CN1489904A - Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof - Google Patents
Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof Download PDFInfo
- Publication number
- CN1489904A CN1489904A CNA031345204A CN03134520A CN1489904A CN 1489904 A CN1489904 A CN 1489904A CN A031345204 A CNA031345204 A CN A031345204A CN 03134520 A CN03134520 A CN 03134520A CN 1489904 A CN1489904 A CN 1489904A
- Authority
- CN
- China
- Prior art keywords
- polyhydroxy
- fatty acid
- naphthaldehyde
- naphthaldehydes
- preparations
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
A polyhydroxy binaphthylaldehyde-fatty acid product used as a novel broad-spectrum antiviral agricultural chemical for agricultural crops, fruit tree, vegetables, flower, forest and medicinal herbs is prepared from polyhydroxy binaphthylaldehyde and fatty acid. Its advantages are high treating and preventing effect and safety, and low dependency.
Description
Technical field
The present invention relates to a kind of agricultural chemicals, particularly a kind of two naphthaldehyde fatty acid preparations of polyhydroxy and preparation method who is used for the virus disease control of plants such as crops, fruit tree, vegetables, flowers, forest, medicinal material.
Background technology
Inquire into the chemical control of virus disease abroad since the seventies, found that at first polyhydric phenols, tannin, alkaloid and flavonoids etc. in the plant corpus have inhibitory action to virus infection, afterwards, found the antivirus action that has of 2-deracil, the assorted nitrogen purine of 8-, pyridine, 2.4-D and gibberellin again.Successively the antiviral drugs of synthetic has virazole (Virazole, Germany, 1972), morpholine methyl tetrahydropyrimidine (DD13,1982; 1996), benzoyl polyamine class (French Roussel-UCLAF company, 1991), triazines and derivative (Germany, 1992) etc.Wherein great majority to animal virus effectively and to the plant virus DeGrain, some medicine often has poisoning to plant growing, complicated cost is higher when synthetic, antiviral activity is low, factor such as residual contamination is arranged for chemical constitution in addition, has limited to produce and use.From the production and the environmental angle of pollution-free food, exploring efficient, nuisanceless viral pesticide is development trend.Developed country such as the U.S., Japan has aimed at this market, and efficient, nontoxic, the pollution-free natural antiviral substance of screening is a goal in research from plant.Successively filter out antiviral protein PAP (Harris, K.F.1982 respectively from dyers' grapes (Phytolacca americana) and [common (Mirabilisjalapa); Lodge, J.K.1993) and MAP (Kubo, S.1990; Habuka, N.1991), these albumen have unique single-chain nucleic acid ribosome deactivation function, single-minded inhibition plant RNA virus replication.
Domestic plant virus pesticide research starts from the beginning of the eighties, at first develops high fat film and NS-83.To the end of the year 2000, the product that domestic registration is produced has 9 kinds of three classes: the first kind, it is the medicine of producing with the former medicine registration of Moroxydine Hydrochloride, with 20% Moroxydine Hydrochloride. copper wetting powder registration virus of A (PDN41-96 arranged, Qiqihaer City four friendly chemical industry Industrial Co., Ltd.), viral jinx (LS97933, double star chemical plant, Shouguang, Shandong), clean (LS95591, Shuguang Pharmaceutic Plant, Shijiazhuang City) 3 kinds of virus.Also have 40% Moroxydine Hydrochloride. zeatin wetting powder (LS9588, Jiashan, Zhejiang county microorganism factory) and 20% Moroxydine Hydrochloride. copper wetting powder (LS97963, Shandong agricultural medicine packing Co., Ltd).Second class is the medicine that raw material is produced with fatty acid, and 10% fatty acid mixed aqua (LS94319, Beijing Agricultural University's pilot plant) and 10% fatty acid mixed aqua (83 increase anti-agent, LS93480, the auspicious precious biotechnology in Beijing development company) are arranged.The 3rd class is the fertile dual-purpose kind of growth regulator, medicine, and 1.5% ZhiBingLing(SIC) emulsion medicaments such as (LS92357, Dalian, Liaoning Province rainbow subsidiary factories of insecticide factory) is arranged.Use in the land for growing field crops the 3-5 kind.Except that external minority kind is the chemosynthesis class, domestic great majority are number of chemical material Compositional type or chemical classes and biological complex agent type.Its main component is that, deactivation matter, defense response exciton and physiologically active of plant are regulated class mixed things such as material.
Virus disease is the important disease of a class on crops, gourd, fruit and vegetable and the economic crops, kind surplus frequent species has 2000, become a key factor of the agriculture good year production of restriction, the whole world is annual because the economic loss that virus disease harm causes reaches 20,000,000,000 dollars according to estimates, and only harm of tobacco mosaic virus (TMV) just causes about more than 100,000,000 dollars loss.This class disease control is the serious problems that face in the whole world plant protection, becomes the great research field in the phytovirology theory and practice.Therefore, explore the new and effective viral pesticide of screening, not only theoretical to abundant control, and also significant to instructing control to put into practice, also have huge economic benefit and market potential.Estimate that according to the expert national annual viral pesticide demand is more than 100,000 tons, and domestic be that the product such as virus of A, moroxydine, viral jinx of raw material production is about ten thousand tons of 4-5 with the Moroxydine Hydrochloride, owing to the product drug effect limited and other etc. reason, national virus disease medication area is less than 50%.
At present, both at home and abroad most drug to prevent and treat principle be the direct operational virus of medicament or resist virus indirectly by medicament inducing plant disease resistance, be aided with physiological activator again and regulate the comprehensive processing method that plant metabolism makes its rejuvenation.But,, also do not have a kind of control efficiency of product to account for leading position, market till now with outstanding because virus not high according to patience and medicament active ingredient activity to host cell causes the level of control not high.The subject matter that exists is at present: (1) lacks the high activity unification compound of direct operational virus.(2) great majority are (closing) preparations that are mixed that contain multiple composition, and based on preventive effect, control efficiency is many at 60-86%, and is low to virus-specific, is the main cause that restriction China and other national viroses of plant of the world are prevented and treated level.
Summary of the invention
Defective or deficiency at above-mentioned prior art exists the objective of the invention is to, and two naphthaldehyde fatty acid preparations of a kind of polyhydroxy and preparation method are provided.
Bore from 1986 the Ministry of Agriculture " six. five " emphasis problem " the melon virus disease in the Northwest is identified several study on prevention ", begin to explore the field control of watermelon, melon viruses disease.On the basis of consulting domestic and international high amount of drug control document, having carried out (1) has carried out measuring one by one to treatment, prevention and inactivate activity about 142 kinds of important compound, confirming has 2 kinds of compound concentrations result of treatment when 50ppm can reach 80-90%, and the preventive effect of most drug is better than result of treatment.(2) activity of natural anti-virus material in 12 kinds of antivirus plants of external report and domestic important 142 various plants has been carried out biologicall test, reach 80% above standard by concentration at 100ppm and following control efficiency, filter out the many naphthaldehydes of hydroxyl (WCT) antiviral substance.
The present invention screens the two naphthaldehydes of polyhydroxy first at home and abroad and has the high efficiency anti plant virus activity, inquires into out with acetone, acetic acid extraction method extraction conditions and technological process.And develop the virus disease control that the antiviral agricultural chemicals of a kind of New-type wide-spectrum is used for plants such as crops, fruit tree, vegetables, flowers, forest, medicinal material with two naphthaldehydes of polyhydroxy and the best proportioning of fatty acid.Find out the aqua of agricultural chemicals and its preparation process of emulsifiable concentrate.
The technical solution that realizes the foregoing invention purpose is: the two naphthaldehyde fatty acid preparations of polyhydroxy comprise:
1) the two naphthaldehydes (polyhydroxy dinaphthaldehyde) of polyhydroxy;
Its chemical name is: 1, and 1`6,6`, 7,7`-Hexahydroxy-5,5`-di-iso-propy-3,3`-dimrthyl[2,2`-binaphthalene]-8,8`-dicarboxaldechyde;
Molecular structural formula is:
2) fatty acid
Structural formula: CH
3(CH
2)
7CH=CH (CH
2)
7COOH
Molecular formula: C
18H
34O
2
Relative molecular mass: 282
It is characterized in that:
Two naphthaldehydes of polyhydroxy and fatty acid are synthetic, and its ratio is: 1: 9～9: 1, concentration was 5%
Realize its preparation process of the two naphthaldehyde fatty acid preparations of above-mentioned polyhydroxy, it is characterized in that, may further comprise the steps:
1) the two naphthaldehyde preparations of polyhydroxy:
The argy wormwood, sweet wormwood, rape seed, high mallow bar, thief's lacquer, careless cortex gossypii radicis, the root of Beijing euphorbia etc. that 1. will contain the plant tissue of the two naphthaldehydes of polyhydroxy by coarse crushing, essence pulverizing as raw meal;
2. take by weighing 75% acetone of 500g raw meal adding 500ml, fully stir, filter, collect filtrate;
3. 75% acetone that in residue, adds 500ml again, fully agitation and filtration is collected filtrate;
4. repeat to extract once by 3. step again;
The filtrate of 5. mixing three times, decompression distillation concentrates, and reclaims acetone, and vapor (steam) temperature is 32 ℃-58 ℃;
6. obtain concentrating sample 100ml, add the 35ml glacial acetic acid,, the two naphthaldehyde crystallizations of polyhydroxy are separated out at-20 ℃ of down iced 2h;
7. filter with filter paper, obtain the two naphthaldehyde crystallizations of polyhydroxy;
2) two naphthaldehyde crystallizations of polyhydroxy and fatty acid are mixed, its ratio is:
The two naphthaldehyde crystallizations of polyhydroxy: fatty acid=(1～9): (9～1), concentration are 5%.
The two naphthaldehyde fatty acid preparations of polyhydroxy of the present invention are mainly by suppressing the synthetic of plant cell inner virus RNA and related protein, break virus propagation assembling process, the propagation and the propagation of controlling plant body inner virus.Thereby reach treatment and prevention, reduce the dependence of plant corpus, improve the safety of crop products, improve the antitoxin sick ability of crops and reduce the M ﹠ M of crops chemical pesticide to the viroses of plant.
Embodiment
The invention will be further described below in conjunction with embodiment that accompanying drawing and inventor provide.
The present invention screens the two naphthaldehydes of polyhydroxy first at home and abroad and has the high efficiency anti plant virus activity, and develops the antiviral agricultural chemicals of a kind of New-type wide-spectrum with two naphthaldehydes of polyhydroxy and the best proportioning of fatty acid.
The two naphthaldehyde fatty acid preparations of polyhydroxy comprise:
1) the two naphthaldehydes (polyhydroxy dinaphthaldehyde) of polyhydroxy;
Its chemical name is: 1, and 1`6,6`, 7,7`-Hexahydroxy-5,5`-di-iso-propy-3,3`-dimrthyl[2,2`-binaphthalene]-8,8`-dicarboxaldechyde;
Molecular structural formula is:
2) fatty acid
Structural formula: CH
3(CH
2)
7CH=CH (CH
2)
7COOH
Molecular formula: C
18H
34O
2
Relative molecular mass: 282 (by international relative atomic mass in 1997)
Biologically active: surfactant, antibacterial etc.
Fusing point: 0 ℃
Dissolubility: dissolve in acetone, ethanol, benzinum, n-butanol, be slightly soluble in chloroform, ether, water insoluble;
Stability: can not mix with alkali compounds, run into humidity, illumination is become sour, instability.
The source: market or reagent shop are bought.
Two naphthaldehydes of polyhydroxy and fatty acid are synthetic, and its ratio is: 1: 9～9: 1
Realize its preparation process of the two naphthaldehyde fatty acid preparations of above-mentioned polyhydroxy, may further comprise the steps:
1) the two naphthaldehyde preparations of polyhydroxy:
The argy wormwood, sweet wormwood, rape seed, high mallow bar, thief's lacquer, careless cortex gossypii radicis, the root of Beijing euphorbia etc. that 1. will contain the plant tissue of the two naphthaldehydes of polyhydroxy by coarse crushing, essence pulverizing as raw meal;
2. take by weighing the 500g raw meal and add 75% acetone of 500ml, fully stir, filter, collect filtrate;
3. 75% acetone that in residue, adds 500ml again, fully agitation and filtration is collected filtrate;
4. repeat to extract once by 3. step again;
The filtrate of 5. mixing three times, decompression distillation concentrates, and reclaims acetone, and vapor (steam) temperature is 32 ℃-58 ℃;
6. obtain concentrating sample 100ml, add the 35ml glacial acetic acid,, the two naphthaldehyde crystallizations of polyhydroxy are separated out at-20 ℃ of iced 2h;
7. filter with filter paper, obtain the two naphthaldehyde crystallizations of polyhydroxy; Filtrate can be used for the extraction of next group material.
The chemical property of the two naphthaldehydes of polyhydroxy is as follows:
Color: aubergine crystallization
Smell: tasteless
To heat endurance: stable;
1.0Pa, 180 ℃～182 ℃ of fusing points;
Dissolubility in water: insoluble
Dissolubility in organic solvent: be dissolved in most of organic solvents: as be dissolved in benzinum, ether, acetone, n-butanol, be slightly soluble in chloroform, ethanol;
Can not mix use with sodium bicarbonate solution, ferrous sulfate, sodium sulphate, magnesium sulfate etc.;
Hydrolysis and condition: hydrolysis under the alkali condition;
Photolysis under certain condition: stable to light;
2) two naphthaldehyde crystallizations of polyhydroxy and fatty acid are mixed, its ratio is:
The two naphthaldehyde crystallizations of polyhydroxy: fatty acid=(1～9): (9～1)
The toxicity test test:
To the control efficiency and the toxicity test test of two naphthaldehydes of polyhydroxy and the individualized compound of fatty acid, adopt two naphthaldehydes of polyhydroxy and the individualized compound control of fatty acid tomato virus respectively, after measured:
The two naphthaldehydes of polyhydroxy are respectively y=4.3193+0.5684x to the virulence regression equation of tobacco mosaic virus (TMV), correlation coefficient r=0.9866, concentration LC50=1.1975mg/L in effectively suppressing.Illustrate that the two naphthaldehydes of polyhydroxy have the obvious suppression effect to tobacco mosaic virus (TMV).
Fatty acid is respectively y=-0.1386+1.1239x to the virulence regression equation of tobacco mosaic virus (TMV), correlation coefficient r=0.9020, concentration LC50=42.42mg/L in effectively suppressing.Illustrate that fatty acid has the obvious suppression effect to tobacco mosaic virus (TMV).
Below be the embodiment that the inventor provides by technique scheme, but be not limited to this embodiment.
According to technical scheme of the present invention, the test of pesticide effectiveness result of the control tomato virus disease (tobacco mosaic virus) of two naphthaldehydes of polyhydroxy and the individualized compound of fatty acid sees, have significant synergies respectively with two naphthaldehydes of polyhydroxy and fatty acid, but it is the most remarkable that the two carries out the compound synergic degree with which kind of ratio, then must could determine by indoor bioassay.
Best proportioning screening test:
Based on the LC50 value of two naphthaldehydes of polyhydroxy and copper sulphate, measure the two LC50 dosage respectively with 9: 1～1: 9 different proportionings control efficiency, and ask the expection control rate and the toxicity ratio of each proportioning tomato virus disease, the result is as follows:
| The two naphthaldehyde LC50 dosage % of polyhydroxy | 100 | 90 | ?80 | ?70 | ?60 | ?50 | ?40 | ?30 | ?20 | ?10 | ?0 |
| Copper sulphate LC50 dosage % | 0 | 10 | ?20 | ?30 | ?40 | ?50 | ?60 | ?70 | ?80 | ?90 | ?100 |
| Actual measurement control rate % | 50.3 | 57.6 | ?69.3 | ?75.2 | ?85.6 | ?97.9 | ?99.5 | ?73.1 | ?65.8 | ?55.2 | ?49.5 |
| Prediction control rate % | 50.3 | 50.2 | ?50.1 | ?50.0 | ?49.9 | ?49.9 | ?49.8 | ?49.7 | ?49.6 | ?49.5 | ?49.5 |
| The virulence ratio | 1 | 1.15 | ?1.38 | ?1.50 | ?1.72 | ?1.96 | ?2.00 | ?1.47 | ?1.33 | ?1.12 | ?1 |
Hence one can see that, and two naphthaldehydes of polyhydroxy and fatty acid were used with 9: 1～1: 9, and its toxicity ratio is all greater than 1, and wherein the toxicity ratio maximum to use at 2: 3 is 2.00, and it is the most remarkable illustrate that two naphthaldehydes of polyhydroxy and fatty acid act on to be mixed at 2: 3.Adopting two naphthaldehydes of polyhydroxy and fatty acid proportioning at last is 2: 3, and the ultimate density of the two naphthaldehyde fatty acid preparation products of polyhydroxy is 5%.
This medicine through Shaanxi Province's drug identification and the field experiment on ground continuous 2 years (2000-2001) such as the Chinese Academy of Agricultural Sciences Xi'an, vegetable or flower place and Beijing prove, control efficiency to masaic of tomato is 86.5% and 82.36, and western muskmelon mosaic disease, tobacco mosaic and corn disease viral disease etc. are had broad spectrum activity.
Claims (4)
1. two naphthaldehyde fatty acid preparations of polyhydroxy comprise:
The two naphthaldehydes (polyhydroxy dinaphthaldehyde) of polyhydroxy
Its chemical name is: 1, and 1`6,6`, 7,7`-Hexahydroxy-5,5`-di-iso-propy-3,3`-dimrthyl[2,2`-binaphthalene]-8,8`-dicarboxaldechyde;
Molecular structural formula is:
Fatty acid
Structural formula: CH
3(CH
2)
7CH=CH (CH
2)
7COOH
Molecular formula: C
18H
34O
2
Relative molecular mass: 282
It is characterized in that:
Two naphthaldehydes of polyhydroxy and fatty acid are mixed, and its ratio is: (1: 9)～(9: 1), concentration are 5%.
2. the two naphthaldehyde fatty acid preparations of polyhydroxy as claimed in claim 1 is characterized in that, the optimal proportion that two naphthaldehydes of described polyhydroxy and fatty acid mix is 2: 3.
3. realize its preparation process of the two naphthaldehyde fatty acid preparations of the described polyhydroxy of claim 1, it is characterized in that, may further comprise the steps:
1) the two naphthaldehyde preparations of polyhydroxy
The argy wormwood, sweet wormwood, rape seed, high mallow bar, thief's lacquer, careless cortex gossypii radicis, the root of Beijing euphorbia etc. that 1. will contain the plant tissue of the two naphthaldehydes of polyhydroxy by coarse crushing, essence pulverizing as raw meal;
2. take by weighing 75% acetone of 500g raw meal adding 500ml, fully stir, filter, collect filtrate;
3. 75% acetone that in residue, adds 500ml again, fully agitation and filtration is collected filtrate;
4. repeat to extract once by 3. step again;
The filtrate of 5. mixing three times, decompression distillation concentrates, and reclaims acetone, and vapor (steam) temperature is 32 ℃-58 ℃;
6. obtain concentrating sample 100ml, add the 35ml glacial acetic acid,, the two naphthaldehyde crystallizations of polyhydroxy are separated out at-20 ℃ of down iced 2h;
7. filter with filter paper, obtain the two naphthaldehyde crystallizations of polyhydroxy;
2) two naphthaldehyde crystallizations of polyhydroxy and fatty acid are mixed, its ratio is:
The two naphthaldehyde crystallizations of polyhydroxy: fatty acid=(1～9): (9～1), concentration are 5%.
4. its preparation process of the two naphthaldehyde fatty acid preparations of polyhydroxy as claimed in claim 3 is characterized in that, the optimal proportion that two naphthaldehydes of described polyhydroxy and fatty acid mix is 2: 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031345204A CN1489904A (en) | 2003-08-27 | 2003-08-27 | Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031345204A CN1489904A (en) | 2003-08-27 | 2003-08-27 | Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1489904A true CN1489904A (en) | 2004-04-21 |
Family
ID=34154514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031345204A Pending CN1489904A (en) | 2003-08-27 | 2003-08-27 | Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1489904A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351289A (en) * | 2013-05-31 | 2013-10-16 | 江苏省中国科学院植物研究所 | New Kosteletzkya virginica (L.) Presl. sesquiterpene compound, and preparation method and use thereof |
| CN109042652A (en) * | 2018-09-11 | 2018-12-21 | 江苏省农业科学院 | A kind of biodegrading process of sweet potato chlorotic stunt virus capsid protein |
| CN109105366A (en) * | 2018-09-11 | 2019-01-01 | 江苏省农业科学院 | A method of utilizing gossypol degradation Sweet Potato Feathery Mottle Virus capsid protein |
-
2003
- 2003-08-27 CN CNA031345204A patent/CN1489904A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351289A (en) * | 2013-05-31 | 2013-10-16 | 江苏省中国科学院植物研究所 | New Kosteletzkya virginica (L.) Presl. sesquiterpene compound, and preparation method and use thereof |
| CN109042652A (en) * | 2018-09-11 | 2018-12-21 | 江苏省农业科学院 | A kind of biodegrading process of sweet potato chlorotic stunt virus capsid protein |
| CN109105366A (en) * | 2018-09-11 | 2019-01-01 | 江苏省农业科学院 | A method of utilizing gossypol degradation Sweet Potato Feathery Mottle Virus capsid protein |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104855440B (en) | A kind of botanical pesticide and preparation method thereof | |
| CN101851356A (en) | Shitake mushroom extract and application thereof | |
| JPH10245312A (en) | Plant protecting agent and its production | |
| CN101720791A (en) | Matrine pure plant source pesticide | |
| CN102812972A (en) | Plant extract composition for preventing and treating apple tree canker, and preparation method thereof | |
| CN103918651A (en) | Pesticide composition for preventing and treating root knot nematode disease and method | |
| CN101233867A (en) | Matrine agent plant pesticide and preparation thereof | |
| CN101116451A (en) | Plant miticide derived from artemisia annul l and method for preparing the same | |
| CN101766174B (en) | Application of whiteflower hogfennel root coumarin III in inducing paddy rice to resist rice blast and cold | |
| CN1218643C (en) | Eupatorine pesticide and its prepn | |
| CN1631172A (en) | Prophylaxis insect repellant made from pure plants and its making method | |
| CN1957713A (en) | New composition of pesticide, preparation method, and purpose | |
| CN1489904A (en) | Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof | |
| CN114287450B (en) | Pesticide composition for preventing and treating sugarcane thrips | |
| CN1895050A (en) | Kosam seeds plant-resisting virusagent and preparation thereof | |
| KR20170021931A (en) | eco-friendly composition for controlling plant viruses | |
| CN102657219B (en) | Dufulin-containing ultra low volume liquid formulation | |
| CN109832300B (en) | Pesticide composition for preventing and treating plant virus diseases and preparation method and application thereof | |
| CN114835523A (en) | Medium trace element fertilizer and preparation method and application thereof | |
| CN113647415A (en) | Microemulsion prepared from herba Veronicae Divaricatae, and its preparation method and application | |
| CN1319447C (en) | Drought resishing aphicide and its use | |
| CN101044854A (en) | Compound acaricide composition | |
| CN1316901C (en) | New use of dittany bark prepn in preventing and controlling spot blight of gentian | |
| RU2670253C1 (en) | Method for preparing soils polluted by heavy metals for phytoremediation | |
| CN1316903C (en) | New use of chinaberry fruit prepn in preventing and confrolling spot blight of gentian |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |