CN106719630A - Optical Response controlled release nanometer pesticidal preparations and its preparation method and application - Google Patents
Optical Response controlled release nanometer pesticidal preparations and its preparation method and application Download PDFInfo
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- CN106719630A CN106719630A CN201611030754.7A CN201611030754A CN106719630A CN 106719630 A CN106719630 A CN 106719630A CN 201611030754 A CN201611030754 A CN 201611030754A CN 106719630 A CN106719630 A CN 106719630A
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The present invention relates to optical Response controlled release nanometer pesticidal preparations and its preparation method and application, said preparation controlled release of active ingredients is amphipathic carboxymethyl chitosan derivative, and it is obtained by adjacent nitro benzyl monomester succinate and carboxymethyl chitosan reaction.Said preparation is made up of following methods：The aqueous solution of carboxymethyl chitosan is taken, is 1 according to the sugar unit of carboxymethyl chitosan and the mol ratio of adjacent nitro benzyl monomester succinate：(0.01~1) organic solution of the adjacent nitro benzyl monomester succinate activated through NHS and EDCHCl is added, 6h is reacted at room temperature, then dialysis, freeze-drying, obtain optical Response carboxymethyl chitosan derivative；The derivative and agricultural chemicals are dispersed in water simultaneously, the ultrasonic controlled release pesticide nano grain for obtaining optical Response of interval.This controlled release nanometer pesticidal preparations may be selected to be sprayed under conditions of no light in target plant and insect surface or internal；Once acting on target plant and insect surface or internal, extraneous sun light stimulus release agricultural chemicals can be at any time responded.
Description
Technical field
The present invention relates to controlled release nanometer pesticidal preparations, more particularly to a kind of optical Response controlled release nanometer pesticidal preparations and its
Preparation method and application.
Background technology
Agriculturally widely using for agricultural chemicals helps to realize world food safety, but is also brought not to the mankind and environment
Good influence.With the presence of the use problems of up to 90% traditional agricultural chemicals：Never reach action target spot, reach action target spot hair
The medication amount waved time of drug effect not enough or reach target spot is not reaching to require, so as to be difficult to occur expected biological effect
Should.
The reason for causing this phenomenon is the non-specific of these agricultural chemicals and repeatedly applies.Which not only improves agricultural chemicals
Use cost, and cause environmental pollution.Because the high cost to substitute existing agricultural chemicals of synthesizing new compound and
Other a variety of limiting factors, people transfer to direct attention to develop pesticide action-controlling transmission system.Pesticide action-controlling agent is peculiar because of its
Following advantage, as administer agricultural chemicals negative issue new hope：(1) high poison kind low toxicity can be made, it is to avoid or mitigate high
Malicious pesticide species are in use to people, animal and beneficial microorganism acute poisoning and injury, it is also possible to avoid or mitigate agriculture
Pollution of the medicine to environment.(2) agricultural chemicals can be made to reduce photodissociation, hydrolysis, biodegradation, volatilization, loss in the environment etc., is used
Dose greatly reduces, and the lasting period greatly prolongs.(3) because medicament releasing dosage and time can be controlled, thus medicament
Feature be improved.
The amphipathic nature polyalcohol being made up of hydrophilic radical and hydrophobic grouping recently is led in biotechnology and pharmaceutical preparation application
People's growing interest is triggered in domain.In aqueous, this amphipathic nature polyalcohol can be self-assembly of the nanometre glue of nucleocapsid structure
Beam or self-aggregate, its hydrophobic nuclear energy serve as the various hydrophobic bioactivators of Drug Storage hydrophobic region packing；By hydrophilic chain
The shell of Duan Zucheng can assign micella water solubility and three-dimensional stability, and it can protect the medicine for containing from inactivating in a fluid.More
For importantly, polymer micelle is diluted due to relatively low overlooking micellar concentration energy Antagonistic Environment, with the glue based on surface-active
Beam is compared to stability higher.In view of good biocompatibility, biodegradability and low toxicity, using hydrophilic
Natural polysaccharide is matrix, and amphipathic nature polyalcohol is prepared by hydrophobically modified, and polymer micelle is then self-assembled into aqueous,
Carrier as various hydrophobic bioactive materials is considered as one of direction of controlled formulation technique field most prospect.
Stimulating responsive polymer nano-micelle is that a kind of energy responds extraneous light stimulus and form or structural change occur
Particulate.Successfully develop so far various including pH, temperature, light, the sensitive polymer of the stimulation such as reduction potential and enzyme
Nano-micelle, wherein optical Response polymer nano micelle are used as pharmaceutical carrier, due to can on space-time easily regulating
Thing discharges, thus is received much concern in drug delivery and controlled release field.In general, building photoresponse nanoparticle needs to use one
Light triggering group (phototrigger) skimmetine methylene epoxide, 2- nitrobenzoyls epoxide and 7- nitroindoline quinolines etc..
In these light triggering group, 2- nitrobenzoyl epoxides are more attractive, because it can occur under ultraviolet light or near infrared light
Photolysis, destroys the close and distant balance of the amphipathic nature polyalcohol containing 2- nitrobenzoyl epoxides, causes the rupture of self-assembly system.
For example, MengL et al. designs have synthesized the micellar system based on the amphipathic chitose containing 2- nitrobenzoyl epoxides
(Biomacromolecules, 14,2601-2610), the system can respond ultraviolet light stimulus release hydrophobic anticancer drug camplotheca acuminata
Alkali, good cytotoxicity is shown to MCF-7 cancer cells.However, the photoresponse nanoparticle reported in document so far is main
Carrier as controlled release drug, for the design of agricultural chemicals control release, there is not been reported.
The content of the invention
The technical problems to be solved by the invention are：In order to solve problems of the prior art, there is provided a kind of new
Controlled release nanometer pesticidal preparations of optical Response and its preparation method and application.The method not only process is simple, it is easy to operate, and
And the nano-pesticide formulation for preparing has preferable optical Response, can be by selecting to spray effect target under conditions of no light
Plant and insect surface or internal；Once being applied to target plant and insect surface or internal, extraneous sun polished bard can be at any time responded
Swash release agricultural chemicals.
The present invention solves its technical problem and uses following technical scheme：
The optical Response controlled release nanometer pesticidal preparations that the present invention is provided, its controlled release of active ingredients is amphipathic carboxymethyl chitosan
Sugar derivatives, it is obtained by adjacent nitro benzyl monomester succinate and carboxymethyl chitosan reaction.
Described amphipathic carboxymethyl chitosan derivative, can be made up of following methods：
The aqueous solution of carboxymethyl chitosan is first taken, according to sugar unit and the adjacent nitro benzyl mono succinate of carboxymethyl chitosan
The mol ratio of ester is 1：(0.01~1) having for adjacent nitro benzyl monomester succinate (NBS) that is activated through EDCHCl and NHS is added
In machine solution, 6h is reacted at room temperature, obtain amphipathic carboxymethyl chitosan solution；The organic solution is dimethyl sulfoxide (DMSO)
(DMSO), one kind in dimethyl formamide solution, or its two kinds mixed solutions of any weight proportion composition；Again through dialysis,
Freeze-drying, obtains amphipathic carboxymethyl chitosan derivative, and it is optical Response carboxymethyl chitosan derivative.
In the above method, by 1:0.2 mol ratio, optical Response carboxymethyl chitosan derivative and agricultural chemicals are scattered in simultaneously
In water, ultrasonic 3min obtains optical Response controlled release nanometer pesticidal preparations.
Described agricultural chemicals is the one kind in Insecticides (tech) ＆ Herbicides (tech) or plant growth regulator, or several mixtures.
The preparation method of the optical Response controlled release nanometer pesticidal preparations that the present invention is provided, specifically uses and comprises the following steps
Method：
(1) preparation of carboxymethyl chitosan sugar aqueous solution：
The carboxymethyl chitosan that degree of substitution by carboxymethyl is 0.1~1.8 is added to the water, carboxymethyl chitosan sugar aqueous solution
Weight percent concentration is 0.08~10%, is then stirred at room temperature, obtains the carboxymethyl chitosan sugar aqueous solution；
(2) synthesis of adjacent nitro benzyl monomester succinate：
It is 1 first to weigh mol ratio:2 nitro alcohol is dissolved in chloroform with succinyl oxide, adds catalyst 4- diformazans
Aminopyridine (DMAP), under nitrogen environmental protection, back flow reaction 24h, after stopping reaction, vacuum distillation removes part chloroform, remains
Remaining reaction solution is washed three times with the HCl solution of mass concentration 10% (w/w), then with the sodium bicarbonate solution extracting and washing of saturation
Afterwards, water phase pH to 5 is adjusted with the HCl solution of mass concentration 10% (w/w), white depositions is collected, then by white depositions
In 40 DEG C of vacuum drying, the adjacent nitro benzyl monomester succinate is obtained；
(3) preparation of the adjacent nitro benzyl monomester succinate organic solution of NHS and EDCHCl activation：
Adjacent nitro benzyl monomester succinate is first dissolved in organic solvent, is stirred at room temperature, percentage by weight is obtained
Concentration is 5%~85% adjacent nitro benzyl monomester succinate organic solution；The organic solution is cooled to 0-5 DEG C again, by neighbour
Nitrobenzyl monomester succinate：N-hydroxy-succinamide (NHS)：1- (3- dimethylamino-propyls) -3- ethyl carbodiimide salt
Hydrochlorate (EDCHCl) is 1：1.1：1.1 mol ratio delivers NHS and EDCHCl successively, then in room temperature reaction 24h, will be anti-
Answer liquid to filter, obtain the adjacent nitro benzyl monomester succinate organic solution of the NHS and EDCHCl activation；
(4) preparation of optical Response carboxymethyl chitosan derivative：
The aqueous solution of carboxymethyl chitosan is first taken, according to the sugar unit and the mol ratio of adjacent nitro benzyl ester of carboxymethyl chitosan
It is 1：(0.01~1) the adjacent nitro base monomester succinate organic solution activated through NHS and EDCHCl is added, in deionized water
Dialysis 48h, then freeze-drying dialyzate, obtain the optical Response carboxymethyl chitosan derivative；
(5) preparation of optical Response controlled release nanometer pesticidal preparations：
Medicine method is carried using original position, optical Response carboxymethyl chitosan derivative and agricultural chemicals is dispersed in water simultaneously, ultrasound
After dispersion, the controlled release nanometer pesticidal preparations of the optical Response are obtained final product.
In the above method, the reduced pressure distillation process is：Using Rotary Evaporators, 100 revs/min of rotating speed, temperature setting
35℃。
In the above method, the freeze drying process is：First by sample in minus 20 degrees pre-freeze overnight, by freeze drier
Vacuumize, when temperature drops to subzero 100 degrees Celsius, be put into the good sample of pre-freeze, taken out after 24 hours.
In the above method, the ultrasonic disperse technique is：At room temperature, Ultrasound Instrument power is 100W, during working time/interval
Between be 2s/2s, totally 3 minutes.
In the above method, mass percent concentration is taken for 0.01%~5% photoresponse carboxymethyl chitosan derivative is water-soluble
Liquid, addition is accounted in the agricultural chemicals of the derivative aqueous solution quality 5%~50%, and the agricultural chemicals is Insecticides (tech) ＆ Herbicides (tech), plant growth tune
One kind in section agent, or several mixtures.
Optical Response controlled release nanometer pesticidal preparations prepared by the above method that the present invention is provided, it is under conditions of no light
Spray with target plant and insect surface or in vivo in application；Once said preparation is located at uses target plant and insect surface or internal,
Extraneous sun light stimulus release agricultural chemicals is then responded at any time.
The present invention has following major advantage compared with prior art：
(1) this dosage surface is negatively charged, and blade surface is positively charged, therefore the nano-particle can be adsorbed and kept away on blade face
Exempt from rain drop erosion, improve utilization ratio of drug.
(2) this preparation is first contained in photoresponse nanoparticle agricultural chemicals, response can be realized under sunshine, and can reach slow
The effect (release more than 95% in 8 hours) of Slow release, under unglazed irradiation, without drug leakage, (drug release rate is small substantially
In 4%), spraying times can be reduced, improve medicine functioning efficiency.
(3) nanoparticle that this preparation is formed by two molecular self-assemblings, with preferable anti-dilution stability (critical micell
Concentration is low up to 0.019mg/ml), with the micellar phase based on surface-active than with stability higher.
Brief description of the drawings
Fig. 1 is that (NBS is in CDCl for the nuclear magnetic spectrum of adjacent nitro benzyl monomester succinate for preparing of the present invention3In1H-NMR schemes
Spectrum).
Fig. 2 is that (carboxymethyl chitosan (CMCS) is in D for the nuclear magnetic spectrum of carboxymethyl chitosan for preparing of the present invention2In O1H-
NMR spectra).
Fig. 3 is nuclear magnetic spectrum (the amphipathic carboxymethyl shell of photoresponse of optical Response carboxymethyl chitosan prepared by the present invention
Polysaccharid derivative (NBS-CMCS) is in DMSO-d6/D2O(1:3, v/v) in1H-NMR collection of illustrative plates).
Fig. 4 is the infared spectrum of carboxymethyl chitosan prepared by the present invention and optical Response carboxymethyl chitosan.
Fig. 5 is that optical Response carboxymethyl chitosan prepared by the present invention radiates different time sections under 365nm ultraviolet lights
Ultraviolet absorption curve.
Fig. 6 is transmission electron microscope picture of the optical Response controlled release nanometer micella of present invention preparation before 365nmUV illumination.
Fig. 7 is transmission electron microscope picture of the optical Response controlled release nanometer micella of present invention preparation after 365nmUV illumination.
Fig. 8 is the tablets in vitro curve map of optical Response controlled release nanometer pesticidal preparations prepared by the present invention, and the figure is reflected
Optical Response controlled release nanometer preparation prepared by embodiment 1 and embodiment 4 has illumination or non-illuminated conditions in pH7.0 cushioning liquid
Lower medicine releasing curve diagram (being model agricultural chemicals with diuron).As control sample, under conditions of light radiation, diuron is loaded
Two kinds of controlled release nanometer pesticidal preparations only 4.33% and 3.35% diuron is released respectively in 4h in the cushioning liquid of pH7.0
Put；And under simulated solar light irradiation, within two hours, there is 75.80% and 71.80% diuron from two kinds of samples respectively
In discharge.Further extend following exposure to the time under simulated solar irradiation, the release of diuron may proceed to increase, accumulation
Release rate respectively reaches 98.30% and 96.60% in 5h.In Fig. 8：(200-2500nm spectrum are defeated for ■ simulated solars light irradiation
Go out, 50W radiant outputs)；Irradiation that ▲ is unglazed.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described, but is not limited solely to the following examples.
Embodiment 1：
(1) preparation of adjacent nitro benzyl monomester succinate：
It is 1 to weigh mol ratio:2 nitro alcohols are dissolved in chloroform with succinyl oxide, are incorporated as the amount of raw material
The catalyst DMAP (DMAP) of 0.2 times of amount, under nitrogen environmental protection, back flow reaction 24h, after stopping reaction,
Vacuum distillation removes part chloroform, residual reaction liquid with concentration of volume percent for 10% (v/v) HCl solution washs three times, so
It is that 10% (v/v) HCl solution adjusts water phase pH with concentration of volume percent after using the sodium bicarbonate solution extracting and washing of saturation afterwards
To 5, there are a large amount of white precipitates to generate.White depositions are collected, in 40 degrees Celsius of vacuum drying, adjacent nitro benzyl butanedioic acid is obtained final product
Monoesters (NBS).
The vacuum drying process parameter is：Vacuum<133Pa, temperature：40 DEG C, drying time：24h.
(2) preparation of the adjacent nitro benzyl monomester succinate DMSO solution of NHS and EDCHCl activation：
Take adjacent nitro benzyl monomester succinate and be dissolved in DMSO, be stirred at room temperature uniformly, it is 10% that weight percent concentration is obtained
Adjacent nitro benzyl monomester succinate DMSO solution.The solution is cooled to 0-5 DEG C, by adjacent nitro benzyl monomester succinate：N- hydroxyls
Base succinimide (NHS)：1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDCHCl) is 1：1.1：
1.1 mol ratio delivers NHS and EDCHCl successively, and room temperature reaction 24h, reacting liquid filtering is obtained and lived through NHS and EDCHCl
The adjacent nitro benzyl monomester succinate DMSO solution of change.
(3) preparation of optical Response carboxymethyl chitosan：
It is the carboxymethyl chitosan sugar aqueous solution that 0.75, weight percent concentration is 2.0% to take degree of substitution by carboxymethyl, according to carboxylic
Methyl chitosan unit is 1 with adjacent nitro benzyl monomester succinate mol ratio:0.07 adds the neighbour activated through NHS and EDCHCl
The DMSO solution of nitrobenzyl monomester succinate, in after the lower reaction 6h of room temperature, lucifuge and nitrogen protection, with deionized water dialyse to
Neutrality, freeze-drying obtains optical Response carboxymethyl chitosan.
The freeze drying process parameter is：Temperature：- 100 DEG C, vacuum：<10Pa, time：24h.
(4) the optical Response carboxymethyl chitosan sugar aqueous solution that weight percent concentration is 2% is taken, addition accounts for the derived material
The herbicide of amount 35%, ultrasonic oxidation sulfydryl obtains final product optical Response carboxymethyl chitosan controlled release nanometer pesticidal preparations.Can when using
Effective dose according to herbicide is suitably added water preparation, and spraying is used.
The ultrasonic oxidation sulfydryl technique is：Power 100W, ultrasonic 3min.
Embodiment 2：
(1) preparation of adjacent nitro benzyl monomester succinate：
With embodiment 1.
(2) preparation of the adjacent nitro benzyl monomester succinate DMF solution of NHS and EDCHCl activation：
Take adjacent nitro benzyl monomester succinate and be dissolved in DMF, it is 20% that uniformly prepared weight percent concentration is stirred at room temperature
Adjacent nitro benzyl monomester succinate DMF solution.The solution is cooled to 0-5 DEG C, by adjacent nitro benzyl monomester succinate：N- hydroxyl ambers
Amber acid imide (NHS)：1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDCHCl) is 1：1.1：1.1
Mol ratio delivers NHS and EDCHCl successively, and room temperature reaction 24h, reacting liquid filtering obtains what is activated through NHS and EDCHCl
Adjacent nitro benzyl monomester succinate DMF solution.
(3) preparation of optical Response carboxymethyl chitosan
It is the carboxymethyl chitosan sugar aqueous solution that 1.2, weight percent concentration is 1.0% to take degree of substitution by carboxymethyl, according to carboxylic
Methyl chitosan unit is 1 with adjacent nitro benzyl monomester succinate mol ratio:0.3 adds the neighbour activated through NHS and EDCHCl
The DMF solution of nitrobenzyl monomester succinate, in after the lower reaction 6h of room temperature, lucifuge and nitrogen protection, with deionized water dialyse to
Neutrality, freeze-drying obtains optical Response carboxymethyl chitosan.
(4) the optical Response carboxymethyl chitosan sugar aqueous solution that weight percent concentration is 4% is taken, addition accounts for the derived material
The plant growth regulator of amount 6%, ultrasonic disperse obtains final product optical Response carboxymethyl chitosan controlled release nanometer pesticidal preparations.When using
Can suitably be added water preparation according to the effective dose of plant growth regulator, spraying is used.
Embodiment 3：
(1) preparation of adjacent nitro benzyl monomester succinate：
With embodiment 1.
(2) preparation of the adjacent nitro benzyl monomester succinate DMF solution of NHS and EDCHCl activation：
Take adjacent nitro benzyl monomester succinate and be dissolved in DMF, it is 15% that uniformly prepared weight percent concentration is stirred at room temperature
Adjacent nitro benzyl monomester succinate DMF solution.The solution is cooled to 0-5 DEG C, by adjacent nitro benzyl monomester succinate：N- hydroxyl ambers
Amber acid imide (NHS)：1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDCHCl) is 1：1.1：1.1
Mol ratio delivers NHS and EDCHCl successively, and room temperature reaction 24h, reacting liquid filtering obtains what is activated through NHS and EDCHCl
Adjacent nitro benzyl monomester succinate DMF solution.
(3) preparation of optical Response carboxymethyl chitosan
It is the carboxymethyl chitosan sugar aqueous solution that 1.6, weight percent concentration is 5.0% to take degree of substitution by carboxymethyl, according to carboxylic
Methyl chitosan unit is 1 with adjacent nitro benzyl monomester succinate mol ratio:0.5 adds the neighbour activated through NHS and EDCHCl
The DMF solution of nitrobenzyl monomester succinate, in after the lower reaction 6h of room temperature, lucifuge and nitrogen protection, with deionized water dialyse to
Neutrality, freeze-drying obtains optical Response carboxymethyl chitosan.
(4) the optical Response carboxymethyl chitosan sugar aqueous solution that weight percent concentration is 1% is taken, addition accounts for the derived material
The insecticide of amount 30%, ultrasonic disperse obtains final product optical Response carboxymethyl chitosan controlled release nanometer pesticidal preparations.Can basis when using
The effective dose of the agent of desinsection is suitably added water preparation, and spraying is used.
Embodiment 4：
(1) preparation of adjacent nitro benzyl monomester succinate：
With embodiment 1.
(2) preparation of the adjacent nitro benzyl monomester succinate DMSO solution of NHS and EDCHCl activation：
With embodiment 1.
(3) preparation of optical Response carboxymethyl chitosan
It is the carboxymethyl chitosan sugar aqueous solution that 0.75, weight percent concentration is 5.0% to take degree of substitution by carboxymethyl, according to carboxylic
Methyl chitosan unit is 1 with adjacent nitro benzyl monomester succinate mol ratio:0.15 adds the neighbour activated through EDCHCl and NHS
Nitrobenzyl monomester succinate DMSO solution, in after the lower reaction 6h of room temperature, lucifuge and nitrogen protection, is dialysed into deionized water
Property, freeze-drying obtains optical Response carboxymethyl chitosan.
(4) the optical Response carboxymethyl chitosan sugar aqueous solution that weight percent concentration is 2% is taken, addition accounts for the derived material
The herbicide of amount 40%, ultrasonic disperse obtains final product optical Response carboxymethyl chitosan controlled release nanometer pesticidal preparations.Can basis when using
The effective dose of herbicide is suitably added water preparation, and spraying is used.
Embodiment 5：
(1) preparation of adjacent nitro benzyl monomester succinate：
With embodiment 1.
(2) preparation of the adjacent nitro benzyl monomester succinate DMSO and DMF mixed solutions of NHS and EDCHCl activation：
Take adjacent nitro benzyl monomester succinate and be dissolved in DMSO and DMF (volume ratios 1：10) uniformly prepared weight, is stirred at room temperature
Percent concentration is 15% adjacent nitro benzyl monomester succinate DMSO and DMF mixed solutions.The solution is cooled to 0-5 DEG C, presses
Adjacent nitro benzyl monomester succinate：N-hydroxy-succinamide (NHS)：1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride (EDCHCl) is 1：1.1：1.1 mol ratio delivers NHS and EDCHCl, room temperature reaction 24h, reaction solution mistake successively
Filter, obtains the adjacent nitro benzyl monomester succinate DMSO and DMF mixed solutions activated through NHS and EDCHCl.
(3) preparation of optical Response carboxymethyl chitosan
It is the carboxymethyl chitosan sugar aqueous solution that 1.6, weight percent concentration is 5.0% to take degree of substitution by carboxymethyl, according to carboxylic
Methyl chitosan unit is 1 with adjacent nitro benzyl monomester succinate mol ratio:1.0 add the neighbour activated through NHS and EDCHCl
DMSO and the DMF mixed solution of nitrobenzyl monomester succinate, in after the lower reaction 6h of room temperature, lucifuge and nitrogen protection, spend from
Sub- water is dialysed to neutrality, and freeze-drying obtains optical Response carboxymethyl chitosan.
(4) the optical Response carboxymethyl chitosan sugar aqueous solution that weight percent concentration is 3% is taken, addition accounts for the derived material
The insecticide of amount 35%, ultrasonic disperse obtains final product optical Response carboxymethyl chitosan controlled release nanometer pesticidal preparations.Can basis when using
The effective dose of insecticide is suitably added water preparation, and spraying is used.
Embodiment 6：
(1) preparation of adjacent nitro benzyl monomester succinate：
With embodiment 1.
(2) preparation of the adjacent nitro benzyl monomester succinate DMF and DMSO mixed solutions of NHS and EDCHCl activation：
Take adjacent nitro benzyl monomester succinate and be dissolved in DMF and DMSO (volume ratios 1：50) uniformly prepared weight, is stirred at room temperature
Percent concentration is 60% adjacent nitro benzyl monomester succinate DMF and DMSO mixed solutions.The solution is cooled to 0-5 DEG C, presses
Adjacent nitro benzyl monomester succinate：N-hydroxy-succinamide (NHS)：1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride (EDCHCl) is 1：1.1：1.1 mol ratio delivers NHS and EDCHCl, room temperature reaction 24h, reaction solution mistake successively
Filter, obtains the adjacent nitro benzyl monomester succinate DMF and DMSO mixed solutions activated through EDCHCl and NHS.
(3) preparation of optical Response carboxymethyl chitosan
It is the carboxymethyl chitosan sugar aqueous solution that 0.8, weight percent concentration is 0.8% to take degree of substitution by carboxymethyl, according to carboxylic
Methyl chitosan unit is 1 with adjacent nitro benzyl monomester succinate mol ratio:1.1 add the neighbour activated through NHS and EDCHCl
DMF and the DMSO mixed solution of nitrobenzyl monomester succinate, in after the lower reaction 6h of room temperature, lucifuge and nitrogen protection, spend from
Sub- water is dialysed to neutrality, and freeze-drying obtains optical Response carboxymethyl chitosan.
(4) the optical Response carboxymethyl chitosan sugar aqueous solution that weight percent concentration is 0.05% is taken, addition accounts for the derivative
The herbicide of amount of substance 50%, ultrasonic disperse obtains final product optical Response carboxymethyl chitosan controlled release nanometer pesticidal preparations.Can when using
Effective dose according to herbicide is suitably added water preparation, and spraying is used.
Take the optical Response carboxymethyl chitosan prepared in above-described embodiment 1,2,3,4,5 and 6, the spoke of UV at 365nm
Penetrate down, determine change of its ultraviolet absorption curve with UV radiated times, characterize its UV photodissociation behavior.
The blank formulation sample (without the sample of agricultural chemicals) prepared in above-described embodiment 1,2,3,4,5 and 6 is taken, using saturating
Metamorphosis before and after the radiation of radio sem observation UV, characterizes its photoresponse behavior.
After the optical Response controlled release nanometer pesticidal preparations freeze-drying that will be prepared in above-described embodiment 1,2,3,4,5 and 6, point
It is not dissolved in the cushioning liquid that pH is 7.0, under different illumination conditions, with tiring out for Syrups by HPLC nano-pesticide formulation
Product medicine realeasing rate, studies its tablets in vitro behavior.It is specific as follows：
After nano-pesticide formulation freeze-drying in above-described embodiment, a certain amount of sample dispersion is taken in PBS
In (0.1M, pH7.0), bag filter (cutoff is then put into：14000).Bag filter is introduced and is delayed equipped with 80mL phosphate
In the plunger taper bottle of fliud flushing, and conical flask is put into constant-temperature table, control temperature is at 25 ± 1 DEG C, and earthquake state is underlying
In radiation under uviol lamp.In being spaced between in due course, 2mL sample solutions are taken out, add new 2mLPBS, examined using HPLC
Survey insoluble drug release.There is no the sample of illumination as control sample.
Radiated using simulated solar irradiation substitution UV, nano-pesticide formulation releases in the evaluable above-described embodiment of same method
Medicine behavior.Solar simulator is 300W xenon arc lamps (200-2500nm spectrum are exported, 50W radiant outputs).
Drug concentration is calculated by pesticide standard curve.The cumulative release rate (Re) of agricultural chemicals is calculated using below equation：
Re=Mt/M0
In formula：Re is the cumulative release rate of nanometer formulation；MtFor nanometer formulation is released in cushioning liquid in the accumulation of time t
Dose；M0It is the agricultural chemicals gross mass contained in nanometer formulation.
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 controlled release nanometer pesticidal preparations, it is characterized in that said preparation controlled release of active ingredients is amphipathic carboxymethyl shell
Polysaccharid derivative, it is obtained by adjacent nitro benzyl monomester succinate and carboxymethyl chitosan reaction.
2. optical Response controlled release nanometer pesticidal preparations according to claim 1, it is characterised in that described amphipathic carboxylic first
Base enclosure polysaccharid derivative, is made up of following methods：
The aqueous solution of carboxymethyl chitosan is first taken, according to sugar unit and the adjacent nitro benzyl monomester succinate of carboxymethyl chitosan
Mol ratio is 1：(0.01~1) in adjacent nitro benzyl monomester succinate organic solution of the addition through EDCHCl and NHS activation, room
The lower reaction 6h of temperature, obtains amphipathic carboxymethyl chitosan solution；The organic solution is molten dimethyl sulfoxide (DMSO), dimethylformamide
One kind in liquid, or its two kinds mixed solutions of any weight proportion composition；
Again through dialysis, freeze-drying, amphipathic carboxymethyl chitosan derivative is obtained, it is that optical Response carboxymethyl chitosan spreads out
It is biological.
3. optical Response controlled release nanometer pesticidal preparations according to claim 2, it is characterized in that pressing 1:0.2 mol ratio, by light
Response carboxymethyl chitosan derivative and agricultural chemicals are dispersed in water simultaneously, and ultrasonic 3min obtains optical Response controlled release nanometer agricultural chemicals
Preparation.
4. optical Response controlled release nanometer pesticidal preparations according to claim 3, it is characterised in that described agricultural chemicals is desinsection
One kind in agent, herbicide or plant growth regulator, or several mixtures.
5. a kind of preparation method of optical Response controlled release nanometer pesticidal preparations, it is characterized in that using comprising the following steps method：
(1) preparation of carboxymethyl chitosan sugar aqueous solution：
The carboxymethyl chitosan that degree of substitution by carboxymethyl is 0.1~1.8 is added to the water, the weight of carboxymethyl chitosan sugar aqueous solution
Percent concentration is 0.08~10%, is then stirred at room temperature, obtains the carboxymethyl chitosan sugar aqueous solution；
(2) synthesis of adjacent nitro benzyl monomester succinate：
It is 1 first to weigh mol ratio:2 nitro alcohol is dissolved in chloroform with succinyl oxide, adds catalyst 4- dimethylaminos
Pyridine, under nitrogen environmental protection, back flow reaction 24h, after stopping reaction, vacuum distillation removes part chloroform, and residual reaction liquid is used
The HCl solution of mass concentration 10% (w/w) is washed three times, then with the sodium bicarbonate solution extracting and washing of saturation after, it is dense with quality
The HCl solution regulation water phase pH to 5 of 10% (w/w) is spent, white depositions are collected, then white depositions are done in 40 DEG C of vacuum
It is dry, obtain the adjacent nitro benzyl monomester succinate；
(3) preparation of the adjacent nitro benzyl monomester succinate organic solution of NHS and EDCHCl activation：
Adjacent nitro benzyl monomester succinate is first dissolved in organic solvent, is stirred at room temperature, weight percent concentration is obtained
It is 5%~85% adjacent nitro benzyl monomester succinate organic solution；The organic solution is cooled to 0-5 DEG C again, by adjacent nitro
Benzyl monomester succinate：N-hydroxy-succinamide (NHS)：1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides
(EDCHCl) it is 1：1.1：1.1 mol ratio delivers NHS and EDCHCl successively, then in room temperature reaction 24h, by reaction solution
Filtering, obtains the adjacent nitro benzyl monomester succinate organic solution of the NHS and EDCHCl activation；
(4) preparation of optical Response carboxymethyl chitosan derivative：
The aqueous solution of carboxymethyl chitosan is first taken, is 1 according to the sugar unit of carboxymethyl chitosan and the mol ratio of adjacent nitro benzyl ester：
(0.01~1) the adjacent nitro base monomester succinate organic solution activated through NHS and EDCHCl is added, is dialysed in deionized water
48h, then freeze-drying dialyzate, obtain the optical Response carboxymethyl chitosan derivative；
(5) preparation of optical Response controlled release nanometer pesticidal preparations：
Medicine method is carried using original position, optical Response carboxymethyl chitosan derivative and agricultural chemicals is dispersed in water simultaneously, ultrasonic disperse
Afterwards, the controlled release nanometer pesticidal preparations of the optical Response are obtained final product.
6. the preparation method of optical Response controlled release nanometer pesticidal preparations according to claim 5, it is characterised in that described to subtract
Pressure distillation technique be：Using Rotary Evaporators, 100 revs/min of rotating speed, 35 DEG C of temperature setting.
7. the preparation method of optical Response controlled release nanometer pesticidal preparations according to claim 5, it is characterised in that described cold
Lyophilized drying process is：First by sample in minus 20 degrees pre-freeze overnight, freeze drier is vacuumized, temperature drops to subzero 100 and takes the photograph
When family name spends, the good sample of pre-freeze is put into, is taken out after 24 hours.
8. the preparation method of optical Response controlled release nanometer pesticidal preparations according to claim 5, it is characterised in that described super
Sound dispersing technology is：At room temperature, Ultrasound Instrument power is 100W, and working time/intermittent time is 2s/2s, totally 3 minutes.
9. the preparation method of optical Response controlled release nanometer pesticidal preparations according to claim 5, it is characterised in that：Take quality
Percent concentration is 0.01%~5% photoresponse carboxymethyl chitosan derivative aqueous solution, and addition accounts for the derivative aqueous solution matter
In the agricultural chemicals of amount 5%~50%, the agricultural chemicals is the one kind in Insecticides (tech) ＆ Herbicides (tech), plant growth regulator, or several mixing
Thing.
10. the optical Response controlled release nanometer pesticidal preparations that in claim 5 to 9 prepared by any methods described, it is in no light
Under the conditions of spray with target plant and insect surface or in vivo in application；Once said preparation be located at target plant and insect surface or
In vivo, then extraneous sun light stimulus release agricultural chemicals is responded at any time.
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| CN109769803A (en) * | 2017-11-14 | 2019-05-21 | 北京纳威克生物科技开发有限公司 | A kind of pesticide polyelectrolyte nano-micelle and preparation method thereof |
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| CN110651786B (en) * | 2018-06-29 | 2021-09-03 | 澳门大学 | Sunlight sensitive type herbicide nanocapsule and preparation method and application thereof |
| CN108969480A (en) * | 2018-07-23 | 2018-12-11 | 武汉理工大学 | A kind of near infrared light responsiveness light moves controlled drug delivery system and preparation method thereof |
| CN111296425A (en) * | 2020-03-31 | 2020-06-19 | 陕西地建土地工程技术研究院有限责任公司 | Preparation method of light-operated pesticide release control agent and light-operated pesticide release control agent |
| CN111919843A (en) * | 2020-08-13 | 2020-11-13 | 贵州大学 | Photoresponsive chitosan-based nano pesticide and preparation method thereof |
| CN113082083A (en) * | 2021-04-26 | 2021-07-09 | 杭州仁德医药有限公司 | Easily-torn traditional Chinese medicine ointment patch for allergic dermatitis and preparation method thereof |
| CN116199799A (en) * | 2022-12-08 | 2023-06-02 | 安徽工业大学 | Photo-crosslinking GSH/ROS response targeting chitosan-based drug carrier, preparation method and application |
| CN116199799B (en) * | 2022-12-08 | 2024-06-04 | 安徽工业大学 | Photo-crosslinking GSH/ROS response targeting chitosan-based drug carrier, preparation method and application |
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