JP2022133693A - Radical-generating composition, bactericidal composition, and organic matter-decomposing composition - Google Patents

Abstract

To provide a radical-generating composition, bactericidal composition or organic matter-decomposing composition that provides an excellent Fenton reaction and can further suppress the effects on the human body and the environment.SOLUTION: The radical-generating composition contains an edible mushroom juice and/or extract thereof and an iron-feed raw material. The edible mushroom preferably consists of one or more members selected from family Marasmiaceae genus Lentinula edodes (Shiitake), family Lyophyllaceae genus Hypsizygus ulmarius, family Pleurotus genus Pleurotus (oyster mushroom), family Agaricaceae genus Agaricus, and order Polyporales family Meripilaceae genus Grifola (maitake).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to a radical-generating composition utilizing the Fenton reaction, a disinfecting composition containing the radical-generating composition, and a composition for decomposing organic matter.

In the fields of agriculture and food processing, sterilization and treatment to remove harmful substances are important. However, when a chemical is used as in many conventional methods, the chemical may remain in food or agricultural products, which is undesirable. In addition, sterilization with hypochlorous acid has the drawback of generating a chlorine odor. Therefore, in the field of food, ozone sterilization can be mentioned as a sterilization method that does not leave odors in food, but there is a problem that an ozone generator is expensive and difficult to introduce except for large-scale facilities. Under these circumstances, there is a high need in many industrial fields for the development of inexpensive sterilization technology that does not affect the human body.

The Fenton reaction is attracting attention as a technique for solving such problems. The inventors have so far developed a Fenton reaction catalyst in which a reducing organic substance and an iron feedstock are mixed in the presence of water and the resulting reaction product is used as an active component (for example, Patent Documents 1 to 3). Also, a technique for sterilizing fungi using the strong oxidizing power of the Fenton reaction has been disclosed (see Patent Document 4).

The Fenton reaction is the action of hydrogen peroxide on iron to generate powerful active oxygen called hydroxyl radicals. Hydroxy radicals have extremely high reactivity and can be used for sterilization, decomposition of organic matter, and the like. In addition, after the Fenton reaction is completed, hydrogen peroxide changes into oxygen and water, so the burden on the human body and the environment can be suppressed.

By the way, mushrooms are known to contain hydrogen peroxide (see Non-Patent Documents 1 and 2). Patent Document 5 describes sterilization of hydrogen peroxide extracted from mushrooms belonging to the family Agaricus. and techniques for decolorizing and decomposing pigments by the Fenton reaction.

Under these circumstances, development of a technology that can be used for sterilization or decomposition of organic matter, obtains an excellent Fenton reaction, and can further suppress the effects on the human body and the environment has been expected.

Japanese Patent No. 6179957 Japanese Patent No. 6202770 Japanese Patent No. 6478209 JP 2009-062350 A Japanese Patent Application Laid-Open No. 2004-305013

Assessment of the antimicrobial, antioxidant and cytotoxic activities of the wild edible mushroom Agaricus lanipes (F.H. Moller & Jul. Schaeff.) Hlavacek, Cytotechnology, Vol.69 No.1 Page.135-144 (2017.01) Content of Hydrogen Peroxide in Agricultural Products, Livestock Products, Marine Products and Their Processed Products, Journal of Japan Food Industry Association, Vol.37, No.2, 111-123, 1990

The present invention solves the above problems and provides a radical-generating composition, a bactericidal composition, or a composition for decomposing organic matter, which is capable of obtaining an excellent Fenton reaction and further suppressing the effects on the human body and the environment. With the goal.

In view of such circumstances, the present inventors conducted extensive studies and found that a reaction product obtained by mixing mushrooms and iron is endowed with extremely strong Fenton reaction ability.

The present disclosure is made based on these findings.
That is, the radical-generating composition according to the present disclosure comprises an edible mushroom squeeze and/or extract thereof and an iron feedstock.
The disinfectant composition according to the present disclosure also comprises a radical-generating composition as described above, comprising an edible mushroom squeeze and/or extract thereof, and an iron source.
Also, the organic decomposition composition according to the present disclosure includes a radical-generating composition as described above, and includes an edible mushroom squeezed and/or extract thereof and an iron feedstock.

According to the present disclosure, the Fenton reaction between iron and high concentrations of hydrogen peroxide contained in edible mushroom juices and/or extracts thereof generates powerful reactive oxygen species called hydroxyl radicals. In addition, since naturally occurring hydrogen peroxide contained in edible mushroom juice and/or its extract is used as hydrogen peroxide, the effects on the human body and the environment can be appropriately suppressed. Therefore, an excellent Fenton reaction can be obtained, and a radical-generating composition, a bactericidal composition, or a composition for decomposing organic matter, which can further suppress the effects on the human body and the environment, can be provided.

1 is a photographic image of a squeezed shiitake mushroom used in a hydrogen peroxide detection experiment in Experimental Example 1 and a hydrogen peroxide test paper after inspection. 1 is a photographic image of Bunashimeji mushrooms used in an experiment to detect hydrogen peroxide in Experimental Example 1 and a hydrogen peroxide test paper after inspection. FIG. 1 is a photographic image of oyster mushrooms used in an experiment to detect hydrogen peroxide in Experimental Example 1 and a hydrogen peroxide test paper after inspection. FIG. 1 is a photographic image of a mushroom used in a hydrogen peroxide detection experiment in Experimental Example 1 and a hydrogen peroxide test paper after inspection. FIG. 1 is a photographic image of a maitake mushroom used in a hydrogen peroxide detection experiment in Experimental Example 1 and a hydrogen peroxide test paper after inspection. FIG. 1 is a photographic image showing experimental results of the effect of decomposing methylene blue by a composition for decomposing an organic substance containing a squeezed shiitake mushroom juice and an iron salt of Example 1. FIG. 2 is a graph showing experimental results of the effect of decomposing methylene blue by the composition for decomposing organic matter containing the squeezed shiitake mushroom juice and iron salt of Example 2. FIG. FIG. 10 is a diagram showing the measurement results of the ESR spectrum of the composition for decomposing an organic matter containing a squeezed shiitake mushroom liquid and an iron salt in Example 2. FIG. FIG. 10 is a photographic image showing experimental results of the bactericidal effect by the Fenton reaction of the bactericidal composition containing the squeezed shiitake mushroom liquid and iron salt of Example 3. FIG.

The radical-generating composition of the present disclosure comprises an edible mushroom squeeze and/or extract thereof and an iron feedstock. In addition, the method for generating radicals using the radical-generating composition of the present disclosure includes the step of mixing a squeezed edible mushroom and/or its extract with an iron feedstock to generate hydroxyl radicals from hydrogen peroxide. ,including.
The radical-generating composition is used in this specification to mean "a composition that generates radicals" (pro-oxidant). That is, the composition is a composition that generates hydroxyl radicals by the Fenton reaction by reacting hydrogen peroxide (in the present disclosure, hydrogen peroxide contained in the squeezed liquid and / or extract of edible mushrooms) and iron. Therefore, it is defined as a “radical generating composition”.
A bactericidal composition as a first embodiment of the radical-generating composition of the present disclosure and a composition for decomposing organic matter as a second embodiment will be described below, but the present disclosure is limited to the following embodiments and the like. not something.

(First embodiment: bactericidal composition)
A sterilizing composition according to a first embodiment of the present disclosure comprises an edible mushroom squeezed and/or extract thereof and an iron feedstock. In addition, in the sterilization method using the sterilization composition according to the first embodiment, the edible mushroom juice and/or its extract is mixed with the iron feedstock to generate hydroxyl radicals from hydrogen peroxide. and the step of allowing

[Edible mushroom juice and/or its extract]
The sterilizing composition according to the first embodiment uses, as a hydrogen peroxide supply material, "edible mushroom juice and/or its extract" containing a large amount of naturally occurring hydrogen peroxide. In general, among fungi, the fruiting body (basidiocarp) itself, which is visible to the naked eye and consists of a stalk, cap, filamentous body, globular body, etc., is called a "mushroom". In addition, the tip of the fruiting body is called an ishizuki. In addition, edible mushrooms are cultivated by inoculating fungi on a base material such as sawdust, on an artificial medium containing chlorinated nutrients such as bran, bean curd refuse, rice bran, and the like. An artificial medium containing this strain is called a fungal bed.

In this embodiment and subsequent embodiments, the term "mushroom" includes not only the fruiting body but also the fungal bed (the "stone tip" is also included in the "fungal bed"). In addition, in the first embodiment, by using "edible mushrooms" that are eaten by humans, etc., as a raw material for supplying hydrogen peroxide, naturally-derived hydrogen peroxide can be used, and the effects on the human body and the environment can be appropriately reduced. Suppression is possible.

This "edible mushroom" consists of at least one of a fruiting body and a fungal bed. Both the fruiting body and the fungal bed contain hydrogen peroxide. The content of hydrogen peroxide in the "edible mushroom" is preferably 5 ppm or more, particularly preferably 100 ppm or more. "Edible mushrooms" are preferably those that have not been dried or heated, and can retain an appropriate content of hydrogen peroxide.

By the way, in the artificial cultivation of mushrooms, the mushroom bed after harvesting the fruiting body is discarded as a waste mushroom bed. Thousands of tons of this waste mushroom bed are discharged annually, and the disposal cost (incineration cost) puts pressure on the management of mushroom cultivators and is an obstacle to increased production. Therefore, there is a strong demand for the development of a technique for disposing of a large amount of waste fungus beds at low cost and in a short period of time. Therefore, by using the waste mushroom bed as a raw material for supplying hydrogen peroxide, it is possible not only to provide a composition that can obtain a Fenton reaction suitable for sterilization and decomposition of organic matter, but also to In addition to the establishment of new reuse technology, new business opportunities can also be created.

The “edible mushroom” may be any mushroom that can be eaten by humans, and may be either natural or artificially cultivated. The types of "edible mushrooms" are not particularly limited, but for example, mushrooms belonging to the order Agaricus, the order Agaricus, etc. contain a large amount of naturally occurring hydrogen peroxide, have no effect on the human body and the environment, and are available at low cost. etc., it is preferable.

More specifically, "edible mushrooms" include shiitake mushrooms (Agarices, Agarices, Agaricaceae, genus Shiitake), bunashimeji (Agarices, Agarices, Agaricaceae, Agaricaceae, genus Pleurotus), oyster mushrooms (Agarices, Agarices, Agaricaceae, genus Agaricus) ), maitake mushrooms (Agaricaceae order, Pyrrhoid maitake genus), Enokitake mushrooms (Aragariformes, Pleurotus family, Enokitake genus), Pleurotus oyster mushrooms (Aragariformes, Oysteraceae, Pleurotus genus), Chanametsumutake (Agaricles, Pleurotus, Pleurotus genus), Mukitake (Agaricorders, Botanical family) genus), Shimeji mushrooms (Agaricles, Agaricaceae, Agaricaceae), Yamabushitake (Aragicaceae, Russulales, Coral agaricus, Coral agaricus), Kamiharitake (Agaricaceae, Ezoharitakeaceae, Asteraceae), Nameko (Agarices, Agarices, Agaricaceae), Numeri mushrooms (Agarics) Pleurotus coccineus genus), red fungus (genus Pleurotus genus Pleurotus genus Auricle), genus Pleurotus oyster mushroom (genus Oysteraceae oyster mushroom, genus Oyster mushroom, genus Oyster mushroom, genus Oyster mushroom, genus Oyster mushroom, genus Oyster mushroom, genus Pleurotus oyster mushroom, genus Oyster mushroom, genus Oyster mushroom, genus Oyster mushroom of the family Arachnids, order Agaricaceae), licorice (genus Pleurotus leucorrhoeaceae), etc. are preferably mentioned, and one or more selected from these is preferable.

Among these, as "edible mushrooms", shiitake mushrooms (Aragariformes, Agaricaceae, Agaricaceae, genus Shiitake), Bunashimeji (Agaricles, Agarices, Agaricaceae, Agaricaceae, genus), oyster mushrooms (Agaricles, Agarices, Agaricaceae, genus Agaricus), and maitake (Granus maitake, genus Grifolia, order Pleurotus), and it is preferable to select one or more of them. These are the most suitable feedstocks for hydrogen peroxide because they contain 100 ppm or more of naturally occurring hydrogen peroxide, are widely available on the market, and are suitable for reusing waste fungus beds. be.

In addition, "squeezed edible mushrooms" (also called "squeezed juice") is a liquid obtained by applying strong pressure to edible mushrooms or crushing them, or a liquid obtained by filtering this to remove solids. be. The "edible mushroom extract" may be the residue after filtering the squeezed liquid, or a predetermined component (extract) extracted from the squeezed liquid or the residue. Water, hot water, alcohol (especially ethanol), water-containing alcohol (especially water-containing ethanol), and the like are suitable as the extraction solvent for the extract.

[Iron feedstock]
The sterilizing composition according to the first embodiment contains at least one of a bivalent iron feedstock and a trivalent iron feedstock as a raw material for supplying elemental iron. Moreover, as a raw material for supplying the iron element, a polyphenol iron complex or a raw material for supplying metallic iron can be used. Also, a plurality of selected from these can be mixed and used. By using these iron feedstocks, it is possible to obtain a bactericidal composition that can suppress the effects on the human body and the environment. Furthermore, in the first embodiment, since naturally-derived hydrogen peroxide is used, by using a naturally-derived iron feedstock among the iron feedstocks described below, the effects on the human body and the environment are significantly reduced. It is possible to provide a naturally-derived bactericidal composition (naturally-derived radical-generating composition) capable of suppressing

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

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; 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 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 (non soils containing crystalline minerals); natural iron ores such as pyrite, marcasite, siderite, magnetite, and goethite; derived substance; and the like.

In addition, examples of "supply raw materials of metallic iron" include iron materials such as smelted iron and alloys. In addition, rust can also be used as the "supply material of metallic iron".

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 the carbon contained in the above-mentioned edible mushrooms. An aqueous solution containing divalent iron ions and/or trivalent iron ions in which the iron compound is dissolved in water can also be used.

Among the above iron feedstocks, it is preferable to use a water-soluble divalent iron compound or trivalent iron compound in order to efficiently generate the Fenton reaction. In particular, it is preferable to use inexpensive iron chloride, iron sulfate, or the like. In addition, in order to manufacture in consideration of raw material cost and stable supply, it is preferable to use natural soil (especially Akadama soil, Kanuma soil, loam, etc.) and metallic iron as iron supply raw materials.

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, as described in the above-mentioned Patent Documents 1 to 3, etc. , divalent iron ions (Fe ²⁺ ) form a complex structure with polyphenols.

Here, the presence of water means that polyphenols and iron can react under 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 mixing ratio of polyphenols and iron, the amount of water, the mixing temperature, the mixing time, the mixing means, etc. during mixing can be the same as those described in Patent Documents 1 to 3.

As the iron feedstock, one or more iron feedstocks selected from the group consisting of divalent iron compounds, trivalent iron compounds, soil, iron ore, and metallic iron are used.

The mixing ratio of the polyphenols or the feedstock thereof and the iron feedstock is 0.1 parts by weight or more and 100 parts by weight of the iron feedstock 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. The ratio should be mixed so that it is less than 1 part.

"Polyphenols" is a generic term for phenolic molecules having multiple hydroxy groups. "Polyphenols" are compounds 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, flavanone, flavanol, flavonol, isoflavone, etc.), flavone, chalcone (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).

The "polyphenols" used in the polyphenol-iron complex may be one of the above, or may be a composition consisting of two or more.

Moreover, a polyphenol composition extracted from a certain plant may be referred to as a polyphenol 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. By using such a naturally-derived feedstock as the "polyphenol feedstock", the effects on the human body and the environment can be more appropriately suppressed.

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 (lemon, lime, orange, grapefruit, navel, yuzu, kumquat, kabosu, summer orange, hassaku, iyokan, lime, unshu orange, 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, amacha, akebi, Japanese horse chestnut , 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 mangrove, Sakishimasuounoki, burdock, turmeric, lotus root, seaweed (seaweed, wakame seaweed, kelp, sea lettuce, ara , etc.) and the like.

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.

Examples of "processed products" of polyphenol-containing plants include dried products, juices, extracts, and liquid extracts of polyphenol-containing plants. Further, the squeezed liquid or the extract may be further dried.

As the "dry matter", it is desirable to treat it by crushing, pulverizing, pulverizing, or the like. 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 a polyphenol-containing plant body or its processed product with water or hot water can also be suitably used. Examples of such extraction residue include coffee grounds, used tea leaves, and the like.

"Coffee grounds" refers to the residue left after roasted and ground coffee beans are extracted 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 left after tea leaves or ground tea leaves are extracted 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 the "tea leaves" which are the raw material of used tea leaves, any tea leaves can be used as long as they are obtained by plucking the stems and leaves of the tea tree. 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 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 viscous 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.

[Mixing processing of edible mushroom juice and/or its extract and iron feedstock]
The sterilizing composition according to the first embodiment is obtained by mixing the above-described edible mushroom squeezed liquid and/or its extract with the iron feedstock (or iron ions) as described above. is generated, and a strong bactericidal power is obtained.

The mixing ratio of the edible mushroom juice and/or its extract and the iron feedstock is as follows: per 100 parts by weight of the dry weight of the edible mushroom juice and/or its extract, the iron feedstock is added to the weight of the iron element. 0.1 parts by weight or more, preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, still more preferably 2 parts by weight or more, particularly preferably 3 parts by weight or more, and still more preferably 4 parts by weight or more should be mixed. If the proportion of the iron element is too low (the proportion of the edible mushroom mixed with the iron element is too high), the Fenton reaction is suppressed by scavenging radicals, which is not preferable.

The upper limit of the amount of iron element is 10 parts by weight or less, preferably 8 parts by weight or less, and more preferably 6 parts by weight or less in terms of the weight of iron element. If the ratio of the iron element is too high (the ratio of the edible mushrooms to the iron element is too low), sludge of iron oxide is generated, and the radical elimination of the generated sludge suppresses the Fenton reaction. I don't like it.

The mixing operation of the raw materials is carried out in the presence of water, and the presence of water may be any condition in which the edible mushroom juice and/or its extract can react with iron using water as a medium. Since the sterilizing composition according to the first embodiment uses a liquid such as an edible mushroom squeezed liquid or an extract (extract liquid), the liquid can be directly added without adding a new medium such as water. can be mixed and reacted with the iron feedstock. However, water may be added when using a substance with a low water content, such as a residue or an extract.

As the mixing operation, simple stirring and mixing with a stirring rod or the like may be performed, but it can also be performed with a stirrer, mixer, large stirring tank, vortex, shaker, or the like. Here, the temperature of the water is a temperature at which the water is in a liquid state (for example, 1°C or higher), which inactivates hydrogen peroxide-degrading enzymes such as catalase contained in the edible mushrooms, so that the peroxides in the edible mushrooms are Any temperature can be used as long as the loss of hydrogen can be suppressed, and the treatment can be performed at a low temperature (10°C to 60°C), more preferably at room temperature (eg, 10°C to 40°C) without the need for heating.

In addition, when a specific natural product (specifically, soil) is used as an iron supply raw material, or when an insoluble iron compound is the main component, it is possible to extract iron and edible mushrooms by taking a long reaction time after mixing. Treatment is required to render the liquid and/or extract more reactive.

In addition, the mixing time may be about 10 seconds or more until the edible mushroom juice and/or extract and iron are sufficiently in contact, but in order to improve uniformity, it is preferably 3 minutes or more. A mixed treatment is desirable. Moreover, the upper limit of the mixing time is preferably 240 hours or less in order to prevent putrefaction due to propagation of microorganisms.

As described above, in the first embodiment, the squeezed juice and/or the extract of an edible mushroom containing a large amount of naturally occurring hydrogen peroxide is used as the hydrogen peroxide supply material. can appropriately control the impact on Also, hydrogen peroxide and iron contained in the edible mushroom juice and/or its extract provide a stable Fenton reaction. Therefore, an excellent Fenton reaction can be obtained, and a bactericidal composition that can further suppress the effects on the human body and the environment can be provided.

Specific examples of objects to be sterilized include medical instruments, hospital room walls, affected areas of patients, clothes, bedding, food manufacturing equipment lines, foodstuffs, cutting boards, kitchen utensils such as kitchen knives, tableware, toilet seats, handrails, and agricultural equipment. , equipment for hydroponics and nutrient solutions. By using the sterilization composition of the first embodiment for these sterilizations, the use of hydrogen peroxide is significantly (about 99 to 99.9%) compared to the usual sterilization method using only hydrogen peroxide. It is possible to reduce the amount. In addition, the use of naturally occurring hydrogen peroxide contained in the squeezed liquid and/or extract of edible mushrooms can remarkably suppress the effects on the human body and the environment.

In addition, since the effect on the human body and the environment is extremely small, the sterilizing composition of the first embodiment can be used in various applications such as medicine, food, public health, agriculture, industry, and the like. That is, as hydrogen peroxide, naturally occurring hydrogen peroxide contained in edible mushroom juice and/or its extract is used, and after the Fenton reaction is completed, hydrogen peroxide changes to oxygen and water. In particular, it is expected to be used in the food field. Furthermore, by using the waste mushroom bed of edible mushrooms as a raw material for supplying hydrogen peroxide, it is possible to reduce the raw material cost, reuse the waste mushroom bed, and reduce the disposal cost. It is expected to be used in fields such as

In the first embodiment, the implementation may differ depending on whether the object to be sterilized is solid or liquid. When the object to be sterilized is solid, a solution containing an edible mushroom squeezed and/or its extract and an iron feedstock is prepared, and the object to be sterilized can be sprayed, applied, kneaded, or the like. The sterilization can also be performed by immersing the object to be sterilized in the solution. It can also be carried out by applying or kneading the iron supply material to the object to be sterilized, and spraying the liquid containing the squeezed edible mushroom and/or its extract.

In addition, when the object to be sterilized is a liquid, the sterilization can be carried out by adding, mixing, etc. the liquid of the edible mushroom and/or its extract and the iron feedstock to the object to be sterilized.

The amount of the edible mushroom squeezed liquid and/or its extract and the iron feedstock used in the solution used for sterilization may be prepared at a concentration that allows the above-mentioned Fenton reaction to occur. In addition, the amount of hydrogen peroxide released from the edible mushroom juice and/or its extract may be extremely small, and may be used so as to contain about 0.1 to 20 mM. Since the sterilization effect is extremely strong, a remarkable sterilization effect can be obtained by, for example, immersion for several minutes.

(Second embodiment: composition for decomposing organic matter)
A composition for decomposing organic matter according to a second embodiment of the present disclosure includes an edible mushroom squeezed liquid and/or an extract thereof, and an iron feedstock. In addition, the method for decomposing organic matter using the composition for decomposing organic matter according to the second embodiment includes mixing edible mushroom juice and/or its extract with an iron feedstock, and and generating hydroxyl radicals.

The composition for decomposing organic matter according to the second embodiment uses "edible mushroom juice and/or its extract" containing a large amount of naturally occurring hydrogen peroxide as a raw material for supplying peroxide water. This "squeezed edible mushroom and/or its extract" is the same as the "squeezed edible mushroom and/or its extract" used in the "sterilizing composition" of the first embodiment described above. can be used, detailed description is omitted.

Further, the "iron feedstock" is used for the decomposition composition for organic matter of the second embodiment. This "iron feedstock" can also be the same as the "extract of iron feedstock" used in the "sterilizing composition" of the first embodiment described above, so detailed description is omitted. .

In addition, the mixing operation, mixing ratio, etc. of the edible mushroom juice and/or its extract and the iron feedstock in the second embodiment are the same as those of the "sterilization composition" in the first embodiment. Therefore, detailed description is omitted.

In the second embodiment, the naturally occurring hydrogen peroxide contained in the edible mushroom juice and/or its extract is used as the hydrogen peroxide, so that the effects on the human body and the environment can be appropriately suppressed. In addition, a stable Fenton reaction can be obtained with the naturally occurring hydrogen peroxide and iron contained in the edible mushroom juice and/or its extract. Therefore, an excellent Fenton reaction can be obtained, the effects on the human body and the environment can be further suppressed, and an inexpensive composition for decomposing organic substances can be provided.

In particular, the composition for decomposing organic matter according to the second embodiment can be suitably used for decomposing organic matter, specifically, for decomposing organic pollutants and harmful substances. Useful.

Here, pollutants and harmful substances refer to substances that cause water pollution, soil pollution, and air pollution. For example, domestic wastewater, night soil water, industrial wastewater, polluted river and lake water, landfill soil, industrial waste, agricultural land, and abandoned factory sites contain organic substances that affect the human body and the environment. be done.

Specific organic matter to be decomposed includes, for example, detergents, food and drink residues, night soil, feces, pesticides, malodorous substances, waste oils, dioxins, PCBs, DNA, RNA, proteins and other organic wastes.

In the second embodiment as well, the form of the organic matter decomposition composition may differ depending on whether the organic matter to be decomposed is solid or liquid. When the object to be decomposed is solid, it can be carried out by preparing a solution containing an edible mushroom squeezed liquid and/or its extract and an iron feedstock, and spraying, spreading, applying, kneading, etc. onto the object. . In addition, it can also be carried out by mixing and immersing an object to be decomposed in the solution. It can also be carried out by applying or kneading the iron feedstock to the decomposition target, and spraying the liquid containing the squeezed edible mushroom and/or its extract.

In addition, when the decomposition target is a liquid, it can be carried out by adding, mixing, sprinkling, immersing, etc. the edible mushroom juice and/or its extract and the iron feedstock to the decomposition target.

The amounts of the squeezed edible mushroom liquid and/or its extract and the iron feedstock in the solution used for decomposing organic matter may be prepared and used at concentrations that provide the above-mentioned Fenton reaction catalytic ability. In addition, the amount of hydrogen peroxide released from the edible mushroom juice and/or its extract may be extremely small, and may be used so as to contain about 0.1 to 100 mM. Since the decomposition effect is extremely strong, a remarkable decomposition effect can be achieved by, for example, immersion for about 30 minutes.

As described above, according to the first and second embodiments, since the edible mushroom squeezed liquid and / or its extract and the iron feedstock are included, the high concentration contained in the edible mushroom The Fenton reaction between hydrogen peroxide and iron generates a strong active oxygen called a hydroxyl radical, which provides strong oxidizing power. In addition, as hydrogen peroxide, naturally derived hydrogen peroxide contained in the squeezed liquid of edible mushrooms and / or its extract is used. It is possible to provide a bactericidal composition or a composition for decomposing organic matter that can further suppress the impact on the environment. Therefore, by containing an edible mushroom squeezed liquid and/or its extract and an iron feedstock, an excellent Fenton reaction can be obtained, and a radical-generating composition capable of further suppressing the effects on the human body and the environment. can provide things.

In addition, the edible mushrooms used in each of the above-described embodiments are the genus Shiitake, the family Agaricus, the family Agaricus, the genus Shirohypsis, the genus Agaricus, the family Agaricus, the genus Agaricus, the family Agaricus, and the genus Agaricus, the family Agaricus. , one or more selected from Since these edible mushrooms contain a large amount of naturally occurring hydrogen peroxide at a high concentration, the Fenton reaction can be obtained more appropriately, and a stronger bactericidal effect or organic substance decomposition effect can be obtained. In addition, it becomes possible to stably supply the raw material for hydrogen peroxide at a low cost.

In addition, in each of the above embodiments, not only fruiting bodies of edible mushrooms, but also fungal beds that have been discarded as waste mushroom beds, and damaged and non-standard products that have been discarded as waste are treated with hydrogen peroxide. available as feedstock. For this reason, the possibility of reusing the waste fungus bed and waste is expanded, and the cost of their disposal can be greatly reduced.

Further, the iron feedstock used in each of the above embodiments is one or more selected from the group consisting of polyphenol iron complexes, divalent iron compounds, trivalent iron compounds, soil, iron ore, and metallic iron. Therefore, a stable Fenton reaction that can stably maintain divalent iron for a long period of time is obtained, and a more appropriate bactericidal effect or organic substance decomposition effect is obtained. In addition, since these are inexpensive, the cost of iron supply materials can be reduced, stable supply can be achieved, and the impact on the human body and the environment can be suppressed, and they can be suitably used in fields such as agriculture, food, and medicine. In addition, soil, metallic iron, and the like can be suitably used when it is desirable to use natural products as raw materials, such as when using in organic agriculture.

In particular, by using a polyphenol iron complex as an iron feedstock, it is possible to stably maintain divalent iron for a long period of time and generate a stable Fenton reaction. Also, trivalent iron and metallic iron can be converted into divalent iron and maintained stably for a long period of time, making it possible to generate a stable Fenton reaction. The polyphenol iron complex is a polyphenol or its feedstock, and one or more iron feedstocks selected from the group consisting of divalent iron compounds, trivalent iron compounds, soil, iron ore, and metallic iron, in the presence of water. It is a reaction product obtained by mixing at and is an iron feedstock that is easy to manufacture and can suppress the effects on the human body and the environment.

EXAMPLES The present disclosure will be specifically described below with reference to Examples and Experimental Examples, but the present disclosure is not limited to the following Examples and the like.

(Experimental example 1)
[Detection of hydrogen peroxide contained in edible mushrooms]
For the edible mushrooms shown in Table 1 below, a hydrogen peroxide detection experiment was conducted.
experimental method:
A squeezed liquid was prepared from each of the samples shown in Table 1 and purified. Specifically, a commercially available garlic press (garlic squeezer) is prepared, a filter paper is set in this garlic press, each sample is put in and manually compressed to squeeze out and filter the liquid from the mushroom. to obtain a refined squeezed liquid. The presence or absence of hydrogen peroxide was examined for the squeezed liquid of each sample using a hydrogen peroxide test paper.
Experimental result:
Table 1 below shows the names, scientific names, and test results of the verified edible mushrooms. "+" in Table 1 indicates that hydrogen peroxide was detected.

As shown in Table 1 above, hydrogen peroxide was detected from the squeezed liquid of all the samples (edible mushrooms). Among these, in particular, shiitake mushrooms (shiitake mushrooms grown on sawtooth oak logs), bunashimeji mushrooms, oyster mushrooms, mushrooms, and maitake mushrooms were found to have hydrogen peroxide concentrations so high that the test paper turned blue. Hydrogen peroxide detected. Figures 1 to 5 show the squeezing of shiitake mushrooms, bunashimeji mushrooms (fruiting bodies), oyster mushrooms (fruiting bodies), mushrooms (fruiting bodies), and maitake mushrooms (fruiting bodies) used in the experiment, and hydrogen peroxide test paper after inspection. indicate.

(Example 1)
As Example 1, an organic matter decomposition composition containing an edible mushroom (shiitake) squeezed liquid and an iron salt (iron sulfate) was prepared. Using this decomposing composition, an experiment was conducted to verify the effect of decomposing organic matter by the Fenton reaction using squeezing edible mushrooms and iron salt.
experimental method:
200 ml of methylene blue solution was placed in a beaker, 20 g of shiitake mushrooms and 200 mg of iron sulfate were added, stirred, and left to stand. The shiitake mushrooms were generally brown, flaky and badly damaged, and were in a state where they crumbled and exuded liquid just by squeezing them by hand without pressing.

Experimental result: Most of the methylene blue was decomposed within 30 minutes after stirring. FIG. 6 is a photographic image showing experimental results of the effect of decomposing methylene blue by the composition for decomposing organic matter containing the squeezed shiitake mushroom juice and iron salt of Example 1. FIG. The left figure on the page of FIG. 6 is a photographic image of the methylene blue solution before stirring, and the right figure on the page is a photographic image of the methylene blue solution after 30 minutes of stirring. As shown in FIG. 6, the color of the methylene blue solution was blue before stirring, but the blue color almost disappeared 30 minutes after stirring.

In addition, FIG. 7 shows a measurement graph of the methylene blue concentration of the methylene blue solution to which shiitake mushroom juice and iron salt are not added (untreated area) and the methylene blue solution to which shiitake mushroom and iron sulfate are added (30 minutes after stirring). From the graph of FIG. 7, it can be seen that most of the methylene blue solution was decomposed by the Fenton reaction between hydrogen peroxide and iron sulfate in the shiitake mushroom juice. Therefore, from the results of FIGS. 6 and 7, it was found that the composition for decomposing organic matter of Example 1 exhibited excellent Fenton reaction and was excellent in the effect of decomposing organic matter. In addition, even when using edible mushrooms that are damaged to the point that they are unsuitable for eating and have to be discarded, it was found that an excellent sterilization effect can be obtained, and it is possible to reduce waste and make effective use of waste. Become.

(Example 2)
[Examination of radical generation by reaction between shiitake mushroom juice and iron salt]
ESR spin trapping method was used to identify hydroxyl radicals (.OH) generated by the reaction of hydrogen peroxide and iron salts in shiitake mushrooms.
Experimental (measurement) method:
Hydroxyl radicals were measured by the ESR method using a spin trap for the reactant (organic decomposition composition of Example 2) obtained by reacting the squeezed shiitake mushroom liquid containing hydrogen peroxide with the iron salt.
Measurement equipment: Magnettech ESR5000 EPR spectrometer Analysis conditions: Magnetic field, 337.5mT
Field modulation frequency: 100kHz
Field modulation width: 0.16mT
Sweep time: 60s
Microwave frequency: 9.463GHz;
Microwave power: 5mW
Preparation of analytical samples:
1) DMPO (spin trapping agent) 220 mM solution 100 μL
2) Phosphate buffer pH7.4 100μL
3) Iron sulfate 1mM solution 10μL
4) Shiitake mushroom juice 100μL
The above reagents 1) to 4) were placed in a reaction sail and measured.

·Experimental result:
FIG. 8 shows the measurement results of the ESR spectrum as the result of the hydroxyl radical identification experiment by the ESR method using the spin trap. In FIG. 8, the locations indicated by arrows are characteristic spectra that occur only when hydroxyl radicals (.OH) are present. Therefore, it was shown that hydroxyl radicals (.OH) are generated by the reaction between hydrogen peroxide and iron salts in the shiitake juice.

(Example 3)
[Experiment on the bactericidal effect of Escherichia coli by Fenton reaction using shiitake mushroom juice and iron salt]
The bactericidal effect of the Fenton reaction using shiitake mushroom juice and iron salt was verified using Escherichia coli.
experimental method:
To 890 μL of shiitake mushroom juice, 10 μL of E. coli bacterial solution (1.0×10 ⁶ cfu/m) was added and mixed. 100 μL of iron salt solution (10 mM Fe) was mixed with this mixture and stirred. The bactericidal composition of Example 3 is the reaction product of the shiitake juice and the iron salt. As a control, a mixture of 990 µL of distilled water and 10 µL of E. coli was prepared. After 30 minutes of stirring, 0.1 mL of each solution was taken and plated on LB medium to confirm the survival of E. coli.

Experimental result:
Experimental results are shown in FIG. (1) in FIG. 9 is a photographic image showing the bactericidal effect of a mixture of distilled water and E. coli (control), and (2) in FIG. 1 is a photographic image showing the bactericidal effect of a mixed solution of E. coli, iron salt, and E. coli. As shown in FIG. 9, in the control group in which distilled water and E. coli were mixed, E. coli survived, whereas in the mixture of shiitake mushroom juice, iron salt, and E. coli, E. coli was killed in 30 minutes. was annihilated. This experiment showed that the bactericidal composition of Example 3 exhibited a strong bactericidal action due to the Fenton reaction between the hydrogen peroxide contained in the shiitake mushroom and the iron salt.

The bactericidal composition and the organic matter decomposition composition of the present disclosure exhibit strong oxidizing power due to the Fenton reaction, and can also suppress the effects on the human body and the environment. It is expected to be widely used for sterilization and decomposition of organic matter in the field.

Claims (6)

A radical-generating composition comprising an edible mushroom squeeze and/or extract thereof and an iron source. The edible mushroom is selected from one or more selected from the following: Agarices, Agarices, Agarices, Agaricus, Agarices, Agarices, Agarices, Agarices, Agarices, Agarices, Agarices, and Agarices, Agaricaceae, Myrtle Mushrooms. The radical-generating composition according to claim 1, comprising: 3. The radical according to claim 1 or 2, wherein the iron feedstock is one or more selected from the group consisting of polyphenol iron complexes, divalent iron compounds, trivalent iron compounds, soil, iron ore, and metallic iron. Generation composition. The polyphenol iron complex comprises polyphenols or their feedstocks, and one or more iron feedstocks selected from the group consisting of divalent iron compounds, trivalent iron compounds, soil, iron ore, and metallic iron, in the presence of water. 4. The radical-generating composition of claim 3, which is a reaction product obtained by mixing below. A disinfecting composition comprising the radical-generating composition according to any one of claims 1 to 4. A composition for decomposing organic matter, comprising the radical-generating composition according to any one of claims 1 to 4.

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