Antioxidant components

Abstract

The present invention addresses the problem of providing an antioxidant composition having durable antioxidant activity.　The present invention provides: an antioxidant composition containing, as an active ingredient, a light-irradiated product of a grape pomace extract or a new compound contained in said light-irradiated product; and a method for producing a durable antioxidant material, the method including a step for pressing a grape raw material in a wine production process to obtain a grape pomace extract including grape skin and seeds, and a step for irradiating the obtained grape pomace extract with light.

Description

【Technical Field】 【0001】 The present invention relates to an antioxidant composition having sustainable antioxidant activity. 【Background Art】 【0002】 In vivo, the amount of reactive oxygen species generated and the amount of reactive oxygen species reduced by reactive oxygen scavenging enzymes are balanced, so the amount of reactive oxygen species in the living body is kept constant. However, it has been found that reactive oxygen species in the living body increase due to the influence of living environments such as aging, stress, unbalanced diet, and poor lifestyle. Representative types of reactive oxygen species generated in vivo are hydroxyl radicals, superoxide, and singlet oxygen, and among them, the particularly toxic one is the hydroxyl radical. When reactive oxygen species are excessively generated in the living body, it causes acceleration of aging, lifestyle-related diseases such as arteriosclerosis and hypertension, cancer, and reduction of immune function. 【0003】 Therefore, antioxidant substances having an action of removing excessive reactive oxygen species have been attracting attention as effective ingredients for preventing lifestyle-related diseases and preventing aging. Among antioxidant substances, polyphenols are a typical example, including anthocyanins, catechins, isoflavones, sesamin, sesaminol, theaflavin, and the like. 【0004】 Wine is well known to contain a large amount of polyphenols, but the grape pressing residue generated in the production process also contains various useful substances including polyphenols, so its effective utilization has been studied. The present inventors have reported that this grape wine processing residue has an extremely high hydroxyl radical scavenging ability, which is an index of antioxidant activity, compared to existing raw materials in circulation such as grape seed extract and catechin (Non-Patent Document 1). 【0005】 However, antioxidant raw materials generally have their activity decreased after achieving the antioxidant purpose due to the principle of oxidation-reduction. Therefore, a material having sustainable antioxidant activity is desired. 【Prior Art Documents】 【Non-Patent Documents】 【0006】 [Non-Patent Document 1] Tsukada M, Nakashima T, Kamachi T, Niwano Y. PLoS One 2016, Jun 24;11(6):e0158197. Prooxidative Potential of Photo-Irradiated Aqueous Extracts of Grape Pomace, a Recyclable Resource from Winemaking Process. [Overview of the project] [Problems that the invention aims to solve] 【0007】 In view of the above circumstances, the object of the present invention is to provide an antioxidant composition having sustained antioxidant activity. [Means for solving the problem] 【0008】 The inventors of this invention conducted extensive research to solve the above problems and discovered that by irradiating grape pressing residue, which has high antioxidant activity, with light in a predetermined wavelength range, the antioxidant activity can be further enhanced and its persistence can be improved. Furthermore, they succeeded in identifying a novel compound that is the main component of the activity from the light-irradiated grape pressing residue, thus completing the present invention. 【0009】 In other words, the present invention encompasses the following inventions. (1) An antioxidant composition containing a photo-irradiated product of grape pressing residue as an active ingredient. (2) The antioxidant composition according to (1), wherein the wavelength of the light irradiation is 200 to 700 nm. (3) The antioxidant composition according to (1) or (2), wherein the grape pressing residue is the pomace left over after grape pressing, which is a waste product in wine production. (4) An antioxidant composition containing a compound represented by the following general formula (I) as an active ingredient. [Chemical formula] (In the formula, the bonds represented by solid and dotted lines of (a) to (g) are single bonds or double bonds, when (a) and (c) are double bonds and (b) and (d) are single bonds, R 1 represents an oxygen atom, R 2 represents a hydroxy group, and when (a) and (c) are single bonds and (b) and (d) are double bonds, R 1 represents a hydroxy group, R 2 represents an oxygen atom, R 3 , R 4 , and R 7 each independently represent a hydrogen atom or a hydroxy group, when (e) and (g) are single bonds and (f) is a double bond, R 5 and R 6 represent hydroxy groups, and when (e) and (g) are double bonds and (f) is a single bond, R 5 and R 6 represent oxygen atoms, R 8 and R 9 each independently represent a hydrogen atom or a hydroxy group, or R 8 and R 9 together form a single bond.) (5) The antioxidant composition according to (4), wherein the compound represented by the general formula (I) is a compound represented by the following structural formula (1), (2) or (3). [Chemical formula] [Chemical formula] [Chemical formula] (6) The antioxidant composition according to (1) or (4), wherein the antioxidant composition is a cosmetic, a pharmaceutical product, or a food or drink product. (7) The antioxidant composition according to (1) or (4), wherein the antioxidant composition is a hygiene product, a cleaning agent, a textile product, a food packaging material, a filter product, or a paper product. (8) A method for producing a sustainable antioxidant material, comprising the steps of pressing grape raw materials in the wine production process to obtain a grape pressing residue containing grape skins and seeds, and subjecting the obtained grape pressing residue to light irradiation. (9) The manufacturing method according to (8), wherein the grape pressing residue is extracted before the light irradiation treatment. (10) A novel compound represented by the following general formula (I). [ka] (In the formula, the bonds represented by the solid and dotted lines in (a) to (g) are single bonds or double bonds, If (a) and (c) are double bonds and (b) and (d) are single bonds, then R 1 is an oxygen atom, R 2 R indicates a hydroxyl group, and if (a) and (c) are single bonds and (b) and (d) are double bonds, then R 1 R is a hydroxyl group, 2 This represents an oxygen atom. R 3 , R 4 , and R 7 Each of these independently represents a hydrogen atom or a hydroxyl group. If (e) and (g) are single bonds and (f) is a double bond, then R 5 and R 6 indicates a hydroxyl group, and if (e) and (g) are double bonds and (f) is a single bond, then R 5 and R 6 This represents an oxygen atom. R 8 and R 9 Each of these independently represents a hydrogen atom or a hydroxyl group, or R 8 and R 9 They come together to form a single bond. (11) A novel compound according to (10), wherein the compound represented by the general formula (I) is the compound represented by the following structural formula (1), (2), or (3). [ka] [ka] [ka] A method for producing a novel compound as described in (12), (10), or (11), characterized in that the grape pressing residue is subjected to light irradiation followed by solvent extraction, or the grape pressing residue is subjected to solvent extraction followed by light irradiation, and the compound is separated and purified from the treated product. 【0010】 This application claims priority to Japanese Patent Application No. 2024-003399, filed on 12 January 2024, and encompasses the contents described in the specification of said patent application. [Effects of the Invention] 【0011】 The present invention provides an antioxidant composition having sustained antioxidant activity and a method for producing a sustained antioxidant material. The antioxidant composition of the present invention is effective in improving and preventing various diseases and pathological conditions involving reactive oxygen species. [Brief explanation of the drawing] 【0012】 [Figure 1] This shows the hydroxyl radical (·OH) scavenging ability of grape pressing residue (without light irradiation treatment, and after 72 hours of light irradiation (302 nm) treatment). [Figure 2] This shows the superoxide (O2-·) scavenging ability of grape pressing residue (without light irradiation treatment, and after 72 hours of light irradiation (302 nm) treatment). [Figure 3-1] Figure 3-1 shows the LC-MS analysis results of epigallocatechin (EGC) before light irradiation and after 72 hours of light irradiation (302 nm). [Figure 3-2] Figure 3-2 shows the LC-MS analysis results of grape pressing residue (GPE) before light irradiation and after 72 hours of light irradiation (302 nm). [Figure 4-1] Figure 4-1 shows the LC-MS analysis results of catechin (Cat) before light irradiation and after 72 hours of light irradiation (302 nm). [Figure 4-2]Figure 4-2 shows the LC-MS analysis results of epicatechin (EC) before light irradiation and after 72 hours of light irradiation (302 nm). [Figure 5] Figure 5 shows the sunburned skin condition of mice in the following groups: UVB non-irradiated / normal diet group (control), UVB non-irradiated / GPE-containing diet group, UVB irradiated / normal diet group, and UVB irradiated / GPE-containing diet group. [Figure 6] Figure 6 shows the time course of melanin levels in sunburnt skin of mice in the following groups: C: no UVB irradiation / normal diet group (control, n=4), T1: no UVB irradiation / GPE-containing diet group (n=4), T2: UVB irradiation / normal diet group (n=6), and T3: UVB irradiation / GPE-containing diet group (n=6) (aa: P<0.01 (vs C), b: P<0.05 (vs T1), bb: P<0.01 (vs T1), cc: P<0.01 (vs T2), mean ± standard deviation; Tukey-Kramer Test). [Figure 7] Figure 7 shows the time course of redness in sunburnt skin of mice in the following groups: C: no UVB irradiation / normal diet group (control, n=4), T1: no UVB irradiation / GPE-containing diet group (n=4), T2: UVB irradiation / normal diet group (n=6), and T3: UVB irradiation / GPE-containing diet group (n=6) (a: P<0.05 (vs C), aa: P<0.01 (vs C), b: P<0.05 (vs T1), bb: P<0.01 (vs T1), cc: P<0.01 (vs T2), mean ± standard deviation; Tukey-Kramer Test). [Figure 8] Figure 8 shows the d-ROM test results for mice in the following groups: C: UVB non-irradiated / normal diet group (control, n=2), T1: UVB non-irradiated / GPE-containing diet group (n=2), T2: UVB irradiated / normal diet group (n=3), and T3: UVB irradiated / GPE-containing diet group (n=4). [Figure 9] Figure 9 shows the d-ROM test results for healthy rats in the normal diet group (control), the 1% GPE-containing diet group, and the 2% GPE-containing diet group (*: P<0.05). [Figure 10]Figure 10 shows the macroscopic findings of the hindlimb joints in healthy rats (control) fed a normal diet, rheumatoid arthritis model rats (AA group) fed a normal diet, and rheumatoid arthritis model rats fed a diet containing 2% GPE (AA+GPE group). [Figure 11] Figure 11 shows CT image findings of the hindlimb joints in healthy rats (control) fed a normal diet, rheumatoid arthritis model rats (AA group) fed a normal diet, and rheumatoid arthritis model rats (AA+GPE group) fed a diet containing 2% GPE. [Figure 12] Figure 12 shows the von Frey test results for healthy rats on a normal diet (control, n=7), rheumatoid arthritis model rats on a normal diet (AA group, n=7), and rheumatoid arthritis model rats on a diet containing 2% GPE (AA+GPE group, n=7) (*: P<0.05, **: P<0.01, mean ± standard deviation; Tukey-Kramer Test). [Figure 13] Figure 13 shows the results of aggression tests for social isolation stress model rats in a normal diet group (control, n=7), a 1% GPE-containing diet group (stress + 1% GPE group, n=7), and a 2% GPE-containing diet group (stress + 2% GPE group, n=7) (*: P<0.05, **: P<0.01, mean ± standard deviation; Tukey's post-hoc test). [Modes for carrying out the invention] 【0013】 The present invention will be described in detail below. 1. Antioxidant composition The antioxidant composition according to the first aspect of the present invention contains a photo-irradiated product of grape pressing residue as an active ingredient. Here, "grape pressing residue" refers to the pomace, which is the residue after grape pressing that becomes waste in the wine production process, but it may also include sediment that settles at the bottom of the wine tank after grape pressing. 【0014】 In the present invention, the grape varieties used as raw materials for the grape pressing residue are not particularly limited and may be either white wine grape varieties or red wine grape varieties. Examples of white wine grape varieties include Neo Muscat, Treppiano, Niagara, Kerner, Alexandria, Buffalo, Chardonnay, Semillon, Riesling, Sauvignon Blanc, Müller-Thurgau, Verdelé, Koshu, Traminer, and Delaware, while examples of red wine grape varieties include Merlot, Cabernet Sauvignon, Cabernet Franc, Pinot Noir, Syrah, Alicante, Nebbiolo, Muscat Bailey A, and Black Queen. 【0015】 In this invention, the wavelength of light irradiation applied to the grape pressing residue can be exemplified by, for example, 200 to 700 nm, preferably 280 to 400 nm. The illuminance of the light irradiation can also be, for example, 0.01 to 100 mW / cm². 2 Preferably 0.1 to 50 mW / cm² 2 Examples include the following. Furthermore, examples of light irradiation time include, for example, 0.5 to 100 hours, preferably 10 to 24 hours. 【0016】 The photo-irradiated grape pressing residue can be used as is, or dried, pulverized, or otherwise processed into a slurry, fine granule, granule, or powder. However, for ease of handling when used in a product, it is preferable to subject it to extraction and use an extract obtained by extracting grape-derived polyphenol components. Examples of grape-derived polyphenol components include epicatechin (EC), catechin (Cat), epigallocatechin (EGC), epigallocatechin gallate (EGCg), procyanidin B2 (dimer), procyanidin C1 (trimer), etc. Extraction may also be performed on the grape pressing residue before photoirradiation. 【0017】 The extraction method is not particularly limited and may include, for example, continuous extraction or immersion extraction. It may also be a heated extraction method, or an extraction method at room temperature or cold temperature. Examples of solvents used for extraction include water, lower alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, etc.), liquid polyhydric alcohols (1,3-butylene glycol, propylene glycol, glycerin, etc.), ketones (acetone, methyl ethyl ketone, etc.), acetonitrile, esters (ethyl acetate, butyl acetate, etc.), hydrocarbons (hexane, heptane, liquid paraffin, etc.), and ethers (ethyl ether, tetrahydrofuran, propyl ether, etc.). Among these solvents, water (or hot water) and lower alcohols are preferred. These solvents may be used individually or in combination of two or more. In addition, a solvent with pH adjusted by adding an acid or alkali to the above extraction solvent may be used. 【0018】 There are no particular limitations on the amount of extraction solvent used; for example, it should be 10 times or more, preferably 20 times or more, relative to the dry weight of the extraction material. However, for convenience in operations such as concentration or isolation after extraction, it is preferable to use 100 times or less. The extraction temperature and time depend on the target plant and the type of solvent used, but examples include 10 to 100°C, preferably 30 to 90°C, and 1 minute to 24 hours, preferably 1 to 10 hours. 【0019】 The extract may be used as is, but if necessary, it may be used after treatment such as concentration (concentration by organic solvent, vacuum concentration, membrane concentration, etc.), dilution, filtration, decolorization with activated carbon, deodorization, or ethanol precipitation, to the extent that it does not affect its effectiveness. Furthermore, the extracted solution may be treated by concentration to dryness, spray drying, freeze-drying, etc., and used as a dried product. 【0020】 The antioxidant composition according to a second aspect of the present invention contains a compound represented by the following general formula (I) as an active ingredient. [ka] (In the formula, the bonds represented by the solid and dotted lines in (a) to (g) are single bonds or double bonds, If (a) and (c) are double bonds and (b) and (d) are single bonds, then R 1 is an oxygen atom, R 2 R indicates a hydroxyl group, and if (a) and (c) are single bonds and (b) and (d) are double bonds, then R 1 R is a hydroxyl group, 2 This represents an oxygen atom. R 3 , R 4 , and R 7 Each of these independently represents a hydrogen atom or a hydroxyl group. If (e) and (g) are single bonds and (f) is a double bond, then R 5 and R 6 indicates a hydroxyl group, and if (e) and (g) are double bonds and (f) is a single bond, then R 5 and R 6 This represents an oxygen atom. R 8 and R 9 Each of these independently represents a hydrogen atom or a hydroxyl group, or R 8 and R 9 They come together to form a single bond. 【0021】 More specifically, the compounds represented by the above general formula (I) include the following compounds represented by structural formulas (1) to (3) (referred to as compounds 1 to 3, respectively). 【0022】 [ka] 【0023】 [ka] 【0024】 [ka] 【0025】 The antioxidant composition according to a second aspect of the present invention contains at least one compound selected from the group consisting of compounds 1, 2, and 3 as an active ingredient. Compounds 1 to 3 may be contained individually or in combination of two or more. 【0026】 Compounds 1-3 can be separated and purified from photo-irradiated grape pressing residue. Specifically, after obtaining an extract from the photo-irradiated grape pressing residue by the method described above, or after photo-irradiating the extract of grape pressing residue, the residue and solid-liquid separation can be performed by conventional methods such as filtration or centrifugation to obtain an extract. The active fraction can then be separated from the obtained extract by solvent fractionation using one or more organic solvents such as methanol, ethanol, propanol, butanol, dichloromethane, chloroform, ethyl acetate, toluene, hexane, benzene, and acetone. Furthermore, if necessary, purification can be performed by combining one or more appropriate separation and purification methods such as alumina column chromatography, silica gel chromatography, ODS column chromatography, gel filtration chromatography, ion exchange chromatography, hydrophobic chromatography, and high-performance liquid chromatography. 【0027】 Furthermore, the separation and identification of compounds 1 to 3 from the photo-irradiated grape pressing residue can be carried out specifically according to the description in Example 1(4). 【0028】 Thus, compounds 1 to 3 of the present invention can be separated and purified from light-irradiated grape pressing residues. However, the method of producing these compounds is not limited to this. The compounds may also be synthesized based on known chemical synthesis methods, or they may be produced by treating substances obtained from natural products other than grapes with reactions or other processes. 【0029】 Since the photo-irradiated grape pressing residue and compounds 1-3 have extremely high antioxidant activity and high persistence, they can be incorporated as active ingredients in antioxidant compositions, either alone or in combination with appropriate additives within a range that does not impair the effects of the present invention. 【0030】 In this invention, "antioxidant activity" refers to the activity of scavenging reactive oxygen species and bioactive radicals through at least one of reactive oxygen species scavenging activity and radical scavenging activity. Here, reactive oxygen species include superoxide, hydrogen peroxide, hydroxyl radical, singlet oxygen, etc. Radicals refer to molecules or atoms having one or more unpaired electrons, and include superoxide, hydroxyl radical, DPPH (diphenylpicryl hydrazide), lipid peroxides, etc. 【0031】 The form of the antioxidant composition is not particularly limited, but examples include cosmetics, pharmaceuticals, and food and beverages. Since the active ingredient of the antioxidant composition of the present invention is derived from natural products, it is highly safe and has no side effects, and when used as a cosmetic, pharmaceutical, or food and beverage, it can be continuously ingested or administered to mammals such as humans, mice, rats, rabbits, dogs, and cats. 【0032】 Because the skin is directly exposed to environmental factors such as ultraviolet rays, it is an organ that easily generates reactive oxygen species. As a result, the concentration of reactive oxygen species increases, and the production of lipid peroxides is likely to occur, which can easily lead to problems such as melanin production, age spots, and fine wrinkles. Therefore, it is preferable to provide the antioxidant composition of the present invention, which has excellent antioxidant activity, in the form of a cosmetic product that removes melanin accumulated by ultraviolet rays, suppresses redness caused by ultraviolet rays, and prevents and / or improves pigmentation (age spots), wrinkles, rough skin, etc. 【0033】 The dosage form of the cosmetic may be any of the following: aqueous solution, solubilized, emulsified, powder, powder dispersion, oil-liquid, gel, ointment, aerosol, water-oil two-layer system, or water-oil-powder three-layer system. Furthermore, the cosmetic may be manufactured by selecting and appropriately blending various components, additives, bases, etc., commonly used in topical skin preparations, along with the above-mentioned light-irradiated grape pressing residue, according to the type of cosmetic, and following methods known in the art. Its form may be any of the following: liquid, emulsion, cream, gel, paste, spray, etc. 【0034】 Examples of cosmetic products include toners, lotions, gels, serums, general creams, sunscreens, face masks, facial cleansers, cosmetic soaps, foundations, face powders, body lotions, shampoos, and hair growth products. 【0035】 When the antioxidant composition of the present invention is to be used as a pharmaceutical product, it can be mixed with pharmacologically and pharmaceutically acceptable additives and formulated into various formulations suitable for application to the affected area. Pharmacologically and pharmaceutically acceptable additives may include, depending on the dosage form and application, formulation bases or carriers, excipients, diluents, binders, lubricants, coatings, disintegrants or disintegration aids, stabilizers, preservatives, antiseptics, bulking agents, dispersants, wetting agents, buffers, solubilizers or solubilizers, isotonic agents, pH adjusters, propellants, colorants, sweeteners, flavoring agents, fragrances, etc., which can be appropriately added to prepare various formulations that can be administered orally or parenterally systemically or topically by various known methods. When providing the pharmaceutical product of the present invention in any of the above forms, it can be manufactured by methods commonly used by those skilled in the art, such as those described in the individual articles of the General Provisions for Formulations of the Japanese Pharmacopoeia [2]. 【0036】 The form of the pharmaceutical product is not particularly limited, but examples include oral preparations such as tablets, sugar-coated tablets, capsules, lozenges, granules, powders, liquids, pills, emulsions, syrups, suspensions, and elixirs; parenteral preparations such as injections (e.g., subcutaneous injections, intravenous injections, intramuscular injections, intraperitoneal injections), drips, suppositories, transdermal preparations, transmucosal preparations, and patches. It may also be provided as a dried product that is redissolved before use, and in the case of injection preparations, it is provided in the form of a unit dose ampoule or a multi-dose container. When the pharmaceutical product of the present invention is used to treat, improve, or prevent pigmentation (spots), a suitable form is a topical preparation, such as an ointment, cream, gel, liquid, patch, foam, spray, or aerosol. 【0037】 When the antioxidant composition of the present invention is used as a pharmaceutical, it is effective in treating, improving, and preventing diseases and conditions caused by reactive oxygen species due to oxidative stress. Diseases and conditions caused by reactive oxygen species due to oxidative stress include, but are not limited to, arteriosclerosis, cancer, skin aging (spots, wrinkles, etc.), skin diseases (atopic dermatitis, photosensitive dermatitis, etc.), rheumatoid arthritis, mental illnesses (schizophrenia, autism, etc.), dementia, eye diseases (cataracts, retinitis pigmentosa, age-related macular degeneration, etc.), neurological diseases (Parkinson's disease, Alzheimer's disease), respiratory diseases (bronchitis, etc.), cardiovascular diseases (ischemic arrhythmia, myocardial infarction, cerebral infarction, hypertension, etc.), digestive diseases (gastric ulcer, colitis, fatty liver, etc.), diabetes, etc. 【0038】 The amount of the cosmetic or pharmaceutical product used or administered according to the present invention can be appropriately determined according to its type and form, the age, sex, weight, and severity of symptoms of the person using or administering it. For example, when administered orally to an adult, the amount of the photo-irradiated grape pressing residue is 0.1 to 1000 mg / day, preferably 1 to 500 mg / day, more preferably 5 to 300 mg / day, administered once to several times a day. In some cases, an amount less than the above dosage range may be sufficient, and in other cases, it may be necessary to administer an amount exceeding the range. 【0039】 When the light-irradiated grape pressing residue is incorporated into the above-mentioned cosmetics and pharmaceuticals, the amount is not particularly limited, but it is usually in the range of 0.001 to 99% by weight (w / w) relative to the total weight of the formulation (composition), preferably 0.01 to 90% by weight (w / w), and more preferably 10 to 85% by weight (w / w), so that the daily dose can be controlled so that the above-mentioned daily intake for adults can be consumed. Furthermore, the method of adding the active ingredient in formulation may be to add it in advance or during manufacturing, and the method should be appropriately selected considering workability. 【0040】 Furthermore, the above-mentioned photo-irradiated grape pressing residue or compounds 1-3 can also be incorporated into food and beverages. In the present invention, "food and beverages" refers to general food and beverages, as well as foods other than pharmaceuticals that can be consumed for the purpose of maintaining or promoting health, such as health foods, functional foods, health functional foods, or foods for special dietary uses. Health foods include foods provided under names such as nutritional supplements, health supplements, and supplements. Health functional foods are defined by the Food Sanitation Act or the Food Promotion Act and include foods for specified health uses and nutrient functional foods that can display specific health effects, the functions of nutritional components, or the reduction of disease risk. The form of food and beverages may be any form suitable for consumption, such as solid, liquid, granular, granular, powder, capsule, cream, or paste. 【0041】 Examples of food and beverage products include, but are not limited to, bread, noodles, confectionery, dairy products, processed seafood and livestock products, oils and fats and processed oils and fats products, seasonings, various beverages (soft drinks, carbonated drinks, beauty drinks, nutritional drinks, fruit drinks, dairy drinks, etc.), and concentrated liquids and powders for adjusting such beverages. 【0042】 The food and beverages of the present invention may contain additives that are commonly used depending on their type. Any additive that is permissible from a food hygiene standpoint can be used, but examples include sweeteners such as glucose, sucrose, fructose, isomerized liquid sugar, aspartame, and stevia; acidulants such as citric acid, malic acid, and tartaric acid; excipients such as dextrin and starch; binders, diluents, flavorings, colorings, buffers, thickeners, gelling agents, stabilizers, preservatives, emulsifiers, dispersants, suspending agents, and antiseptics. 【0043】 The amount of the photo-irradiated grape pressing residue used in the food and beverage of the present invention should be set appropriately, taking into consideration the general intake amount of the food and beverage, the form of the food and beverage, efficacy and effects, taste, palatability, and cost. 【0044】 Other forms of antioxidant compositions include sanitary products (nonwoven masks, disposable diapers, wet wipes, etc.), cleaning agents (laundry detergents, kitchen detergents, bathroom detergents, household detergents, etc.), textile products (sheets, towels, underwear, etc.), food packaging materials (freshness preservation sheets, freshness preservation bags, etc.), filter products (air conditioner filters, air purifier filters, vacuum cleaner filters, ventilation fan filters, etc.), and paper products (tissue paper, toilet paper, wrapping paper, etc.). For example, when used as a nonwoven fabric product with antioxidant and reactive oxygen species scavenging effects, it can be manufactured by applying an aqueous solution of light-irradiated grape pressing residue to a nonwoven fabric and drying it. 【0045】 2. Method for manufacturing antioxidant materials The photo-irradiated grape pressing residue, which is the active ingredient of the above antioxidant composition, can be used as a sustained antioxidant material. The antioxidant material of the present invention can be produced by a method that includes the steps of pressing grape raw materials in the wine production process to obtain grape pressing residue containing grape skins and seeds, and subjecting the obtained grape pressing residue to photoirradiation treatment. 【0046】 The process of obtaining grape pressing residue is carried out by recovering the residue (including skins and seeds) left over after pressing grapes in normal wine production. The process of treating the obtained grape pressing residue with light irradiation can be carried out according to the light irradiation conditions described above. In addition, a step of extracting the grape pressing residue according to the extraction conditions described above may be included before the light irradiation treatment. [Examples] 【0047】 The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. 【0048】 [Example 1] (1) Production of light-treated grape pressing residue The residue from grapes (varieties 1-8) immediately after pressing was collected, dried, and finely ground. 10 mL of solvent (water) was added to 1 g of the resulting dried powder, and the mixture was extracted at room temperature for 1 hour. The mixture was then centrifuged at 4,000 rpm for 15 minutes, and the resulting extract was irradiated with 302 nm light for 72 hours. 【0049】 (2) Antioxidant activity of grape pressing residue before and after light irradiation (1) Hydroxyl radical (·OH) scavenging ability of the extract obtained before and after light irradiation and superoxide radical (O 2- •) We investigated the erasure ability. 【0050】 The hydroxyl radical (·OH) scavenging ability test involved artificially producing hydroxyl radicals using the Fenton reaction, and then measuring the amount of hydroxyl radicals scavenged when a 10-fold dilution of each sample was added, thereby calculating the scavenging rate. Superoxide radical (O) 2- • The scavenging ability test measured the amount of superoxide radicals scavenged when a 100-fold dilution of each sample was added, using the principle of the HPX-XOD generation system. All tests were performed using an electron spin resonance (ESR) spectrometer. 【0051】 The hydroxyl radical scavenging ability increased from 20-46% before light irradiation to 32-51% after light irradiation. Activity increased after light irradiation in all varieties (Figure 1). 【0052】 The superoxide scavenging ability increased from 67-75% before light irradiation to 70-80% after light irradiation. Activity increased after light irradiation in all varieties (Figure 2). 【0053】 (3) Component analysis by LC / MS As samples, the above-mentioned grape pressing residue (GPE), epigallocatechin (EGC), catechin (Cat), and epicatechin (EC) were used, and each was irradiated with light under the same conditions as in (1). LC / MS analysis was performed on the samples before and after light irradiation. A Xevo G2 Q Tof (Waters) system was used for the analysis. Sample preparation involved centrifugation at 19600g, and 4 μL of the supernatant was used for analysis. A Waters Symmetry C18 column (length 150 mm, inner diameter 2.1 mm, particle size 3.5 μm) was used as the analytical column, and a linear gradient method using a 0.1% formic acid aqueous solution based on 0.1% formic acid acetonitrile was used as the mobile phase. Q-Tof measurements using positive ion electrospray ionization (ESI) revealed a new peak around 0.89 min in the grape pomace (GPE) sample after photoirradiation (Figure 3-2), but no new peak was detected around 0.89 min in the epigallocatechin (EGC) sample after photoirradiation (Figure 3-1). Furthermore, based on the new peaks detected in the catechin (Cat) and epicatechin (EC) samples after photoirradiation (Figures 4-1, 4-2), it was estimated that the photoirradiated grape pomace (GPE) contains at least several components, including catechin and epicatechin, as well as novel components. 【0054】 (4) Structural analysis of novel components (extraction and separation of compounds from photo-irradiated grape press residue (GPE)) (4-1) Analysis method Since epicatechin was found in a new peak (around 0.89 min on LC / MS) that is presumed to contain a novel component, the sample containing the target compound was isolated from the epicatechin standard using HPLC. 【0055】 A 1 mM aqueous solution of (-)-Epicatechin was irradiated with ultraviolet light at a wavelength of 302 nm for 24 hours, and then freeze-dried. After dissolving the freeze-dried product, the target compound was isolated by reverse-phase HPLC using an ODS column. A 5% (v / v) acetonitrile / 0.1% (v / v) trifluoroacetic acid aqueous solution was used as the mobile phase at a flow rate of 8 mL / min. A TSK-gel 80TS column (inner diameter: 20 mm, length: 250 mm) was used. 【0056】 To determine the structure of the target compound, IR spectroscopy, mass spectrometry (MS), and nuclear magnetic resonance (NMR) were performed using the following instruments and conditions. Nuclear magnetic resonance (NMR) was performed using the following instruments: 1 H-NMR spectrum, 13 In addition to 13C-NMR spectra, data were collected from two-dimensional spectra [HH COSY, HSQC (Heteronuclear Single Quantum Coherence), HMBC (Heteronuclear Multiple Bond Correlation), INADEQUATE (Incredible Natural Abundance Double Quantum Transfer Experiment)]. 【0057】 <IRスペクトル> Equipment: FT / IR-4X1typeA (manufactured by JASCO) Measurement method: FT / IR-ATR method - Attenuated Total Reflection (ATR measurement method) Measurement conditions: Measurement range 4000.6cm -1 From 399.193cm -1 , resolution 4cm -1 , cumulative number of times: 16, sample chamber temperature: 293K 【0058】 <Mass spectrometry (MS)> Device: JMS-DART-TOF-MS T100LP Ion source: DART Mass spectrometry department: TOF Measurement conditions: Ion source temperature 250°C, DART gas He 【0059】 <Various Magnetic Resonance (NMR) Analysis Methods> Equipment: JNM-ECZ800MHz( 13 (C-NMR measurement only) and JNM-ECZ500MHz Measurement solvent: DMSO-d6 【0060】 (4-2) Analysis results <IRスペクトル> 3190cm -1 Nearby are alcohols or phenolic hydroxyl groups (OH), 1644 cm -1 Absorption due to carbonyl group (C=O) stretching was observed in the vicinity. Therefore, it was revealed that the sample contained an alcohol or a phenolic hydroxyl group and a carbonyl group. 【0061】 <Mass spectrometry (MS)> MS:m / z [M+H] + , calc for [C 15 H 12 O6] + =289.07;found 289.07 MS:m / z [M+H] + , calc for [C 15 H 12 O7] + =305.07; found 305.07 【0062】 <Nuclear magnetic resonance (NMR)> 1 H-NMR(500MHz,DMSO-d6) δ 6.87(s,1H), 6.19(s,1H), 5.21(d,J=1.5Hz,1H), 5.17(d,J=1Hz,1H), 4.14(d,J=8Hz,1H), 3.97(ddd,J=12,8,4.5Hz 1H), 2.05(dd,J=13.5,10.5Hz,1H), 1.95(dd,J=13.5,4.5Hz,1H) 13 C-NMR(200MHz,DMSO-d6) δ 170~190, 170~190, 170~190, 145.1, 144.8, 132.1, 124.7, 114.7, 112.9, 99.8, 98.5, 72.5, 69.0, 51.2, 36.9 【0063】 1 H-NMR, 13 The results obtained from 13C-NMR, HH COSY, HSQC, and HMBC measurements are summarized in Table 1 below. 【0064】 [Table 1] 【0065】 Based on the above results, the compounds contained in the photo-irradiated grape pressing residue are represented by the structural formulas shown in Table 2 below: Compound 1 (molecular weight 289.07, molecular formula C 15 H 12 O6), compound 2 (molecular weight 289.07, molecular formula C 15 H 12 O6), compound 3 (molecular weight 305.07, molecular formula C 15 H 12 It was estimated to be O7. 【0066】 [Table 2] 【0067】 [Example 2] Efficacy test on sun-tanned model mice Sunburn model mice were created by inducing inflammatory redness and melanin production in HRM-2 hairless mice by UVB irradiation. The study then investigated whether there were differences in inflammatory redness and melanin pigmentation appearing on the skin surface between the group that ingested grape pressing residue (hereinafter referred to as "GPE") and the group that did not. In this study, the "GPE" used was an extract of the pressing residue of grape variety A prepared in Example 1 (without light irradiation). 【0068】 The experiment was conducted according to previously reported findings (Biol. Pharm. Bull. 2017 40, 1381-1388, Cancer Epidemiol Biomarkers Prev. 2011 Aug;20(8):1622-8.), with UVB irradiation conditions set to an intensity that would not cause rapid and significant skin inflammation in mice (wavelength: 302 nm, intensity: 38 mJ / cm²). 2 (72 hours). UVB irradiation was performed six times, every other day. 【0069】 For UVB-irradiated mice, a diet containing 3% grape pomace powder (GPE powder) or a regular diet was administered starting four weeks before UVB irradiation. Skin color, specifically "melanin levels" and "redness," was measured using a simple skin colorimeter (Delphine Technologies). 【0070】 The results are shown in Figures 5-7. In mice irradiated with UVB and fed a GPE-containing diet (UVB irradiation / GPE-containing diet group), inflammation and darkening due to sunburn were significantly suppressed compared to mice fed a normal diet (UVB irradiation / normal diet group) (Figure 5). Regarding melanin levels, a significant difference was observed between irradiated and unirradiated mice on day 8 of UVB irradiation, and on day 12, the UVB irradiation / GPE-containing diet group showed a significant melanin-suppressing effect compared to the UVB irradiation / normal diet group (Figure 6). Regarding redness, a significant difference was observed between irradiated and unirradiated mice from day 2 of UVB irradiation, and on day 6, the UVB irradiation / GPE-containing diet group showed a significant redness-suppressing effect compared to the UVB irradiation / normal diet group, suggesting that the redness-suppressing effect persisted until day 10 (Figure 7). Furthermore, there was a tendency for the degree of redness to decrease relatively after day 8, when melanin levels increased. 【0071】 Furthermore, on the 14th day after the start of UVB irradiation, the level of oxidative stress was measured by the concentration of hydroperoxide in the blood, which is a marker, according to the d-ROM test. In the UVB-irradiated / GPE-containing feed group, the increase in oxidative stress due to UVB irradiation was suppressed (Figure 8). 【0072】 [Example 3] Efficacy study in a rheumatoid arthritis model rat Rheumatoid arthritis model rats were created by administering 0.1 mL of complete Freund's adjuvant to the hindlimb joints of male Wistar rats. The study then investigated whether there were differences in joint surface irregularities and pain thresholds for rheumatoid arthritis between the group that ingested grape crushing residue and the group that did not. 【0073】 First, the antioxidant capacity of grape pressing residue was investigated in vivo using healthy rats. Male Wistar rats were divided into three groups: a control group (normal diet), a group fed a diet containing 1% GPE, and a group fed a diet containing 2% GPE. The GPE-containing diet group was given ad libitum access to a diet mixed with 1% or 2% GPE. One, two, and three weeks after the start of intake, the plasma hydroperoxide concentration, a marker, was measured by the d-ROM test. 【0074】 The measurement results are shown in Figure 9. In the normal diet group (control), the plasma oxidative stress level (Diacron-Reactive Oxygen Metabolites: dROM value) increased significantly, but in the 2% GPE-containing diet group, no increase was observed at all. From these results, it was confirmed that grape pressing residue has antioxidant capacity in vivo. 【0075】 Next, we examined the effects on a rheumatoid arthritis model. Figure 10 shows the results of comparing the macroscopic findings of the hindlimb joints in three groups: healthy rats on a normal diet (control), rheumatoid arthritis model rats on a normal diet (AA group), and rheumatoid arthritis model rats on a diet containing 2% GPE (AA+GPE group). Compared to the control group, the AA group showed marked swelling and redness extending from around the hindlimb joints to the toes. In contrast, the AA+GPE group showed swelling of the hindlimb joints, but it was milder compared to the AA group. 【0076】 Furthermore, CT scans of the hindlimb joints were performed on the three groups mentioned above, and the results of comparing the image findings are shown in Figure 11. In the control group, smooth cortical bone and neatly arranged tarsal bones were observed, but in the AA group, in addition to irregular joint surfaces and osteophyte formation, the presence of loose bodies was observed. These findings strongly suggested that the AA group had developed clear arthritis in the hindlimb joints, leading to bone destruction and cartilage destruction. In contrast, although mild joint irregularities were observed in the AA+GPE group, the progression of bone destruction was clearly suppressed compared to the AA group. 【0077】 Furthermore, Figure 12 shows the results of pain assessment using the von Frey test for the three groups mentioned above. While the pain threshold decreased in the AA group, this decrease was significantly suppressed in the AA+GPE group. 【0078】 Based on the above test results, it was suggested that grape pomace is effective in alleviating the symptoms of rheumatoid arthritis, and that the antioxidant properties of grape pomace are involved in this effect. 【0079】 [Example 4] Efficacy study in a social isolation stress model rat Mental illnesses such as schizophrenia and autism have been reported to be caused by oxidative stress. Therefore, we investigated the effectiveness of grape pomace in treating mental illnesses. 【0080】 As a model of mental illness, social isolation stress model rats were created by keeping them in isolation for 28 days. At the start of isolation, they were fed a normal diet, a diet containing 1% GPE, and a diet containing 2% GPE. 28 days after the start of isolation, another rat was introduced into the cage as an intruder. Within 10 minutes of the rat being placed in the cage, the time (in seconds) during which the three groups of social isolation stress model rats attacked the newly introduced rat was counted. 【0081】 The results are shown in Figure 13. The average attack time for socially stressed rats in the normal diet group (control) was 250 seconds, while in socially stressed rats in the 1% GPE-containing diet group (Sress+1%GPE group) and the 2% GPE-containing diet group (Sress+2%GPE group), the attack time decreased to approximately 150 seconds and approximately 70 seconds, respectively, indicating a concentration-dependent decrease in attack time. 【0082】 [Example 5] Antioxidant activity of novel compounds In Example 1, the structure of the newly formed compounds contained in the photo-irradiated grape pressing residue was determined. The antioxidant activity of Compound 1 was evaluated as its hydroxyl radical (·OH) scavenging ability. Epigallocatechin gallate (EGCG), which has been highly evaluated for its antioxidant activity, was used as a comparative compound. The hydroxyl radical (·OH) scavenging ability test was performed in the same manner as in Example 1, by generating hydroxyl radicals via the Fenton reaction, measuring the amount of hydroxyl radicals scavenged by the sample, and calculating the scavenging rate. Specifically, the absorbance of the well containing only the solvent (without Compound 1) was taken as the radical intensity at 100%, and the radical intensity of the well containing Compound 1 (10-fold dilution) was expressed as a relative percentage (%). From this value, the 50% inhibitory concentration (IC50) of hydroxyl radicals (·OH) was calculated. The results are shown in Table 3. 【0083】 [Table 3] 【0084】 As shown in Table 3, epigallocatechin gallate (EGCG) was found to have a 50% inhibitory concentration (IC) in this experimental system. 50 The IC value was 720 μg / mL, while the IC value for compound 1 was 720 μg / mL. 50 The value was 14.8 μg / mL, indicating approximately 50 times higher antioxidant activity. 【0085】 Furthermore, the hydroxyl radical scavenging rate of compound 1 increased from 50% before photoirradiation to 60% after photoirradiation. On the other hand, the hydroxyl radical scavenging rate of EGCG decreased from 50% before photoirradiation to 28% after photoirradiation (Table 4). Therefore, the hydroxyl radical scavenging rate of compound (1) was proven to be persistent. 【0086】 [Table 4] [Industrial applicability] 【0087】 The antioxidant composition of the present invention has sustained antioxidant activity in vivo or in vitro. Therefore, the present invention can be used in the manufacturing fields of cosmetics, pharmaceuticals, food products, etc., for treating, improving, and preventing diseases and pathological conditions caused by reactive oxygen species due to oxidative stress. All publications, patents, and patent applications cited herein are incorporated herein by reference in their entirety.

Claims

[Claim 1] An antioxidant composition containing a compound represented by the following structural formula (1) or (2) as an active ingredient. 【Chemistry 1】 【Chemistry 2】 [Claim 2] The antioxidant composition according to claim 1, wherein the antioxidant composition is a cosmetic, a pharmaceutical, or a food or beverage. [Claim 3] The antioxidant composition according to claim 1, wherein the antioxidant composition is a sanitary product, a cleaning agent, a textile product, a food packaging material, a filter product, or a paper product. [Claim 4] A novel compound represented by the following structural formula (1) or (2). 【Transformation 3】 【Chemistry 4】 [Claim 5] A method for producing a novel compound according to claim 4, characterized in that the grape pressing residue is subjected to light irradiation followed by solvent extraction, or the grape pressing residue is subjected to solvent extraction followed by light irradiation, and the compound is separated and purified from the treated product.

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