CN112450222B - Nanometer pesticide controlled release agent and preparation method thereof - Google Patents
Nanometer pesticide controlled release agent and preparation method thereof Download PDFInfo
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- CN112450222B CN112450222B CN202011520383.7A CN202011520383A CN112450222B CN 112450222 B CN112450222 B CN 112450222B CN 202011520383 A CN202011520383 A CN 202011520383A CN 112450222 B CN112450222 B CN 112450222B
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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
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- 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
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- 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
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- C01P2006/16—Pore diameter
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- 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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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, pesticide active components loaded on the modified carrier and pore blocking agents distributed on the modified carrier; wherein the pore blocking agent is sodium carboxymethyl cellulose; the modification carrier is a nano silicon dioxide carrier modified by a modifier, and the modifier is at least one of 3-aminopropyl triethoxysilane, (3-aminopropyl) dimethyl ethoxysilane and aminopropyl aminoethyl 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, only responds to release in fungi with cellulase, and has small influence on toxic and side effects of aquatic organisms such as people, fish and the like without cellulase.
Description
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
While conventional pesticides generally have an effective utilization rate of less than 30% by weight due to the loss of poor dispersibility, biodegradation and the like, and while conventional pesticide formulations such as pesticide Microemulsion (ME), water Dispersible Granule (WDG) and the like can release very high active ingredients in a short period of time, only 0.1% by weight of the pesticide can reach a target site due to the loss and degradation of the active ingredients caused by the environmental factors such as photolysis, hydrolysis, microbial degradation or oxidation/reduction, and the like, and the rest of the pesticide enters the environment to cause harm to non-target organisms including human beings and the environment, more and more researchers are devoted to the development of sustained and controlled release pesticide systems.
Compared with the traditional pesticide, the sustained and controlled release pesticide has the following advantages: the evaporation of the pesticide is controlled or reduced, the residual bioactivity is longer, the safety to non-target organisms including human beings is increased, and the physicochemical decomposition or biodegradation of the pesticide is reduced, so that the use amount of the pesticide is reduced.
However, the sustained and controlled release pesticide systems synthesized by most researchers currently mainly face two problems: firstly, the release behavior of the loaded medicine is mostly slow release without selectivity, and the loaded medicine can be slowly released in the environment, the disease body, the human body and the aquatic organism, which can cause the pollution of pesticides to the environment and the toxic and side effects to the human body and other organisms; secondly, the drug loading is lower, and the common drug loading is 5-20 wt%, so that the dosage form with higher concentration is needed if the nanometer dosage form with lower drug loading reaches high insecticidal effect, thereby not only increasing the production cost of users, but also increasing the difficulty of dosage forms in the aspects of preparation, spraying and the like.
Therefore, research on a novel intelligent nano pesticide controlled release agent with high drug loading capacity and only releasing drugs selectively 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 medicines and low medicine carrying quantity of a sustained and controlled release pesticide system in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a controlled release agent for a nano pesticide, which comprises a modified carrier, a pesticide active ingredient supported on the modified carrier and a pore blocking agent distributed on the modified carrier;
wherein the pore blocking agent is sodium carboxymethyl cellulose;
the modified carrier is a nano silicon dioxide carrier modified by a modifier,
the modifier is at least one selected from 3-aminopropyl triethoxysilane, (3-aminopropyl) dimethyl ethoxysilane and aminopropyl aminoethyl 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 controlled release agent for a nano pesticide, the method 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 a 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 blocking agent is sodium carboxymethyl cellulose;
the modifier is at least one selected from 3-aminopropyl triethoxysilane, (3-aminopropyl) dimethyl ethoxysilane and aminopropyl aminoethyl 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 controlled release agent for a nano pesticide prepared by the method of the second aspect.
Compared with the prior art, the nano pesticide controlled release agent provided by the invention has at least 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 residues in the environment and reduce environmental pollution;
(2) The nano pesticide controlled release agent provided by the invention has specific enzyme responsiveness, only responds to release in fungi with cellulase, and has small influence on toxic and side effects of aquatic organisms such as people, fish and the like without cellulase.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is a transmission electron microscope image of the first intermediate and the nano silica carrier prepared in example 1, wherein fig. 1 (a) is a transmission electron microscope image of the first intermediate, and fig. 1 (b) is a transmission electron microscope image of the nano silica carrier;
FIG. 2 is a nitrogen adsorption and desorption isotherm of the nano silica carrier prepared in example 1;
FIG. 3 is a graph showing the release profile of pesticide active ingredients of the nano pesticide controlled release agent prepared in example 1 under the condition of response of cellulases with different concentrations;
FIG. 4 is a graph showing the release of the pesticidal active ingredient from the modified vehicle carrying the pesticidal active ingredient without blocking the pores prepared in comparative example 1 in the presence or absence of cellulase;
FIG. 5 is a graph showing the release profile of pesticide active ingredient under different enzyme conditions of the nano pesticide controlled release agent prepared in example 1;
FIG. 6 is a toxicity test curve of co-culture of the controlled release agent of nano pesticide and zebra fish prepared by using pyraclostrobin technical and the preparation method of example 1 respectively.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a controlled release agent for nano pesticides, which comprises a modified carrier, a pesticide active ingredient loaded on the modified carrier and a pore blocking agent distributed on the modified carrier;
wherein the pore blocking agent is sodium carboxymethyl cellulose;
the modified carrier is a nano silicon dioxide carrier modified by a modifier,
the modifier is at least one selected from 3-aminopropyl triethoxysilane, (3-aminopropyl) dimethyl ethoxysilane and aminopropyl aminoethyl 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 diameter of the nano silicon dioxide carrier is 100-600nm, the average thickness of the wall is 10-50nm, the average pore diameter of the pore canal is 1-10nm, the surface potential of the carrier is 10-50mV, and the specific surface area of the carrier is 100-1200m 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 blocking agent is 3-60 wt%, based on the total weight of the controlled release agent.
In the invention, the pore blocking agent can be wrapped on the outer layer of the modified carrier, can block pores in a mode of blocking pore channels of the modified carrier, or can be a combination of the pore blocking agent and the modified carrier.
Preferably, in the modified carrier, the content of the modifier is 1 to 30% by weight 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, more preferably, the insecticide is at least one selected from pyraclostrobin, chlorpyrifos, cypermethrin, diazinon, endosulfan, thiophos, malathion, methomyl, dibromophosphorus, fluoroureide, deltamethrin, imidacloprid, permethrin and methamphetamine.
According to another preferred embodiment of the present invention, the pesticidal active ingredient is an antibacterial agent, more preferably, the antibacterial agent is at least one selected from azoxystrobin, difenoconazole, chlorothalonil, propamocarb, fenamidone, fluopicolide, mancozeb, metalaxyl, metiram, pyraclostrobin, zoxamide, dimethomorph, copper preparation, cymoxanil, famoxadone and fluazinam.
Preferably, the dosage form of the controlled release agent is at least one of wettable powder, microcapsule suspending agent, water suspending agent, dispersible oil suspending agent, aqueous emulsion, granule and microemulsion.
As previously described, the second aspect of the present invention provides a method for preparing a controlled release agent for a nano pesticide, the method 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 a 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 blocking agent is sodium carboxymethyl cellulose;
the modifier is at least one selected from 3-aminopropyl triethoxysilane, (3-aminopropyl) dimethyl ethoxysilane and aminopropyl aminoethyl 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 nanosilica support has an average particle diameter of 100 to 600nm, the average thickness of the wall is 10 to 50nm, the average pore diameter of the pore is 1 to 10nm, the surface potential of the support is 10 to 50mV, and the specific surface area of the support is 100 to 1200m 2 /g。
Preferably, according to the method of the second aspect of the present invention, the modified carrier, the pesticide active ingredient and the pore blocking agent are used in amounts such that the content of the modified carrier is 10 to 80 wt%, the content of the pesticide active ingredient is 10 to 80 wt% and the content of the pore blocking agent is 3 to 60 wt% based on the total weight of the controlled release agent in the prepared controlled release agent.
Preferably, according to the method of the second aspect of the present invention, 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 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 pesticidal active ingredient is an insecticide and/or an antibacterial agent.
Preferably, according to the method of the second aspect of the present invention, the insecticide is selected from at least one of pyraclostrobin, chlorpyrifos, cypermethrin, diazinon, endosulfan, thioimine, malathion, methomyl, dibromophosphorus, fluoroureide, deltamethrin, imidacloprid, permethrin and methamphetamine.
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, dimethomorph, copper preparation, cymoxanil, famoxadone and fluazinam.
Two preferred embodiments are provided below for the method of preparing the nanosilica support.
According to a first preferred embodiment of the inventionThe method according to the second aspect of the present invention further comprises preparing the nanosilica support by:
(a) First mixing a pore-forming agent with a precursor silicon source in the presence of a first solvent and ammonia water to obtain a first intermediate;
(b) Performing second mixing on the first intermediate and a strong alkaline substance to obtain a second intermediate;
(c) Thirdly mixing the second intermediate with acid in the presence of a second solvent to obtain a nano silicon dioxide carrier;
wherein the precursor silicon source is tetraethyl orthosilicate (TEOS).
Preferably, the pore-forming agent is at least one selected from Cetyl Trimethyl Ammonium Bromide (CTAB), tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and octadecyl trimethoxy silane, more preferably cetyl trimethyl ammonium bromide, and the pore canal of the prepared nano silicon dioxide carrier is distributed more uniformly, so that the subsequent loading of pesticide active components is facilitated.
Preferably, the strong alkaline substance is at least one selected from 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 the step (b), the weight ratio of the first intermediate to the strongly alkaline substance is 1:1-5.
Preferably, in step (c), the second intermediate and the acid are used in a weight ratio of 1:1-4.
Preferably, in step (a), the conditions of the first mixing include: the temperature is 0-80 ℃ and the time is 1-12h.
Preferably, in step (b), the conditions of the second mixing include: the temperature is 0-100deg.C, and the time is 2-48h.
Preferably, in step (c), the conditions of the third mixing include: the temperature is 0-100deg.C, and the time is 1-24h.
Preferably, in step (a), step (b) and step (c), the method further comprises: and separating and drying the first mixed material, the second mixed material and the third mixed material respectively and sequentially to obtain the first intermediate, the second intermediate and the carrier.
The drying conditions in step (a), step (b) and step (c) may be the same or different, and preferably, the drying conditions include: the temperature is 20-100deg.C, and the time is 4-48h.
The specific mode of the separation is not particularly limited in the present invention, and may be a conventional separation method known in the art, for example, centrifugal separation.
The type and amount of the first solvent and the second solvent are not particularly limited 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 nanosilica support by:
(I) In the presence of a solvent and ammonia water, carrying out a first reaction on a pore-forming 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;
(III) calcining the second intermediate to obtain the nano silica support.
Wherein the precursor silicon source is tetraethyl orthosilicate (TEOS).
Preferably, the porogen is selected from at least one of cetyltrimethylammonium bromide (CTAB), tetradecyltrimethylammonium bromide, cetyltrimethylammonium chloride, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, octadecyl trimethoxysilane.
Preferably, the strong alkaline substance is at least one selected from 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 the step (II), the weight ratio of the first intermediate to the strongly alkaline substance is 1:1-5.
Preferably, in step (I), the conditions of the first reaction include: the temperature is 0-80 ℃ and the time is 1-12h.
Preferably, in step (II), the conditions of the second reaction include: the temperature is 0-100deg.C, and the time is 2-48h.
Preferably, in step (III), the conditions of the calcination include: the temperature is 400-1000 ℃ and the time is 1-24h.
Preferably, in step (I), step (II), the method further comprises: and separating and drying the material obtained after the first reaction and the material obtained after the second reaction respectively and independently in sequence to obtain the first intermediate and the second intermediate respectively.
The drying conditions in step (I), step (II) may be the same or different, preferably the drying conditions include: the temperature is 20-100deg.C, and the time is 4-48h.
The specific mode of the separation is not particularly limited in the present invention, and may be a conventional separation method known in the art, for example, centrifugal separation.
The kind and amount of the solvent in the step (I) are not particularly limited as long as the porogen is sufficiently dissolved and thus the first reaction can be sufficiently performed, and for example, the solvent may be at least one selected from 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 contact include: the temperature is 0-80 ℃ and the time is 2-12h.
Preferably, according to the method of the second aspect of the present invention, in step (2), the conditions of the second contact include: the temperature is 0-100deg.C, and the time is 2-48h.
Preferably, according to the method of the second aspect of the present invention, in step (3), the conditions of the third contact include: the temperature is 0-100deg.C, and the time is 1-24h.
In the method according to the second aspect of the present invention, post-treatment steps well known in the art such as ultrasonic treatment, washing and dialysis to separate impurities may be further included, and the present invention will not be described herein, and specific operations of several post-treatments are exemplified in the subsequent examples of the present invention, and those skilled in the art should not understand the limitation of the present invention.
According to a preferred embodiment of the invention, the method according to the second aspect of the invention comprises:
(1) In the presence of a first solvent and ammonia water, dissolving a pore-forming agent, and then carrying out first mixing with a precursor silicon source, wherein the weight ratio of the pore-forming agent to the precursor silicon source is 1:1-3, the conditions of the first mixing comprising: the temperature is 0-80 ℃ and the time is 1-12h, and a first intermediate is obtained;
(2) The first intermediate and the strong alkaline substance are mixed for the second time, and the weight ratio of the first intermediate to the strong alkaline substance is 1:1-5, the conditions of the second mixing comprising: the temperature is 0-100 ℃ and the time is 2-48h, and a second intermediate is obtained;
(3) Third mixing the second intermediate with an acid in the presence of a second solvent, wherein the weight ratio of the second intermediate to the acid is 1:1-4, the conditions of the third mixing comprising: the temperature is 0-100 ℃ and the time is 1-24h; obtaining a nano silicon dioxide carrier;
(4) Carrying out first contact on the nano silicon dioxide carrier prepared in the step (3) and a modifier, wherein the first contact conditions comprise: the temperature is 0-80 ℃ and the time is 2-12h, and the modified carrier is obtained;
(5) Subjecting the modified carrier prepared in step (4) to a second contact with a pesticidally active component, the conditions of the first contact comprising: the temperature is 0-100 ℃ and the time is 2-48 hours, and the modified carrier loaded with the pesticide active component is obtained;
(6) Performing third contact on sodium carboxymethyl cellulose and the modified carrier loaded with the pesticide active component obtained in the step (5), wherein the third contact conditions comprise: the temperature is 0-100 ℃ and the time is 1-24 hours, and the nano pesticide controlled release agent is obtained.
As previously described, a third aspect of the present invention provides a controlled release agent for a nano pesticide prepared by the method of the second aspect.
The present invention will be described in detail by way of examples in which all raw materials are commercially available without particular explanation, wherein:
precursor silicon source: tetraethyl orthosilicate (TEOS) is available from national pharmaceutical systems and chemical reagent Co., ltd, trade mark 78-10-4;
pore-forming agent: cetyl trimethylammonium bromide (CTAB) is purchased from Shanghai Bi De medical science and technology Co., ltd, and is sold under the trademark 3069-42-9; octadecyltrimethoxysilane is available from Shanghai Michelson chemical technology Co., ltd under the trademark 3069042-9;
and (3) a modifier: 3-aminopropyl triethoxysilane (APTES) is available from Shanghai A Ding Shenghua technologies Co., ltd under the trade designation 919-30-2; (3-aminopropyl) dimethylethoxysilane is purchased from Wuhan Xinshen chemical engineering Co., ltd., trade name 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 sample in distilled water to obtain a liquid to be tested, taking 500 mu L of the liquid to be tested, and placing the liquid to be tested in an electrode cuvette for testing under the following conditions: the test time was 120s and the temperature was 25 ℃.
b. Particle size and morphology determination: transmission Electron Microscope (TEM), available from FEI company, usa under the model TecnaiG2 20TWIN;
c. specific surface area and porosity determination: full-automatic specific surface area and pore size analyzer, available from Kang Da, U.S. Pat. No. 5, model AUTOSORB-IQ2;
d. component content determination of the nano pesticide controlled release agent: is obtained by ultraviolet analysis test, taking example 1 as an example, the specific process is as follows:
all supernatants of the centrifuge washes of example 1, step (6), were collected and UV analyzed. The content of the pesticide component in the supernatant is measured by comparing the standard curve, and the formula is as follows: pesticide content= (total mass of pesticide added-total mass of pesticide supernatant)/total mass of nano pesticide controlled release agent to obtain content of pesticide component;
and dialyzing and freeze-drying the supernatant to obtain the mass of the residual pore blocking agent in the supernatant. According to the formula: hole plugging agent content= (total mass of plugged hole agent added-total mass of supernatant plugged hole agent)/total mass of nano pesticide controlled release agent to obtain the content of plugged hole agent;
e. content of modifier in modified vector: is obtained by testing through a thermogravimetric analysis method.
Example 1
(1) 150mL of absolute ethyl alcohol, 250mL of distilled water and 0.7347g of CTAB are added into a round-bottom flask, after the CTAB is stirred at 30 ℃ until the CTAB is completely dissolved, 1.0499g of TEOS is weighed and added into the CTAB solution for reaction at 30 ℃ for 30min, 1.330mL of 28 wt% ammonia water is taken by a pipette for reaction for 6h, and then drying is carried out at 50 ℃ for 12h, so as to obtain a first intermediate;
(2) 50mL of 0.3mol/L Na was added to the first intermediate obtained in step (1) 2 CO 3 Stirring the solution at 60 ℃ for 6 hours, centrifuging, transferring the centrifuged solid into a dialysis bag, dialyzing (molecular weight 3500) with distilled water as a dialysis solution, changing distilled water every 2 hours, dialyzing for 24 hours, centrifuging after the dialysis is finished, and drying at 50 ℃ for 12 hours 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 2 hours at 80 ℃, centrifuging, transferring the centrifuged solid into a dialysis bag, dialyzing (molecular weight 3500) by using distilled water as a dialysis solution, changing distilled water every 2 hours, dialyzing for 2 days, centrifuging after dialyzing, and drying at 50 ℃ for 12 hours to obtain the nano silicon dioxide carrier.
(4) In a round bottom flask, 10mg of the nano silica carrier prepared in the step (3) and 6.83mg of APTES are taken for first contact, wherein the conditions of the first contact comprise: the temperature is 80 ℃ and the time is 12 hours, and the modified carrier is obtained;
(5) Taking 10mg of the modified vector prepared in the step (4), 30mg of pyraclostrobin and 10mL of 50 vol% ethanol (V) EtOH :V H2O =1:1) was added to a round bottom flask, dispersed well, stirred at 30 °cStirring for 24 hours for 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 :V H2O In the process of the pesticide composition =1:1), the modified carrier loaded with the pesticide active component obtained in the step (5) is stirred for 24 hours at 30 ℃ for third contact, and then centrifuged and washed with ethanol, and dried for 12 hours at 50 ℃ to obtain the nano pesticide controlled release agent.
The content of pesticide active components in the nano pesticide controlled release agent is 25 weight percent, the content of pore blocking agent is 9 weight percent, and the balance is modified carrier.
Example 2
In a similar manner to example 1, except that 4.98mg of (3-aminopropyl) dimethylethoxysilane was used instead of APTES in example 1, the rest was the same as in example 1, to prepare a nano pesticide controlled release agent.
Example 3
In a similar manner to example 1, except that 0.6797g of octadecyltrimethoxysilane was used instead of CTAB in step (1) of example 1, and step (3) was a step of placing the second intermediate obtained in step (2) in a tube furnace and calcining at 550℃for 6 hours, a nanosilica support was obtained.
The rest is the same as in the example 1, and the nano pesticide controlled release agent is prepared.
Comparative example 1
The procedure was carried out in a similar manner to example 1, except that step (6) was not carried out in this comparative example, that is, no pore blocking agent was added, and only a modified carrier carrying the pesticidal active ingredient was obtained and was designated as sample CS1.
Test case
1. Structural characterization test
(1) Surface potential testing of materials
The present invention illustratively provides the surface potential test results of the first intermediate, the second intermediate, the nanosilica support and the modified support of example 1, with the specific results being shown in table 1.
TABLE 1
| Test sample | Surface potential/mV |
| First intermediate | -24.8 |
| Second intermediate | -18.2 |
| Nano silicon dioxide carrier | -37.3 |
| Modified vector | 23.1 |
From the results of table 1, it can be seen that the surface potential of the first intermediate, the second intermediate, and the nano silica support all have negative values when the nano silica support is prepared. After the 3-aminopropyl triethoxysilane modifies the carrier, the surface potential of the modified carrier is changed from-37.3 mV to 23.1mV, which proves that the nano silicon dioxide carrier is successfully modified to obtain the modified carrier.
(2) Particle size and morphology observations
The present invention illustratively provides a transmission electron micrograph of the first intermediate and nanosilica support of example 1, as shown in fig. 1:
from fig. 1 (a), it can be seen that the nanoparticle of the first intermediate has an obvious core-shell structure, is relatively complete in morphology, relatively uniform in size, relatively good in dispersibility, has a particle diameter of about 250nm, relatively loose in particle surface, and can observe fine pore channels;
from fig. 1 (b), it can be seen that the nano-silica carrier nano-particles have an obvious hollow structure, the particle size is relatively uniform, the dispersibility is relatively good, the particle diameter is about 250nm, the wall thickness is about 25nm, and the cavity volume of the carrier is relatively large, so that the carrier has relatively good drug carrying capacity.
(3) Specific surface area and porosity test
The invention exemplarily provides a nitrogen adsorption and desorption isotherm of the nano silicon dioxide carrier prepared in the embodiment 1, as shown in fig. 2, a mesoporous structure exists in the nano silicon dioxide carrier and the average pore diameter is 4.570nm as can be seen from capillary condensation phenomenon and hysteresis loop contained in the nitrogen adsorption and desorption isotherm in fig. 2;
meanwhile, the present invention exemplarily provides 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/m 2 /g |
| First intermediate | 42.006 |
| Carrier body | 368.529 |
As can be seen from the results of Table 2, the specific surface area of the first intermediate was 42.006m 2 Per gram, the specific surface area of the nano silicon dioxide carrier is 368.529m 2 /g, well above said first intermediate,further demonstrated the formation of channels and internal hollow structures on the nanosilicon supports.
2. Enzyme response test
(1) Release of pesticide active ingredient under different concentration cellulase response conditions
The nanometer pesticide controlled release agent prepared by the above example is used for testing, and specifically, the following steps are adopted for testing:
s1: placing 5mL of distilled water and 2.5mg of the nano pesticide controlled release agent solid prepared in the above example in an EP tube, performing ultrasonic dispersion, equally dividing into five parts by a pipette, respectively placing the five parts in 6 50mL centrifuge tubes with the number of A, B, C, D, E, F, centrifuging, discarding the supernatant, and repeating the operation for three times;
s2: adding 40mL of 60.0U, 30.0U, 15.0U, 3.0U and 0.3U of cellulase solution and 40mL of mixed solution of distilled water and ethanol (volume ratio is 9:1) into 6 50mL centrifuge tubes numbered A, B, C, D, E, F respectively, then placing the 6 centrifuge tubes at room temperature for drug release, centrifuging after 2 hours, taking 40mL of supernatant, simultaneously placing the centrifuged products into new 50mL centrifuge tubes, then supplementing 40mL of corresponding solution respectively, releasing drugs at room temperature, repeating the above operation, taking the supernatant once every 2 hours, and taking six times; after 12 hours, taking supernatant once every 4 hours, and taking four times; after 48h, taking supernatant once every 12h, and taking the supernatant once; taking supernatant every 24 hours until 180 hours;
and respectively testing the content of the pesticide active components in the supernatant to obtain the release condition of the pesticide active components under the response conditions of the cellulases with different concentrations.
The invention exemplarily provides the release condition of pesticide active components of the nano pesticide controlled release agent prepared in the example 1 under the response condition of cellulases with different concentrations, and the specific result is shown in fig. 3; the invention also provides a modified carrier carrying the pesticide active component without the pore blocking agent prepared in the comparative example 1, which has the pesticide active component release condition under the condition of the presence or absence of cellulase, and the specific result is shown in figure 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 drug to release the drug, and shows excellent pesticide slow release effect, the higher the enzyme activity is under the condition of adding cellulase, the higher the release rate is, for example, the accumulated release rate in water for 168h is only 4.03 wt%, and the accumulated release rate in water for 168h is 44.82 wt% under the condition of 30.0U of enzyme activity.
As can be seen from fig. 4, the drug release rate of the modified carrier carrying the pesticidal active ingredient of comparative example 1 without pore blocking agent was not affected by cellulase, and the cumulative release rate for 48 hours was 48.22 wt%.
(2) Release of pesticidally active components under conditions of different enzyme types
The nanometer pesticide controlled release agent prepared by the above example is tested, specifically by the following steps:
s1: placing 3mL of distilled water and 1.5mg of the nano pesticide controlled release agent solid prepared in the above example in an EP tube, performing ultrasonic dispersion, dividing the dispersion into three parts by a pipetting gun, respectively placing the three parts in 350 mL centrifuge tubes with the number of A, B, C, centrifuging, discarding the supernatant, and repeating the operation for three times;
s2: adding 40mL of a mixed solution of distilled water and ethanol (volume ratio (9:1)) and 30.0U of alpha-amylase solution and 30.0U of cellulase solution into 3 centrifuge tubes with the number of A, B, C, respectively, placing the 3 centrifuge tubes at room temperature to release medicines, centrifuging after 2 hours, taking 40mL of supernatant, simultaneously placing the centrifuged products into new 50mL centrifuge tubes, respectively supplementing 40mL of corresponding solution, placing the solution at room temperature to release medicines, repeating the above operation, taking the supernatant every 2 hours, and taking six times; after 12 hours, taking supernatant once every 4 hours, and taking four times; after 48h, taking supernatant once every 12h, and taking the supernatant once; taking supernatant once every 24 hours until 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 the response conditions of different types of enzymes.
The invention provides the release condition of pesticide active components under the condition of different types of enzymes by using the nano pesticide controlled release agent prepared in the embodiment 1, and the specific result is shown in fig. 5.
As can be seen from FIG. 5, the cumulative release rate of the nano pesticide controlled release agent is 3.38% by weight under the condition of no enzyme, the cumulative release rate of the nano pesticide controlled release agent is 4.59% by weight under the condition of alpha-amylase, and the cumulative release rate of the nano pesticide controlled release agent is 30.85% by weight under the condition of cellulase, so that the nano pesticide controlled release agent provided by the invention has good selectivity and can be released in a large amount under the action of the cellulase, and the amylase existing in a large amount in human body and fish body has little influence on the drug release behavior of the nano pesticide controlled release agent.
3. Toxicity test
(1) Toxicity test in fish body
The comparative test is carried out by respectively adopting pyraclostrobin and the nano pesticide controlled release agent prepared in the example 1, 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 fish fries;
s2: and (3) fish fry observation: the fish fries used in the experiment are of the type of the red-spotted horse fish with the length of about 1-1.5cm, firstly, the red-spotted horse fish is observed in a fish tank for one week to ensure that the fish fries do not die naturally, then 20 fish fries are added into a reaction tank with 5L of water, and the red-spotted horse fish is observed for two days to ensure that the fish fries do not die naturally;
s3: co-culturing pesticides and fish with a series of concentrations: 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 respectively, and the mortality of the zebra fish was tested, and the specific results are shown in fig. 6.
As can be seen from FIG. 6, pyraclostrobin has a relatively high toxicity to zebra fish, and its semi-lethal dose (mortality rate reaches 50%) is about 0.05mg/L. The toxicity of the nano pesticide controlled release agent in the fish body is obviously reduced, and the semi-lethal dose is increased to about 0.18mg/L, so that 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 pesticides to aquatic organisms.
(2) In vitro test for germ inhibition
The invention tests germ inhibition in vitro comparison experiments of sheath blight germ, bakanae disease germ and gummy stem blight germ of rice by using pyraclostrobin and the nano pesticide controlled release agent prepared in the embodiment 1, and the specific test process is as follows:
s1: activating bacterial strain of Rhizoctonia solani, taking out small mycelia from the freezing tube, transferring onto PDA plate, culturing in incubator for 3 days, transferring onto PDA plate again for bioassay;
s2: pyraclostrobin was formulated as a drug substance 10000 μg/ml and diluted to 2000 μg/ml, 1000 μg/ml, 500 μg/ml, 250 μg/ml, 125 μg/ml, 62.5 μg/ml, respectively, for performing bioassay experiments. The above agents were added to PDA plates numbered A, B, C, D, E, F, respectively, 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 group, and a dish (diameter: 5 mm) was removed from the PDA plate in step S1, and the plates were connected to PDA plates containing different concentrations of the agent, 3 PDA plates each, and then all PDA plates were incubated at 25℃for 2 days;
s3: the same operation as S2 is carried out on the nano pesticide controlled release agent prepared in the embodiment 1;
s4: after two days, colony diameters of each PDA plate were measured, and the hypha growth inhibition rate was calculated.
Wherein growth inhibition ratio = (control diameter-treatment diameter)/(control diameter-5) ×100%; according to the reagent concentration logarithmic value and inhibition rate probability value, linearly obtaining a regression equation, and calculating EC 50 The values (i.e., half-inhibition concentration) and specific results are shown in Table 3.
The test procedures of the bakanae disease germ and the gummy stem blight germ are the same as those of the sheath blight germ, and are not repeated here, and the specific test results are shown in table 3.
TABLE 3 Table 3
As can be seen from Table 3, compared with the original drug, the nano pesticide controlled release agent provided by the invention has better inhibition effect on various common pathogens, and the half inhibition rate concentration is lower than that of the original drug, which indicates that the nano pesticide controlled release agent provided by the invention can release loaded pesticide in pathogens and has good inhibition effect.
From the results, the nano pesticide controlled release agent provided by the invention has small release amount in natural environment, can effectively reduce pesticide residues in the environment and reduce pollution to the environment; the nano pesticide controlled release agent provided by the invention has specific enzyme responsiveness, only responds to release in fungus bodies with cellulase, and has small influence on toxic and side effects of aquatic organisms such as people, fish and the like without cellulase; the nano pesticide controlled release agent provided by the invention has a good inhibition effect on various common pathogens, and the half inhibition rate concentration of the nano pesticide controlled release agent is lower than that of the original pesticide, so that the nano pesticide controlled release agent has a good inhibition effect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (8)
1. A method for preparing a controlled release agent of a nano pesticide, comprising:
(a) First mixing a pore-forming agent with a precursor silicon source in the presence of a first solvent and ammonia water to obtain a first intermediate; the weight ratio of the pore-forming agent to the precursor silicon source is 1:1-3;
(b) Performing second mixing on the first intermediate and a strong alkaline substance to obtain a second intermediate; the weight ratio of the first intermediate to the strong alkaline substance is 1:1-5;
(c) Thirdly mixing the second intermediate with acid in the presence of a second solvent to obtain a nano silicon dioxide carrier; the weight ratio of the second intermediate to the acid is 1:1-4;
(1) Carrying out first contact on a modifier and the 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 a 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 blocking agent is sodium carboxymethyl cellulose; the precursor silicon source is tetraethyl orthosilicate;
the pore-forming agent is at least one selected from cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer and octadecyl trimethoxy silane;
the modifier is at least one selected from 3-aminopropyl triethoxysilane, (3-aminopropyl) dimethyl ethoxysilane and aminopropyl aminoethyl trimethoxysilane;
the nano silicon dioxide carrier is of a hollow structure, and pore channels are distributed on the wall forming the hollow structure;
the average grain diameter of the nano silicon dioxide carrier is 100-600nm, the average thickness of the wall is 10-50nm, the average pore diameter of the pore canal is 1-10nm, the surface potential of the carrier is 10-50mV, and the specific surface area of the carrier is 100-1200m 2 /g；
The dosages of the modified carrier, the pesticide active component and the pore blocking agent are such that 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 blocking agent is 3-60 wt% based on the total weight of the controlled release agent in the prepared controlled release agent;
the amount of the modifier and the amount of the nano silicon dioxide 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.
2. The method of claim 1, wherein the first mixing conditions comprise: the temperature is 0-80 ℃ and the time is 1-12h.
3. The method of claim 1, wherein the second mixing conditions comprise: the temperature is 0-100deg.C, and the time is 2-48h.
4. The method of claim 1, wherein the third mixing conditions comprise: the temperature is 0-100deg.C, and the time is 1-24h.
5. The method of claim 1, wherein the conditions of the first contact comprise: the temperature is 0-80 ℃ and the time is 2-12h.
6. The method of claim 1, wherein the conditions of the second contact comprise: the temperature is 0-100deg.C, and the time is 2-48h.
7. The method of claim 1, wherein the conditions of the third contact comprise: the temperature is 0-100deg.C, and the time is 1-24h.
8. A controlled release agent for a nano pesticide prepared by the method of any one of claims 1 to 7.
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| CN107419599A (en) * | 2017-06-28 | 2017-12-01 | 徐州力志纤维素科技有限公司 | A kind of Modified by Carboxymethyl Cellulose nano silicon |
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| CN107419599A (en) * | 2017-06-28 | 2017-12-01 | 徐州力志纤维素科技有限公司 | A kind of Modified by Carboxymethyl Cellulose nano silicon |
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