JP7578267B2 - Methyl mercaptan and/or hydrogen sulfide generation inhibitor - Google Patents

Description

The present invention relates to a methyl mercaptan and/or hydrogen sulfide generation inhibitor that contains barley, rahma, and water shield. More specifically, the present invention relates to a breath odor inhibitor or deodorant that contains barley, rahma, and water shield as a methyl mercaptan and/or hydrogen sulfide generation inhibitor.

Methyl mercaptan and hydrogen sulfide are known to have strong odors, and are designated by government ordinance as specific odorous substances under the Offensive Odor Prevention Law, which regulates odors generated by activities in factories and business establishments. Methyl mercaptan and hydrogen sulfide are the main causes of odors not only from industrial activities, but also from everyday life such as bad breath, garbage odor, and fecal odor, so removing methyl mercaptan and hydrogen sulfide is extremely important in suppressing odors.

However, because methyl mercaptan and hydrogen sulfide are stable substances, they are difficult to remove through adsorption or decomposition. For this reason, it is important to suppress the generation of methyl mercaptan and hydrogen sulfide.

Methyl mercaptan and hydrogen sulfide are generated by enzyme reactions using sulfur-containing amino acids such as methionine and cysteine as substrates. These enzymes are called sulfur-containing amino acid lyases, and methionine gamma-lyase is known as an enzyme that produces methyl mercaptan, while cystathionine gamma-lyase and cystathionine beta-synthase are known as enzymes that produce hydrogen sulfide (Non-Patent Documents 1 and 2).

In order to suppress the production of methyl mercaptan and hydrogen sulfide, it is also important to inhibit this sulfur-containing amino acid lyase, so various attempts have been made focusing on the inhibition of sulfur-containing amino acid lyase.

Patent Document 1 discloses an inhibitor of the formation of volatile sulfur compounds, an inhibitor of the enzyme that produces methyl mercaptan from methionine, and an inhibitor of the enzyme that produces hydrogen sulfide. Patent Documents 2 to 5 disclose methyl mercaptan-producing enzyme inhibitors that contain plant extracts such as tomato or ginger extract and water-soluble grape seed extract, or minosinic acid as an active ingredient. Patent Document 6 discloses a hydrogen sulfide-producing enzyme inhibitor that contains catechins as an active ingredient.

However, the inhibitors and suppressors that have already been disclosed have problems such as being harmful to the human body or not being effective enough.

JP 2008-173441 A JP 2013-75860 A JP 2002-3353 A JP 2003-160459 A JP 2008-31062 A JP 2011-51946 A

Biochim Biophys Acta, 1794:1414-1420 (2009) Folia Pharmacol. Jpn. , 152:216-222 (2018)

The object of the present invention is to provide a methyl mercaptan and/or hydrogen sulfide generation inhibitor that is highly safe for the human body and exhibits its full effect. More specifically, the object is to provide a breath odor suppressant or deodorant that contains barley, rahma and water shield as methyl mercaptan and/or hydrogen sulfide generation inhibitors.

As a result of intensive research conducted by the inventors to solve the above problems, they discovered that a combination of barley (Hordeum vulgare) belonging to the genus Hordeum of the family Poaceae, A. serrata (Rahuma) belonging to the genus Basilica of the family Apocynaceae, and A. serrata (Water Shield) belonging to the genus Water Shield of the family Nymphaeaceae, provides an extremely excellent effect of inhibiting the generation of methyl mercaptan and/or hydrogen sulfide, and further discovered that a combination of barley, A. serrata, and A. serrata provides an excellent effect of inhibiting bad breath and of deodorizing, thus completing the present invention.

The present invention achieves the effect of inhibiting the generation of methyl mercaptan and/or hydrogen sulfide, thereby providing an extremely excellent breath odor suppressant and deodorant.

The present invention will be described in detail below. Barley (Hordeum vulgare L.) used in the present invention is an annual or perennial grass plant belonging to the genus Hordeum of the family Poaceae, and is widely distributed mainly in the temperate zones of the Northern Hemisphere and South America, and in South Africa. Barley is classified into two-row barley, four-row barley, six-row barley, naked barley, wild barley, etc. based on the difference in ear shape, and any of them can be used in the present invention. In addition, barley with purple, black, or white (not colored) glumes or caryopsis, for example, can also be used. In some cases, barley with colored stems and leaves can also be used in the present invention. The part of the barley used is not particularly limited, but examples include the entire plant body, organs (flowers, leaves, stems, roots, bark, fruit, pericarp, seeds, or mixtures thereof, etc.), etc., and it is particularly preferable to use stems, leaves, and seeds, etc., and it is even more preferable to use seeds.

The Apocynum venetum L. used in the present invention is a perennial plant belonging to the Apocynum genus of the Apocynum family, which grows wild mainly in northwestern China. Any part of Apocynum venetum can be used, including the leaves, stems, and roots, but it is particularly preferable to use the leaves.

The water shield (Brasenia schreberi J.F.G mel.) used in the present invention is a perennial aquatic plant belonging to the genus Water shield of the Nymphaeaceae family, and is widely distributed from temperate to tropical regions. Any part of Water shield, such as leaves, stems, or roots, can be used, but it is particularly preferable to use buds or young leaves covered with mucilage.

In the present invention, the plant body or a part or organ of the plant body may be used as it is, or may be treated by drying, crushing, shredding, etc. Also, an extract with a solvent may be used. For extraction, the plant body or a part or organ of the plant body may be used as it is, or may be treated by drying, crushing, shredding, etc. before extraction. Examples of the solvent 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, etc.), and ethers (ethyl ether, tetrahydrofuran, propyl ether, etc.). These solvents may be used alone or in combination of two or more. Polar solvents such as water and lower alcohols are preferable, and water is particularly preferable.

The extract may be used as it is in the form of an extracted solution, or may be used after processing such as concentration, dilution, filtration, decolorization with activated carbon, deodorization, ethanol precipitation, etc., as necessary. Furthermore, the extracted solution may be concentrated to dryness, spray-dried, freeze-dried, etc., and used as a dried product.

The amount of the extract used in the present invention varies depending on the form, purpose, age, body weight, etc. When used as a breath odor suppressant, it can be used in the range of 0.01 μg to 10 mg/time, preferably 0.02 μg to 5 mg/time, more preferably 0.1 μg to 1 mg/time, once to several times a day. When used as a deodorant, it can be used in the range of 0.1 μg to 10 mg/time, preferably 0.2 μg to 5 mg/time, more preferably 1 μg to 1 mg/time, once to several times a day. In some cases, an amount less than the above range is sufficient, and in other cases, it is necessary to use an amount exceeding the range. In addition, the method of adding the medicinal ingredient in the formulation may be added in advance or during the manufacturing process, and can be selected appropriately in consideration of workability.

When the methyl mercaptan and/or hydrogen sulfide generation inhibitor of the present invention is used as an oral odor suppressant, it can be used in any of quasi-drugs, foods, and pharmaceuticals. As for the form, any form that can be used in the oral cavity, such as toothpaste, liquid toothpaste, mouthwash, oral gel, mouth spray, mouth rinse, lozenges, candies, gummies, and chewing gum, can be used. In addition, forms that can be used from the oral cavity to the digestive system, such as tablets, granules, and powders, can also be used.

When the methyl mercaptan and/or hydrogen sulfide generation inhibitor of the present invention is used as a deodorant, it may be in any form, such as liquid, spray, aerosol, powder, granules, or solid. Depending on the form, it can be directly sprayed onto food waste, feces, etc. It can also be sprayed onto drains, exhaust vents, etc. of toilets, washrooms, bathrooms, kitchens, sinks, etc.

The methyl mercaptan and/or hydrogen sulfide generation inhibitor of the present invention may contain ingredients such as excipients, stabilizers, preservatives, binders, disintegrants, hydrocarbons, fatty acids, vitamins, alcohols, esters, pH adjusters, preservatives, and fragrances as necessary, within the limits that do not impair the effectiveness of the agent.

The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited to these. The percentages of content shown in the examples are by weight.

Production Example 1 Hot Water Extract of Barley 500 mL of purified water was added to 25 g of crushed barley seeds, and extraction was carried out for 2 hours at 95 to 100° C. The filtrate was concentrated under reduced pressure and freeze-dried to obtain 2.1 g of a hot water extract of barley.

Preparation Example 2: 50% Ethanol Extract of Barley 500 mL of 50 (v/v)% ethanol was added to 25 g of crushed barley seeds, and extraction was carried out at room temperature for 5 days. The filtrate was concentrated to dryness under reduced pressure to obtain 0.9 g of 50% ethanol extract of barley.

Preparation Example 3 Ethanol extract of barley 1 L of ethanol was added to 100 g of crushed barley seeds, and extraction was carried out at room temperature for 7 days. The filtrate was concentrated to dryness under reduced pressure to obtain 3.1 g of an ethanol extract of barley.

Production Example 4 Hot Water Extract of Rahma 150 g of dried Rahma leaves were added with 10 L of purified water and extracted for 2 hours at 95-100° C. The filtrate was concentrated under reduced pressure and freeze-dried to obtain 11.5 g of hot water extract of Rahma.

Preparation Example 5: 50% Ethanol Extract of Rahma 100 g of dried leaves of Rahma was added with 3 L of 50 (v/v)% ethanol and extracted at room temperature for 5 days. The filtrate was concentrated to dryness under reduced pressure to obtain 5.5 g of 50% ethanol extract of Rahma.

Preparation Example 6 Ethanol Extract of Rahma 1 L of ethanol was added to 200 g of dried leaves of Rahma and extracted at room temperature for 7 days. The filtrate was concentrated to dryness under reduced pressure to obtain 8.3 g of ethanol extract of Rahma.

Production Example 7 Hot Water Extract of Water Shield 20 L of purified water was added to 2000 g of dried young leaves of Water Shield, and extraction was carried out for 2 hours at 95 to 100° C. The filtrate was concentrated under reduced pressure and freeze-dried to obtain 35.2 g of a hot water extract of Water Shield.

Preparation Example 8: 50% ethanol extract of Water Shield 8 L of 50 (v/v)% ethanol was added to 1000 g of dried young leaves of Water Shield, and extraction was carried out at room temperature for 5 days. The filtrate was concentrated to dryness under reduced pressure to obtain 15.7 g of 50% ethanol extract of Water Shield.

Preparation Example 9 Ethanol extract of Water Shield 1 L of ethanol was added to 200 g of dried young leaves of Water Shield, and extraction was carried out at room temperature for 7 days. The filtrate was concentrated to dryness under reduced pressure to obtain 2.7 g of ethanol extract of Water Shield.

Production Example 10 Mixture of hot water extracts of barley, rahma, and water shield 1 g of the barley hot water extract of Production Example 1, 1 g of the hot water extract of rahma of Production Example 4, and 1 g of the hot water extract of water shield of Production Example 7 were mixed to obtain 3 g of a mixture of the three types of extracts.

Formulation Example 1 Mouthwash Formulation Content (%)
1. Hot water extract of barley (Production Example 1) 0.001
2. Hot water extract of Rahma (Production Example 4) 0.001
3. Hot water extract of Water Shield (Production Example 7) 0.001
4. Ethanol 20,000
5. Glycerin 10,000
6. Sodium saccharin 0.100
7. Fragrance 0.100
8. Polyoxyethylene hydrogenated castor oil (60 E.O.) 1,500
9. Ethyl parahydroxybenzoate 0.100
10. Add water to make the total volume 100. <Production method>
Components 1 to 3 were dissolved in component 10, and then components 5 and 6 were dissolved (composition A). Components 7 to 9 were dissolved in component 4 (composition B). Compositions A and B were thoroughly mixed to obtain a mouthwash.

Comparative Example 1 Comparative Example 1 was prepared by replacing the hot water extract of barley, the hot water extract of Rhagonia arbutifolia, and the hot water extract of Water Shield in Conventional Mouthwash Formulation Example 1 with water.

Formulation Example 2 Deodorizing granules <Formulation>
Ingredient Content (%)
1. 50% ethanol extract of barley (Production Example 2) 0.0005
2. 50% ethanol extract of Rhabdomad (Production Example 5) 0.0005
3. 50% ethanol extract of Water Shield (Production Example 8) 0.0005
4. Cellulose 20.0000
5. Lactose 79.9985
<Production Method>
Components 1 to 5 were mixed with water in appropriate amounts and kneaded. The mixture was extruded through a screen with a diameter of 2 mm, granulated, and dried to obtain granules.

Comparative Example 2 Comparative Example 2 was prepared by removing the 50% ethanol extract of barley, the 50% ethanol extract of rahma, and the 50% ethanol extract of water shield from Conventional Granule Formulation Example 2, and adjusting the total amount to 100 with lactose.

Formulation example 3 Deodorizing spray <Formulation>
Ingredient Content (%)
1. Barley hot water extract (Production Example 1) 0.002
2. Hot water extract of Rahmania (Production Example 4) 0.002
3. Hot water extract of Water Shield (Production Example 7) 0.002
4. Ethanol 30,000
5. Polyoxyethylene hydrogenated castor oil 0.200
6. Citric acid 0.100
7. Sodium citrate 0.100
8. Fragrance 0.100
9. Add water to make the total amount 100. <Production Method> Components 1 to 3 were dissolved in component 9 (composition A). Components 6 and 7 were dissolved in component 9 and mixed with composition A (composition B). Components 5 and 8 were dissolved in component 4 (composition C). Compositions B and C were thoroughly mixed to obtain a deodorant spray.

Comparative Example 3 Comparative Example 3 was prepared by removing the hot water extract of barley, the hot water extract of rahma and the hot water extract of water shield from Conventional Spray Formulation Example 3, and adjusting the total amount to 100% with water.

Test Example 1: Inhibitory effect on methyl mercaptan generation Saliva was collected from five subjects and measured by the following method. 1 mL of saliva was placed in a glass container, and methionine, the substrate of methyl mercaptan, was dissolved in water to a final concentration of 10 mmol/L, and a mixture of hot water extracts of barley, rahma, and water shield (Production Example 10) was dissolved in water to a final concentration of 50 μg/mL and 200 μg/mL, and 1 mL of the solution was added to the saliva, sealed, and left at 37°C for 24 hours. The generated methyl mercaptan was collected using a solid phase microextraction fiber and measured by GC-MS.

The results of Test Example 1 are shown in Table 1. When the amount of methyl mercaptan generated without the addition of a mixture of hot water extracts of barley, rahma, and water shield is taken as 100, the addition of a mixture of hot water extracts of barley, rahma, and water shield at a final concentration of 50 μg/mL suppressed the generation of methyl mercaptan by 29%, and the addition of 200 μg/mL suppressed the generation of methyl mercaptan by 15%, demonstrating an excellent effect. This effect is believed to be due to the hot water extracts of barley, rahma, and water shield inhibiting sulfur-containing amino acid lyase.

Test Example 2: Bad breath suppression effect Test was conducted on 10 subjects. 10 mL of the mouthwash of Formulation Example 1 was placed in the mouth, rinsed for about 20 seconds, and then spat out. On another day, the mouthwash of Comparative Example 1 was used in the same manner. Before use and one hour after use, the concentration of bad breath components (methyl mercaptan, hydrogen sulfide) was measured using an oral odor measuring device Oralchroma (manufactured by Nissha FIS Co., Ltd.).

The results of Test Example 2 are shown in Tables 2 and 3. The mouthwash (Formulation Example 1) containing the hot water extract of barley, the hot water extract of rahma, and the hot water extract of water shield was found to have an excellent effect of suppressing the generation of bad breath components. This effect is believed to be due to the hot water extracts of barley, rahma, and water shield inhibiting sulfur-containing amino acid lyase.

Test Example 3: Deodorizing effect of food waste Cabbage, onion, and minced pork were weighed out in equal weight ratios, chopped, and mixed well to obtain simulated food waste. 500g of food waste was placed in a 5L sealed container, and 10g each of the deodorizing granules of Formulation Example 2 and the granules of Comparative Example 2 were added and mixed well. The mixture was placed in a thermostatic chamber at 35°C, and after 1 and 2 days, monitors (10 people) were asked to smell the mixture, and the deodorizing effect was evaluated based on the difference in the sensory odor between Formulation Example 2 and Comparative Example 2.

The results of Test Example 3 are shown in Table 4. An excellent deodorizing effect was observed for the deodorizing granules (Formulation Example 2) containing a 50% ethanol extract of barley, a 50% ethanol extract of rafuma, and a 50% ethanol extract of water shield. This effect is believed to be due to the 50% ethanol extracts of barley, rafuma, and water shield inhibiting sulfur-containing amino acid lyase.

Test Example 4: Feces deodorizing effect 0.1 g of cat feces was placed in a glass bottle, and 1 mL each of the deodorizing spray of Formulation Example 3 and the spray of Comparative Example 3 was sprayed onto the bottle, which was then sealed. The bottle was placed in a thermostatic chamber at 35°C, and after 3 hours and 12 hours, monitors (10 people) were asked to smell the bottle. The deodorizing effect was judged based on the difference in sensory odor between Formulation Example 3 and Comparative Example 3.

The results of Test Example 4 are shown in Table 5. An excellent deodorizing effect was observed in the deodorizing spray (Formulation Example 3) containing a hot water extract of barley, a hot water extract of rahma, and a hot water extract of water shield. This effect is believed to be due to the hot water extracts of barley, rahma, and water shield inhibiting sulfur-containing amino acid lyase.

The methyl mercaptan and/or hydrogen sulfide generation inhibitor of the present invention has been shown to have an excellent effect of inhibiting the generation of methyl mercaptan and/or hydrogen sulfide, and can therefore be used as an agent for suppressing bad breath having an excellent effect of suppressing bad breath or as a deodorant having an excellent effect of deodorizing.

Claims (4)

A methyl mercaptan generation inhibitor containing barley, rahma and water shield, characterized in that the inhibition of methyl mercaptan generation is due to inhibition of sulfur-containing amino acid lyase . A hydrogen sulfide generation inhibitor containing barley, rahma and water shield, characterized in that the inhibition of hydrogen sulfide generation is achieved by inhibition of sulfur-containing amino acid lyase . A deodorant containing the methyl mercaptan generation inhibitor according to claim 1. A deodorant comprising the hydrogen sulfide generation inhibitor according to claim 2.