WO2022172649A1

WO2022172649A1 - Polyphenol-iron complex capsule, hydrogen peroxide capsule, fenton reaction kit, and method for breeding fish and shellfish or treating diseases of fish and shellfish

Info

Publication number: WO2022172649A1
Application number: PCT/JP2022/000108
Authority: WO
Inventors: 森川クラウジオ健治
Original assignee: 国立研究開発法人農業・食品産業技術総合研究機構
Priority date: 2021-02-09
Filing date: 2022-01-05
Publication date: 2022-08-18
Also published as: JP2022122169A

Abstract

Provided is a polyphenol-iron complex by which stable reaction efficiency can be obtained even when an existing polyphenol-iron complex is improved and used in an environment having a certain degree of width. Also provided is a technique in which the time and/or period for causing a Fenton reaction or a photocatalytic reaction can be freely controlled using a polyphenol-iron complex. Further, provided is a method for breeding fish and shellfish or treating diseases of fish and shellfish using a polyphenol-iron complex without damaging fish and shellfish.　Provided are: a polyphenol-iron complex capsule obtained by sealing a polyphenol-iron complex in alginic acid gel; a hydrogen peroxide capsule obtained by sealing hydrogen peroxide in alginic acid gel; and a method for breeding fish and shellfish or treating diseases of fish and shellfish using the same.

Description

Polyphenol iron complex capsule, hydrogen peroxide capsule, Fenton reaction kit, and method for breeding or treating disease of seafood

The present disclosure includes a polyphenol iron complex capsule in which a polyphenol iron complex is encapsulated in an alginic acid gel, a hydrogen peroxide capsule in which hydrogen peroxide is encapsulated in an alginic acid gel, and the polyphenol iron complex capsule and the hydrogen peroxide capsule. The present invention relates to a Fenton reaction kit and a method for raising fish and shellfish or treating diseases using the capsule.

In the Fenton reaction, hydrogen peroxide acts on iron to generate powerful active oxygen called hydroxyl radicals. Hydroxy radicals are extremely reactive and can be used for sterilization and decomposition of organic matter.

It is known that iron functions efficiently as a Fenton reaction catalyst only in the state of divalent iron ions (Fe ²⁺ ). However, bivalent iron ions are very unstable and are easily oxidized to change into trivalent iron ions, losing the ability to catalyze the Fenton reaction. Therefore, in order to put the Fenton reaction catalyst into practical use, a technique for stabilizing iron in the state of divalent iron ions is required.

The inventor of the present application has so far developed a polyphenol iron complex that can maintain iron in the state of divalent iron ions using reducing organic substances, used tea leaves, coffee grounds, etc. (see Patent Documents 1 to 5). This polyphenol iron complex is not only useful as a Fenton reaction catalyst or a divalent iron ion supplier, but also has a function as a photocatalyst that exhibits activity by absorbing light of a wide range of wavelengths including visible light (Patent Document 6). , 7).

On the other hand, alginic acid is an intercellular polysaccharide contained in seaweed bodies, and the water-soluble alginate obtained by industrially extracting and refining it is used in a wide range of industries such as food, medicine, and industry. Alginates have the property of reacting with polyvalent metal ions and gelling. An encapsulation technique that utilizes this property is applied to artificial salmon roe, food capsules, and the like (see, for example, Non-Patent Document 1).

Japanese Patent No. 5733781 Japanese Patent No. 5804454 Japanese Patent No. 6057227 Japanese Patent No. 6179957 Japanese Patent No. 6202770 Japanese Patent No. 6340657 Japanese Patent No. 6478209

The polyphenol iron complexes of Patent Documents 1 to 7 have the characteristic of being able to stably maintain divalent iron ions for a long period of time, but the reaction efficiency decreases due to adsorption on the surrounding solids, resulting in the Fenton reaction and photocatalysis. The reaction ends in a short time. Therefore, conventional polyphenol iron complexes have a problem that it is difficult to obtain stable reaction efficiency in an environment having a certain extent of space.

In addition, conventional polyphenol iron complexes are highly reactive substances, so when used in an environment where useful organisms such as ornamental fish and farmed fish grow, they also cause damage to these useful organisms. Furthermore, the hydrogen peroxide required for the Fenton reaction is a very reactive substance and disappears quickly. Therefore, it has been desired to develop a technique for controlling the reactivity of the polyphenol iron complex and hydrogen peroxide and controlling the timing and duration of the Fenton reaction and photocatalytic reaction.

Therefore, an object of the present disclosure is to improve existing polyphenol iron complexes and provide polyphenol iron complexes that provide stable reaction efficiency even when used in an environment with a certain extent of space.

In addition, an object of the present disclosure is to provide a technique for sustaining the reactivity of hydrogen peroxide for a long period of time.

Furthermore, an object of the present disclosure is to provide a technique capable of freely controlling the timing and/or duration of the Fenton reaction or photocatalytic reaction using the polyphenol iron complex.

Another object of the present disclosure is to provide a method for raising fish or treating diseases without harming fish and shellfish using a polyphenol iron complex.

In order to solve the above problems, the inventor of the present application investigated encapsulation of a polyphenol iron complex and hydrogen peroxide. Various polymers were used to encapsulate the polyphenol iron complex and hydrogen peroxide, and as a result of intensive research on combining them, the stability was improved by encapsulating the polyphenol iron complex and hydrogen peroxide in the alginate gel. They have found that capsules can be obtained that are high and controllable in timing and period of reaction.

The inventors of the present application have found that by administering these capsules to fish tanks, it is possible to treat diseases of fish and shellfish in a short period of time without harming the fish and shellfish. Based on these findings, the present disclosure was completed.

That is, the present disclosure provides a polyphenol-iron complex capsule in which a polyphenol-iron complex is encapsulated in an alginic acid gel.

Here, the polyphenol iron complex may further contain water-soluble vitamins and/or trace elements. The polyphenol iron complex capsule may be in the shape of aquatic plants, seaweed, shells, corals or pebbles.

The present disclosure also provides a hydrogen peroxide capsule in which hydrogen peroxide is encapsulated in alginic acid gel.

Furthermore, the present disclosure provides a Fenton reaction kit containing the polyphenol iron complex capsule and the hydrogen peroxide capsule.

In addition, the present disclosure provides a method for breeding seafood or treating diseases using the polyphenol iron complex capsule.

Here, the polyphenol iron complex capsules may be used in combination with the hydrogen peroxide capsules. Also, one or more of ultraviolet light, visible light, and infrared light can be irradiated. Furthermore, a visible-light-responsive porous photocatalyst formed by solidifying alkaline earth metal peroxides with cement may be used in combination.

Since the polyphenol-iron complex capsule of the present disclosure has a structure in which the polyphenol-iron complex is enclosed in an alginate gel, it is more stable than conventional polyphenol-iron complexes and is less susceptible to environmental temperature and pH. can do. Therefore, stable reaction efficiency can be obtained even when the polyphenol iron complex is used in an environment having a certain extent of space.

In addition, by encapsulating the polyphenol-iron complex in alginate gel, it is possible to control the reaction, such as gradually releasing the polyphenol-iron complex over a long period of time, or adjusting the timing of capsule disintegration to release the polyphenol-iron complex at the appropriate time. Become. As a result, the polyphenol iron complex can be used for the prevention or treatment of diseases, sterilization, decomposition of harmful substances, etc., without damaging useful organisms such as ornamental fish and cultured fish. Furthermore, by encapsulating the polyphenol-iron complex, which is usually liquid or powdery, it is easy to handle and has the effect of preventing accidental ingestion by useful organisms.

The hydrogen peroxide capsule of the present disclosure has a structure in which hydrogen peroxide is encapsulated in alginic acid gel, so it is possible to prevent loss of hydrogen peroxide and maintain reactivity for a long period of time. In addition, by encapsulating the toxic hydrogen peroxide, it is easy to handle and has the effect of preventing damage to useful organisms.

The Fenton reaction kit of the present disclosure contains the above-described polyphenol iron complex capsules and hydrogen peroxide capsules, so that the Fenton reaction can be performed efficiently and continuously, and the Fenton reaction can be freely controlled. Become. In addition, the use of encapsulated polyphenol-iron complex and hydrogen peroxide facilitates handling and has the effect of preventing damage to useful organisms.

In the fish and shellfish breeding or disease treatment method of the present disclosure, by using the above-described polyphenol iron complex capsule, the fish and shellfish are supplied with divalent iron ions to maintain the health of the fish and shellfish, and Disease can be prevented or treated. Furthermore, the action of sterilization by the Fenton reaction or photocatalytic reaction, decomposition of harmful substances, etc., can improve and maintain the water quality environment. Since polyphenol iron complex capsules can maintain these effects for a long period of time, the frequency of administration of capsules can be reduced, facilitating health management of fish and shellfish.

It is a figure which shows the manufacturing process of the polyphenol iron complex capsule of 1st embodiment. FIG. 2 is a photographic image diagram showing the manufacturing process of the polyphenol iron complex capsule of the first embodiment and the manufactured capsule. It is a figure which shows the manufacturing process of the hydrogen peroxide capsule of 2nd embodiment. FIG. 4 is a photographic image diagram showing the manufacturing process of the hydrogen peroxide capsule of the second embodiment and the manufactured capsule. FIG. 10 is a photographic image showing polyphenol iron complex capsules having different sizes produced in Example 7. FIG. Fig. 2 is a photographic image comparing encapsulated polyphenol iron complexes, iron (III) chloride and iron (II) sulfate (Test Example 1). FIG. 10 is a photographic image showing the bactericidal effect of Escherichia coli by combined treatment of polyphenol iron complex capsules and hydrogen peroxide capsules (Test Example 2). In the figure, (a) shows the control group (no capsule added), and (b) shows the combined treatment group. FIG. 10 is a diagram showing a method for breeding fish and shellfish or treating a disease with light irradiation using a polyphenol iron complex capsule and a hydrogen peroxide capsule. In the figure, "PP-Fe" indicates a polyphenol iron complex. FIG. 11 is a photographic image showing the therapeutic effect of water mold disease in goldfish by polyphenol iron complex capsules and hydrogen peroxide capsules (Example 11). In the figure, (a) shows the condition before treatment, and (b) shows the condition after treatment. FIG. 11 is a photographic image showing a method for breeding fish and shellfish or treating a disease using a polyphenol iron complex capsule and a visible-light-responsive porous photocatalyst (Example 12). In the figure, (a) shows a porous photocatalyst and (b) shows a polyphenol iron complex capsule, respectively. (Example 14) (Example 14). (Example 15) (Example 15). (Example 15) (Example 15). In the figure, (a) shows the control group (no capsule added), and (b) shows the combined treatment group (with light irradiation), respectively.

[Polyphenol iron complex capsule]
Hereinafter, the polyphenol iron complex capsule of the first embodiment will be described in detail. A polyphenol-iron complex capsule according to the first embodiment is obtained by encapsulating a polyphenol-iron complex in an alginic acid gel.

The "polyphenol iron complex" is a reaction product obtained by mixing polyphenols or a feedstock thereof with an iron feedstock in the presence of water, which are described in the above-mentioned Patent Documents 1 to 7. It is formed by divalent iron ions (Fe ²⁺ ) forming a complex structure with polyphenols.

"Polyphenols" is a generic term for phenolic molecules with multiple hydroxy groups. It is a compound contained in most plants, and various types such as flavonoids and phenolic acids are known.

Examples of specific compounds include catechins (epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, etc.), tannic acid, tannin, chlorogenic acid, caffeic acid, neochlorogenic acid, cyanidin, proanthocyanidins, Thearubigin, rutin, flavonoids (quercitrin, anthocyanin, flavanones, flavanols, flavonols, isoflavones, etc.), flavones, chalcones (naringenin chalcone, etc.), xanthophyll, carnosic acid, eriocitrin, nobiletin, tangeretin, magnolol, honokiol, ellagic acid, Lignans, curcumin, coumarin, catechol, procyanidins, theaflavin, rosmarinic acid, xanthone, quercetin, resveratrol, gallic acid, phlorotannin, and the like. Also included are compounds having one or more of these compounds in the molecule (for example, complexes in which these compounds are combined to form a polymer).

"Polyphenols" in the first embodiment may be one of the above, or may be a composition consisting of two or more.

In addition, polyphenol compositions extracted from a certain plant are sometimes called polyphenols with the name of the plant. For example, polyphenols extracted from grapes are called grape polyphenols.

As the "supply raw material of polyphenols", a plant body containing polyphenols (hereinafter referred to as "polyphenol-containing plant body") or a processed product thereof can be used. Here, the "plant body" includes one or more selected from fruit, seed, stem, leaf, outer skin, bud, flower, root, and rhizome of a plant body.

Examples of "polyphenol-containing plants" include herbs (lavender, mint, coriander, cumin, sage, lemongrass, mugwort, comfrey, perilla, lemon balm, oregano, catnip, common thyme, dill, dark opal, basil, hyssop, peppermint, lamb's ear, etc.), houttuynia cordata, marigold, grapes, coffee (coffee tree), tea (tea), cacao, acacia, cedar, pine, sugar cane, mango, banana, papaya, avocado, apple, cherry (cherry), Guava, olive, potatoes (sweet potato, purple potato (sweet potato containing a lot of purple pigment), potato, yam, taro (taro, shrimp, etc.), konjac potato, etc.), persimmon, mulberry, blueberry, poplar, ginkgo biloba , Chrysanthemum, Sunflower, Bamboo, Citrus Fruits (Lemon, Lime, Orange, Grapefruit, Navel, Yuzu, Kumquat, Kabosu, Natsumikan, Hassaku, Iyokan, Lime, Satsuma Mandarin, Shikuwasa, Mandarin, etc.), Strawberry, Blackberry, Cranberry, Raspberry , bilberry, huckleberry, plum, peach, plum, pear, pear, loquat, kiwi fruit, mangosteen, shishito, prune, melon, dragon fruit, wolfberry, cassis, cashew, viburnum, pomegranate, acai, aronia, eggplant, tomato, Soybeans, black soybeans, adzuki beans, green beans, peanuts, black sesame seeds, buckwheat, tartary buckwheat, sesame seeds, purple cabbage, sumac, nurde, shungiku, broccoli, spinach, komatsuna, mitsuba, okra, butterbur, onions, mulukhiya, shungiku, garlic, purple Onion, asparagus, parsley, eucalyptus, udo, gymnema sylvestre, senna, dandelion, horsetail, fern (bracken, fern, etc.), oak, sawtooth oak, maple, sequoia, metasequoia, cypress, red-crested wrinkle, hawthorn tsume, gynophila, akebi, Japanese sycamore , Ryoubu, Tamushiba, Magnolia magnolia, Arunashi, Shiromoji, Kuromoji, Koshiabura, Kusagi, Magnolia, Actinidia, Banaba, Rooibos, Rafuma, Kudzu, Megusurinoki, Urin, Merbao, Aogiri, Suou, Brazilwood, Melinjo, Sakura, Magnolia, Yerba ・Yerba mate, Mehirgi, Hirugi, Yaeyama Hirugi, Hama pomegranate, Nippa palm, Mangrove mangrove, Mangrove mandarinus, Sakishimasuounoki, burdock, turmeric, lotus root, seaweed (seaweed, wakame seaweed, kelp, sea lettuce, sea lettuce) Lame, Sagarame, etc.) and the like can be mentioned.

Among them, grapes, coffee (coffee tree), tea (tea), cacao, acacia, cedar, pine, yuzu, lemon, herbs (lavender, mint, coriander, cumin, sage, perilla, lemongrass, mugwort, comfrey, lemon balm , oregano, catnip, common thyme, dill, dark opal, basil, hyssop, peppermint, lamb's ear, etc.), Houttuynia cordata, marigold, sugar cane, mango, banana, papaya, avocado, apple, cherry, guava, olive, potato (sweet potato, purple potato (sweet potato containing a lot of purple pigment), potato, yam, taro (taro, shrimp, etc.), konjac potato, etc.), persimmon (persimmon), mulberry, blueberry, poplar, ginkgo, chrysanthemum, sunflower, Bamboo is preferably used.

"Processed products" of polyphenol-containing plant bodies include dried products of polyphenol-containing plant bodies, juices, extracts, and liquid extracts. Further, the squeezed liquid or the extract may be further dried.

"Dried matter" is preferably one that has undergone processing such as crushing, pulverization, or powderization. In addition, considering the reaction efficiency with iron, a powder with a small particle size is preferable.

Suitable extraction solvents for the "extract" and "extract" are water, hot water, alcohol (especially ethanol), and hydrous alcohol (especially hydrous ethanol).

As a feedstock for polyphenols, the residue remaining after extracting the polyphenol-containing plant body or its processed product with water or hot water can also be suitably used. Examples of such extraction residues include coffee grounds and used tea leaves.

"Coffee grounds" refers to the residue after extracting roasted and ground coffee beans with water or hot water. Coffee grounds contain a large amount of polyphenols, and since they are waste products, the raw material cost can be kept low, so they are suitable as raw materials for supplying polyphenols. In addition, components obtained by extracting roasted and ground coffee beans with water or hot water (so-called components of brewed coffee), coffee beans, their roasted products, ground products, etc., also contain large amounts of polyphenols. , can be preferably used.

"Tea leaves" refers to the residue after extracting tea leaves or their pulverized material with water or hot water. Used tea leaves contain an extremely large amount of polyphenols, and since they are waste products, the cost of raw materials can be kept low, so they are suitable as raw materials for supplying polyphenols.

As for the "tea leaves" that are the raw material for used tea leaves, any stems and leaves of the tea tree can be used. Specific examples include green tea (sencha, bancha, stem tea, hojicha, etc.), blue tea (oolong tea, etc.), black tea, black tea (pu-erh tea, etc.), and the like. Among them, green tea, black tea, and oolong tea are preferable.

In addition, components obtained by extracting tea leaves or their pulverized products with water or hot water (so-called components of brewed tea), tea leaves, their processed products, pulverized products, etc., also contain large amounts of polyphenols. It can be suitably used as a feedstock.

In the first embodiment, a dry distillation solution (plant dry distillation solution) obtained by thermally decomposing a polyphenol-containing plant body or its processed product in a reducing state can also be suitably used as a feedstock for polyphenols. .

In addition to containing a large amount of polyphenols, this plant dry distillate contains many reducing organic molecules such as phenols, organic acids, carbonyls, alcohols, amines, basic components, and other neutral components. is presumed to contain Here, the term "reducing organic matter" refers to an organic matter that has a strong reducing power and has the action of reducing trivalent iron to divalent iron.

The dry distillate of the plant is a sticky liquid with a reddish-brown to dark brown appearance. There are types such as wood vinegar, bamboo vinegar, rice vinegar, etc., depending on the plant body used as the raw material, and any of them can be suitably used. These vegetable dry distillation solutions can be used as they are, but they can also be used as concentrated solutions, diluted solutions, or dried products thereof.

Only one type of the above polyphenols may be used, or two or more types may be mixed and used.

As the "iron feedstock", any of a bivalent iron feedstock, a trivalent iron feedstock, or a metallic iron feedstock can be used. Also, a plurality of materials can be mixed and used.

Here, as the "supply material of divalent iron", iron (II) chloride, iron (II) nitrate, iron (II) sulfate, iron (II) hydroxide, iron (II) oxide, iron (II) acetate , Water-soluble divalent iron compounds such as iron (II) lactate, sodium iron (II) citrate, iron (II) gluconate; water-insoluble divalent iron compounds such as iron (II) carbonate and iron (II) fumarate compounds can be mentioned.

As a "feedstock of trivalent iron", water-soluble trivalent iron(III) chloride, iron(III) sulfate, iron(III) citrate, ammonium iron(III) citrate, iron(III) EDTA, etc. Iron compounds: water-insoluble trivalent iron compounds such as iron(III) oxide, iron(III) nitrate, iron(III) hydroxide, and iron(III) pyrophosphate.

In addition, as natural raw materials containing a large amount of these trivalent iron compounds, Akadama soil, Kanuma soil, loam (soil containing a lot of allophane iron), laterite (soil containing a lot of iron oxide (III)), goethite (amorphous natural iron ores such as pyrite, marcasite, siderite, magnetite, and goethite; iron sand obtained by turning the iron ore into dust; substances derived from living organisms such as heme iron and shells; can also be used as a feedstock for trivalent iron.

In addition, iron materials such as smelted iron and alloys can be mentioned as "supply raw materials of metallic iron". In addition, rust can also be used as an iron feedstock.

It should be noted that even if the above-mentioned iron feedstock is water-insoluble, it can be used directly as an iron feedstock because it is water-soluble due to the chelating ability of polyphenols.

Among the above iron feedstocks, it is preferable to use a water-soluble divalent iron or trivalent iron compound in order to efficiently produce a polyphenol iron complex. In particular, it is preferable to use inexpensive iron chloride, iron sulfate, or the like. From the viewpoint of raw material cost and stable supply, it is preferable to use natural soil (particularly Akadama soil, Kanuma soil, loam, etc.) and metallic iron as iron supply raw materials.

In the first embodiment, the polyphenol iron complex is obtained by mixing polyphenols or a feedstock thereof with an iron feedstock in the presence of water.

The mixing ratio of these raw materials is such that the iron feedstock is added in an amount of 0.1 part by weight or more, preferably 1 part by weight in terms of the weight of the iron element, with respect to 100 parts by weight of the dry weight of the polyphenols or the feedstock of the polyphenols. parts or more, more preferably 4 parts by weight or more, still more preferably 10 parts by weight or more, particularly preferably 20 parts by weight or more. If the proportion of the iron element is too small (if the proportion of the polyphenols mixed with respect to the iron element is too high), the excess polyphenols function as radical scavenging substances (scavengers), so the Fenton reaction and photocatalyst May inhibit reactions.

In addition, the upper limit of the mixing ratio of the iron feedstock is 100 parts by weight or less in terms of the weight of the iron element with respect to 100 parts by weight of the dry weight of the polyphenols or the feedstock of the polyphenols. , preferably 80 parts by weight or less, more preferably 60 parts by weight or less. If the ratio of the iron element is too high (if the mixing ratio of the polyphenols is too low relative to the iron element), the iron ions cannot be maintained in a divalent state, and the efficiency of the Fenton reaction or photocatalytic reaction decreases. I don't like it.

In addition, when the extract or extract of the polyphenol-containing plant is used as the raw material for the polyphenols, the dry weight of the polyphenol-containing plant used as the raw material for extraction is referred to as the "dry weight of the raw material for the polyphenols. The above mixing ratio can be calculated by considering the above as "weight". For example, it is assumed that dry tea leaves are used as the feedstock for the polyphenols, and an extract obtained by hot water extraction of the tea leaves is reacted with the iron feedstock. In this case, the weight of the dried tea leaves is used as the "dry weight of the polyphenol feedstock" to calculate the mixing ratio with the iron feedstock.

Similarly, when the processed product of the polyphenol-containing plant body is used as the raw material for the polyphenols, the dry weight of the polyphenol-containing plant used as the raw material for processing is referred to as the "dry weight of the raw material for the polyphenols". , the above mixing ratio can be calculated.

The mixing operation of the raw materials is performed in the presence of water. Here, the presence of water may be any condition as long as the polyphenols and iron can react with each other using water as a medium. Specifically, the reaction is presumed to be a reaction in which the polyphenol reduces iron ions (the state of Fe ²⁺ , which is a divalent iron ion) to form a complex.

The amount of water should be sufficient to allow at least mixing and stirring of the raw materials, and may be an amount sufficient to wet the mixture of raw materials (polyphenols and iron).

In addition, when plant body juice or plant dry distillation liquid is used as a raw material for polyphenols, it can be directly mixed with the iron raw material and reacted without adding a new medium.

As for the mixing operation, simple stirring and mixing with a stirrer, etc., can be performed, but it can also be performed with a mixer, large stirring tank, vortex, shaker, etc.

The temperature of the water during mixing should be the temperature at which the water is in a liquid state (for example, 1 to 100°C at 1 atm). It is possible to adopt about room temperature (for example, 10 to 35 ° C.) that does not require heating, but when heating, heating at 40 ° C. or higher, preferably 50 ° C. or higher, generates a polyphenol iron complex. is promoted and suitable.

The upper limit of the temperature of water during mixing can be 200 ° C. (in the case of pressurized heating), but from the viewpoint of production costs, the boiling point of normal heating under normal pressure conditions is 100 ° C. or less, preferably 90 ° C. °C or below, more preferably 70°C or below. In addition, under the reaction conditions of 100° C. or higher, it is preferable to carry out the reaction in a closed container in order to suppress thermal decomposition of the polyphenols.

The mixing time may be about 10 seconds or more until the polyphenols and iron are sufficiently contacted, but in order to improve uniformity, it is preferably 1 minute or more, more preferably 3 minutes or more, and still more preferably Mixing for 5 minutes or more is desirable.

In addition, the upper limit of the mixing time is 10 days or less, preferably 7 days or less, more preferably 5 days or less, even more preferably 3 days or less, and particularly preferably 1 day, in order to prevent organic matter from spoiling due to propagation of microorganisms. It is desirable to perform within However, there is no particular upper limit when sterilization is involved.

The reaction product (reaction product of polyphenols and iron) obtained through the above mixing treatment has excellent divalent iron ion-supplying activity, Fenton reaction catalytic activity, and photocatalytic activity. In the reaction product, it is presumed that the polyphenols convert iron into a divalent iron ion (Fe ²⁺ ) state to form a complex (that is, a polyphenol iron complex).

As for the reaction product obtained by the above-described mixing treatment, the supernatant obtained after the reaction or the precipitate in a water-containing state can be used as it is as the polyphenol iron complex in the present embodiment. In addition, the separated and collected supernatant or precipitate, the dried product obtained by drying (natural drying, roasting, hot air drying, etc.), and the suspension obtained by further dissolving the dried product in water Turbid matter, its supernatant, etc. can also be used as the polyphenol iron complex in the present embodiment.

The polyphenol-iron complex capsule according to the first embodiment is a capsule made of alginic acid gel containing the polyphenol-iron complex. Here, "alginic acid gel" is a gel formed by ionically cross-linking alginic acid molecules with polyvalent cations.

The polyphenol-iron complex capsule is a core-shell type capsule in which the inner layer containing the polyphenol-iron complex is covered with the outer layer of the alginate gel, or a matrix-type capsule in which the polyphenol-iron complex is dispersed inside the particles of the alginate gel. Capsules.

Also, the shape of the polyphenol iron complex capsule may be spherical or non-spherical. Moreover, it may be a mononuclear structure having only one inner layer, or a multinuclear structure having two or more inner layers. In any of the above forms, the effect of stabilizing the polyphenol-iron complex and achieving sustained release remains the same.

Alginic acid is a heteropolysaccharide composed of D-mannuronic acid (M) and L-guluronic acid (G). Since gelation of alginic acid is caused by cross-linking of guluronic acid moieties, the physical properties of the obtained polyphenol iron complex capsules vary depending on the composition ratio of M and G, that is, the M/G ratio. For example, if alginic acid with a large M/G ratio, that is, with a large mannuronic acid content, is used, the capsule will be soft and easily disintegrated, and if alginic acid with a small M/G ratio, that is, with a large guluronic acid content, is used, the capsule will be hard and disintegrate. It becomes a difficult capsule.

Therefore, the M/G ratio of alginic acid may be appropriately set according to the application and usage environment of the polyphenol iron complex capsule so that the capsule has desired physical properties. Specifically, the M/G ratio of alginic acid can usually be about 0.05 to 5.0.

The size of the polyphenol-iron complex capsule may be appropriately set according to the application, usage environment, etc. For example, a spherical capsule may have a diameter ranging from 1 nm to 1 m. For example, when it is used in a fish tank, the size may be set so as to prevent accidental ingestion by the target fish. Specifically, in the case of small aquarium fish raised in home aquariums, spherical capsules can have a diameter of about 2 to 10 mm. Also, when targeting medium-sized fish, the diameter can be about 10 to 100 mm, and when targeting large fish, the diameter can be about 10 to 100 cm.

In addition, the polyphenol iron complex capsule may have a shape that imitates aquatic plants, seaweed, shells, coral, pebbles, etc., so as not to spoil the scenery in a fish tank. In that case, the size of the capsule may be appropriately set according to the size of actual aquatic plants, seaweed, shells, corals, pebbles, and the like.

The content of the alginic acid gel in the polyphenol iron complex capsule is usually 0.001 to 99% by weight, preferably 0.1 to 10% by weight.

The content of the polyphenol iron complex in the polyphenol iron complex capsule is not particularly limited. For example, it can be 0.0001 to 99% by weight, preferably 0.01 to 10% by weight.

The polyphenol-iron complex capsule may contain components other than the polyphenol-iron complex as long as the above effects are not hindered. Examples of the "other ingredients" include nutrients necessary for the growth and proliferation of useful organisms such as animals and plants such as fish and shellfish, algae, and microorganisms.

Specifically, water-soluble vitamins such as B vitamins and vitamin C or derivatives thereof; trace elements such as copper, zinc, cobalt, manganese, molybdenum, boron and iron, or compounds thereof; The above are mentioned. The trace element may be contained in the form of a polyphenol complex because it can react with an excessive amount of the polyphenols in the capsule to form a complex.

The _B vitamins include vitamin _B1 _, vitamin B2, niacin (vitamin B3), pantothenic acid (vitamin _B5 ), vitamin _B6 , biotin (vitamin _B7 ), folic acid (vitamin _B9 ), vitamin B ₁₂ or derivatives thereof.

Examples of the trace element compounds include copper sulfate, zinc sulfate, cobalt chloride, manganese chloride, manganese sulfate, sodium molybdate, boric acid, iron chloride, and iron sulfate.

The total content of the "other ingredients" and the content of each ingredient in the polyphenol iron complex capsule may be appropriately set according to the application of the capsule, and is not particularly limited. For example, the total content is usually 99% by weight or less, preferably 0.0001 to 95% by weight, more preferably 0.5 to 75% by weight, and even more preferably 5 to 60% by weight.

As a specific example, an example of the composition of the B vitamins and the trace elements contained in the polyphenol iron complex capsule for the purpose of raising seafood or treating diseases is shown below. The following composition may be concentrated or diluted and contained in the polyphenol iron complex capsule.

As a specific example, an example of the composition of the trace element contained in the polyphenol iron complex capsule for the purpose of plant cultivation is shown below. The following composition may be concentrated or diluted and contained in the polyphenol iron complex capsule.

The polyphenol iron complex capsules described above can be produced, for example, as follows.

(1) First, the polyphenol iron complex is prepared by mixing the polyphenols or the feedstock thereof and the iron feedstock in the presence of water by the method described above.

(2) Next, the obtained polyphenol iron complex and alginate are mixed to prepare an alginic acid aqueous solution (liquid 1) (see FIG. 1).

Here, the "alginate" may be any soluble salt of alginic acid, and specific examples include sodium alginate, potassium alginate, and ammonium alginate.

The M/G ratio of alginic acid may be appropriately set according to the application and usage environment of the polyphenol iron complex capsule so that the capsule has desired physical properties. Specifically, the M/G ratio of alginic acid can usually be about 0.05 to 5.0.

The content of the alginate in the alginic acid aqueous solution is usually 0.001 to 99% by weight, preferably 0.1 to 10% by weight.

The content of the polyphenol iron complex in the aqueous alginic acid solution is not particularly limited. For example, it can be 0.0001 to 99% by weight, preferably 0.01 to 10% by weight.

The aqueous alginic acid solution may contain components other than the polyphenol iron complex as long as the above effects are not hindered. The "other ingredients" are as described above, for example, water-soluble vitamins such as B vitamins and vitamin C or derivatives thereof; trace elements such as copper, zinc, cobalt, manganese, molybdenum, boron, iron, or one or more selected from the group consisting of the compound;

The total content of the "other components" and the content of each component in the aqueous alginic acid solution may be appropriately set according to the application of the polyphenol iron complex capsule, and are not particularly limited. For example, the total content is usually 99% by weight or less, preferably 0.0001 to 95% by weight, more preferably 0.5 to 75% by weight, and even more preferably 5 to 60% by weight.

As a specific example, an example of the composition of the B vitamins and the trace elements in the alginic acid aqueous solution when producing the polyphenol iron complex capsules used for the purpose of breeding seafood or treating diseases is shown below. In addition, the following composition can also be concentrated or diluted and blended.

As a specific example, an example of the composition of the trace elements in the alginic acid aqueous solution when producing the polyphenol iron complex capsules used for plant cultivation is shown below. In addition, the following composition can also be concentrated or diluted and blended.

(3) Then, as shown in FIG. 1, the aqueous solution of alginic acid (liquid 1) prepared in (2) above is added dropwise into the solution (liquid 2) in which polyvalent cations are dissolved, thereby turning alginic acid into a gel. to produce the polyphenol iron complex capsule (see FIG. 2). As a dropping method, a conventionally known method may be used.

"Polyvalent cations" include, for example, calcium salts and iron salts. More specifically, calcium chloride, calcium lactate, ferric sulfate, ferric chloride, etc. are preferred, and calcium chloride is particularly preferred because it accelerates gelation. Although the concentration of the polyvalent cation solution is not particularly limited, it can usually be 0.01 to 60% by weight.

By the above method, matrix-type spherical capsules are obtained in which the ingredients such as the polyphenol iron complex are dispersed inside the alginate gel particles.

Alternatively, the polyphenol iron complex is added to the inside of the alginate gel film by dropping the above-described polyphenol iron complex and other components from the inner cylinder of the concentric double nozzle and the alginate aqueous solution from the outer cylinder into the polyvalent cation solution. It is also possible to produce core-shell type spherical capsules in which ingredients such as are encapsulated.

In addition, an alginic acid aqueous solution (alginate concentration: about 0.5 to 10% by weight) added with a component such as the above-mentioned polyphenol iron complex was stirred well to form a gel, which was formed into a block of a desired size. Capsules of the desired size can also be produced by subsequent hardening by dipping in a polyvalent cation solution.

Furthermore, the alginic acid aqueous solution gelled as described above is placed in a mold of a desired shape made of silicon or the like and allowed to stand for about 20 minutes to 1 hour. By immersing it in water and hardening it, it is also possible to produce irregular shaped capsules of a desired shape imitating aquatic plants, seaweed, shells, corals, pebbles, and the like.

The polyphenol iron complex capsules obtained by any of the above manufacturing methods are included in the polyphenol iron complex capsules according to the first embodiment.

Next, the usage and effects of the polyphenol iron complex capsules described above will be explained.

In the polyphenol iron complex capsule of the first embodiment, the alginate gel having a porous structure gradually releases the polyphenol iron complex into the environment. The action effect can be sustained for a long time.

In addition, it is also possible to control the duration of the effect by controlling the release rate of the polyphenol iron complex from the alginate gel or by controlling the disintegration timing of the capsule.

Furthermore, since the polyphenol iron complex capsule is a highly safe substance for the human body and the environment, it can be used in various fields such as medicine, food, public health, fisheries, agriculture, and industry.

- Sterilization The polyphenol iron complex capsule can be used as a Fenton reaction catalyst to sterilize various objects regardless of whether they are liquid or solid by utilizing the property of generating hydroxyl radicals from hydrogen peroxide. Here, examples of objects that can be sterilized include not only bacteria but also eukaryotic microorganisms, algae, archaea, viruses, viroids, and the like.

Specifically, the sterilization target includes water tanks such as homes and aquariums; restaurants, fish farms, fish cages for transportation, etc.; nutrient tanks such as hydroponics; water in pools, ponds, lakes, sewage treatment plants, etc. kitchen utensils such as cutting boards, kitchen knives and tableware; skin of animals, humans, etc.;

As a sterilization method using the polyphenol iron complex capsule, when the sterilization target is solid, sterilization can be performed by immersing the sterilization target in a solution to which the polyphenol iron complex capsule is added. The solution may contain other bactericidal components, contaminants, useful organisms, etc., as long as they do not interfere with the above effects.

Alternatively, sterilization can be performed by adding the polyphenol iron complex capsules to water or hydrous alcohol and spraying them on the object or space to be sterilized using a sprayer or the like.

Further, when the object to be sterilized is liquid or dispersed in a solution, sterilization can be performed by adding the polyphenol iron complex capsules to the liquid or solution.

In addition, if the sterilization target is the organism itself, or if the liquid sterilization target or the solution in which the sterilization target is dispersed or the solution in which the solid sterilization target is immersed contains the organism, the sterilization target or Since a small amount of biogenic hydrogen peroxide is already generated in the solution, it is possible to perform sterilization using only the polyphenol iron complex capsule.

However, by adding hydrogen peroxide together with the polyphenol iron complex capsules, a higher bactericidal effect can be obtained. Moreover, the hydrogen peroxide capsule according to the second embodiment may be used as the hydrogen peroxide.

The amount of the polyphenol iron complex capsule added in the sterilization method is not particularly limited, and may be an amount that provides the desired sterilization effect. Specifically, it can be 0.5 g or more, preferably 1 to 30 g, and more preferably 5 to 10 g per liter of water or solution. Also, the amount of hydrogen peroxide to be added may be extremely small, and may be an amount of about 0.1 to 20 mM.

The duration of the bactericidal effect of the polyphenol iron complex capsules varies depending on the sustained release and disintegration properties of the alginate gel, the content of the polyphenol iron complex, etc., but may be, for example, several days to several tens of months. can be done. During this time, the bactericidal action can be obtained simply by leaving the polyphenol iron complex capsule in the solution in which the solid object to be sterilized is immersed, in the solution in which the object to be sterilized is dispersed, or in the liquid object to be sterilized. However, by generating a water flow using an air pump, agitation, or the like, the polyphenol iron complex can be distributed throughout the solution or liquid to be sterilized, so that a higher sterilization effect can be obtained.

In addition, as described above, since the polyphenol iron complex also has photocatalytic activity, a higher bactericidal effect can be obtained by irradiating the polyphenol iron complex capsule with light. As the light, one or more light selected from sunlight, light in a wide wavelength range of 200 to 1400 nm, ie, ultraviolet light, visible light, and infrared light can be used.

Here, "ultraviolet rays" refer to light in the wavelength range of 380 nm or less. "Visible light" refers to light with a wavelength of 380 to 750 nm, which is the wavelength range visible to the human eye. Specifically, "visible light" includes 380-450 nm (violet light), 450-495 nm (blue light), 495-570 nm (green light), 570-590 nm (yellow light), 590-620 nm (orange light). ), including light in the wavelength range of 620-750 nm (red light). Also, "infrared" refers to light in a wavelength range of 750 nm or more.

Among them, the polyphenol iron complex capsule exhibits extremely strong photocatalytic activity when irradiated with the ultraviolet rays. In particular, by irradiating light with a wavelength of 200 to 380 nm, which is near-ultraviolet, it exhibits much higher photocatalytic activity (bactericidal action) than titanium oxide, which is a conventional photocatalyst.

In addition, the polyphenol iron complex capsules exhibit strong photocatalytic activity (bactericidal action) even when irradiated with visible light and infrared light, which are wavelength regions in which titanium oxide does not exhibit activity. In visible light, it shows strong activity in the wavelength range of violet light to blue light (380-495 nm), which has particularly short wavelengths. In infrared rays, it exhibits strong activity in the near-infrared wavelength range of 750 to 1400 nm (especially around 900 to 1300 nm, more especially around 1100 to 1300 nm).

Since the photocatalytic activity of the polyphenol iron complex capsule is extremely strong, for example, in the case of surface sterilization, sufficient sterilization effect can be obtained by irradiating sunlight for several minutes, preferably 10 minutes or more, more preferably 20 minutes or more. demonstrated. Even when relatively weak light such as LED or fluorescent lamp is applied, a sufficient sterilization effect can be obtained by treatment for 1 hour or longer, preferably 6 hours or longer, and more preferably 12 hours or longer.

•Decomposition of Organic Substances The polyphenol iron complex capsule can be used to decompose various organic substances due to its Fenton reaction catalytic activity. In particular, since it can be suitably used for decomposing organic pollutants and harmful substances, it is useful in one step of environmental purification.

Here, pollutants and harmful substances refer to substances that cause water pollution, soil pollution, and air pollution. Examples of organic substances that are harmful to the human body and the environment include domestic wastewater, night soil water, industrial wastewater, polluted river and lake water, landfill soil, industrial waste, agricultural land, and factory sites. can.

Examples of specific organic substances to be decomposed include organic waste such as detergents, food and drink residues, night soil, feces, pesticides, malodorous substances, waste oils, dioxins, PCBs, DNA, RNA, and proteins. can.

The specific method for decomposing these organic substances using the polyphenol iron complex capsule is the same as the sterilization method described above.

That is, when the decomposition target is solid, decomposition can be performed by immersing the decomposition target in a solution to which the polyphenol iron complex capsule is added.

Alternatively, decomposition can be performed by adding the polyphenol iron complex capsules to water or hydrous alcohol and spraying them onto the decomposition target using a sprayer or the like.

Further, when the decomposition target is liquid or dispersed in a solution, decomposition can be performed by adding the polyphenol iron complex capsule to the liquid or solution.

When the liquid decomposition target, the solution in which the decomposition target is dispersed, or the solution in which the solid decomposition target is immersed already contains biologically derived hydrogen peroxide, only the polyphenol iron complex capsule is used. It is possible to perform decomposition by

The amount of the polyphenol iron complex capsule added in the decomposition method is not particularly limited, and may be an amount that provides the desired decomposition effect. Specifically, the addition amount can be the same as in the case of the sterilization. Also, the amount of hydrogen peroxide to be added may be extremely small, and may be an amount of about 0.1 to 20 mM.

The duration of the organic substance decomposition effect of the polyphenol iron complex capsule can be, for example, several days to several tens of months. Further, a higher decomposition effect can be obtained by generating a water flow using an air pump, stirring, or the like in the solution in which the solid decomposition target is immersed, the solution in which the decomposition target is dispersed, or the liquid decomposition target.

In addition, similarly to the sterilization method, by irradiating the polyphenol iron complex capsules with light, it is possible to decompose organic substances in a shorter time. As the light, one or more light selected from sunlight, light in a wide wavelength range of 200 to 1400 nm, ie, ultraviolet light, visible light, and infrared light can be used. The irradiation time can be the same as in the sterilization method described above.

- Supply of iron The polyphenol iron complex capsule has the property of being able to stably and sustainably release water-soluble ferric ions for a long period of time. Moreover, this ability to supply water-soluble iron is stably exhibited even under alkaline conditions. Therefore, the polyphenol iron complex capsule can be suitably used as an iron supply agent.

Here, the target of iron supply is not particularly limited, and can be applied to all organisms such as plants, animals, and microorganisms.

When used to supply iron to plants, the polyphenol iron complex capsules can be used for any normal plant cultivation in agriculture and horticulture. In particular, it is effective for cultivation in alkaline soil where iron deficiency is likely to occur, and for use in hydroponics (hydroponics).

Here, alkaline soil refers to alkaline soil with a pH of about 7-10. The polyphenol iron complex capsules can exhibit iron supplying ability even in strongly alkaline soil with a pH of 9 or higher. Not usable at all.

As a method for using the iron supply agent for plant cultivation, which consists of the polyphenol iron complex capsules, when the target is a plant, the polyphenol iron complex capsules are mixed in the cultivation soil; sprayed on the cultivation soil; Add ferric ions to the water storage space of the pot together with water so that the water containing ferric ions is supplied to the cultivation soil; add to the nutrient solution for hydroponics; can be supplied.

The amount of the polyphenol iron complex capsules added in the iron supply method is not particularly limited, and may be an amount that provides the desired effect. Specifically, when it is used by adding to water, it can be 0.5 g or more, preferably 1 to 70 g, per 1 L of water. Moreover, when it is used by adding to the soil, it can be 0.1 to 10% by weight based on the soil.

The duration of the iron supply effect of the polyphenol iron complex capsules varies depending on the sustained release and disintegration properties of the alginate gel, the content of the polyphenol iron complex, and the like, but is, for example, several days to several tens of months. be able to.

[Hydrogen peroxide capsule]
The hydrogen peroxide capsule of the second embodiment will be described in detail below.

A hydrogen peroxide capsule according to the second embodiment is formed by encapsulating hydrogen peroxide in an alginic acid gel. That is, the capsule is a capsule made of alginic acid gel containing hydrogen peroxide.

The hydrogen peroxide capsule is a core-shell type capsule in which an inner layer containing hydrogen peroxide is covered with an outer layer of the alginate gel, or a matrix type capsule in which hydrogen peroxide is dispersed inside the alginate gel particles. , may be either.

Also, the shape of the hydrogen peroxide capsule may be spherical or non-spherical. Moreover, it may be a mononuclear structure having only one inner layer, or a multinuclear structure having two or more inner layers. In any of the above forms, the effect of stabilizing hydrogen peroxide and enabling sustained release remains the same.

The M/G ratio of alginic acid may be appropriately set according to the application and use environment of the hydrogen peroxide capsule so that the capsule has desired physical properties. Specifically, the M/G ratio of alginic acid can usually be about 0.05 to 5.0.

The size of the hydrogen peroxide capsule may be appropriately set according to the application, usage environment, etc. For example, a spherical capsule may have a diameter ranging from 1 nm to 1 m. For example, when it is used in a fish tank, the size may be set so as to prevent accidental ingestion by the target fish. Specifically, in the case of small aquarium fish raised in home aquariums, spherical capsules can have a diameter of about 2 to 10 mm. Also, when targeting medium-sized fish, the diameter can be about 10 to 100 mm, and when targeting large fish, the diameter can be about 10 to 100 cm.

In addition, the hydrogen peroxide capsule may have a shape that imitates aquatic plants, seaweed, seashells, coral, pebbles, etc., so as not to spoil the scenery in a fish tank. In that case, the size of the capsule may be appropriately set according to the size of actual aquatic plants, seaweed, shells, corals, pebbles, and the like.

The content of the alginic acid gel in the hydrogen peroxide capsule is usually 0.001 to 99% by weight, preferably 0.1 to 10% by weight.

The content of the hydrogen peroxide in the hydrogen peroxide capsule is not particularly limited. For example, it can be 0.0001 to 35% by weight, preferably 0.001 to 6.0% by weight.

The hydrogen peroxide capsule may contain ingredients other than the hydrogen peroxide as long as the above effects are not hindered.

The hydrogen peroxide capsule described above can be produced, for example, as follows.

(1) First, an alginic acid aqueous solution (liquid 1) containing hydrogen peroxide and alginate is prepared (see FIG. 3).

The M/G ratio of alginic acid may be appropriately set according to the application and usage environment of the hydrogen peroxide capsule so that the capsule has desired physical properties. Specifically, the M/G ratio of alginic acid can usually be about 0.05 to 5.0.

The content of the hydrogen peroxide in the aqueous alginic acid solution is not particularly limited. For example, it can be 0.0001 to 35% by weight, preferably 0.001 to 6.0% by weight.

The alginic acid aqueous solution may contain components other than hydrogen peroxide as long as the above effects are not hindered.

(2) Next, as shown in FIG. 3, the aqueous solution of alginic acid (liquid 1) prepared in (1) above is added dropwise into the solution (liquid 2) in which polyvalent cations are dissolved, thereby dissolving alginic acid. It is allowed to gel to produce the hydrogen peroxide capsules (see FIG. 4). As a dropping method, a conventionally known method may be used.

"Polyvalent cations" include, for example, calcium salts. More specifically, calcium chloride, calcium lactate, and the like are preferred, and calcium chloride is particularly preferred because it accelerates gelation. Although the concentration of the polyvalent cation solution is not particularly limited, it can usually be 0.01 to 60% by weight.

By the above method, matrix-type spherical capsules are obtained in which hydrogen peroxide is dispersed inside the alginate gel particles.

Alternatively, the hydrogen peroxide solution is dropped from the inner cylinder of the concentric double nozzle and the alginate aqueous solution from the outer cylinder into the polyvalent cation solution, respectively, so that hydrogen peroxide is enclosed inside the alginate gel film. , core-shell type spherical capsules can also be produced.

In addition, the above-described alginic acid aqueous solution (alginate concentration: about 0.5 to 10% by weight) to which hydrogen peroxide has been added is stirred well to form a gel, and after forming it into a mass of a desired size, a polyvalent Capsules of a desired size can also be produced by immersion in a cationic solution and curing.

Furthermore, the alginic acid aqueous solution gelled as described above is placed in a mold of a desired shape made of silicon or the like and allowed to stand for about 20 minutes to 1 hour. By immersing it in water and hardening it, it is also possible to produce irregular shaped capsules in a desired shape imitating aquatic plants, seaweed, shells, corals, pebbles, and the like.

The hydrogen peroxide capsules obtained by any of the above manufacturing methods are included in the hydrogen peroxide capsules according to the second embodiment.

Next, we will explain how to use the above hydrogen peroxide capsules and their effects.

In the hydrogen peroxide capsule of the second embodiment, the alginic acid gel having a porous structure gradually releases the hydrogen peroxide into the environment. Therefore, when used in combination with the polyphenol iron complex capsules of the first embodiment, the Fenton reaction can be maintained with high reaction efficiency for a long period of time.

In addition, since hydrogen peroxide alone exhibits a bactericidal action and an organic matter decomposing action, the hydrogen peroxide capsules can be used alone as a bactericidal agent, a purifying agent, a deodorant, an organic matter decomposing agent, and the like.

Targets that can be sterilized by the hydrogen peroxide capsule include not only bacteria but also eukaryotic microorganisms, algae, archaea, viruses, viroids, and the like. In addition, as sterilization targets, specifically, water tanks such as homes and aquariums; restaurants, fish farms, fish cages for transportation, etc.; nutrient tanks such as hydroponics; pools, ponds, lakes, sewage treatment plants water; kitchen utensils such as cutting boards, kitchen knives, and tableware; skins of animals, humans, etc.;

Examples of specific organic substances to be decomposed by the hydrogen peroxide capsule include organic waste such as detergents, food and drink residues, night soil, feces, agricultural chemicals, malodorous substances, waste oil, dioxins, PCBs, DNA, RNA, and proteins. things can be mentioned.

The method of using the hydrogen peroxide capsule can be the same as that of the polyphenol iron complex capsule of the first embodiment. Specifically, a method of immersing a solid object in a solution to which the hydrogen peroxide capsule is added; A method of spraying; a method of adding the hydrogen peroxide capsule to a liquid object or a solution in which the object is dispersed; and the like.

In addition, it is also possible to control the duration of the effect by controlling the rate of release of the hydrogen peroxide from the alginate gel or by controlling the disintegration timing of the capsule. The duration of the effect of the hydrogen peroxide capsule can be, for example, several days to several tens of months.

Furthermore, the hydrogen peroxide capsules are made from naturally-derived ingredients, and can be used in various fields such as medicine, food, public health, fisheries, agriculture, and industry.

[Fenton reaction kit]
The Fenton reaction kit of the third embodiment will be described in detail below. A Fenton reaction kit according to the third embodiment contains the polyphenol iron complex capsule of the first embodiment and the hydrogen peroxide capsule of the second embodiment.

Only by adding effective amounts of the polyphenol iron complex capsules and the hydrogen peroxide capsules contained in this kit to a solution, the polyphenol iron complex and hydrogen peroxide are gradually released into the solution, and the hydrogen peroxide is released. The Fenton reaction that generates hydroxyl radicals can be sustained with high reaction efficiency.

Since hydroxy radicals exhibit extremely strong bactericidal action and organic substance decomposing action, the kit can be effectively used as a bactericidal agent, water purification agent, deodorant, organic matter decomposing agent, and the like. The method of using the kit is as described for the first embodiment.

The kit may contain components other than the polyphenol iron complex capsules and the hydrogen peroxide capsules as long as they do not interfere with the above effects. The kit may also contain a visible light-responsive porous photocatalyst described in a fourth embodiment described later.

[Method for Raising Seafood or Treating Disease]
Hereinafter, the method for raising fish and shellfish or treating diseases according to the fourth embodiment will be described in detail.

A method for raising fish or treating diseases according to the fourth embodiment is characterized by using the polyphenol iron complex capsule of the first embodiment.

The polyphenol iron complex capsule can be used for breeding fish and shellfish or for treating diseases by utilizing the above-described bactericidal action, water purification (organic substance decomposition) action, and divalent iron ion supply action.

That is, by introducing the polyphenol iron complex capsule into the breeding environment of fish and shellfish, iron is supplied to the fish and shellfish, pathogenic microorganisms present in the water are killed, and the organic system is improved. The effect of decomposing pollutants is continuously exhibited.

This makes it possible to treat individuals infected with pathogenic microorganisms and prevent other healthy individuals from being infected. Moreover, hydroxyl radicals decompose in a short time and remain in individuals. Not at all. At the same time, it is possible to purify the water quality, so it is possible to greatly reduce the time and effort required for water changes and cleaning.

Here, the "fish and shellfish" that are the target of breeding and disease treatment are not particularly limited. Specifically, all aquatic products such as fish, shellfish, crustaceans, and mollusks can be mentioned, regardless of whether they are freshwater organisms or seawater organisms.

The "disease" to be treated is not particularly limited as long as it is a disease caused by iron deficiency or a disease caused by microbial or viral infection. This is because hydroxyl radicals exhibit strong bactericidal and decomposing actions against all kinds of microorganisms and viruses.

As a method for breeding or treating diseases of fish and shellfish using the polyphenol iron complex capsules, it is possible to breed or treat diseases by adding an effective amount of the polyphenol iron complex capsules to an aquarium of the fish and shellfish. Since the water in the aquarium is considered to already contain biogenic hydrogen peroxide, the addition of only the polyphenol iron complex capsules produces the above effects.

In addition, when hydrogen peroxide is added together with the polyphenol iron complex capsules, stronger sterilization and water purification effects are exhibited. Therefore, for the purpose of treating diseases of fish and shellfish, it is preferable to use not only the polyphenol iron complex capsules but also hydrogen peroxide.

The amount of the polyphenol iron complex capsule added can be 0.01 g or more, preferably 0.5 to 50 g, more preferably 1 to 20 g, and particularly preferably 5 to 10 g per 1 L of water in the water tank. The amount of hydrogen peroxide to be added may be extremely small, and may be such that the concentration of hydrogen peroxide in water is about 0.1 to 20 mM.

It is preferable to use the hydrogen peroxide capsules according to the second embodiment as the hydrogen peroxide. This is because the hydrogen peroxide capsules are capable of stabilizing and sustaining release of hydrogen peroxide, and therefore stable Fenton reaction efficiency can be obtained by using them together with the polyphenol iron complex capsules.

The replacement timing of the polyphenol iron complex capsules and the hydrogen peroxide capsules varies depending on the sustained release and disintegration properties of the alginic acid gel, the content of the polyphenol iron complex and hydrogen peroxide, etc., but for example, from several days to Dozens of months later. Since the alginic acid gel is composed of food-derived raw materials, there is no problem even if it remains in water even after the expiration date.

In the method for breeding or treating diseases of fish and shellfish, the above-mentioned effects can be obtained simply by leaving the polyphenol iron complex capsules in the fish and shellfish tank. By allowing the polyphenol iron complex to spread throughout the breeding environment of the fish and shellfishes, a higher effect can be obtained.

In addition, by irradiating the polyphenol iron complex capsules with light, photocatalytic activity is also exhibited, so stronger sterilization and water purification effects are exhibited. As the light, one or more light selected from sunlight, light in a wide wavelength range of 200 to 1400 nm, ie, ultraviolet light, visible light, and infrared light can be used.

Preferably, it exhibits extremely strong photocatalytic activity by irradiating it with ultraviolet light, particularly light with a wavelength of 200 to 380 nm, which is near ultraviolet light. In addition, it exhibits strong photocatalytic activity when irradiated with visible light, particularly short wavelength light in the wavelength range of violet to blue light (380 to 495 nm). In addition, it exhibits strong activity when irradiated with light in the wavelength range of 750 to 1400 nm (especially near 900 to 1300 nm, more particularly near 1100 to 1300 nm), which is infrared light, preferably near infrared light.

As for the light irradiation time, a sufficient effect can be exhibited by, for example, irradiating with sunlight for 3 hours or more, preferably 6 hours or more per day. Even when relatively weak light such as an LED or fluorescent lamp is irradiated, a sufficient effect can be exhibited by treatment for 12 hours or more, preferably 20 hours or more per day.

In the fourth embodiment, a visible-light-responsive porous photocatalyst can be used in combination as a material that supplies oxygen and hydrogen peroxide and at the same time produces sterilization and water purification effects based on visible-light-responsive photocatalytic activity.

"Visible light responsive porous photocatalyst" (hereinafter sometimes abbreviated as "porous photocatalyst") refers to a porous body formed by solidifying alkaline earth metal peroxide with cement and exhibits visible-light-responsive photocatalytic activity.

Although the shape of the porous photocatalyst is not particularly limited, it is preferable to set the thickness in the range of 0.1 to 10 cm, for example, because light can easily reach the inside. In particular, when used in a fish tank or the like, it may be shaped like a shell, coral, pebble, etc. so as not to spoil the landscape.

Examples of "alkaline earth metal peroxides" (hereinafter sometimes abbreviated as "peroxides") include calcium peroxide, magnesium peroxide, strontium peroxide, barium peroxide, beryllium peroxide, Radium peroxide may be mentioned, but calcium peroxide and magnesium peroxide are preferred, and calcium peroxide is particularly preferred.

The peroxide is known to have the property of reacting with water to generate hydrogen peroxide and generate oxygen. However, the present inventor surprisingly discovered that the peroxide itself exhibits visible light-responsive photocatalytic activity.

Examples of "cement" include Portland cement, mixed cement, and ecocement. In particular, from the viewpoint of light transmission, white cement is preferably used among Portland cements. Moreover, you may use white cement as a main component, and other types of cements and binders may be mixed and used.

The porous photocatalyst can be basically produced by mixing the peroxide, the cement, and water, and drying. Since the peroxide reacts with water to generate oxygen, the bubbles form a porous structure.

By having such a porous structure, the porous photocatalyst has a large surface area and can achieve high reaction efficiency. In particular, it is desirable that the specific gravity is lighter than that of water and that it floats on the water surface.

The content weight ratio of the cement in the total solid content of the porous photocatalyst is usually 17 to 80%, preferably 20 to 70%, more preferably 30 to 65%, and particularly preferably 40 to 60%. can be done. If the content weight ratio of the cement is more than the above range, the formation of the porous structure is insufficient, the reaction efficiency is lowered, and the specific gravity of the porous photocatalyst increases and it sinks in water, which is not preferable. On the other hand, if the content weight ratio of the cement is less than the above range, the durability of the porous photocatalyst body is lowered, and it is likely to collapse in water, which is not preferable.

In addition, when the content weight ratio of the cement in the total solid content of the porous photocatalyst is 30 to 60%, only the peroxide and the cement are used as raw materials other than water, and high reaction It is possible to construct the porous photocatalyst having efficiency, floating property on water surface, and durability. These raw materials are particularly safe to the human body and the environment, and are inexpensive. Therefore, the porous photocatalyst composed only of these raw materials has extremely high industrial utility.

On the other hand, the content weight ratio of the peroxide in the total solid content of the porous photocatalyst can be usually 20 to 83%, preferably 50 to 75%, more preferably 60 to 70%.

The porous photocatalyst may contain other photocatalysts, additives, etc. in addition to the raw materials as long as the above effects are not hindered.

"Other photocatalysts" can be used without limitation as long as they have photocatalytic activity. Specific examples include the polyphenol iron complex of the first embodiment and titanium oxide. These other photocatalysts may be used singly or in combination.

Examples of "additives" include foaming agents that contribute to the formation of a porous structure by generating gases such as carbon dioxide, oxygen, and nitrogen by heating or reacting with an alkali. These additives may be used alone or in combination of multiple types.

As the "foaming agent", for example, one or more selected from sodium hydrogen carbonate, ammonium carbonate, powdered aluminum, and aluminum chloride can be used.

The weight ratio of the "other photocatalyst" to the total solid content of the porous photocatalyst can usually be 60% or less. In addition, the content weight ratio of the "additive" in the total solid content of the porous photocatalyst can be usually 10% or less. The content weight ratio of the "foaming agent" in the total solid content of the porous photocatalyst can usually be 0.4 to 4.0%.

The porous photocatalyst absorbs light in a wide wavelength range, including visible light, and exhibits strong photocatalytic activity. Specifically, by irradiating with sunlight or light in a wide wavelength range of 200 to 1200 nm, that is, one or more light selected from ultraviolet light, visible light, and infrared light, a strong sterilization and water purification action is shown. be

Above all, the porous photocatalyst exhibits strong photocatalytic activity when irradiated with light having a wavelength of 390 to 660 nm among the visible light. In particular, it exhibits extremely strong photocatalytic activity (sterilization, water purification action) when irradiated with yellow or green light with a wavelength of 570 to 590 nm.

In addition, the porous photocatalyst exhibits strong photocatalytic activity even when irradiated with ultraviolet rays and infrared rays. In the case of ultraviolet rays, it exhibits strong activity, especially when exposed to light with a wavelength of 200-390 nm. In the case of infrared rays, it shows strong activity especially when exposed to light with a wavelength of 800 to 1200 nm.

Therefore, when the polyphenol iron complex capsule and the porous photocatalyst are used together, it is preferable to irradiate light with a wide range of wavelengths, and light with a wavelength of 200 to 1200 nm is particularly preferable. The light irradiation time is the same as in the case of using only the polyphenol iron complex capsules.

When the porous photocatalyst is put into water and the light is irradiated, hydrogen peroxide and oxygen are eluted into the water due to the reaction between the peroxide and water, and hydroxyl radicals are also generated by photocatalytic activity.

　Because the peroxide is poorly soluble in water, oxygen and hydrogen peroxide are gradually eluted over a long period of time. Moreover, the photocatalytic activity is stably maintained for a long period of time.

The duration of the effect of the porous photocatalyst against the pathogenic microorganisms varies depending on the content of the peroxide, and can be, for example, several months to several years. Since the porous photocatalyst is composed of a material that is highly safe for the human body and the environment, there is no problem even if it remains in the water after the service life has passed.

The amount of the porous photocatalyst to be used is not particularly limited, and may be an amount that provides the desired effect. Specifically, the weight of the porous photocatalyst to 1 L of water can be 10 g or more, preferably 20 to 200 g.

When dirt, algae, etc. adhere to the surface of the porous photocatalyst, the photocatalytic activity is reduced. Since self-cleaning is possible by , the photocatalytic activity can be recovered. Here, "strong light" can be light of, for example, 100 cd (candela) or more, preferably 150 cd or more.

The porous photocatalyst described above can be produced, for example, as follows.

(1) First, the alkaline earth metal peroxide and the cement are mixed so as to have the above content weight ratio in the total solid content of the porous photocatalyst. These raw materials are preferably powdery or granular, and particularly preferably have a particle size of 5 mm or less.

Also, when using raw materials other than the above raw materials (excluding water), they are mixed at this stage.

(2) Next, water is added to and mixed with the raw materials mixed in (1) above. The water content can be 50 to 80% by weight, preferably 50 to 70% by weight, based on the total solid content of the raw material.

At this time, the alkaline earth metal peroxide reacts with water to generate oxygen. Moreover, when the foaming agent is contained, gas is also generated from the foaming agent. These gases form bubbles and form a porous structure.

(3) Then, the mixture obtained in (2) above is molded. Although the shape is not limited, it is preferable to set the thickness in the range of 0.1 to 10 cm, for example, because the light can easily reach the inside of the porous photocatalyst.

Especially when used in a fish tank, etc., it may be molded into a shape that imitates shells, corals, pebbles, etc., so as not to disturb the scenery. In this case, it is preferable to attach a weight so that the porous photocatalyst does not float. Also, the molding means is not particularly limited.

(4) Further, the molding obtained in (3) above is dried and solidified.

The drying method is not particularly limited as long as the porous body is solidified, but examples include hot air or blast drying, heat drying, and the like. The drying conditions are also not particularly limited, but for example, at a temperature of 20 to 98° C., preferably 30 to 80° C., more preferably 40 to 60° C., for 1 to 36 hours, preferably 4 to 24 hours, more preferably 6 hours. can be ~18 hours.

By using such a porous photocatalyst in combination with the polyphenol iron complex capsule, it exhibits a very high effect in raising fish and shellfish or treating diseases.

Specifically, by putting the porous photocatalyst into the water of the fish tank, oxygen is supplied to the fish and shellfish, and hydrogen peroxide is eluted. The hydrogen peroxide is used in the Fenton reaction with the polyphenol iron complex. Furthermore, due to its visible-light-responsive photocatalytic activity, it absorbs light of a wide range of wavelengths, and sterilizes and purifies water. These actions and effects are sustained for a long period of time, and self-cleaning is also possible, so that management costs can be greatly reduced.

The present embodiment will be described in detail below with reference to examples.

(Example 1) Production of polyphenol iron complex capsules that can be used for raising fish and shellfish and treating diseases (1) Preparation of liquid 1 (aqueous alginic acid solution) First, 10 g of dried tea leaves as a polyphenol-containing plant were added to 900 mL of distilled water and heated under pressure at 120° C. for 20 minutes. This was filtered with filter paper to obtain a tea leaf extract. 8.71 g of iron (III) chloride (about 3 g as iron element) was added to the tea leaf extract, distilled water was added to make 1000 mL, and the mixture was stirred to obtain a polyphenol iron complex solution.

Next, 3 mL of the polyphenol iron complex solution and 4 g of sodium alginate were added to 300 mL of distilled water and stirred to prepare an aqueous alginic acid solution.

The mixing ratio of the polyphenol feedstock (dried tea leaves) and the iron feedstock (iron (III) chloride) here is about 30 parts by weight of the iron feedstock as an iron element with respect to 100 parts by weight of the polyphenol feedstock. part ratio.

It is thought that the polyphenol-iron complex solution contains a polyphenol-iron complex in which iron ions derived from iron (III) chloride are chelated in the form of Fe ²⁺ by polyphenols extracted from tea leaves.

　3 mL of the polyphenol iron complex mixture and 4 g of sodium alginate were added to 300 mL of distilled water and stirred to prepare an alginic acid aqueous solution (liquid 1) (see Fig. 1).

(2) Preparation of Capsules 30 g of calcium sulfate was dissolved in 300 mL of distilled water to prepare an aqueous calcium sulfate solution (liquid 2). 200 g of polyphenol iron complex capsules (see FIG. 2) were produced by dropping the above alginic acid aqueous solution (liquid 1) into liquid 2 as shown in FIG. 1 while stirring this with a stirrer.

The obtained capsules were spherical with a diameter of about 5.0 mm and had a dark brown color. Dark brown is the color of the tea leaf extract. The capsule contains about 0.04% by weight of polyphenol iron complex in terms of elemental iron. The manufactured capsules were stored in distilled water at 4°C until use.

(Example 2) Production of polyphenol iron complex capsules that can be used for raising fish and shellfish and treating diseases (1) Preparation of liquid 1 (alginic acid aqueous solution) First, a vitamin mixture and a trace element mixture are prepared according to the following formulations. did.

(Prescription example of vitamin mixture)
Distilled water was added to the vitamins in Table 5 below to make a total of 1000 mL.

(Prescription example of trace element mixture)
Distilled water was added to the trace elements in Table 6 below to make a total of 100 mL.

Next, 10 g of dried tea leaves as a polyphenol-containing plant were placed in 900 mL of distilled water and heated under pressure at 120°C for 20 minutes. This was filtered with filter paper to obtain a tea leaf extract.

To the tea leaf extract, add 8.71 g of iron (III) chloride (about 3 g as iron element), 1 mL each of the above vitamin mixture and the above trace element mixture, add distilled water to make 1000 mL, and stir. Thus, a polyphenol iron complex mixed solution was obtained.

It is believed that the polyphenol-iron complex mixed solution contains a polyphenol-iron complex in which iron ions derived from iron (III) chloride are chelated in the form of Fe ²⁺ by polyphenols extracted from tea leaves. . Moreover, it is considered that the polyphenol-iron complex mixed solution also contains the trace element in the form of a chelate complex with polyphenols.

(2) Preparation of Capsules 30 g of calcium sulfate was dissolved in 300 mL of distilled water to prepare an aqueous calcium sulfate solution (Liquid 2). 200 g of polyphenol iron complex capsules were produced by dropping the above alginic acid aqueous solution (liquid 1) into liquid 2 as shown in FIG. 1 while stirring this with a stirrer.

(Example 3) Production of polyphenol iron complex capsules that can be used for raising fish and shellfish and treating diseases (1) Preparation of liquid 1 (aqueous solution of alginic acid) A liquid was prepared. Next, 10 g of dried chrysanthemum flowers as a polyphenol-containing plant body were placed in 900 mL of distilled water and heated at 120° C. for 20 minutes under pressure. This was filtered with filter paper to obtain a chrysanthemum flower extract.

To the chrysanthemum flower extract, 8.71 g of iron (III) chloride (about 3 g as iron element), 1 mL each of the above vitamin mixture and the above trace element mixture are added, and distilled water is added to make 1000 mL, A polyphenol iron complex mixed solution was obtained by stirring.

The mixing ratio of the polyphenols feedstock (chrysanthemum flower) and the iron feedstock (iron (III) chloride) here is about 30% of the iron feedstock as an iron element with respect to 100 parts by weight of the polyphenols feedstock. It becomes the ratio of parts by weight.

The polyphenol-iron complex mixed solution contains a polyphenol-iron complex in which iron ions derived from iron chloride (III) are chelated in the state of Fe ²⁺ by polyphenols extracted from chrysanthemum flowers. Conceivable. Moreover, it is considered that the polyphenol-iron complex mixed solution also contains the trace element in the form of a chelate complex with polyphenols.

The capsules obtained were spherical with a diameter of about 4 mm and had a dark brown color. Dark brown is the color of the chrysanthemum flower extract. The capsule contains about 0.04% by weight of polyphenol iron complex in terms of elemental iron. The manufactured capsules were stored in distilled water at 4°C until use.

(Example 4) Production of polyphenol iron complex capsules that can be used for cultivating plants (1) Preparation of liquid 1 (alginic acid aqueous solution) First, 10 g of dried tea leaves as a polyphenol-containing plant body were added to 700 mL of distilled water. Heated at 120° C. for 20 minutes under pressure. This supernatant was filtered with filter paper to obtain a tea leaf extract.

To 700 mL of the tea leaf extract, 15 g of iron (II) sulfate (about 5.5 g as iron element), 3 g of boric acid, 2 g of manganese sulfate, 0.22 g of zinc sulfate, 0.05 g of copper sulfate, and 0.01 g of sodium molybdate , and stirred to obtain a polyphenol iron complex mixed solution.

In addition, the mixing ratio of the polyphenol feedstock (tea leaves) and the iron feedstock (iron (II) sulfate) here is about 55 parts by weight of the iron feedstock as an iron element with respect to 100 parts by weight of the polyphenol feedstock. ratio.

It is believed that the polyphenol-iron complex mixed solution contains a polyphenol-iron complex in which iron ions derived from iron (II) sulfate are chelated in the form of Fe ²⁺ by polyphenols extracted from tea leaves. .

The obtained capsules were spherical with a diameter of about 4.0 mm and had a dark brown color. Dark brown is the color of the tea leaf extract. The capsule contains about 0.04% by weight of polyphenol iron complex in terms of elemental iron. The manufactured capsules were stored in distilled water at 4°C until use.

(Example 5) Production of polyphenol iron complex capsules that can be used for cultivating plants (1) Preparation of liquid 1 (alginic acid aqueous solution) First, 10 g of dried coffee grounds as a polyphenol-containing plant body was added to 700 mL of distilled water. , which was heated at 120° C. for 20 minutes under pressure. The supernatant was filtered with filter paper to obtain a coffee grounds extract.

To 700 mL of the coffee grounds extract, 15 g of iron (II) sulfate (about 5.5 g as iron element), 3 g of boric acid, 2 g of manganese sulfate, 0.22 g of zinc sulfate, 0.05 g of copper sulfate, and 0.2 g of sodium molybdate were added. 01 g, and stirred to obtain a polyphenol iron complex mixed solution.

The mixing ratio of the polyphenols feedstock (coffee grounds) and the iron feedstock (iron (II) sulfate) here is about 55 parts by weight of the iron feedstock as an iron element with respect to 100 parts by weight of the polyphenols feedstock. part ratio.

It is believed that the polyphenol-iron complex mixture contains a polyphenol-iron complex in which iron ions derived from iron sulfate (II) are chelated in the form of Fe ²⁺ by polyphenols extracted from coffee grounds. be done.

The obtained capsules were spherical with a diameter of about 10 mm and had a dark brown color. Dark brown is the color of the coffee grounds extract. The capsule contains about 0.04% by weight of polyphenol iron complex in terms of elemental iron. The manufactured capsules were stored in distilled water at 4°C until use.

(Example 6) Production of hydrogen peroxide capsules (1) Preparation of liquid 1 (alginic acid aqueous solution) First, 3 mL of 35% hydrogen peroxide solution and 4 g of sodium alginate are added to 300 mL of distilled water and stirred to obtain alginic acid. An aqueous solution (liquid 1) was prepared (see FIG. 3).

(2) Production of Capsules 30 g of calcium chloride was dissolved in 300 mL of distilled water to prepare an aqueous calcium chloride solution (Liquid 2). 200 g of hydrogen peroxide capsules (see FIG. 4) were produced by dropping the above alginic acid aqueous solution (liquid 1) into liquid 2 as shown in FIG. 3 while stirring this with a stirrer.

The capsules obtained were spherical with a diameter of about 10 mm and had a translucent white color. The capsule contains about 0.35% by volume of hydrogen peroxide. The manufactured capsules were stored in distilled water at 4°C until use.

(Example 7) Production of polyphenol iron complex capsules of different sizes Polyphenol iron complex capsules of different sizes were produced by a method different from the dropping method in the above example.

First, 10 g of dry tea leaves as a polyphenol-containing plant were placed in 900 mL of distilled water and heated under pressure at 120°C for 20 minutes. This was filtered with filter paper to obtain a tea leaf extract. 8.71 g of iron (III) chloride (about 3 g as iron element) was added to the tea leaf extract, distilled water was added to make 1000 mL, and the mixture was stirred to obtain a polyphenol iron complex solution.

Next, 100 mL of the polyphenol iron complex solution was mixed with 6 g of sodium alginate and stirred until gelation (alginic acid reacts with the polyphenol iron complex (Fe ²⁺ ) to gel). When the mixture solidifies into a gel, it is formed into a spherical shape with a diameter of 1 to 2 cm or 4 to 5 cm, and immersed in a 10 (w/v)% calcium chloride aqueous solution for 5 minutes to form a polyphenol iron complex capsule (see FIG. 5). manufactured.

Fig. 5 shows the obtained polyphenol iron complex capsules. In FIG. 5, the left end shows the polyphenol iron complex capsules produced by the method of Example 1 as a control, and the center and right ends show the polyphenol iron complex capsules of different sizes produced above, respectively.

(Test Example 1) Examination of stability of polyphenol iron complex Capsules of polyphenol iron complex and iron (II) sulfate were produced in the same manner as in Example 7, and the stability of divalent iron was compared. Similar capsules were prepared using iron(III) chloride as a control.

(1) Production of Polyphenol-Iron Complex Capsules First, 10 g of dried tea leaves as a polyphenol-containing plant were placed in 900 mL of distilled water and heated under pressure at 120° C. for 20 minutes. This was filtered with filter paper to obtain a tea leaf extract. 8.71 g of iron (III) chloride (about 3 g as iron element) was added to the tea leaf extract, distilled water was added to make 1000 mL, and the mixture was stirred to obtain a polyphenol iron complex solution.

Next, 100 mL of the polyphenol iron complex solution was mixed with 6 g of sodium alginate and stirred until gelation. When the mixture solidified into a gel, it was formed into a sphere with a diameter of 1 to 2 cm and immersed in a 10 (w/v)% calcium chloride aqueous solution for 5 minutes to produce a polyphenol iron complex capsule (see left in FIG. 6). .

(2) Production of Iron (II) Sulfate Capsules First, 900 mL of distilled water was heated at 120° C. for 20 minutes under pressure. To this, 15 g of iron (II) sulfate (about 5.5 g as iron element) was added, and distilled water was added to make 1000 mL to obtain an iron (II) sulfate solution.

Next, 100 mL of the above iron (II) sulfate solution was mixed with 6 g of sodium alginate and stirred until gelation (alginic acid and iron (II) sulfate react to gel). By immersing this in a 10 (w/v) % calcium chloride aqueous solution for 5 minutes, an iron (II) sulfate capsule (see the right side of FIG. 6) was produced.

(3) Preparation of iron (III) chloride capsule (control) First, 900 mL of distilled water was heated at 120°C for 20 minutes under pressure. 8.71 g of iron (III) chloride (about 3 g as elemental iron) was added to the solution, and distilled water was added to bring the total volume to 1000 mL, thereby obtaining an iron (III) chloride solution.

Next, 100 mL of the iron (III) chloride solution was mixed with 6 g of sodium alginate and stirred until gelation (alginic acid and iron (III) chloride react to gel). By immersing this in a 10 (w/v) % calcium chloride aqueous solution for 5 minutes, iron (III) chloride capsules (see the center of FIG. 6) were produced.

(4) Results and discussion Fig. 6 shows the appearance of the three types of capsules obtained above about 12 hours after production. As can be seen from FIG. 6, the polyphenol iron complex capsules remained dark brown with no change in color, whereas the iron (II) sulfate capsules changed color from transparent immediately after production to yellow. The control iron (III) chloride capsule remained yellowish brown and showed no change in color.

　Yellow or yellowish brown indicates that iron is trivalent iron ion. The iron (II) sulfate capsule turned yellow, indicating that ferric ions were oxidized to ferric ions. These results indicate that ferric ions that are not chelated by polyphenols are not stabilized as ferrous ions even when encapsulated in alginate gel, and their catalytic ability for the Fenton reaction is weakened.

(Test Example 2) Verification of bactericidal effect by combined treatment of polyphenol iron complex capsules and hydrogen peroxide capsules The polyphenol iron complex capsules of Example 1 and the hydrogen peroxide capsules of Example 6 were used in combination to verify the bactericidal effect against Escherichia coli. did.

First, 50 mL of LB medium (tryptone 10 g/L, yeast extract 5 g/L, sodium chloride 10 g/L) containing 1.2×10 ⁵ cfu of E. coli (ATCC43888) was placed in a 100 mL beaker. To this beaker, 1 g each of the polyphenol iron complex capsules of Example 1 and the hydrogen peroxide capsules of Example 6 were added, stirred, and allowed to stand for 30 minutes. As a control, the above LB medium without capsules was used.

After standing still for 30 minutes, 100 μL of the LB medium was collected and applied to an E. coli detection plate. After culturing at 37° C. for 24 hours, survival of E. coli was observed.

The results are shown in Figure 7. FIG. 7(a) shows a control group (no capsule added), and (b) shows a combined treatment group. From FIG. 7, it was found that E. coli survived in (a) the control group, whereas E. coli was completely destroyed in the (b) combined treatment group. From this, it was shown that sterilization is possible in a short time by using polyphenol iron complex capsules and hydrogen peroxide capsules together.

(Example 8) Breeding of seafood using both polyphenol iron complex capsules and hydrogen peroxide capsules Using both the polyphenol iron complex capsules of Example 1 and the hydrogen peroxide capsules of Example 6, I raised seafood.

Seafood (2 goldfish) were bred in a tank containing 30L of water. 0.5 g/L each of the polyphenol iron complex capsules of Example 1 and the hydrogen peroxide capsules of Example 6 were added at intervals of one week, and normal rearing was carried out. Continuous irradiation with a visible light LED (380-660 nm) was performed for 12 hours every day. Oxygen was constantly supplied by an air pump. The breeding period was 6 months.

By simply adding polyphenol iron complex capsules and hydrogen peroxide capsules, it was possible to raise fish and shellfish without harming them. During the breeding period, no damage caused by the polyphenol iron complex was observed in the fish and shellfish, and no disease occurred. Also, the water in the tank is less likely to become dirty.

From these results, it is thought that the long-term elution of the polyphenol iron complex and hydrogen peroxide from the capsule into the aquarium water sustained the iron supply, sterilization, and water purification effects. In addition, it is considered that the photocatalytic activity was exerted by irradiating the visible light LED, and the density of pathogenic bacteria in the aquarium water could be further reduced.

(Example 9) Breeding of seafood and treatment of disease using polyphenol iron complex capsules and hydrogen peroxide capsules together Using the polyphenol iron complex capsules of Example 1 and the hydrogen peroxide capsules of Example 6 together, Seafood was reared and treated as indicated.

　In a tank containing 2L of water, 6 fish and shellfish (medaka) affected by tail rot were placed. 10 g each of the polyphenol iron complex capsules of Example 1 and the hydrogen peroxide capsules of Example 6 were added, and the aquarium water and the capsules were replaced with new ones every day. Continuous irradiation with a visible light blue LED (380-500 nm) was performed for 24 hours every day. Except for the above, the animals were bred for 3 days in a normal manner.

By simply adding polyphenol iron complex capsules and hydrogen peroxide capsules, tail rot disease improved in 3 days without harming seafood. It is thought that pathogenic microorganisms were sterilized without damaging the medaka by the polyphenol iron complex and hydrogen peroxide eluted from the capsule, and the irradiation of the visible light blue LED.

(Example 10) Breeding of seafood and treatment of disease using polyphenol iron complex capsules and hydrogen peroxide capsules together Using the polyphenol iron complex capsules of Example 2 and the hydrogen peroxide capsules of Example 6 together, Seafood was reared and treated as indicated.

　In a tank containing 4L of water, one fish (iron fish) with red spot disease was placed. 5 g/L each of the polyphenol iron complex capsules of Example 2 and the hydrogen peroxide capsules of Example 6 were added, and the aquarium water and the capsules were replaced with new ones every day. Continuous irradiation with a visible light blue LED (380-500 nm) was performed for 20 hours every day. Except for the above, the animals were bred for 7 days in a normal manner.

By simply adding polyphenol iron complex capsules and hydrogen peroxide capsules, the red spot disease improved in 7 days without harming the seafood. It is thought that pathogenic microorganisms were sterilized without harming the iron fish by the polyphenol iron complex and hydrogen peroxide eluted from the capsule and the irradiation of visible light blue LED.

(Example 11) Breeding of seafood and treatment of disease using polyphenol iron complex capsules and hydrogen peroxide capsules together Using the polyphenol iron complex capsules of Example 3 and the hydrogen peroxide capsules of Example 6 together, Seafood was reared and treated as indicated.

　One fish (goldfish) with water mold disease was placed in a tank containing 2L of water. 5 g/L each of the polyphenol iron complex capsules of Example 3 and the hydrogen peroxide capsules of Example 6 were added, and the aquarium water and the capsules were replaced with new ones every day. Continuous irradiation with a visible light blue LED (380-500 nm) was performed for 20 hours every day. Except for the above, the animals were bred for 7 days in a normal manner.

As shown in Fig. 9, simply adding the polyphenol iron complex capsules and the hydrogen peroxide capsules did not harm the fish and shellfish, and the water mold disease was improved in 7 days. In FIG. 9, (a) shows the condition before treatment, and (b) shows the condition after treatment.

From these results, it is believed that the polyphenol iron complex and hydrogen peroxide eluted from the capsule, as well as the irradiation of the visible light blue LED, sterilized pathogenic microorganisms without harming the goldfish.

(Example 12) Breeding of fish and shellfish using both polyphenol iron complex capsules and visible-light-responsive porous photocatalysts

Using both the polyphenol iron complex capsule and the visible light-responsive porous photocatalyst, fish and shellfish were bred as shown in FIG. In FIG. 10, (a) shows a porous photocatalyst and (b) shows a polyphenol iron complex capsule, respectively.

(1) Production of porous photocatalyst First, a porous photocatalyst was produced as follows. 15 g of calcium peroxide (manufactured by Sigma-Aldrich) and 10 g of white cement (manufactured by Katei Kagaku Kogyo) were mixed, and 20 mL of distilled water was further added and mixed. This mixture was molded into an oval shape having a thickness of about 30 mm and then dried by hot air drying at 50° C. for 12 hours to obtain one porous photocatalyst.

The obtained porous body is white, has a small specific gravity, and floats on the water surface. Two such porous bodies were produced.

(2) Preparation of polyphenol iron complex capsules Polyphenol iron complex capsules were prepared as follows. First, 10 g of dried coffee grounds as a polyphenols feedstock was placed in 900 mL of distilled water and heated under pressure at 120° C. for 20 minutes. This was filtered with filter paper to obtain a coffee grounds extract. 8.71 g of iron (III) chloride (about 3 g as iron element) was added to the coffee grounds extract, distilled water was added to make 1000 mL, and the solution was stirred to obtain a polyphenol iron complex solution.

The mixing ratio of the polyphenols feedstock (dried coffee grounds) and the iron feedstock (iron (III) chloride) here is about 30% of the iron feedstock as an iron element per 100 parts by weight of the polyphenols feedstock. It becomes the ratio of parts by weight.

It is believed that the polyphenol-iron complex solution contains a polyphenol-iron complex in which iron ions derived from iron chloride (III) are chelated in the form of Fe ²⁺ by polyphenols extracted from coffee grounds. .

Next, 3 mL of the polyphenol iron complex solution and 4 g of sodium alginate were added to 300 mL of distilled water and stirred to prepare an alginic acid aqueous solution (liquid 1) (see FIG. 5). This alginic acid aqueous solution (liquid 1) was dropped into a 10% by weight calcium sulfate aqueous solution (liquid 2) while stirring with a stirrer to produce 200 g of polyphenol iron complex capsules (see FIG. 6).

The obtained capsules were spherical with a diameter of about 5.0 mm and had a dark brown color. Dark brown is the color of the coffee grounds extract. The capsule contains about 0.04% by weight of polyphenol iron complex in terms of elemental iron. The manufactured capsules were stored in distilled water at 4°C until use.

(3) Fish and shellfish breeding test Two water tanks containing 4 L of water were prepared, and 10 guppies were put in each tank and bred. In one water tank, two porous photocatalysts prepared above were floated, and 8 g of the polyphenol iron complex capsules prepared above were added, but in the other water tank, neither the porous photocatalyst nor the capsules were added. (Control group). Both water tanks were continuously irradiated with a visible light LED (470 to 490 nm) for 8 hours every day, and constantly supplied with oxygen by an air pump. The breeding period was 7 days.

After the end of the breeding period, 100 μL of water was sampled from each water tank, applied to a bacteria detection plate and cultured, and the number of viable bacteria in the water tank was determined. As a result, the bacteria density was 5 to 56 cfu/mL in the water tank using both the porous photocatalyst and the capsules, whereas it was 2.7×10 ⁶ cfu/mL or more in the control area.

From this, it was shown that by adding a porous photocatalyst and capsules and breeding while irradiating visible light, the growth of various bacteria in the aquarium can be suppressed. Therefore, it was shown that the above method can also treat and prevent diseases in fish and shellfish.

In addition, by simply adding a porous photocatalyst and polyphenol iron complex capsules, it was possible to breed fish and shellfish without causing any damage. During the breeding period, no damage caused by the polyphenol iron complex was observed in the fish and shellfish, and no disease occurred. Also, the water in the tank is less likely to become dirty.

From these results, oxygen and hydrogen peroxide are supplied from the porous photocatalyst, and the polyphenol iron complex is eluted from the capsule, thereby supplying Fe ²⁺ ions to the fish and shellfish, and promoting health and preventing and treating diseases. and the Fenton reaction occurred, resulting in sterilization, algicidal and water purification effects by hydroxyl radicals.

In addition, by irradiating the visible light LED, it is believed that the photocatalytic activity of both the porous photocatalyst and the polyphenol iron complex was exhibited, and the density of bacteria including pathogenic microorganisms in the water tank was able to be further reduced.

(Example 13) Bactericidal effect of combined use of polyphenol iron complex capsules and visible light responsive porous photocatalyst Using the porous photocatalyst and polyphenol iron complex capsules produced in the same manner as in Example 12, visible light irradiation A sterilization test was performed.

First, I prepared two water tanks containing 4L of water. Two porous photocatalysts were floated in one of the water tanks, and 8 g of polyphenol iron complex capsules were added thereto, while neither the porous photocatalysts nor the capsules were added to the other water tank (control group). Both water tanks were continuously irradiated with a visible light LED (470-490 nm) for 12 hours every day, and constantly supplied with oxygen by an air pump.

Five days after the start of the test, 100 μL of water was sampled from each water tank, applied to a bacteria detection plate and cultured to determine the number of viable bacteria in the water tank. As a result, 2.2×10 ⁵ cfu of bacteria proliferated in the control tank, whereas the number in the tank using both the porous photocatalyst and the capsule was 5×10 ² cfu or less. From this, it was shown that the growth of various bacteria including pathogenic microorganisms in the water tank can be suppressed simply by adding the porous photocatalyst and the polyphenol iron complex capsule and irradiating with visible light.

Oxygen and hydrogen peroxide are eluted from the porous photocatalyst, and polyphenol iron complexes (Fe ²⁺ ions) are eluted from the polyphenol iron complex capsules into water, and these are highly safe for seafood and the environment. It is matter. In addition, hydroxy radicals generated by photocatalytic reaction and Fenton reaction disappear immediately, and there is no concern that they will remain in the bodies of fish and shellfish. Therefore, it is considered that the method of breeding or treating diseases of fish and shellfish using a porous photocatalyst and a capsule is an excellent method that does not adversely affect fish and shellfish and the environment compared to conventional methods using chemical solutions. be done.

(Example 14) Use of polyphenol iron complex capsules as iron supply agent for plant cultivation Using the polyphenol iron complex capsules of Example 4 as a slow-release fertilizer (iron supply agent), as shown in FIG. cultivated.

A water storage space is provided at the bottom of the pot, and water in the water storage space is supplied to the pot by capillary action along a water supply sheet provided between the water storage space and the pot. Prepared a pot with

Cyclamen was planted in this pot with a water storage function, 10 g of the polyphenol iron complex capsules of Example 4 and 200 mL of water were placed in the water storage space, and the water in the water storage space was supplied to the soil along the water supply sheet. The cultivation period was 13 weeks.

By simply adding polyphenol iron complex capsules to the water in the water storage space, it is possible to supply divalent iron ions and trace elements to plants. No leaf yellowing symptoms due to iron deficiency were observed during the cultivation period. The gradual elution of the polyphenol iron complex and trace elements from the capsules enabled fertilization in accordance with plant growth.

Conventional slow-release fertilizers use chemical fertilizers coated with artificial resin. Since the fertilizer component gradually dissolves into the soil, the effect is slow and lasts for several months. However, since artificial resin is difficult to decompose, it remains in the soil, and it has been pointed out that it affects the environment. In contrast, the polyphenol-iron complex capsule of the present embodiment is composed of natural substances such as alginic acid, polyphenol, and iron, and is characterized by less environmental load.

(Example 15) Use of polyphenol iron complex capsules and hydrogen peroxide capsules as a disinfectant for water for cut flowers As shown in FIG. 12, cut flowers were arranged.

100 mL of distilled water, 1 g of polyphenol iron complex capsules of Example 5, and 1 g of hydrogen peroxide capsules of Example 6 were added to two transparent vases, respectively. Two cut flowers (roses) were arranged in each vase, and one of them was continuously irradiated with a visible light white LED (380 to 660 nm) from the bottom of the vase for 12 hours every day. Flower freshness was observed for 11 days.

Furthermore, 100 μL of the water in the vase after 11 days was collected and applied to the bacteria detection plate. After culturing for 48 hours, the viability of the bacteria was observed.

As a result, it was possible to maintain the freshness of cut flowers simply by adding polyphenol iron complex capsules and hydrogen peroxide capsules to water. In the control group without capsules, the freshness of the flowers lasted only 7 days (withered), whereas in the group treated with the polyphenol iron complex capsules and hydrogen peroxide capsules, regardless of the presence or absence of LED irradiation, It was possible to maintain the freshness of the flowers until 11 days later.

In addition, as shown in FIG. 13, in the combined treatment group (with light irradiation), no bacteria were detected from the water in the vase after 11 days, whereas bacteria were detected in the control group (no capsule added). rice field. In the combined treatment group, it was shown that the bactericidal effect persisted even after 11 days. In FIG. 13, (a) shows the control group (no capsule added), and (b) shows the combined treatment group (with light irradiation).

The embodiments and examples of the present disclosure have been described in detail above with reference to the drawings. Included in disclosure.

For example, in the above examples, capsules containing a polyphenol iron complex using polyphenols extracted from tea leaves or coffee grounds were described, but the capsules are not limited to these, and include grapes, cacao, acacia, cedar, sugarcane, Mango, banana, papaya, avocado, apple, cherry, guava, olive, potatoes, oyster, mulberry, blueberry, poplar, chrysanthemum, sunflower, bamboo, polyphenols, catechin, tannic acid, tannin , chlorogenic acid, caffeic acid, neochlorogenic acid, cyanidin, proanthocyanidin, thearubigin, rutin, flavonoids, flavones, chalcones, xanthophyll, carnosic acid, eriocitrin, nobiletin, tangeretin, magnolol, honokiol, ellagic acid, lignans , curcumin, coumarin, catechol, procyanidins, theaflavins, rosmarinic acid, xanthones, quercetin, resveratrol, gallic acid, phlorotannins can also be used as polyphenols of the present disclosure or as a source thereof.

Further, for example, in the above examples, the polyphenol-iron complex capsules produced by dropping an alginic acid aqueous solution containing a polyphenol-iron complex into a polyvalent cation solution were described, but the present invention is not limited to this. The polyphenol-iron complex capsules produced by dropping a polyvalent cation solution containing a polyphenol-iron complex into an aqueous alginic acid solution can also be included in the present disclosure.

Cross-reference to related applications

This application claims priority based on Japanese Patent Application No. 2021-019327 filed with the Japan Patent Office on February 9, 2021, the entire disclosure of which is fully incorporated herein by reference.

Claims

A polyphenol iron complex capsule in which a polyphenol iron complex is encapsulated in an alginic acid gel.
The polyphenol iron complex capsule according to claim 1, further containing water-soluble vitamins and/or trace elements.
The polyphenol iron complex is a reaction product obtained by mixing polyphenols or a feedstock thereof and an iron feedstock in the presence of water,
Sources of said polyphenols include grapes, coffee trees, tea trees, cacao, acacia, cedar, pine, perilla, yuzu, lemons, herbs, Houttuynia cordata, marigolds, sugarcane, mangoes, bananas, papaya, avocados, apples, cherries, One or more parts of leaves, stems, roots and fruits of one or more plants selected from the group consisting of guava, olive, tubers, persimmon, mulberry, blueberry, poplar, ginkgo biloba, chrysanthemum, sunflower and bamboo,
The iron feedstock is one or more selected from the group consisting of divalent iron compounds, trivalent iron compounds, soil, iron ore, and metallic iron,
The mixing ratio of the polyphenols or the feedstock thereof and the iron feedstock is 0.1 in terms of the weight of the iron element per 100 parts by weight of the dry weight of the polyphenols or the feedstock thereof. 3. The polyphenol iron complex capsule according to claim 1 or 2, wherein the mixing ratio is from 100 parts by weight to 100 parts by weight.
The polyphenol iron complex capsule according to any one of claims 1 to 3, which has the shape of aquatic plants, seaweed, shells, corals or pebbles.
A hydrogen peroxide capsule in which hydrogen peroxide is encapsulated in alginic acid gel.
A Fenton reaction kit containing the polyphenol iron complex capsule according to any one of claims 1 to 4 and the hydrogen peroxide capsule according to claim 5.
A method for raising fish or shellfish or treating a disease using the polyphenol iron complex capsule according to any one of claims 1 to 4.
The method for breeding or treating diseases of seafood according to claim 7, wherein the hydrogen peroxide capsule according to claim 5 is used in combination.
The method for rearing or treating diseases of fish and shellfish according to claim 7 or 8, wherein one or more of ultraviolet light, visible light, and infrared light is irradiated.
10. The method for rearing or treating diseases of fishes and shellfishes according to any one of claims 7 to 9, wherein a visible-light-responsive porous photocatalyst formed by solidifying alkaline earth metal peroxides with cement is also used.