CN112450222A - Nano pesticide controlled release agent and preparation method thereof - Google Patents

Nano pesticide controlled release agent and preparation method thereof Download PDF

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CN112450222A
CN112450222A CN202011520383.7A CN202011520383A CN112450222A CN 112450222 A CN112450222 A CN 112450222A CN 202011520383 A CN202011520383 A CN 202011520383A CN 112450222 A CN112450222 A CN 112450222A
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carrier
pesticide
nano
pore
release agent
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CN112450222B (en
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肖旺
杨光富
郝格非
张彩霞
毛雪伟
丁磊
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Central China Normal University
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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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties

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  • Wood Science & Technology (AREA)
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  • Pest Control & Pesticides (AREA)
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Abstract

The invention relates to the field of pesticide preparations and discloses a nano pesticide controlled release agent and a preparation method thereof, wherein the controlled release agent comprises a modified carrier, a pesticide active component loaded on the modified carrier and a pore blocking agent distributed on the modified carrier; wherein the pore-plugging agent is sodium carboxymethylcellulose; the modified carrier is a nano silicon dioxide carrier modified by a modifier, and the modifier is selected from at least one of 3-aminopropyltriethoxysilane, (3-aminopropyl) dimethylethoxysilane and aminopropylaminoethyl trimethoxysilane; the nano silicon dioxide carrier has a hollow structure, and pore channels are distributed on the wall forming the hollow structure. The nano pesticide controlled release agent provided by the invention can effectively reduce pesticide residues in the environment, has specific enzyme responsiveness, responds to release of the pesticide only in fungi in the presence of cellulase, and has small influence on toxic and side effects of human, fish and other aquatic organisms without the cellulase.

Description

Nano pesticide controlled release agent and preparation method thereof
Technical Field
The invention relates to the field of pesticide preparations, in particular to a nano pesticide controlled release agent, a method for preparing the nano pesticide controlled release agent and the nano pesticide controlled release agent prepared by the method.
Background
The effective utilization rate of the traditional pesticide is usually lower than 30 wt% due to the loss caused by poor dispersibility, biodegradation and other factors, meanwhile, although the traditional pesticide formulations such as pesticide Microemulsion (ME), Water Dispersible Granules (WDG) and the like can release high effective components in a short period of time, only 0.1 wt% of pesticide can reach the target part due to the loss and degradation of the effective components caused by photolysis, hydrolysis, microbial degradation or oxidation/reduction and other environmental factors, and the remaining pesticide enters the environment and is harmful to non-target organisms including human beings and the environment, so more and more researchers are engaged in the development of sustained and controlled release pesticide systems.
Compared with the traditional pesticide, the sustained and controlled release pesticide has the following advantages: control or reduce evaporation of the pesticide, longer residual bioactivity, increased safety to non-target organisms including humans, reduced physicochemical decomposition or biodegradation of the pesticide thereby reducing the amount of pesticide used.
However, the controlled release pesticide systems synthesized by most researchers at present mainly face two problems: firstly, the release behavior of the loaded drug is mostly slow release without selectivity, and the drug can be slowly released in the environment, in a disease body, in a human body and in an aquatic organism, which can cause the pollution of pesticide to the environment and the toxic and side effect to the human body and other organisms; secondly, the drug loading is low, the common drug loading is 5-20 wt%, so if the nano dosage form with low drug loading achieves high insecticidal effect, a higher concentration dosage form is needed, which not only increases the production cost of users, but also increases the difficulty of the dosage form in the aspects of preparation, spraying and the like.
Therefore, the research on the novel intelligent nano pesticide controlled release agent which has high drug loading capacity and selectively releases the drug only aiming at diseases has important practical significance.
Disclosure of Invention
The invention aims to overcome the defects of low safety to non-target organisms, incapability of selectively releasing medicaments and low medicament loading rate of a sustained-release pesticide system in the prior art.
In order to achieve the above object, the present invention provides a nano pesticide controlled release agent, which comprises a modified carrier, a pesticide active component loaded on the modified carrier, and a pore blocking agent distributed on the modified carrier;
wherein the pore-plugging agent is sodium carboxymethylcellulose;
the modified carrier is a nano silicon dioxide carrier modified by a modifier,
the modifier is selected from at least one of 3-aminopropyltriethoxysilane, (3-aminopropyl) dimethylethoxysilane and aminopropylaminoethyl trimethoxysilane;
the nano silicon dioxide carrier has a hollow structure, and pore channels are distributed on the wall forming the hollow structure.
In a second aspect, the present invention provides a method for preparing a nano pesticide controlled-release agent, comprising:
(1) carrying out first contact on a modifier and a nano silicon dioxide carrier to obtain a modified carrier;
(2) carrying out second contact on the modified carrier and the pesticide active component to obtain the modified carrier loaded with the pesticide active component;
(3) carrying out third contact on the modified carrier loaded with the pesticide active component and a pore plugging agent;
wherein the pore-plugging agent is sodium carboxymethylcellulose;
the modifier is selected from at least one of 3-aminopropyltriethoxysilane, (3-aminopropyl) dimethylethoxysilane and aminopropylaminoethyl trimethoxysilane;
the nano silicon dioxide carrier has a hollow structure, and pore channels are distributed on the wall forming the hollow structure.
In a third aspect, the present invention provides a nano pesticide controlled release agent prepared by the method of the second aspect.
Compared with the prior art, the nano pesticide controlled release agent provided by the invention has the following advantages:
(1) the nano pesticide controlled release agent provided by the invention has little pesticide release amount in natural environment, can effectively reduce pesticide residue in the environment and reduce pollution to the environment;
(2) the nano pesticide controlled release agent provided by the invention has specific enzyme responsiveness, responds to release of the pesticide only in fungi in the presence of cellulase, and has small influence on toxic and side effects of aquatic organisms such as people, fish and the like without the cellulase.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
Drawings
Fig. 1 is a transmission electron micrograph of a first intermediate and a nano-silica support prepared in example 1, wherein fig. 1(a) is a transmission electron micrograph of the first intermediate, and fig. 1(b) is a transmission electron micrograph of the nano-silica support;
FIG. 2 is a nitrogen adsorption desorption isotherm of the nano-silica carrier prepared in example 1;
FIG. 3 is a release profile of the pesticidal active ingredient of the nano-pesticide controlled-release agent prepared in example 1 under different concentrations of cellulase response conditions;
fig. 4 is a drug release profile of the modified carrier loaded with the pesticidal active ingredient of the non-plugging agent prepared in comparative example 1 with or without cellulase;
FIG. 5 is a release profile of the pesticidal active ingredient of the nano-controlled release formulation prepared in example 1 under different kinds of enzyme conditions;
fig. 6 is a toxicity test curve of co-culture of the pyraclostrobin original drug and the nano pesticide controlled release agent prepared in example 1 and zebra fish.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a nano pesticide controlled release agent, which comprises a modified carrier, a pesticide active component loaded on the modified carrier, and a pore blocking agent distributed on the modified carrier;
wherein the pore-plugging agent is sodium carboxymethylcellulose;
the modified carrier is a nano silicon dioxide carrier modified by a modifier,
the modifier is selected from at least one of 3-aminopropyltriethoxysilane, (3-aminopropyl) dimethylethoxysilane and aminopropylaminoethyl trimethoxysilane;
the nano silicon dioxide carrier has a hollow structure, and pore channels are distributed on the wall forming the hollow structure.
In the nano pesticide controlled-release agent of the present invention, in order to achieve an excellent controlled-release effect thereof, the "pesticide active ingredient supported on the modified carrier" is preferably mainly located in the hollow cavity structure of the modified carrier and on the inner wall of the cavity structure.
Preferably, the average particle size of the nano-silica carrier is 100-600nm, the average thickness of the wall is 10-50nm, the average pore diameter of the pore channel is 1-10nm, the surface potential of the carrier is 10-50mV, and the specific surface area of the carrier is 100-1200 m-2/g。
Preferably, the content of the modified carrier is 10-80 wt%, the content of the pesticide active component is 10-80 wt%, and the content of the pore-plugging agent is 3-60 wt%, based on the total weight of the controlled release agent.
In the invention, the pore-plugging agent can be coated on the outer layer of the modified carrier, or can plug pores in a mode of plugging pore channels of the modified carrier, or can be both the pore-plugging agent and the pore-plugging agent.
Preferably, the modifying agent is present in the modified carrier in an amount of 1 to 30 wt.%, based on the total weight of the modified carrier.
According to a preferred embodiment of the present invention, the pesticidal active ingredient is an insecticide, and more preferably, the insecticide is selected from at least one of pyraclostrobin, chlorpyrifos, cypermethrin, diazinon, endosulfan, phosmet, malathion, methomyl, naled, novaluron, deltamethrin, imidacloprid, permethrin and phorate.
According to another preferred embodiment of the present invention, the pesticidally active component is an antibacterial agent, more preferably the antibacterial agent is selected from at least one of azoxystrobin, difenoconazole, chlorothalonil, propamocarb, fenamidone, fluopicolide, mancozeb, metalaxyl, metiram, pyraclostrobin, zoxamide, cyprodinil, dimethomorph, copperant, cymoxanil, famoxadone and fluazinam.
Preferably, the controlled release agent is in the form of at least one of wettable powder, microcapsule suspension, water suspension, dispersible oil suspension, aqueous emulsion, granules and microemulsion.
As described above, the second aspect of the present invention provides a method for preparing a nano pesticide controlled-release agent, which comprises:
(1) carrying out first contact on a modifier and a nano silicon dioxide carrier to obtain a modified carrier;
(2) carrying out second contact on the modified carrier and the pesticide active component to obtain the modified carrier loaded with the pesticide active component;
(3) carrying out third contact on the modified carrier loaded with the pesticide active component and a pore plugging agent;
wherein the pore-plugging agent is sodium carboxymethylcellulose;
the modifier is selected from at least one of 3-aminopropyltriethoxysilane, (3-aminopropyl) dimethylethoxysilane and aminopropylaminoethyl trimethoxysilane;
the nano silicon dioxide carrier has a hollow structure, and pore channels are distributed on the wall forming the hollow structure.
Preferably, according to the method of the second aspect of the present invention, the average particle size of the nano-silica support is 100-600nm, the average thickness of the wall is 10-50nm, the average pore diameter of the pore channel is 1-10nm, the surface potential of the support is 10-50mV, and the specific surface area of the support is 100-1200 m-2/g。
Preferably, according to the method of the second aspect of the present invention, the modified carrier, the pesticide active component and the pore-plugging agent are used in an amount such that the modified carrier, the pesticide active component and the pore-plugging agent are contained in the prepared controlled-release agent in an amount of 10 to 80 wt%, 10 to 80 wt% and 3 to 60 wt%, respectively, based on the total weight of the controlled-release agent.
Preferably, according to the method of the second aspect of the present invention, the amount of the modifying agent and the amount of the nano silica carrier are such that the modifying agent is contained in the prepared modified carrier in an amount of 1 to 30 wt% based on the total weight of the modified carrier.
Preferably, according to the method of the second aspect of the present invention, the pesticidally active ingredient is an insecticide and/or an antimicrobial agent.
Preferably, according to the method of the second aspect of the present invention, the pesticide is selected from at least one of pyraclostrobin, chlorpyrifos, cypermethrin, diazinon, endosulfan, malathion, methomyl, phosphorus dibromide, novaluron, deltamethrin, imidacloprid, permethrin and phorate.
Preferably, according to the method of the second aspect of the present invention, the antibacterial agent is selected from at least one of azoxystrobin, difenoconazole, chlorothalonil, propamocarb, fenamidone, fluopicolide, mancozeb, metalaxyl, metiram, pyraclostrobin, zoxamide, ametoctradin, dimethomorph, copal, cymoxanil, famoxadone and fluazinam.
Two preferred embodiments are provided below for the preparation method of the nano-silica support.
According to a first preferred embodiment of the inventionThe method according to the second aspect of the present invention further comprises preparing the nano silica support by the following steps:
(a) in the presence of a first solvent and ammonia water, carrying out first mixing on a pore-foaming agent and a precursor silicon source to obtain a first intermediate;
(b) carrying out second mixing on the first intermediate and a strong alkaline substance to obtain a second intermediate;
(c) in the presence of a second solvent, carrying out third mixing on the second intermediate and an acid to obtain a nano silicon dioxide carrier;
wherein the precursor silicon source is tetraethyl orthosilicate (TEOS).
Preferably, the pore-forming agent is selected from at least one of Cetyl Trimethyl Ammonium Bromide (CTAB), tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and octadecyl trimethoxy silane, and more preferably, the prepared nano silica carrier has more uniform pore distribution, which is beneficial to the subsequent loading of pesticide active components.
Preferably, the strong alkaline substance is selected from at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
Preferably, the acid is selected from at least one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid.
Preferably, in step (a), the weight ratio of the porogen to the precursor silicon source is 1: 1-3.
Preferably, in step (b), the first intermediate and the strongly basic substance are used in a weight ratio of 1: 1-5.
Preferably, in step (c), the weight ratio of the amount of the second intermediate to the amount of the acid is 1: 1-4.
Preferably, in step (a), the conditions of the first mixing include: the temperature is 0-80 ℃ and the time is 1-12 h.
Preferably, in step (b), the conditions of the second mixing include: the temperature is 0-100 ℃ and the time is 2-48 h.
Preferably, in step (c), the conditions of the third mixing include: the temperature is 0-100 ℃ and the time is 1-24 h.
Preferably, in the step (a), the step (b) and the step (c), the method further comprises: and respectively and independently separating and drying the material obtained after the first mixing, the material obtained after the second mixing and the material obtained after the third mixing in turn to respectively obtain the first intermediate, the second intermediate and the carrier.
The drying conditions in step (a), step (b), step (c) may be the same or different, preferably the drying conditions comprise: the temperature is 20-100 ℃ and the time is 4-48 h.
The present invention is not particularly limited in particular to the specific manner of the separation, and may be a conventional separation method known in the art, for example, centrifugation.
The first solvent and the second solvent are not particularly limited in kind and amount, as long as the porogen and the second intermediate can be sufficiently dissolved and the first mixing and the third mixing can be sufficiently performed, and for example, the first solvent and the second solvent may be each independently selected from at least one of ethanol, deionized water, and distilled water.
According to a second preferred embodiment of the inventionThe method according to the second aspect of the present invention further comprises preparing the nano silica support by the following steps:
(I) in the presence of a solvent and ammonia water, carrying out a first reaction on a pore-foaming agent and a precursor silicon source to obtain a first intermediate;
(II) carrying out a second reaction on the first intermediate and a strong alkaline substance to obtain a second intermediate;
and (III) calcining the second intermediate to obtain the nano silicon dioxide carrier.
Wherein the precursor silicon source is tetraethyl orthosilicate (TEOS).
Preferably, the porogen is selected from at least one of Cetyl Trimethyl Ammonium Bromide (CTAB), tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and octadecyl trimethoxy silane.
Preferably, the strong alkaline substance is selected from at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
Preferably, in step (I), the weight ratio of the porogen to the precursor silicon source is 1: 1-3.
Preferably, in step (II), the first intermediate and the strongly basic substance are used in a weight ratio of 1: 1-5.
Preferably, in step (I), the conditions of the first reaction include: the temperature is 0-80 ℃ and the time is 1-12 h.
Preferably, in step (II), the conditions of the second reaction include: the temperature is 0-100 ℃ and the time is 2-48 h.
Preferably, in step (III), the calcination conditions include: the temperature is 400 ℃ and 1000 ℃, and the time is 1-24 h.
Preferably, in step (I), step (II), the method further comprises: and respectively and independently separating and drying the material obtained after the first reaction and the material obtained after the second reaction in turn to respectively obtain the first intermediate and the second intermediate.
The drying conditions in step (I) and step (II) may be the same or different, and preferably, the drying conditions include: the temperature is 20-100 ℃ and the time is 4-48 h.
The present invention is not particularly limited in particular to the specific manner of the separation, and may be a conventional separation method known in the art, for example, centrifugation.
The kind and amount of the solvent used in step (I) are not particularly limited as long as the solvent can sufficiently dissolve the porogen and thus the first reaction can be sufficiently performed, and for example, the solvent may be selected from at least one of ethanol, deionized water and distilled water.
Preferably, according to the method of the second aspect of the present invention, in step (1), the conditions of the first contacting include: the temperature is 0-80 ℃ and the time is 2-12 h.
Preferably, according to the method of the second aspect of the present invention, in the step (2), the conditions of the second contacting include: the temperature is 0-100 ℃ and the time is 2-48 h.
Preferably, according to the method of the second aspect of the present invention, in step (3), the conditions of the third contacting include: the temperature is 0-100 ℃ and the time is 1-24 h.
In the method according to the second aspect of the present invention, post-treatment steps known in the art, such as ultrasound, cleaning, and dialysis, may also be included, and the present invention is not described herein in detail, and in the following examples of the present invention, several specific operations of post-treatment are exemplified, and those skilled in the art should not understand the limitation of the present invention.
According to a preferred embodiment of the present invention, the method according to the second aspect of the present invention comprises:
(1) in the presence of a first solvent and ammonia water, dissolving a pore-foaming agent, and then mixing the dissolved pore-foaming agent and a precursor silicon source for the first time, wherein the weight ratio of the pore-foaming agent to the precursor silicon source is 1: 1-3, the conditions of the first mixing including: the temperature is 0-80 ℃, and the time is 1-12h, so as to obtain a first intermediate;
(2) and secondly mixing the first intermediate with a strong alkaline substance, wherein the weight ratio of the first intermediate to the strong alkaline substance is 1: 1-5, the second mixing conditions comprising: the temperature is 0-100 ℃, and the time is 2-48h, so as to obtain a second intermediate;
(3) and thirdly mixing the second intermediate with acid in the presence of a second solvent, wherein the weight ratio of the second intermediate to the acid is 1: 1-4, the third mixing conditions comprising: the temperature is 0-100 ℃, and the time is 1-24 h; obtaining a nano silicon dioxide carrier;
(4) carrying out first contact on the nano-silica carrier prepared in the step (3) and a modifier, wherein the conditions of the first contact comprise: the temperature is 0-80 ℃, and the time is 2-12h, so as to obtain the modified carrier;
(5) and (3) carrying out second contact on the modified carrier prepared in the step (4) and a pesticide active component, wherein the conditions of the first contact comprise: the temperature is 0-100 ℃, and the time is 2-48h, so as to obtain the modified carrier loaded with the pesticide active component;
(6) and (3) carrying out third contact on sodium carboxymethyl cellulose and the modified carrier loaded with the pesticide active component obtained in the step (5), wherein the conditions of the third contact comprise: the temperature is 0-100 ℃, and the time is 1-24h, so as to obtain the nano pesticide controlled release agent.
As mentioned above, the third aspect of the present invention provides the nano controlled-release pesticide prepared by the method of the second aspect.
The present invention will now be described in detail by way of examples, in which, unless otherwise specified, all starting materials are commercially available, and wherein:
precursor silicon source: tetraethyl orthosilicate (TEOS) is purchased from the national pharmaceutical group chemical reagents, Inc. under the brand number of 78-10-4;
pore-forming agent: cetyl Trimethyl Ammonium Bromide (CTAB) is available from Shanghai Bidi pharmaceutical science and technology Inc. under the trademark 3069-42-9; octadecyltrimethoxysilane was purchased from Shanghai Michelle chemical technology, Inc. under the designation 3069042-9;
modifying agent: 3-Aminopropyltriethoxysilane (APTES) was purchased from Shanghai Allantin Biotechnology Ltd under the designation 919-30-2; the (3-aminopropyl) dimethylethoxysilane was purchased from Wuhanxin chemical science and technology Ltd under the brand number 18306-79-1.
In the following examples:
a. the surface potential of the material was tested using the following method: dispersing a small amount of nano particle samples in distilled water to obtain a solution to be tested, placing 500 mu L of the solution to be tested in an electrode cuvette for testing, wherein the testing conditions comprise: the test time was 120s and the temperature was 25 ℃.
b. Particle size and morphology determination: transmission Electron Microscope (TEM) available from FEI corporation, usa under the model TecnaiG 220 TWIN;
c. specific surface area and porosity determination: a fully automatic specific surface area and aperture analyzer, available from corna, usa under model number AUTOSORB-IQ 2;
d. the component content determination of the nano pesticide controlled release agent comprises the following steps: obtained by ultraviolet analysis test, taking the example 1 as an example, the specific process is as follows:
all supernatants from the centrifugal washing during step (6) of example 1 were collected and subjected to UV analysis. Measuring the content of the pesticide component in the supernatant by comparing with a standard curve according to the formula: the content of the pesticide is (the total mass of the added pesticide-the mass of the supernatant pesticide)/the total mass of the nano pesticide controlled release agent, and the content of the pesticide component is obtained;
and dialyzing and freeze-drying the supernatant, and weighing the mass of the residual pore-plugging agent in the supernatant. According to the formula: the content of the pore-plugging agent is (the total mass of the added pore-plugging agent-the mass of the supernatant pore-plugging agent)/the total mass of the nano pesticide controlled release agent, so as to obtain the content of the pore-plugging agent;
e. content of modifying agent in modified carrier: obtained by thermogravimetric analysis.
Example 1
(1) Adding 150mL of absolute ethyl alcohol, 250mL of distilled water and 0.7347g of CTAB into a round-bottom flask, stirring at 30 ℃ until the CTAB is completely dissolved, weighing 1.0499g of TEOS, dropwise adding the TEOS into a CTAB solution, reacting at 30 ℃ for 30min, taking 1.330mL of 28 wt% ammonia water by using a pipette, reacting for 6h, and drying at 50 ℃ for 12h to obtain a first intermediate;
(2) 50mL of 0.3mol/L Na was added to the first intermediate obtained in step (1)2CO3Stirring the solution at 60 ℃ for 6h, centrifuging, transferring the centrifuged solid into a dialysis bag, dialyzing with distilled water (molecular weight of 3500) as dialysate, changing distilled water every 2h, dialyzing for 24h, centrifuging after dialysis, and drying at 50 ℃ for 12h to obtain a second intermediate;
(3) adding 100mL of absolute ethyl alcohol into the second intermediate obtained in the step (2), then dropwise adding 3mL of 35 wt% hydrochloric acid by using a pipette, reacting for 2h at 80 ℃, centrifuging, transferring the centrifuged solid into a dialysis bag, dialyzing by using distilled water as dialysate (molecular weight is 3500), changing the distilled water once every 2h, dialyzing for 2 days, centrifuging after dialysis, and drying for 12h at 50 ℃ to obtain the nano-silica carrier.
(4) Taking 10mg of the nano silica carrier prepared in the step (3) and 6.83mg of APTES in a round-bottom flask for first contact, wherein the conditions of the first contact comprise: the temperature is 80 ℃, and the time is 12 hours, so as to obtain a modified carrier;
(5) taking 10mg of the modified carrier prepared in the step (4), 30mg of pyraclostrobin and 10mL of 50 vol% ethanol (V)EtOH:VH2O1:1), adding the mixture into a round-bottom flask, uniformly dispersing, and stirring at 30 ℃ for 24 hours to perform second contact to obtain a modified carrier loaded with the pesticide active component;
(6) 10mg of sodium carboxymethylcellulose was dissolved in 10mL of 50 vol% ethanol (V)EtOH:VH2O1:1), then performing third contact with the modified carrier loaded with the pesticide active component obtained in the step (5) at 30 ℃ for 24 hours under stirring, then centrifuging, washing with ethanol, and drying at 50 ℃ for 12 hours to obtain the compoundTo the nano pesticide controlled release agent.
Tests show that the content of the pesticide active component in the nano pesticide controlled release agent is 25 wt%, the content of the pore blocking agent is 9 wt%, and the balance is the modified carrier.
Example 2
A nano-sized controlled-release agent for agricultural chemicals was prepared in a similar manner to example 1, except that 4.98mg of (3-aminopropyl) dimethylethoxysilane was used in place of APTES in example 1, and the rest was the same as in example 1.
Example 3
In a similar manner to example 1, except that 0.6797g of octadecyltrimethoxysilane was used in place of CTAB in step (1) of example 1, and step (3) was carried out by placing the second intermediate obtained in step (2) in a tube furnace and calcining at 550 ℃ for 6 hours to obtain a nano-silica support.
The rest is the same as the example 1, and the nano pesticide controlled release agent is prepared.
Comparative example 1
A similar procedure was followed as in example 1, except that in this comparative example, step (6) was not carried out, i.e., no pore-blocking agent was added, and only the modified carrier carrying the pesticidal active ingredient, designated as sample CS1, was obtained.
Test example
1. Structural characterization test
(1) Surface potential testing of materials
The invention exemplarily provides the surface potential test results of the first intermediate, the second intermediate, the nano-silica carrier and the modified carrier in example 1, and the specific results are shown in table 1.
TABLE 1
Test sample Surface potential/mV
First intermediate body -24.8
Second intermediate -18.2
Nano silicon dioxide carrier -37.3
Modified vectors 23.1
From the results in table 1, it can be seen that the surface potentials of the first intermediate, the second intermediate and the nano-silica carrier are all negative values when the nano-silica carrier is prepared. After the 3-aminopropyltriethoxysilane modifies the carrier, the surface potential of the modified carrier is changed from-37.3 mV to 23.1mV, which can prove that the invention successfully modifies the nano silicon dioxide carrier to obtain the modified carrier.
(2) Particle size and morphology observations
The invention exemplarily provides a transmission electron micrograph of the first intermediate and the nanosilica support of example 1, as shown in fig. 1:
as can be seen from fig. 1(a), the nanoparticles of the first intermediate have an obvious core-shell structure, are relatively complete in morphology, relatively uniform in size, and relatively good in dispersibility, have a particle diameter of about 250nm, are relatively loose on the particle surface, and can observe fine channels;
from fig. 1(b), it can be seen that the nanoparticles of the nano-silica carrier have an obvious hollow structure, the particle size is uniform, the dispersibility is good, the particle diameter is about 250nm, the wall thickness is about 25nm, the cavity volume of the carrier is relatively large, and the carrier has good drug loading capacity.
(3) Specific surface area and porosity measurements
The present invention exemplarily provides a nitrogen adsorption and desorption isotherm of the nano-silica carrier prepared in example 1, as shown in fig. 2, it can be seen from the capillary coagulation phenomenon and the presence of a hysteresis loop contained in the nitrogen adsorption and desorption isotherm in fig. 2 that a mesoporous structure having an average pore diameter of 4.570nm exists in the nano-silica carrier;
meanwhile, the present invention exemplarily provides the specific surface area test results of the nano-silica support and the first intermediate of example 1, and the specific results are shown in table 2.
TABLE 2
Test sample Specific surface area/m2/g
First intermediate body 42.006
Carrier 368.529
As can be seen from the results of Table 2, the specific surface area of the first intermediate was 42.006m2The specific surface area of the nano silica carrier is 368.529m2The concentration is far higher than that of the first intermediate, and the formation of the pore channel and the internal hollow structure on the nano silica carrier is further proved.
2. Enzyme response assay
(1) Release of pesticidal active ingredients under different concentrations of cellulase response conditions
The nano pesticide controlled-release agent prepared by the above example is used for testing, and specifically, the testing is carried out by adopting the following steps:
s1: placing 5mL of distilled water and 2.5mg of the nano pesticide controlled release solid prepared in the above example into an EP tube, ultrasonically dispersing, uniformly dividing into five parts by using a pipette, respectively placing the five parts into 6 centrifugal tubes with the number of A, B, C, D, E, F and 50mL, centrifuging, removing supernate, and repeating the operation for three times;
s2: respectively adding 40mL of 60.0U, 30.0U, 15.0U, 3.0U and 0.3U cellulase solution and 40mL of mixed solution of distilled water and ethanol (volume ratio is 9: 1) into 6 50mL centrifuge tubes with the number of A, B, C, D, E, F, then placing the 6 centrifuge tubes at room temperature to release drugs, centrifuging after 2 hours, taking 40mL of supernatant, simultaneously placing the centrifuged product into a new 50mL centrifuge tube, respectively supplementing 40mL of corresponding solution, placing at room temperature to release drugs, repeating the operation, taking supernatant every 2 hours, and taking six times; after 12h, taking supernatant every 4h for four times; after 48 hours, taking the supernatant once every 12 hours, and taking the supernatant once in all; then taking the supernatant every 24 hours till 180 hours;
and respectively testing the content of the pesticide active component in the supernatant to obtain the release condition of the pesticide active component under the response condition of the cellulase with different concentrations.
The invention exemplarily provides the release conditions of the pesticide active components of the nano pesticide controlled-release agent prepared in the example 1 under the response conditions of different concentrations of cellulase, and the specific results are shown in figure 3; the invention also exemplarily provides the release condition of the pesticide active component loaded modified carrier of the non-pore-plugging agent prepared in the comparative example 1 in the presence or absence of cellulase, and the specific result is shown in fig. 4.
As can be seen from fig. 3, the nano pesticide controlled release agent provided by the invention can control the release rate of the pesticide to release the pesticide, and shows an excellent pesticide slow release effect, wherein the higher the enzyme activity is, the higher the release rate is, for example, the cumulative release rate of 168h in water is only 4.03 wt%, and the cumulative release rate of 168h under the condition that the enzyme activity is 30.0U is 44.82 wt%.
As can be seen from fig. 4, the modified carrier loaded with the pesticidal active ingredient of comparative example 1, which did not contain the pore-blocking agent, exhibited a drug release rate not affected by cellulase, and a cumulative release rate of 48.22 wt% at 48 h.
(2) Release of pesticidal active ingredients under conditions of different classes of enzymes
The nano pesticide controlled-release agent prepared by the above example is used for testing, and specifically, the testing is carried out by the following steps:
s1: putting 3mL of distilled water and 1.5mg of the nano pesticide controlled-release agent solid prepared in the above example into an EP tube, ultrasonically dispersing, uniformly dividing into three parts by using a pipette, respectively putting the three parts into 350 mL centrifuge tubes with the number of A, B, C, centrifuging, removing supernate, and repeating the operation for three times;
s2: respectively adding 40mL of mixed solution of distilled water and ethanol (volume ratio (9: 1)), 30.0U of alpha-amylase solution and 30.0U of cellulase solution into 3 centrifuge tubes with the number of A, B, C and the volume ratio being 50mL, placing the 3 centrifuge tubes at room temperature for drug release, centrifuging after 2 hours, taking 40mL of supernatant, simultaneously placing the centrifuged product into a new centrifuge tube with the volume ratio being 30.0U, respectively supplementing 40mL of corresponding solution, placing the centrifuged product at room temperature for drug release, repeating the operation, taking the supernatant every 2 hours, and taking six times in total; after 12h, taking supernatant every 4h for four times; after 48 hours, taking the supernatant once every 12 hours, and taking the supernatant once in all; taking the supernatant every 24 hours till 180 hours;
and respectively testing the content of the pesticide active components in the supernatant to obtain the release conditions of the pesticide active components under different enzyme response conditions.
The invention exemplarily provides the release conditions of the pesticide active components of the nano pesticide controlled-release agent prepared in the example 1 under the conditions of different kinds of enzymes, and the specific results are shown in figure 5.
As can be seen from FIG. 5, the cumulative release rate of the nano pesticide controlled release agent in the absence of enzyme for 72 hours is 3.38 wt%, the cumulative release rate in the presence of alpha-amylase for 72 hours is 4.59 wt%, and the cumulative release rate in the presence of cellulase for 72 hours can reach 30.85 wt%, so that the nano pesticide controlled release agent provided by the invention has good selectivity and can release a large amount of pesticide under the action of cellulase, and the amylase existing in a large amount in human bodies and fish bodies has little influence on the drug release behavior of the nano pesticide controlled release agent.
3. Toxicity testing
(1) Toxicity test in Fish
The pyraclostrobin and the nano pesticide controlled release agent prepared in example 1 are respectively adopted for comparison test, and the specific test process is as follows:
s1: standing water: standing the water used in the experimental process for more than two days to ensure that no chlorine exists in the water, and introducing oxygen before adding the fry;
s2: and (4) observing the fry: the type of the fry used in the experiment is the zebra fish with the length of about 1-1.5cm, the fry is firstly observed in a fish tank for one week to ensure that the fry does not die naturally, and then 20 fries are added into a reaction tank with 5L of water to be observed for two days to ensure that the fry does not die naturally;
s3: co-culturing pesticides of a series of concentrations with fish: the pyraclostrobin with different concentrations and the nano pesticide controlled-release agent solution prepared in example 1 were co-cultured with zebra fish for 72 hours, and the mortality of the zebra fish was tested, with specific results shown in fig. 6.
As can be seen from FIG. 6, pyraclostrobin has a great toxicity to zebrafish, with a half-lethal dose (mortality up to 50%) of about 0.05 mg/L. The toxicity of the nano pesticide controlled release agent in the fish body is obviously reduced, the semilethal dose is increased to about 0.18mg/L, and the nano pesticide controlled release agent provided by the invention has less release amount in water and the fish body, and can effectively reduce the toxicity of pesticide to aquatic organisms.
(2) In vitro test for germ inhibition
The invention tests the in-vitro contrast experiment of the bacterial inhibition of the rice sheath blight bacteria, the rice bakanae bacteria and the watermelon vine blight bacteria respectively by adopting pyraclostrobin and the nano pesticide controlled release agent prepared in the embodiment 1, taking the rice sheath blight bacteria as an example, and the specific test process is as follows:
s1: activating the bacterial strain of the rice sheath blight bacterium, taking out small pieces of hypha from the freezing storage tube, transferring the hypha to a PDA flat plate, culturing the hypha in an incubator for 3 days, and transferring the hypha to the PDA flat plate again for bioassay;
s2: pyraclostrobin is prepared into 10000 mug/ml raw pesticide and is respectively diluted into 2000 mug/ml, 1000 mug/ml, 500 mug/ml, 250 mug/ml, 125 mug/ml and 62.5 mug/ml medicaments for carrying out biological assay experiments. The above agents were added to each PDA plate numbered A, B, C, D, E, F, and water was added so that the final concentrations of each PDA plate were 2. mu.g/ml, 1. mu.g/ml, 0.5. mu.g/ml, 0.25. mu.g/ml, 0.125. mu.g/ml, 0.0625. mu.g/ml, respectively, as treatment groups; in addition, the same volume of sterile water was added to the PDA plate numbered G as a control, a bacterial dish (diameter 5mm) was punched out of the PDA plate in step S1, and they were attached to PDA plates containing different concentrations of the drug, 3 PDA plates per concentration, respectively, and then all the PDA plates were incubated at 25 ℃ for 2 days;
s3: the nano pesticide controlled release agent prepared in the example 1 is subjected to the same operation as the S2;
s4: after two days, the colony diameter of each PDA plate is measured, and the hypha growth inhibition rate is calculated.
Wherein the growth inhibition rate is (control diameter-treated diameter)/(control diameter-5) × 100%; obtaining a regression equation according to the logarithm value of the concentration of the medicament and the probability value of the inhibition rate in a linear way, and calculating EC50The values (i.e., half inhibitory concentration) are shown in Table 3.
The test process of the rice bakanae disease and the watermelon fusarium oxysporum is the same as the test process of the rice rhizoctonia solani, the detailed description of the test process is omitted, and the specific test results are shown in table 3.
TABLE 3
Figure BDA0002849282780000191
As can be seen from table 3, compared with the original drug, the nano pesticide controlled release agent provided by the present invention has a better inhibition effect on various common pathogens, and the half inhibition rate concentration thereof is lower than that of the original drug, which indicates that the nano pesticide controlled release agent provided by the present invention can release the loaded pesticide in the pathogens and has a good inhibition effect.
The results show that the release amount of the nano pesticide controlled release agent provided by the invention in a natural environment is small, the pesticide residue in the environment can be effectively reduced, and the pollution to the environment is reduced; the nano pesticide controlled release agent provided by the invention has specific enzyme responsiveness, responds to release of the pesticide only in fungi in the presence of cellulase, and has small influence on toxic and side effects of aquatic organisms such as people, fish and the like without the cellulase; the nano pesticide controlled release agent provided by the invention has a good inhibition effect on various common germs, has a half inhibition rate concentration lower than that of a raw pesticide, and has a good inhibition effect.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A nano pesticide controlled release agent is characterized in that the controlled release agent contains a modified carrier, a pesticide active component loaded on the modified carrier and a pore blocking agent distributed on the modified carrier;
wherein the pore-plugging agent is sodium carboxymethylcellulose;
the modified carrier is a nano silicon dioxide carrier modified by a modifier,
the modifier is selected from at least one of 3-aminopropyltriethoxysilane, (3-aminopropyl) dimethylethoxysilane and aminopropylaminoethyl trimethoxysilane;
the nano silicon dioxide carrier has a hollow structure, and pore channels are distributed on the wall forming the hollow structure;
preferably, the average particle size of the nano-silica carrier is 100-600nm, the average thickness of the wall is 10-50nm, the average pore diameter of the pore channel is 1-10nm, the surface potential of the carrier is 10-50mV, and the specific surface area of the carrier is 100-120-0m2/g。
2. The controlled release agent according to claim 1, wherein the modified carrier is contained in an amount of 10 to 80 wt%, the pesticidal active ingredient is contained in an amount of 10 to 80 wt%, and the pore-plugging agent is contained in an amount of 3 to 60 wt%, based on the total weight of the controlled release agent;
preferably, the modifying agent is present in the modified carrier in an amount of 1 to 30 wt.%, based on the total weight of the modified carrier.
3. The controlled-release agent according to claim 1 or 2, wherein the pesticidal active ingredient is an insecticide and/or an antibacterial agent,
preferably, the pesticide is selected from at least one of pyraclostrobin, chlorpyrifos, cypermethrin, diazinon, endosulfan, malathion, methomyl, naled, novaluron, deltamethrin, imidacloprid, permethrin and phorate;
preferably, the antibacterial agent is selected from at least one of azoxystrobin, difenoconazole, chlorothalonil, propamocarb, fenamidone, fluopicolide, mancozeb, metalaxyl, metiram, pyraclostrobin, zoxamide, ametoctradin, dimethomorph, copper preparations, cymoxanil, famoxadone and fluazinam.
4. The controlled-release agent according to any one of claims 1 to 3, wherein the controlled-release agent is in the form of at least one of wettable powder, microcapsule suspension, aqueous suspension, dispersible oil suspension, aqueous emulsion, granule and microemulsion.
5. A method for preparing a nano pesticide controlled release agent, which comprises the following steps:
(1) carrying out first contact on a modifier and a nano silicon dioxide carrier to obtain a modified carrier;
(2) carrying out second contact on the modified carrier and the pesticide active component to obtain the modified carrier loaded with the pesticide active component;
(3) carrying out third contact on the modified carrier loaded with the pesticide active component and a pore plugging agent;
wherein the pore-plugging agent is sodium carboxymethylcellulose;
the modifier is selected from at least one of 3-aminopropyltriethoxysilane, (3-aminopropyl) dimethylethoxysilane and aminopropylaminoethyl trimethoxysilane;
the nano silicon dioxide carrier has a hollow structure, and pore channels are distributed on the wall forming the hollow structure;
preferably, the average particle size of the nano-silica carrier is 100-600nm, the average thickness of the wall is 10-50nm, the average pore diameter of the pore channel is 1-10nm, the surface potential of the carrier is 10-50mV, and the specific surface area of the carrier is 100-1200 m-2/g；
Preferably, the modified carrier, the pesticide active component and the pore-plugging agent are used in amounts such that the content of the modified carrier, the content of the pesticide active component and the pore-plugging agent in the prepared controlled-release agent are 10-80 wt%, 10-80 wt% and 3-60 wt%, respectively, based on the total weight of the controlled-release agent;
preferably, the amount of the modifier and the amount of the nano-silica carrier are such that the content of the modifier in the prepared modified carrier is 1-30 wt% based on the total weight of the modified carrier.
6. The method of claim 5, further comprising preparing the nanosilica support using the steps of:
(a) in the presence of a first solvent and ammonia water, carrying out first mixing on a pore-foaming agent and a precursor silicon source to obtain a first intermediate;
(b) carrying out second mixing on the first intermediate and a strong alkaline substance to obtain a second intermediate;
(c) in the presence of a second solvent, carrying out third mixing on the second intermediate and an acid to obtain a nano silicon dioxide carrier;
wherein the precursor silicon source is tetraethyl orthosilicate;
preferably, the porogen is selected from at least one of cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and octadecyl trimethoxy silane.
7. The method of claim 6, wherein in step (a), the porogen and the precursor silicon source are used in a weight ratio of 1: 1-3;
preferably, in step (b), the first intermediate and the strongly basic substance are used in a weight ratio of 1: 1-5;
preferably, in step (c), the weight ratio of the amount of the second intermediate to the amount of the acid is 1: 1-4.
8. The method of claim 6 or 7, wherein the conditions of the first mixing comprise: the temperature is 0-80 ℃, and the time is 1-12 h;
preferably, the conditions of the second mixing include: the temperature is 0-100 ℃, and the time is 2-48 h;
preferably, the conditions of the third mixing include: the temperature is 0-100 ℃ and the time is 1-24 h.
9. The method of any one of claims 5-8, wherein the conditions of the first contacting comprise: the temperature is 0-80 ℃, and the time is 2-12 h;
preferably, the conditions of the second contacting include: the temperature is 0-100 ℃, and the time is 2-48 h;
preferably, the conditions of the third contacting include: the temperature is 0-100 ℃ and the time is 1-24 h.
10. The nano pesticide controlled release agent prepared by the method of any one of claims 5 to 9.
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