A composition for inhibiting degradation and odor of ergothioneine and use thereof

Abstract

The application discloses a composition for inhibiting degradation and odor of ergothioneine, which is compounded by ergothioneine, liquorice extract and cyclodextrin, and the mass ratio of the ergothioneine, the liquorice extract and the cyclodextrin is 1:(0.5-20):(5-200). The composition can improve the stability of the ergothioneine under high-temperature light, light and normal-temperature conditions in a solution and skin care products, inhibit degradation of the ergothioneine, and obviously improve product odor; in addition, the liquorice extract is a plant-derived extract, is widely applied and has good safety, and triterpenoids such as glycyrrhizic acid contained in the liquorice extract can synergistically improve the antioxidant effect of the ergothioneine, so that the composition can be well applied in the field of cosmetics. The application further discloses an application of the composition for inhibiting degradation and odor of ergothioneine.

Description

Technical Field

[0001] This invention relates to a composition for inhibiting ergothioneine degradation and odor, and its application. Background Technology

[0002] Ergothioneine (EGT), also known as 2-mercaptohistidine betaine, is a natural chiral amino acid antioxidant. Numerous studies both domestically and internationally have confirmed its remarkable efficacy in scavenging free radicals, inhibiting inflammation, promoting cellular immunity, and maintaining DNA synthesis and cell growth. Among many natural antioxidants, ergothioneine stands out; it not only chelates metal ions but also acts as an antioxidant in the stabilizing mechanisms of cellular metabolism, protecting cells from free radical damage. With its unique biological and pharmacological properties and safety profile, ergothioneine shows broad application prospects in cosmetics, functional foods, and biomedicine.

[0003] Ergothioneine, as a cosmetic ingredient, has excellent water solubility. However, in actual formulation and stability tests, it was found that the content of ergothioneine decreased significantly under high temperature, light, or strong acid and alkali conditions, and it produced a strong odor, affecting the stability of cosmetic products and giving consumers a poor user experience, thus limiting its use in products.

[0004] Patent application CN201910687360.6 discloses a combination of hyaluronic acid salt and ergothioneine, which can effectively inhibit the photodegradation of ergothioneine. This composition, used in food, health products, and cosmetics, exhibits good moisturizing properties and efficacy stability. Patent application CN202310054350.5 discloses an oil-controlling composition for cosmetics with oil-controlling effects, which can improve the photostability of ergothioneine. This oil-controlling composition combines ergothioneine with glucosylrutin and Vaccaria segetalis extract, improving the photostability of ergothioneine and exhibiting good oil-controlling effects. Patent application CN202310378084.1 discloses a stabilized ergothioneine formulation, which has beneficial effects such as good photostability and high transdermal penetration. However, the patent texts above did not evaluate the odor stability of ergothionein in the product, and only examined the degradation of ergothionein under light conditions, without proving whether ergothionein is equally stable under more extreme conditions such as high temperature and light. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a composition that inhibits the degradation and odor of ergothioneine, improves the stability of ergothioneine in solutions and skin care products, inhibits odor generation, and synergistically enhances its antioxidant effects.

[0006] Another object of the present invention is to provide an application of a composition that inhibits ergothioneine degradation and odor.

[0007] One technical solution to achieve the above objective is: a composition for inhibiting the degradation and odor of ergothioneine, which is composed of ergothioneine, licorice extract and cyclodextrin, wherein the mass ratio of ergothioneine, licorice extract and cyclodextrin is 1:(0.5-20):(5-200).

[0008] The composition described above for inhibiting the degradation and odor of ergothioneine, wherein the mass ratio of ergothioneine, licorice extract and cyclodextrin is 1:4:(50-200).

[0009] The above-mentioned composition for inhibiting the degradation and odor of ergothioneine, wherein the purity of the ergothioneine is above 99%; and the licorice extract is a powdered licorice extract with a glycyrrhizic acid content of above 3%.

[0010] The composition described above for inhibiting ergothioneine degradation and odor, wherein the cyclodextrin is any one or more of α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), and γ-cyclodextrin (γ-CD).

[0011] The above-mentioned composition for inhibiting ergothioneine degradation and odor, wherein the cyclodextrin is β-cyclodextrin (β-CD) and / or hydroxypropyl-β-cyclodextrin (HP-β-CD).

[0012] The present invention also provides the application of the above-mentioned composition for inhibiting ergothioneine degradation and odor as an antioxidant active ingredient in solutions or cosmetics.

[0013] The above-mentioned composition for inhibiting ergothioneine degradation and odor is used, wherein the cosmetic includes face cream, toner, and mask.

[0014] The application of the above-mentioned composition for inhibiting ergothioneine degradation and odor, wherein the face cream comprises the following components in the following mass fractions: 0.01-0.50 wt% acrylates, 0.8-1.2 wt% polydimethylsiloxane, 1-5 wt% glycerin, 0.01-0.30 wt% xanthan gum, 0.5-2 wt% glyceryl stearate, 1-3 wt% tridecyl trimellitate, 2-5 wt% pentanediol, 0.05-0.15 wt% aminomethylpropanol, 0.0065-2 wt% ergothioneine and its composition, and the balance being water; the sum of the mass fractions of all components of the face cream is 100 parts.

[0015] The above-mentioned composition for inhibiting ergothioneine degradation and odor is used in a solution or cosmetic, wherein the ergothioneine content in the solution or cosmetic is 0.001 wt% to 0.1 wt%.

[0016] The above-mentioned composition for inhibiting ergothioneine degradation and odor is used, wherein the ergothioneine content in the solution or cosmetic is 0.001 wt% to 0.04 wt%.

[0017] The above-mentioned composition for inhibiting ergothioneine degradation and odor is used, wherein the ergothioneine content in the solution or cosmetic is 0.01 wt%.

[0018] The technical solution of the composition for inhibiting ergothioneine degradation and odor of the present invention and its application involves compounding ergothioneine with licorice extract and cyclodextrin. This can improve the high-temperature and light stability of ergothioneine in aqueous solutions, repair waters, and cream formulations, and can also significantly inhibit the abnormal odor produced by ergothioneine under various conditions. In addition, licorice extract is a plant-derived extract with wide applications and good safety. The triterpenoids such as glycyrrhizic acid contained therein can synergistically enhance the antioxidant efficacy of ergothioneine. This composition can be well applied in the cosmetic field. Attached Figure Description

[0019] Figure 1 The HPLC chromatogram is shown after standardization of a solution containing ergothioneine.

[0020] Figure 2 HPLC chromatogram for ergothioneine-containing repair water standardization;

[0021] Figure 3 This is an HPLC chromatogram of a face cream containing ergothioneine for standardization. Detailed Implementation

[0022] To enable those skilled in the art to better understand the technical solution of this invention, its specific embodiments are described in detail below:

[0023] Example 1: Stability of a composition of ergothioneine, licorice extract, and cyclodextrin in an aqueous solution containing 1,2-pentanediol

[0024] Licorice extract powder and β-cyclodextrin (or hydroxypropyl-β-cyclodextrin) were dissolved in an aqueous solution containing 3 wt% 1,2-pentanediol. The solution was vortexed until completely dissolved, and then 0.01 wt% or 0.04 wt% ergothioneine powder was added. Control schemes 4 and 5 consisted of an aqueous solution containing only 0.01 wt% or 0.04 wt% ergothioneine in a 3 wt% 1,2-pentanediol solution. The solutions for schemes 1–5 are shown in Table 1 below.

[0025] Table 1 shows the content of each component in schemes 1-5:

[0026]

[0027]

[0028] Products from schemes 1 to 5 were placed for 7 days under five different conditions: 5℃, 25℃, 49℃, room temperature under light, and 40℃+ under light. Samples were taken on the second and seventh days to test the ergothioneine content in the solution. The ergothioneine content in the solution stored at 5℃ in each scheme was used as a control. The degradation rate of ergothioneine content was calculated using the following formula:

[0029]

[0030] Where C0 represents the ergothioneine content of the sample at 5℃, and C N The content of ergothioneine after treatment at 25℃, 49℃, room temperature light exposure, and 40℃+ light exposure was determined.

[0031] Please see Figure 1 Ergothioneine content was determined by high-performance liquid chromatography (HPLC) under the following conditions: column: HILIC-Z column (100 mm × 2.1 mm, 2.7 μm); column temperature: 35 ℃; mobile phase: 0.05 wt% formic acid & 0.1 wt% triethylamine aqueous solution: acetonitrile (30:70); flow rate: 0.2 mL / min; detection wavelength: 258 nm; injection volume: 2 μL; ergothioneine elution time: 2.6 min. Solution samples and repair water samples could be directly filtered through a 0.45 μm filter before HPLC injection. Cream samples required pretreatment: approximately 1 g of sample was weighed into a 10 mL volumetric flask, diluted to the mark with pure methanol, sonicated for 10 min, centrifuged at 3000 rpm for 10 min, and the supernatant was filtered through a 0.45 μm filter before HPLC injection. The degradation rates of ergothioneine content in the solutions for each method are shown in Table 2.

[0032] Table 2. Results of Ergothionein Degradation Rate in Solution:

[0033]

[0034]

[0035] Three evaluators conducted sensory evaluations of the odor of the samples in each group of schemes. The odor levels were defined as follows: 1. No odor; 2. Slight odor, acceptable; 3. Odor, acceptable; 4. Obvious odor, unacceptable; 5. Odor too strong, intolerable. The average value was used as the final odor level of the sample, and the results are shown in Table 3.

[0036] Table 3, Odor Evaluation Results:

[0037]

[0038] The results in Tables 2 and 3 show that ergothioneine undergoes significant degradation under light exposure at 40℃+ and room temperature, and the samples produce a noticeable off-odor. However, combining licorice extract powder and β-cyclodextrin (or hydroxypropyl-β-cyclodextrin) with ergothioneine inhibits the degradation of ergothioneine under light exposure at 40℃+ and room temperature, while also reducing the off-odor in the samples.

[0039] Example 2: Stability of the ergothioneine, licorice extract, and cyclodextrin composition in a repair water. The preparation processes for repair waters in schemes 6, 7, and 8 are as follows:

[0040] In beaker A, add glycerol and butylene glycol raw materials, mix well, then add a purified aqueous solution containing disodium ethylenediaminetetraacetate. Stir and heat to 80-85℃, then start cooling. When the temperature of the material in the beaker drops to 75℃, add p-hydroxyacetophenone raw material, stir until completely dissolved, continue cooling to 45℃, add 1,2-pentanediol raw material, stir and mix well, and cool to room temperature. Take a sample to test the pH, and adjust the pH of the material to 5.0-5.5 with a pH adjuster. In beaker B, dissolve licorice extract powder and β-cyclodextrin (or hydroxypropyl-β-cyclodextrin) in an aqueous solution containing 3wt% 1,2-pentanediol, vortex until the powder is completely dissolved, add ergothioneine powder and continue stirring until fully dissolved. Add beaker B to beaker A, homogenize for 5 minutes until well mixed. In control scheme 8, beaker B contains only 3wt% 1,2-pentanediol aqueous solution containing ergothioneine; the rest of the process is the same as schemes 6 and 7. The repair water formulas for schemes 6 to 8 are shown in Table 4.

[0041] Table 4, Content of each component in schemes 6-8:

[0042]

[0043] The repair water products in schemes 6-8 were placed for 7 days under five conditions: 5℃, 25℃, 49℃, room temperature light, and 40℃+ light. Samples were taken on the second and seventh days to test the ergothioneine content and evaluate the odor level. Please refer to [link to relevant documentation]. Figure 2 The ergothioneine content was determined using high-performance liquid chromatography (HPLC), and the content testing method and odor grade classification were the same as in Example 1. The degradation rate of ergothioneine in the repaired aquatic products is shown in Table 5. The odor grade evaluation of the repaired aquatic products is shown in Table 6.

[0044] Table 5. Results of Ergothionein Degradation Rate in Repair Water:

[0045]

[0046] Table 6. Odor Level Evaluation Table for Repaired Aquatic Products:

[0047]

[0048] According to the results in Tables 5 and 6, the combination of licorice extract powder and β-cyclodextrin (or hydroxypropyl-β-cyclodextrin) with ergothioneine can inhibit the degradation of ergothioneine under light at 40℃+ and at room temperature, while also reducing the generation of off-flavors in aquatic products.

[0049] Example 3: Stability of a composition of ergothioneine, licorice extract and cyclodextrin in a face cream

[0050] The preparation processes for face creams in schemes 9-11 are as follows:

[0051] In beaker A, add acrylate / C10-30 alkanol acrylate crosspolymer and xanthan gum. Add glycerol, pentylene glycol, and purified water, disperse evenly, and heat to 80-85℃. In beaker B, add glycerol stearate / PEG-100 stearate, tridecyl trimellitate, and polydimethylsiloxane, and heat and stir until homogeneous. Mix phases A and B thoroughly and homogenize (6000 rpm, 5 min). After homogenization, begin cooling. When the temperature drops to 45℃, take a sample to test the pH and adjust the pH of the mixture to 5.0-5.5 using a pH adjuster. In beaker C, dissolve licorice extract powder and β-cyclodextrin (or hydroxypropyl-β-cyclodextrin) in an aqueous solution containing 3 wt% 1,2-pentanediol. Vortex until the powder is completely dissolved. Add ergothioneine powder and continue stirring until fully dissolved. Add beaker C to the homogenized mixture of phases A and B, and homogenize for 5 minutes until evenly mixed. In control group Scheme 11, beaker C contained a 3 wt% aqueous solution of 1,2-pentanediol containing only ergothioneine; the remaining processes were the same as in Schemes 9 and 10. The cream formulations for Schemes 9–11 are shown in Table 7.

[0052] Table 7 shows the content of each component in schemes 9-11:

[0053]

[0054]

[0055] The face cream products in schemes 9-11 were placed for 14 days under five conditions: 5℃, 25℃, 49℃, room temperature light exposure, and 40℃+ light exposure. Since no obvious off-odor appeared in any samples on the seventh day, the stability test period was extended to fourteen days. Samples were taken on the second and fourteenth days to test the ergothioneine content and evaluate the odor level. Please refer to [link to relevant documentation]. Figure 3The ergothioneine content was determined using high-performance liquid chromatography (HPLC), and the content testing method and odor grade classification were the same as in Example 1. The degradation rate of ergothioneine in the face cream is shown in Table 8. The odor grade evaluation of the face cream is shown in Table 9.

[0056] Table 8. Results of Ergothionein Degradation Rate in Face Cream Products:

[0057]

[0058] Table 9. Evaluation Table of Odor Grades for Face Cream Products:

[0059]

[0060]

[0061] According to the results in Tables 8 and 9, the combination of licorice extract powder and β-cyclodextrin (or hydroxypropyl-β-cyclodextrin) with ergothioneine can inhibit the degradation of ergothioneine under light at 40℃+ and room temperature light, while reducing the generation of odor in face cream products.

[0062] Example 4: Free radical scavenging test of ergothioneine, licorice extract and cyclodextrin solution

[0063] Sample A is an aqueous solution containing 0.04 wt% ergothioneine; Sample B is an aqueous solution containing 0.04 wt% ergothioneine and 2 wt% β-cyclodextrin; Sample C is an aqueous solution containing 0.04 wt% ergothioneine, 2 wt% β-cyclodextrin and 0.16 wt% licorice extract; Sample D is an aqueous solution containing 0.16 wt% licorice extract; Sample E is an aqueous solution containing 0.16 wt% licorice extract and 2 wt% β-cyclodextrin; Sample F is an aqueous solution containing 2 wt% β-cyclodextrin; and Sample G is an aqueous solution containing 0.04 wt% ergothioneine and 0.16 wt% licorice extract.

[0064] Weigh 10 mg of DPPH, dissolve it in anhydrous ethanol using sonication, and bring the volume to 100 mL (0.1 mg / mL). Dilute sample AE 50 times with anhydrous ethanol. Divide the 96-well microplate into sample and blank groups, with two replicates per group. For the sample group, add 150 μL of sample solution + 150 μL of DPPH ethanol solution; for the blank group, add 150 μL of sample solution + 150 μL of anhydrous ethanol. Protect the plate from light. After adding the solution, incubate at room temperature in the dark for 30 min, shaking well. Measure the absorbance at 517 nm. Calculate the DPPH scavenging rate for each sample using the following formula:

[0065] Clearance rate = [1 - (Asample - Asampleblank) / (Acontrol - Acontrolblank)] x 100%

[0066] In the formula:

[0067] Asample: The absorbance of the sample group was measured.

[0068] Asampleblank: Absorbance measurement of the blank sample group;

[0069] Acontrol: The control group measures absorbance.

[0070] Acontrolblank: The control group measures absorbance.

[0071] For substances with large differences in antioxidant activity, the synergistic effect is evaluated by comparing it to the ratio of the theoretical summation value, i.e., the theoretical summation value = the sum of the antioxidant activity values ​​of individual substances. When the measured value > the theoretical summation value, the two have a synergistic effect; when the measured value = the theoretical summation value, the two have an additive effect; when the measured value < the theoretical summation value, the two have an antagonistic effect. The results are shown in Table 10.

[0072] Table 10. DPPH scavenging rate results for samples A to F:

[0073] sample DPPH removal rate Synergy assessment Sample A 43.6％ - Sample B 40.8％ Antagonism Sample C 53.9％ Collaboration Sample D 4.3％ - Sample E 1.3％ Antagonism Sample F 0.2％ - Sample G 49.7％ Collaboration

[0074] Based on the results in Table 10, it can be seen that when ergothioneine is combined with licorice extract and β-cyclodextrin (sample C), its DPPH scavenging rate is higher than that of the individual compounds ergothioneine, licorice extract, and β-cyclodextrin (the sum of samples A, D, and F). Sample C is also higher than the sum of the DPPH scavenging rates of the solution synthesized from one of the ergothioneine, licorice extract, and β-cyclodextrin groups and the individual components of the other group (the sum of samples B, D, F, and G).

[0075] Comparative Example 1: Stability of ergothioneine and other compositions in deionized aqueous solutions containing 1,2-pentanediol

[0076] 0.16 wt% licorice extract, 0.16 wt% green tea extract, 0.16 wt% black tea extract, 0.16 wt% grape seed extract, 0.16 wt% perilla leaf extract, 0.16 wt% rosemary extract, 0.16 wt% yucca extract, 0.16 wt% myrrh resin extract, 2 wt% β-cyclodextrin, and 2 wt% hydroxypropyl-β-cyclodextrin were dissolved in an aqueous solution containing 3 wt% 1,2-pentanediol. After vortexing until the powder was completely dissolved, 0.04 wt% ergothioneine powder was added to each of the following: licorice extract, green tea extract, black tea extract, grape seed extract, perilla leaf extract, rosemary extract, yucca extract, myrrh resin extract, β-cyclodextrin, and hydroxypropyl-β-cyclodextrin were added sequentially as Comparative Examples 1 to 10.

[0077] The solution products of Comparative Examples 1-10 were placed for 7 days under three conditions: 5°C, 49°C, and 40°C + light. Samples were taken on the seventh day to test the ergothioneine content and evaluate the odor level. The content testing method and odor level classification were the same as in Example 1. The degradation rate results of ergothioneine content in Comparative Examples 1-10 are shown in Table 11, and the odor level evaluation of Comparative Examples 1-10 is shown in Table 9.

[0078] Table 11, Results of Ergothionein Content Degradation Rate in Comparative Examples 1-10:

[0079]

[0080] Table 12, Odor rating table for comparative examples 1-10:

[0081]

[0082] In Comparative Example 6, the evaluators all reported that there were other odors besides fishy smell in the samples exposed to light at 49℃ and 40℃+.

[0083] Based on the results in Tables 11 and 12, it can be seen that when plant extracts or cyclodextrins such as licorice extract, green tea extract, black tea extract, grape seed extract, perilla leaf extract, rosemary extract, yucca extract, myrrh resin extract, β-cyclodextrin, and hydroxypropyl-β-cyclodextrin are combined with ergothioneine to form a solution, compared with Scheme 5 in Example 1 (containing only 0.04 wt% ergothioneine in a 3 wt% 1,2-pentanediol aqueous solution), the green tea extract, black tea extract, grape seed extract, and perilla leaf extract all promote the... Ergothioneine degraded under light conditions at 49°C and 40°C+, and the odor rating was poor. Samples containing rosemary extract exposed to light at 49°C and 40°C+ exhibited odors other than a fishy smell, and their odor ratings were also unsatisfactory. Yucca extract and myrrh resin extract showed no significant inhibitory effect on ergothioneine degradation. Licorice extract, β-cyclodextrin, and hydroxypropyl-β-cyclodextrin all inhibited the degradation of ergothioneine under light conditions at 49°C and 40°C+, and the odor ratings of the corresponding three comparative examples were superior to those of Scheme 5 in Example 1.

[0084] In summary, the composition of the present invention for inhibiting ergothioneine degradation and odor can improve the stability of ergothioneine under high temperature, light, and room temperature conditions in solutions and skin care products, inhibit the degradation of ergothioneine, and significantly improve the odor of products. In addition, licorice extract is a plant-derived extract with wide applications and good safety. The triterpenoids such as glycyrrhizic acid contained therein can synergistically enhance the antioxidant efficacy of ergothioneine. This composition can be well applied in the cosmetic field, especially suitable for repair water and face cream. This composition performs best in face cream.

[0085] Those skilled in the art should recognize that the above embodiments are merely illustrative of the present invention and are not intended to limit the present invention. Any variations or modifications to the above embodiments that are within the spirit and essence of the present invention will fall within the scope of the claims of the present invention.

Claims

1. A composition for inhibiting ergothioneine degradation and odor, characterized in that, It is a compound made of ergothioneine, licorice extract and cyclodextrin, wherein the mass ratio of ergothioneine, licorice extract and cyclodextrin is 1:(0.5-20):(5-200); The purity of the ergothioneine is over 99%; the licorice extract is a powdered licorice extract with a glycyrrhizic acid content of over 3%. The cyclodextrin used is β-cyclodextrin and / or hydroxypropyl-β-cyclodextrin.

2. The composition for inhibiting ergothioneine degradation and odor as described in claim 1, characterized in that, The mass ratio of ergothioneine, licorice extract and cyclodextrin is 1:4:(50-200).

3. The use of a composition for inhibiting ergothioneine degradation and odor as described in any one of claims 1 to 2 as an antioxidant active ingredient in cosmetics.

4. The application of the composition for inhibiting ergothioneine degradation and odor as described in claim 3, characterized in that, The cosmetics include face creams, toners, and face masks.

5. The application of the composition for inhibiting ergothioneine degradation and odor as described in claim 4 in a face cream, characterized in that, The face cream comprises the following components by mass fraction: 0.01-0.50 wt% acrylates, 0.8-1.2 wt% polydimethylsiloxane, 1-5 wt% glycerin, 0.01-0.30 wt% xanthan gum, 0.5-2 wt% glyceryl stearate, 1-3 wt% tridecyl trimellitate, 2-5 wt% pentanediol, 0.05-0.15 wt% aminomethylpropanol, 0.0065-2 wt% ergothioneine and its composition, with the balance being water; the sum of the mass fractions of all components of the face cream is 100 parts.

6. The application of the composition for inhibiting ergothioneine degradation and odor as described in claim 3, characterized in that, When the composition is used in cosmetics, the ergothioneine content in the cosmetic is 0.001 to 0.1 wt%.

7. The application of the composition for inhibiting ergothioneine degradation and odor as described in claim 6, characterized in that, The ergothioneine content in the cosmetic is 0.001–0.04 wt%.

8. The application of the composition for inhibiting ergothioneine degradation and odor as described in claim 7, characterized in that, The ergothioneine content in the cosmetic is 0.01 wt%.

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