CN110477032A - A kind of hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan carries powder and preparation method thereof - Google Patents

A kind of hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan carries powder and preparation method thereof Download PDF

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Publication number
CN110477032A
CN110477032A CN201910633498.8A CN201910633498A CN110477032A CN 110477032 A CN110477032 A CN 110477032A CN 201910633498 A CN201910633498 A CN 201910633498A CN 110477032 A CN110477032 A CN 110477032A
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chitosan
preparation
carboxymethyl chitosan
hydroxypropyl
aieas
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张清仲
贾志欣
曾雪淇
贾德民
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN201910633498.8A priority Critical patent/CN110477032A/en
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/26Biocides, 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 in coated particulate form
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/26Biocides, 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 in coated particulate form
    • A01N25/28Microcapsules or nanocapsules
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N65/00Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08Magnoliopsida [dicotyledons]
    • A01N65/12Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Mycology (AREA)
  • Microbiology (AREA)
  • Natural Medicines & Medicinal Plants (AREA)
  • Biotechnology (AREA)
  • Pest Control & Pesticides (AREA)
  • Toxicology (AREA)
  • Botany (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of, and the hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan carries powder and preparation method thereof.Drug used in the present invention is the extract of Eupatorium adenophorum, is named as AIEAS, it is the compound polyelectrolyte formed with hydroxypropyl chitosan and carboxymethyl chitosan by electrostatic interaction that hydroxypropyl chitosan/carboxymethyl chitosan, which carries powder,.The compound polyelectrolyte, which is dispersed in water phase, is presented light blue opalescence, by granularmetric analysis and scanning electron microscopic observation, it is found that it is a kind of micron-sized polydispersion spherical particle.Hydroxypropyl chitosan of the invention/carboxymethyl chitosan, which carries powder, has slow release, biological degradability, not only clean and environmental protection, but also can come into full contact with crop.From the selection of carrier base material, chitosan and its derivative has the functions such as many characteristics, such as disinfection and deinsectization, pesticide synergistic, not only extends the application range of Eupatorium adenophorum, new direction is also opened for pesticide slow-release dosage form.

Description

A kind of hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan load Powder and preparation method thereof
Technical field
The invention belongs to carry powder subdomains, and in particular to and a kind of hydroxypropyl chitosan based on purple stem boneset extract/ Carboxymethyl chitosan carries powder and preparation method thereof.
Background technique
Along with the rapid development of chemical pesticide, there are the problem of gradually display.Since chemical pesticide toxicity is big, It is not easily decomposed, can cause largely to remain in the soil after long-time service, and then threaten human health or even the entire ecosystem.Often Year largely using after pesticide, the only pesticide of 0.1 % or so can act on target disease pest weeds, the pesticide of 99.9 % then into Enter Agro-ecological System.Eupatorium adenophorum is a kind of invasive weeds, threatens the ecological environment balance in China for a long time.From purple It can extract the substances such as alkaloid, terpenes, flavones, Phenylpropanoid Glycosides, steroidal in stem Herba Lycopi, there is desinsection, food refusal, inhibit growth hair The effects of educating, is antibacterial substitutes traditional chemical pesticide with purple stem boneset extract, can play to Eupatorium adenophorum a degree of It prevents and kill off, moreover it is possible to turn bane into boon, acquisition toxicity is smaller, remains less botanical pesticide.But since botanical pesticide belongs to plant Secondary metabolite, performance is unstable, is easy to be degraded in the natural environment, so research and develop one kind can coating medicine to maintain Pesticide stability, and the drug delivery technologies of pesticide sustained release can be made extremely urgent.
Pesticide water fundamental mode dosage form is a kind of novel sustained-release dosage type, not only clean and environmental protection, but also can be come into full contact with crop.From load It is seen in the selection of body host material, chitosan and its derivative has the function such as many characteristics, such as disinfection and deinsectization, pesticide synergistic Can, these features make chitosan and its derivative more attract attention in the preparation and application of pesticide slow-release system.
Studies have shown that introducing carboxymethyl in chitosan structure, water-soluble good polyampholyte carboxylic first is produced Base enclosure glycan (Carboxymethyl Chitosan, CMC).And in the case where not changing chitosan alkalinity and electropositive situation, In Hydroxypropyl is introduced on chitosan, and water-soluble positively charged hydroxypropyl chitosan (hydroxyl isopropyl can be prepared chitosan HPCTS).It is positively charged in neutral aqueous phase solution according to the formation basic theory of compound polyelectrolyte HPCTS can form Compound Water dispersed particle by electrostatic interaction with negatively charged CMC, prepare aqua type agriculture based on this Medicine sustained release preparation.Research of the country in relation to aqua type pesticide slow-release dosage form is less at present.
Summary of the invention
The drawbacks of the purpose of the present invention is being directed to existing chemical pesticide and the unstable deficiency of botanical pesticide, provide one Hydroxypropyl chitosan of the kind based on purple stem boneset extract/carboxymethyl chitosan carries powder and preparation method thereof.Of the invention Raw material have the functions such as many characteristics, such as disinfection and deinsectization, pesticide synergistic, and biodegradable, not only extend purple stem pool Blue application range, opens new direction also for pesticide slow-release dosage form.
AIEAS is coated in macromolecule carrier by the present invention by electrostatic interaction, is then successively adsorbed in outer layer positively charged Hydroxypropyl chitosan and electronegative carboxymethyl chitosan, ultimately form micron-sized drug-loaded polyelectrolyte compound.
The purpose of the present invention is achieved through the following technical solutions.
A kind of hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan load powder, load powder It is made of the raw material of following parts by weight:
1-10 parts of hydroxypropyl chitosan
1-10 parts of carboxymethyl chitosan
50 parts of water
1-5 parts of AIEAS;
The AIEAS is the extract of Eupatorium adenophorum.
A kind of above-described hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan carries powder Preparation method, comprising the following steps:
(1) stirring is lower prepares hydroxypropyl sugar juice and carboxymethyl chitosan solution;
(2) under agitation, isometric carboxymethyl chitosan solution is added dropwise into hydroxypropyl sugar juice, is added dropwise After the completion, continue to stir, obtain complex solution;
(3) AIEAS is added to the water ultrasonic dissolution, under the conditions of magnetic agitation, is added dropwise into hydroxypropyl sugar juice Carboxymethyl chitosan solution is added dropwise after being blended uniformly in AIEAS solution, continues stirring after being added dropwise to complete to get based on purple stem The hydroxypropyl chitosan of Herba Lycopi extract/carboxymethyl chitosan carries powder.
Preferably, step (1) stirring carries out under 90 DEG C of water-baths.
Preferably, the time of step (1) described stirring is 1-3h.
Preferably, the speed of step (2) described stirring is 500-1500rpm.
Preferably, in step (2), after being added dropwise to complete, continue to stir 10-30min.
Preferably, step (3) described AIEAS preparation the following steps are included:
Eupatorium adenophorum stem and leaf are dried, powder is beaten and are sieved, then hot reflux is carried out to dry powder with organic solvent, is revolved by decompression It steams, water phase removal of impurities is filtered for multiple times to obtain clear liquid, last forced air drying to constant weight obtains the extract A IEAS of Eupatorium adenophorum.
It is further preferred that the organic solvent is one of ethyl alcohol, methanol and ethyl acetate or a variety of;The air blast Dry is dry 48-96h under the conditions of 60-80 DEG C.
Preferably, the time of step (3) described blending is 3-7 min.
Preferably, in step (3), carboxymethyl chitosan solution continues to stir 10-30 min after being added dropwise to complete.
HPCTS/CMC/AIEAS of the invention is carried in powder, and HPCTS and CMC are respectively polycation and polyanion, Water-soluble good and biodegradable, the two can form compound polyelectrolyte by electrostatic interaction in neutral aqueous solution, with Aqua type medicament slow release dosage form is prepared based on this.Wherein chitosan and its derivative has disinfection and deinsectization, pesticide synergistic etc. all More characteristics are widely used in controlled drug delivery systems, pharmaceutical carrier.It is multiple that purple stem boneset extract AIEAS is covered by polyelectrolyte It closes in object structure, drug slow release, achievees the purpose that make to carry the sub- lasting medicine of powder.The combination of these components and each component Above-mentioned blend range, pass through many experiments determine.
The present invention carries the medicament slow release performance of powder by the test of absorption delaying agents immersion method.
Compared with prior art, the present invention has the advantage that
1, the drug used in the present invention is the extract A IEAS of Eupatorium adenophorum, belongs to the secondary metabolite of plant, in natural ring Not the problems such as not will cause residual difficult to degrade in border.
2, HPCTS/CMC/AIEAS of the invention, which carries powder, has slow release, biological degradability, is a kind of novel delay Release dosage form, not only clean and environmental protection, but also can be come into full contact with crop.
3, the botanical pesticide AIEAS that HPCTS/CMC/AIEAS of the invention is carried in powder can be compound from polyelectrolyte It is slowly released in object, drug release time is up to 168 hours.
Detailed description of the invention
Fig. 1 is the grain size distribution of HPCTS/CMC/AIEAS compound in embodiment 1.
Fig. 2 is the SEM picture of HPCTS/CMC/AIEAS compound in embodiment 2.
Fig. 3 is the cumulative release curve graph of AIEAS in the compound for using absorption delaying agents immersion method to measure in embodiment 3.
Specific embodiment
Specific implementation of the invention is further described below in conjunction with example and attached drawing, but embodiments of the present invention It is without being limited thereto.
Embodiment 1
(1) Eupatorium adenophorum stem, leaf are dried, beats powder, 15g dry powder is weighed after forced air drying and is wrapped up with filter paper, 100ml is then added Dehydrated alcohol extracts 12h.By extract vacuum rotary steam, water phase displacement removal of impurities repeatedly filters and obtains clear liquid, forced air drying to constant weight Up to botanical pesticide AIEAS.
(2) carboxymethyl chitosan of 0.2 g and the hydroxypropyl chitosan of 0.6 g are weighed respectively, under 90 DEG C of water-baths respectively Stirring is configured to the polyelectrolyte solution of 1 mg/ml and 3mg/ml.
(3) 50 mg AIEAS are taken, 10 ml deionized water ultrasonic dissolutions are added.Under the conditions of magnetic agitation, to 50 ml AIEAS solution is added dropwise in the HPCTS solution of 3mg/ml, after 3 min are blended, dropwise by the CMC solution of 50 ml 1mg/ml It is added in blended liquid, continues to stir 30 min after being added dropwise to complete.The complex solution made is sealed, is stored at room temperature.
(4) partial size of load powder is characterized using laser particle analyzer, Fig. 1 is HPCTS/CMC/AIEAS compound Grain size distribution.The result shows that the system particle central diameter is 17.67 μm, and is distributed in polydispersion.It is immersed using absorption delaying agents Method Experimental Characterization carries the cumulative release behavior of AIEAS in powder, and the entire test period is 7 days.Experiment show AIEAS with The time increase cumulative release amount be gradually increased, cumulative release amount is reaching 57.6% after a week.
Embodiment 2
(1) Eupatorium adenophorum stem, leaf are dried, beats powder, 15g dry powder is weighed after forced air drying and is wrapped up with filter paper, 100ml is then added Dehydrated alcohol extracts 12h.By extract vacuum rotary steam, water phase displacement removal of impurities repeatedly filters and obtains clear liquid, forced air drying to constant weight Up to botanical pesticide AIEAS.
(2) carboxymethyl chitosan of 0.4 g and the hydroxypropyl chitosan of 1.2 g are weighed respectively, under 90 DEG C of water-baths respectively Stirring is configured to the polyelectrolyte solution of 2 mg/ml and 6 mg/ml.
(3) 100 mg AIEAS are taken, 20 ml deionized water ultrasonic dissolutions are added.Under the conditions of magnetic agitation, to 100 ml Be added dropwise AIEAS solution in the HPCTS solution of 6mg/ml, after 5 min are blended, by the CMC solution of 100 ml 2mg/ml by It is added dropwise in blended liquid, continues to stir 25 min after being added dropwise to complete.The complex solution made is sealed, room temperature is protected It deposits.
(4) using the microscopic appearance of scanning electron microscope observation HPCTS/CMC/AIEAS compound.Fig. 2 is HPCTS/ Square structure is presented under Electronic Speculum by freeze-drying sample preparation, load powder in the SEM picture of CMC/AIEAS compound, discovery, The hexagonal crystal system being similar in crystallographic system.Illustrate after drug AIEAS is added, crystal seed can be provided in aqueous solution, then makees in electrostatic With with the hexagonal crystal grain to form HPCTS/CMC/AIEAS of gradually growing up under mechanical shearing double action.It is immersed using absorption delaying agents Method Experimental Characterization carries the cumulative release behavior of AIEAS in powder, and the entire test period is 14 days.Experiment show AIEAS with The time increase cumulative release amount be gradually increased, cumulative release amount reaches 73.4% after two weeks.
Embodiment 3
(1) Eupatorium adenophorum stem, leaf are dried, beats powder, 15g dry powder is weighed after forced air drying and is wrapped up with filter paper, 100ml is then added Dehydrated alcohol extracts 12h.By extract vacuum rotary steam, water phase displacement removal of impurities repeatedly filters and obtains clear liquid, forced air drying to constant weight Up to botanical pesticide AIEAS.
(2) carboxymethyl chitosan of 0.2 g and the hydroxypropyl chitosan of 0.8 g are weighed respectively, under 90 DEG C of water-baths respectively Stirring is configured to the polyelectrolyte solution of 1 mg/ml and 4 mg/ml.
(3) 50 mg AIEAS are taken, 10 ml deionized water ultrasonic dissolutions are added.Under the conditions of magnetic agitation, to 50 ml Be added dropwise AIEAS solution in the HPCTS solution of 4mg/ml, after 5 min are blended, by the CMC solution of 50 ml 1mg/ml by It is added dropwise in blended liquid, continues to stir 20 min after being added dropwise to complete.The complex solution made is sealed, room temperature is protected It deposits.
(4) the cumulative release behavior of AIEAS in powder is carried using absorption delaying agents immersion method Experimental Characterization, Fig. 3 is HPCTS/CMC/AIEAS compound is immersed in the water the cumulative release curve of rear AIEAS.Experiment shows that AIEAS increases with the time Cumulative release amount is gradually increased, and the rate of release of AIEAS is very fast in first 12 hours, and in t=12 h, cumulative release amount reaches To 41.5%.It is in 12-168 h immersing the time, the rate of release of AIEAS gradually becomes smaller, this is because in first 12 hours A large amount of drug is released, medication amount in HPCTS/CMC/AIEAS is caused to reduce, so the sustained release rate of later period AIEAS slows down.

Claims (10)

1. a kind of hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan carries powder, which is characterized in that should Powder is carried to be made of the raw material of following parts by weight:
1-10 parts of hydroxypropyl chitosan
1-10 parts of carboxymethyl chitosan
50 parts of water
1-5 parts of AIEAS;
The AIEAS is the extract of Eupatorium adenophorum.
2. preparing a kind of hydroxypropyl chitosan based on purple stem boneset extract described in claim 1/carboxymethyl chitosan to carry The method of powder, which comprises the following steps:
(1) stirring is lower prepares hydroxypropyl sugar juice and carboxymethyl chitosan solution;
(2) under agitation, isometric carboxymethyl chitosan solution is added dropwise into hydroxypropyl sugar juice, is added dropwise After the completion, continue to stir, obtain complex solution;
(3) AIEAS is added to the water ultrasonic dissolution, under the conditions of magnetic agitation, is added dropwise into hydroxypropyl sugar juice Carboxymethyl chitosan solution is added dropwise after being blended uniformly in AIEAS solution, continues stirring after being added dropwise to complete to get based on purple stem The hydroxypropyl chitosan of Herba Lycopi extract/carboxymethyl chitosan carries powder.
3. preparation method according to claim 2, which is characterized in that step (1) stirring carries out under 90 DEG C of water-baths.
4. preparation method according to claim 2, which is characterized in that the time of step (1) described stirring is 1-3h.
5. preparation method according to claim 2, which is characterized in that the speed of step (2) described stirring is 500- 1500rpm。
6. preparation method according to claim 2, which is characterized in that in step (2), carboxymethyl chitosan solution is dripped Cheng Hou continues to stir 10-30min.
7. preparation method according to claim 2, which is characterized in that the preparation of step (3) described AIEAS includes following step It is rapid:
Eupatorium adenophorum stem and leaf are dried, powder is beaten and are sieved, then hot reflux is carried out to dry powder with organic solvent, is revolved by decompression It steams, water phase removal of impurities is filtered for multiple times to obtain clear liquid, last forced air drying to constant weight obtains the extract A IEAS of Eupatorium adenophorum.
8. preparation method according to claim 7, which is characterized in that the organic solvent is ethyl alcohol, methanol and acetic acid second One of ester is a variety of;The forced air drying is dry 48-96h under the conditions of 60-80 DEG C.
9. preparation method according to claim 2, which is characterized in that the time of step (3) described blending is 3-7 min.
10. preparation method according to claim 2, which is characterized in that in step (3), carboxymethyl chitosan solution is added dropwise Continue to stir 10-30 min after the completion.
CN201910633498.8A 2019-07-15 2019-07-15 A kind of hydroxypropyl chitosan based on purple stem boneset extract/carboxymethyl chitosan carries powder and preparation method thereof Pending CN110477032A (en)

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Publication number Priority date Publication date Assignee Title
AU2002304373A1 (en) * 2002-02-12 2003-09-04 Ranbaxy Laboratories Limited Glucosamine-polyacrylate inter-polymer complex and applications thereof
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CN1698901A (en) * 2005-06-15 2005-11-23 蒋斯扬 Chitosan or its derivative as drug carrier for carrying red sage root extract
CN101317588A (en) * 2007-06-08 2008-12-10 中国农业科学院植物保护研究所 Application of eupatorium adenophorum extracting solution as plant source pesticide
CN101856432A (en) * 2010-05-19 2010-10-13 南京农业大学 Preparation method of chitosan nanoparticles encapsulated tea polyphenol
CN105055372A (en) * 2015-08-18 2015-11-18 华中农业大学 Method for preparing carboxymethyl konjac glucomannan nano drug carrying microspheres
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