阅读说明：本技术 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 (Water-soluble naphthoquinone derivative composition and method for producing same, water-soluble composition for controlling harmful algae, large-scale harmful algae control method, and large-scale ha) 是由 徐海东 韩明洙 于 2020-01-22 设计创作，主要内容包括：本发明涉及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。根据本发明的一个实施例,提供一种水溶性萘醌衍生物组合物制备方法,其中,使1,4-萘醌化合物和N,N-二乙基乙烯基二胺发生反应,得到化学式2的中间产物,在化学式2的中间产物反应盐酸,得到化学式1的化合物。另外,提供一种由化学式1表示的水溶性萘醌衍生物组合物。进一步地,提供一种有害藻类控制用水溶性组合物、利用有害藻类控制用水溶性组合物的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。(The present invention relates to a water-soluble naphthoquinone derivative composition and a preparation method thereof, a water-soluble composition for harmful algae control, a large-scale harmful algae control method, and a large-scale harmful algae artificial intelligence monitoring, removal, and prevention automation system. According to an embodiment of the present invention, there is provided a method for preparing a water-soluble naphthoquinone derivative composition, in which a 1,4-naphthoquinone compound and N, N-diethylvinyldiamine are reacted to obtain an intermediate product of chemical formula 2, and hydrochloric acid is reacted in the intermediate product of chemical formula 2 to obtain a compound of chemical formula 1. In addition, a water-soluble naphthoquinone derivative composition represented by chemical formula 1 is provided. Further, a water-soluble composition for harmful algae control, a large-scale harmful algae control method using the water-soluble composition for harmful algae control, and a large-scale harmful algae artificial intelligence monitoring, removing, and preventing automation system are provided.)

1. A method for preparing a water-soluble naphthoquinone derivative composition,

reacting a 1,4-naphthoquinone compound with N, N-diethylethylenediamine to obtain an intermediate product of the following chemical formula 2,

reacting hydrochloric acid in the intermediate of the following chemical formula 2 to obtain the compound of the following chemical formula 1,

chemical formula 1

Chemical formula 2

2. The method for producing a water-soluble naphthoquinone derivative composition according to claim 1,

the intermediate of chemical formula 2 is produced by adding the N, N-diethylvinyldiamine to a mixture in which the 1,4-naphthoquinone compound is mixed with methanol to react,

the compound of chemical formula 1 is produced by mixing the intermediate product of chemical formula 2 and diethyl ether with the mixed solution of hydrochloric acid and diethyl ether.

3. A water-soluble naphthoquinone derivative composition represented by the following chemical formula 1,

chemical formula 1

4. A water-soluble composition for controlling harmful algae, which comprises the water-soluble naphthoquinone derivative composition according to claim 3 as an active ingredient.

5. The water-soluble composition for controlling harmful algae according to claim 4, wherein the water-soluble naphthoquinone derivative composition is prepared by the preparation method of claim 1 or 2.

6. The water-soluble composition for controlling harmful algae according to claim 4, wherein the harmful algae controlled by the water-soluble composition for controlling harmful algae is selected from the group consisting of algae belonging to the class Cyanophyceae, the class Diatomae, the class Lagophyceae, and the class Nematophyceae.

7. The water-soluble composition for harmful algae control according to claim 6,

the algae of Cyanophyceae is selected from the group consisting of Microcystis, Long-spore algae, and Aphanizomenon,

the algae of class Zodiaceae is selected from the group consisting of Cyclotella polycycloxus, Alexandrium tamarense, Prorocentrum donii, Red Tibet algae,

the algae of the class of the needle cytophyceae is heterosigma akashiwo algae.

8. The water-soluble harmful-algae-controlling composition according to any one of claims 4 to 7, wherein the water-soluble harmful-algae-controlling composition is formulated into one of a powder, a granule, a capsule, and a liquid.

9. A large-scale harmful algae control method characterized in that the water-soluble composition for controlling harmful algae according to any one of claims 4 to 7 is spray-treated without an organic solvent to a water area where large-scale harmful algae are produced or a sign of the production is observed.

10. The large-scale harmful algae control method according to claim 9, wherein the water-soluble composition for controlling harmful algae is spray-treated in one form of powder type, granule type, capsule type to an aqueous solution form.

11. The large-scale harmful algae control method according to claim 10, wherein the water-soluble composition for controlling harmful algae is spray-treated to a large-scale water area using one of a remotely-controlled unmanned ship and an unmanned aircraft.

12. An automated system for large scale artificial intelligence monitoring, removal and prevention of unwanted algae, comprising:

a monitoring device which is installed in a large-scale water area having a history of harmful algae production or a large-scale water area having a sign of the harmful algae production predicted or the surrounding area, and monitors the production of the harmful algae;

an unmanned spraying apparatus, which is one or more of a remotely controlled unmanned ship and an unmanned aircraft, and which is provided with a device for spraying the water-soluble composition for controlling harmful algae according to any one of claims 4 to 7 under remote control; and

and a control device for transmitting the monitoring result from the monitoring device, judging whether the harmful algae are generated, and controlling the unmanned spraying device to spray when the harmful algae based on the set standard are generated.

Technical Field

The present invention relates to a water-soluble naphthoquinone derivative composition and a preparation method thereof, a water-soluble composition for harmful algae control, a large-scale harmful algae control method, and a large-scale harmful algae artificial intelligence monitoring, removal, and prevention automation system. And more particularly, to a water-soluble naphthoquinone derivative composition and a preparation method thereof, a water-soluble composition for harmful algae control, a large-scale harmful algae control method, and a large-scale harmful algae artificial intelligence monitoring, removal, and prevention automation system, which can be directly used in on-site water without an organic solvent due to improved water solubility.

Background

In the eutrophic water ecosystem in temperate regions of korea, based on abundant nutritional components, an environment favorable for the growth of primary producers such as phytoplankton is created, and bloom of harmful algae is explosively repeated every year (environmental ministry 2012). In the domestic water system of korea, the residence time of water is increased in rivers or dams due to the retention time of fresh water, and the like, and the water conservancy and hydrological environment and climate are changed, thereby further accelerating the mass propagation of harmful algae. In particular, a new vocabulary of 'green tide latte iron' appears in the whole south Han Jiang and north Han Jiang including Luo Dong Jiang, so that the green tide becomes a social problem.

On the one hand, disasters caused by harmful algae are not limited to fresh water ecosystems, and the red tide disasters of oceans are serious. Harmful red tide organisms have toxicity such as PSP, DSP, ASP and the like, and are concentrated in fish and shellfish, so that the harmful red tide organisms cause death not only to humans ingesting the fish and shellfish but also to algae, mammals, pets and livestock on the waterside or seaside.

Not only korea but also the world has been studied in many ways to control the green and red tide phenomena, but it is expected that large-scale harmful algae cannot be protected by the technology commercialized so far.

Conventionally, for controlling harmful algae, chemical algicides (algicides) such as copper (copper), renone (regalone) a, potassium permanganate (potassium permanganate), chlorine (chlorine), Simazine (Simazine), etc., coagulants such as clay, phosphorus-locking agents, etc., have been directly sprayed on water systemsAnd the like, phosphorus reduction treatment. The refractory materials such as heavy metals belonging to the above chemical method have a problem of secondary pollution such as toxicity caused by bio-concentration through a food chain, and the coagulant requires secondary treatment by recovering sludge, so that costs for manpower and equipment operation are incurred, and especially the precipitant such as loess is predicted to be unbalanced in the benthic ecosystem and is limited. Due to the disadvantages of the respective technologies, not only is there a problem that it is difficult to use on site, but also ecosystem stability may be threatened.

On the other hand, in order to overcome the problems described above, a technique has been proposed relating to a composition for controlling harmful algae, which is prepared from a naphthoquinone derivative having an algae-killing effect on harmful algae and uses the naphthoquinone derivative. As also proposed in the patent documents described later, the conventional naphthoquinone-based algae removal agent is not easily soluble in water and is insoluble. Therefore, in order to be used uniformly in an aqueous system, it is necessary to first dilute the solution with an organic solvent such as a Dimethylsulfoxide (DMSO) solution. Most of organic solvents such as DMSO used in the conventional naphthoquinone-based harmful algae removal composition exhibit ecotoxicity at high concentration, and thus have a problem that there may be some degree of ecosystem imbalance. In addition, in order to dilute the solvent at one time, it is necessary to further increase transportation units and infrastructure, and thus the existing naphthoquinone-based composition requiring an organic solvent becomes a cause of reducing the economy of the harmful algae defense operation.

Disclosure of Invention

The present invention relates to a naphthoquinone derivative capable of removing harmful algae by selectively destroying only the harmful algae, and a composition for controlling harmful algae and a control method using the same. The present invention has been made in view of the above problems, and it is an object of the present invention to provide a water-soluble naphthoquinone derivative composition and a method for preparing the same, a water-soluble composition for controlling harmful algae, a method for controlling harmful algae, and an automated system for artificial intelligent monitoring, removal, and prevention of harmful algae in a large scale, which can enhance water solubility without using an organic solvent, and can be used by directly dissolving a powder in water on site.

In order to accomplish the above objects, according to an aspect of the present invention, there is provided a method for preparing a water-soluble naphthoquinone derivative composition, in which a 1,4-naphthoquinone compound and N, N-diethylvinyl diamine are reacted to obtain an intermediate of the following chemical formula 2, and hydrochloric acid is reacted in the intermediate of the chemical formula 2 to obtain a compound of the following chemical formula 1.

Chemical formula 1

Chemical formula 2

In this case, in one example, the intermediate product of chemical formula 2 may be produced by adding the N, N-diethylvinyldiamine to a mixture of methanol and a 1,4-naphthoquinone compound and reacting the mixture, and the compound of chemical formula 1 may be produced by reacting the intermediate product of chemical formula 2 and a mixed solution of diethyl ether and hydrochloric acid mixed with a mixed solution of diethyl ether.

Next, according to still another aspect of the present invention, there is provided a water-soluble naphthoquinone derivative composition represented by the chemical formula 1.

In addition, according to still another aspect of the present invention, there is provided a water-soluble composition for controlling harmful algae, which contains the above-mentioned water-soluble naphthoquinone derivative composition as an active ingredient in the water-soluble composition for controlling harmful algae.

At this time, in one example, the water-soluble naphthoquinone derivative composition may be prepared by one of the above-described water-soluble naphthoquinone derivative composition preparation methods.

In addition, in one example, the harmful algae controlled by the water-soluble composition for controlling harmful algae may be selected from the group of algae consisting of cyanophyceae, diatoms, synechophytes, and conidiophores.

In this case, in another example, the algae of the cyanobacteria class may be selected from the group consisting of Microcystis (Microcystis), hyphomycete (dolichoma), and Aphanizomenon (Aphanizomenon), the algae of the Zostera class may be selected from the group consisting of Cochloridinium polycyclodonium (Cochloridium polyckoides), Alexandrium tamarense (Alexandrium tamarens), Prorocentrum (Prorocentrum), and Red Tinctoria (Akashiwo sanguinea), and the algae of the Nostophyceae class may be Heterophycus Akashiwo (Heterosporidium Akashiwo).

In addition, in one example, the water-soluble composition for controlling harmful algae may be prepared in one of a powder, a granule, a capsule, and a liquid.

In addition, according to still another aspect of the present invention, there is provided a large-scale harmful algae control method in which the water-soluble composition for harmful algae control according to any one of the above-described examples is spray-treated without an organic solvent to a water area where harmful algae are produced or a sign of harmful algae production is observed.

At this time, in one example, the water-soluble composition for controlling harmful algae may be spray-treated in one form of powder type, granule type, capsule type to aqueous solution form.

In yet another example, the harmful-algae-controlling water-soluble composition may be spray-treated to a large-scale water area using one of a remotely-controlled unmanned ship and an unmanned aircraft.

Further, according to still another aspect of the present invention, there is provided an automated system for large-scale artificial intelligence monitoring, removal and prevention of harmful algae, comprising: a monitoring device which is installed in a large-scale water area having a history of harmful algae production or a large-scale water area having a sign of the harmful algae production predicted or the surrounding area thereof, and monitors the production of the harmful algae; an unmanned spraying apparatus that is one or more of a remotely controlled unmanned ship and an unmanned aerial vehicle, and that is provided with a device for spraying the water-soluble composition for controlling harmful algae according to any one of the above-described examples in accordance with remote control; and a control device for transmitting the monitoring result from the monitoring device, judging whether harmful algae are generated, and controlling the unmanned spraying device to perform spraying treatment when the harmful algae based on the set standard are generated.

Effects of the invention

According to the present invention, unlike the conventional naphthoquinone-based harmful algae removal material which requires an organic solvent to dissolve a material in a powder state, water solubility can be enhanced without using an organic solvent, and thus the powder can be directly dissolved in water on site for use. Thus, according to one example of the present invention, water is directly sprayed on the spot without a solvent or without using an organic solvent, so that only harmful algae can be selectively destroyed for removal.

According to an example of the present invention, since an algicide, for example, can be directly dissolved in water on site without using any other solvent, the economical efficiency and convenience are improved, and the possibility of causing disasters such as ecotoxicity due to the solvent can be reduced.

In addition, according to an example of the present invention, when a harmful algae removal substance that can be easily dissolved in on-site water without using an organic solvent is used on-site, convenience is excellent compared to conventional substances, and thus, the substance can have an advantage of being used for transportation and movement of the substance. Further, the convenience of use of the substance can be used as a very important core technology in order to remove large-scale green algae.

It should be clear that a person having ordinary knowledge in the art can derive various effects not directly mentioned from various constitutions according to the embodiments of the present invention according to various embodiments of the present invention.

Drawings

Fig. 1 is a result of an algae removal effect test of a composition according to an embodiment of the present invention on various microalgae.

Fig. 2 is a biodegradability test result of a composition according to still another embodiment of the present invention.

Detailed Description

In order to achieve the above-described object, an embodiment of the present invention will be described with reference to the drawings. In the present description, the same reference numerals denote the same components, and additional description may be omitted to allow those having ordinary knowledge in the art to understand the present invention.

It is to be noted that even if a singular expression is described in this specification, the singular expression may be used as a concept representing a plurality of integral components without departing from the concept of the invention or without explicit difference or contradictory explanations. In the present specification, the terms "including", "having", "including", "constituted by including …", and the like are to be understood as having the existence or possibility of addition of one or more other constituent elements or a combination thereof.

The present invention will be described in more detail below.

Copper sulfate, copper organic compounds, and the like, which have been conventionally used as algicides for harmful algae, have an excellent control effect on harmful algae, but have problems of secondary pollution due to toxicity and bio-concentration, and ecological imbalance due to the inability to selectively control algae.

On the other hand, the conventional harmful algae control composition including naphthoquinone derivatives, which is proposed for selectively controlling algae against harmful algae, is not easily soluble in water and requires an organic solvent such as a Dimethylsulfoxide (DMSO) solution, which shows eco-toxicity at a high concentration and has a possibility of a certain degree of ecosystem imbalance, and further has a problem of cost increase because equipment is further increased for one dilution of the solvent.

The present invention relates, as a solution to the above problems, to a naphthoquinone-based composition and a derivative thereof that can selectively destroy only harmful algae for removal, and a large-scale harmful algae control method using the composition. In the present invention, the water solubility is enhanced by the use of salt, and therefore, the powder can be used by dissolving it in water on site without using an organic solvent. According to the embodiment of the present invention, harmful algae can be removed by spraying the water system only once, sludge is not generated at all, and additional management is not required. In addition, because of its high water solubility, it can be prepared and used in various forms such as powder, capsule, granule, and liquid for convenience. Therefore, the stability of the ecotoxicity caused by the organic solvent is greatly improved, and the cost is saved without using the organic solvent, so that the economical efficiency is improved, and the harmful algae in a large-scale water area can be removed only by simple equipment.

In one example of the present invention, it can be basically used in waters (fresh water/seawater) where large-scale harmful algae occur, but it can be variously used according to purposes. In particular, it can be used regardless of the depth of water, weather, and environmental factors of an applicable water system, and thus can be applied or used in large-scale lakes, rivers, lakes and marshes, ecological ponds, farms, water purification plants, and various facilities. In particular, in order to effectively perform algae removal work in large-scale waters, it is possible to combine with unmanned ship, unmanned aerial vehicle (unmanned aerial vehicle) technology. In particular, since the pesticide spraying technology using the unmanned aerial vehicle has recently reached the commercialization level, a large synergistic effect can be expected by combining with the technology. In addition, by combining with the field-setting type artificial intelligence automatic microalgae monitoring and sprinkling device technology, the algae production monitoring and preventing technology can be used as a real-time algae production monitoring and preventing technology.

In one aspect, the term "harmful algae (harmfull algae)" as used herein refers to algae that inhabit fresh water or sea water and exert a bad influence, such as green and/or red tide phenomenon, on aquatic environment and economic activities.

[ WATER-SOLUBLE NAPHTHOLONE DERIVATIVE COMPOSITION AND PROCESS FOR PRODUCING THE SAME ]

A water-soluble naphthoquinone derivative composition according to one example of the present invention and a preparation method thereof were observed. At this time, the method for preparing the water-soluble naphthoquinone derivative composition was observed first, and then the water-soluble naphthoquinone derivative composition was observed.

Water-soluble naphthoquinone derivative composition and preparation method thereof

First, a method for preparing a water-soluble naphthoquinone derivative composition according to one example of the present invention was observed. The method for producing the water-soluble naphthoquinone derivative composition described below can be a method for producing the water-soluble composition for controlling harmful algae, which will be described later. In addition, the preparation method described below is one example of a preparation method of the water-soluble naphthoquinone derivative composition according to one example of the present invention, and the preparation method may be changed by a person having ordinary skill in the art through various modifications.

According to one exemplary method of preparing the water-soluble naphthoquinone derivative composition, 1,4-naphthoquinone (1,4-naphthoquinone) compound and N, N-diethylvinyldiamine (N, N-diethylvinylenediamine) are reacted to obtain an intermediate of the following chemical formula 2, and hydrochloric acid is reacted in the intermediate of the chemical formula 2 to obtain a compound of the following chemical formula 1, thereby preparing. The intermediate of the following chemical formula 2 is 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione (2- ((2- (diethylamino) ethyl) amino) naphthalene-1, 4-dione).

Chemical formula 1

Chemical formula 2

For example, in one example, the intermediate of chemical formula 2 may be generated by adding the N, N-diethylvinyldiamine to a mixture of a 1,4-naphthoquinone compound mixed with methanol to perform a reaction. The compound of chemical formula 1 may be produced by mixing a mixed solution of hydrochloric acid and diethyl ether with a mixed solution of the intermediate product of chemical formula 2 and diethyl ether, and reacting the mixture.

[ examples ] A method for producing a compound

Hereinafter, a process of preparing a water-soluble composition for controlling harmful algae, or even a water-soluble naphthoquinone derivative composition according to an example of the present invention, will be specifically illustrated. The following specific examples are merely illustrative and should not be construed as limiting the scope of the invention.

The preparation process according to the specific example is represented by the formula below.

First, a process for obtaining 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione (2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione) as an intermediate of chemical formula 2 from a 1,4-naphthoquinone (1,4-naphthoquinone) compound will be described. To a solution obtained by mixing 1,4-naphthoquinone (1,4-naphthoquinone) compound 1 (represented by "1" in the above chemical formula, 1.00g, 6.0mmol) with methanol (MeOH; 60mL) and uniformly stirring at normal temperature was added N, N-diethylvinyldiamine (N, N-diethylvinylenediamine; 1.00mL, 6.0 mmol). The reaction mixture was stirred at room temperature for 12 hours, and a dark brown precipitate was formed. The resulting mixture was concentrated in vacuo and filtered through a plug of silica gel with a methanol/dichloromethane ratio of 1:15(methanol/dichloromethane ═ 1: 15). The filtered solution was concentrated under vacuum with diethyl ether (Et)₂O) and filtered through filter paper. The filtered solution was concentrated under vacuum to provide substantially pure compound 2-0 (represented by "2-0" in the above formula), i.e., 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione (1.42g, yield 82%).

Next, it will be explained that 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione (2- ((2- (diethylamino) ethyl) amino) naphthalene-1, 4-dione; compound 2.0 in the above formula) as a final product was obtained from 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione as an intermediate of formula 2Process for the preparation of, 4-diketohydrochloride (2- ((2- (diazylamine) ethyl) amino) naphthane-1, 4-dione HCl; represented by "2-0-HCl" in the above formula) or 2- ((1,4-dioxo-1, 4-dihydronaphthalenone-2-yl) amino) -N, N-diethylethane-1-ammonium chloride (2- ((1, 4-diox-1, 4-dihydronaphthaline-2-yl) amino) -N, N-diethylethane-1-aminium chloride). To a flask filled with 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione (e.g., 8g, 29.3mmol) represented by chemical formula 2 was added diethyl ether ((C) at normal temperature₂H₅)₂O to Et₂O; e.g., 800 mL). After 10 minutes, at ambient temperature (rt), it will be in diethyl ether (Et)₂O) solution (e.g., 2M, 44mL, 3equiv) with hydrochloric acid (HCl) dissolved therein was added to the above solution (2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione with diethyl ether (Et)₂O) solution). The mixture is shaken vigorously, for example for 1 hour, whereupon the precipitate is filtered off and washed with diethyl ether (Et)₂O) washing and drying was completed under reduced pressure, and 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione hydrogen chloride (2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione HCl) was calculated.

At this time, 2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione hydrochloride (2- ((2- (diethylamino) ethyl) amino) naphthalene-1,4-dione HCl salt) was slightly soluble in ethanol (EtOH), 1,4-dioxane (1,4-dioxane), and readily soluble in dimethyl sulfoxide (DMSO). Therefore, diethyl ether (Et) is recommended for washing₂O)。

¹H NMR of 2-0HCl(400MHz,D₂O):8.02(dd,J＝7.6,1.16Hz,1H),7.94(dd,J＝7.8,1.2Hz,1H),7.83(td,J＝7.5,1.3Hz,1H),7.74(td,J＝7.6,1.3Hz,1H),5.79(s,1H),3.73(q,J＝6.3Hz,2H),3.48(t,J＝6.3Hz,2H),3.34-3.32(m,4H),1.32(t,J＝7.3Hz,6H).

Water-soluble naphthoquinone derivative composition

An exemplary water-soluble naphthoquinone derivative composition according to the present invention is represented by the chemical formula 1.

In one example, the water-soluble naphthoquinone derivative composition represented by chemical formula 1 may be prepared by the above-described example of the preparation method. The above-described preparation method is an example of a preparation method of a water-soluble naphthoquinone derivative composition according to an example of the present invention, and should not be construed as limiting the scope of rights of the water-soluble naphthoquinone derivative composition according to an example of the present invention.

[ WATER-SOLUBLE COMPOSITION FOR CONTROLLING HAIR ALGASES ]

Next, a water-soluble composition for controlling harmful algae according to still another example of the present invention is explained.

The water-soluble composition for controlling harmful algae according to one example contains the above-described water-soluble naphthoquinone derivative composition as an active ingredient. That is, the harmful algae control composition contains the water-soluble naphthoquinone derivative composition represented by chemical formula 1 as an active ingredient. In this case, the harmful algae control composition may be prepared by the above-described preparation method or various modification methods.

For example, in one example, the water-soluble naphthoquinone derivative composition as an effective ingredient of the water-soluble composition for controlling harmful algae may be prepared according to one of the above-described methods for preparing the water-soluble naphthoquinone derivative composition.

In addition, in one example, the water-soluble composition for controlling harmful algae may be prepared in one of a powder, a granule, a capsule, and a liquid, for example. Other types of formulation forms not mentioned can also be made.

For example, in one example, the harmful algae controlled by the water-soluble composition for controlling harmful algae may be selected from the group of algae consisting of cyanophyceae, diatoms, synechophytes, and porphyromonas.

For example, the algae of the class cyanobacteria may be selected from the group consisting of Microcystis (Microcystis), cochliobolus (dolichlorum), and synechocystis (aphanizomon).

The alga belonging to the class Anastodiaceae may be selected from the group consisting of Cochlodinium polykrikoides (Cochlodinium polykrikoides), Alexandrium tamarense (Alexandrium tamarens), Prorocentrum (Prorocentrum), and Red Tinctoria (Akashiwo sanguinea).

Further, the alga of the class of the conidiomycete may be Heterosigma akashiwo (Heterosigma akashiwo).

[ Large-Scale harmful algae control method ]

Next, a large-scale harmful algae control method according to an example of the present invention is explained.

The large-scale harmful algae control method according to one example may be one of embodiments of spray-treating the water-soluble composition for harmful algae control described above without an organic solvent to water areas where large-scale harmful algae are produced or where signs of production are observed. For example, the harmful algae control composition may be in the form of, for example, granules, powders, capsules, or the like, but is not limited thereto.

For example, in one example, the water-soluble composition for controlling harmful algae may be spray-treated in one form of powder type, granule type, capsule type to aqueous solution form.

For example, in yet another example, the harmful-algae-controlling water-soluble composition may be spray-treated to a large-scale water area using one of a remotely-controlled unmanned ship and an unmanned aircraft.

[ EXAMPLES ]

For example, a reservoir on the scale of 1000 tons produces a 5X 10⁵Regarding the number of harmful algae cells at the level of cells/mL, about 430g of the powder of the water-soluble composition for controlling harmful algae represented by chemical formula 1 prepared according to the example described later was mixed with the field water and then uniformly sprayed to the water layer where green algae were produced. The green algae can be controlled to below the algae warning level (5,000cells/mL) as short as a few days or within a week.

Automatic system for large-scale artificial intelligent monitoring, removing and preventing of harmful algae

Next, a large-scale harmful algae artificial intelligence monitoring, removing, and preventing automation system according to still another example of the present invention will be described. An automated system for large scale artificial intelligence monitoring, removal and prevention of harmful algae according to one example of the present invention includes a monitoring device, an unmanned spraying device, and a control device.

The monitoring device is installed in or around a large-scale water area having a history of harmful algae production or a sign of the occurrence of the harmful algae prediction, and monitors the production of the harmful algae. For example, the monitoring apparatus is provided with a video device, and can perform artificial intelligence or automatic monitoring by photographing a large water area and reading a photographed image according to a setting, but is not limited thereto.

The unmanned spraying device may then be one or more of a remotely controlled unmanned ship and an unmanned aerial vehicle. At this time, the unmanned ship, the unmanned aerial vehicle each have an automated spray processor, that is, an apparatus for treating the water-soluble composition for harmful algae control according to one of the above-described examples according to remote control spraying.

Then, the control device transmits the monitoring result from the monitoring device, judges whether harmful algae are generated, and controls the unmanned spraying device to perform spraying treatment when harmful algae based on the set reference are generated. For example, the control device is configured by a server system, and can control the monitoring devices installed in a plurality of areas, and can also automate large-scale harmful algae artificial intelligence monitoring, removal, and prevention for a plurality of areas.

According to the present invention, harmful algae in the water system can be effectively removed. Compared with the prior art, the water solubility of the naphthoquinone-based algae removal material is greatly improved, so that other organic solvents are not needed. Not only improves the use convenience of the naphthoquinone material for removing harmful algae, but also has the cost saving effect and solves the danger factor of the ecological system unbalance of the solvent. In addition, as shown in the experimental results described later, the substance of the present invention is ecologically safe, and can be used on site in large-scale waters since it is proved to be a biodegradable substance. In addition, in ponds, reservoirs, lakes, rivers, seacoasts, coasts, and the like, only harmful algae generated by abnormal propagation of harmful algae (blue algae, flagellates, and the like) can be selectively controlled, so that it is possible to prevent a large amount of harmful algae generated in fresh water or seawater and effectively use it in preventing water pollution. In addition, harmful algae can be removed only with a very small amount, so that the method can be smoothly combined with IT technologies such as artificial intelligence automatic spraying, unmanned plane wood grafting and the like.

[ experiment on algae removal Effect ]

With the composition according to the present invention, an algae extermination effect experiment on various kinds of microalgae including harmful algae was performed.

Fig. 1 is a result of an algae removal effect test of a composition according to an embodiment of the present invention on various microalgae.

The algicidal effect on harmful algae at various inoculation concentrations of the compound according to one example of the invention was determined. For this purpose, as the treatment group, as the harmful algae in fresh water, Microcystis aeruginosa, Dolichospermum circinate, aphanizomon sp, Pseudoanabaena sp, which are blue algae, were used; stephanodiischus hantzschii (early spring crown. sp. in the middle and lower reaches of hanjiang), Synedra sp. (synechocystis sp.); scenedesmus sp (Scenedesmus sp.) as a green algae, Trichodesmium sp (blue algae) as a blue algae used as a marine harmful algae; alexandrium tamarens (Alexandrium tamarense), Cochloridium polykrikoides (Cochlodinium polycycloxum), Prorocentrum minium (Prorocentrum minium) as algae of the genus Alexandrium; heteroosigma akashiwo (Heteroshikaea akashiwo) as a subgroup of Neurospora species; pseudo-nitzschia pungens (Trypanosoma acuminatum) as diatoms. The culture conditions are shown in table 1 below. Table 1 shows the culture medium and culture conditions of algae that cause mainly green algae.

[ TABLE 1 ]

Specifically, the experiment was conducted to prepare a cell density of 5.0X 10 in the case of a fresh water species³-9.0×10⁴5mL of cells/mL of culture, when seeded in seawater, was prepared at a cell density of 1.0X 10²-1.0×10⁴cells/mL 5mL of culture. After each culture was prepared, the compound represented by chemical formula 1 prepared according to the example was inoculated at various concentrations and processed to final concentrations of 1, 2, and 6 μ M, respectively. Then, the user can use the device to perform the operation,the culture was performed under the culture conditions of table 1, in which the culture was performed under continuous light conditions, and observed for 72 hours. The number of cells was counted by an SR-chamber or hemocytometer under an upright or inverted microscope, the number of cells before, 24 hours, 48 hours, and 72 hours after the treatment was counted, and the reduction rate (reduction ratio) as compared with the cells before the treatment, that is, the algae removal activity (%) was calculated by using the following formula 1.

(1-Tt/Ct) x 100. the algae removal activity (%) is as shown in formula 1

In formula 1, T represents the density of cells after treatment of the compound, C represents the density of cells without treatment of the compound, and T represents the culture time.

Based on the formula 1, the algae removal activity of the compound is marked as below 60%, 60-80% and above 80%. When the algae removal activity reached 80% within 48 hours at a certain compound concentration, it was judged that the effect was obtained at a concentration higher than that, and the experiment was terminated at a high concentration.

The experimental results are illustrated with reference to fig. 1. Referring to fig. 1, the composition of chemical formula 1 according to the present invention shows more than 90% of algae removal performance at a concentration of more than 1 μ M for Microcystis of blue algae (Microcystis) and spirulina (Dolichospermum) which are main causative species of green algae of fresh water. Further, Aphanizomenon (Aphanizomenon) belonging to the same blue algae shows an algae removal effect of 80% or more at a concentration of 2. mu.M or more. In addition, it shows 90% or more of algae removal effect from a concentration of 1 μ M or more against the major red tide dinoflagellate multinuclear furrows (chloredinium polykrikoides) causing disasters almost every year along the coast of korea, and 90% or more of algae removal effect at a concentration of 1 μ M or more against Alexandrium tamarens (Alexandrium tamarens) which produces paralytic shellfish poisoning and causes disasters to fish and shellfish farms. In addition, the red tide Heterosigma Akashiwo (Heterosigma Akashiwo) which frequently causes red tides worldwide shows 90% or more of algae removal effect at a concentration of 2. mu.M or more, and the red tide algae (Akashiwo sanguinea) shows 80% or more of algae removal effect at a concentration of 6. mu.M or more.

On the one hand, it showed a weak algae removal effect for diatoms and green algae, and for syndinaria (Synedra), the next day algae removal effect was also 70% at 1 μ M, whereas cell regrowth was observed. In particular, Scenedesmus (Scenedesmus) which is a green alga shows little algae removal effect. In general, green algae contain many useful organisms and few reports have been made to cause disasters, so the exemplary composition according to the present invention hardly affects the species, and on the contrary, it was confirmed that it has an excellent algae removal effect on harmful algae causing serious problems due to green and red tide phenomena at home and abroad.

[ eco-toxicity test ]

Experiments were conducted to evaluate the ecotoxicity of exemplary compositions according to the present invention.

To illustrate the influence of the compound according to one example of the present invention, i.e., the composition according to chemical formula 1, on the ecosystem, the ecotoxicity evaluation was performed using Vibrio fischeri (Vibrio fischeri), Daphnia magna (Daphnia magna) as the ecotoxicity evaluation index organisms.

First, in the case of Vibrio fischeri, an experiment was conducted according to the water pollution process test method, and as a sample for evaluating the ecotoxicity, the compound labeled in example 1 was added to the blue algae Microcystis aeruginosa (10,488cells/mL) at a concentration of 1. mu.M, and then the supernatants after 24 hours, 48 hours, and 72 hours were extracted and injected into Vibrio fischeri. Then, the relative luminosity of the treated group was measured as compared with the control group, and the effect of reducing luminosity was confirmed, thereby attempting to evaluate the toxicity of each sample.

Next, in the case of daphnia magna, an experiment was conducted according to the water pollution process test method, and as a sample for evaluating the ecotoxicity, the compound labeled in example 1 was added to the blue algae microcystis aeruginosa (10,488cells/mL) at a concentration of 1 μ M, and then supernatants after 24 hours, 48 hours, and 72 hours were extracted, and after dropping daphnia magna into each solution, the number of individuals in which swimming inhibition was observed after 24 hours was counted.

Experimental result, in the samples to which the composition represented by chemical formula 1 prepared according to the example was inputted, the relative luminosity of vibrio fischeri was not different from that of the control group (table 2), and daphnia magna was an individual showing no swimming hindrance at all. Therefore, the present compound was judged to be a substance suitable for use in aquatic ecosystems in reservoirs, rivers, lakes, and the like because it did not exhibit ecotoxicity at a concentration of 1 μ M, which is an applicable concentration of the present compound. The following Table 2 shows the relative luminosity of Vibrio fischeri in the sample after a certain time has elapsed after the addition of the algicidal substance.

[ TABLE 2 ]

	After 24 hours	After 48 hours	After 72 hours
				Control group	100％	100％	100％
Treatment groupa	100％	100％	100％

^a: after a lapse of a certain period of time, a sample introduced at a final concentration of 1 μ M was used as a sample to be evaluated for toxicity.

[ biodegradability test of algae-exterminating substance ]

Experiments were conducted to evaluate the ecotoxicity of exemplary compositions according to the present invention.

Fig. 2 is a biodegradability test result of a composition according to still another embodiment of the present invention.

In order to evaluate biodegradability in an aqueous system of the compound of chemical formula 1 according to an example of the present invention, experiments were performed. First, the field water of Zhonglangchuan, Seoul, was sprayed at a substance concentration of 6.5. mu.M, and then trained at a constant temperature of 20 ℃. The experiment was carried out in an experimental volume of 350mL, and samples were extracted at 1-3 day intervals, 5mL each time. The sample was filtered through a GF/F filter, stored frozen, thawed at room temperature for analysis, filtered through a 0.45 μm nylon filter, and then subjected to the following analysis conditions.

-a device: agilent 1290Infinity (UHPLC-DAD)

-a chromatographic column: eclipse Puls-C19(4.6mm 100mm 3.5 μm)

-column temperature: 40 deg.C

-a mobile phase: isocratic > A: 0.1% phosphoric acid in D.W, B: ACN: 70:30

-analysis time: 7min

-flow rate: 1.0mL/min

-a detector: DAD Detector (measuring wavelength: 260nm)

-injection amount: 1 μ L

Fig. 2 shows the results of the biodegradability test. As a result of the experiment, the concentration of the algicidal substance was maintained at the input concentration level by the first 2 days, but then decreased to 70% of the initial input concentration by the second 7 days. When observed together with the results of the algae removal effect experiment of the composition of chemical formula 1 prepared according to the examples, most of the subject algae showing algae removal activity showed effects within 3 days, and thus it was judged that the biodegradable characteristics of the present substance did not affect the algae removal efficiency. Further, generally, physiological activities of bacteria are proportional to water temperature, and the biodegradable process may be more smooth in a high water temperature environment in summer where harmful algae actually flourish. Therefore, it is determined that the substance does not remain permanently in the water ecosystem, and there is no danger in the water ecosystem due to the deposition and remaining of living organisms.

The above-described embodiments and the drawings are described as examples for helping those having ordinary knowledge in the art to understand the present invention, and are not intended to limit the scope of the present invention. In addition, embodiments according to various combinations of the above-described constitutions may be explicitly realized by those skilled in the art from the foregoing detailed description. Therefore, various embodiments of the present invention can be realized in modified forms without departing from the essential characteristics of the present invention, and the scope of the present invention should be interpreted from the invention described in the patent claims, and includes various modifications, substitutions, and equivalents by those having ordinary knowledge in the art.

Industrial applicability

The present invention relates to a water-soluble naphthoquinone derivative composition and a method for preparing the same, which can remove and prevent harmful algae, and thus have industrial applicability.