CN108157364B - PH-responsive pesticide sustained-release preparation and preparation method thereof - Google Patents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
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Abstract
The invention discloses a pH responsive pesticide sustained release preparation and a preparation method thereof. The invention adopts a one-step method to synthesize drug-loaded mesoporous silicon, and introduces metal ions to carry out coordination modification, thereby preparing a pesticide slow-release preparation with pH responsiveness; the surface structure and the slow release performance of the pesticide slow release preparation are regulated and controlled by modifying different metal ions. The preparation method disclosed by the invention is simple in process and short in synthesis period, and the template agent and the pesticide generate a synergistic effect without removal, so that a new idea is provided for further development of pesticide formulations. The pesticide slow-release preparation can improve the stability of the pesticide, shows pH responsiveness, can reduce the diffusion, digestion and loss of the pesticide in the environment, prolongs the pesticide lasting period, and reduces the pesticide application times, so the pesticide dosage can be reduced and the environment can be protected.
Description
Technical Field
The invention relates to the technical field of slow-release pesticides, in particular to a pH-responsive pesticide slow-release preparation and a preparation method thereof.
Background
The mesoporous silicon material has a larger specific surface area and a highly ordered pore structure, has good biocompatibility, and can be used as a medicine and pesticide slow release carrier. In order to endow the mesoporous silicon with environmental responsiveness, a post-grafting method and a copolycondensation method are generally adopted to modify the surface of the mesoporous silicon. Wu Jun topic group (Tian Y, Kong Y, Li X J, et al. light-and pH-activated intracellular drug free polymeric mesoporous silicas [ J ]. Colloids and Surfaces B: Biointerfaces,2015,134: 147-. Sun Jihong group of subjects (Jin X Q, Wang Q, Sun J, et al (pH-and temperature-) viscous Mesoporous silica nanoparticles core and copolymer shell for controlled-up-front-reflection [ J ]. Micropore and Mesoporous Materials,2017.) modified Mesoporous silica with silane coupling agent and isopropylacrylamide-acrylic acid copolymer, and their loading and sustained-release studies found that the sustained-release rate was faster at pH 2. The topic group (Chen H Y, Lin Y S, Zhou H J, et al. Synthesis and characterization of chloriporos/copper (II) schiff base pesticide with pH sensitivity for pesticide contained release [ J ]. Journal of Agricultural and Food Chemistry,2016,64(43):8095 × 8102.) adopts copolycondensation method to construct functional mesoporous silicon-metal-pesticide slow-release material, and utilizes coordination between metal ions with electron empty orbitals and model pesticide to endow system pH responsiveness, so that pesticide can be released at different rates according to the difference between insect body fluid and environment pH. Although the pH responsiveness of the pesticide slow-release material can be endowed by virtue of a post-grafting method and a copolycondensation method, the preparation period is long, and the application of the slow-release material is not facilitated.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a pH responsive pesticide sustained release preparation, which is prepared by synthesizing drug-loaded mesoporous silicon by a one-step method and introducing metal ions for coordination modification, and provides a new idea for further developing pesticide formulations.
The invention also provides a preparation method of the pH-responsive pesticide slow-release preparation, which can endow the pesticide slow-release preparation with pH responsiveness, has a short preparation period and is beneficial to popularization and application of a pesticide slow-release material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a pH-responsive pesticide sustained-release preparation comprises the following steps: mixing a template agent and a silicon source, oscillating in a water bath until the template agent is completely dissolved, adding a pesticide solution when the temperature of the water bath is 35-45 ℃, oscillating for 0-15 min, adding a metal ion solution, fully reacting for 15-90 min, removing the solvent by rotary evaporation, drying, grinding and sieving to obtain the pH-responsive pesticide slow-release preparation.
In the technical scheme, the pesticide-carrying mesoporous silicon is synthesized by a one-step method, and metal ions are introduced for coordination modification to prepare the pesticide slow-release preparation with pH responsiveness. The invention utilizes the coordination function between the metal ions with electron empty orbits and the model pesticide to endow the system with pH responsiveness, so that the pesticide can be released at different rates according to the difference between the body fluid of the insect and the pH of the environment. The preparation method disclosed by the invention is simple in process and short in synthesis period, and the template agent and the pesticide generate a synergistic effect without removal, so that a new idea is provided for further development of pesticide formulations.
As a preferable embodiment of the method for preparing the pH-responsive pesticide sustained-release preparation of the present invention, the templating agent is a polyalkylene oxide-based olefin block copolymer or a nonionic surfactant; the silicon source is at least one of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.
As a preferable embodiment of the method for producing a pH-responsive agricultural chemical sustained release preparation according to the present invention, the polyalkylene oxide-based olefin block copolymer is at least one of an F127 block copolymer, a P123 block copolymer, and an F108 block copolymer; the nonionic surfactant is at least one of Brij56, Brij76, Brij58 and Brij 700.
As a preferable embodiment of the method for preparing the pH-responsive pesticide sustained-release preparation of the present invention, the mass ratio of the template agent to the silicon source is 1: 1 to 3.
As a preferable embodiment of the method for preparing the pH-responsive pesticide sustained-release preparation of the present invention, the pesticide is abamectin, triazolone, diflubenzuron, acetamiprid, chlorpyrifos, imidacloprid, tebuconazole or hexaconazole.
The abamectin is a macrolide disaccharide biopesticide, has low toxicity and high insecticidal efficiency, is applied to agriculture and animal husbandry, contains a large amount of oxygen-containing aromatic heterocycles in the structural composition, and lone pair electrons on oxygen atoms can form coordinate bonds with empty orbitals of metal ions in a slow release system, so the abamectin can be used as a model medicament for producing a pH-responsive slow release material by virtue of coordination.
As a preferable embodiment of the method for preparing the pH-responsive pesticide sustained-release preparation, the concentration of the pesticide in the pesticide solution is 10-20 g/L, and the mass ratio of the silicon source to the pesticide is 50-100: 1.
As a preferable embodiment of the preparation method of the pH-responsive pesticide sustained-release preparation, the molar ratio of the template to the metal ions is 1: 2.5-5.1; the metal ions are divalent metal ions or trivalent metal ions.
As a preferable embodiment of the method for producing a pH-responsive pesticide sustained-release preparation according to the present invention, the metal ion is a copper ion or a zinc ion.
In the technical scheme, the coordination action between the metal ions with electron empty orbits and the model pesticide is utilized to endow the system with pH responsiveness, so that the pesticide can be released at different rates according to the difference between the body fluid of the insect and the pH of the environment; the surface structure and the slow release performance of the pesticide slow release preparation are regulated and controlled by utilizing different metal ion modification. The metal ions have stronger coordination capacity with pesticides, and can remarkably improve the pH responsiveness of the pesticide sustained-release preparation.
As a preferable embodiment of the method for preparing the pH-responsive pesticide sustained-release preparation, the concentration of the metal ions in the metal ion solution is 0.2-0.4 mol/L.
The invention also provides a pH responsive pesticide slow release preparation prepared by the method.
The pesticide slow-release preparation of the technical scheme can improve the stability of the pesticide, shows pH responsiveness, can reduce the diffusion, digestion and loss of the pesticide in the environment, prolongs the pesticide lasting period, and reduces the application times, so the dosage can be reduced and the environment can be protected.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a one-step method to synthesize the drug-loaded mesoporous silicon, introduces metal ions to carry out coordination modification, prepares the pesticide slow-release preparation with pH responsiveness, and regulates and controls the surface structure and the slow-release performance of the pesticide slow-release preparation by utilizing the modification of different metal ions. The preparation method disclosed by the invention is simple in process and short in synthesis period, and the template agent and the pesticide generate a synergistic effect without removal, so that a new thought is provided for further development of pesticide formulations.
Drawings
FIG. 1 is an SEM photograph of AVM/Zn-HOMS (a, b) and AVM/Cu-HOMS (c, d) of the pesticide sustained-release preparations prepared in examples 1-2.
FIG. 2 is FTIR spectra of avermectin AVM, a template F127, the pesticide sustained release preparations of examples 1-2, HOMS of comparative example 1 and AVM/HOMS of comparative example 2.
FIG. 3 is a graph showing the nitrogen adsorption/desorption isotherm (a) and the pore size distribution (b).
FIG. 4 is a TG curve of avermectin AVM, a template F127 and the pesticide sustained-release preparation prepared in examples 1-2.
FIG. 5 is a drug release curve of the pesticide sustained release preparations AVM/Zn-HOMS (a) and AVM/Cu-HOMS (b) at different pH values.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Block copolymer polyether F127(AR, Sigma-Aldrich Corporation), F127 has a molecular weight of 12600; block copolymer P123(AR, Sigma-Aldrich Corporation), P123 has a molecular weight of 5800, methyl orthosilicate (TMOS) (AR, alatin reagent limited); block copolymer F108(AR, Sigma-Aldrich Corporation), F108 has a molecular weight of 14600; brij56(AR, alatin reagent limited), average molecular weight 683; CuCl2·2H2O and ZnCl2(AR, Fochen chemical industries, Tianjin); absolute ethanol and methanol (AR, majol chemical industries, tianjin); concentrated hydrochloric acid (AR, guangzhou chemical reagent ii, inc.) at 36% by mass; an abamectin active compound (CP, mass fraction is more than or equal to 97%, Henan Kai Rui agricultural chemical product Co., Ltd.).
Example 1
In an embodiment of the method for preparing a pH-responsive pesticide sustained-release preparation according to the present invention, the method for preparing a pH-responsive pesticide sustained-release preparation according to the present embodiment includes the following steps:
mixing 1.2g F127 and 3.0g of TMOS in a 250mL round bottom flask, oscillating in a water bath at 40 ℃ until F127 is completely dissolved, adding 2mL of abamectin methanol solution with the mass concentration of 15g/L into the mixture, oscillating for 5min, adding 1.5g of copper ion hydrochloric acid aqueous solution (the concentrations of copper ions and hydrochloric acid are 0.33 mol/L and 0.05mol/L respectively), oscillating, fully reacting for 30min, removing the solvent by using a rotary evaporator, drying at 70 ℃ to obtain a blocky solid, grinding, and sieving by using a 200-mesh sieve to obtain the copper ion modified powdery pesticide sustained release preparation AVM/Cu-HOMS.
Example 2
In an embodiment of the method for preparing a pH-responsive pesticide sustained-release preparation according to the present invention, the method for preparing a pH-responsive pesticide sustained-release preparation according to the present embodiment includes the following steps:
mixing 1.2g F127 and 3.0g of TMOS in a 250mL round bottom flask, oscillating in a water bath at 40 ℃ until F127 is completely dissolved, adding 2mL of abamectin methanol solution with the mass concentration of 15g/L into the mixture, oscillating for 5min, adding 1.5g of zinc ion hydrochloric acid aqueous solution (the concentrations of zinc ions and hydrochloric acid are 0.33 mol/L and 0.05mol/L respectively), oscillating, fully reacting for 30min, removing the solvent by using a rotary evaporator, drying at 70 ℃ to obtain a blocky solid, grinding, and sieving by using a 200-mesh sieve to obtain the zinc ion modified powdery pesticide sustained release preparation AVM/Zn-HOMS.
Example 3
In an embodiment of the method for preparing a pH-responsive pesticide sustained-release preparation according to the present invention, the method for preparing a pH-responsive pesticide sustained-release preparation according to the present embodiment includes the following steps:
mixing 1.0g of Brij56 and 1.0g of tetraethoxysilane in a 250mL round-bottom flask, oscillating in a 35 ℃ water bath until Brij56 is completely dissolved, adding 2mL of triazolone methanol solution with the mass concentration of 10g/L into the mixture, oscillating for 10min, adding 18.3g of copper ion ionic acid aqueous solution (the concentrations of copper ions and hydrochloric acid are 0.2mol/L and 0.05mol/L respectively), oscillating, fully reacting for 15min, removing the solvent by using a rotary evaporator, drying at 70 ℃ to obtain a blocky solid, grinding, and sieving by using a 200-mesh sieve to obtain the copper ion modified powdery pesticide sustained-release preparation AVM/Cu-HOMS.
Example 4
In an embodiment of the method for preparing a pH-responsive pesticide sustained-release preparation according to the present invention, the method for preparing a pH-responsive pesticide sustained-release preparation according to the present embodiment includes the following steps:
mixing 1.0g F108 and 3.0g of propyl orthosilicate in a 250mL round bottom flask, oscillating in a water bath at 45 ℃ until F108 is completely dissolved, adding 2mL of diflubenzuron methanol solution with the mass concentration of 20g/L into the mixture, oscillating for 15min, adding 0.68g of zinc ion hydrochloric acid aqueous solution (the concentrations of zinc ions and hydrochloric acid are 0.4mol/L and 0.05mol/L respectively), oscillating, fully reacting for 90min, removing the solvent by using a rotary evaporator, drying at 70 ℃ to obtain a blocky solid, grinding, and sieving by using a 200-mesh sieve to obtain the zinc ion modified powdery pesticide sustained-release preparation AVM/Zn-HOMS.
Example 5
In an embodiment of the method for preparing a pH-responsive pesticide sustained-release preparation according to the present invention, the method for preparing a pH-responsive pesticide sustained-release preparation according to the present embodiment includes the following steps:
mixing 1.0g P123 and 2.0g of propyl orthosilicate in a 250mL round bottom flask, oscillating in a water bath at 45 ℃ until P123 is completely dissolved, adding 2mL of diflubenzuron methanol solution with the mass concentration of 20g/L, oscillating for 10min, adding 2.0g of zinc ion hydrochloric acid aqueous solution (the concentrations of zinc ions and hydrochloric acid are 0.25mol/L and 0.05mol/L respectively), oscillating, fully reacting for 60min, removing the solvent by using a rotary evaporator, drying at 70 ℃ to obtain a blocky solid, grinding, and sieving by using a 200-mesh sieve to obtain the zinc ion modified powdery pesticide sustained-release preparation AVM/Zn-HOMS.
Comparative example 1
The preparation method of the mesoporous silicon of the comparative example comprises the following steps:
mixing 1.2g F127 and 3.0g TMOS in a 250mL round bottom flask, oscillating in a water bath at 40 ℃ until F127 is completely dissolved, fully reacting for 30min, removing the solvent by a rotary evaporator, drying at 70 ℃ to obtain a block solid, grinding, and sieving with a 200-mesh sieve to obtain mesoporous silicon (HOMS).
Comparative example 2
The preparation method of the avermectin-loaded pesticide sustained release preparation AVM/HOMS comprises the following steps:
mixing 1.2g F127 and 3.0g of TMOS in a 250mL round bottom flask, oscillating in a water bath at 40 ℃ until F127 is completely dissolved, adding 2mL of abamectin methanol solution with the mass concentration of 15g/L into the flask, fully reacting for 30min, removing the solvent by using a rotary evaporator, drying at 70 ℃ to obtain a blocky solid, grinding, and sieving by using a 200-mesh sieve to obtain the abamectin-loaded pesticide sustained release preparation (AVM/HOMS).
Performance testing of pesticide sustained-release preparations
(1) SEM analysis
The morphology of the pesticide sustained-release preparation prepared in examples 1 to 2 was observed by an SU8020 scanning electron microscope (Hitachi corporation, japan), and the result is shown in fig. 1.
Fig. 1 is an SEM image of different pesticide sustained release formulations. It can be seen that the mesoporous silicon synthesized by the one-step method is of a blocky structure, and both the AVM/Zn-HOMS and the AVM/Cu-HOMS present a layered structure. The AVM/Zn-HOMS surface is relatively smooth, and the material has high crystallinity. The AVM/Cu-HOMS surface presents a spongy loose porous structure. The results show that the surface structure of the pesticide sustained-release preparation can be regulated and controlled by utilizing different metal ion modification.
(2) FTIR analysis
FTIR analysis was performed on Avermectin AVM, template F127, the pesticide sustained-release preparations of examples 1 to 2, HOMS of comparative example 1 and AVM/HOMS of comparative example 2 by a Spectrum-100 Fourier transform infrared spectrometer (PerkinElmer Co., U.S.A.) and a scanning wavelength range of 450 to 4000cm-1And preparing a sample by adopting a KBr tabletting method. FIG. 2 is an FTIR spectrum of AVM, F127, HOMS, AVM/Cu-HOMS, and AVM/Zn-HOMS.
As can be seen from the results in FIG. 2, the spectral line of mesoporous silicon and avermectin-loaded mesoporous silicon is 3470cm-1The wider peak corresponds to the stretching vibration characteristic peak of silicon hydroxyl Si-OH on the surface of the mesoporous silicon, wherein the peak of the mesoporous silicon spectral line c subjected to roasting treatment at the position tends to be smooth, which indicates that the number of the hydroxyl on the surface of the material is reduced to a certain degree. 1070cm-1The peak is the antisymmetric stretching vibration absorption peak of the Si-O-Si bond, 948cm-1At the bending vibration peak of the Si-O bond of 820cm-1Belongs to the Si-O tetrahedron symmetric stretching vibration peak. Lines d, e, f, g at 2967, 1458, 1342, 785 and 595cm-1Characteristic absorption peaks of C-H and aromatic heterocycle of the abamectin appear, which shows that the abamectin is loaded in the mesoporous silicon, and the characteristic peaks have different degrees of deviation and broadening phenomena under the action of F127 in the system.
(3) Nitrogen adsorption-desorption isothermal curve analysis
By Quadrasorb SI type N2An adsorption-desorption apparatus (Quantachrome company, USA) performs nitrogen adsorption-desorption isothermal curve analysis on the pesticide sustained release preparations of examples 1-2, the HOMS of comparative example 1 and the AVM/HOMS of comparative example 2, and N is adopted2Testing parameters such as specific surface area, pore diameter and the like of a sample by an adsorption-desorption instrument, wherein the calculation method comprises a BET method and a BJH method, vacuum degassing is carried out for 12h at 200 ℃ before testing, and N of each group of pesticide slow-release preparation2The adsorption-desorption isotherms and the corresponding pore size distribution profiles are shown in fig. 3, and the pore structure parameters of each group of pesticide sustained-release preparations are shown in table 1.
TABLE 1 pore channel structure parameters of each group of pesticide sustained-release preparations
The isotherms in fig. 3 are both Langmuir type iv curves with H2 type hysteresis loops, indicating that the material is mesoporous. It was also demonstrated that the coordination of the metal ions with F127 did not cause a change in the pore structure, which is characteristic of the ink bottle structure, since the pore size calculated from the desorption branch is generally the size of the pore window. The low-pressure section adsorption and desorption branches of the isothermal adsorption lines of the HOMS and the AVM/HOMS cannot coincide, which indicates that the material undergoes volume expansion in the adsorption process. As can be seen from table 1, the introduction of metal ions can increase the specific surface area of the mesoporous silicon, and the loading of the drug and the addition of the metal ions can increase the pore volume of the mesoporous silicon, while the pore diameter does not change much.
(4) TG analysis
TG analysis was performed on the pesticide sustained-release preparations prepared in AVM, F127 and examples 1 to 2 by using Q500 thermogravimetric analyzer (TA of America), and the change of the weight loss rate of the sample was measured, with the temperature rise range of 40 to 800 ℃, the temperature rise rate of 10 ℃/min and the nitrogen flow rate of 50mL/min, and the results are shown in FIG. 4.
As can be seen from fig. 4, the weight loss of the pesticide sustained-release preparation prepared in examples 1 to 2 at 50 to 100 ℃ belongs to the water volatilization on the surface of the medium pore silicon in the sustained-release material and the physical desorption of the water in the pore channel, and the weight loss of the pesticide sustained-release preparation prepared in examples 1 to 2 at 200 to 650 ℃ is caused by the decomposition of F127 and avermectin together by combining the weight loss curve analysis of avermectin and F127, and the weight loss rates of the two sustained-release materials AVM/Zn-HOMS and AVM/Cu-HOMS are 46% and 47% respectively. The temperature for starting decomposition of the abamectin is 200 ℃, and after the mesoporous silicon pore channel is loaded, the decomposition temperature is increased to 300 ℃, which shows that the sustained-release material improves the stability of the abamectin.
(5) Test of sustained Release Performance
The sustained release performance of the pesticide sustained release preparation prepared in example 1-2 was measured, and the drug Loading (LC) was calculated according to the formula (1):
in the formula: m0Is the original drug amount (mg) contained in 1mL of original avermectin methanol solution; m1 is the mass (g) of the sustained-release material after drying.
Weighing pesticide sustained release preparation (M)1Mg) of the compound, putting the compound into a dialysis bag, placing the compound into 50mL of 40% ethanol aqueous solution with pH values of 4, 7 and 10 respectively, transferring 1mL of sample liquid by using a liquid transfer gun at intervals of a certain time (t), supplementing an equal amount of 40% ethanol aqueous solution into the flask, scanning the flask by using a UV method to measure the absorbance, and obtaining the compound according to a standard curve A of 0.0317c-0.00456 (R)20.998) to obtain the concentration of avermectin varying with time, and calculating the cumulative release rate (R) according to the formula (2)i) Drawing t-RiThe curve is taken as the slow release kinetics curve of the avermectin.
In the formula: and rho i is the mass concentration (mg/L) of abamectin in the ith extraction liquid.
The drug loading rates LC, AVM/Zn-HOMS and AVM/Cu-HOMS 2 pesticide sustained-release preparations are respectively 24.79, 27.52 and 24.49mg/g according to the formula (1).
Fig. 5 is a drug release profile of the pesticide sustained release formulation at different pH. As can be seen from fig. 5(a) and 5(b), the introduction of zinc ions and copper ions enables the cumulative release rate of the pesticide sustained-release preparation in the equilibrium to show obvious pH responsiveness, which indicates that the coordination capacity of the zinc ions, the copper ions and the abamectin is obviously affected by the change of the environmental pH, wherein the addition of the zinc ions enables the pesticide sustained-release preparation to show a better sustained-release effect in the alkaline environment, while the addition of the copper ions enables the pesticide sustained-release preparation to show a better sustained-release capacity in the neutral environment, the cumulative release rate of the AVM/Cu-HOMS in the acidic environment is larger, which indicates that the competitive action of protons, the copper ions and abamectin molecules has a destructive effect on the coordinate bond formed by the copper ions and the abamectin in the acidic environment. In addition, the 2 pesticide slow release preparations all have burst release phenomena of different degrees, which are caused by the release of abamectin adsorbed on the outer surface of the mesoporous silicon.
In conclusion, the pesticide slow-release preparation with pH responsiveness is prepared by synthesizing the drug-loaded mesoporous silicon by a one-step method and introducing metal ions for coordination modification, and the surface structure and the slow-release performance of the pesticide slow-release preparation are regulated and controlled by utilizing the modification of different metal ions.
The preparation method disclosed by the invention is simple in process and short in synthesis period, the template agent and the pesticide generate a synergistic effect, and the removal is not required, so that a new thought is provided for further development of pesticide formulations; the pesticide slow-release preparation can improve the stability of the pesticide, shows pH responsiveness, can reduce the diffusion, digestion and loss of the pesticide in the environment, prolongs the pesticide lasting period, and reduces the pesticide application times, so the pesticide dosage can be reduced and the environment can be protected.
In the invention, copper ions and zinc ions are replaced by other divalent metal ions or trivalent metal ions, and a pesticide slow-release preparation with certain pH responsiveness can also be prepared.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A preparation method of a pH-responsive pesticide sustained-release preparation is characterized by comprising the following steps: mixing a template agent and a silicon source, oscillating in a water bath until the template agent is completely dissolved, wherein the temperature of the water bath is 35-45 ℃, adding a pesticide solution, oscillating for 0-15 min, adding a metal ion solution, fully reacting for 15-90 min, removing the solvent by rotary evaporation, drying, grinding and sieving to obtain the pH-responsive pesticide slow-release preparation; wherein the template agent is a poly (alkylene oxide) olefin block copolymer or a nonionic surfactant; the silicon source is at least one of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate; the polyalkylene oxide olefin block copolymer is at least one of an F127 block copolymer, a P123 block copolymer and an F108 block copolymer; the nonionic surfactant is at least one of Brij56, Brij76, Brij58 and Brij 700; the pesticide is abamectin, triazolone, diflubenzuron, acetamiprid, chlorpyrifos, imidacloprid, tebuconazole or hexaconazole.
2. The method for preparing a pH-responsive pesticide sustained-release preparation according to claim 1, wherein the mass ratio of the template agent to the silicon source is 1: 1 to 3.
3. The method for preparing a pH-responsive pesticide sustained-release preparation according to claim 1, wherein the concentration of the pesticide in the pesticide solution is 10 to 20g/L, and the mass ratio of the silicon source to the pesticide is 50 to 100: 1.
4. The method for preparing the pH-responsive pesticide sustained-release preparation according to claim 1, wherein the molar ratio of the template agent to the metal ions is 1: 2.5-5.1, and the metal ions are divalent metal ions or trivalent metal ions.
5. The method for producing a pH-responsive pesticide sustained-release preparation according to claim 1, characterized in that the metal ion is a copper ion or a zinc ion.
6. The method for preparing a pH-responsive pesticide sustained-release preparation according to claim 1, wherein the concentration of metal ions in the metal ion solution is 0.2 to 0.4 mol/L.
7. The pH-responsive pesticide sustained-release preparation prepared by the method according to any one of claims 1 to 6.
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