alkaline condition, and centrifuging to obtain hollow mesoporous silica nanoparticles with the specific surface area of 676.7m 2 G, average pore diameter 2.7nm. CN109160519A is prepared by dissolving a cationic surfactant and an oil phase in a mixed solvent of water and an organic solvent, adding an organic silicon source and ammonia water under stirring, reacting under the condition of an alkaline solution, centrifuging, washing, drying, and calcining at 300-600 ℃ for 2-6 h to obtain hollow mesoporous silica microspheres, wherein the specific surface area of the prepared hollow mesoporous silica is 496.2m 2 G, pore volume 1.84cm 3 G, pore diameter of 13.97nm. Nie Zhixin and the like, and then uses tetraethoxysilane as a silicon source to synthesize solid silicon dioxide spheres, and then uses Na 2 CO 3 And CTAB selectively etching the nano-spheres in one step to obtain the hollow mesoporous silica nanospheres with the specific surface area of 890m 2 The pore volume reaches 1.05 and the pore diameter reaches 6.26nm. The specific surface area, the pore size and the particle size of the mesoporous silica nanoparticles directly influence the loading capacity and the release performance of the pesticide. The improvement of the specific surface area of the hollow mesoporous silica, the increase of the pesticide loading capacity and the adjustment of the release performance become the main improvement directions of the nano pesticide particles.
Disclosure of Invention
The invention aims to provide a slow-release pyrethroid nanoparticle as well as a preparation method and application thereof. The slow-release pyrethroid nanoparticle provided by the invention has an ultra-long lasting period, is safe to crops and has a good insect prevention effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
one object of the invention is to provide a preparation method of a slow-release pyrethroid nanoparticle, which comprises the following steps:
uniformly mixing absolute ethyl alcohol, deionized water, cetyl Trimethyl Ammonium Bromide (CTAB) and cyclohexane, adding tetraethyl orthosilicate (TEOS) and ammonia water, stirring and reacting for 10-24h at room temperature, and centrifugally drying to obtain solid silicon dioxide;
dispersing the solid silicon dioxide in water, adding anhydrous sodium carbonate, heating to 50-80 ℃, stirring for reaction for 4-6h, centrifuging the obtained precipitate, and reacting in hydrochloric acid-hot ethanol for 1-4h to obtain hollow mesoporous silicon dioxide nanoparticles (HMSN);
dispersing the hollow mesoporous silica nanoparticles in an organic solvent, adding a pyrethroid original drug, stirring for 10-24h, centrifuging and drying to obtain the slow-release pyrethroid nanoparticles.
Preferably, the proportion of the absolute ethyl alcohol, the deionized water, the CTAB, the cyclohexane, the TEOS and the ammonia water is 30-90ml:60-150ml:0.2-0.4g:1-3g:2-4ml:1-3ml.
Preferably, the mass ratio of the solid silica to the anhydrous sodium carbonate is 0.4-1:2-3.
Preferably, the temperature of the hydrochloric acid-hot ethanol is 50-70 ℃, wherein the volume ratio of the hydrochloric acid to the absolute ethanol is 0.4-1:150-300.
Preferably, the specific surface area of the hollow mesoporous silica nanoparticle of the invention is 1318m 2 Per g, pore volume 1.52cm 3 (ii)/g, pore diameter of 3.09nm, and average particle diameter of 183nm.
Preferably, the organic solvent of the present invention is dichloromethane, xylene or methanol.
Preferably, the mass ratio of the hollow mesoporous silica nanoparticles to the pyrethroid pesticide is 1:0.5-4.
The invention also discloses the slow-release pyrethroid nanoparticle prepared by the preparation method. The optional pyrethroid is beta-cypermethrin, pyraclostrobin, deltamethrin, lambda-cyhalothrin, fenvalerate, etc.
As an embodiment, the slow-release pyrethroid nanoparticle is a beta-cypermethrin nanoparticle, and the loading rate of the beta-cypermethrin in the beta-cypermethrin nanoparticle reaches 32.53%.
The invention also comprises the application of the slow-release pyrethroid nanoparticle in controlling agricultural pests, wherein the control effect of the slow-release pyrethroid nanoparticle is more than 30 days.
Compared with the prior art, the invention has the following advantages and effects:
the invention uses hollow mesoporous silicon dioxide to load pyrethroid original medicine, has higher medicine-loading rate and can adjust the release performance of the pyrethroid pesticide. The slow-release pyrethroid pesticide nano-particles have good slow-release performance, are quickly released in the early stage, continuously and slowly release pyrethroid pesticide molecules in the later stage, have the lasting period of over 30 days, and have obvious insect prevention and control effects. The invention improves the release performance of the quick-release pyrethroid pesticide preparation, enlarges the application range and the period of the pesticide, and reduces the application times and the labor cost.
According to the invention, the hollow mesoporous silica is prepared by using a self-template method, and when the solid silica is prepared, the template CTAB and cyclohexane are added, so that the affinity between CTAB and cyclohexane can influence the formation of a mesoporous structure. Cyclohexane is used as a hydrophobic group to be dissolved and inserted into the CTAB phase to form micelle, so that the diameter of the micelle is enlarged, and the pore diameter is enlarged. The nano-particles prepared by the method have the advantages of spherical appearance, regular appearance, no adhesion, thin shell, large cavity, large pore diameter, pore volume and specific surface, are beneficial to the entry of pyrethroid pesticide molecules to improve the drug loading rate, and become an ideal pyrethroid pesticide controlled release agent carrier.
Drawings
FIG. 1 is a TEM image of the synthesized HMSN of example 1;
FIG. 2 is a TEM image of synthesized β -CP/HMSN of example 4;
FIG. 3 is a nitrogen adsorption-desorption curve (A) and a pore size distribution diagram (B) of HMSN synthesized by different etching times and temperatures in comparative example 1 and by adding cyclohexane in example 1;
FIG. 4 shows the nitrogen adsorption-desorption curve (A) and the pore size distribution diagram (B) of HMSN synthesized in example 1 and beta-CP/HMSN synthesized in example 4;
FIG. 5 is a particle size distribution of HMSN synthesized in example 1 and β -CP/HMSN synthesized in example 4;
FIG. 6 is an infrared spectrum of beta-CP/HMSN and an active compound of beta-cypermethrin;
FIG. 7 is the thermogravimetric curves of the technical grade of beta-CP/HMSN, the technical grade of beta-cypermethrin;
FIG. 8 is an XRD image of beta-CP/HMSN and HMSN of beta-cypermethrin;
FIG. 9 is a 277nm standard curve of beta-cypermethrin in a sustained release medium;
FIG. 10 is the release curve of beta-CP/HMSN in DMF water solution;
FIG. 11 is a graph of mortality of various concentrations of beta-CP/HMSN at various times on corn borer larvae;
FIG. 12 is a safety evaluation of HMSN and beta-CP/HMSN on corn seedling roots and aerial parts.
Detailed Description
The invention provides a preparation method of a slow-release pyrethroid nanoparticle, which comprises the following steps: uniformly mixing absolute ethyl alcohol, deionized water, CTAB and cyclohexane, adding TEOS and ammonia water, stirring and reacting for 10-24h at room temperature, and centrifugally drying to obtain solid silicon dioxide; dispersing the solid silicon dioxide in water, adding anhydrous sodium carbonate, heating to 50-80 ℃, stirring for reaction for 4-6h, centrifuging the obtained precipitate, and reacting in hydrochloric acid-hot ethanol for 1-4h to obtain hollow mesoporous silicon dioxide nano particles; dispersing the hollow mesoporous silica nanoparticles in an organic solvent, adding a pyrethroid original drug, stirring for 10-24h, centrifuging and drying to obtain the slow-release pyrethroid nanoparticles.
The invention adopts a self-template method to prepare the hollow mesoporous silica, template agent CTAB and cyclohexane are added when the solid silica is prepared, then the solid silica is used as a basic template, water is used as an etching agent to regulate and control reaction conditions to prepare the hollow mesoporous silica, and the HMSN which has the advantages of spherical shape, complete appearance, no adhesion, thin shell and large cavity can be formed.
In the invention, the proportion of the absolute ethyl alcohol, the deionized water, CTAB, cyclohexane, TEOS and ammonia water is preferably 30-90ml:60-150ml:0.2-0.4g:1-3g:2-4ml:1-3ml, more preferably 50-60ml:100-130ml:0.3-0.4g:1.5-3g:2-3ml:2-3ml. The ammonia water of the invention refers to ammonia water with the concentration of 25-28%. In the present invention, the raw material components are reacted under stirring at room temperature, preferably for 12 to 20 hours, more preferably for 15 to 18 hours. The stirring rate is not particularly limited in the present invention, and is preferably 250 to 350r/min. The invention centrifugalizes the solution after reaction, and the obtained precipitate is dried after being washed to obtain the solid silicon dioxide. The washing is preferably absolute ethanol washing, and further 2-3 times of washing. As an embodiment, the drying is drying at 50-70 ℃ for 10-12h, or spray drying.
According to the invention, CTAB and cyclohexane are added when the solid silica is prepared, and the cyclohexane is used as a hydrophobic group, and is dissolved with the CTAB to form micelles in an inserting manner, so that the diameter of the micelles is enlarged, and the pore diameter after etching is enlarged. The mode of operation can also affect the pore size, pore volume and specific surface area of the HMSN produced. According to the invention, all the components are added at one time for reaction, and the aperture, pore volume and specific surface area of the synthesized HMSN are increased.
The invention disperses the solid silicon dioxide in water, and takes water as an etching agent to prepare the hollow mesoporous silicon dioxide. As an embodiment, the solid silica is ultrasonically dispersed in water to improve the dispersion effect, and anhydrous sodium carbonate is added into the dispersion solution, and the mass ratio of the solid silica to the anhydrous sodium carbonate is preferably 0.4-1:2 to 3, more preferably 0.5 to 0.7:2-2.5. According to the invention, the etching temperature is preferably 55-70 ℃, more preferably 60-65 ℃, and the etching time is preferably 5-5.5h. And after the reaction is finished, centrifuging the reaction solution, and washing the precipitate by using deionized water to obtain the silica particles with the mesoporous shell structure. The present invention is not particularly limited in terms of the manner of centrifugation, and any conventional method in the art may be used. As an embodiment, the centrifugation is carried out at a rotating speed of 6000 to 9000r/min for 3 to 10min. As an embodiment, deionized water washes 2-3 times.
The invention removes template CTAB by reacting the obtained precipitate in hydrochloric acid-hot ethanol. Preferably, the temperature of the hydrochloric acid-hot ethanol is 50-70 ℃, and further preferably 60-65 ℃; the reaction time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours. Wherein the volume ratio of the hydrochloric acid to the absolute ethyl alcohol is preferably 0.4-1:150 to 300, more preferably 0.5 to 0.7:200-260 percent of hydrochloric acid with the concentration of 36-38 percent. And obtaining the hollow mesoporous silica nano particles (HMSN) after the reaction is finished.
According to the inventionThe hollow mesoporous silica nano-particles are spherical, have complete appearance and no adhesion, have a thin shell and a large cavity, and have a specific surface area of 1318m 2 G, pore volume 1.52cm 3 (ii)/g, pore diameter of 3.09nm, and average particle diameter of 183nm. The invention utilizes the hollow mesoporous silica nanoparticles as the carriers to prepare the slow-release pyrethroid nanoparticles so as to change the release performance of pyrethroid pesticides and improve the application range of the pesticides.
The invention disperses the hollow mesoporous silicon dioxide nano particles in an organic solvent, adds the technical pesticide of the pyrethroid pesticide, stirs for 10-24h, and centrifugally dries to obtain the slow-release pyrethroid nano particles. The organic solvent of the present invention includes, but is not limited to, dichloromethane, xylene or methanol. The pyrethroid pesticide raw pesticide of the invention includes but is not limited to beta-cypermethrin, pyraclostrobin, deltamethrin, lambda-cyhalothrin, fenvalerate and the like. According to the invention, the mass ratio of the hollow mesoporous silicon dioxide nanoparticles to the pyrethroid pesticide raw pesticide is preferably 1:0.5 to 4, more preferably 1:2-3. The stirring is carried out at room temperature, and the stirring load time is further preferably 12 to 20 hours. And after loading is finished, centrifugally drying the solution to obtain the slow-release pyrethroid nano particles. The drying mode can be drying or spray drying.
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples. The experimental methods used in the examples are conventional methods unless otherwise specified, and the materials, reagents and the like used therein are commercially available unless otherwise specified.
Example 1
Preparation of hollow mesoporous silica nanoparticles
60mL of absolute ethyl alcohol, 120mL of deionized water and 0.35g of CTAB, adding 2g of cyclohexane, uniformly stirring, adding 2mL of TEOS and 2mL of ammonia water, stirring and reacting at room temperature for 12 hours, centrifuging after the reaction is finished, washing with absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 10 hours to obtain the solid silicon dioxide.
Adding solid silicon dioxide into 240mL of deionized water, performing ultrasonic dispersion, adding 2.12g of anhydrous sodium carbonate, heating to 65 ℃, stirring for reaction for 4 hours, centrifuging, and washing with deionized water for 3 times; adding the precipitate into 240mL of absolute ethyl alcohol, adding 0.54mL of hydrochloric acid, stirring and reacting at 60 ℃ for 2h, and removing the template CTAB to obtain the HMSN.
Example 2
Preparation of hollow mesoporous silica nanoparticles
30mL of absolute ethyl alcohol, 60mL of deionized water, 0.2g of CTAB, 2.6g of cyclohexane, 3mL of TEOS and 1mL of ammonia water are added, the mixture is stirred and reacted for 24 hours at room temperature, centrifugation is carried out after the reaction is finished, the mixture is washed for 3 times by the absolute ethyl alcohol, and the solid silicon dioxide is obtained after the reaction is dried for 10 hours at 60 ℃.
Adding solid silicon dioxide into 300mL of deionized water, performing ultrasonic dispersion, adding 2.5g of anhydrous sodium carbonate, heating to 60 ℃, stirring for reaction for 5 hours, centrifuging, and washing with deionized water for 3 times; adding the precipitate into 170mL of absolute ethanol, adding 0.4mL of hydrochloric acid, stirring at 65 ℃ and reacting for 3 hours to remove a template CTAB, and obtaining the HMSN.
Example 3
Preparation of hollow mesoporous silica nanoparticles
Absolute ethyl alcohol 90mL, deionized water 150mL, CTAB 0.3g, adding 1.5g cyclohexane, stirring uniformly, adding TEOS 4mL, ammonia water 3mL, stirring at room temperature for reaction for 18h, centrifuging after the reaction is finished, washing with absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 10h to obtain solid silicon dioxide.
Adding solid silicon dioxide into 200mL of deionized water for ultrasonic dispersion, adding 3g of anhydrous sodium carbonate, heating to 70 ℃, stirring for reaction for 4.5 hours, centrifuging, and washing with deionized water for 3 times; adding the precipitate into 200mL of absolute ethyl alcohol, adding 0.8mL of hydrochloric acid, stirring and reacting at 70 ℃ for 4h, and removing the CTAB template to obtain the HMSN.
Comparative example 1
Unlike example 1, cyclohexane was not added during the preparation process, and HMSN was prepared by adjusting the etching temperature and time. The method comprises the following specific steps:
60mL of absolute ethyl alcohol, 120mL of deionized water and 0.35g of CTAB, 2mL of TEOS and 2mL of ammonia water are added, the mixture is stirred and reacted for 12 hours at room temperature, the reaction product is centrifuged after the reaction is finished, washed for 3 times by the absolute ethyl alcohol, and dried for 10 hours at 60 ℃ to obtain the solid silicon dioxide.
Solid silicon dioxide is added into 240mL deionized water for ultrasonic dispersion, and 2.12g of anhydrous sodium carbonate is added for etching under the following conditions: 24 hours at 50 ℃, 18 hours at 60 ℃, 14 hours at 70 ℃ and 10 hours at 80 ℃, and after the reaction is finished, centrifuging the reaction solution and washing the reaction solution with deionized water for 3 times; adding the precipitate into 240mL of absolute ethyl alcohol, adding 0.5mL of hydrochloric acid, stirring and reacting at 60 ℃ for 2h, and removing the CTAB template to obtain the HMSN.
Example 4
Preparation of efficient cypermethrin nano drug-carrying particles
Dispersing 50mg of HMSN into dichloromethane, adding 100mg of beta-CP as a raw material of beta-cypermethrin, stirring at room temperature for 24h, centrifuging at 8000r/min for 5min, and drying at 60 ℃ for 10h to obtain the beta-CP/HMSN.
Example 5
Preparation of pyraclostrobin drug-loaded nanoparticles
Dispersing 50mg of HMSN into methanol, adding 100mg of pyraclostrobin original drug, stirring at room temperature for 12h, centrifuging at 8000r/min for 5min, and drying at 60 ℃ for 10h to obtain the pyraclostrobin drug-loaded nanoparticles.
Example 6
Preparation of deltamethrin nano drug-loaded particles
Dispersing 50mg of HMSN into methanol, adding 150mg of deltamethrin technical, stirring at room temperature for 20h, centrifuging at 8000r/min for 5min, and drying at 60 ℃ for 10h to obtain the deltamethrin drug-loaded nanoparticles.
Example 7
Preparation of efficient cyhalothrin nano drug-loaded particles
Dispersing 50mg of HMSN into xylene, adding 80mg of cyhalothrin raw pesticide, stirring at room temperature for 12h, centrifuging at 8000r/min for 5min, and drying at 60 ℃ for 10h to obtain the efficient cyhalothrin drug-loaded nanoparticles.
Example 8
Preparation of fenvalerate nano drug-carrying particles
Dispersing 50mg of HMSN into methanol, adding 120mg of fenvalerate raw drug, stirring at room temperature for 18h, centrifuging at 8000r/min for 5min, and drying at 60 ℃ for 10h to obtain the fenvalerate nano drug-loaded particles.
Example 9
Characterization of the HMSN and beta-CP/HMSN nanoparticles prepared in example 1, comparative example 1, and example 4
1. Appearance and appearance
And observing the appearance of the HMSN and the beta-CP/HMSN by adopting a transmission electron microscope. As can be seen from FIG. 1, the HMSN of the present invention is spherical, relatively complete and free from adhesion, and has a relatively thin shell and a relatively large cavity. FIG. 2 is a beta-CP/HMSN image, in which the obvious shaded part in HMSN indicates that the technical grade of beta-cypermethrin enters HMSN.
2. Nitrogen adsorption and desorption curve
Degassing the nano particles at 200 ℃ for 4h, measuring saturated pressure in a nitrogen atmosphere, measuring adsorption volumes under different adsorption pressures to obtain an adsorption-desorption isothermal curve, and calculating the specific surface area and the pore diameter. The specific surface area was determined using the Brunauer-Emmett-Teller (BET) equation and the pore size and pore size distribution were calculated using the Barrett-Joyner-Halenda (BJH) method.
Fig. 3 shows the nitrogen adsorption-desorption curves and pore size distributions of HMSN synthesized under different conditions. It is seen from fig. 3A that the nitrogen adsorption-desorption isotherm is a typical type IV isotherm. In FIG. 3B, it is found that the pore size of HMSN of comparative example 1 is mainly concentrated in 1-2nm for different etching temperatures and times, and the pore size of HMSN of the present invention with cyclohexane addition is mainly concentrated in 3-4nm. As is apparent from FIG. 3, HMSN synthesized by adding cyclohexane of the invention has higher specific surface area and pore volume which reach 1318m 2 /g、1.52cm 3 (ii) in terms of/g. The specific surface areas of the HMSN synthesized by the comparative example 1 are all 100-200 m 2 Per g, pore volume less than 0.5cm 3 G, pore size less than 2nm (see Table 1). In the field of pesticide loading, the large pore diameter is beneficial to pesticide molecules to enter so as to improve the drug loading rate, while the small pore diameter is difficult to enter the pore canal, and the small pore volume and the small specific surface area cannot achieve higher pesticide loading rate. From fig. 4 and table 1, it can be seen that the specific surface area and pore volume of the beta-CP/HMSN ratio HMSN are significantly reduced, indicating that the technical grade of beta-cypermethrin enters HMSN.
Table 1 mesoporous structure characterization of nanoparticles
3. Nanoparticle size determination
The HMSN of example 1 and the β -CP/HMSN of example 4 were prepared as 100mg/L aqueous solutions for particle size analysis by Dynamic Light Scattering (DLS).
It can be seen from FIG. 5 that the particle size distributions of HMSN of example 1 and β -CP/HMSN of example 4 are substantially the same, mainly centered in the range of 100-400nm, with the β -CP/HMSN being slightly larger than the HMSN particle size. The HMSN average particle size is 183nm, and the beta-CP/HMSN is 189nm. The side proves that the beta-cypermethrin active compound enters the aperture of the HMSN. Meanwhile, the particle size measured by the nano particles is a hydrated particle size, so that the particle size is larger.
4. Fourier transform infrared spectrometry
The spectral analysis was performed by potassium bromide tabletting. Respectively taking appropriate amount of beta-CP/HMSN at 4000-400cm -1 And (4) analyzing under a wave band.
FIG. 6 is the infrared spectrum of beta-CP/HMSN and its active compound. The nano-particle HMSN is 1085cm -1 A strong and wide absorption band which is the antisymmetric stretching vibration peak of Si-O-Si and 804cm -1 The peak is the symmetric stretching vibration and bending vibration of Si-O; 3422cm -1 Is a structural water-OH antisymmetric telescopic vibration peak at 2800cm -1 ～3000cm -1 No absorption peak was observed, and it was confirmed that organic substances such as CTAB and cyclohexane were removed. The peak shape of the drug-loaded particles beta-CP/HMSN is basically consistent with the infrared spectrograms of HMSN and beta-CP, and is 1085cm -1 And 3422cm -1 And a characteristic absorption peak appears, which proves that physical adsorption and no chemical reaction occur between HMSN and beta-CP, and shows that the HMSN has good stability as a pesticide slow-release agent carrier and does not influence the original pesticide. 748cm -1 The peak appeared at 1630cm caused by the C-Cl stretching vibration of beta-cypermethrin -1 Is caused by the stretching vibration of C = O. High-efficiency cypermethrin is successfully loaded on HMSN.
5. Thermogravimetric analysis
The thermal stability of the technical grade of the beta-CP/HMSN, the HMSN and the technical grade of the beta-CP/HMSN at the temperature of 20-800 ℃ is measured by a thermal analyzer at the temperature rising rate of 10 ℃/min under nitrogen.
Thermogravimetric analysis of beta-CP/HMSN, beta-cypermethrin, HMSN and its parent drug is shown in FIG. 7. The sample is heated to 800 ℃ from 20 ℃, the mass fraction of the high-efficiency cypermethrin raw pesticide is rapidly reduced from 180 ℃, and the high-efficiency cypermethrin raw pesticide is almost completely degraded at 800 ℃; HMSN exhibits a high thermal stability, almost constant at the test temperature, the sharp drop before 100 ℃ is mainly the decomposition of moisture and other molecular species of HMSN, with a loss of 5.56%. The co-loss of the beta-CP/HMSN of the drug-carrying particles is 38.085 percent, so that the loading rate of the beta-CP/HMSN of the drug-carrying particles is presumed to be 32.53 percent.
6. X-ray diffraction (XRD) analysis
Spreading the raw efficient cypermethrin and the beta-CP/HMSN sample to a sample pool, and measuring by using an X-ray diffractometer, wherein the scanning range is 5-40 degrees.
The X-ray diffraction pattern of the beta-CP/HMSN is shown in figure 8. As can be seen from figure 8, the raw beta-cypermethrin exhibits clear diffraction peaks at 12.58 °, 13.85 °, 16.70 °, 20.28 °, 22.60 ° and 25.10 °, which indicates that the raw beta-cypermethrin exists in a crystal form. The HMSN has no characteristic diffraction peak and is an amorphous structure. The beta-CP/HMSN has no obvious diffraction peak and is an amorphous structure, which indicates that the technical product of the beta-CP/HMSN is completely wrapped in the HMSN.
Example 10
Efficient cypermethrin nano drug-loaded particle release performance determination
The release performance of beta-CP and beta-CP/HMSN is studied by dialysis bag method. Because the technical grade of the beta-cypermethrin has poor water solubility, a solvent solution is selected as a release medium. The releasing medium such as methanol with low boiling point is different from the reference cell solution, so the solvent DMF (N, N-dimethylformamide) with high boiling point is selected as the releasing medium.
5mg of the sample are dissolved in 5mL of release medium (DMF: water = 6:4), then 95mL of release medium are placed, stirred at 25 ℃ in the dark at 100r/min, 3mL of release medium are taken at intervals, and the same volume of blank medium is added. The concentration of beta-cypermethrin was determined by an ultraviolet spectrophotometer at 277 nm. The cumulative release rate is calculated as follows.
In the formula: e p Cumulative release,%; v e For removing the release medium volume (L); c i The mass concentration of the high-efficiency cypermethrin in the release medium during the sampling of the ith time is mg/L; v 0 Is the total volume of release medium (L); c n The mass concentration of the high-efficiency cypermethrin in the released medium during the nth sampling is mg/L; m is a unit of p Is the total mass (mg) of the sample.
As can be seen from FIG. 9, in the concentration range of 40-120 mg/L, the concentration of beta-cypermethrin is linearly related to the absorbance value of the solution, the linear equation is Y =0.0046X +0.0249, R 2 =0.9995, the linearity is good. FIG. 10 shows the release curves of beta-CP/HMSN in release medium and beta-cypermethrin. As can be seen from FIG. 10, the release rate of the technical grade of beta-CP/HMSN is obviously higher than that of the technical grade of the beta-cypermethrin in the release medium. The raw pesticide of the beta-cypermethrin is quickly released in a release medium, and the cumulative release rate is higher than 95 percent within 12 hours and is almost completely released; the cumulative release rate of the beta-CP/HMSN within 170h reaches about 50%, the release rate in the first 5h is higher, the pesticide molecules loaded on the surfaces of the nano particles are released quickly, and then the high-efficiency cypermethrin pesticide molecules are released slowly and continuously. The release rate of the beta-CP/HMSN is obviously lower than that of the beta-CP/HMSN raw pesticide.
Example 11
Determination of biological activity of efficient cypermethrin nano drug-loaded particles
1. Indoor biological activity assay
Spraying the liquid medicine on corn leaves by taking second-instar corn borer larvae as model insects, taking the corn leaves after 0, 3, 7, 14, 20 and 30 days, placing 10 corn borer larvae in a culture dish with the corn leaves, and recording the number of dead insects after 72 hours. Test medicine beta-CP/HMSN is prepared into three concentrations of 0.18mg/L, 0.135mg/L and 0.09mg/L, 4.5 percent high-efficiency cypermethrin emulsifiable oil is used as a medicament control (0.18 mg/L), and the treatment is repeated for 3 times, and a blank control is set.
TABLE 2 prevention effect of 4.5% high-efficiency cypermethrin emulsifiable and beta-CP/HMSN on corn borer larva
The bioassay result shows that the beta-cypermethrin nano drug-carrying particles have longer lasting period, and 4.5 percent of beta-cypermethrin emulsifiable solution has quick-acting insecticidal property. The beta-cypermethrin nano drug-loaded particles have remarkable controlled-release performance, the insecticidal effect begins to slowly reduce after 20 days, and the death rates of 0.09mg/L, 0.135mg/L and 0.18mg/L after 30 days are 34.4 percent, 47.12 percent and 54.14 percent respectively. The 4.5 percent of beta-cypermethrin emulsifiable concentrate has the highest pest mortality rate of 79 percent after 3 days, the insecticidal performance is gradually reduced, and the pest mortality rate is 23.7 percent after 30 days.
2. Determination of field biological Activity
The test is carried out in the corn field of Zhengguan officer in Baoding city of Hebei province, and the variety is Zhengdan 958. The cell area is 20m 2 There are protection rows, 3 times of repetition, and random arrangement of each cell. Including test agent treatment, control agent and blank control, the specific dosage is shown in table 2. Investigating population base number before pesticide application, investigating live insect number 1, 3, 7, 14 and 30d after pesticide application, wherein the investigating method comprises sampling 5 points per cell, marking 5 plants per point, investigating live insect number, calculating population reduction rate and preventing and treating effect.
TABLE 3 test design of test agents
The field test result also proves that the beta-cypermethrin nano drug-carrying particles have longer lasting period, less drug consumption and good control effect. The beta-cypermethrin nano drug-loaded particles have the insect population reduction rate of 91.4 percent in 30 days, the control effect of 89.64 percent, the control effect of 4.5 percent of beta-cypermethrin emulsifiable solution is reduced after 7 days, the control effect of 30 days is 10.84 percent, and the effect of preventing and treating pests cannot be achieved.
TABLE 4 mortality of field pests at different concentrations of beta-CP/HMSN at different times
Example 12
Safety evaluation of efficient cypermethrin nano drug-loaded particles
Two leaf maize seedlings were sprayed with HMSN (example 1) and β -CP/HMSN (example 4) solutions containing 1, 2, 4, 8mg/L, with 4.5% high performance cypermethrin cream sprayed at the same mass concentration and with unsprayed maize plants as controls. 7 days after spraying, the corn plants were collected, washed, air dried and weighed to determine the fresh weight of the aerial parts and roots of the corn. After the maize plants were allowed to dry for 7 days at 37 ℃ after weighing, the dry weight of the aerial parts and roots was weighed and recorded, each treatment being repeated 3 times.
The safety evaluation of HMSN and beta-CP/HMSN on the roots and aerial parts of maize seedlings is shown in FIG. 12. The figure shows that the growth of the corn seedlings treated by the 4.5 percent high-efficiency cypermethrin emulsifiable solution has a certain inhibiting effect on the roots of the corn along with the increase of the concentration, and has no obvious influence on the growth of the overground part; the growth of the roots and the overground parts of the maize seedlings treated by the HMSN and the beta-CP/HMSN is not influenced, and the growth of the roots and the overground parts of the maize seedlings is promoted to a certain extent. The beta-cypermethrin nano drug-loaded particles are safe to crops, can reduce the harm of the effective ingredients of the pesticide to the crops and are beneficial to the growth of the crops.
The above embodiments are the best mode for carrying out the invention, but the embodiments of the invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the invention should be construed as equivalents thereof, and they are included in the scope of the invention.
Claims (10)
1. A preparation method of a slow-release pyrethroid nanoparticle is characterized by comprising the following steps:
uniformly mixing absolute ethyl alcohol, deionized water, CTAB and cyclohexane, adding TEOS and ammonia water, stirring and reacting for 10-24h at room temperature, and centrifugally drying to obtain solid silicon dioxide;
dispersing the solid silicon dioxide in water, adding anhydrous sodium carbonate, heating to 50-80 ℃, stirring for reaction for 4-6h, centrifuging the obtained precipitate, and reacting in hydrochloric acid-hot ethanol for 1-4h to obtain hollow mesoporous silicon dioxide nano particles;
dispersing the hollow mesoporous silica nanoparticles in an organic solvent, adding a pyrethroid original drug, stirring for 10-24h, centrifuging and drying to obtain the slow-release pyrethroid nanoparticles.
2. The method according to claim 1, wherein the ratio of the absolute ethanol, deionized water, CTAB, cyclohexane, TEOS and ammonia water is 30-90ml:60-150ml:0.2-0.4g:1-3g:2-4ml:1-3ml.
3. The method according to claim 1, wherein the mass ratio of the solid silica to the anhydrous sodium carbonate is 0.4 to 1:2-3.
4. The method according to claim 1, wherein the temperature of the hydrochloric acid-hot ethanol is 50-70 ℃, and the volume ratio of the hydrochloric acid to the absolute ethanol is 0.4-1:150-300.
5. The method according to claim 1, wherein the hollow mesoporous silica nanoparticles have a specific surface area of 1318m 2 G, pore volume 1.52cm 3 /g。
6. The method according to claim 1, wherein the organic solvent is dichloromethane, xylene or methanol.
7. The preparation method according to claim 1, wherein the mass ratio of the hollow mesoporous silica nanoparticles to the pyrethroid original drug is 1:0.5-4.
8. The slow-release pyrethroid nanoparticle prepared by the preparation method of any one of claims 1-7.
9. The preparation method according to claim 1, wherein the slow-release pyrethroid nanoparticle is a beta-cypermethrin nanoparticle, and the loading rate of the beta-cypermethrin in the beta-cypermethrin nanoparticle is up to 32.53%.
10. Use of a slow-release pyrethroid nanoparticle according to claim 8 or 9 for controlling agricultural pests, characterized in that the slow-release pyrethroid nanoparticle has a controlling effect for more than 30 days.
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