Antioxidant composition and its applications

Abstract

The present invention provides a composition for skin antioxidant, belonging to the technical field of cosmetics. The composition of the present invention is characterized by containing hyaluronic acid lysine and ergothioneine in a ratio of 100-200:1, and may also contain a hyaluronic acid dimethylsilanol complex and / or panthenol, as well as common cosmetics preservatives. The composition of the present invention has significant moisturizing and anti-photoaging effects when used to prepare skin care products.

Description

Technical Field

[0001] The present invention belongs to the technical field of cosmetics, and relates to a skin care composition containing lysine hyaluronate and ergothioneine and its application in cosmetics. Background Art

[0002] Hyaluronic acid (HA) is a chain-like polyanionic mucopolysaccharide composed of repeating disaccharide units of (1-β-4) D-glucuronic acid and (1-β-3) N-acetyl-D-glucosamine. It is one of the main components of the extracellular matrix of the skin. Due to its significant lubricating and moisturizing effects, it is widely used in cosmetics. Lysine hyaluronate (LH) is an organic salt compound formed by the ionic bond combination of hyaluronic acid and L-lysine. Since HA binds to lysine with moisturizing, antioxidant and anti-allergic effects, in addition to having good moisturizing effects, it also has certain antioxidant effects, and has certain anti-aging and whitening effects when applied to skin care products. LH has been applied in the cosmetics field for more than ten years. Due to its weak antioxidant effect, it is mostly used as a moisturizer in skin care products.

[0003] Ergothioneine (EGT) is a natural sulfur-containing amino acid. It was first isolated from ergot fungi by French pharmacist Charles Tanret in 1909, and was later also found to exist in mushrooms such as Ganoderma lucidum and Tricholoma matsutake. Exogenous ergothioneine can scavenge reactive oxygen and nitrogen to protect cells from oxidative apoptosis damage, and is a highly efficient antioxidant. Since EGT can enter the cell mitochondria and exert an antioxidant effect more than 6 times that of astaxanthin, it is an ideal anti-aging ingredient. When applied to skin care products, it has effects such as whitening, radiation protection and anti-inflammation. EGT can inhibit lipid peroxidation damage, scavenge hydroxyl radicals (·OH), superoxide and singlet oxygen ( 1 O 2), and other reactive oxygen species (ROS) substances, and is an excellent skin photosensitizer protector [Reference: Markova N G, Karaman-Jurukovska N, Dong K K, et al. Skin cells and tissue are capable of using L-ergothioneine as an integral component of their antioxidant defense system. Free Radic Biol Med, 2009, 46(8): 1168-1176.]. The most direct manifestation of the body's aging is skin aging. In addition to the internal factors of natural aging, the factors causing skin aging also come from external factors such as the natural environment, trauma, and exposure to certain chemicals. The most common of these is sun exposure, i.e., photoaging. When ultraviolet radiation in sunlight irradiates human epidermal cells, it can produce 1 O 2 , ·OH and other harmful substances, inducing damage to DNA, proteins, and cell tissues, resulting in skin aging and damage. By irradiating a solution of the photosensitizer rhodamine B (RhB) with ultraviolet light to induce a free radical system including 1 O 2 (UV-RhB system), a skin photoaging model caused by reactive oxygen species generated by simulating ultraviolet irradiation of human skin was established to study the antioxidant performance of EGT. The results showed that the antioxidant performance of 0.75 mg / ml EGT was equivalent to that of 1 mg / ml vitamin C, and both had a good dose-effect relationship [Sun He, Wang Lili, Kang Chuanli, etc. Experimental study on the inhibition of free radicals induced by ultraviolet radiation by ergothioneine, Food and Drug, No. 6, 2023].

[0004] As one of the natural antioxidants with significant efficacy, EGT is used by many daily chemical enterprises in skin care products, and the market demand is increasing day by day. However, due to factors such as low yield, high production cost, and complex process in its production methods, whether it is biological extraction, chemical synthesis, or biosynthesis, the raw material price of EGT remains high, ranging from several hundred thousand yuan per kilogram, which limits its use.

[0005] The present invention combines EGT with LHA, uses a lower amount of EGT, and improves the antioxidant effect of LHA. The composition of the present invention is used to prepare cosmetics with anti-aging and whitening effects, reducing the production cost of the product while ensuring the effect. Summary of the Invention

[0006] The object of the present invention is to provide a skin antioxidant composition containing hyaluronic acid lysine and ergothioneine, and the application of the composition in the field of skin care cosmetics.

[0007] The technical solution adopted by the present invention is as follows:

[0008] A composition for skin antioxidant, characterized in that it contains at least two components, lysine hyaluronate and ergothioneine. Among them, the weight ratio of lysine hyaluronate to ergothioneine is 100-200:1, and preferably the weight ratio of lysine hyaluronate to ergothioneine is 120-150:1.

[0009] The lysine hyaluronate (LHA) is an organic salt formed by the ionic bond combination of hyaluronic acid and L-lysine. The number of L-lysine molecules combined with each disaccharide unit molecule constituting hyaluronic acid is 0.4-1, that is, the content range of L-lysine in LHA is 10-30% (g / g), and preferably the content range of L-lysine is 13-19% (g / g).

[0010] The ergothioneine (EGT), also known as 2-thioimidazole amino acid, with the chemical name of mercaptohistidine trimethyl inner salt, can be extracted from the fruiting bodies of edible fungi, pig blood, animal tissues, ergot and grains, or obtained by chemical synthesis methods, or obtained by biosynthesis fermentation methods, such as biosynthesizing, extracting and purifying by using the deep fermentation technology of fungal mycelium.

[0011] The average molecular weight range of the above lysine hyaluronate is 7 kDa-1000 kDa, preferably the average molecular weight range is 10 kDa-600 kDa, and more preferably the average molecular weight range is 100 kDa-300 kDa.

[0012] The skin antioxidant composition of the present invention is characterized by further containing a hyaluronic acid dimethylsilanol complex and / or panthenol. Among them, the hyaluronic acid dimethylsilanol complex can be a complex of dimethylsilanol and hyaluronic acid, or a complex of dimethylsilanediol and hyaluronic acid, or a mixture of the two. It can be obtained by using the disclosed preparation methods, such as mixing a hyaluronic acid solution and a sodium silanol solution and then adjusting the pH with a cation exchange resin to obtain an aqueous complex solution (FR2561915), mixing an aqueous silanol solution and an aqueous hyaluronic acid solution in proportion (EP0289366), reacting an organosilicon compound with hyaluronic acid in a water and ethanol solution and then evaporating the solvent (EP0867445), or reacting a chlorosilane with hyaluronic acid suspended in an organic solution and then obtaining a solid complex by precipitation (CN103450368). Among them, panthenol is selected from DL-panthenol, D-panthenol and / or L-panthenol, preferably D-panthenol. D-panthenol is also known as dextrorotatory panthenol, provitamin B5, and its chemical name is (R)-(+)-2,4-dihydroxy-N-(3-hydroxypropyl)-3,3-dimethylbutyramide. D-panthenol can be derived from chemical synthesis or from microbial fermentation extraction, including D-pantolactone obtained by microbial enzymatic or chemical methods and reacting with 3-aminopropanol to obtain D-panthenol.

[0013] The skin antioxidant composition of the present invention is characterized in that the content range of the hyaluronic acid dimethylsilanol complex is 0.05-20%, preferably 0.1-10%, more preferably 0.5-5%.

[0014] The skin antioxidant composition of the present invention is characterized in that the content range of panthenol is 0.05-5%, preferably 0.1-20%, preferably 0.5-10%, more preferably 1-5%.

[0015] The skin antioxidant composition of the present invention can be used to prepare single-dose products without preservatives, or multi-dose packaged products containing preservatives. The latter usually contains commonly used cosmetics preservatives, selected from methyl paraben, propyl paraben, p-methylbenzyl alcohol, 1,2-propanediol, 1,2-hexanediol, 1,2-pentanediol, p-hydroxyacetophenone, 3-[2-(ethylhexyl)oxy]-1,2-propanediol, 1,2-octanediol, butanediol, phenethyl alcohol, octyldecanol, and phenoxyethanol, or a mixture of one or more of them.

[0016] The skin antioxidant composition of the present invention is characterized in that it is embodied in the form of a gel and / or a solution. That is, the product form can be a gel, a solution, or a mixture of a gel and a solution. When the average molecular weight of lysine hyaluronate in the composition is relatively low and / or the content is relatively small, the product can be in a solution state; when the average molecular weight of lysine hyaluronate in the composition is relatively high and / or the content is relatively large, the product can be in a gel state.

[0017] The antioxidant composition of the present invention can be used to prepare skin-care cosmetics with moisturizing, anti-aging, and whitening effects.

[0018] The antioxidant composition of the present invention can be directly applied to the surface of facial and body skin, or the composition of the present invention can be diluted with purified water or added with common ingredients in cosmetics to be formulated into various forms such as solutions, gels, creams, ointments, or lotions. For example, toners, creams, facial masks, sunscreen creams, after-sun repair gels, body lotions, and moisturizing sprays, etc., for skin care of the body surface and face.

[0019] The antioxidant composition of the present invention can play roles such as preventing photoaging, reducing the formation of wrinkles and age spots when applied to the skin of the body surface. Detailed implementation manners

[0020] The following examples are for better illustrating the present invention and do not limit the present invention.

[0021] Example 1 The components and contents (g) in every 100 g of the antioxidant composition are as shown in the following table.

[0022] Table 1 Components and contents of antioxidant compositions with different formulations (%, g / g)

[0023]

[0024] According to the above composition formula, using lysine hyaluronate with different average molecular weights to prepare the following compositions can obtain products in a solution state or a gel state.

[0025] Table 2 States of compositions with different formulations

[0026]

[0027] The above compositions can be directly applied to the surface of facial and body skin, or can be diluted with purified water or added with common ingredients in cosmetics to be formulated into various forms such as solutions, gels, creams, ointments, or lotions. For example, various forms such as toners, creams, facial masks, sunscreen creams, after-sun repair gels, body lotions, and moisturizing sprays, etc., for skin care of the body surface and face.

[0028] For example, Composition 1-1 can be added to a conventional emollient lotion formulation at an addition amount of 10 parts; Composition 1-1 can be added to a conventional toner at an addition amount of 5 parts; Composition 1-3 can be diluted 3-fold with purified water to prepare a moisturizing spray; Composition 1-4 can be added to a conventional after-sun repair gel formulation at an addition amount of 3 parts; Composition 1-5 can be added to a conventional cream formulation at an addition amount of 2 parts.

[0029] Example 2 Inhibitory effect of different formulated antioxidant compositions on free radicals induced by ultraviolet radiation

[0030] Hyaluronic acid lysine with an average molecular weight of 360 kDa and a lysine content of 16.2% was selected, and samples with different ratios were prepared according to the following table.

[0031] Table 3 Main components and contents (mg / ml) of different ratio formulations

[0032]

[0033] Test for inhibiting free radicals induced by ultraviolet radiation

[0034] Determination was carried out according to the literature method [Sun He, Wang Lili, Kang Chuanli, etc. Experimental study on the inhibition of free radicals induced by ultraviolet radiation by ergothioneine, Food and Drug, Vol. 6, 2023]: Using phosphate buffer solution (PBS, pH 7.2, take 2.2 g of Na 2 HPO 4 , 0.3 g of NaH 2 PO 4 and 8.5 g of NaCl, dissolve in water and make up to 1000 ml) as the solvent, dilute the above sample 1000-fold as the test solution, and add rhodamine B solution (RhB) to a concentration of 0.001%. Place under ultraviolet light (wavelength 254 nm, light intensity 5 mW / cm 2 ) for irradiation. At 0 h and 1 h respectively, use an enzyme-labeled instrument to measure the absorbance at a wavelength of 555 nm ( A 0 and A 1 ), each sample in parallel for 3 replicates, calculate the average value of the change in absorbance at 0 h and 1 h (Δ A ), taking Δ A 空白 as the baseline, and calculate the antioxidant performance of the test sample according to the following formula ( F ).

[0035]

[0036] In the formula, Δ A 空白 : The change in absorbance of the blank control solution ( A0空白 - A 1空白 ); Δ A 样品 : The change amount of the absorption value of the sample solution ( A 0样品 - A 1样品 ).

[0037] And calculate the antioxidant performance (F value) of the active substances in the system. The results are as follows.

[0038] Table 4 Antioxidant performance of different test samples

[0039]

[0040] The results show that when the content of ergothioneine is reduced to 1 μg / ml, its inhibitory effect (antioxidant performance) on free radicals induced by ultraviolet radiation is only 1.16%. When combined with hyaluronic acid lysine contents of 110, 138, and 184 μg / ml, it can significantly increase the F value of the latter. For example, compared with group A, the F value of group D increased by 20%, showing an obvious synergistic effect. The addition of hyaluronic acid dimethylsilanol complex and panthenol can both increase the F value of the composition, and the addition of a small amount of ergothioneine can also significantly increase the F value of the composition. For example, compared with group G, the F value of group I increased by 12%, showing an obvious synergistic effect...

[0041] The above results show that: in the technical solution of the present invention, a lower amount of EGT is used in combination with LHA, and the two play a synergistic role, which can significantly improve the antioxidant capacity of the composition. Using it to prepare cosmetics with anti-aging and whitening effects can effectively reduce the raw material cost of the product while ensuring the antioxidant effect of the product.

Claims

1. A composition for skin antioxidant, characterized by comprising: a) hyaluronic acid lysine and b) ergothioneine; wherein, the weight ratio of hyaluronic acid lysine to ergothioneine is 120 - 150:1; the average molecular weight of the hyaluronic acid lysine is 10KDa - 600kDa, and the content range of L-lysine is 10 - 30% (g / g).

2. The composition according to claim 1, characterized in that it further contains a hyaluronic acid dimethylsilanol complex and / or panthenol.

3. The composition according to claim 1, characterized in that it further contains common cosmetics preservatives.

4. The composition according to any one of claims 1, 2, and 3, characterized in that the composition is embodied in the form of a gel and / or a solution.

5. Use of the composition according to any one of claims 1, 2, and 3 for preparing a skin care product.

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