KR20210034530A - Hydrogen gas generating composition and hydrogen gas trapping nanostructure - Google Patents

Abstract

The present invention relates to a hydrogen gas generating composition and a hydrogen gas capturing nanostructure, wherein the hydrogen gas generating composition comprises: a self-assembly peptide; a hydrogen compound; an acid; and a carrier. The hydrogen gas capturing nanostructure comprises: a carrier supporting hydrogen gas generated by the hydrogen compound and the acid; and a nano-membrane composed of the self-assembled peptide formed outside the carrier.

Description

Hydrogen gas generating composition and hydrogen gas trapping nanostructure {HYDROGEN GAS GENERATING COMPOSITION AND HYDROGEN GAS TRAPPING NANOSTRUCTURE}

The present invention relates to a hydrogen gas generating composition and a hydrogen gas trapping nanostructure using a peptide that stably forms a self-assembled nanostructure through self-alignment between molecules in a solution.

It is known that when hydrogen gas is generated in an aqueous solution, the oxidation-reduction potential of water is lowered, resulting in an aqueous composition having a reducing power.

The reducing composition in aqueous solution has antioxidant activity, so it is generated during metabolism in the body or caused by external environmental factors, and reacts with active oxygen known as the main factor of aging to change into non-toxic water, which can effectively remove active oxygen. It is a substance, and for this reason, various hydrogen gas-generating products have been developed in the fields of cosmetics, beauty products, and skin care products.

As a method of generating hydrogen gas in an aqueous solution, first, there is a method of generating hydrogen and oxygen by electrolyzing water to obtain hydrogen at the cathode and collecting it (Republic of Korea Patent Registration No. 10-1988686). In addition to being expensive, there is a problem in that sufficient contact time is not provided to the required part because the hydrogen gas dissolved in the aqueous solution rapidly flies into the air from the moment the final product is opened.

Accordingly, recently, compositions that generate hydrogen gas by dissolving hydrogen compounds of alkali metals or alkaline earth metals such as sodium, potassium, magnesium, and calcium in water have been developed. Usually, these hydrogen compounds react explosively when they come into contact with water. There is a problem that the gas is blown out at a time and the reaction is terminated in a short time, so that no more hydrogen gas is generated.

Accordingly, there is a need for a new composition for generating hydrogen gas in which a high concentration of hydrogen gas can be continuously generated for a certain period of time by controlling the generation concentration of hydrogen gas in an aqueous solution.

Korean Patent Registration No. 10-1988686

The present invention improves the problem that a metal salt-containing hydrogen compound as a material that reacts with water to generate hydrogen gas reacts quickly with water and instantaneously reacts with water to generate hydrogen, so that it cannot be used as it is. In order to do so, it is to control the reaction rate of a hydrogen compound that reacts quickly with water, and to provide a composition for generating hydrogen gas that is easy to handle.

In addition, the present invention uses a peptide that stably forms a self-assembled nanostructure through self-alignment between molecules in a solution, and a hydrogen gas generating composition including a self-assembled peptide that maximizes hydrogen gas generation and retention time, and hydrogen It is intended to provide a gas trapping nanostructure.

However, the problem to be solved by the present application is not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those of ordinary skill in the art from the following description.

In order to solve the above problems, the present invention provides a novel hydrogen gas generating composition using a nanostructure of a self-assembled peptide to generate hydrogen gas by dissolving a hydrogen compound in an aqueous solution while controlling the concentration and rate of the generation. The self-assembled peptide contained in the hydrogen gas generating composition creates a thin nano-film on the surface of the aqueous solution or the surface of a solid carrier or support to induce hydrogen gas to be contained in the aqueous solution, and to support hydrogen gas by hydrogen bonding force. While playing a role, it can be controlled so that a high concentration of hydrogen gas can be continuously generated for a certain period of time.

The present invention provides a composition for generating hydrogen gas comprising a self-assembly peptide, a hydrogen compound, an acid, and a carrier.

In addition, the present invention, a carrier for carrying a hydrogen gas generated by a hydrogen compound and an acid (acid); And it provides a hydrogen gas trapping nanostructure comprising a nano-membrane made of a self-assembled peptide formed on the outside of the carrier.

The hydrogen gas generating composition of the present invention provides an effect of continuously generating a high concentration of hydrogen gas for a certain period of time by controlling the generation of hydrogen gas when the composition of a mixture of a hydrogen compound and a self-assembled peptide is dissolved in an aqueous solution.

In addition, since the hydrogen gas generating composition of the present invention can be molded in any form such as powder type, granule type, tablet type, block type, etc., it provides an effect of easy handling.

1 is a graph showing a change in concentration of hydrogen gas over time of a composition for generating hydrogen gas according to Example 6 of the present invention.

The present invention relates to a novel hydrogen gas generation composition, a hydrogen gas trapping nanostructure, and a hydrogen gas generation control method using the same, which controls the generation of hydrogen gas using a self-assembled peptide nanostructure and maintains the hydrogen concentration in an aqueous solution.

More specifically, by using a self-assembled peptide that forms a thin nano-film on the interface between water and air in an aqueous solution or on the surface of a solid material, the rate of hydrogen gas generation in the composition is controlled to induce continuous generation, and the concentration of hydrogen in the aqueous solution. It relates to a composition capable of removing active oxygen from skin cells by maintaining and a method for controlling generation of hydrogen gas using the same.

The present invention relates to a novel hydrogen gas generating composition in which hydrogen gas is continuously generated in a solution by mixing a self-assembled peptide and a hydrogen compound to maintain a stable concentration for a certain period of time. It removes free radicals from cells and maintains moisture due to water molecules formed when hydrogen gas removes free radicals.

In general, hydride alkali metals such as lithium hydride (LiH), sodium hydride (NaH), and potassium hydride (KH), magnesium hydride (MgH ₂ ), calcium hydride (CaH ₂ ), hydrogenation to generate hydrogen gas by dissolving in water Hydrogenated alkaline earth metals such as barium (BaH ₂ ), beryllium hydride (BeH ₂ ), strontium hydride (SrH _{2 ), and borohydride metal salts such as lithium borohydride (LiBH 4} ) and sodium borohydride (NaBH ₄ ) as hydrogen compounds do.

The hydrogen compounds dissolve in water and generate hydrogen gas, and the reaction proceeds very violently to the extent that fine powders are scattered into the air.The hydrogen gas is released into the air at once within a short time and then the generation is completed and does not remain in the solution. Therefore, there is a problem in that it is difficult to use cosmetics or quasi-drugs for applying the reducing power of hydrogen gas.

In the present invention, the self-assembled peptide envelops the hydrogen compound, thereby mitigating the reactivity of the hydrogen compound when it comes into contact with water, and controlling the hydrogen gas to be continuously generated to maintain a stable concentration for a certain period of time. By forming a thin film in the form of a nano film at the interface between water and air or on the surface of solid materials, it controls the generation of hydrogen gas, protects the skin from external stimuli, and penetrates the skin cells with hydrogen gas and physiologically active substances in the composition. It provides an effect that helps.

<Hydrogen gas generating composition and hydrogen gas trapping nanostructure>

The hydrogen gas generating composition of the present invention includes a self-assembled peptide, a hydrogen compound, an acid and a carrier, and may further include one or more selected from a high molecular compound, a low molecular compound, other additives, and water.

In addition, the hydrogen gas trapping nanostructure of the present invention includes a carrier supporting hydrogen gas generated by a hydrogen compound and an acid; And a nano-membrane made of a self-assembled peptide formed outside the carrier.

Self-assembled peptide

The hydrogen gas generating composition or the hydrogen gas trapping nanostructure of the present invention includes a self-assembled peptide, and the self-assembled peptide may control hydrogen gas generation by forming a nano-film on the outside of a carrier to be described later.

In the present invention, the self-assembled peptide is a peptide sequence group having a structure of'X ^{1 aYX 2 b'.}

In the above formula, X ¹ and X ² are each independently a D- or L-type natural or non-natural amino acid or derivative thereof having a side chain capable of pi-pi interaction, and X ¹ And X ² may have the same sequence from each other, or may be left-right symmetric around Y. Specifically, X ¹ and X ² each independently contain one or more of D- or L-type tyrosine, tryptophan, alanine, phenylalanine, and derivatives thereof. can do.

In addition, Y is D- or L-type natural or unnatural cysteine, homocysteine, penicillamine, selenocysteine, histidine, lysine, It may be ornithine, aspartic acid, glutamic acid, asparagine or glutamine, and cysteine is preferred.

In addition, a and b are each independently the same or different integers of 1 to 10.

For example, the self-assembling peptide is composed of YYCYY (SEQ ID NO: 1), YYYCYYY (SEQ ID NO: 2), YYACAYY (SEQ ID NO: 3), YYAACAAYY (SEQ ID NO: 4), YFCFY (SEQ ID NO: 5) and derivatives thereof. It may mean a self-assembled nanostructure that is selected from the sequence of a group, and shows self-assembly to create a three-dimensional nanostructure by bonding of peptide molecules to each other in an aqueous solution even without applying external stimulus or energy. It is possible to form a thin, biocompatible nanofilm of nanometer thickness.

The term "amino acid" as used above refers to 20 amino acids found in nature and non-natural amino acids, amino acids that are modified after translation in vivo such as phosphoserine and phosphorthreonine; And other rare amino acids such as 2-aminoadipic acid, hydroxylysine, nor-valine, nor-leucine; It includes modifications to improve cell permeation or stability in vivo, and includes both D- and L-forms, which are enantiomers.

The terms used for the amino acids are natural and non-natural, the former refers to a type of compound found in cells, tissues or in vivo, and the latter refers to artificial modifications to such compounds for various purposes.

The term "peptide" as used above refers to the native amino acid or its degradation products, synthetic peptides, recombinantly produced peptides, peptide mimetics (typically synthetic peptides) and peptide analogs such as peptoids and semipeptoids. And those modified to improve cell penetration or stability in vivo, and such modifications are not limited thereto, but are not limited thereto, but N-terminal modifications, C-terminal modifications, -CH ₂ -NH-, -CH ₂ -S-,- Peptide bond modifications such as CH ₂ -S=O-, -CH ₂ -CH ₂ -, backbone modifications, and side chain modifications are included.

The term "pi-pi interaction" as used above refers to a bond formed by overlapping two pi orbital functions with each other by chemical bonds formed by pi electrons. The self-assembled peptide sequence used in the present invention includes such interactions. It includes an amino acid having a residue capable of functioning, for example, an amino acid having an aromatic side chain, such as tyrosine, tryptophan, or phenylalanine, and variants, derivatives or analogs thereof.

The term “crosslinking” as used above includes a coordination bond to a metal in an aqueous solution, an ionic bond to a surrounding ion, and a hydrogen bond to a hydrogen atom in a peptide molecule in addition to a covalent bond. The association of molecules can be induced by hydrogen bonding between surrounding water molecules. For example, it includes a disulfide bond through a thiol (-SH) functional group of the amino acid side chain, and is an amino acid capable of coordinating, ionic, and hydrogen bonding, such as cysteine, homocysteine, penicillamine, histidine, lysine, ornithine, arginine, Aspartic acid, glutamic acid, asparagine, or glutamine.

The self-assembled peptide may be easily formed in a large area by self-assembly, and may be formed in the form of a nano-membrane outside the carrier. Peptide monomers can grow into nanostructures, that is, films, which are structurally two-dimensional through disulfide bonds, coordination bonds by metal ions, ionic bonds, hydrogen bonds, and hydrophobic bonds with other peptide monomers. Amino acids capable of crosslinking associate peptides with other amino acids through covalent bonds, and can form nanostructures having a more robust flat surface.

The monomeric peptide forms a dimeric peptide by such a bond, and the peptide is continuously accumulated by the bond of amino acid side chains capable of pi-pi interaction in the dimeric peptide, and the face-to-face bond, and through lateral and vertical expansion, a solid monolayer or multilayer Structured nanostructures can be formed. The thickness of the single-layer structure is about 1.4 nm, and in the case of a multi-layer, various thicknesses are possible depending on the number of layers, and are about 50 to 400 nm.

In addition, the content of the self-assembled peptide may be included in an amount of 0.01 to 2.0% by weight, preferably 0.1 to 0.5% by weight, based on the total weight of the composition. When the self-assembly peptide is included within the above range, self-assembly is rapidly expressed and nanofilm formation is easy. If the content is lower than the above content range, the rate at which self-assembly is expressed is significantly lowered, so that the nanofilm is not formed, and when it is higher than the content range, other three-dimensional structures in the form of nanotubes or nanospheres are formed. Cases arise.

Hydrogen compound

The hydrogen gas generating composition or the hydrogen gas trapping nanostructure of the present invention includes a hydrogen compound, and in the present specification, the term "hydrogen compound" is used to include a substance capable of generating hydrogen by reacting with water. I can.

In the present invention, the hydrogen compound may include one or more of a metal powder, an alkali metal hydride, an alkaline earth metal hydride, and a metal borohydride salt.

Specifically, the hydrogen compound is a powder of an alkali metal or alkaline earth metal such as sodium, potassium, magnesium, and calcium; Alkali hydride metals, such as lithium hydride (LiH), sodium hydride (NaH), and potassium hydride (KH); Magnesium hydride (MgH _2), calcium hydride (CaH _2), barium hydride (BaH _2), beryllium hydride (BeH _2), strontium hydride alkaline earth metal hydride such as (SrH _2); And a combination of at least one selected from among borohydride metal salts such as lithium borohydride (LiBH ₄ ) and sodium borohydride (NaBH ₄ ), and in cosmetic terms, alkali metal hydride, alkaline earth metal hydride and metal borohydride It is preferable to contain at least one of them, and among them, magnesium hydride, calcium hydride, and sodium borohydride are relatively stable in air and are more preferable hydrogen compounds.

The content of the hydrogen compound may be included in an amount of 0.01 to 1.0% by weight, preferably 0.05 to 0.5% by weight, based on the total weight of the composition. When the hydrogen compound is contained within the above range, generation of hydrogen gas is effective, and when the content is lower than the above range, hydrogen gas is hardly generated, and when the content is higher than the above range, hydrogen gas is rapidly generated and the amount of generation It is inconvenient to use because it is difficult to control.

Acid

The hydrogen gas generating composition or hydrogen gas trapping nanostructure of the present invention contains an acid.

In general, when hydrogen compounds react with water, metal hydroxides are formed, so an aqueous solution in which they are dissolved becomes strongly alkaline. Acids are mixed to control this into a neutral to weakly acidic water-soluble composition.In particular, acids are used in which hydrogen compounds react with water. It can play a role in facilitating things.

In the present invention, the acid is preferably in a solid form, and includes at least one of organic acids and derivatives thereof, polymer carboxylic acids, amino acids, and inorganic acids, and may be a single component or a mixed component.

For example, as organic acids, carboxylic acids such as fumaric acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, tartaric acid, malic acid, citric acid, oxalic acid, malonic acid, ascorbic acid and various derivatives thereof, and polyacrylic acid, polymetha Amino acids such as polymeric carboxylic acids such as acrylic acid and glutamic acid are included, and inorganic acids may include sulfamic acid, boric acid, metaboric acid, boron oxide, and the like. In particular, since citric acid and/or succinic acid are registered as cosmetic raw materials, they are preferable in terms of being suitable for use as general cosmetic raw materials.

The content of the organic acid may be included in an amount of 0.1 to 5.0% by weight, preferably 0.5 to 2.0% by weight, based on the total weight of the composition. When the hydrogen compound is included within the above range, it is preferable to adjust the generation of hydrogen gas and minimize skin irritation by adjusting the pH of the final composition to 5.5 to 6.0. In the case of a content lower than the above range, hydrogen gas is generated slowly and it is difficult to expect an effect, and in the case of a content higher than the above range, hydrogen gas is rapidly generated within a short time and thus is not maintained for a certain period of time.

carrier

The hydrogen gas generating composition or hydrogen gas trapping nanostructure of the present invention includes a carrier, and the carrier serves to trap hydrogen gas generated by the hydrogen compound and acid.

In the present invention, the carrier is a solid material, which is a solid material at room temperature, and is a hydrophilic material that can be dissolved in water or mixed with water.

The carrier includes at least one hydrophilic solid material among inorganic substances in powder or particle form, natural polymer derivatives, and synthetic polymer derivatives.

Inorganic substances include calcium carbonate in powder and particle form, pearl powder, shell, bentonite, kaolin, etc., and in polymer form, it is a crosslinked natural polymer derivative such as starch, dextrin, cellulose, agarose, hyaluronic acid, chitosan, etc. Synthetic polymers such as polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, and the like may include derivatives in a single or combined form.

The content of the carrier may be included in an amount of 1.0 to 30% by weight, preferably 5 to 15% by weight, based on the total weight of the composition. When the carrier is included within the above range, generation of hydrogen gas can be effectively controlled, and the feeling of use of the entire composition is the most excellent, so it is preferable. When the content is lower than the above range, hydrogen gas is generated at a significantly lower concentration, and when the content is higher than the above range, the carrier does not dissolve in water, thereby reducing the feeling of use and causing discomfort.

High-molecular compounds and low-molecular compounds

The hydrogen gas generating composition or hydrogen gas trapping nanostructure of the present invention further includes at least one selected from a high molecular compound and a low molecular compound.

In the present invention, the polymer compound is a separate component from the carrier, is a water-soluble polymer material that is solid at room temperature and is soluble in water, and includes at least one of a synthetic polymer compound, a natural polymer compound, and a cellulose derivative. Specifically, synthetic polymer compounds include polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polymethacrylic acid or salts thereof, and natural polymer compounds include starch, dextrin, Carrageenan, xanthan gum, guar gum, xanthan gum, hyaluronic acid, chitosan, etc. are included, and as natural polymer derivatives, cellulose derivatives such as methylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, or salts thereof May be included.

The content of the polymer compound may be included in an amount of 30 to 90% by weight, preferably 60 to 80% by weight, based on the total weight of the composition. When the polymer compound is contained within the above range, it is preferable because the feeling of use of the entire composition is excellent and generation of hydrogen gas can be effectively controlled. When the content is lower than the above range, the composition ratio of the basic formulation material is low and the feeling of use is not very good, and when the content is higher than the above range, the composition ratio of the hydrogen generating materials is lowered and thus hydrogen gas is hardly generated.

In the present invention, the low molecular weight compound may include one or more of saccharides, amino acids and salts thereof, polyhydric alcohols, glycerin, carbonate and inorganic salts. Specifically, xylose, xylitol, glucose, glucitol, fructose, mannose, sorbitol multitol, sucrose, starch sugar, racuchitol, sucrose, maltose, trehalose, raffinose, cyclodextrin, etc. Monosaccharides and oligosaccharides; Amino acids such as glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, lysine, arginine, histidine, aspartic acid, glutamic acid, asparagine, glutamine, cysteine, methionine, serine, threonine, and proline, and salts thereof; Polyhydric alcohols such as butylene glycol, propylene glycol, pentylene glycol, and hexylene glycol; Glycerin, such as glycerin, diglycerin, and polyglycerin, may be included, and carbonates such as sodium hydrogen carbonate and sodium carbonate, inorganic salts such as sodium chloride, sodium sulfate, sodium nitrate, and sodium borate may be included.

The content of the low molecular weight compound may be included in an amount of 1.0 to 20% by weight, preferably 5.0 to 10% by weight, based on the total weight of the composition. When the low molecular weight compound is contained within the above range, it is preferable because the feeling of use of the entire composition is excellent and generation of hydrogen gas can be effectively controlled. If the content is higher than the above range, there is a disadvantage in that the effect is deteriorated by preventing the generation of hydrogen gas.

Other additives

The hydrogen gas generating composition or the hydrogen gas trapping nanostructure of the present invention may further include other pharmaceutically or cosmetically acceptable additives without denaturation when generating hydrogen gas.

Other additives in the present invention include retinol, retinyl palmitate, retinyl acetate, retinoic acid, coenzyme Q10, elastin, collagen, hyaluronic acid, ceramide, collagen, caffeine, chitosan, ascorbic acid, ascorbyl glucoside, alpha bisabolol, Vitamins such as tocopherol, tocopherol acetate, arbutin, niacinamide, adenosine, retinol acetate, vitamins A, D, E, peptides such as cuptripeptide-1, palmitoylpentapeptide-4, acetylhexapeptide-8, and It may be at least one selected from the group consisting of natural extracts, wherein the natural extract is avocado, moringa, aloe, green tea, ginseng, red ginseng, centella asiatica, pearl, wood vinegar, pine needles, ginkgo leaves, propolis, mulberry leaves, silkworms, snails Slime, Kakadu Plum, Kamukamu, Yasiyaza, Squalane, Caviar, Broccoli, Blueberry, Witch Hazel, Acerola, Chlorella, Mangosteen, Guava, Cornus, Carrot, Caffeine, Hamamelis, Spirulina, Salmon Roe, Ecklonia , Giant kelp, balsam, machihyeon, green raspberry, agaric, mulberry root, raspberry, raspberry, hepatica, hatban, edelweiss, chamomile, lavender, peppermint, eucalyptus, lemon balm, oregano, tea tree, gold, oleracea, mountain birch and citron It is preferably at least one selected from the group consisting of, but is not limited thereto, and includes all cosmetic ingredients and nutritional ingredients capable of delivering an effective effect to the skin.

In addition, in the present invention, water may be included as a residual amount, and the residual amount means a residual amount such that the weight of the total composition further including the essential components of the present invention and other components is 100% by weight.

As described above, according to the present invention, it is possible to obtain a new composition for generating hydrogen gas that allows a high concentration of hydrogen gas to be continuously generated for a predetermined period of time.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples.

<Example>

The concentration of hydrogen gas in the aqueous solution used in this example was measured using a dissolved hydrogen meter ENH-1000 (Trustlex), and the hydrogen compound magnesium powder, magnesium hydride, calcium hydride, sodium borohydride, etc. I did. Self-assembled peptides were extracted from natural peptide aqueous solutions such as dolphin peptide, oat peptide, wheat peptide, which are known as film forming agents, and separated, and then separated and purified to use a freeze-dried form. High-performance liquid chromatography (HPLC) All of the analysis confirmed the purity of 95% or more.

In the calculation of the composition ratio in the following examples, the “%” mark is “mass%” unless otherwise stated, and the generation of hydrogen gas over time is measured by changing the concentration and type of organic acids, hydrogen compounds, and self-assembled peptides in the basic formulation. I did.

Preparation of self-assembled peptide

Dolkong peptide (Glycine soja peptide, 10 wt% aqueous solution), oat peptide (Avena sativa peptide, 10 wt% aqueous solution), wheat peptide (Tricicum aestivum peptide, 10 wt% aqueous solution) were prepared from the peptide ingredients obtained in nature. The mixture was mixed in a volume ratio of 5:3:2, and 5 kg of the mixed peptide aqueous solution raw material was lyophilized for 10 days. After lyophilization, 435 g of the light brown powder obtained is dissolved in 2 L of water, mixed with ethyl acetate to remove organic impurities in the powder, extracted three times, and the aqueous layer is separated and purified by high performance liquid chromatography (Preparative high performance liquid). chromatography) was obtained by separating only the self-assembled peptide portion for each sequence. Separated YYCYY (SEQ ID NO: 1), YYYCYYY (SEQ ID NO: 2), YYACAYY (SEQ ID NO: 3), YYAACAAYY (SEQ ID NO: 4), YFCFY (SEQ ID NO: 5) aliquots were each concentrated with a rotary evaporator, and the resulting solution was added to 10 After freeze-drying for a day, all were secured in the form of white powder after freeze-drying. The obtained self-assembled peptide raw materials were all confirmed to have a purity of 95% or more by high-performance liquid chromatography (HPLC) analysis.

In the following Examples and Comparative Examples, pearl powder (origin: China), hydrogen compounds, and self-assembled peptides were dispersed in distilled water and allowed to stand at room temperature for 24 hours, so that the hydrogen compounds were completely decomposed into hydrogen gas and were impregnated in pearl powder. After confirmation, pearl powder dispersed in the aqueous solution was filtered to obtain. The powder impregnated with hydrogen gas was mixed with the basic formulation components to finally obtain a white powder.

The composition of the basic formulation powder is 45% by mass of dextrin, 15% by mass of xanthan gum, 5% by mass of trehalose, 5% by mass of hyaluronic acid, 2% by mass of sodium hydrogen carbonate, 1% by mass of sodium sulfate, 1% by mass of potassium citrate, 1% by mass of calcium carbonate %, 1% by mass of ascorbic acid, 1% by mass of aspartic acid, 1% by mass of glutamic acid, 1% by mass of sorbitol, and 1% by mass of Centella asiatica extract. Here, 10% by mass of various types of organic acids, 10% by mass of self-assembled peptide component, and 10% by mass of pearl powder impregnated with hydrogen gas were all mixed and pulverized, and then classified into a uniform powder form using a standard mesh. . After dissolving the prepared powder-type raw material in distilled water, the concentration of hydrogen gas in the aqueous solution was measured after 10 minutes, 30 minutes, 1 hour, 2 hours, and 6 hours, respectively.

Example 1

Pearl powder 10.0 g, magnesium powder 1.0 g, self-assembled peptide YYCYY (SEQ ID NO: 1) 1.0 g was dispersed in 100 ml of distilled water, allowed to stand at room temperature for 24 hours, and then filtered to obtain a powder. A hydrogen gas-generating composition powder was prepared by mixing 1.0 g of the obtained powder with 8.0 g of the basic formulation powder and 1.0 g of citric acid, and the resulting hydrogen gas concentration was measured after dissolving 0.5 g of the final powder in 25 ml of distilled water. It is summarized in Table 1.

Examples 2 to 15

Examples 2 to 15 were carried out in the same manner as in Example 1, with only different types of hydrogen compounds, self-assembling peptides, and/or organic acids.

The results according to the component composition change of Examples 2 to 15 are summarized in Table 1 below. In addition, the hydrogen gas concentration change over time of the hydrogen gas generating composition according to Example 6 is shown in FIG. 1.

division Hydrogen compound
(1.0 g) Self-assembly
Peptide (1.0 g) Organic acid
(1.0 g) Hydrogen gas generation concentration (ppb) 10 minutes 30 minutes 1 hours 2 hours 6 hours Example
One magnesium
powder YYCYY
(SEQ ID NO: 1) Citric acid 714 643 546 437 306 Example 2 Hydrogenation
magnesium YYCYY
(SEQ ID NO: 1) Citric acid 510 459 390 312 218 Example 3 Hydrogenation
calcium YYCYY
(SEQ ID NO: 1) Citric acid 408 367 312 250 175 Example 4 Boron hydride
salt YYCYY
(SEQ ID NO: 1) Citric acid 1,224 1,102 936 749 524 Example 5 Boron hydride
salt YYCYY
(SEQ ID NO: 1) Citric acid 1,020 959 882 776 621 Example 6 Boron hydride
salt YYYCYYY
(SEQ ID NO: 2) Citric acid 1,530 1,438 1,323 1,164 931 Example 7 Boron hydride
salt YYACAYY
(SEQ ID NO: 3) Citric acid 918 863 794 699 559 Example 8 Boron hydride
salt YYAACAAYY
(SEQ ID NO: 4) Citric acid 1,326 1,127 902 631 379 Example 9 magnesium
powder YFCFY
(SEQ ID NO: 5) Citric acid 765 719 662 582 466 Example 10 Hydrogenation
magnesium YYACAYY
(SEQ ID NO: 3) Citric acid 612 575 529 466 373 Example 11 Hydrogenation
calcium YYACAYY
(SEQ ID NO: 3) Citric acid 459 431 397 349 279 Example 12 magnesium
powder YYACAYY
(SEQ ID NO: 3) Succinic acid 610 572 525 461 370 Example 13 Hydrogenation
magnesium YYACAYY
(SEQ ID NO: 3) Succinic acid 510 479 441 388 310 Example 14 Hydrogenation
calcium YYACAYY
(SEQ ID NO: 3) Succinic acid 306 288 265 233 186 Example 15 Boron hydride
salt YYACAYY
(SEQ ID NO: 3) Succinic acid 969 911 838 737 590

Example 16

To measure the change in hydrogen gas evolution according to the change in the concentration of the hydrogen compound, pearl powder 10.0 g, sodium borohydride 2.0 g, and self-assembled peptide YYACAYY (SEQ ID NO: 3) 1.0 g were dispersed in 100 ml of distilled water and 24 at room temperature. After standing for a period of time, it was filtered to obtain a powder. A hydrogen gas-generating composition powder was prepared by mixing 1.0 g of the obtained powder with 8.0 g of the basic formulation powder and 1.0 g of citric acid, and the resulting hydrogen gas concentration was measured after dissolving 0.5 g of the final powder in 25 ml of distilled water. It is summarized in Table 2.

Examples 17-19

The same procedure as in Example 16 was conducted, and the concentration of hydrogen gas generation was compared by varying the amounts of sodium borohydride and the organic acid.

The results according to the composition ratio change of Examples 17 to 19 are summarized in Table 2 below.

division Hydrogen compound Self-assembly
Peptide Organic acid Hydrogen gas generation concentration (ppb) 10 minutes 30 minutes 1 hours 2 hours 6 hours Example
16 Boron hydride
salt
(2.0 g) YYACAYY
(SEQ ID NO: 3)
(1.0 g) Citric acid
(1.0 g) 1,010 949 873 768 615 Example 17 Boron hydride
salt
(2.0 g) YYACAYY
(SEQ ID NO: 3)
(1.0 g) Succinic acid
(1.0 g) 908 853 785 691 553 Example 18 Boron hydride
salt
(5.0 g) YYACAYY
(SEQ ID NO: 3)
(1.0 g) Citric acid
(0.5 g) 867 815 750 660 528 Example 19 Boron hydride
salt
(0.5 g) YYACAYY
(SEQ ID NO: 3)
(1.0 g) Citric acid
(2.0 g) 1,734 1,261 874 481 124

Example 20

To measure the change in hydrogen gas evolution according to the change in the concentration of the self-assembled peptide, 10.0 g of pearl powder, 1.0 g of sodium borohydride, and 10.0 g of the self-assembled peptide YYACAYY (SEQ ID NO: 3) were dispersed in 100 ml of distilled water and at room temperature. After standing at for 24 hours, it was filtered to obtain a powder. A hydrogen gas-generating composition powder was prepared by mixing 1.0 g of the obtained powder with 8.0 g of the basic formulation powder and 1.0 g of citric acid, and the resulting hydrogen gas concentration was measured after dissolving 0.5 g of the final powder in 25 ml of distilled water. It is summarized in Table 3.

Example 21 and Comparative Example 1

The same procedure as in Example 20 was carried out, and the concentration of hydrogen gas generation was compared by changing the amount of the self-assembled peptide.

The results according to the composition ratio change of Example 21 and Comparative Example 1 are summarized in Table 3 below.

division Hydrogen compound
(1.0 g) Self-assembled peptide Organic acid
(1.0 g) Hydrogen gas generation concentration (ppb) 10 minutes 30 minutes 1 hours 2 hours 6 hours Example
20 Boron hydride
salt YYACAYY (10.0 g)
(SEQ ID NO: 3) Citric acid 1,753 1,643 1,532 1,416 1,289 Example 21 Boron hydride
salt YYACAYY (5.0 g)
(SEQ ID NO: 3) Citric acid 1,653 1,543 1,432 1,216 1,193 Comparative Example 1 Boron hydride
salt - Citric acid 1,734 339 28 - -

As can be seen in Table 3, in the case of Comparative Example 1 in which the self-assembled peptide was not added, it was confirmed that no hydrogen gas was generated after 2 hours.

Example 22

In the final hydrogen gas generating composition, other peptides, which are known to improve skin wrinkles, were mixed as an additive to confirm the presence or absence of degeneration when hydrogen gas was generated.

Pearl powder 10.0 g, sodium borohydride 1.0 g, self-assembling peptide YYACAYY (SEQ ID NO: 3) 1.0 g, palmitoyl peptapeptide-4 (PP-4) 0.1 g dispersed in 100 ml of distilled water and allowed to stand at room temperature for 24 hours After filtration, a powder was obtained. A hydrogen gas-generating composition powder was prepared by mixing 1.0 g of the obtained powder with 8.0 g of the basic formulation powder and 1.0 g of citric acid, and the resulting hydrogen gas concentration was measured after dissolving 0.5 g of the final powder in 25 ml of distilled water. It is summarized in 4.

division Hydrogen compound Peptide Organic acid Hydrogen gas generation concentration (ppb) 10 minutes 30 minutes 1 hours 2 hours 6 hours Example 22 Boron hydride
salt YYACAYY
(SEQ ID NO: 3)
+ PP-4 Citric acid 1,530 1,424 1,311 1,177 923

In addition, after 6 hours, palmitoyl pentapeptide-4 was extracted from the aqueous solution using a dichloromethane organic solvent, and the presence of denaturation was confirmed using high-performance liquid chromatography (HPLC). It was confirmed that it was maintained.

<110> GOLDnSNOW WORLDWIDE INC. <120> A HYDROGEN GAS GENERATING COMPOSITION COMPRISING A SELF-ASSEMBLY PEPTIDE NANOSTRUCTURES <130> HY190411 <150> KR 10-2019-0116237 <151> 2019-09-20 <160> 5 <170> KoPatentIn 3.0 <210> 1 <211> 5 <212> PRT <213> Artificial Sequence <220> <223> Peptide forming nanostructure <400> 1 Tyr Tyr Cys Tyr Tyr 1 5 <210> 2 <211> 7 <212> PRT <213> Artificial Sequence <220> <223> Peptide forming nanostructure <400> 2 Tyr Tyr Tyr Cys Tyr Tyr Tyr 1 5 <210> 3 <211> 7 <212> PRT <213> Artificial Sequence <220> <223> Peptide forming nanostructure <400> 3 Tyr Tyr Ala Cys Ala Tyr Tyr 1 5 <210> 4 <211> 9 <212> PRT <213> Artificial Sequence <220> <223> Peptide forming nanostructure <400> 4 Tyr Tyr Ala Ala Cys Ala Ala Tyr Tyr 1 5 <210> 5 <211> 5 <212> PRT <213> Artificial Sequence <220> <223> Peptide forming nanostructure <400> 5 Tyr Phe Cys Phe Tyr 1 5

Claims (12)

A hydrogen gas generating composition comprising a self-assembly peptide, a hydrogen compound, an acid and a carrier.
The method according to claim 1,
The self-assembled peptide has a structure ^{of X 1} aYX ^{2 b,}
X ¹ and X ² each independently include a D- or L-type amino acid or a derivative thereof including a side chain capable of pi-pi interaction,
Y is D- or L-type cysteine, homocysteine, penicillamine, selenocysteine, histidine, lysine, ornithine, asparte Acid (aspartic acid), glutamic acid (glutamic acid), asparagine (asparagine) or glutamine (glutamine),
a and b are each independently an integer of 1 to 10, hydrogen gas generating composition.
The method according to claim 2,
X ¹ and X ² are each independently D- or L-type of tyrosine, tryptophan, alanine, phenylalanine, and one or more of these derivatives. Composition.
The method according to claim 2,
X ¹ and X ² are the same as each other or comprising a sequence symmetrical to each other about Y, hydrogen gas generating composition.
The method according to claim 2,
The self-assembled peptide is selected from a sequence consisting of YYCYY (SEQ ID NO: 1), YYYCYYY (SEQ ID NO: 2), YYACAYY (SEQ ID NO: 3), YYAACAAYY (SEQ ID NO: 4) and YFCFY (SEQ ID NO: 5) or derivatives thereof. That, hydrogen gas generating composition.
The method according to claim 1,
The hydrogen compound comprises at least one of a metal powder, an alkali metal hydride, an alkaline earth metal hydride, and a metal borohydride salt.
The method of claim 6,
The metal powder contains at least one selected from sodium, potassium, magnesium, and calcium powder,
The alkali metal hydride includes at least one selected from lithium hydride (LiH), sodium hydride (NaH) and potassium hydride (KH),
The alkaline earth metal hydride comprises magnesium hydride (MgH _2), calcium hydride (CaH _2), barium hydride (BaH _2), beryllium hydride (BeH ₂₎ strontium and hydrogenating at least one member selected from (SrH _2),
The boron hydride metal salt comprises at _{least one selected from lithium borohydride (LiBH 4} ) and sodium borohydride (NaBH ₄ ), hydrogen gas generating composition.
The method according to claim 1,
The acid includes one or more of organic acids and derivatives thereof, polymer carboxylic acids, amino acids and inorganic acids,
The organic acid and its derivatives include at least one selected from fumaric acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, tartaric acid, malic acid, citric acid, oxalic acid, malonic acid, carboxylic acid, ascorbic acid, and derivatives thereof. and,
The polymeric carboxylic acid includes at least one selected from polyacrylic acid and polymethacrylic acid,
The amino acid includes glutamic acid,
The inorganic acid comprises at least one selected from sulfamic acid, boric acid, metaboric acid and boron oxide, hydrogen gas generating composition.
The method according to claim 1,
The carrier is an inorganic material in the form of powder or particles, a natural polymer derivative, and a hydrophilic solid material comprising at least one of a synthetic polymer derivative.
The method of claim 9,
The inorganic material in the form of powder or particles includes at least one selected from calcium carbonate, pearl powder, shell, bentonite, and kaolin,
The natural polymer derivative includes at least one selected from starch, dextrin, cellulose, agarose, hyaluronic acid and chitosan,
The synthetic polymer derivative comprises at least one selected from polyethylene glycol, polyvinyl alcohol, polyacrylic acid and polymethacrylic acid, hydrogen gas generating composition.
The method according to claim 1,
The hydrogen gas generating composition further comprises at least one selected from a high molecular compound and a low molecular compound, hydrogen gas generating composition.
The method of claim 11,
The polymer compound includes at least one of a synthetic polymer compound, a natural polymer compound, and a cellulose derivative,
The synthetic polymer compound includes at least one selected from polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polymethacrylic acid, and salts thereof,
The natural polymer compound includes at least one selected from starch, dextrin, carrageenan, xanthan gum, guar gum, xanthan gum, hyaluronic acid and chitosan,
The cellulose derivative is methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxy methyl cellulose and a hydrogen gas generating composition comprising at least one selected from the salts thereof.

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