WO2017095051A2 - Composition contenant un dérivé de naphtoquinone pour lutter contre les algues nuisibles et procédé pour lutter contre les algues nuisibles l'employant - Google Patents

Composition contenant un dérivé de naphtoquinone pour lutter contre les algues nuisibles et procédé pour lutter contre les algues nuisibles l'employant Download PDF

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WO2017095051A2
WO2017095051A2 PCT/KR2016/013447 KR2016013447W WO2017095051A2 WO 2017095051 A2 WO2017095051 A2 WO 2017095051A2 KR 2016013447 W KR2016013447 W KR 2016013447W WO 2017095051 A2 WO2017095051 A2 WO 2017095051A2
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formula
algae
compound
water
harmful algae
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WO2017095051A3 (fr
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한명수
주재형
박종성
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한양대학교 산학협력단
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material

Definitions

  • the present invention relates to a harmful algae control composition comprising a naphthoquitone derivative and a method for controlling the harmful algae using the same.
  • Harmful algal blooms are causing various industrial problems, depending on their habitat.
  • the outbreaks of harmful algae in lakes, streams, reservoirs, fish farms, etc. include: 1) aquatic deaths (Duke et al., Weed Sci. 50: 138-151, 2002); 2) It produces off-flavor substances and degrades the quality of drinking water and farmed fish.
  • aquatic deaths Duke et al., Weed Sci. 50: 138-151, 2002
  • the fish smell off- flavors Duke et al., Weed Sci.
  • Toxins that are harmful to humans and animals are produced, for example, some birds, such as the genus Microcystis, Nodularia, Anabaena, and Aphanizomenon. Are known to produce toxins that are harmful to humans and animals, respectively, microcystins, nodularin, anatoxin and saxitoxin (Haider et al., Chemosphere 52: 1-21, 2003); 4) causing discomfort and impeding leisure and industrial activity due to the coloring of water and the formation of scum; 5) Over-treatment of chlorine is necessary due to filter paper closure and inhibition of flocculation sedimentation during water treatment, causing economic loss.
  • Techniques known to date include chemical spraying, ultrasonic and ozone treatment, sponge recovery and sedimentation, and yellow soil spraying.
  • Controlling waterborne contaminants (self-producing organics: green algae) caused by the outbreak of harmful algae in eutrophic lakes and streams is an essential part of solving water resource problems, and the technology to be applied is also economical and has the least amount of ecosystem disruption.
  • the chemical spraying method has been used since the past as a method of spraying copper sulfate (CuSO4), chlorine dioxide (ClO2), simazine (Simazine), etc.
  • CuSO4 copper sulfate
  • ClO2 chlorine dioxide
  • Simazine simazine
  • copper sulfate which is widely used because it is the lowest cost, It can affect other marine organisms, cause problems in terms of toxicity and corrosion to other organisms in the water, and because it only shows temporary effects, it must be used repeatedly, and copper sulfate becomes unstable under the high alkaline environmental conditions accompanying red tide. Because of the large amount of processing has to be disadvantageous.
  • Ultrasonic treatment is the method of destroying cells of red tide causative organisms by ultrasonic waves (160 ⁇ 400kHz), and ozone treatment is a method to neutralize the toxic effects of red tide by putting high pressure ozone in the water where red tide is generated. It is not yet reached.
  • Sponge recovery and sedimentation is a method of generating bubbles by using a pressure flotation device consisting of a centrifuge, agglomeration main tank, a mixing tank, and a pressure flotation tank to adsorb, float, and recover red tide organisms from the sea surface.
  • a pressure flotation device consisting of a centrifuge, agglomeration main tank, a mixing tank, and a pressure flotation tank to adsorb, float, and recover red tide organisms from the sea surface.
  • Is adsorbed and precipitated red tide organisms in seawater, and aluminum ions in loess destroy the cells of living organisms.
  • the yellow soil is sprayed in seawater, suspended solids are increased, and there is a problem that fish gill closure may affect living organisms such as respiratory failure in fish farms and fish farms where settlement organisms live in the lower layers.
  • the present invention has been made to solve the above problems, the present invention is to provide a harmful algae control composition comprising a naphthoquinone derivative that can selectively control the growth of harmful algae.
  • the present invention is to provide a method for controlling or preventing abnormal growth of harmful algae using the harmful algae control composition.
  • the present invention provides a composition for controlling harmful algae comprising a compound selected from the group consisting of compounds represented by the following [Formula 1] to [Formula 5] or a salt thereof as an active ingredient:
  • X is O, S or NR 2 ,
  • R 1 is hydrogen, halogen, CF 3 , a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms,
  • R 2 is hydrogen, acetyl (Ac) or t-butoxycarbonyl (Boc),
  • R 3 is any one selected from the following [Formula 1],
  • the present invention provides a method for controlling harmful algae comprising treating the harmful algae control composition in a region in which harmful algae is busy or in a region in which developmental symptoms are observed.
  • the harmful algae control composition according to the present invention can selectively control only harmful algae in which abnormal proliferation occurs in ponds, reservoirs, lakes, lakes, rivers, or rivers, thereby preventing the occurrence of harmful algae in fresh or seawater and preventing water pollution. It can be very useful to prevent this. In addition, it can be utilized as an important antifouling agent or paint for green algae and red tide has the advantage that the possibility of commercialization is very large.
  • 1 is a view showing the results of testing the green algae control effect on the freshwater microalgae of the harmful algae control composition according to an embodiment of the present invention.
  • FIG. 2 is a view showing the results of testing the green algae control effect on the seawater microalgae of the harmful algae control composition according to an embodiment of the present invention.
  • Figure 3 of the harmful algae control composition according to the present invention for Selenastrum capricornutum, Daphnia magna, Zebrafish (Danio rerio) as indicator organisms for the US EPA standard ecotoxicity assessment A diagram showing the results of the ecotoxicity assessment.
  • Figure 4 is a graph measuring the amount of change in phytoplankton in the microcosm during the treatment of harmful algae control composition according to the present invention for the field water of the Nakdong river dominated by Stephanodiscus (Stephanodiscus).
  • Figure 5 is a graph measuring the change in phytoplankton except for stephanodiscus in the microcosm when the composition for controlling harmful alga according to the present invention with respect to the site number of the Nakdong river dominated by Stephanodiscus (Stephanodiscus).
  • Figure 6 is a graph showing the change in species diversity index of phytoplankton in microcosm when the composition for controlling harmful alga according to the present invention with respect to the field water of the Nakdong River dominated by Stephanodiscus (Stephanodiscus).
  • Copper sulfate or copper organic compounds which have been conventionally used as algae killing agents for harmful algae, have excellent control effects on harmful algae, but are costly, toxic to other organisms, and secondary environmental pollution by chemicals. There was a problem causing. In addition, there was a problem that the selective algae control is not possible to cause a wide range of damage to harmless bird species. There was a problem of causing secondary disturbance in the ecosystem.
  • the present invention is a solution to the conventional harmful algae control technology described above, which has a selective control effect only on harmful algae to prevent a wide range of damage to aquatic organisms and ecosystem secondary disturbances and harmful algae using the same It relates to a method of controlling.
  • the present invention provides a harmful algae control composition
  • a harmful algae control composition comprising a compound selected from the group consisting of compounds represented by the following [Formula 1] to [Formula 5] or a salt thereof as an active ingredient:
  • X is O, S or NR 2 ,
  • R 1 is hydrogen, halogen, CF 3 , a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms,
  • R 2 is hydrogen, acetyl (Ac) or t-butoxycarbonyl (Boc),
  • R 3 is any one selected from the following [Formula 1],
  • the compound represented by the above [Formula 1] to [Formula 5] comprises a compound selected from the compound represented by the following [Formula 6] to [Formula 56] or homologue compounds thereof, or salts thereof as an active ingredient. :
  • the salts of the compounds can be prepared in situ or separately reacted with an inorganic base or an organic base during the final separation, purification and synthesis of the compounds of the present invention.
  • the salt may form a salt with a base when the compound of the present invention contains an acidic group.
  • the salt include, but are not limited to, alkali metals such as lithium salts, sodium salts or potassium salts. Salts of; Salts with alkaline earth metals such as barium or calcium; Salts with other metals such as magnesium salts; Organic base salts such as salts with dicyclohexylamine; Salts with basic amino acids such as lysine or arginine.
  • an acid addition salt may be formed.
  • acid addition salt include, but are not limited to, inorganic acids, especially hydrofluoric acid (eg, hydrofluoric acid, hydrobromic acid, Hydroiodic acid or hydrochloric acid), salts with nitric acid, carbonate, sulfuric acid or phosphoric acid; Salts with lower alkyl sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or ethanesulfonic acid; Salts with benzenesulfonic acid or p-toluenesulfonic acid; Salts with organic carboxylic acids such as acetic acid, fumaric acid, tartaric acid, oxalic acid, maleic acid, malic acid, succinic acid or citric acid; And salts with amino acids such as glutamic acid or aspartic acid.
  • hydrofluoric acid eg, hydrofluoric acid, hydrobromic acid, Hydroiodic acid or hydrochloric acid
  • Compound 1 to [Formula 5] or “Compound 6-56” according to the present invention is the compound itself, salts, hydrates, and solvates thereof. Can be used as a concept including all isomers.
  • hydrate includes a compound of the present invention comprising a stoichiometric or non-stoichiometric amount of water bound by a non-covalent intermolecular force. Or salts thereof.
  • solvate refers to a compound of the present invention or a salt thereof comprising a stoichiometric or nonstoichiometric amount of solvent bound by noncovalent intermolecular forces.
  • the compounds according to the invention can be prepared and used by methods known in the art, by their modified methods or by the method according to the invention, or can be purchased and used commercially.
  • the reaction solvent that can be used in the production process is not particularly limited as long as it is not involved in the reaction, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane; Halogenated hydrocarbons such as dichloromethane and chloroform; Amines such as pyridine, piperidine and triethylamine, acetone; Alkyl ketones such as methyl ethyl ketone and methyl isobutyl; Alcohols such as methanol, ethanol and propanol; Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, hexamethyl phosphate triamide, and the like, and especially non-reactive used in organic synthesis.
  • ethers such as diethyl ether, tetrahydrofuran, dioxane
  • Halogenated hydrocarbons such as dichloromethane and
  • a solvent capable of separating the water generated during the reaction by the Dean-Stark trap is preferred.
  • examples of such a solvent include, but are not limited to, benzene, toluene, xylene, and the like.
  • Separation and purification of the reaction product is carried out through a process such as concentration, extraction, and the like, which is commonly performed in organic synthesis, and separation and purification may be performed through purification by column chromatography on silica gel, if necessary.
  • the invention also includes any modification to the methods for the preparation of the compounds, wherein the intermediate product obtainable in any of its steps can be used as starting material for the remaining steps, the starting material being reacted under reaction conditions. Formed within, or the reaction components can be used in the form of its salts or optically enantiomers.
  • the present invention relates to a method for preparing the compound of the above [Formula 1] to [Formula 5] from another viewpoint.
  • the preparation method is merely an exemplary method thereof, and may be suitably modified by various methods based on the art.
  • the separation and purification of non-exemplified compounds according to the present invention Modifications apparent to those skilled in the art can be successfully carried out, for example, by appropriately protecting the interferer, replacing it with another suitable reagent known in the art, or by customarily changing the reaction conditions.
  • algae inhabit the sea or fresh water and affect the ecosystem a lot
  • the term "harmful algae” used in the present invention causing the algae or red tide phenomena that adversely affects the following A bird that adversely affects the environment and economic activities.
  • Red tide is a phenomenon in which the color of the sea turns red, reddish brown, tan, green, yellow green and yellow due to abnormal growth of plankton due to the influx of organic pollutants, nitrogen and phosphorus from the land to the sea.
  • the causes of such red tide are mainly flagella algae and diatoms, and in addition, ciliated insects, cyanobacteria and red bacteria are known to cause red tide.
  • the present invention has an algicidal effect against the flagella algae and diatoms, cyanobacteria, etc. which cause the red tide.
  • the present invention is very effective in suppressing the growth of red algae as well as the above-described red algae.
  • Green algae refers to a phenomenon in which floating algae, or phytoplankton, multiply and accumulate on the surface of water in eutrophic lakes or slow-flowing streams, thereby turning the color of the green color significantly green.
  • Green algae is a symbolic phenomenon of water eutrophication, causing severe taste and toxic substances and destroying the balance and order of the entire aquatic ecosystem as well as its value as a water resource.
  • Green algae generally occur only in fresh water. Plant wastewater, domestic sewage, fertilizers, pesticides, livestock and human manure, and other land pollutants enter rivers or lakes, are sedimented in the lower part of the body of water, decomposed by bacteria and decomposed. Organics produce nitrogen and phosphorus, which feed plankton, causing green algae in sea and fresh water. These green algae reduce dissolved oxygen in the water, produce toxic green algae and various green alga planktons, killing fish and aquatic organisms, and depositing heavy metals in the bottom of the water where organic matters from the land are deposited. It can pollute and poison fish, and cause many problems such as environmental damage and damage to natural beauty.
  • algae blooming in rivers and lakes are mainly cyanobacteria in summer and diatoms in spring and winter, but various species of algae, such as wa- chyloid and small silver flanking seedlings, vary depending on the region. It is caused by.
  • the green algae is a symbolic phenomenon of water eutrophication, causing severe odors and generating toxic substances, which destroys the balance and order of the entire aquatic ecosystem as well as its value as a water resource.
  • composition for controlling harmful algae containing the compound of [Formula 1] to [Formula 6] according to the present invention is a microalgae (namzo, diatoms, green algae, in freshwater or seawater such as ponds, reservoirs, lakes, lakes, rivers or rivers) It is possible to more effectively control the occurrence of green algae caused by abnormal proliferation of euglejo steel, whiskey imitation steel and yellow wool imitation steel, brown schist imitation steel and redness steel).
  • the harmful algae that may exhibit the algae effect of the present invention include Namjo River, Diatom Steel, Green Algae River, Waco-Modulated Steel, Needle-Shaped Hair Steel, Euglenazo Steel, Yellow Knitted Steel, Brown Knitted Steel and Contains red algae algae.
  • the Cyanophyceae algae is a microcystis, Anabena, Aphanizomenon, Oscillatoria, and Waronichinia genus algae. It may be selected, and preferably may be algae of the genus Microcystis or Anabaena.
  • the diatom steel (Bacillariophyceae) algae are Stefanodiscus, Cyclotella, Cyclostaphanos, Aulacoseira, Mellosira, Thalassiosira, Ketose Chatoceros Skeletonema, Achnanthes, Asterionella, Acanthoceras, Navicula, Nitzschia, Diploloneis ), Cymbella, Gomphonema, Surirella, Synedra, Frazilaria, Cylindrotheca, Eucampia, Kosmarium ( Cosmarium, and a group consisting of birds of the genus Tabellaria, and may preferably be a bird of the genus Stepanoodiscus, Cyclolotella, or Aulacoseira. .
  • the algae (Chlorophyceae) algae are Closteriopsis (Closteriopsis), Closterium (Closterium), Hydrotheca (Hydrotheca), Spirogyra (Spirogyra), Gonatozygon (Aconastrum), Micractinium, Lagerheimia, Westella, Eudorina, Pandorina, Volvox, Dictiospaerium, Clarococum (Chlorococcum), Botryococcus, Staurastrum, Closterium, Monoraphidium, Ankistrodesmus, Kirchneriella , Pediastrum, Senedesmus, Coelastrium, Clamydomonas and Chlorella genus.
  • the Euglenophyceae algae may be selected from a crowd consisting of Trachelomonas, Phacus, and Euglena.
  • the algae (Dinophyceae) algae (Alecandrium), Coclodinium (Cochlodinium), heterocapsa (Heterocapsa), Prorocentrum (Prorocentrum), Peridinium (Ceratium), the crowd consisting of algae Can be selected from.
  • the needle-like imitation steel (IRaphidophyceae) algae may be a genus Chattonella (Chattonella).
  • the Chrysophyceae algae may be selected from the group consisting of Dinobryon, Euroglena, Synura, and Malolomonas algae.
  • the brown flagella steel (Cryptophyceae) algae may be Cryptomonas algae.
  • the red blood (Phodophyceae) algae may be algae of the genus Rhodomonas.
  • the present invention provides a composition for controlling harmful algae containing a compound selected from the group consisting of compounds represented by the above [Formula 1] to [Formula 5] or a salt thereof as an active ingredient.
  • the harmful algae control composition of the present invention can be prepared in a variety of forms according to known methods, formulations for the stable expression of the effect within the range that does not inhibit the effect, enhanced adhesion to the organism to be applied, simplicity of transport and treatment It may further comprise a surfactant such as an academically acceptable solid carrier, liquid carrier, liquid diluent, liquefied gas diluent, solid diluent, or other suitable adjuvant such as emulsifiers, dispersants or foaming agents.
  • a surfactant such as an academically acceptable solid carrier, liquid carrier, liquid diluent, liquefied gas diluent, solid diluent, or other suitable adjuvant such as emulsifiers, dispersants or foaming agents.
  • the harmful algae control composition of the present invention may preferably be formulated into an emulsion, an hydrating agent, a granule, a powder, a capsule and a gel, and is preferably provided as a contact agent for buoyancy of the preparation.
  • the present invention is harmful including the treatment of a compound selected from the group consisting of the compounds represented by the above [Formula 1] to [Formula 5] or salts thereof to the area where the harmful algae occurred or to the area of development Provides a method for controlling algae.
  • compositions in the form of a powder or a high concentration of liquid form by spraying locally on the area where the green algae occurred or visible signs using a simple green alga within a few days to a week can be controlled and prevented.
  • the present invention It is a technology (green control or prevention) that can be applied to the restoration and preservation management of small-scale water systems, and applied to artificial farms, golf courses, parks, amusement parks, ponds in recreational facilities, reservoirs, lakes, rivers, and agricultural reservoirs scattered throughout the country. Preventing damage and controlling harmful algae does not cause other environmental pollution. In addition, it can be used as a major component of antifouling paint used in ships, wharf facilities, swimming pools, buildings, etc., and replaces toxic conventional paints. It can also be prevented.
  • Naphthoquinone derivatives according to the present invention were prepared by the following method.
  • Formula 19] Formula 20: 1- (6-Methoxy-2-(((1,4,5,8-tetramethoxynaphthalen-2-yl) methyl) -amino) -1H-benzo [d] imidazol- 1-yl) ethan-1-one, 1- (5- methoxy -2-(((1,4,5,8- tetramethoxynaphthalen -2- yl ) methyl) amino) -1H-benzo [d] imidazol-1-yl) ethan-1-one
  • the compound of [Formula 49] was prepared using 5 mL of methanol in 158 mg of stirred naphthalen-1,4-dione in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain the compound of [Formula 49]. Yield: 68%
  • the compound of [Formula 50] was prepared using 5 mL of methanol in 158 mg of stirred naphthalen-1,4-dione in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain a compound of [Formula 50]. Yield: 57%
  • the compound of [Formula 51] was prepared using 5 mL of methanol in 158 mg of naphthalen-1,4-dione, which was stirred in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain the compound of [Formula 51]. Yield: 62%
  • the compound of [Formula 52] was prepared by using 5 mL of methanol in 158 mg of naphthalen-1,4-dione, which was stirred in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain the compound of [Formula 52]. Yield: 60%
  • the compound of [Formula 53] was prepared by using 5 mL of methanol in 158 mg of naphthalen-1,4-dione, which was stirred in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain the compound of [Formula 53]. Yield: 60%
  • the compound of [Formula 54] was prepared using 5 mL of methanol in 158 mg of stirred naphthalen-1,4-dione in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain the compound of [Formula 54]. Yield: 29%
  • the compound of [Formula 55] was prepared using 5 mL of methanol in 158 mg of naphthalen-1,4-dione, which was stirred in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain the compound of [Formula 55]. Yield: 25%
  • the compound of [Formula 56] was prepared using 5 mL of methanol in 158 mg of naphthalen-1,4-dione, which was stirred in 5 mL of methanol. Specifically, after 24 hours of reaction at room temperature, the reaction mixture was concentrated in vacuo and purified by flash column chromatography (100% EtOAc) to obtain the compound of [Formula 56]. Yield: 21%
  • Treatment conditions were directly counted visually by SR-chamber or heamocytometer under incubation or inverted microscope while incubating for 7 days or 10 days under incubation conditions of algae. After 7 or 10 days after treatment, the reduction ratio of the cells, ie, the algal activity (%), was calculated using the following formula.
  • Algal activity (%) (1- Tt / Ct ) x 100
  • T represents the density of cells after compound treatment
  • C represents the density of cells not treated with compound
  • t represents culture time
  • the algae effect was derived by inoculating the substances developed for various phytoplankton including harmful algae at concentrations of 1, 5, 10, and 20M, respectively.
  • Algal activity of each compound obtained on the basis of the above formula was expressed as ⁇ 60, 70, 80, 90%.
  • the algicidal effects of the compounds were screened using a Microplate assay.
  • the synthesized derivatives were inoculated into each algal species in each log growth period at a concentration of 1 to 20 uM and cultured and counted for 7 days.
  • On day 0, 1, 2, 4, and 7, take 10-50 ul of sample from each well, place on a Neubauer hemocytometer or SR chamber, count the intact algae cells under an IX71 microscope (Olympus, Japan).
  • the killing ability (%) of the substance was determined by measuring the cell number decreased compared to the control.
  • the cell counts of the 7th day of the experiment showed the killing ability of the corresponding algae according to the concentration of each algae.
  • FIG. 1 is a view showing the results of testing the green algae control effect on the freshwater microalgae of the harmful algae control composition according to an embodiment of the present invention
  • Figure 2 is a composition of the harmful algae control composition according to an embodiment of the present invention
  • the compounds of [Formula 6] to [Formula 56] according to the present invention showed more than 90% of the killing ability at 1, 5, 10, 20 uM concentrations of cyanobacteria Anabaena sp. And Microcystis sp. Especially, even at very low concentration of 1 uM, more than 90% of the effects could be observed, and only harmful cyanobacteria could be specifically controlled. Especially, Anabaena sp. Showed more than 90% algae effect at low concentration of 1 uM, and it was the main causative species of algae in winter and the diatoms Stephanodiscus sp. At 1, 5, 10, 20 uM showed more than 80% of the killing effect.
  • composition containing the compounds of the present invention as an active ingredient is Aulacoseira. granulata , Synedra While it has little effect on species that are relatively less problematic in freshwater and brackish waters such as acus , it has been found that there is an excellent algae effect against harmful algae that cause green algae and red tide phenomena at home and abroad.
  • Selenastrium an indicator organism for evaluating ecotoxicity of OECD, EPA, to investigate the effects of compounds according to the present invention on ecosystem capricornutum (selenastrium capricornium ) , Daphnia magna , Danio Ecotoxicity assessment was performed using rerio (zebrafish ) .
  • Selenastrum capricornutum (selenastrum capricornium ) was prepared and inoculated with a new compound to prepare a starting density and inoculation concentration of the indicator organism at 1 ⁇ 10 4 cells / mL, 2, 1, 0.5, 0.2, and 0.1 ⁇ M, respectively. .
  • Mixed cultures were incubated under the optimal growth conditions of indicator organisms (20 ° C., 50 mol / m 2 s, EG: JM medium, 12hr light: 12hr dark cycle). The change in the number of indicator organisms was directly observed under an optical microscope for 72 hours at 12 hours.
  • Figure 3 of the composition for controlling harmful algae according to the present invention for Selenastrium capricornutum, Daphnia magna, Zebrafish (Danio rerio) as indicator organisms for the EPA standard ecotoxicity assessment A diagram showing the results of the ecotoxicity assessment.
  • the compounds according to the present invention are Selenastrum capricortrum, Daphnia magna, Danio according to the inoculation concentration
  • the compounds according to the present invention are Selenastrum capricortrum, Daphnia magna, Danio according to the inoculation concentration
  • Example 3 10 L scale Microcosm test for species diversity enhancing effect
  • Stephanodiscus sp To determine whether the algae control technology using the composition for controlling harmful algae containing the compounds according to the present invention affects aquatic ecosystem restoration and species diversity. Microcosm experiments were performed using the predominant Nakdong River field water.
  • Figure 4 is a graph measuring the amount of change in phytoplankton in microcosm when the harmful algae control composition according to the present invention with respect to the field number of the Nakdong River dominant stephanodiscus, Figure 5 except for stephanodiscus in microcosm It is a graph measuring the change in phytoplankton, Figure 6 is a graph showing the change in species diversity index of phytoplankton in the microcosm.
  • Stephanodiscus sp. A target bird, increased from 3.9 ⁇ 10 3 cells / mL to 9.1 ⁇ 10 4 cells / mL in the control group during the experimental period, but in the treatment group inoculated with the compound according to the present invention from day 2 to 10 after inoculation continue to decrease until the 10th day, the target species Stephanodiscus While the sp. species decreased to 6.4 ⁇ 10 2 cells / ml, the algae effect was observed to be 99%, whereas for phytoplankton other than the target species Stephanodiscus sp., in the control group, the Stephanodiscus sp.
  • According to the present invention can be very useful for preventing harmful algae generation and fresh water pollution occurring in fresh or sea water.
  • it can be utilized as an important antifouling agent or paint for green algae and red tide has the advantage that the possibility of commercialization is very large.

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Abstract

La présente invention concerne une composition contenant un dérivé de naphtoquinone pour lutter contre les algues nuisibles et un procédé pour lutter contre les algues nuisibles l'employant. La composition pour lutter contre les algues nuisibles selon la présente invention peut lutter sélectivement seulement contre les algues nuisibles qui prolifèrent de façon anormale dans une mare, un réservoir, un lac, un marais, un ruisseau, une rivière ou un lieu similaire, et ainsi, la composition selon la présente invention est très utile pour empêcher la formation d'une grande quantité d'algues nuisibles dans l'eau douce ou l'eau salée et empêcher la contamination de l'eau.
PCT/KR2016/013447 2015-12-03 2016-11-22 Composition contenant un dérivé de naphtoquinone pour lutter contre les algues nuisibles et procédé pour lutter contre les algues nuisibles l'employant WO2017095051A2 (fr)

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KR1020150171282A KR101829962B1 (ko) 2015-12-03 2015-12-03 나프토퀴논 유도체를 포함하는 유해조류 제어용 조성물 및 이를 이용한 유해조류 제어방법
KR10-2015-0171282 2015-12-03

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CN113544116A (zh) * 2019-02-19 2021-10-22 韩明洙 水溶性萘醌衍生物组合物和其制备方法、有害藻类控制用水溶性组合物、大规模有害藻类控制方法、以及大规模有害藻类人工智能监控、去除以及预防自动化系统

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KR20220053326A (ko) * 2020-10-22 2022-04-29 엘지전자 주식회사 식물 재배 장치
CN113994946A (zh) * 2021-10-12 2022-02-01 广东海洋大学 邻羟基肉桂酸在清除有害底栖硅藻中的应用

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JP2006036746A (ja) 2004-06-24 2006-02-09 Sanei Gen Ffi Inc 赤潮原因藻駆除剤、及びそれを用いる赤潮防御方法
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KR101436792B1 (ko) * 2011-07-08 2014-09-05 한양대학교 산학협력단 나프토퀴논 화합물을 함유하는 유해조류 제어용 조성물
KR101405275B1 (ko) * 2012-02-28 2014-06-11 조선대학교산학협력단 나프토퀴논 유도체를 유효성분으로 포함하는 적조 방제용 조성물

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113544116A (zh) * 2019-02-19 2021-10-22 韩明洙 水溶性萘醌衍生物组合物和其制备方法、有害藻类控制用水溶性组合物、大规模有害藻类控制方法、以及大规模有害藻类人工智能监控、去除以及预防自动化系统

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WO2017095051A3 (fr) 2017-07-20
CN108601352A (zh) 2018-09-28
KR20170065171A (ko) 2017-06-13

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