CN105123789A - Rhubarb free anthraquinone nanometer emulsion preparation for preventing and treating plant red spider disease - Google Patents

Rhubarb free anthraquinone nanometer emulsion preparation for preventing and treating plant red spider disease Download PDF

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Publication number
CN105123789A
CN105123789A CN201510623246.9A CN201510623246A CN105123789A CN 105123789 A CN105123789 A CN 105123789A CN 201510623246 A CN201510623246 A CN 201510623246A CN 105123789 A CN105123789 A CN 105123789A
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rheum
percent
nanometer emulsion
nano
rhubarb
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CN105123789B (en
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史彦斌
李金成
李红玉
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Sheng Xin Source Biological Technical Developing Co ltd
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Lanzhou University
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Abstract

The invention belongs to the technical field of biopesticide, and particularly relates to a recipe and a preparation process of a rhubarb free anthraquinone nanometer emulsion preparation, and application of the rhubarb free anthraquinone nanometer emulsion preparation to the prevention and the treatment of the plant red spider disease. The rhubarb free anthraquinone is extracted from traditional Chinese medicine sorrel, rheum tanguticum or rheum officinale. Through being metered by the mass percentage of each ingredient contained in the nanometer emulsion, the content of the rhubarb free anthraquinone in the nanometer emulsion accounts for 0.05 to 0.16 percent; the oil phase in the nanometer emulsion accounts for 18 to 22 percent; the emulsifiers account for 16 to 20 percent; co-emulsifiers account for 4 to 6 percent; water accounts for 50 to 61 percent; stabilizing agents account for 1.0 percent; preservatives account for 0.1 percent; attaching agents account for 0.1 percent. The rhubarb free anthraquinone nanometer emulsion preparation can be used for preventing and treating the plant red spider disease. The free anthraquinone from the rhubarb free anthraquinone nanometer emulsion preparation disclosed by the invention is from the traditional chinese medicine rhubarb; the applicability of the extraction process is high; the raw material obtaining cost is low; the nanometer emulsion preparation is automatically formed; the process is simple; the quality is controllable; the mass production can be easily realized; excellent prevention and treatment effects are achieved on the plant red spider disease.

Description

A kind of free anthraquinones extracted from rheum nano-emulsion preparation for preventing and treating plant two spotted spider mite disease
Technical field
The invention belongs to pesticide field, particularly relating to a kind of free anthraquinones extracted from rheum nano-emulsion preparation for preventing and treating plant two spotted spider mite disease.
Background technology
Plant two spotted spider mite disease is extensively present on the plant stem-leafs such as various crop, vegetables, flowers, trees, the crops such as main harm Solanaceae, Curcurbitaceae, pulse family, Liliaceae and grass family.The two spotted spider mite kind of China, based on Tetranychus cinnabarinus, belongs to arachnids, Acarina, Tetranychidae, and distributed areas are extensive, and feeding habits are mixed, and can endanger 110 various plants.Two spotted spider mite breeding amount is large, and polypide is little not easily to be found, once find that it endanger, transfer velocity is fast, insect pest area greatly, and repeatedly superinfection crops.Hazard approach thrusts in blade with mouthpart to suck juice, and chlorophyll is damaged, and blade presents sallow point or patch, until whole blade orange, come off, the serious normal growth of plant that hinders is grown, and causes huge economic loss.At present the main agricultural chemicals used has the control plant two spotted spider mite such as propargite, dicofol, Rogor, pink bollworm are clean, Belmark sick.But along with the long-time use of chemical agent, two spotted spider mite is to the resistance which created in various degree, and control efficiency significantly reduces, and day by day the manifesting of the drawback such as chemical agent environmental pollution and high residue.Therefore, develop toxicity little, pollute little, residual less, the biopesticide of drug resistance can be avoided to be the task of top priority.
Botanical fungicide has person poultry safety, environmental friendliness, can natural degradation and the advantages such as noresidue.Rheum officinale [comprises sorrel (Rheumpalmatum); secondary to Rheum tanguticum Maxim (Rheumpalmatumvar.tanguticum) and Rheum officinale (Rheumofficinale)] be one of conventional plant resource Chinese medicine; its extract have rush down under, the effect such as anti-infective and neuroprotective activity, but have no the research of its inhibitory or killing effect to plant two spotted spider mite.Pharmaceutical dosage form can produce significant impact to the control efficiency of medicine, but kills activity as wetting powder and supensoid agent present by means of only the contacting of pathogenic microorganism on solid drug particles and plant corpus surface, but kills weak effect to the pathogenic microorganism of inside plants; Missible oil is not good in the adhesiveness of plant surface, ductility, farthest can not play the effect of medicine; The particle diameter of microemulsion usually at micron order, but effectively can not kill the pathogenic microorganism of inside plants tissue through the epidermis of plant stem-leaf.Nano-emulsion is less because playing particle diameter, has good mobility, can more effectively infiltrate in plant base of leaf, plays the biologically active of medicine, and preparation technology simple, can mix with arbitrary proportion with water, do not block shower nozzle, easy to use.Up to now, do not find that the sick active technology of the anti-plant two spotted spider mite of free anthraquinones extracted from rheum nano-emulsion preparation is open.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, there is provided a kind of using traditional Chinese medicine rheum officinale as raw material, the free anthraquinones extracted from rheum that obtained by acidolysis, abstraction and purification (mainly containing archen, aloe-emodin, Chrysophanol, Physcion and Rhein) is bulk drug, research and develop a kind of be exclusively used in control plant two spotted spider mite disease nano-emulsion preparation.
Technical scheme of the present invention: a kind of free anthraquinones extracted from rheum nano-emulsion preparation for preventing and treating plant two spotted spider mite disease, make with following raw material: with the mass percent of each component contained in nano-emulsion, free anthraquinones extracted from rheum content is 0.05-0.16%, and the oil phase in nano-emulsion accounts for 18 ~ 22%, emulsifier 16 ~ 20%, assistant for emulsifying agent 4 ~ 6%, water 50 ~ 61%, stabilizing agent 1.0%, preservative 0.1%, adhesive agent 0.1%.
Described oil phase is selected from isopropyl myristate, Sefsol 218, ethyl oleate, isopropyl palmitate, Miglyol 812N, castor oil and combination thereof.Wherein, preferred further Sefsol 218 and the mixture with ethyl oleate thereof, oil phase concentration is less than 30%.Described emulsifier is selected from polyoxyethylene-40-rilanit special, Labraso, Gelucire 44/14, Tween-80, poloxamer-188 and combination thereof.Wherein, preferred further polyoxyethylene-40-rilanit special; Described assistant for emulsifying agent is selected from TC, Macrogol 600, PEG400,1,2-PD, glycerine and combination thereof.Wherein preferred further TC, the amount of assistant for emulsifying agent is less than 20%; The mass ratio of emulsifier and assistant for emulsifying agent is 2:1.Described water is solvent, and stabilizing agent is oleic acid or enuatrol or sodium citrate, preferred oleic acid; Preservative is Sodium Benzoate and ethylparaben, preferred sodium benzoate; Adhesive agent is disilicon trioxide.
A kind of free anthraquinones extracted from rheum nano-emulsion preparation for preventing and treating plant two spotted spider mite disease of the present invention, its preparation method is: be dissolved in by free anthraquinones extracted from rheum in oil phase, add stabilizing agent, and emulsifier/assistant for emulsifying agent mixture, stirs.Dropwise add water, stir, self-emulsifying forms the nano-emulsion preparation of clear, after ultrasonic process 15-30min, with 1mol/LNaOH regulating system pH to 6.0-7.0, then adds preservative and adhesive agent in proportion.Emulsifier need 35-40 DEG C of heating and melting before using, magnetic agitation speed 200-300rpm.Directly use during the packing of gained nano-emulsion preparation in the water system filtering with microporous membrane in 0.22 μm of aperture to sterilized brown plastic containers.
Nanoemulsion particle diameter of the present invention between 20-100nm, ζ-potential between-20 ~-50mV, viscosity between 8-12cP, pH between 6.0-7.0.
Free anthraquinones extracted from rheum nano-emulsion of the present invention has the purposes of control plant two spotted spider mite disease, and excellent effect.
The invention has the beneficial effects as follows:
The raw materials used medicine of first product of the present invention is traditional Chinese medicine free anthraquinones extracted from rheum extract, nontoxicly within the scope of using dosage to have no drug resistance, safety is high, Financial cost is lower;
It two is that product of the present invention can be rendered as the homogeneous system of transparent and stable with the mixing of the water of arbitrary proportion, and preparation technology is simple, is easy to produce in enormous quantities, and emulsion droplet size is little, and viscosity is little, and field is sprayed and do not blocked sprayer, easy to use;
It three is that the two spotted spider mite disease of product of the present invention to the crops such as cucumber, eggplant, corn and flowers has significant control efficiency, and its effect is equivalent or to be better than flowers pink bollworm clean.
Accompanying drawing explanation
Fig. 1 is the free anthraquinones extracted from rheum nano-emulsion transmission electron microscope photo (× 15000) of the embodiment of the present invention 2
Fig. 2 is the sick photo of control plant two spotted spider mite of embodiment 4.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.Wherein emulsifier polyoxyethylene-40-rilanit special is on sale in BASF Chemical Co., Ltd.; Sefsol 218, TC, Gelucire 44/14, Labraso are on sale in French Gattefosse company; PLURONICS F87 is on sale in Adamas company of Switzerland.Other each raw material components all can be buied in market.
Embodiment 1: the extraction of free anthraquinones extracted from rheum
Experiment condition
Rheum officinale, purchased from Xin Sheng source, Li County biotechnology development corporation, Ltd., gets the Rhubarb pulverized and sieved, and add 20% sulfuric acid heating acidolysis, the dregs of a decoction are washed to neutral post-drying.Bulk drug pressed by rheum officinale hydrolysis dry powder: 90% ethanol=1:30 (w/v) mixes, ultrasonic extraction, suction filtration while hot, filtrate reduced in volume to without alcohol taste, with chloroform extraction, it is colourless that chloroform extraction liquid is extracted to upper liquid with 5%NaOH again, merge alkali extract, adjust pH about to 2, centrifuging and taking precipitates, and be washed to neutrality, obtain free anthraquinones extracted from rheum crude product.After crude product drying, by bulk drug: methyl alcohol=1:10 adds methyl alcohol ultrasonic dissolution, the decompression of centrifuging and taking supernatant is spin-dried for, and obtains free anthraquinones extracted from rheum (wherein five kinds of dissociated anthraquinones account for more than 98% of gross mass).
Embodiment 2: the prescription of free anthraquinones extracted from rheum nano-emulsion and preparation
Prescription one:
Free anthraquinones extracted from rheum 0.130g, oil phase 19.5g, emulsifier 16.5g, assistant for emulsifying agent 4.5g, stabilizing agent 1.0g, preservative 0.1g, adhesive agent 0.1g, purified water 58.4g, gross weight is about 100.0g.
Prescription two:
Free anthraquinones extracted from rheum 0.098g, oil phase 18.4g, emulsifier 16.0g, assistant for emulsifying agent 4.0g, stabilizing agent 1.0g, preservative 0.1g, adhesive agent 0.1g, purified water 60.5g, gross weight is about 100.0g.
In prescription: free anthraquinones extracted from rheum is main ingredient, oil phase is the mixture (prescription one) of Sefsol 218 (prescription two) or itself and ethyl oleate, emulsifier is polyoxyethylene-40-rilanit special, assistant for emulsifying agent is TC, stabilizing agent is oleic acid, preservative is Sodium Benzoate, and adhesive agent is disilicon trioxide.
Preparation method is:
Free anthraquinones extracted from rheum and stabilizing agent are dissolved in oil phase, add the mixture of emulsifier/assistant for emulsifying agent, stir.Dropwise add water, at the uniform velocity stir, self-emulsifying forms the nano-emulsion of clear, and regulating system pH6.0-7.0, then add preservative and adhesive agent.Emulsifier is at room temperature solid, therefore needs 35-40 DEG C of heating and melting before use.During the packing of gained nano-emulsion preparation, directly with in the water system filtering with microporous membrane in 0.22 μm of aperture to sterilized brown plastic containers.
Embodiment 3: the type of free anthraquinones extracted from rheum nano-emulsion, character, assay and stability
Experimental condition: the nano-emulsion that embodiment 2 prescription one is obtained, test as follows:
Nano-emulsion type identification: adopt decoration method to differentiate nano-emulsion type, the speed utilizing oil-soluble dyes tonyred and water-soluble dye methylene blue to spread in nano-emulsion is to judge the type of nano-emulsion.
Nano-emulsion character: mode of appearance, light transmittance, pH value, viscosity, particle diameter and Zeta potential.
Assay: get free anthraquinones extracted from rheum nano-emulsion 1ml, add 10ml methyl alcohol, ultrasonic emulsion breaking, the filtering with microporous membrane of 0.45 μm, high performance liquid chromatography instrument (HPLC) is analyzed, and calculates total free anthraquinone content in free anthraquinones extracted from rheum nano-emulsion.
Study on the stability: (1) influence factor is tested: by under nano-emulsion respectively high light, high temperature and hot conditions, in sampling in the 5th day, the 10th day, whether the character of observing free anthraquinones extracted from rheum nano-emulsion changed.(2) centrifugal acceleration test: after centrifugal for nano-emulsion 12000rpm 30min, observes whether have layering or precipitation.(2) normal temperature keeps sample test: free anthraquinones extracted from rheum nano-emulsion is placed 90 days at normal temperatures, respectively at sampling in the 30th day, 60 days, 90 days, investigates nano-emulsion character and medicament contg.Result of the test:
Free anthraquinones extracted from rheum nano-emulsion type is O/W type, and under transmission electron microscope, observe emulsion droplet is spheroidal, and light transmittance is 99.0-99.9%, pH is 6.4-6.7, and viscosity is 10.0-11.5cP, and particle diameter is between 20-100nm, and ζ-potential is-25.0 ~-35.0mV.
In free anthraquinones extracted from rheum nano-emulsion, free anthraquinone content is 0.122% (w/w).Nano-emulsion preparation measure each component of free anthraquinones extracted from rheum between ratio and extract in each component ratio scope substantially close, its error mainly derives from the same treatment of different batches rheum officinale, and this is acceptable for traditional Chinese medicine material extract.
Stability test shows that free anthraquinones extracted from rheum nano-emulsion is placed under these conditions, and form is clear still, and the phenomenon such as layering, flocculation does not occur.In centrifugal acceleration test, after the centrifugal 30min of nano-emulsion 12000rpm, still clear is homogeneous.The normal temperature test that keeps sample shows that nano-emulsion room temperature places 90 days, and physical stability is good, and the content of rhubarb free general anthraquinone and each monomer remains unchanged substantially.
The test of embodiment 4 free anthraquinones extracted from rheum nano-emulsion anti-plant two spotted spider mite disease
Major target disease: eggplant two spotted spider mite is sick
Test field: * * * vegetable field
Test grouping: blank group need not any reagent (being labeled as E respectively in following table); Drug component three dilution groups: be respectively free anthraquinones extracted from rheum nano-emulsion 100 times, 250 times and 500 times of dilutions (being labeled as A, B, C respectively in following table); Positive controls is 800 times of dilutions (being labeled as D respectively in following table) of the clean every 10g of flowers pink bollworm.
Testing program: eggplant (cool eggplant No. 2, Wuwei Institute of agricultural sciences seed selection), the two spotted spider mite onste phase, often processes 3 repetitions, often repeats to spray 5m 2, often repeat to select 2 strain eggplants at random before spray medicine, select 2 intact leafs of two spotted spider mite generation moderate quatity before spray medicine at every strain different parts, hang label and look into several movable mite number.2nd, 5 day investigative action mite number after spray medicine, calculates Revision insect recluced rate and control efficiency.Compare with blank group, calculate Revision insect recluced rate and control efficiency.
Borer population alive before Revision insect recluced rate rate %=[borer population of living after borer population-dispenser of living before dispenser] × 100/ dispenser
Control efficiency %=[treatment region decline rate-check plot decline rate] × 100/ [100-check plot Revision insect recluced rate]
Result of the test (table 1):
Table 1 different agents is to the controlling experiment of eggplant two spotted spider mite disease
As can be seen from the test results, in medicament of participating in the experiment used, free anthraquinones extracted from rheum nano-emulsion 100 times of dilutions are best to two spotted spider mite control efficiency, and effective drug duration is long, strong to the control of two spotted spider mite, are a kind of favourable agents preventing and treating two spotted spider mite; Free anthraquinones extracted from rheum nano-emulsion 250 times is suitable with pink bollworm clean 800 times of dilution process control efficiency of 2 to 5 days, all more than 85%, all can promote the use of aborning.
Find in preventive effect fact-finding process, although the control efficiency of free anthraquinones extracted from rheum nano-emulsion 100 times of dilutions to eggplant two spotted spider mite disease is fabulous, it accelerates the withered of eggplant leaf, demonstrates certain poisoning.And obvious poisoning does not appear in free anthraquinones extracted from rheum nano-emulsion 250 times of dilutions, can use safely.Optimum control period about 5 days, optionally row sprays medicine more afterwards.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, under the premise of not departing from the present invention, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.

Claims (4)

1. a free anthraquinones extracted from rheum composition, is characterized in that, described free anthraquinones extracted from rheum composition stems from the extract of traditional Chinese medicine sorrel, Rheum tanguticum Maxim or Rheum officinale.
2. a free anthraquinones extracted from rheum nano-emulsion preparation, it is made up of following raw material:
Free anthraquinones extracted from rheum 0.05 ~ 0.16%, Sefsol 218 13 ~ 16%, ethyl oleate 4 ~ 6%, polyoxyethylene-40-rilanit special 16 ~ 20%, TC 4 ~ 6%, oleic acid 1.0%, Sodium Benzoate 0.1%, disilicon trioxide 0.1%, purified water 50 ~ 61%.
3. a kind of free anthraquinones extracted from rheum nano-emulsion preparation as claimed in claim 2, prepare as follows: free anthraquinones extracted from rheum and stabilizing agent are dissolved in Sefsol 218 and ethyl oleate, add polyoxyethylene-40-rilanit special, TC, stir, dropwise add water, Keep agitation, until the liquid forming clear, 1mol/LNaOH regulating system pH6.0-7.0 after ultrasonic process 15-30min, then add Sodium Benzoate and disilicon trioxide.Polyoxyethylene-40-rilanit special needs 35-40 DEG C of heating and melting, magnetic agitation speed 200-300rpm before using.
4. a kind of free anthraquinones extracted from rheum nano-emulsion as described in claim 1-3 has the purposes of control plant two spotted spider mite disease.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110448534A (en) * 2019-07-29 2019-11-15 兰州大学 A kind of free anthraquinones extracted from rheum self-emulsifying microemulsion piece and preparation method thereof
CN113244302A (en) * 2021-02-22 2021-08-13 兰州大学 Rhubarb free anthraquinone composition for regulating blood fat

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CN1345597A (en) * 2000-09-26 2002-04-24 上海市中药研究所 Extract of free anthraquinone extracted from rhubarb and preparation process thereof
CN101347516A (en) * 2008-08-01 2009-01-21 石任兵 Method for preparing total free anthraquinones extract from rhubarb
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CN103330754A (en) * 2013-06-19 2013-10-02 陇东学院 Method for extracting total anthraquinone from fresh rheum officinale
CN104586961A (en) * 2014-12-29 2015-05-06 南通市第三人民医院 Method for extracting total anthraquinones in rhubarb
CN104642312A (en) * 2015-02-13 2015-05-27 兰州大学 Rheum officinale free anthraquinone composition for preventing plant powdery mildew and nano emulsion preparation

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US4602004A (en) * 1984-06-14 1986-07-22 Maurice Cohen Aloin and aloe-emodin containing pesticides
CN1345597A (en) * 2000-09-26 2002-04-24 上海市中药研究所 Extract of free anthraquinone extracted from rhubarb and preparation process thereof
CN101347516A (en) * 2008-08-01 2009-01-21 石任兵 Method for preparing total free anthraquinones extract from rhubarb
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110448534A (en) * 2019-07-29 2019-11-15 兰州大学 A kind of free anthraquinones extracted from rheum self-emulsifying microemulsion piece and preparation method thereof
CN113244302A (en) * 2021-02-22 2021-08-13 兰州大学 Rhubarb free anthraquinone composition for regulating blood fat

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