CN106172380B - A kind of preparation method of the controllable carrier micelle of blade face compatibility - Google Patents

A kind of preparation method of the controllable carrier micelle of blade face compatibility Download PDF

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CN106172380B
CN106172380B CN201610552152.1A CN201610552152A CN106172380B CN 106172380 B CN106172380 B CN 106172380B CN 201610552152 A CN201610552152 A CN 201610552152A CN 106172380 B CN106172380 B CN 106172380B
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pdlla
peg
pesticide
organic solvent
polymer
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CN106172380A (en
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曾章华
梁洁
崔海信
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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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
    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a kind of preparation methods of agricultural carrier micelle, this method includes that polylactic acid poly ethylene glycol amphiphilic diblock polymer is added in organic solvent and dissolves with slightly solubility pesticide or the amphiphilic diblock polymer, fluorescer and slightly solubility pesticide, then plus water forms colloid, it is stirred overnight, dialysis obtains polymer medicament carrying micelle, it is freeze-dried again, obtains its solid powder.Polylactic acid poly ethylene glycol nano drug-carrying micella good water solubility of the present invention does not contain organic solvent and auxiliary agent, and insecticidal effect is good, is environmentally friendly nano pesticide novel form.

Description

A kind of preparation method of the controllable carrier micelle of blade face compatibility
[technical field]
The invention belongs to pesticide production technology fields.More particularly it relates to which a kind of blade face compatibility controllably carries medicine The preparation method of micella.
[background technique]
Pesticide is the material base defendd important biological disaster and ensure national food security.As the important of agricultural production Substance is put into, huge contribution is made that agricultural development and mankind's food supply.Statistical data shows that world wide internal cause makes Three one-tenth of total output of grain or more are accounted for agricultural disease, worm and the crop smothering loss that pesticide avoids and retrieves.China is in the world One pesticide producing and use big country, since 2000, be sprayed at about 2.8 hundred million hm per year over 1500000 tons of pesticidal preparations2Soil On, wherein about 80% from Target crops blade face be lost be directly entered environment.With the increase of usage amount and lifespan, pesticide is residual It stays and gradually increases, residual region is gradually expanded, and three-dimensional pollution is produced, so that Environmental Pesticide pollution is in rise year by year Gesture not only exacerbates threat of the pollution of agricultural products to human health, also induces the drug resistance of harmful organism, results in ecological ring Border is degenerated to be destroyed with bio-diversity.2014, the Ministry of Agriculture proposed to realize " it is basic that a control two subtracts three ", proposed from State-level Reduce pesticide dosage.To the year two thousand twenty, staple crops pest and disease damage green prevention and control coverage rate reaches 30%, chemical pesticide usage amount control It realizes zero growth rate, to realize this target, it is still very arduous.
Nano material has the characteristics such as small-size effect, surface-interface effect, quantum size effect and quantum tunneling effect, The Strange properties that many traditional materials do not have are shown, nanotechnology has obtained swift and violent hair as the new branch of science newly to emerge Exhibition.In recent years, nanotechnology has formd a very active emerging cross discipline in agriculture application study, wherein will Nanotechnology is combined with the development of pesticide, develops nano pesticide novel form using nanometer material and technology, be it is current in the world One of the research hotspot of nanotechnology agricultural application field forms an emerging nano pesticide research field, is alleviating agriculture Before environmental pollution, harmful organism drug resistance, the loss of biodiversity caused by medicine abuse etc. shows good application Scape not only greatly reduces dosage, improves drug effect, is also broken through on usage economy.Traditional formulations of pesticide are in field Between in application because of wind, solarization, drench with rain caused by effective component be lost up to 70-90%, be such as with protected crop Practical target, effective rate of utilization are typically less than 30%, such as practical by medicine calculation with harmful organism, and utilization rate is not in most cases Foot 0.1%.Although pesticide variety is various, the mode of action is complicated, they are in common trait present on delivering path, first It first needs to be deposited in crop surface, then again via blade face, by the dosage transfer process such as diffusion, interior suction and transhipment, finally The pest infestation that is transferred to inside and outside plant endangers position, it is made to be poisoned or dead and actively or passively contacting. Therefore, deposition efficiency of the pesticide active ingredient on blade face is improved, and via blade face surface materials to pest infestation portion The efficiency of transmission divided reduces being scattered and being lost for Environment Oriented system, is the general character science for improving pesticide validity and safety Approach.
[summary of the invention]
Technical problems to be solved
The object of the present invention is to provide a kind of preparation methods of the affine controllable carrier micelle in blade face.
It is a further object to provide a kind of preparation methods of fluorescent type nano drug-carrying micella.
Technical solution
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of preparation methods of the affine controllable carrier micelle in blade face.
The step of preparation method, is as follows:
By COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Or CH3O-PEG5000-PDLLA5000Amphipathic two Block polymer is added in organic solvent with slightly solubility pesticide to be dissolved, and then plus water forms colloid, is stirred overnight, allowing described has Solvent volatilization, then dialysis obtains average grain diameter as the polymer medicament carrying micelle of 100~300nm, then is freeze-dried to obtain it Solid powder.
According to another preferred method of implementation of the present invention, the amphiphilic diblock polymerization is being added into organic solvent Rhodamine 6G fluorescer is added while object and slightly solubility pesticide, obtains a kind of fluorescent type nano drug-carrying micella solid powder.
According to another preferred method of implementation of the present invention, the slightly solubility pesticide is emamectin benzoate benzoic acid Salt or betacyfluthrin.
According to another preferred method of implementation of the present invention, the organic solvent be selected from acetone, methylene chloride, chloroform or N, N-dimethylformamide.
According to another preferred method of implementation of the present invention, the weight ratio of amphiphilic diblock polymer and slightly solubility pesticide 1:0.1~0.6.
According to another preferred method of implementation of the present invention, in terms of milligram amphiphilic diblock polymer with ml in respect of machine The ratio of solvent is 1:0.05~0.4.
According to another preferred method of implementation of the present invention, amphiphilic diblock polymer and the water in terms of ml in terms of milligram Than being 1:0.4~3.
According to another preferred method of implementation of the present invention, the amphiphilic diblock polymer and rhodamine 6G fluorescence The weight ratio of agent is 1:0.01~0.03.
The present invention is described in more detail below.
The present invention relates to a kind of preparation methods of the affine controllable carrier micelle in blade face.
The step of preparation method, is as follows:
Respectively by COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Or CH3O-PEG5000-PDLLA5000Amphiphilic Property diblock polymer be added in organic solvent and dissolve with slightly solubility pesticide, then plus water forms colloid, is stirred overnight, and allows described Organic solvent volatilization, then dialysis obtains the polymer medicament carrying micelle that average grain diameter is 100~300nm, then is freeze-dried To its solid powder.
The COOH-PEG that the present invention uses5000-PDLLA5000、NH2-PEG5000-PDLLA5000Or CH3O-PEG5000- PDLLA5000Amphiphilic diblock polymer is prepared according to following preparation steps:
A, polylactic acid is prepared
Its reaction equation is as follows:
Specifically, 50g lactic acid is added in the four-hole boiling flask of configuration thermometer, blender and water circulation vavuum pump, starting Water circulation vavuum pump and blender vacuumize and are decompressed to 4000Pa and reach 10min, then open electric jacket heating when temperature rises to At 65 DEG C, boiling in flask adjusts heating power, so that it is maintained boiling dehydration 2h, obtains dehydration product, stops heating and drops again Temperature opens nitrogen valve and is passed through nitrogen 10min, close vacuum pump to 25 DEG C, and stannous octoate is added, and starting stirring dress device makes its mixing Uniformly, nitrogen valve is closed, starting vacuum pump is evacuated to 400Pa, then opening heating mantle heats to micro-boiling, and makes its holding The state.10h is reacted at this temperature, obtains polylactic acid crude product.This polymer crude product is dissolved in by tetrahydrofuran The in the mixed solvent formed with DMF according to volume ratio 1:1, filtering, then precipitate in methyl alcohol, it filters, obtained sediment is placed in 12h is dried in vacuum drying oven under temperature 60 C, obtains dry pure PDLLA5000Product.Using routine1HNMR analytical technology is to institute Obtained reaction product is analyzed, and result is as follows:
PDLLA5000:1H NMR(400MHz,CDCl3,δ):1.43-1.52(m,222H),4.34(s,1H),5.64-5.81 (m,73H)。
B, polylactic acid poly diethanol amphiphilic block copolymer is prepared
Its reaction is as follows:
Specifically, the carboxy blocking poly-dl-lactide (PDLLA for being 5000 by 10g molecular weight5000) it is dissolved in 500mL bis- In chloromethanes, 0.3g n-hydroxysuccinimide and 0.6g1- ethyl-(3- dimethylaminopropyl) phosphinylidyne are then sequentially added Diimmonium salt hydrochlorate is uniformly mixed, is stirred at room temperature 4 hours until not precipitating, obtains a kind of organic reaction liquid.According to having Then machine reaction solution and subacidity aqueous solution volume ratio 1:2, the organic reaction liquid are pressed with pH=5 subacidity aqueous solution extraction 3 times According to organic reaction liquid and micro alkaline solution volume ratio 1:2, which uses pH=7.4 micro alkaline solution to extract 2 again It is secondary, organic phase is collected, is dried overnight with anhydrous sodium sulfate, is concentrated, is recrystallized in ether at room temperature, obtained crystal is through true PDLLA is obtained after sky is dry5000- NHS active ester.
By above-mentioned PDLLA5000- NHS active ester the NH with equimolar quality respectively2-PEG5000-OCH3、NH2-PEG5000- COOH、NH2-PEG5000- NH-Boc is reacted in methylene chloride overnight, according still further to reaction solution and micro alkaline solution volume ratio 1: 2, obtained reaction solution is extracted 3 times with the micro alkaline solution of pH=7.4, and the organic phase of collection by dry, filtering and is concentrated, It is redissolved in acetone, by dialysis, freeze-drying respectively obtains the polylactic acid poly diethanol amphiphilic of three kinds of different base group modifications Block copolymer, i.e. ether modify (CH3O-PEG5000-PDLLA5000), carboxyl modified (COOH-PEG5000-PDLLA5000) and ammonia Base protection modification (Boc-NH-PEG5000-PDLLA5000) polylactic acid poly diethanol amphiphilic block copolymer.
1g amido protecting is modified into (Boc-NH-PEG5000-PDLLA5000) it is dissolved in 30ml methylene chloride and trifluoroacetic acid mixing In solvent (volume ratio 2:1), 5h is stirred at normal temperature, solvent evaporated, then twice with ether precipitating, vacuum drying obtains ammonia Base modifies (H2N-PEG5000-PDLLA5000) polylactic acid poly diethanol amphiphilic block copolymer.
Using routine1H NMR analytical technology analyzes obtained three kinds of reaction products, and result is as follows:
CH3O-PEG5000-PDLLA5000:1H NMR(400MHz,CDCl3,δ):1.37—1.51(m,222H),3.39- 3.65(m,463H),4.41(s,1H),5.54—5.71(m,73H)；
COOH-PEG5000-PDLLA5000:1H NMR(400MHz,CDCl3,δ):1.45—1.55(m,222H),2.58(s, 2H),3.33-3.68(m,461H),4.39(s,1H),5.55—5.79(m,73H)；
H2N-PEG5000-PDLLA5000:1H NMR(400MHz,CDCl3,δ):1.41—1.54(m,222H),3.21-3.74 (m,463H),4.39(s,1H),5.55—5.79(m,73H)。
In the present invention, first respectively by COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Or CH3O- PEG5000-PDLLA5000Amphiphilic diblock polymer is added in organic solvent with slightly solubility pesticide to be dissolved.
The organic solvent should be that one kind can dissolve amphiphilic diblock polymer of the present invention, and at room temperature It is easy to the organic solvent to volatilize.All these amphiphilic diblock polymer that can dissolve again will not be to pesticide, crop or environment Generating dysgenic organic solvent may be used to the present invention, also all within that scope of the present invention.What the present invention used For organic solvent for example selected from acetone, methylene chloride, chloroform or n,N dimethylformamide, they are all current market sales of Product.
According to the present invention, the slightly solubility pesticide is it should be understood that its solubility in water is less than the pesticide of 0.1g/L. It is all to can satisfy solubility requirement, and dysgenic pesticide will not be generated to crop or environment and may be used to the present invention, Also all within that scope of the present invention.The slightly solubility pesticide that the present invention uses be, for example, emamectin-benzoate or Betacyfluthrin, they are all current market sales of products.
According to the present invention, weight ratio 1:0.1~0.6 of amphiphilic diblock polymer and slightly solubility pesticide.If amphiphilic Property diblock polymer and the weight ratio of slightly solubility pesticide be greater than 1:0.1, then drugloading rate is low, at high cost, and micella wall thickness pesticide is difficult With release.If the weight ratio of amphiphilic diblock polymer and slightly solubility pesticide is less than 1:0.6, drugloading rate is too high, causes The sedimentation of slightly solubility pesticide.Therefore, it is reasonable that the weight ratio of amphiphilic diblock polymer and slightly solubility pesticide, which is 1:0.1~0.6, , preferably 1:0.18~0.52, more preferably 1:0.26~0.38.
In the present invention, in terms of milligram amphiphilic diblock polymer and with ml in respect of the ratio of solvent be 1:0.05~ 0.4.If in gram amphiphilic diblock polymer and with ml in respect of solvent ratio be greater than 1:0.05, dissolved after water is added Degree reduces rapidly, and can accelerate pesticide sinking speed.If the ratio of amphiphilic diblock polymer and organic solvent is less than 1:0.4, Then a large amount of organic solvents cause evaporation rate to slow down, and influence the self-service dress mode of micella.Therefore, amphiphilic diblock polymer with have The ratio of solvent is that 1:0.05~0.4 is appropriate, preferably 1:0.08~0.35, more preferably 1:0.15~0.28.
Then, amphiphilic diblock polymer is dissolved in obtained solution in organic solvent with slightly solubility pesticide and then adds Into water, formed a kind of using the polymer and pesticide as the colloid of dispersed phase.
According to the present invention, the amphiphilic diblock polymer and ratio of water is 1:0.4~3 in terms of ml in terms of milligram.If two The ratio of parent's property diblock polymer and water is less than 1:0.4, then the concentration of amphipathic nature block polymer is lower than critical aggregation concentration (CMC), it will be unable to form micella, wrap up slightly solubility pesticide.If the ratio of amphiphilic diblock polymer and water is greater than 1:3, The concentration of micella improves, and Second Aggregation can occur in aqueous solution, and influences the package of pesticide.Therefore, amphiphilic diblock is poly- It is appropriate, preferably 1:0.8~2.6 that the ratio for closing object and water, which is 1:0.4~3, more preferably 1:1.2~2.2.
The bag filter that the present invention uses is current market sales of product.
The average grain diameter of obtained polymer medicament carrying micelle Malvern particle size analyzer determination.
Obtained polymer medicament carrying micelle be in the freeze drying equipment sold by EYELA company with trade name FD-81 0.01 DEG C of temperature be freeze-dried under conditions of pressure 610.5Pa, obtaining water content is the solid less than 1% by weight Powder.
The invention further relates to a kind of preparation methods of fluorescent type nano drug-carrying micella.The preparation method is according to above-mentioned blade face parent It is carried out with controllable carrier micelle preparation method, is only adding the amphiphilic diblock polymer and indissoluble into organic solvent Property pesticide while add rhodamine 6G fluorescer, obtain a kind of fluorescent type nano drug-carrying micella solid powder.
Specifically, the step of fluorescent type nano drug-carrying micella preparation method is as follows:
By COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Or CH3O-PEG5000-PDLLA5000Amphipathic two Block polymer, rhodamine 6G fluorescer and slightly solubility pesticide are added in organic solvent and dissolve, and then plus water forms colloid, stirring Overnight, the organic solvent is allowed to volatilize, then dialysis obtains the fluorescent type nano drug-carrying glue that average grain diameter is 100~300nm Beam, then be freeze-dried to obtain its solid powder.
It is prepared by fluorescent type nano drug-carrying micella preparation method and previously described amphiphilic diblock polymer medicament carrying micelle Method is identical, and only the method use rhodamine 6G fluorescer, the weight ratio of amphiphilic diblock polymer and fluorescer is 1:0.01~0.03.
The grain size distribution of these micellas is had detected using Malvern particle size analyzer, such as attached drawing 3 is package methylamino AVM hereinafter The COOH-PEG of rhzomorph benzoate5000-PDLLA5000Micellar particle size distribution map, attached drawing 5 are package emamectin benzoate benzene first The NH of hydrochlorate2-PEG5000-PDLLA5000Micellar particle size distribution map, attached drawing 7 are the CH for wrapping up betacyfluthrin3O-PEG5000- PDLLA5000Micellar particle size distribution map.Attached drawing 1 is the CH for wrapping up emamectin-benzoate3O-PEG5000-PDLLA5000 Micellar particle size distribution map is as control.It can be seen that attached drawing 3 by these grain size distributions and wrap up emamectin benzoate benzene first The COOH-PEG of hydrochlorate5000-PDLLA5000Micella average grain diameter is 134nm, attached drawing 5 wraps up emamectin-benzoate NH2-PEG5000-PDLLA5000The average grain diameter of micella is 179nm, attached drawing 7 wraps up the CH of betacyfluthrin3O- PEG5000-PDLLA5000The average grain diameter of micella is 193nm.The CH of the package emamectin-benzoate of attached drawing 13O- PEG5000-PDLLA5000The average grain diameter of micella is 153nm.It can thus be seen that amphiphilic diblock polymer wrapped slightly solubility Pesticide can form the micella that particle diameter distribution is relatively narrow, and size is closer to.
The case where amphiphilic diblock polymer, slightly solubility pesticide and organic solvent, is as previously described, and details are not described herein. Medicine carrying system of polymer micelle of the invention is a kind of its micella row of orientation in such a way that hydrophilic radical is outside and lipophilic group is inside Column, slightly solubility pesticide are located at the slightly solubility pesticide delivery system among these micellas.Utilize confocal microscope and living body Phosphorimager detects to obtain, and attached drawing 4 is the COOH-PEG for wrapping up emamectin-benzoate5000-PDLLA5000Micella TEM figure.Attached drawing 6 is the NH for wrapping up emamectin-benzoate2-PEG5000-PDLLA5000Micella TEM figure.Fig. 8 is packet Wrap up in the CH of betacyfluthrin3O-PEG5000-PDLLA5000Micella TEM figure.Attached drawing 2 is package emamectin benzoate benzene first The CH of hydrochlorate3O-PEG5000-PDLLA5000Micella TEM figure is as control.The nanometer of preparation is apparent that by these attached drawings Micella is the spheroidal particle of regular shape, size uniformity.
Water and CH prepared by the present invention are had detected using these methods3O-PEG5000-PDLLA5000Nano-micelle, COOH- PEG5000-PDLLA5000Nano-micelle, NH2-PEG5000-PDLLA5000Contact angle figure of the nano-micelle on cucumber blade face, referring to Attached drawing 9-12.By these attached drawings it will already have become clear that COOH-PEG5000-PDLLA5000Nano-micelle is formed on cucumber blade face Contact angle is minimum, NH2-PEG5000-PDLLA5000Contact angle figure of the nano-micelle on cucumber blade face is maximum, it was demonstrated that COOH- PEG5000-PDLLA5000There is good compatibility on nano-micelle and blade face, blade face to sprawl effect best.
It is measured using by upper marine morning digital technology Co., Ltd with the contact angle instrument that trade name JC2000D2M is sold CH3O-PEG5000-PDLLA5000、COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Nano-micelle is on cucumber blade face On contact angle, droplet size is 2 μ l, and content 1 ‰ is repeated 5 times, is averaged, and obtains its drop contact angle value, result column In table 1.
Table 1: contact angle determination result of the different nano-micelles on cucumber blade face
Pass through CH in table 13O-PEG5000-PDLLA5000、COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000It receives The contact angle comparison on cucumber blade face of rice glue beam, which is can be found that, has COOH-PEG5000-PDLLA5000Nano-micelle is formed on blade face Contact angle it is minimum, best in the blade face spreadability of cucumber, compatibility is best.
CH is had detected using these methods3O-PEG5000-PDLLA5000、COOH-PEG5000-PDLLA5000、NH2-PEG5000- PDLLA5000Fluorescence co-focusing figure of the fluorescence nano micella on cucumber blade face, referring to attached drawing 13, CH3O-PEG5000- PDLLA5000、COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Fluorescence imaging of the nano-micelle on cucumber blade face Figure, referring to attached drawing 13.By these attached drawings it will already have become clear that fluorescence nano carrier micelle can be adsorbed on cucumber blade face, The micella of different base group modifications is different to the adsorptivity on blade face, and fluorescence intensity is different.By comparing it can be found that COOH- PEG5000-PDLLA5000Adhesion amount of the fluorescence nano micella on cucumber blade face is maximum, and fluorescence residual quantity is also maximum after flushing.
Microcosmic fluorescent characteristic of the nano-micelle on cucumber blade face:
500 μ l, three kinds of fluorescence nano micellar solutions of the invention are taken, is uniformly sprayed on cucumber leaves, is passed through with high-pressure spray gun 5h cuts partial blade, is rinsed with water 1 minute, blade face is dried, and preparation is in blocks, with laser scanning co-focusing fluorescence microscope Observation.Observation indicate that three kinds of nano-micelle pesticides, which carry powder, to be effectively deposited on cucumber surface, after rinsing It was found that COOH-PEG5000-PDLLA5000Hold-up it is obviously more than both other, there is higher compatibility, and these are received Rice glue beam is mainly deposited on the vein on blade face.
Macroscopical fluorescent characteristic of the nano-micelle on cucumber blade face:
Three kinds of fluorescence nano micellas for taking 500 μ l to prepare, are uniformly sprayed on cucumber leaves with spray gun, by 5h, are passed through Living body fluorescent imager (excitation wavelength 555nm, Detection wavelength 570-590nm) observation, comparison blade rinse the fluorescence of front and back, lead to The variation for calculating and rinsing front and back fluorescence is crossed, COOH-PEG is calculated5000-PDLLA5000、NH2-PEG5000-PDLLA5000、CH3O- PEG5000-PDLLA5000Hold-up of the fluorescence nano micella after the flushing on cucumber blade face is 38.4%, 86.1% and respectively 8.5%.Find that surface has the nanometre glue of carboxyl by comparing the fluorescence intensity that blade is washed after preceding fluorescence intensity and blade flushing Deposition and hold-up highest of the bundle of particle on cucumber blade face show better blade face compatibility, and surface has amino Nano-micelle blade face compatibility it is poor, therefore, by change surface group can regulate and control well nano-micelle blade face it is affine Property.
Fluorescent type nano drug-carrying micella prepared by the present invention is uniformly sprayed on cucumber blade face, it is aobvious using fluorescence co-focusing Micro mirror and the observation of living body fluorescent imager, significant changes occur for cucumber blade face fluorescence intensity after discovery before flushing, this explanation three Kind fluorescent type nano drug-carrying micella has compatibility to cucumber blade mask.
Beneficial effect
The beneficial effects of the present invention are:
Test result shows CH3O-PEG5000-PDLLA5000、COOH-PEG5000-PDLLA5000The desinsection of carrier micelle is imitated Fruit is suitable with market milk oil dispersant, but their LC50Well below commercially available solid dispersion, good desinsection effect is presented Fruit.And NH2-PEG5000-PDLLA5000The insecticidal effect of carrier micelle is suitable with commercial solid dispersing agent, illustrates with amino base The blade face compatibility of the nano drug-carrying micella of group is lower than other two kinds of micellas.In missible oil dispersing agent because containing a large amount of organic molten Agent and auxiliary agent make it have stronger insecticidal activity, polylactic acid poly ethylene glycol nano drug-carrying micella good water solubility, without containing organic Solvent and auxiliary agent, insecticidal effect is good, is environmentally friendly nano pesticide novel form.
[Detailed description of the invention]
Fig. 1 is the CH for wrapping up emamectin-benzoate3O-PEG5000-PDLLA5000Micellar particle size distribution map.
Fig. 2 is the CH for wrapping up emamectin-benzoate3O-PEG5000-PDLLA5000Micella TEM figure.
Fig. 3 is the COOH-PEG for wrapping up emamectin-benzoate5000-PDLLA5000Micellar particle size distribution map.
Fig. 4 is the COOH-PEG for wrapping up emamectin-benzoate5000-PDLLA5000Micella TEM figure.
Fig. 5 is the NH for wrapping up emamectin-benzoate2-PEG5000-PDLLA5000Micellar particle size distribution map.
Fig. 6 is the NH for wrapping up emamectin-benzoate2-PEG5000-PDLLA5000Micella TEM figure.
Fig. 7 is the CH for wrapping up betacyfluthrin3O-PEG5000-PDLLA5000Micellar particle size distribution map.
Fig. 8 is the CH for wrapping up betacyfluthrin3O-PEG5000-PDLLA5000Micella TEM figure.
Fig. 9 is contact angle figure of the water on cucumber blade face.
Figure 10 is CH3O-PEG5000-PDLLA5000Contact angle figure of the nano-micelle on cucumber blade face.
Figure 11 is COOH-PEG5000-PDLLA5000Contact angle figure of the nano-micelle on cucumber blade face.
Figure 12 is NH2-PEG5000-PDLLA5000Contact angle figure of the nano-micelle on cucumber blade face.
Figure 13 is CH3O-PEG5000-PDLLA5000、COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Nanometer Fluorescence co-focusing figure of the micella on cucumber blade face.
Figure 14-1 to Figure 14-6 is CH3O-PEG5000-PDLLA5000、COOH-PEG5000-PDLLA5000、NH2-PEG5000- PDLLA5000Living body fluorescent image of the nano-micelle on cucumber blade face.
[specific embodiment]
It will be better understood that the present invention by following embodiments.
Embodiment 1: controllable carrier micelle preparation that blade face is affine
The implementation steps of the embodiment are as follows:
COOH-PEG is prepared first, in accordance with the method that this specification describes5000-PDLLA5000Amphiphilic diblock polymerization Object；
According to COOH-PEG5000-PDLLA5000The weight ratio 1:0.18 of amphiphilic diblock polymer and slightly solubility pesticide, By COOH-PEG5000-PDLLA5000Amphiphilic diblock polymer is added to emamectin-benzoate slightly solubility pesticide Dissolved in acetone organic solvent, wherein in terms of milligram amphiphilic diblock polymer and in terms of ml acetone organic solvent ratio be 1: 0.15, then according to the amphiphilic diblock polymer in terms of milligram and in terms of ml, the ratio of water is 1:0.6 into acetone organic solvent Add water to form colloid, be stirred overnight, the organic solvent is allowed to volatilize, average grain diameter is the polymer drug-carried glue of 100~300nm Beam reuses in the freeze drying equipment that EYELA company is sold with trade name FD-81 in 0.01 DEG C of temperature and pressure 610.5Pa Under conditions of be freeze-dried, obtaining water content is the solid powder less than 1% by weight.
Using Malvern particle size analyzer determination nano drug-carrying micella manufactured in the present embodiment, micellar solution is added drop-wise to copper mesh Above, using Japan Electronics Corporation with the morphosis of the trade name JEM-2100F Flied emission transmission electron microscope observing micella sold. Micella manufactured in the present embodiment is added drop-wise to cucumber blade face, upper marine morning digital technology Co., Ltd is with trade name JC2000D2M The contact angle of the contact angle instrument measurement micella of sale.As a result it referring to attached drawing 3,4,9 and 11, can be seen that by these attached drawings COOH-PEG5000-PDLLA5000The micellar particle size narrow distribution that amphiphilic diblock polymer and slightly solubility pesticide are formed, dispersion Coefficient is smaller, and shape is more regular, uniform spherical shape.Spreadability of the micella on cucumber blade face is preferable, the contact of drop Angle is smaller.
Embodiment 2: controllable carrier micelle preparation that blade face is affine
The implementation steps of the embodiment are as follows:
NH is prepared first, in accordance with the method that this specification describes2-PEG5000-PDLLA5000Amphiphilic diblock polymerization Object；
According to NH2-PEG5000-PDLLA5000The weight ratio 1:0.32 of amphiphilic diblock polymer and slightly solubility pesticide, will NH2-PEG5000-PDLLA5000Amphiphilic diblock polymer, which is added to methylene chloride with betacyfluthrin slightly solubility pesticide, to be had Dissolved in solvent, wherein in terms of milligram amphiphilic diblock polymer and in terms of ml methylene chloride organic solvent ratio be 1: 0.28, then according to the amphiphilic diblock polymer in terms of milligram and in terms of ml, the ratio of water is 1:0.8, organic molten toward methylene chloride In agent plus water forms colloid, is stirred overnight, the organic solvent is allowed to volatilize, and obtains the polymerization that average grain diameter is 100~300nm Object carrier micelle reuses in the freeze drying equipment that EYELA company is sold with trade name FD-81 in 0.01 DEG C of temperature and pressure It is freeze-dried under conditions of 610.5Pa, obtains water content as the solid powder less than 1% by weight.
Using Malvern particle size analyzer determination nano drug-carrying micella manufactured in the present embodiment, micellar solution is added drop-wise to copper mesh Above, using Japan Electronics Corporation with the morphosis of the trade name JEM-2100F Flied emission transmission electron microscope observing micella sold. Micella manufactured in the present embodiment is added drop-wise to cucumber blade face, upper marine morning digital technology Co., Ltd is with trade name JC2000D2M The contact angle of the contact angle instrument measurement micella of sale.Its result referring to attached drawing 5,6,9 and 12, by these attached drawings can be seen that by These attached drawings can be seen that NH2-PEG5000-PDLLA5000The micella grain that amphiphilic diblock polymer and slightly solubility pesticide are formed Diameter narrow distribution, the coefficient of dispersion is smaller, and shape is more regular, uniform spherical shape.Spreadability of the micella on cucumber blade face Preferably, the contact angle of drop is smaller.
Embodiment 3: controllable carrier micelle preparation that blade face is affine
The implementation steps of the embodiment are as follows:
CH is prepared first, in accordance with the method that this specification describes3O-PEG5000-PDLLA5000Amphiphilic diblock polymerization Object；
According to CH3O-PEG5000-PDLLA5000The weight ratio 1:0.1 of amphiphilic diblock polymer and slightly solubility pesticide, will CH3O-PEG5000-PDLLA5000It is organic molten that amphiphilic diblock polymer with betacyfluthrin slightly solubility pesticide is added to chloroform It is dissolved in agent, wherein the amphiphilic diblock polymer and ratio of chloroform organic solvent is 1:0.05 in terms of ml in terms of milligram, then The ratio of water is 1:0.68 according to the amphiphilic diblock polymer in terms of milligram and in terms of ml, and into chloroform organic solvent plus water is formed Colloid is stirred overnight, and the organic solvent is allowed to volatilize, and obtains the polymer medicament carrying micelle that average grain diameter is 100~300nm. It reuses in the freeze drying equipment that EYELA company is sold with trade name FD-81 in the item of 0.01 DEG C of temperature and pressure 610.5Pa It is freeze-dried under part, obtains water content as the solid powder less than 1% by weight.
Using Malvern particle size analyzer determination nano drug-carrying micella manufactured in the present embodiment, micellar solution is added drop-wise to copper mesh Above, using Japan Electronics Corporation with the morphosis of the trade name JEM-2100F Flied emission transmission electron microscope observing micella sold. Micella manufactured in the present embodiment is added drop-wise to cucumber blade face, upper marine morning digital technology Co., Ltd is with trade name JC2000D2M The contact angle of the contact angle instrument measurement micella of sale.Its result referring to attached drawing 7,8,9 and 12, by these attached drawings can be seen that by These attached drawings can be seen that CH3O-PEG5000-PDLLA5000The micella grain that amphiphilic diblock polymer and slightly solubility pesticide are formed Diameter narrow distribution, the coefficient of dispersion is smaller, and shape is more regular, uniform spherical shape.Spreadability of the micella on cucumber blade face Preferably, the contact angle of drop is smaller.
Embodiment 4: controllable carrier micelle preparation that blade face is affine
The implementation steps of the embodiment are as follows:
COOH-PEG is prepared first, in accordance with the method that this specification describes5000-PDLLA5000Amphiphilic diblock polymerization Object；
According to COOH-PEG5000-PDLLA5000The weight ratio 1:0.3 of amphiphilic diblock polymer and slightly solubility pesticide, will COOH-PEG5000-PDLLA5000Amphiphilic diblock polymer and betacyfluthrin slightly solubility pesticide are added to N, N dimethyl Dissolved in formamide organic solvent, wherein in terms of milligram amphiphilic diblock polymer in terms of ml n,N dimethylformamide have The ratio of solvent is 1:0.2, and then according to the amphiphilic diblock polymer in terms of milligram and in terms of ml, the ratio of water is that 1:0.89 is past In n,N dimethylformamide organic solvent plus water forms colloid, is stirred overnight, and it is 100~300nm's that dialysis, which obtains average grain diameter, Polymer medicament carrying micelle, reuse in the freeze drying equipment that EYELA company is sold with trade name FD-81 0.01 DEG C of temperature with It is freeze-dried under conditions of pressure 610.5Pa, obtains water content as the solid powder less than 1% by weight.
Using Malvern particle size analyzer determination nano drug-carrying micella manufactured in the present embodiment, micellar solution is added drop-wise to copper mesh Above, using Japan Electronics Corporation with the morphosis of the trade name JEM-2100F Flied emission transmission electron microscope observing micella sold. Micella manufactured in the present embodiment is added drop-wise to cucumber blade face, upper marine morning digital technology Co., Ltd is with trade name JC2000D2M The contact angle of the contact angle instrument measurement micella of sale.Its result can be seen that CH referring to attached drawing 7,8,9, by these attached drawings3O- PEG5000-PDLLA5000The micellar particle size narrow distribution that amphiphilic diblock polymer and slightly solubility pesticide are formed, the coefficient of dispersion compared with Small, shape is more regular, uniform spherical shape.
Embodiment 5: the preparation of fluorescent type nano drug-carrying micella
The implementation steps of the embodiment are as follows:
COOH-PEG is prepared first, in accordance with the method that this specification describes5000-PDLLA5000Amphiphilic diblock polymerization Object；
According to COOH-PEG5000-PDLLA5000The weight ratio 1:0.26 of amphiphilic diblock polymer and slightly solubility pesticide with And the weight ratio 1:0.01 of amphiphilic diblock polymer and rhodamine 6G fluorescer, by NH2-PEG5000-PDLLA5000It is amphipathic It is organic that diblock polymer, rhodamine 6G fluorescer and emamectin-benzoate slightly solubility pesticide are added to methylene chloride It is dissolved in solvent, wherein the amphiphilic diblock polymer and ratio of methylene chloride organic solvent is 1:0.08 in terms of ml in gram； Then according to amphiphilic diblock polymer in gram and in terms of ml, the ratio of water is that 1:1.2 adds water into methylene chloride organic solvent Colloid is formed, the polymer medicament carrying micelle that average grain diameter is 100~300nm is obtained, reuses EYELA company with trade name FD- It is freeze-dried under conditions of 0.01 DEG C of temperature with pressure 610.5Pa in the freeze drying equipment of 81 sale, obtains water and contain Amount is the solid powder less than 1% by weight.
Fluorescent type nano drug-carrying micella manufactured in the present embodiment is uniformly sprayed on cucumber blade face, fluorescence co-focusing is utilized Microscope and the observation of living body fluorescent imager, result can be seen that nano-micelle can referring to attached drawing 13,14, by these attached drawings It is attached to cucumber blade face well, fluorescence intensity with higher, the fluorescence intensity on front and back cucumber blade face is rinsed in comparison, after flushing Fluorescence intensity still with higher, it was demonstrated that COOH-PEG5000-PDLLA5000Fluorescence nano micella has stronger blade face adhesion, And water-fast flushing.
Embodiment 6: the preparation of fluorescent type nano drug-carrying micella
The implementation steps of the embodiment are as follows:
NH is prepared first, in accordance with the method that this specification describes2-PEG5000-PDLLA5000Amphiphilic diblock polymerization Object；
According to NH2-PEG5000-PDLLA5000The weight ratio 1:0.38 of amphiphilic diblock polymer and slightly solubility pesticide with And the weight ratio 1:0.03 of amphiphilic diblock polymer and rhodamine 6G fluorescer, by CH3O-PEG5000-PDLLA5000Amphiphilic Property diblock polymer is added in acetone organic solvent with betacyfluthrin slightly solubility pesticide to be dissolved, wherein amphiphilic in gram The property diblock polymer and ratio of acetone organic solvent is 1:0.35 in terms of ml；Then it polymerize according to amphiphilic diblock in gram The object and ratio of water is 1:2.2 into acetone organic solvent in terms of ml plus water forms colloid, is stirred overnight, allows the organic solvent The polymer medicament carrying micelle for obtaining that average grain diameter is 100~300nm to the greatest extent is evaporated into, reuses EYELA company with trade name FD- It is freeze-dried under conditions of 0.01 DEG C of temperature with pressure 610.5Pa in the freeze drying equipment of 81 sale, obtains water and contain Amount is the solid powder less than 1% by weight.
Fluorescent type nano drug-carrying micella manufactured in the present embodiment is uniformly sprayed on cucumber blade face, fluorescence co-focusing is utilized Microscope and the observation of living body fluorescent imager, result can be seen that nano-micelle in Huang referring to attached drawing 13,14, by these attached drawings The adhesive force on melon blade face weakens, and fluorescence intensity reduces, and the fluorescence intensity on front and back cucumber blade face is rinsed in comparison, after flushing on blade face Fluorescence intensity reduces, it was demonstrated that NH2-PEG5000-PDLLA5000Fluorescence nano micella has weaker blade face adhesion, when cannot be long Between carry out water flushing.
Application Example 1: emamectin-benzoate nano-micelle is on cucumber blade face to melon aphid indoor virulence Measurement
Using leaf dipping method to three kinds of nano drug-carrying micellas, commercially available emamectin-benzoate water dispersion of the invention Granula (wind vane-Qingdao Xingpai Crop Science Co., Ltd), missible oil dispersing agent (it is triumphant rise-promise general letter agrochemical share in Shenzhen is limited Company) to melon aphid in the interior on cucumber blade face toxicity test.By CH3O-PEG5000-PDLLA5000、COOH-PEG5000- PDLLA5000、NH2-PEG5000-PDLLA5000Micella, commercially available solid dispersion and missible oil dispersing agent are configured to 7 by grade ratio Column concentration gradient drug concentration (ppm): 400,200,100,50,25,12.5,6.25.The cucumber leaf of medicament will not contacted Piece breaks into the disk of diameter 7cm, and blade is impregnated 10s in medical fluid, naturally dry indoors after taking-up, pours into about in culture dish Blade reverse side, is affixed in culture dish by 2 millimeters of agar-agar liquid after cooling.Field acquires the biggish cucumber seedling of worm amount, is chosen with writing brush Aptery adult aphid is taken to be connected on blade, 20, every ware is sealed with preservative film, pricks 15-20 aperture with insect needle on film, store, Investigation and statistical method are same as above, and test sets 4 repetitions.The test worm of processing is put in insectary and is normally raised, rearing conditions are L/D=14:10, T=(25 ± 2) DEG C, RH=(75 ± 5) % check dead borer population and borer population living in for 24 hours, after 48h, calculate dead Rate.Half lethal concentration LC is calculated with DPS software50, the results are shown in table 2.
Table 2
By comparison, it was found that the insecticide efficiency of three kinds of emamectin-benzoate polylactic acid nano micellas and they It is related to blade face compatibility, it can be found that CH3O-PEG5000-PDLLA5000、COOH-PEG5000-PDLLA5000The micella of formation Insecticidal effect and commercially available missible oil dispersing agent are suitable, the LC of both carrier micelles50Well below commercially available solid dispersion, exhibition Good insecticidal effect is showed.And NH2-PEG5000-PDLLA5000The insecticidal effect of the micella of formation and commercially available solid dispersion Quite, illustrate the blade face compatibility of the nano-micelle with amino group lower than other two kinds of micellas.In missible oil dispersing agent because Containing a large amount of organic solvent and auxiliary agent, stronger insecticidal activity, polylactic acid poly ethylene glycol nano drug-carrying micella water are made it have Dissolubility is good, does not contain organic solvent and auxiliary agent, insecticidal effect is good, is environmentally friendly nano pesticide novel form.

Claims (4)

1. a kind of preparation method of the controllable carrier micelle of blade face compatibility, it is characterised in that the step of preparation method is as follows:
Respectively by COOH-PEG5000-PDLLA5000、NH2-PEG5000-PDLLA5000Or CH3O-PEG5000-PDLLA5000Amphipathic two Block polymer is added in organic solvent with slightly solubility pesticide to be dissolved, wherein amphiphilic diblock polymer and slightly solubility pesticide Weight ratio 1:0.1~0.6, the amphiphilic diblock polymer and in respect of the ratio of solvent be 1:0.05~0.4 with ml in terms of milligram； Then according to the amphiphilic diblock polymer in terms of milligram and in terms of ml, the ratio of water forms colloid for 1:0.4~3 plus water, stirred Night allows the organic solvent to volatilize, and then dialysis obtains the polymer medicament carrying micelle that average grain diameter is 100~300nm, then cold Jelly is dried to obtain its solid powder.
2. preparation method according to claim 1, it is characterised in that embedding adding described amphipathic two into organic solvent Rhodamine 6G fluorescer is added while section polymer and slightly solubility pesticide, wherein the amphiphilic diblock polymer and sieve The weight ratio of red bright 6G fluorescer is 1:0.01~0.03, obtains a kind of fluorescent type nano drug-carrying micella solid powder.
3. preparation method according to claim 1 or 2, it is characterised in that the slightly solubility pesticide is methylamino Avermectin Plain benzoate or betacyfluthrin.
4. preparation method according to claim 1 or 2, it is characterised in that the organic solvent is selected from acetone, dichloromethane Alkane, chloroform or N, N-dimethylformamide.
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