CN111183998B - 8-hydroxyquinoline calcium-containing bactericidal composition for preventing and treating downy mildew and late blight - Google Patents

8-hydroxyquinoline calcium-containing bactericidal composition for preventing and treating downy mildew and late blight Download PDF

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CN111183998B
CN111183998B CN202010127844.8A CN202010127844A CN111183998B CN 111183998 B CN111183998 B CN 111183998B CN 202010127844 A CN202010127844 A CN 202010127844A CN 111183998 B CN111183998 B CN 111183998B
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范文忠
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Jilin Agricultural Science and Technology College
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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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • 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
    • A01N31/00Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/501,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring

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Abstract

The invention relates to a bactericidal composition containing 8-hydroxyquinoline calcium for preventing and treating downy mildew and late blight and application thereof, wherein the bactericidal composition contains a bactericidal active ingredient A and a bactericidal active ingredient B, the bactericidal active ingredient A is 8-hydroxyquinoline calcium, the bactericidal active ingredient B is selected from one of fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride, and the weight ratio of the bactericidal active ingredient A to the bactericidal active ingredient B is 1: 100-100: 1; in the bactericidal composition, 8-hydroxyquinoline calcium, fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride form a synergistic effect.

Description

8-hydroxyquinoline calcium-containing bactericidal composition for preventing and treating downy mildew and late blight
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a bactericidal composition containing 8-hydroxyquinoline calcium and used for preventing and treating downy mildew and late blight.
Background
Calcium 8-Hydroxyquinoline (Calcium 8-Hydroxyquinoline, Ca (C)9H6NO)2) Quinoline calcium for short; although there are many studies, most of them are in the "research field of organic electroluminescent materials"; the Jilin agricultural science and technology institute cooperates with Jiaxing sinceric science and technology Limited company to successfully apply the compound to prevent and treat one or more of fungal diseases, bacterial diseases or plant nutritional deficiency diseases caused by calcium deficiency of plants, and a patent of 'application of quinoline calcium in preventing and treating plant diseases and a composition thereof' is applied in 2018, and through continuous and intensive research, we find that 8-hydroxyquinoline calcium has good prevention and treatment effects on rice bacterial blight, rice basal rot, cucumber angular leaf spot, tomato early blight, rice bacterial streak, apple alternaria leaf spot and peach bacterial leaf spot, meanwhile, the bacterial strain also has the effects on potato late blight (Phytophthora infestans (Mont.) de Bary), Phytophthora capsici (Phytophthora capsici Leonian), grape downy mildew (Plasmopara Viticola (Berk.et Curtis.) Berl et de Toni), and cucumber downy mildew (Pseudoperonospora cubensis (Berk.et Curt.) Ro.stov.) and the like have good control effect.
Late blight and downy mildew are characterized by typical epidemic diseases: the disease which is easy to spread, explode and spread and easily causes serious loss to crops is difficult to control, and the main reasons are as follows 4 points: 1. the life history of the germs is short, the infection of the germs has multicyclability, and the germs can be attacked for many times in one crop growth period; 2. the physiological race is various, and part of the physiological race has strong spontaneous mutation capability or has the characteristic of potential genetic variation; 3. the adaptive capacity of pathogenic bacteria to the environment is strong, when the environmental condition is proper, the disease is epidemic and rapid, the reproductive capacity is strong, and the chemical control in a short period is difficult to control; 4. most chemical agents for preventing and treating late blight and downy mildew have long use time and similar action mechanisms or have serious drug resistance, and a single agent is difficult to prevent and treat in production, so that in actual production, a plurality of agents are alternately used, and 2-3 agents are used for mixed use each time for field prevention and treatment.
The research finds that the 8-hydroxyquinoline calcium is a protective bactericide, is applied to potato late blight, pepper blight, grape downy mildew and cucumber downy mildew at a proper concentration at the early stage of disease attack, has a good control effect on the potato late blight, the pepper blight, the grape downy mildew and the cucumber downy mildew, and has no related drug resistance report at present; in order to better prevent and treat potato late blight, pepper blight, grape downy mildew and cucumber downy mildew and delay the future drug resistance of 8-hydroxyquinoline calcium, 8-hydroxyquinoline calcium and part of therapeutic bactericides are scientifically mixed, and unexpected results are obtained through indoor toxicity measurement and field efficacy tests.
Fluazinam belongs to pyridylamine derivatives, and dinitroaniline bactericides are mitochondrial oxidative phosphorylation uncouplers, are used for removing the correlation of oxidation and phosphorylation at the tail end of a respiratory chain by acting on ATP synthetase, consume electrochemical potential energy accumulated by electron transfer to the maximum extent, are very distinctive bactericides, and can effectively prevent and treat downy mildew, late blight, gray mold, sclerotinia rot, anthracnose, clubroot and damping-off.
Cyazofamid is a sulfaimidazole bactericide, is developed by Nippon stone Producer corporation, has an action mechanism of blocking the electron transfer of a mitochondrial cytochrome bc1 complex in oomycete pathogenic bacteria to interfere the supply of energy, and has a binding site as the Q center of enzyme; has high bioactivity on downy mildew, epidemic disease, clubroot, damping-off and the like.
Eugenol is a bacteriolytic compound, has a destructive effect on each stage of the life history of oomycetes by destroying the formation of cell walls of pathogenic bacteria, is particularly sensitive in the stage of sporangium peduncle and oospore formation, has strong penetration and systemic effects, has strong touch killing performance, can be conducted up and down, is quick-acting and long in lasting period, and achieves the bactericidal effect. The eugenol is a peronospora and phytophthora lytic agent, is a biological source bactericide, and can prevent and treat gray mold, downy mildew, late blight, sclerotinia, scab, early blight, damping off, root rot and the like.
Fluopyram is a benzamide bactericide and mainly acts on a specific protein-ghost-like protein between a cell membrane and a cell skeleton, so that mitosis of cells is influenced to have good inhibitory activity on each main form of pathogenic bacteria, and the flupyrad has good persistence; the fluopicolide can be distributed from the root part to the whole plant along the xylem of the plant, but can not be conducted along the phloem. The bactericidal composition is mainly applied to various vegetables and grape crops to prevent and treat downy mildew and late blight.
The propamocarb hydrochloride belongs to an aliphatic bactericide, and is a systemic and low-toxicity bactericide; the soil conditioner is low in toxicity and safe, has a good local systemic effect, can be quickly absorbed by root systems after soil treatment and is upwards conveyed to the whole plant, and can be quickly absorbed by leaves to play a role in protection after stem and leaf spraying treatment; the action mechanism is to inhibit the synthesis of phosphoric acid and fatty acid of germ cell membrane components, and inhibit the growth and spread of hyphae, the formation of sporangium and the germination of spores; propamocarb hydrochloride is a broad-spectrum bactericide and has special effect on diseases caused by phycomycetes. Has good control effect on vegetable downy mildew, epidemic disease, damping-off, late blight of solanaceae, phytophthora blight of cruciferae, white rust of cruciferae and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a bactericidal composition, which is characterized by comprising a bactericidal active ingredient A and a bactericidal active ingredient B, wherein the bactericidal active ingredient A is a compound (8-hydroxyquinoline calcium) shown as the following formula (I):
Figure BDA0002394941170000031
the bactericidal active component B is one of fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride.
Among them, the compound of formula (I) is named as calcium 8-hydroxyquinoline in the present invention.
Preferably, in the bactericidal composition, the weight ratio of the bactericidal active ingredient A to the bactericidal active ingredient B is 1:100 to 100: 1; preferably, the weight ratio of the bactericidal active ingredient A to the bactericidal active ingredient B is 1:80 to 80: 1; particularly preferred, the weight ratio of the calcium 8-hydroxyquinoline to the eugenol is from 20:1 to 5: 1; the weight ratio of the 8-hydroxyquinoline calcium to the fluazinam is 1:8 to 8: 1; the weight ratio of the 8-hydroxyquinoline calcium to the cyazofamid is 20:1 to 5: 1; the weight ratio of the 8-hydroxyquinoline calcium to the fluopicolide is 20:1 to 5: 1; the weight ratio of the 8-hydroxyquinoline calcium to the propamocarb hydrochloride is 1:1 to 1: 20.
Preferably, in the above bactericidal composition, the sum of the weight of the bactericidal active ingredient a and the weight of the bactericidal active ingredient B accounts for 10 to 80 percent of the weight of the bactericidal composition, and preferably accounts for 20 to 60 percent of the weight of the bactericidal composition.
Preferably, in the above bactericidal composition, the bactericidal composition further comprises a pesticide carrier and a pesticide adjuvant, and the sum of the weight of the pesticide carrier and the weight of the pesticide adjuvant accounts for 1 to 90 percent of the weight of the bactericidal composition, preferably 20 to 80 percent of the weight of the bactericidal composition.
The auxiliary components of the composition include wetting agents, dispersants, thickeners, antifreezes, preservatives, stabilizers, antifoaming agents, colorants, fillers, and the like, and other known substances useful for stabilizing active ingredients in a formulation or exerting active ingredients in a formulation, and are various components which are generally used in the preparation or are agriculturally allowed to be used, and are not particularly limited, and specific components and amounts thereof are determined by experiments as needed.
The wetting agent is selected from EO/PO block polyether, fatty alcohol-polyoxyethylene ether sulfate, acyl glutamate, fatty alcohol ethoxy compound, tallow ethoxy ammonium salt and alkyl naphthalene sulfonate.
The dispersing agent is selected from sodium lignosulfonate, sodium methylene dinaphthalene sulfonate, sodium naphthalene sulfonic acid condensate, sodium phenol sulfonic acid condensate, sodium methyl naphthalene sulfonate formaldehyde condensate, sodium acrylic acid homopolymer, calcium dodecyl benzene sulfonate, high-molecular polycarboxylate, sodium dioctyl sulfosuccinate, sodium maleic acid-acrylic acid copolymer, sodium acrylic acid homopolymer and diphenyl phenol polyoxyethylene ether formaldehyde condensate.
The solvent is selected from xylene, trimethylbenzene, methylated vegetable oil, epoxidized soybean oil, and p-tert-butyl ether.
The thickener is selected from xanthan gum, magnesium aluminum silicate, starch sodium phosphate, starch sodium octenyl succinate, polyvinyl alcohol, carboxymethyl cellulose, and ethoxylated castor oil.
The stabilizer is selected from epoxidized soybean oil, epichlorohydrin, triphenyl phosphite, glycidyl ether or pentaerythritol.
The defoaming agent is selected from organic silicon defoaming agent, polyether defoaming agent and phosphate ester.
The colorant is selected from titanium oxide, iron oxide and azo dye.
The filler is selected from talcum powder, white carbon black, light calcium carbonate, kaolin and diatomite.
The antifreeze is selected from ethylene glycol, propylene glycol, glycerol, isopropanol, urea and sodium chloride.
The disintegrating agent is selected from sodium chloride, ammonium sulfate, sodium sulfate, and soluble starch.
The preservative is selected from formaldehyde, phenyl salicylate, butyl p-hydroxybenzoate and potassium sorbate.
The water is deionized water or distilled water.
The invention also provides a composition preparation prepared from the composition, and the preparation is a suspending agent, a water dispersible granule, a suspoemulsion and a wettable powder.
The above composition preparation can be prepared by conventional processing method, i.e. mixing active ingredient with liquid carrier or solid carrier, and adding one or more of the above adjuvants such as emulsifier, dispersant, etc. Typically, the germicidal composition includes at least one carrier and at least one surfactant. In each case, a homogeneous distribution of the active ingredient in the above-mentioned compositions should be ensured.
The invention also provides application of the bactericidal composition, and the bactericidal composition is used for preventing and treating plant diseases.
The invention also provides a method for preventing and treating plant diseases by applying the bactericidal composition to stem leaves, roots or plant seeds of plants in a bactericidal effective amount in a spraying mode, a root application mode or a seed coating mode.
Preferably, the plant diseases are rice sheath blight disease, rice bacterial leaf blight, rice bacterial strip spot, rice flax spot, rice bakanae disease, rice seedling rot, corn northern leaf blight, corn bacterial wilt, corn downy mildew, corn curvularia leaf spot, potato ring rot, potato late blight, potato early blight, soybean downy mildew, soybean bacterial blight, apple tree rot, apple rust, apple defoliation, apple anthracnose, apple ring rot, apple heart rot, apple core rot, grape white rot, grape black pox, grape downy mildew, grape anthracnose, grape cob brown rot, tomato leaf mold, tomato canker, tomato blight, tomato early blight, pepper anthracnose, pepper blight, pepper scab, cucumber downy mildew, cucumber bacterial angular leaf spot, cruciferous soft rot, tomato leaf blight, tomato bacterial blight, tomato leaf blight, pepper scab, cucumber downy mildew, cucumber bacterial leaf spot, cucumber bacterial leaf rot, cucumber leaf spot, rice bakanae disease, potato rot, potato leaf spot, etc., and the like, Crucifer downy mildew, crucifer black spot, crucifer clubroot, cucumber sclerotinia, strawberry powdery mildew, strawberry gray mold and the like.
Preferably, the plant diseases are potato late blight, pepper phytophthora blight, grape downy mildew and cucumber downy mildew.
Has the advantages that:
1) the synergistic effect is remarkable: in the bactericidal composition, the 8-hydroxyquinoline calcium, the fluazinam, the cyazofamid, the eugenol, the fluopicolide and the propamocarb hydrochloride form a synergistic effect, namely the synergistic effect of the two components in the composition can enable the total effect to be larger or more durable than the sum of the effects obtained by the two (or more) components independently; in a method of providing control of plant disease wherein synergy is exhibited by a combination of active ingredients applied to a plant or seed, the active ingredients are applied in a synergistic weight ratio. The bactericidal composition can be used for preventing and treating potato late blight, pepper phytophthora blight, grape downy mildew and cucumber downy mildew in a synergistic manner, and an unexpected synergistic effect is obtained.
2) The use cost is reduced: the 8-hydroxyquinoline calcium has obvious synergistic effect with fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride and obviously improved disease prevention effect, so that the application times are reduced, the use cost is reduced, the time and the labor are saved, and the obvious economic benefit and social benefit are achieved.
3) The development of resistance is delayed: the active ingredients of the 8-hydroxyquinoline calcium, fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride have different action mechanisms and bactericidal spectrums, the bactericidal effect is good, the use dosage of a single medicament is obviously reduced, the generation of pathogenic bacteria resistance is favorably delayed, the use range of the product is expanded, and the service life of the product is prolonged.
4) And (3) reduction of environmental pollution: because the 8-hydroxyquinoline calcium and the fluazinam, the cyazofamid, the eugenol, the fluopicolide and the propamocarb hydrochloride have excellent synergistic effect and disease prevention effect, the effects of preventing and controlling germs, resisting bacteria or inhibiting bacteria are improved, the prevention spectrum is expanded, the medication times can be reduced, and the application dosage is obviously reduced, so the environmental pollution is reduced, and the safety to people and livestock is improved.
Detailed Description
First, indoor bioassay embodiment
The combined toxicity determination test process and the results of the compound agent aiming at the 8-hydroxyquinoline calcium, fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride on the potato late blight are as follows.
The test takes potato late blight bacteria sensitive strains in northeast China as objects to carry out formula screening of the compound medicament. The method comprises the steps of dissolving raw materials of 8-hydroxyquinoline calcium, fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride in acetone, and designing a test according to a mass ratio.
The inhibition rate of the bactericidal composition of 8-hydroxyquinoline calcium, fluazinam, cyazofamid, eugenol, fluopicolide, propamocarb hydrochloride single agent and active ingredients with different weights is determined by referring to a Sun-Yunnan-Pay (1960) co-toxicity coefficient method.
The toxicity of each medicament to the potato late blight bacteria is respectively determined by adopting a toxic medium growth rate method. Each bactericide is provided with 5 concentrations of medicine-containing culture media; under aseptic condition, punching a bacterial cake on the edge of a colony of potato late blight pre-cultured for 5d by using a puncher with the diameter of 6mm, inoculating the bacterial cake on a drug-containing flat plate (PDA culture medium) with the front face facing downwards, placing the bacterial cake at the center of the drug-containing culture medium, culturing the bacterial colony for 5d at a constant temperature of 25 ℃, measuring the diameter of the colony by using a cross method, calculating the relative inhibition rate, establishing a linear equation of mass concentration logarithm-several value by using a least square method, and solving a toxicity regression equation and EC of each medicament50Selecting a bactericide A: 8-hydroxyquinoline calcium and bactericide B: fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride are subjected to binary compounding, and the synergistic coefficient is determined by the method for determining the synergistic coefficient by referring to the Wadley method as above.
Relative inhibition (%) - (control group average net growth amount-treatment group average net growth amount)/control group average net growth amount × 100
Single-dose toxicity index TI is standardMedicament EC50Reagent for test EC50×100
Evaluation was carried out by the Wadley method: the synergistic coefficient SR is more than 1.5, which is the synergistic effect; 1.5 SR is more than or equal to 0.5 for additive effect; SR < 0.5 is antagonistic.
Mixture EC50The value (theoretical) (mg/L) is (mass fraction of A in the mixture + mass fraction of B in the mixture)/(mass fraction of A in the mixture/EC of A50Value + mass fraction of B in the mixture/EC of B50Value)
Coefficient of Synergy (SR) ═ EC50Value (theoretical)/EC50Value (actual measurement)
The results of indoor joint toxicity measurement of the single agents of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide, propamocarb hydrochloride and the composition thereof on sensitive strains of potato late blight bacteria in northeast local areas are shown in tables 1, 2, 3, 4, 5 and 6.
Table 1: virulence of different bactericides to potato late blight pathogen
Figure BDA0002394941170000071
Table 2: combined toxicity of 8-hydroxyquinoline calcium and cyazofamid compound on potato late blight bacterium
Figure BDA0002394941170000072
As can be seen from the table, the potato late blight bacteria is taken as a target, the 8-hydroxyquinoline calcium and cyazofamid compound agent has combined toxicity on the potato late blight bacteria and is expressed as synergy or additive effect, the synergistic coefficient SR is more than 1.5 when the ratio of the 8-hydroxyquinoline calcium to the cyazofamid is 20:1, the synergy is expressed as synergy, the extreme value of the synergistic coefficient is 7.26, and the mass ratio is 20:1, so that the optimal ratio is obtained.
Table 3: combined toxicity of 8-hydroxyquinoline calcium and eugenol compound agent on potato late blight pathogen
Figure BDA0002394941170000073
Figure BDA0002394941170000081
As can be seen from the table, the potato late blight bacterium is taken as a target, the combined toxicity of the 8-hydroxyquinoline calcium and eugenol compound agent on the potato late blight bacterium is shown as synergy or addition, and the ratio of the 8-hydroxyquinoline calcium to the eugenol is 20: when 1, the synergistic coefficient SR is more than 1.5, which shows synergy, the extreme value of the synergistic coefficient is 3.76, and the optimal proportion is that the mass ratio is 20: 1.
Table 4: 8-hydroxyquinoline calcium and fluazinam compound agent combined toxicity to potato late blight pathogen
Figure BDA0002394941170000082
As can be seen from the table, the potato late blight bacteria is taken as a target, the 8-hydroxyquinoline calcium and fluazinam compound agent has combined toxicity to the potato late blight bacteria, the synergy is shown, the synergy coefficient SR is more than 1.5 when the ratio of 8-hydroxyquinoline calcium to fluazinam is 1:2, the extreme value of the synergy coefficient is 15.35, and the optimal ratio is 1: 2.
Table 5: 8-hydroxyquinoline calcium and fluopicolide compound agent with combined toxicity on potato late blight pathogen
Figure BDA0002394941170000083
Figure BDA0002394941170000091
As can be seen from the table, the potato late blight bacterium is taken as a target, the 8-hydroxyquinoline calcium and fluopicolide compound agent has combined toxicity to the potato late blight bacterium, the synergy is shown, when the ratio of 8-hydroxyquinoline calcium to fluopicolide is 5:1, the synergy coefficient SR is more than 1.5, the extreme value of the synergy coefficient is 5.77, and the optimal ratio is 5: 1.
Table 6: 8-hydroxyquinoline calcium and propamocarb hydrochloride compound agent with combined toxicity on potato late blight pathogen
Figure BDA0002394941170000092
As can be seen from the table, the potato late blight bacterium is taken as a target, the 8-hydroxyquinoline calcium and propamocarb hydrochloride compound agent has combined toxicity to the potato late blight bacterium, the synergy is shown, the synergy coefficient SR is more than 1.5 when the ratio of the 8-hydroxyquinoline calcium to the propamocarb hydrochloride is 1:1, the extreme value of the synergy coefficient is 3.88, and the optimal ratio is 1: 1.
Second, preparation examples
Formulation example 1: 45% 8-hydroxyquinoline calcium-fluazinam (15.0% + 30.0%) suspension
45% of active compound (15.0% of 8-hydroxyquinoline calcium and 30.0% of fluazinam), 2.0% of sodium dodecyl sulfate, 2.5% of alkylamido taurate, 2.0% of alkylphenol polyoxyethylene ether, 3.0% of macromolecular polycarboxylate, 2.0% of propylene glycol, 0.1% of polyether defoamer, 0.2% of sodium nitrate and 100% of deionized water are added into a high-shear homogenizing emulsifying machine to be sheared at high speed for 45 minutes, then pumped into a sand mill to be sanded for 60 minutes, and the active compound suspending agent with the content of 45% is obtained after filtration.
Formulation example 2: 50% of 8-hydroxyquinoline calcium cyazofamid (45.0% + 5.0%) suspension
50% of active compound (45.0% of 8-hydroxyquinoline calcium and 5.0% of cyazofamid), 2.0% of alkyl naphthalene sulfonate, 1% of acyl glutamate, 2.0% of phenol sulfonic acid condensate sodium salt, 2.0% of methyl naphthalene sodium formaldehyde condensate, 2.0% of xanthan gum, 2.0% of ethylene glycol, 0.3% of potassium sorbate, 0.2% of organic silicon defoamer and 100% of deionized water are added into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 30 minutes, then pumped into a sand mill to be sanded for 60 minutes, and the 50% of active compound suspending agent is obtained after filtration.
Formulation example 3: 33% 8-hydroxyquinoline calcium eugenol (30.0% + 3%) suspension
Fully mixing 60.0% of 8-hydroxyquinoline calcium, 2.0% of sodium lignosulfonate, 1.0% of calcium dodecyl benzene sulfonate, 1.0% of acrylic acid homopolymer sodium salt, 1.0% of p-tert-butyl ether, 2.0% of propylene glycol, 0.1% of gum arabic, 0.1% of phosphate and 44.5% of deionized water, putting into a high-shear homogeneous emulsifier, carrying out high-speed shearing and coarse grinding, pumping into a sand mill, and sanding to a certain particle size to obtain a suspending agent; the suspending agent contains 60.0 percent of 8-hydroxyquinoline calcium, and the particle size of D90 is 3-6 microns. Then 50% of 60.0% of 8-hydroxyquinoline calcium suspending agent, 3.0% of eugenol, 8.0% of ethoxylated castor oil, 3% of oleic acid methyl amino ethyl sodium sulfonate, 4.0% of glycerol, 0.3% of carboxymethyl cellulose, 0.1% of C10-20 saturated fatty acid and deionized water are supplemented, high-speed shearing, homogeneous emulsification and filtration are carried out to prepare the suspoemulsion, and the suspoemulsion contains 33% of active compounds (30.0% of 8-hydroxyquinoline calcium and 3% of eugenol composition).
Formulation example 4: 60.0% 8-hydroxyquinoline calcium fluopicolide (50.0% + 10.0%) water dispersible granule
Adding 60.0% of active compounds (50.0% of 8-hydroxyquinoline calcium and 10.0% of fluopicolide), 3% of diphenyl phenol polyoxyethylene ether formaldehyde condensate, 2% of tallow ethoxy amine salt, 5% of dibutyl naphthalene sodium sulfonate, 10% of sodium carboxymethyl starch, 10% of attapulgite and 100% of white carbon black into a stirrer, uniformly stirring, and then performing airflow crushing to obtain mother powder of the quinoline calcium and the fluopicolide; dissolving 2% of Arabic gum and 2% of polyvinyl alcohol in water to prepare a flowable aqueous solution; spraying the water solution into the mother powder while stirring the mother powder, and mixing to obtain a wet material, wherein the water content is 10-30% of the dry matter weight; and extruding, granulating, drying and finishing the wet material to obtain the 60.0 percent active compound water dispersible granule.
Formulation example 5: 80.0% 8-hydroxyquinoline calcium propamocarb hydrochloride (40.0% + 40.0%) wettable powder
80.0 percent of active compound (40.0 percent of 8-hydroxyquinoline calcium and 40.0 percent of propamocarb hydrochloride), 6 percent of dioctyl sulfosuccinate sodium salt, 2 percent of condensed naphthalene sulfonate, 2 percent of alkyl naphthalene sulfonate, 2 percent of soluble starch, 2 percent of diatomite and 100 percent of kaolin are added into a stirrer to be uniformly stirred and then are pulverized by air flow to obtain 80 percent of active compound wettable powder.
Third, field drug effect test
Aiming at the field efficacy test of different compound agents taking 8-hydroxyquinoline calcium as an active ingredient for preventing and treating potato late blight, pepper blight, grape downy mildew and cucumber downy mildew, the test process and the result are as follows.
8-hydroxyquinoline calcium, fluazinam, cyazofamid, eugenol, fluopicolide, propamocarb hydrochloride single agents and composition preparations thereof are respectively adopted to carry out spray treatment at the early stage of the occurrence of the potato late blight, the pesticide application is carried out twice, the interval is 7 days, and the control effect is investigated 15 days after the second pesticide application; spraying twice at 7 days intervals at the initial stage of downy mildew of grape in a protected area, and investigating 15 days after application; the spray treatment was carried out at the initial stage of occurrence of downy mildew of protected cucumber, the application was carried out twice at intervals of 7 days, and the investigation was carried out 20 days after the application, and the spray treatment was carried out at the initial stage of occurrence of phytophthora blight of protected pepper, the application was carried out twice at intervals of 7 days, and the investigation was carried out 20 days after the application, and the results are shown in tables 7 to 10 below.
The single-dose preparation and the compound preparation used for preventing and treating each disease have the same dosage form, and are generally suspending agents. The formulation is not the key for verifying the synergistic effect of the compound preparation, and sometimes the preparation needs to be adjusted according to actual crops and diseases, but in any adjustment, all the formulations used in the tests aiming at each disease are the same in formulation, and except for the change of the active ingredients, the auxiliary agent is not changed so as to ensure the consistency of the active ingredients.
According to the efficacy evaluation mode of the Gowing method, the calculation formula is as follows: e0X + Y (100-X)/100, wherein X is A single-agent control effect (%), Y is B single-agent control effect (%), E is A, B actual control effect (%) of two single-agents in a mixed mode, and when E-E is used0Synergistic effect when more than 10, E-E0When less than-10, E-E is a reduction effect0An additive effect is obtained when the concentration is within +/-10.
Table 7: field efficacy test of different compound agents for preventing and treating potato late blight
Figure BDA0002394941170000111
Figure BDA0002394941170000121
The synergistic comparison between the compound preparation of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride and the single-agent control room for controlling the potato late blight is carried out, the actual control effect is more than 10 times greater than the theoretical control effect, and the synergistic control of the potato late blight can be realized by the compound composition of the 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride.
Table 8: field efficacy test of different compound agents for preventing and treating grape downy mildew
Figure BDA0002394941170000122
The synergistic comparison between the compound preparation of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride and the single-dose treatment for preventing and treating grape downy mildew is carried out, the actual prevention effect is more than 10 times greater than the theoretical prevention effect, and the compound composition of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride can realize the synergistic prevention and treatment of grape downy mildew.
Table 9: field efficacy test of different compound agents for preventing and treating cucumber downy mildew
Figure BDA0002394941170000123
Figure BDA0002394941170000131
The synergistic comparison between the compound preparation of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride and the treatment for controlling cucumber downy mildew of single agent is carried out, the actual control effect is more than 10 greater than the theoretical control effect, and the compound composition of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride can realize the synergistic control of cucumber downy mildew.
Table 10: field efficacy test of different compound agents for preventing and treating pepper phytophthora blight
Figure BDA0002394941170000132
The synergistic comparison between the compound preparation of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride and the single-dose treatment for controlling pepper phytophthora blight is carried out, the actual control effect is more than 10 times greater than the theoretical control effect, and the synergistic control of the pepper phytophthora blight can be realized by the compound composition of 8-hydroxyquinoline calcium and fluazinam, cyazofamid, eugenol, fluopicolide and propamocarb hydrochloride.

Claims (6)

1. The bactericidal composition is characterized by comprising a bactericidal active ingredient A and a bactericidal active ingredient B, wherein the bactericidal active ingredient A is a compound shown as the following formula (I), namely 8-hydroxyquinoline calcium:
Figure FDA0003109818800000011
the bactericidal active component B is fluazinam, and the weight ratio of the 8-hydroxyquinoline calcium to the fluazinam is 1:8 to 8: 1.
2. The bactericidal composition of claim 1, wherein the sum of the weight of bactericidal active ingredient a and bactericidal active ingredient B is 10-80% of the weight of the bactericidal composition.
3. The bactericidal composition according to claim 2, wherein the sum of the weight of the bactericidal active ingredient a and the weight of the bactericidal active ingredient B accounts for 20 to 60 percent of the weight of the bactericidal composition.
4. The bactericidal composition according to any one of claims 1 to 3, wherein the bactericidal composition comprises a pesticide carrier and a pesticide adjuvant, the sum of the weight of the pesticide carrier and the pesticide adjuvant accounts for 1 to 90 percent of the weight of the bactericidal composition, the pesticide carrier is a liquid carrier or a solid carrier, and the pesticide adjuvant is one or more selected from the group consisting of an emulsifier, a dispersant, a wetting agent, a thickener, an antifoaming agent, an oxidant, an antifreezing agent, a disintegrant and a filler.
5. Use of the fungicidal composition according to any one of claims 1 to 3 for controlling a plant disease which is potato late blight.
6. A method for controlling plant diseases by applying the fungicidal composition according to any one of claims 1 to 3 to the stem and leaf part, root or plant seed of a plant in a manner of spraying, root application or seed coating in a fungicidally effective amount, wherein the plant diseases are potato late blight, pepper blight, grape downy mildew, cucumber downy mildew.
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