CN106719617A - A kind of optical Response pesticide nano micella and preparation method thereof and purposes - Google Patents
A kind of optical Response pesticide nano micella and preparation method thereof and purposes Download PDFInfo
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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
- A01N25/02—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
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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
- A01N25/10—Macromolecular compounds
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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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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Abstract
The invention discloses a kind of optical Response pesticide nano micella and preparation method thereof and purposes, the amphipathic nature polyalcohol precursor agricultural chemical that the micella effectively composition is obtained with the intermediate product (NBA PEG) of PEG (molecular weight 4000) reaction generations for the bromo methyl acid of 3 nitro 4 with agricultural chemicals dichlorphenoxyacetic acid (2,4 D) reaction.The preparation method of the micella includes the preparation process of NBA PEG, optical Response polymer precursor agricultural chemicals and optical Response pesticide nano micella.The micella can pass through spraying or spray function in the surface of target plant under the conditions of lucifuge, then slowly release agricultural chemicals under sun light stimulus.Present invention process is simple, and easily operation, is suitable for industrial production.
Description
Technical field
The present invention relates to nano-pesticide formulation, particularly a kind of optical Response pesticide nano micella and preparation method thereof with
On the way.
Background technology
Agricultural chemicals is made that significant contribution in the grain security for safeguard the mankind.However, the long-term use of agricultural chemicals is also resulted in
A series of negative effect：The resistance to the action of a drug, a large amount of generations of minor pests, environment dirt that residual toxicity, disease pest such as agricultural chemicals are produced
Dye, ecological disruption etc., as people's problem in the urgent need to address.Exploitation novel agrochemical (the i.e. efficiently, agriculture of low toxicity, low-residual
Medicine new varieties) and various eco-friendly pesticide preparations be the emphasis of pesticide research.Due to being devoted to the environmental protection of existing pesticide species
Research and development has the advantages that time saving and input amount is small, an important directions as current pesticide research.China shows
The level of row pesticidal preparations is relatively backward, and the yield of 4 kinds of conventional formulations such as missible oil, wettable powder, pulvis, particle is accounted for
75%.The hazardous solvent such as toluene, dimethylbenzene and freon etc. that these preparations cause to put into every year in natural environment reach 300,000
More than ton, white elephant is brought to environment.In China, every year because Pesticide use it is improper caused by year economic loss just reach
It is billions of, and the pest and disease damage resistance to the action of a drug fiercely rises, peasant's medication burden, have impact on the sustainable development of China's agricultural.By
This is visible, payes attention to and research, exploitation and the production of development pesticidal preparations, especially eco-friendly pesticide preparation are current pesticide fields
Very urgent task.
Photoresponse nanoparticle is that a kind of energy responds extraneous light stimulus and the particulate of form or structural change occurs.This nanometer
Grain is used as pharmaceutical carrier, can the easily regulating drug release on space-time, thus cause scientist in drug delivery field
Highest attention.In general, building photoresponse nanoparticle needs to use light triggering group (phototrigger) such as
Skimmetine methylene epoxide, 2- nitrobenzoyls epoxide and 7- nitroindoline quinolines etc..In these light triggering group, 2- nitrobenzoyls
Epoxide is especially noticeable, because it can issue raw photolysis in ultraviolet light or near infrared light, destruction contains 2- nitrobenzoyls
The close and distant balance of the amphipathic nature polyalcohol of epoxide, causes the rupture of self-assembly system.For example, the design such as Meng L has synthesized being based on
The micellar system of the amphipathic chitose containing 2- nitrobenzoyl epoxides, the system can respond ultraviolet light stimulus release hydrophobic anticancer
Camptothecin drug, good cytotoxicity is shown to MCF-7 cancer cells.However, the photoresponse reported in document so far is received
The grain of rice is mainly used as the carrier of controlled release drug, and for the design of agricultural chemicals control release, there is not been reported.
Controlled release form is developed so far, and the mode that it contains medicine mainly has two kinds of chemical bonding and physically trapping.Due to base
It is difficult to avoid system that medicine leakage occurs during active material is transmitted in the mode of physically trapping, so development is with covalent bond
The amphipathic optical Response agricultural chemicals polymer precursor of connection, is self-assembled into nano-micelle in aqueous, and realization is applied under lucifuge
Medicine, the response sun light stimulus drug release after reaching in target plant body, the utilization rate to solving agricultural chemicals are lowly significant.
The content of the invention
The present invention solves its technical problem：In order to solve problems of the prior art, there is provided a kind of new light
Response controlled release pesticide nano micellar preparation and its preparation method and application.The method not only process is simple, it is easy to operate, and
The nano-pesticide formulation of preparation has preferable optical Response, can lead to by spraying or spray function in the surface of target plant
Cross Inner and gulp down effect into target plant cell, response sun light stimulus release agricultural chemicals.
The present invention solves its technical problem and uses following technical scheme：
The optical Response pesticide nano micella that the present invention is provided, it effectively constitutes and is：3- nitro -4- bromo methyl acids elder generation
With the PEG reaction generations NBA-PEG that number-average molecular weight is 4000；Then NBA-PEG and agricultural chemicals 2,4-D reactions obtain PEG precursors
Agricultural chemicals；Self assembly obtains optical Response pesticide nano micella to the precursor agricultural chemical in aqueous.
Described 3- nitro -4- bromo methyl acids are first that the molar ratio of 4000 PEG is 1 with number-average molecular weight:1.0
~1.9:1.0.
The mol ratio of described agricultural chemicals 2,4-D and NBA-PEG is 1:1~2.0:1.
The preparation method of the optical Response pesticide nano micella that the present invention is provided, its step includes：
(1) preparation of NBA-PEG：
It is in molar ratio first 1:1.0~1.9:1.0 weigh 3- nitro -4- bromo methyl acids and PEG-4000, and its is molten
Catalyst EDC and DMAP are added after 10ml molar concentrations are for the DMF of 12.9mol/L, 24h is reacted at room temperature；Reaction terminates
Molar concentration is slowly added dropwise under condition of ice bath afterwards for 10mol/L ether separates out solid, this solid is dissolved in into molar concentration is
It is 1.0 × 10 through molar concentration in 15.6mol/L dichloromethane-5Mol/ml watery hydrochloric acid is washed, then is with molar concentration
The sodium bicarbonate solution of 0.89mol/L saturations adjusts pH to neutrality, point water removal phase, removes organic phase with revolving method afterwards and is obtained
NBA-PEG；
(2) preparation of optical Response polymer precursor agricultural chemicals：
It is in molar ratio first 1:1~2.0:1 weighs 2,4-D and NBA-PEG, is dissolved in 10ml molar concentrations and is
In the DMF of 12.9mol/L, catalyst KI and TEA being added afterwards, 8h being reacted under the conditions of 50~100 DEG C, adding molar concentration is
10mol/L ether separates out optical Response polymer precursor agricultural chemicals；
(3) preparation of optical Response pesticide nano micella：
Optical Response polymer precursor agricultural chemicals is dissolved in deionized water, ultrasonically treated, the photoresponse being evenly distributed
Property pesticide nano micella.
Described 3- nitro -4- bromo methyl acids and PEG, it is 1.7:When under conditions of 1.0, the yield of NBA-PEG
Highest, is 76.1%.
Described catalyst EDC and DMAP, it is 1.5 with the mol ratio of PEG:0.15:1.0.
Described 2,4-D and NBA-PEG, it is 1.5 in mol ratio:When under conditions of 1, optical Response polymer precursor agriculture
The yield highest of medicine, is 64.8%.
Described catalyst KI and TEA, it is 1.1 with the mol ratio of NBA-PEG:1.1:1.0.
Described is ultrasonically treated, and its technique is：Prepared optical Response polymer precursor agricultural chemicals is dissolved in deionized water
In, ultrasound, makes its self assembly under 100w, obtains final product equally distributed photoresponse pesticide nano micellar solution.
The optical Response pesticide nano micella that the present invention is provided, it is under the conditions of lucifuge by spraying or spray function in target
The surface of plant, then slowly releases agricultural chemicals under sun light stimulus.
Optical Response pesticide nano micella prepared by the above method that the present invention is provided, it is under the conditions of lucifuge by spraying
Or then spray function slowly releases agricultural chemicals in the surface of target plant under sun light stimulus.
The present invention has following major advantage compared with prior art：
(1) present invention uses chemical bonding to carry PEG agricultural chemicals prodrugs prepared by the method for medicine, can realize load medicine in situ, and energy
Firm contains medicine, prevents medicine from revealing in advance.And chitosan nano gel prepared by the chemical optical cross-linking method for using in the past,
Load medicine in situ cannot be realized to the medicine with amido or bioactive molecule.
(2) present invention makes polymer agricultural chemicals prodrug be self-assembly of nanometre glue under using physical method ultrasound condition
Beam, it is simple to operate, and noxious material is not introduced into, and conventional invention uses glutaraldehyde cross-linking agent and prepares nanogel, this
Crosslinking agent severe toxicity, is also no lack of by dialysis process and removes completely.
(3) it is controlled-release material that the present invention uses polyethylene glycol (PEG), and PEG has hypotoxicity, very weak immunogenicity and resists
Originality, excellent biocompatibility, be difficult by protein absorption, the stability of polyether backbone and either in the aqueous solution still
In many organic solvents the advantages of good dissolubility.The Amphiphilic micelle good water solubility that is prepared into PEG, mobility be high,
Stability is strong, is a kind of good material for preparing controlled release preparation.
(4) herbicide that this preparation is used is dichlorphenoxyacetic acid (2,4-D), and 2,4-D drug availabilities are low, and itself can drop
Solve and environment is polluted into meeting after underground water, do harm to huamn body.Pesticides 2.4-D of the present invention is with carrier with chemistry
Bonding, applies under the conditions of without a licence, is avoided that medicine is revealed, so as to reduce to environmental hazard.
(5) this preparation has optical Response, and medicine is just discharged after illumination reaches some strength.Therefore spray and enter target plant
After in vivo, sun light stimulus release medicine can be responded, so as to avoid agricultural chemicals from being discharged on the daytime of night and without sunlight, be conducive to
Greatly improve the utilization rate of agricultural chemicals.
(6) process is simple, easily operation, is suitable to industrialized production.
Brief description of the drawings
Fig. 1 is the nuclear magnetic resonance map after optical Response agricultural chemicals prodrug illumination ten minutes prepared by the present invention.
Fig. 2 is the transmission electron microscope picture before optical Response pesticide nano micella illumination prepared by the present invention.
Fig. 3 is the transmission electron microscope picture after optical Response pesticide nano micella illumination prepared by the present invention.
Fig. 4 is optical Response pesticide nano micella drug release profiles in aqueous prepared by the embodiment of the present invention 3.
Specific embodiment
The present invention is first using the good PEG-4000 of non-toxic water soluble with 3- nitro -4- bromo methyl acids in catalyst
EDC and DMAP acts on lower reaction and intermediate product (NBA-PEG) is obtained successively；Then exist with agricultural chemicals dichlorphenoxyacetic acid (2,4-D)
Mix in DMF solution, add catalyst KI and TEA, reaction is obtained optical Response polymer precursor agricultural chemicals；Last optical Response gathers
Polymer precursor agricultural chemicals is self-assembly of pesticide nano micellar preparation in aqueous.
With reference to embodiment and accompanying drawing, the invention will be further described, but is not limited solely to the following examples.
Embodiment 1：
3- nitro -4- bromo methyl acids (0.39g, 1.5mmol) and PEG4000 (4.00g, 1.00mmol) is taken to be dissolved in
During the molar concentration of 10ml is 12.9mol/L DMF, sequentially add EDC (0.288g, 1.5mmol) and DMAP (0.0183g,
0.15mmol), reaction 24h is stirred at room temperature.Then, molar concentration is added dropwise at 0 DEG C for the ether of 10mol/L separates out white
Solid.White solid is dissolved in the dichloromethane that molar concentration is 15.6mol/L after filtering, with 1.0 × 10-5Mol/ml's is dilute
Salt pickling three times, then adjusts pH to neutrality with the sodium bicarbonate solution of the saturation of 0.89mol/L.Take organic layer rotary evaporation
The most of dichloromethane of instrument evaporation, obtains white clear concentrate, under ice bath to concentrate in the ether of 10mol/L is added dropwise,
Again white precipitate is separated out, is filtered, dried, obtain final product NBA-PEG.Yield is about 75.3%.Above-mentioned all reactions are all in dark situation
Under carry out.
Take NBA-PEG (2.122g, 0.5mmol) and be dissolved in the molar concentration of 10ml in 12.9mol/L DMF, to be subsequently added
2,4-D (0.1658g, 0.75mmol), catalyst KI (0.0913g, 0.55mmol) and TEA (0.077ml, 0.55mmol),
75 DEG C of reaction 8h.After reaction terminates, 0 DEG C is cooled to, molar concentration is added dropwise for the ether of 10mol/L separates out pale yellow precipitate.Produce
Rate is about 64.8%.Take faint yellow solid 10.00mg to be dissolved in 2ml deionized waters, ultrasonic (100W) is processed 30 minutes, obtains final product light
The pesticide nano micellar solution of response.Above-mentioned all reactions are all carried out under dark situation.
Embodiment 2：
3- nitro -4- bromo methyl acids (0.26g, 1.0mmol) and PEG4000 (4.00g, 1.00mmol) is taken to be dissolved in
During the molar concentration of 10ml is 12.9mol/L DMF, sequentially add EDC (0.288g, 1.5mmol) and DMAP (0.0183g,
0.15mmol), reaction 24h is stirred at room temperature.Then, the ether that 10mol/L is added dropwise at 0 DEG C separates out white solid.Filtering
White solid is dissolved in the dichloromethane that molar concentration is 15.6mol/L afterwards, three are washed with the watery hydrochloric acid of 1.0 × 10-5mol/ml
It is secondary, then adjust pH to neutrality with the sodium bicarbonate solution of 0.89mol/L saturations.Take organic layer Rotary Evaporators and evaporate big portion
Point dichloromethane, obtains white clear concentrate, under ice bath to concentrate in the ether of 10mol/L is added dropwise, separate out again white
Color is precipitated, filtering, is dried, and obtains final product NBA-PEG.Yield is about 67.2%.Above-mentioned all reactions are all carried out under dark situation.
Take NBA-PEG (2.122g, 0.5mmol) and be dissolved in the molar concentration of 10ml in 12.9mol/L DMF, to be subsequently added
2,4-D (0.1658g, 0.75mmol), catalyst KI (0.0913g, 0.55mmol) and TEA (0.077ml, 0.55mmol),
75 DEG C of reaction 8h.After reaction terminates, 0 DEG C is cooled to, the ether that 10mol/L is added dropwise separates out pale yellow precipitate.Yield is about
64.1%.Take faint yellow solid 10.00mg to be dissolved in 2ml deionized waters, ultrasonic (100W) is processed 30 minutes, obtains final product optical Response
Pesticide nano micellar solution.Above-mentioned all reactions are all carried out under dark situation.
Embodiment 3：
3- nitro -4- bromo methyl acids (0.442g, 1.7mmol) and PEG4000 (4.00g, 1.00mmol) are dissolved in
During the molar concentration of 10ml is 12.9mol/L DMF, sequentially add EDC (0.288g, 1.5mmol) and DMAP (0.0183g,
0.15mmol), reaction 24h is stirred at room temperature.Then, the ether that 10mol/L is added dropwise at 0 DEG C separates out white solid.Filtering
White solid is dissolved in the dichloromethane that molar concentration is 15.6mol/L afterwards, three are washed with the watery hydrochloric acid of 1.0 × 10-5mol/ml
It is secondary, then adjust pH to neutrality with the sodium bicarbonate solution of 0.89mol/L saturations.Take organic layer Rotary Evaporators and evaporate big portion
Point dichloromethane, obtains white clear concentrate, under ice bath to concentrate in the ether of 10mol/L is added dropwise, separate out again white
Color is precipitated, filtering, is dried, and obtains final product NBA-PEG.Yield is about 76.1%.Above-mentioned all reactions are all carried out under dark situation.
Take NBA-PEG (2.122g, 0.5mmol) and be dissolved in the molar concentration of 10ml in 12.9mol/L DMF, to be subsequently added
2,4-D (0.1658g, 0.75mmol), catalyst KI (0.0913g, 0.55mmol) and TEA (0.077ml, 0.55mmol),
75 DEG C of reaction 8h.After reaction terminates, 0 DEG C is cooled to, the ether that 10mol/L is added dropwise separates out pale yellow precipitate.Yield is about
64.3%.Take faint yellow solid 10.00mg to be dissolved in 2ml deionized waters, ultrasonic (100W) is processed 30 minutes, obtains final product optical Response
Pesticide nano micellar solution.Above-mentioned all reactions are all carried out under dark situation.
Embodiment 4：
3- nitro -4- bromo methyl acids (0.442g, 1.7mmol) and PEG4000 (4.00g, 1.00mmol) are dissolved in
During the molar concentration of 10ml is 12.9mol/L DMF, sequentially add EDC (0.288g, 1.5mmol) and DMAP (0.0183g,
0.15mmol), reaction 24h is stirred at room temperature.Then, the ether that 10mol/L is added dropwise at 0 DEG C separates out white solid.Filtering
White solid is dissolved in the dichloromethane that molar concentration is 15.6mol/L afterwards, three are washed with the watery hydrochloric acid of 1.0 × 10-5mol/ml
It is secondary, then adjust pH to neutrality with the sodium bicarbonate solution of 0.89mol/L saturations.Take organic layer Rotary Evaporators and evaporate big portion
Point dichloromethane, obtains white clear concentrate, under ice bath to concentrate in the ether of 10mol/L is added dropwise, separate out again white
Color is precipitated, filtering, is dried, and obtains final product NBA-PEG.Yield is about 76.1%.Above-mentioned all reactions are all carried out under dark situation.
NBA-PEG (2.122g, 0.5mmol) is dissolved in the molar concentration of 10ml in 12.9mol/L DMF, to be subsequently added
2,4-D (0.1106g, 0.5mmol), catalyst KI (0.0913g, 0.55mmol) and TEA (0.077ml, 0.55mmol), 75
DEG C reaction 8h.After reaction terminates, 0 DEG C is cooled to, the ether that 10mol/L is added dropwise separates out pale yellow precipitate.Yield is about 55.1%.
Take faint yellow solid 10.00mg to be dissolved in 2ml deionized waters, ultrasonic (100W) is processed 30 minutes, obtains final product the agricultural chemicals of optical Response
Nano micellar solution.Above-mentioned all reactions are all carried out under dark situation.
Embodiment 5：
3- nitro -4- bromo methyl acids (0.442g, 1.7mmol) and PEG4000 (4.00g, 1.00mmol) are dissolved in
During the molar concentration of 10ml is 12.9mol/L DMF, sequentially add EDC (0.288g, 1.5mmol) and DMAP (0.0183g,
0.15mmol), reaction 24h is stirred at room temperature.Then, the ether that 10mol/L is added dropwise at 0 DEG C separates out white solid.Filtering
White solid is dissolved in the dichloromethane that molar concentration is 15.6mol/L afterwards, three are washed with the watery hydrochloric acid of 1.0 × 10-5mol/ml
It is secondary, then adjust pH to neutrality with the sodium bicarbonate solution of 0.89mol/L saturations.Take organic layer Rotary Evaporators and evaporate big portion
Point dichloromethane, obtains white clear concentrate, under ice bath to concentrate in the ether of 10mol/L is added dropwise, separate out again white
Color is precipitated, filtering, is dried, and obtains final product NBA-PEG.Yield is about 76.1%.Above-mentioned all reactions are all carried out under dark situation.
NBA-PEG (2.122g, 0.5mmol) is dissolved in the molar concentration of 10ml in 12.9mol/L DMF, to be subsequently added
2,4-D (0.2211g, 1.0mmol), catalyst KI (0.0913g, 0.55mmol) and TEA (0.077ml, 0.55mmol), 75
DEG C reaction 8h.After reaction terminates, 0 DEG C is cooled to, the ether that 10mol/L is added dropwise separates out pale yellow precipitate.Yield is about 64.7%.
Take faint yellow solid 10.00mg to be dissolved in 2ml deionized waters, ultrasonic (100W) is processed 30 minutes, obtains final product the agricultural chemicals of optical Response
Nano micellar solution.Above-mentioned all reactions are all carried out under dark situation.
Embodiment 6：
3- nitro -4- bromo methyl acids (0.442g, 1.5mmol) and PEG4000 (4.00g, 1.00mmol) are dissolved in
During the molar concentration of 10ml is 12.9mol/L DMF, sequentially add EDC (0.288g, 1.5mmol) and DMAP (0.0183g,
0.15mmol), reaction 24h is stirred at room temperature.Then, the ether that 10mol/L is added dropwise at 0 DEG C separates out white solid.Filtering
White solid is dissolved in the dichloromethane that molar concentration is 15.6mol/L afterwards, three are washed with the watery hydrochloric acid of 1.0 × 10-5mol/ml
It is secondary, then adjust pH to neutrality with the sodium bicarbonate solution of 0.89mol/L saturations.Take organic layer Rotary Evaporators and evaporate big portion
Point dichloromethane, obtains white clear concentrate, under ice bath to concentrate in the ether of 10mol/L is added dropwise, separate out again white
Color is precipitated, filtering, is dried, and obtains final product NBA-PEG.Yield is about 75.2%.Above-mentioned all reactions are all carried out under dark situation.
NBA-PEG (2.122g, 0.5mmol) is dissolved in the molar concentration of 10ml in 12.9mol/L DMF, to be subsequently added
2,4-D (0.1658g, 0.75mmol), catalyst KI (0.0913g, 0.55mmol) and potassium carbonate (0.07602g,
0.55mmol), 8h is reacted at 75 DEG C.After reaction terminates, 0 DEG C is cooled to, the ether that 10mol/L is added dropwise separates out pale yellow precipitate.
Yield is about 15.5%.Take faint yellow solid 10.00mg to be dissolved in 2ml deionized waters, ultrasonic (100W) is processed 30 minutes, is obtained final product
The pesticide nano micellar solution of optical Response.Above-mentioned all reactions are all carried out under dark situation.
Embodiment 7：
3- nitro -4- bromo methyl acids (0.442g, 1.5mmol) and PEG4000 (4.00g, 1.00mmol) are dissolved in
During the molar concentration of 10ml is 12.9mol/L DMF, sequentially add EDC (0.288g, 1.5mmol) and DMAP (0.0183g,
0.15mmol), reaction 24h is stirred at room temperature.Then, the ether that 10mol/L is added dropwise at 0 DEG C separates out white solid.Filtering
White solid is dissolved in the dichloromethane that molar concentration is 15.6mol/L afterwards, three are washed with the watery hydrochloric acid of 1.0 × 10-5mol/ml
It is secondary, then adjust pH to neutrality with the sodium bicarbonate solution of 0.89mol/L saturations.Take organic layer Rotary Evaporators and evaporate big portion
Point dichloromethane, obtains white clear concentrate, under ice bath to concentrate in the ether of 10mol/L is added dropwise, separate out again white
Color is precipitated, filtering, is dried, and obtains final product NBA-PEG.Yield is about 75.2%.Above-mentioned all reactions are all carried out under dark situation.
NBA-PEG (2.122g, 0.5mmol) is dissolved in the molar concentration of 10ml in 12.9mol/L DMF, to be subsequently added
2,4-D (0.1658g, 0.75mmol), catalyst KI (0.0913g, 0.55mmol) and TEA (0.077ml, 0.55mmol),
100 DEG C of reaction 8h.After reaction terminates, 0 DEG C is cooled to, the ether that 10mol/L is added dropwise separates out pale yellow precipitate.Yield is about
64.6%.Take faint yellow solid 10.00mg to be dissolved in 2ml deionized waters, ultrasonic (100W) is processed 30 minutes, obtains final product optical Response
Pesticide nano micellar solution.Above-mentioned all reactions are all carried out under dark situation.
Fig. 1 show example 1 prepare photoresponse PEG agricultural chemicals prodrug respectively in following reagent illumination ten minutes nuclear-magnetism
Resonance collection of illustrative plates：(a)D2O, (b) DMSO-d6/D2O(1:5, v/v), (c) DMSO-d6/D2O(1:5,v/v).Curve a and curve b phases
Than the vibration signal peak that proton proton on aromatic rings is belonged at δ=6.60~8.60 is not observed in curve a.This
Any indicates amphipathic PEG agricultural chemicals prodrugs in D2Form micella in O, and 2,4-D hydrophobic side by hydrophilic PEG
Backbone portion is shielded, and is formd with hydrophobic kernel, so that 2,4-D H nuclear signals are shielded, inspection does not measure H cores letter
Number.Compared with curve b, δ=5.10 belong to methylene (2H, ArCH to curve c in curve b2OCO signal peak) is in curve c
Disappear, while δ=10.24 and 11.00 have gone out two signal peaks for being respectively belonging to (H, CHO) and (H, COOH) in curve c,
Show the fracture of the photoresponse group adjacent nitro benzyl of PEG-NBA agricultural chemicals prodrugs, while generating new material.
Fig. 2 shows the transmission electron microscope picture before optical Response nano pesticide micella illumination prepared by example 3, and average grain diameter is about
It is 34nm.
Fig. 3 shows the transmission electron microscope picture after optical Response nano pesticide micella illumination prepared by example 9, and average grain diameter is about
It is 24nm.
Fig. 2 and Fig. 3 results show that the average grain diameter of PEG agricultural chemicals prodrug micelle reduces 10nm or so before and after illumination, and this can
It is attributed to amphipathic PEG agricultural chemicals prodrug nano-micelles light occurs after by ultraviolet light and split reaction, has sloughed Dichlorophenoxy
Acetic acid.In addition, the product after photodissociation is still an amphipathic compound, glue still can be self-assembly of in aqueous
Beam, so electromicroscopic photograph shows core-shell morphology, simply particle diameter slightly diminishes.
Fig. 4 shows optical Response pesticide nano micella drug release profiles in aqueous prepared by example 3.In non-illumination
Under conditions of, do not observe that 2,4-D is discharged from nano-micelle.However, under ultraviolet light, when 2 minutes,
2, the 4-D for just having had 51.8% is discharged from nano-micelle, and further following exposure to the time under ultraviolet light
Extension, 2,4-D release continues to increase, and preparation reached 99.5% at 9 minutes.Under simulated solar light irradiation, light rings
The insoluble drug release of answering property nano pesticide micella then shows certain sustained release performance, by after 9 hours, accumulative release rate reaches
To 99.6%.
Although certain aspects of the invention are illustrated and described herein with reference to the embodiment for being given, it is not intended to
Appended claim is limited in shown details.Conversely, it is contemplated that those skilled in the art can be to these
Details carries out different modifications, wherein these modification should also in the spirit and scope of required theme, and be in order to
Correspondingly explain these claims.
Claims (10)
1. a kind of optical Response pesticide nano micella, it is characterized in that effective composition of the micella is：3- nitro -4- bromomethyl benzene first
Sour is first 4000 PEG reaction generations NBA-PEG with number-average molecular weight；Then NBA-PEG and agricultural chemicals 2,4-D reactions obtain PEG
Precursor agricultural chemical；Self assembly obtains optical Response pesticide nano micella to the precursor agricultural chemical in aqueous.
2. optical Response pesticide nano micella according to claim 1, it is characterised in that described 3- nitro -4- bromomethyls
Benzoic acid is first that the molar ratio of 4000 PEG is 1 with number-average molecular weight:1.0~1.9:1.0.
3. optical Response pesticide nano micella according to claim 1, it is characterised in that described agricultural chemicals 2,4-D and NBA-
The mol ratio of PEG is 1:1~2.0:1.
4. a kind of preparation method of optical Response pesticide nano micella, it is characterized in that the method step includes：
(1) preparation of NBA-PEG：
It is in molar ratio first 1:1.0~1.9:1.0 weigh 3- nitro -4- bromo methyl acids and PEG-4000, are dissolved in
10ml molar concentrations react 24h at room temperature to add catalyst EDC and DMAP after the DMF of 12.9mol/L；After reaction terminates
Molar concentration is slowly added dropwise under condition of ice bath for 10mol/L ether separates out solid, this solid is dissolved in into molar concentration is
It is 1.0 × 10 through molar concentration in 15.6mol/L dichloromethane-5Mol/ml watery hydrochloric acid is washed, then is with molar concentration
The sodium bicarbonate solution of 0.89mol/L saturations adjusts pH to neutrality, point water removal phase, removes organic phase with revolving method afterwards and is obtained
NBA-PEG；
(2) preparation of optical Response polymer precursor agricultural chemicals：
It is in molar ratio first 1:1~2.0:1 weighs 2,4-D and NBA-PEG, is dissolved in 10ml molar concentrations for 12.9mol/L
DMF in, catalyst KI and TEA are added afterwards, react 8h under the conditions of 50~100 DEG C, add molar concentration for 10mol/L second
Ether separates out optical Response polymer precursor agricultural chemicals；
(3) preparation of optical Response pesticide nano micella：
Optical Response polymer precursor agricultural chemicals is dissolved in deionized water, ultrasonically treated, the optical Response agriculture being evenly distributed
Medicine nano-micelle.
5. preparation method according to claim 4, it is characterised in that described 3- nitro -4- bromo methyl acids and PEG,
It is 1.7:When under conditions of 1.0, the yield highest of NBA-PEG, is 76.1%.
6. preparation method according to claim 4, it is characterised in that described catalyst EDC and DMAP, it rubs with PEG's
You are than being 1.5:0.15:1.0.
7. preparation method according to claim 4, it is characterised in that described 2,4-D and NBA-PEG, it is in mol ratio
1.5:When under conditions of 1, the yield highest of optical Response polymer precursor agricultural chemicals, is 64.8%.
8. preparation method according to claim 4, it is characterised in that described catalyst KI and TEA, it is with NBA-PEG's
Mol ratio is 1.1:1.1:1.0.
9. in claim 1 or 2 and 3 any optical Response pesticide nano micella purposes, it is characterised in that：The photoresponse
Property pesticide nano micella under the conditions of lucifuge by spraying or spray function in the surface of target plant, then under sun light stimulus
Slowly release agricultural chemicals.
10. in claim 4 to 9 optical Response pesticide nano micella prepared by any methods described purposes, it is characterised in that：
The optical Response pesticide nano micella passes through spraying or spray function in the surface of target plant under the conditions of lucifuge, then in the sun
Agricultural chemicals is slowly released under light stimulus.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107333759A (en) * | 2017-06-22 | 2017-11-10 | 浙江大学 | Light-operated sustained-release pesticides preparation and preparation method thereof |
| CN114946861A (en) * | 2022-05-28 | 2022-08-30 | 河北上瑞生物科技有限公司 | Pesticide composition containing chitosan and kasugamycin, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601897A (en) * | 2013-11-06 | 2014-02-26 | 北京科技大学 | Preparation method and application of multiple-response nanogel |
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2016
- 2016-11-16 CN CN201611030735.4A patent/CN106719617A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601897A (en) * | 2013-11-06 | 2014-02-26 | 北京科技大学 | Preparation method and application of multiple-response nanogel |
Non-Patent Citations (1)
| Title |
|---|
| KAIKAI DING ET AL.: "Synthesis of photoresponsive polymeric propesticide micelles based on PEG for the controlled release of a herbicide", 《POLYMER CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107333759A (en) * | 2017-06-22 | 2017-11-10 | 浙江大学 | Light-operated sustained-release pesticides preparation and preparation method thereof |
| CN107333759B (en) * | 2017-06-22 | 2022-02-18 | 浙江大学 | Light-operated slow-release pesticide preparation and preparation method thereof |
| CN114946861A (en) * | 2022-05-28 | 2022-08-30 | 河北上瑞生物科技有限公司 | Pesticide composition containing chitosan and kasugamycin, preparation method and application |
| CN114946861B (en) * | 2022-05-28 | 2023-10-31 | 河北上瑞生物科技有限公司 | Pesticide composition containing chitosan and kasugamycin, preparation method and application |
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