CN114391538B - Sterilization composition containing bronopol - Google Patents

Sterilization composition containing bronopol Download PDF

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CN114391538B
CN114391538B CN202210241037.8A CN202210241037A CN114391538B CN 114391538 B CN114391538 B CN 114391538B CN 202210241037 A CN202210241037 A CN 202210241037A CN 114391538 B CN114391538 B CN 114391538B
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bronopol
crops
cupric
active ingredient
cucumber
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CN114391538A (en
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黎振广
胡强
包如胜
李波
陈伟
李洋
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Shunyi Co ltd
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Shunyi Co ltd
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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
    • A01N33/00Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18Nitro compounds
    • A01N33/20Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • 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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives 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
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N41/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a bactericidal composition containing bronopol, a preparation method and an application scheme thereof. The invention provides a sterilization composition containing bronopol, which comprises bronopol and an active ingredient A, wherein the active ingredient A is selected from one of cupric citrate, cupric abietate and allicin. The weight part ratio of the bronopol to the active ingredient A is 99:1-1:99, and the total weight of the bronopol and the active ingredient A is 1-90% of the weight percentage of the bactericidal composition. The composition has higher activity on a series of bacterial diseases on various crops and obvious synergy, is superior to a single dose in quick acting and lasting effect, reduces the dosage and cost of pesticides, and is beneficial to environmental protection and comprehensive treatment of agricultural diseases.

Description

Sterilization composition containing bronopol
Technical Field
The invention relates to a pesticide sterilization composition and the application field thereof, in particular to a sterilization composition containing bronopol, which is applied to the prevention and treatment of crop bacterial diseases.
Background
Bronopol [ JEPTDQ Journal of Environmental Pathology and toxicology 1977,5 (3) ], CAS No.: 52-51-7, english name: bronopol; chemical name: 2-bromo-2-nitro-1, 3-propanediol; the molecular formula: c 3H6BrNO4; the relative molecular weight 199.9.
The bronopol is a high-efficiency broad-spectrum bactericide, is used for preventing and treating potato black shank, rice bakanae disease and kiwi fruit bacterial canker, has the most wide application especially in preventing and treating the rice bakanae disease, and the researches of the Selaginella et al [ pesticide 1989, (03) ] and Yue Zongdai et al [ Jilin agriculture science 1989, (04) ] show that the effect of the bronopol on preventing and treating the rice bakanae disease is obvious, the researches of the Sun Yanmin et al [ China potato 2020,34 (04) ] show that the effect of the bronopol on preventing and treating the potato black shank is obvious, and the researches of the Wang Rui et al [ Jiangsu agriculture science 2019,47 (11) ] show that the effect of the bronopol on kiwi fruit bacterial canker is obvious.
Allicin [ Antimicrobial AGENTS AND chemotherapy.1997,41 (10) ], CAS number: 539-86-6, english name: alicin; chemical name: diallyl thiosulfinate; the molecular formula: c 6H10OS2; relative molecular weight: 162.27.
The allicin is a high-efficiency broad-spectrum bactericide, can be used for preventing and treating tobacco black shank and pinellia soft rot, has a good growth inhibition effect on white candida beads and staphylococcus aureus, yang Lan et al [ Hunan agricultural science 2013, (08) ] research shows that the allicin has a remarkable effect on tobacco black shank, wang Fanfan et al [ Chinese journal of importance 2021, (11) ] research shows that the allicin has a remarkable effect on pinellia soft rot, mukarramah Zainal et al (Saudi Dental journal.2020) research shows that the allicin can effectively inhibit the growth of white candida beads and staphylococcus aureus, and the inventor speculates that the allicin or more plant infection bacteria exist in prevention and treatment application. At present, no data is reported that the allicin and the bronopol have synergistic antibacterial effect on bacteria after being compounded, the inventor obtains the synergistic antibacterial effect on the antibacterial activity of the allicin and the bronopol through a toxicity test, and the field test proves that the combination has implementation feasibility.
Cupric citrate [ Gansu science 2021,28 (23) ], CAS No.: 10402-15-0, english name: copper Citrate, molecular formula: c 6H4Cu2O7·2.5H2 O, relative molecular weight: 360.22.
Up to the present, no data are reported on the compounding of cupric citrate and bronopol, the inventor obtains the bacteriostasis data of cupric citrate on plant pathogenic bacteria through a toxicity test, knows that the cupric citrate and bronopol have a synergistic effect on the bacteriostasis activity of the cupric citrate and bronopol through the toxicity test, and proves that the combination has implementation feasibility through a field efficacy test.
Copper rosinate [ Hebei fruit tree 1998, (S1) ], CAS number: 10248-55-2, english name: 1-Phenanthrenecarboxylicacid, molecular formula: c 40H58CuO4, relative molecular weight: 666.42.
Copper rosinate is a broad-spectrum bactericide used for preventing and treating citrus canker and cucumber bacterial angular leaf spot, jiang Yigong and the like [ Chinese agricultural technology popularization. 2021,37 (06) ] research shows that the effect of copper rosinate on Wobbe canker is obvious, deng Yinbao and the like [ modern gardening.2017, (23) ] research shows that the effect of copper rosinate on cucumber bacterial angular leaf spot is obvious, and the inventor speculates that copper rosinate or more bacterial prevention and treatment applications exist. At present, no data is reported that the copper rosinate and the bronopol have synergistic antibacterial effect on bacteria after being compounded, the inventor obtains the synergistic antibacterial effect on the antibacterial activity of the copper rosinate and the bronopol through a toxicity test, and the field test proves that the combination has implementation feasibility.
Although the present document discloses compositions of bronopol and inorganic copper, and some organic copper, the composition of bronopol and cupric citrate, cupric rosinate in the present invention is significantly different from those disclosed, because of the difference in chemical structure of the organic copper, which brings about a significant difference in biological activity.
Agricultural bacterial diseases refer to plant diseases caused by bacterial pathogen infection, such as soft rot, canker, bacterial wilt and the like. Bacterial diseases are important factors influencing agricultural production values, and the inventor takes cucumber bacterial diseases as an example to state the application advantages of the composition in cucumber bacterial diseases. Zhang Bo et al [ Chinese vegetables 2012, (15) ] and Peng Yue et al [ Chinese vegetables 2021, (03) ] have found that bacterial angular leaf spot disease of cucumber has a high incidence and affects cucumber yield; kennedy Bw et al [ Plant disease.1980,64 (7) ] studies have shown that cucumber bacterial angular leaf spot causes a decrease in cucumber yield in the United states; the Watanabe Y et al [ JARQ-Japan Agricultural Research Quartly.1983, 17 (2) ] study showed that cucumber bacterial angular leaf spot affects cucumber yield in Japan. It is obvious that the bacterial angular leaf spot of cucumber is considered by all nationists to directly influence the cucumber yield. Therefore, the inventor carries out experimental analysis on pathogenic bacteria of the bacterial angular leaf spot of cucumber and GB/T17980.110-2004 pesticide field efficacy test criterion (II) part 110 based on NY/T1156.16-2008 "Bactericide inhibition bacterial growth test turbidity method": the pesticide effect test of the bactericide for preventing and treating the bacterial angular leaf spot of the cucumber is carried out experimental analysis on the field prevention and treatment of the bacterial angular leaf spot of the cucumber. Wherein, the agricultural industry standard NY/T1156.16-2008 ' bactericide inhibition bacterial growth test turbidity method ' of the people's republic of China provides operation basis and methodology for the virulence measurement embodiment of the invention; national standard of the people's republic of China GB/T17980.110-2004 section 110 of pesticide field efficacy test criterion (two): the pesticide effect test of the bactericide for preventing and controlling the bacterial angular leaf spot of the cucumber provides operation basis and methodology for the application of the pesticide effect in the field.
The method for preventing and treating the agricultural resistance diseases is a common method by compounding different types of pesticides. Based on a large number of indoor toxicity, preparation formulation and field efficacy tests, intensive researches on the compounding of allicin, cupric citrate and copper abietate with bronopol are carried out, and the fact that one of allicin, cupric citrate and copper abietate is compounded with bronopol has obvious synergistic effect in a certain proportion range, has good control effect on crop bacterial diseases, and is further researched, and the invention is completed.
Disclosure of Invention
The invention aims to provide a bactericidal composition with remarkable synergistic control effect on crop diseases.
The invention aims to apply the bactericidal composition to control bacterial diseases of crops.
It is an object of the present invention to provide a more efficient bacterial disease control scheme.
The above object of the present invention is achieved by the following technical solutions:
The invention provides a bactericidal composition containing bronopol, which comprises bronopol and an active ingredient A, wherein the active ingredient A is one of garlicin, cupric citrate or cupric abietate. The weight part ratio of the bronopol to the active ingredient A is 99:1-1:99, and the sum of the bronopol and the active ingredient A accounts for 1-90% of the total weight of the bactericidal composition.
The invention further preferably comprises the step that the active ingredient A of the bactericidal composition is selected from one of cupric citrate, cupric abietate and allicin, the weight part ratio of bromonitro alcohol to the active ingredient A is 60:1-1:60, and the total weight of bromonitro alcohol and the active ingredient A accounts for 1-70% of the total weight of the bactericidal composition.
The bactericidal composition can be prepared into wettable powder, soluble powder, water dispersible granules, soluble granules, aqueous emulsion, microemulsion, emulsifiable concentrate, suspending agent, dispersible oil suspending agent, microcapsule suspending agent, soluble liquid, suspending agent-microcapsule suspending agent, aqueous emulsion-microcapsule suspending agent and other dosage forms according to actual requirements.
The bactericidal composition also contains common auxiliary agents required by preparing pesticide preparations, wherein the common auxiliary agents are one or a mixture of a plurality of solvents, emulsifying agents, wetting agents, stabilizing agents, dispersing agents, thickening agents, pH adjusting agents, defoaming agents, antifreezing agents, filling agents and the like, are all known substances, are various auxiliary agents (Liu Anwen and the like) commonly used in pesticide preparations, are used in modern pesticide formulation processing technology books [ D ]. Chemical industry publishers, beijing.), and can be changed according to different conditions, and are not particularly limited.
The bactericidal composition provided by the invention can be used for preventing and controlling bacterial diseases of crops, wherein the crops are selected from grain crops, economic crops, fruits and vegetables and lawn garden crops, the grain crops comprise corn, rice, wheat and the like, the economic crops comprise peanut, cotton, rape, pseudo-ginseng, ginseng and the like, the fruits and vegetables comprise citrus, apple, pomelo, pear, red bayberry, tomato, eggplant, chilli, cabbage, ginger and the like, and the lawn garden crops comprise flowers and plants on the lawn and trees.
The bactericidal composition provided by the invention can be used for preventing and treating crop bacterial diseases, wherein the bacterial diseases are rice bacterial brown spot, corn bacterial leaf spot, cucumber bacterial angular leaf spot, cabbage bacterial leaf spot and the like, rice bacterial leaf blight, cucumber bacterial leaf blight, melon bacterial leaf blight, tomato bacterial wilt, potato bacterial wilt, strawberry bacterial wilt and the like, citrus canker, soybean bacterial leaf spot, tomato fruit bacterial leaf spot, cabbage bacterial soft rot, chrysanthemum root cancer and the like.
The invention provides a bactericidal composition containing bronopol, which acts on plant pathogenic bacteria and/or the environment thereof or plants, plant parts, plant propagation materials and plant organs, soil or cultivation media, materials or spaces which grow later on, and an active ingredient A, wherein the active ingredient A is selected from one of allicin, cupric citrate or cupric abietate.
The invention provides a bactericidal composition containing bronopol, which is generally used by a spray method, can be also used by other application technologies applied in agriculture according to needs, and is generally applied to plants, plant propagation materials and plant organs, cultivation media, materials or spaces growing later by methods such as seed treatment, foliar application, stem application, soaking, instillation, pouring, spraying, powdering, scattering or fuming and the like in an application amount which is generally agronomically effective and basically non-phytotoxic.
Compared with the prior art, the invention has the advantages that:
1. The combination of one of allicin, cupric citrate or cupric abietate and bronopol has remarkable synergistic effect, and the control effect on germs is improved compared with single-dose single-use.
2. The action mechanism of one of allicin, cupric citrate or cupric abietate is different from that of bronopol, and the mixed use can delay the generation of drug resistance of germ.
3. The combination of one of allicin, cupric citrate or cupric abietate and two effective components of bronopol reduces the use amount of pesticides, reduces the use cost and environmental pollution, and accords with the direction of pesticide decrement and synergy.
Detailed Description
For a better understanding of the nature of the present invention, reference will now be made in detail to the following examples, which are not to be construed as limiting the invention, but are set forth in the following examples. In these examples, all percentages are by weight unless otherwise indicated.
The indoor activity determination method comprises the following steps:
The inventors have tested a number of targets and have demonstrated in an indoor activity assay using the Pseudomonas syringae cucumber angular leaf spot disease pathogenic variant Pseudomonas syringae pv.
The test is carried out by referring to the agricultural industry standard NY/T1156.16-2008 "bacteriocide inhibition bacterial growth test turbidity method":
1. test purpose: screening the indoor toxicity of different compound combinations to bacterial disease pathogenic bacteria;
2. experimental conditions
2.1, Test targets: pseudomonas syringae cucumber angular leaf spot disease pathogenic variant Pseudomonas syringae pv.lachrymans (Smith & gt
Bryan)Yong,Dye&Wilkie
2.2, Culture conditions: LB liquid culture medium, temperature 28.0-30.0 ℃;
2.3, experimental instrument: electronic balance, shaking incubator, culture dish, conical flask, pipette, coater, and constant temperature incubator;
3. Test method
3.1, Preparing mother liquor, and preparing treatment concentration according to each treatment for later use;
3.2, sequentially sucking 3.00mL of liquid medicine from low concentration to high concentration according to the test design, adding the liquid medicine into 27.0mL of LB liquid medium, and repeating every 3 times of treatment; and the final concentration of each treatment is respectively the required concentration;
3.3, taking 100.0 mu L of activated fresh bacterial liquid into an LB liquid culture medium;
3.4, 3.00mL of the culture medium was repeatedly taken from one of the treatments and the OD 600 value was measured before starting the culture, and the culture medium was used as a drug control for each treatment;
3.5, placing the mixture into a constant temperature shaking (180 rpm) at 28.0 ℃ for culturing for 24 hours.
4. The test investigation and calculation method comprises the following steps:
The turbidity of each treatment was measured before the start of the culture, and when the control treatment reached the logarithmic growth phase, the turbidity of each treatment was measured and recorded.
Theoretical toxicity index of the mixture
Drug toxicity index =a drug percentage in the mix
+B agent virulence index x percent of agent in the mix
The theoretical toxicity index of the mixture is equal to the sum of the products of the toxicity index of each single agent and the content of each single agent in the mixture, the co-toxicity coefficient is more than 120 and is synergistic, the co-toxicity coefficient is more than or equal to 80 and less than or equal to 120 and is additive, and the co-toxicity coefficient is less than 80 and is antagonistic.
Indoor Activity measurement example 1: bronitol and allicin
According to the verification of a large number of compounding experiments by the inventor, 5 ratios of 30:1, 10:1, 5:1, 1:1 and 1:5 are adopted for carrying out toxicity test and display, and the test dosage design after the pre-experiment is shown in table 1:
TABLE 1 test dose design of bronopol and allicin
Toxicity test turbidity test is carried out by dosage shown in table 1, the OD 600 value of each cell is counted, the growth inhibition rate of each cell is obtained by data analysis, the growth inhibition rate of single dosage of bronopol and allicin is taken for analysis, and the toxicity baseline and EC 50 value of bronopol and tetramycin are shown in table 2:
TABLE 2 results of indoor toxicity determination of bronitol and allicin against pathogenic bacteria of bacterial angular leaf spot of cucumber
As shown in Table 2, the bronopol and the allicin have bacteriostatic activity on pathogenic bacteria of the bacterial angular leaf spot of the cucumber, wherein the bacteriostatic activity EC 50 of the bronopol on pathogenic bacteria of the bacterial angular leaf spot of the cucumber is 41.31mg/L, and the bacteriostatic activity EC 50 of the allicin on pathogenic bacteria of the bacterial angular leaf spot of the cucumber is 55.39mg/L.
The turbidity test is carried out by the dosage of the medicament shown in table 1, the growth inhibition rate of 5 doses of bromonitro alcohol and allicin to pathogenic bacteria of bacterial angular leaf spot of cucumber is obtained, and the results of the toxicity baseline and EC 50 value of each proportion are shown in table 3:
table 3 results of toxicity determination of bronitol and garlicin 5 compound ratios on cucumber bacterial angular leaf spot
As can be seen from Table 3, each compound agent after the bronitol and the allicin are compounded has antibacterial activity on pathogenic bacteria of bacterial angular leaf spot of cucumber. EC 50 of each proportion is 32.63-46.56mg/L, wherein the proportion is 5:1, the highest activity, EC 50, was 32.63mg/L.
The evaluation of the combined effect of 5 compound ratios of bromonitrol and allicin on pathogenic bacteria of bacterial angular leaf spot of cucumber obtained by analyzing EC 50 value data of each group of compound preparations in Table 3 is shown in Table 4:
Table 4 evaluation of the Combined action of bronitol and garlicin 5 compound ratios on pathogenic bacteria of bacterial angular leaf spot of cucumber
As can be seen from Table 4, the co-toxicity coefficient of 5 proportions of bronopol and allicin is between 89.4 and 132.20, and the joint action modes of different proportions on pathogenic bacteria of bacterial angular leaf spot of cucumber are different, wherein bronopol: the highest total toxicity index value of the synergistic effect of the allicin with the ratio of 5:1 is 132.20.
Experiments after the allicin and the bronopol are mixed show that the allicin and the bronopol have synergism, and the combined use can delay the drug resistance of bacterial angular leaf spot of cucumber, improve the prevention effect, reduce the environmental pollution, save the resources and reduce the agricultural cost of the product.
Indoor Activity measurement example 2: bronitol and cupric citrate
According to the verification of a large number of compounding experiments by the inventor, 5 proportions of 9:4, 1:1, 4:9, 1:5 and 1:10 are adopted for carrying out toxicity test and display, and the test dosage design after the pre-experiment is shown in table 5:
TABLE 5 design of test dose of bronopol and cupric citrate
Toxicity test the turbidity test is carried out by the dosage shown in table 5, the OD 600 value of each cell is counted, the growth inhibition rate of each cell is obtained by data analysis, the growth inhibition rate of the single dosage of bronopol and cupric citrate is taken for analysis, and the toxicity baseline and EC 50 values of bronopol and cupric citrate are shown in table 6:
TABLE 6 determination of indoor toxicity of bronitol and cupric citrate against pathogenic bacteria of bacterial angular leaf spot of cucumber
As can be seen from Table 6, bronitol and cupric citrate have bacteriostatic activity on pathogenic bacteria of cucumber bacterial angular leaf spot, wherein bronitol has bacteriostatic activity EC 50 on pathogenic bacteria of cucumber bacterial angular leaf spot of 45.46mg/L, and cupric citrate has bacteriostatic activity EC 50 on pathogenic bacteria of cucumber bacterial angular leaf spot of 73.52mg/L.
The turbidity test is carried out by the dosage of the medicament shown in Table 5, the growth inhibition rate of 5 doses of bromonitro alcohol and cupric citrate to pathogenic bacteria of bacterial angular leaf spot of cucumber is obtained, and the results of analysis and estimation of virulence baseline and EC 50 value of each proportion are shown in Table 7:
TABLE 7 determination of virulence of bronopol and cupric citrate 5 Compound ratios against cucumber bacterial angular leaf spot
As can be seen from Table 7, each compound agent after the bronitol and the cupric citrate are compounded has antibacterial activity on pathogenic bacteria of bacterial angular leaf spot of cucumber. EC 50 of each proportion is 42.07-62.58mg/L, wherein the activity of the mixture ratio of 4:9 is highest, and EC 50 is 42.07mg/L.
The evaluation of the combined effect of 5 compound ratios of bronopol and cupric citrate on pathogenic bacteria of bacterial angular leaf spot of cucumber, which is obtained by analyzing the EC 50 value data of each group of compound preparations in Table 7, is shown in Table 8:
Table 8 evaluation of the Combined action of bronitol and copper citrate 5 Compound ratios on pathogenic bacteria of bacterial angular leaf spot of cucumber
As can be seen from Table 8, 5 proportions of bronopol and cupric citrate have co-toxicity coefficients between 108.58 and 146.86, and different proportions have different combined action modes on pathogenic bacteria of bacterial angular leaf spot of cucumber, wherein bronopol: the copper citrate has the highest synergistic effect when the ratio of the copper citrate to the copper citrate is 4:9, and the total toxicity index value is 146.86.
Through the experiment after the cupric citrate and the bronopol are mixed, the synergistic effect of the cupric citrate and the bronopol is shown, the drug resistance of the bacterial angular leaf spot of the cucumber can be delayed by combining the cupric citrate and the bronopol, the prevention effect is improved, the environmental pollution is reduced, the resources are saved, and the agricultural cost of the product is reduced.
Indoor Activity measurement example 3: bronitol and copper rosinate
According to the verification of a large number of compounding experiments by the inventor, 5 proportions of 50:1, 10:1, 1:1, 1:10 and 1:50 are adopted for carrying out toxicity test and display, and the test dosage design after the pre-experiment is shown in the table 9:
TABLE 9 design of test dose of bronitol and copper rosinate
Toxicity test turbidity test is carried out by the dosage shown in table 9, the OD 600 value of each cell is counted, the growth inhibition rate of each cell is obtained by data analysis, the growth inhibition rate of each single dosage of bronopol and copper rosinate is taken for analysis, and the toxicity baseline and EC 50 value of the bronopol and copper rosinate are shown in table 10:
TABLE 10 determination of indoor toxicity of bronitol and copper rosinate against pathogenic bacteria of bacterial angular leaf spot of cucumber
As is clear from Table 10, bronitol and copper abietate have bacteriostatic activity on pathogenic bacteria of cucumber bacterial angular leaf spot, wherein the bacteriostatic activity EC 50 of bronitol on pathogenic bacteria of cucumber bacterial angular leaf spot is 38.23mg/L, and the bacteriostatic activity EC 50 of copper abietate on pathogenic bacteria of cucumber bacterial angular leaf spot is 112.35mg/L.
The turbidity test is carried out by the dosage of the medicament shown in Table 9, the growth inhibition rate of 5 doses of bromonitro alcohol and copper abietate to pathogenic bacteria of bacterial angular leaf spot of cucumber is obtained, and the results of analysis and estimation of virulence baseline and EC 50 value of each proportion are shown in Table 11:
Table 11 results of determining virulence of 5 Compound ratios of bronitol and copper rosinate on cucumber bacterial angular leaf spot
As can be seen from Table 11, each compound agent after the bronitol and the copper abietate are compounded has antibacterial activity on pathogenic bacteria of bacterial angular leaf spot of cucumber. EC 50 of each ratio is between 27.37 and 82.12mg/L, wherein the ratio is 1:1, the EC 50 is 27.37mg/L.
The evaluation of the combined effect of 5 compound ratios of bronitol and copper abietate on pathogenic bacteria of bacterial angular leaf spot of cucumber, which is obtained by analyzing the EC 50 value data of each group of compound preparations in Table 11, is shown in Table 12:
table 12 evaluation of the Combined action of bronitol and copper rosinate 5 compound ratios on pathogenic bacteria of bacterial angular leaf spot of cucumber
As can be seen from Table 12, the co-toxicity coefficient of 5 ratios of bronopol and copper abietate is between 103.40-170.70, wherein copper citrate: the synergistic effect of the bronopol with the proportion of 1:1 is highest, and the total toxicity index value is 170.70.
Through the experiment after the cupric citrate and the bronopol are mixed, the synergistic effect of the cupric citrate and the bronopol is shown, the drug resistance of the bacterial angular leaf spot of the cucumber can be delayed by combining the cupric citrate and the bronopol, the prevention effect is improved, the environmental pollution is reduced, the resources are saved, and the agricultural cost of the product is reduced.
According to the toxicity test result, the inventor prepares a compound preparation, and selects part of the compound preparation to display the result.
Formulation shaping example 1:24% bronopol garlicin soluble solution (20:4)
The composition of the 24% bronitol-allicin soluble solution is shown in table 13:
TABLE 13 details of 24% bronopol allicin soluble solution components
According to the details of each component in table 13, adding the effective component 2, the cosolvent and the emulsifier into a stirred tank in sequence, mixing for 10min, adding the effective component 1, the solvent and the defoamer after evenly clarifying the materials, continuously stirring for 10min, and obtaining the 24% bronopol-allicin soluble solution of the bactericidal composition according to the invention after completely evenly clarifying, wherein the product standard detection result of the 24% bronopol-allicin soluble solution of the bactericidal composition according to the invention is shown in table 14:
Table 14 details of detection of various indexes of 24% bronopol-allicin soluble solution
As can be seen from Table 14, the 24% bronopol and allicin soluble agent of the bactericidal composition of the invention meets various standards of products and is a qualified product. Formulation shaping example 2:24% bronopol garlicin soluble solution (12:12)
The composition of the 24% bronitol-allicin soluble solution is shown in table 15:
TABLE 15 details of 24% bronopol allicin soluble solution compositions
According to the details of the components in table 15, the active ingredient 2, the cosolvent and the emulsifier are put into a stirred tank in sequence and mixed for 10min, the active ingredient 1, the solvent and the defoamer are added after the materials are evenly clarified, and stirring is continued for 10min until the materials are completely evenly clarified, so that the 24% bronopol-allicin soluble solution of the bactericidal composition is prepared, and the product standard detection results of the 24% bronopol-allicin soluble solution of the bactericidal composition are shown in table 16:
table 16 details of the detection of various indexes of 24% bronopol/allicin soluble solution
As can be seen from Table 16, the 24% bronopol and allicin soluble agent of the bactericidal composition of the invention meets various standards of products and is a qualified product. Product formulation shaping example 3:70% bronopol, cupric citrate water dispersible granule (35:35)
The components of the 70% bronopol-cupric citrate water dispersible granule are shown in table 17:
Table 17 details of 70% bronopol cupric citrate water dispersible granule composition
According to the details of each component in Table 17, the effective component 1, the effective component 2, the dispersing agent, the wetting agent and the filler are put into a screw mixer to be mixed for 10min, the materials are crushed by air flow until D98 is less than or equal to 18 mu m, the crushed materials are mixed with water by the mixer (82-88 kg of deionized water is used for each ton of materials) to enable the materials to have plasticity, the uniformly mixed materials are extruded into columnar particles with the diameter of 0.8mm, and the columnar particles are dried by hot air at the temperature of 90 ℃ until the moisture is less than 2%, so that the 70% bronopol and cupric citrate water dispersible granule of the bactericidal composition is prepared. The product standard detection results of the 70% bronopol-cupric citrate water dispersible granule of the bactericidal composition of the invention are shown in table 18:
Table 18 details of detection of various indexes of 70% bronopol-cupric citrate water dispersible granule
As can be seen from Table 18, the 70% bronopol cupric citrate water dispersible granule of the bactericidal composition of the invention meets various standards of products and is a qualified product.
Product formulation shaping example 4:65% bronopol, cupric citrate water dispersible granule (20:45)
The composition of the 65% bronopol-cupric citrate water dispersible granule is shown in table 19:
Table 19 details of 65% bronopol cupric citrate water dispersible granule composition
According to the details of each component in Table 19, the active ingredient 1, the active ingredient 2, the dispersing agent, the wetting agent and the filler are put into a screw mixer to be mixed for 10min, the materials are crushed by air flow until D98 is less than or equal to 18 mu m, the crushed materials are mixed with water by the mixer (82-88 kg of deionized water is used for each ton of materials) to enable the materials to have plasticity, the uniformly mixed materials are extruded into columnar particles with the diameter of 0.8mm, and the columnar particles are dried by hot air at the temperature of 90 ℃ until the moisture is less than 2%, so that the 65% bronopol and cupric citrate water dispersible granule of the bactericidal composition of the invention can be prepared. The product standard detection results of 65% bronopol-cupric citrate water dispersible granules of the bactericidal composition of the invention are shown in table 20:
table 20 details of detection of various indexes of 65% bronopol-cupric citrate water dispersible granule
As can be seen from Table 20, the 65% bronopol-cupric citrate water dispersible granule of the bactericidal composition of the invention meets various standards of products and is a qualified product.
Product formulation shaping example 5:60% bronopol, cupric citrate water dispersible granule (10:50)
The components of the 60% bronopol-cupric citrate water dispersible granule are shown in table 21:
table 21 details of 60% bronopol cupric citrate water dispersible granule composition
According to the details of each component in Table 21, active ingredient 1, active ingredient 2, dispersing agent, wetting agent and filler are put into a screw mixer to be mixed for 10min, the materials are crushed by air flow until D98 is less than or equal to 18 mu m, the crushed materials are mixed with water by the mixer (82-88 kg of deionized water is used for each ton of materials) to enable the materials to have plasticity, the uniformly mixed materials are extruded into columnar particles with the diameter of 0.8mm, and the columnar particles are dried by hot air at the temperature of 90 ℃ until the moisture is less than 2%, so that the 60% bronopol and cupric citrate water dispersible granule of the bactericidal composition is prepared. The product standard detection results of 60% bronopol-cupric citrate water dispersible granule of the bactericidal composition of the invention are shown in table 22:
Table 22 details of detection of various indexes of 60% bronopol-cupric citrate water dispersible granule
As can be seen from Table 22, the 60% bronopol cupric citrate water dispersible granule of the bactericidal composition of the invention meets various standards of products and is a qualified product.
Product formulation shaping example 6:80% bronitol, copper rosinate wettable powder (40:40)
The composition of the 80% bronitol-copper abietate wettable powder is shown in table 23:
table 23 details of the components of the 80% bronitol copper rosinate wettable powder
According to the details of each component in Table 23, a carrier and an effective component 2 are mixed for 10min by a gravity-free mixer, an effective component 1, a wetting agent, a dispersing agent and a filler are sequentially added, after mixing for 10min, the mixed materials are subjected to jet milling, and the mixed materials are crushed until D98 is less than or equal to 18 mu m, so that 80% of the bromonitro alcohol-copper abietate wettable powder of the bactericidal composition can be prepared, and the standard detection results of the product of the 80% of the bromonitro alcohol-copper abietate wettable powder of the bactericidal composition are shown in Table 24:
Table 24 details of detection of various indexes of 24% bronitol-copper rosinate wettable powder
As can be seen from Table 24, the 80% bronopol-copper rosinate wettable powder of the bactericidal composition of the invention meets various standards of products and is a qualified product.
Product formulation shaping example 7:77% bronitol, copper rosinate wettable powder (7:70)
The composition of the 77% bronitol-copper rosinate wettable powder is shown in table 25:
table 25 details of the components of the 77% bronitol copper rosinate wettable powder
According to the details of the components in Table 25, a carrier and an effective component 2 are mixed for 10min by a gravity-free mixer, the effective component 1, a wetting agent, a dispersing agent and a filler are sequentially added, after the mixture is mixed for 10min, the mixed materials are subjected to jet milling and are crushed to D98 which is less than or equal to 18 mu m, 77% bronopol and copper abietate wettable powder of the bactericidal composition can be prepared, and the product standard detection results of 77% bronopol and copper abietate wettable powder of the bactericidal composition are shown in Table 26:
Table 26 shows the detection details of various indexes of 77% bronitol-copper rosinate wettable powder
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As can be seen from Table 26, the 77% bronopol-copper rosinate wettable powder of the bactericidal composition of the invention meets various standards of products and is a qualified product.
The inventors performed field efficacy tests on the above formulations, as shown in the product formulation forming examples. The field efficacy standard of the product is described as follows:
The inventor verifies the control effect of the medicament in the embodiment of the invention on a large number of targets, and the control effect of the composition of the invention is shown by taking part of preparation embodiment products as examples on bacterial angular leaf spot of cucumber.
The test refers to the national standard GB/T17980.110-2004 section 110 of pesticide field efficacy test criterion (II): the test of the bactericide for preventing and controlling cucumber bacterial angular leaf spot:
1. test purpose: the field control effect of the different compound combination preparations on the bacterial angular leaf spot of the cucumber;
2. Control object: pathogenic Pseudomonas syringae pv.lachrymans of cucumber bacterial angular leaf spot caused by pseudomonas syringae
3. The application method and the water consumption are as follows: spraying method, water consumption per hectare is 1125L (75L/667 square meter)
4. Cell arrangement, area and repetition:
The cell arrangement adopts a random block arrangement mode, and is specifically determined according to the site, about 1 cell is repeated for 4 times every 25m 2.
5. The test investigation and calculation method comprises the following steps:
5.1, investigation time: investigation was performed on day 10 after the last application.
5.2, Investigation method:
the open field diagonal five-point sampling method comprises 5 plants per point, investigating all leaves, and grading according to the percentage of the disease spot area of each leaf to the whole leaf area.
Grading standard:
Level 0: no disease spots;
Stage 1: the area of the disease spots accounts for less than 5% of the whole leaf area;
3 stages: the area of the lesion accounts for 6% -10% of the whole leaf area;
5 stages: the area of the lesion accounts for 11% -25% of the whole leaf area;
7 stages: the area of the lesion accounts for 26% -50% of the whole leaf area;
Stage 9: the area of the disease spots accounts for more than 51% of the whole leaf area.
5.3 Method for calculating efficacy
The experiments were performed on Cheng Cunda shed cucumbers in the Ouhai region of wenzhou, city on days 10, 12 to 11, 5 of 2021. The cucumber variety is fish maw white. Transplanting cucumber seedlings in the middle ten days of 7 months and the late ten days of 9 months, wherein the seedling age is in the three-leaf period during transplanting, and the transplanting specification is as follows: 35cm x 45cm, the field management level is relatively consistent, and the cucumber growth vigor is relatively consistent. In the initial stage of the disease of the bacterial angular leaf spot of the cucumber during the test, the inventor designs according to the table 27, the table 29 and the table 31 that the bacterial angular leaf spot of the cucumber is applied once each of the 10 th month 12 days of 2021, the 10 th month 19 days of 2021 and the 26 th month of 2021, and the bacterial angular leaf spot of the cucumber is applied three times, and the blank control sprays the same amount of clear water:
Product field efficacy example 1: application of allicin and bronopol
TABLE 27 test design for reagents
According to the test design of table 27, the inventors counted the disease index and analyzed the control effect according to the above test investigation and calculation method at 2021, 11 and 5 days, and the results are shown in table 28:
test results of the various preparations of Table 28 for controlling bacterial angular leaf spot of cucumber
As can be seen from Table 28, the field control effect of the product of the preparation of the bronopol and the garlicin with different proportions on the bacterial angular leaf spot of the cucumber is better than that of the single preparation of the bronopol and the garlicin. The dosage of the product preparation shaping example 1 is 150 g/mu, the dosage of the active ingredients is 540g a.i./hm 2, the effect is optimal, and the average prevention effect reaches 84.97%.
Product field efficacy example 2: application of cupric citrate and bronopol
Table 29 test design for reagents
According to the test design of table 29, the inventors counted the disease index and analyzed the control effect according to the above test investigation and calculation method at 2021, 11 and 5 days, and the results are shown in table 30:
Table 30 test results of the individual formulations for controlling bacterial angular leaf spot of cucumber
As can be seen from Table 30, the field control effects of the products of the preparation of bronopol and cupric citrate with different proportions on bacterial angular leaf spot of cucumber are better than those of the single preparation of bronopol and cupric citrate. The dosage of the product preparation shaping example 4 is 88 g/mu, the dosage of the active ingredients is 858g a.i./hm 2, the effect is optimal, and the average prevention effect reaches 89.07%.
Product field efficacy example 3: application of copper rosinate and bronitol
TABLE 31 test design of reagents for test
According to the test design of table 31, the inventors counted the disease index and analyzed the control effect according to the above test investigation and calculation method at 11 and 5 days of the year, and the results are shown in table 32:
Test results of each preparation of Table 32 for controlling bacterial angular leaf spot of cucumber
As can be seen from Table 32, the field control effect of the products of the preparation of bronopol and copper abietate with different proportions on bacterial angular leaf spot of cucumber is better than that of the single preparation of bronopol and copper abietate. The dosage of the product preparation shaping example 6 is 40 g/mu, the dosage of the active ingredients is 480g a.i./hm 2, the effect is optimal, and the average prevention effect reaches 87.83%.
A large number of experiments show that after bromonitrool is mixed with allicin, cupric citrate or cupric abietate, the activity and the sterilization effect are not simple superposition of the activities of the components, but have obvious synergism. Wherein, when bromonitrol is compounded with allicin, cupric citrate or cupric abietate according to the mass ratio of 99:1-1:99, the compound has certain preventing and killing effect on crop bacterial diseases, especially bacterial angular leaf spot of cucumber. When the bronopol is compounded with allicin, cupric citrate or copper abietate according to the mass ratio of 60:1-1:60, the synergistic effect is shown on crop bacterial diseases, especially cucumber bacterial angular leaf spot. When bromonitrol is compounded with allicin, cupric citrate or copper abietate according to the mass ratio of 50:1-1:50, the synergistic effect on crop bacterial diseases, especially cucumber bacterial angular leaf spot is obvious. Wherein the bronopol: when the allicin ratio is 5:1-1:1, the synergistic effect is remarkable, the co-toxicity coefficient reaches 121.0-132.2, and the bronopol is as follows: when the proportion of the cupric citrate is 1:1-1:5, the synergistic effect is obvious, the co-toxicity coefficient reaches 124.08-138.13, and the bronopol is as follows: when the proportion of the copper rosinate is 50:1-1:50, the synergistic effect is obvious, and the co-toxicity coefficient reaches 131.8-170.7.
In conclusion, compared with the existing preparation, the bactericidal composition for preventing and treating the bacterial diseases of crops has obvious synergistic effect and good preventing and treating effect, can slow down the generation of drug resistance of the bacterial diseases, and is worthy of popularization and application in agricultural production.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather to enable any modification, equivalent replacement, improvement or the like to be made within the spirit and principles of the invention.

Claims (10)

1. The sterilization composition containing the bronopol is characterized by comprising the bronopol and an active ingredient A, wherein the active ingredient A is selected from one of cupric citrate and cupric rosinate, the weight ratio of the bronopol to the active ingredient A cupric citrate is 1:1, 4:9 and 1:5, the weight ratio of the bronopol to the active ingredient A cupric rosinate is 1:1, 1:10 and 1:50, and the total weight of the bronopol and the active ingredient A accounts for 1% -90% of the total weight of the sterilization composition.
2. The bactericidal composition of claim 1, wherein the bactericidal composition is formulated as one of a wettable powder, a soluble powder, a water dispersible granule, a soluble granule, an aqueous emulsion, a microemulsion, an emulsifiable concentrate, a suspension, a dispersible oil suspension, a microcapsule suspension, a soluble solution, a suspoemulsion, a suspension-microcapsule suspension, an aqueous emulsion-microcapsule suspension.
3. The bactericidal composition of claim 2, further comprising a common adjuvant required for formulation of the pesticide formulation, wherein the common adjuvant is selected from one or more of solvents, emulsifiers, wetting agents, stabilizers, dispersants, thickeners, pH adjusters, defoamers, antifreeze, and fillers.
4. Use of the fungicidal composition according to claim 1 for controlling bacterial diseases of crops, wherein the pathogenic bacteria of bacterial diseases of crops are pseudomonas syringae cucumber angular leaf spot disease pathogenic varieties Pseudomonas syringae pv. lachrymans.
5. Use of the fungicidal composition according to claim 4 for controlling bacterial diseases of crops, wherein the crops are selected from one of grain crops and commercial crops.
6. Use of the fungicidal composition according to claim 4 for controlling bacterial diseases of crops, wherein the crops are selected from fruits and vegetables.
7. Use of the fungicidal composition according to claim 4 for controlling bacterial diseases of crops, wherein the fungicidal composition acts on plant pathogenic bacteria and/or the environment thereof.
8. Use of the fungicidal composition according to claim 4 for controlling bacterial diseases of crops, wherein the fungicidal composition acts on plants or cultivation media thereof.
9. A method of using the fungicidal composition of claim 1, characterized in that the fungicidal composition of claim 1 is applied to plants or their cultivation media in an agronomically effective and substantially non-phytotoxic application amount by means of seed treatment, foliar application, stem application.
10. A method of using the fungicidal composition of claim 1, wherein the fungicidal composition of claim 1 is applied to plants or their cultivation media in an agronomically effective and substantially non-phytotoxic application amount by dipping, instilling, casting, spraying, dusting or fuming.
CN202210241037.8A 2022-03-11 2022-03-11 Sterilization composition containing bronopol Active CN114391538B (en)

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CN114748453A (en) * 2022-05-16 2022-07-15 湖北至正天辰生物科技有限公司 Bactericidal composition for preventing and treating diseases of aquaculture animals and application thereof
CN117770250A (en) * 2022-05-20 2024-03-29 青岛海利尔生物科技有限公司 Sterilization composition containing bronopol and application thereof
CN115918656A (en) * 2022-10-13 2023-04-07 顺毅股份有限公司 Bactericidal composition containing biological extract

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