Odor-improving composition of ergothioneine and tannin substances and preparation method of odor-improving composition

Abstract

The invention relates to an odor-improving composition of ergothioneine and tannin substances and a preparation method of the odor-improving composition, and belongs to the technical field of ergothioneine. The composition is formed by compounding ergothioneine and tannin substances according to the mass ratio of (1-120): 1, and preferably, the mass ratio is (1-100): 1. The tannin substance is selected from tannin from a plant source or a chemically synthesized tannic acid substance. According to the composition, through chemical crosslinking and synergistic effects of thiol groups of ergothioneine and phenolic hydroxyl groups of tannin, the oxidation resistance is remarkably improved, and the problems of oxidation odor production, volatile odor release and the like are effectively inhibited. In addition, the preparation method is environmentally friendly, controllable, high in product stability and suitable for the fields of cosmetics, medicine and food.

Description

Technical Field

[0001] The present invention belongs to the technical field of ergothioneine, and relates to an odor-improving composition of ergothioneine and tannin substances and a preparation method thereof. Background Art

[0002] As a natural sulfur-containing amino acid antioxidant, ergothioneine (EGT) has been widely used in the fields of cosmetics, medicine, and food in recent years due to its excellent free radical scavenging ability, anti-inflammatory properties, and cell protection function. However, although the mercapto (-SH) structure in its molecule endows it with high activity, it also causes it to be easily degraded under light, high temperature, or extreme pH conditions, generating irritating by-products (such as hydrogen sulfide), seriously affecting the stability of the product and the user experience. Research shows that the retention rate of ergothioneine in a cosmetic formula can drop to 77.5% after two weeks of light exposure, accompanied by obvious abnormal odors, which has become the core bottleneck restricting its commercial application.

[0003] Currently, the industry mainly alleviates the degradation and odor problems of ergothioneine by compounding other ingredients or optimizing the formulation process, but there are the following deficiencies: 1. The contradiction between stability and cost: Although mainstream compounding schemes (such as the combination of licorice extract and cyclodextrin) can improve the light stability and mask abnormal odors, the inhibitory effect on the synergistic action of high temperature and light is limited, and abnormal odors may still be generated after long-term storage, and the compounding ratio needs to be precisely controlled (such as the mass ratio of licorice extract to ergothioneine as high as 20:1), significantly increasing the cost. 2. Functional interference: Some antioxidants (such as polyphenolic substances) may interfere with the biological activity or transdermal absorption efficiency of ergothioneine, weakening its core efficacy. 3. Process complexity: Supramolecular complexes (such as silicone elastomer active substances or ginsenoside binding) rely on non-covalent bonds such as hydrogen bonds and hydrophobic interactions, and the preparation process requires strict control of the solvent ratio and temperature, making it difficult to scale up production. Summary of the Invention

[0004] The purpose of the present invention is to provide an odor-improving composition of ergothioneine and tannin substances and a preparation method thereof. By introducing tannin substances to act synergistically with ergothioneine, its stability under extreme conditions is significantly improved and the generation of abnormal odors is inhibited.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An odor-improving composition of ergothioneine and tannin substances, wherein the composition is a compound of ergothioneine and tannin substances in a mass ratio of 1-120:1.

[0007] As a preferred technical solution of the present invention, the tannin substances are selected from plant-derived tannins or chemically synthesized tannic acid substances.

[0008] As a preferred technical solution of the present invention, the ergothioneine and tannin substances are compounded according to a preferred mass ratio of 1 to 100:1.

[0009] A preparation method of an odor-improving composition of ergothioneine and tannin substances, the specific steps of the preparation method are as follows.

[0010] Add the tannin substances to PBS buffer solution, ultrasonicate for 30 to 60 min, add ergothioneine, stir in the dark at a rotation speed of 450 to 550 r / min at 25 to 37 °C for 6 to 10 h, wash with deionized water and measure the Zeta potential of the solution within the range of -10 to 10 mV, centrifuge for 10 to 20 min, and then freeze-dry at -30 °C for 12 h to obtain the odor-improving composition.

[0011] As a preferred technical solution of the present invention, the tannin substances and PBS buffer solution are mixed according to a mass ratio of (3 to 5):(95 to 97).

[0012] As a preferred technical solution of the present invention, the pH of the PBS buffer solution is 6 to 6.8.

[0013] As a preferred technical solution of the present invention, the ultrasonic power is 6 to 8 kHz.

[0014] As a preferred technical solution of the present invention, the centrifugation speed is 6000 to 8000 r / min.

[0015] An application of an odor-improving composition of ergothioneine and tannin substances in the preparation of cosmetics, medicine and food fields.

[0016] In a buffer system with a pH of 5 to 7, the present invention ingeniously utilizes the electrostatic attraction between ergothioneine and tannin substances. On this basis, stable hydrogen bonds are formed between the phenolic hydroxyl groups of tannins and the thiol groups and amino groups of ergothioneine. This intermolecular interaction further enhances the stability of the composition structure. In the medium of the buffer solution, the molecules of ergothioneine and tannin substances constantly collide, and the positive and negative charge regions preferentially combine. Through charge neutralization and various intermolecular forces, a combined system is gradually constructed. The preparation process of the present invention has the following advantages: First, no exogenous chemical reagents are introduced throughout the preparation process, effectively avoiding the potential toxicity risks that exogenous reagents may bring, and at the same time protecting the original biological activities of ergothioneine and tannin substances from being damaged. Second, the present invention adopts a one-step assembly strategy, without the need for cumbersome multi-step activation or cross-linking reactions, which not only simplifies the operation steps but also effectively shortens the overall production cycle and significantly improves production efficiency. Third, by precisely regulating the charge density, the present invention effectively reduces the aggregation phenomenon between particles and ensures good dispersibility between the composition particles. Finally, through freeze-drying treatment, the stability and storage properties of the composition obtained in the present invention are significantly improved. This treatment can not only resist the influence of adverse environmental factors but also greatly facilitate the long-term storage and transportation of the product, further broadening the application scope and market potential of the product.

[0017] In the 2-mercaptohistidine structure of ergothioneine, the lone pair electrons of the sulfhydryl group (-SH) exhibit high reactivity due to the imidazole ring conjugation effect and are prone to undergo three degradation pathways: oxidative cleavage: reacting with reactive oxygen species to generate sulfinic acid (-SO2H) or disulfide bond (-S-S-), releasing volatile sulfides such as H2S; metal-catalyzed hydrolysis: transition metal ions generate hydroxyl radicals through the Fenton reaction, accelerating the oxidation of the sulfhydryl group; basic dissociation: when pH > 7, the proton of the sulfhydryl group is lost, and the oxidative half-life is shortened.

[0018] The ortho-phenolic hydroxyl groups of tannic acid form multiple intermolecular hydrogen bonds with the sulfhydryl groups of ergothioneine. The hydrogen bonds force the sulfhydryl groups to face the inner side of the benzene ring, restricting the conformational inversion of the sulfhydryl groups through steric hindrance and reducing the contact area with oxygen / free radicals; at the same time, the strong electronegativity of the hydroxyl groups lowers the electron cloud density of the sulfur atom through hydrogen bonds, inhibiting its nucleophilic attack tendency, thereby effectively inhibiting the generation of volatile sulfides.

[0019] The π electron cloud of the benzene ring of tannic acid undergoes delocalization with the 3p empty orbital of the sulfhydryl group of ergothioneine. The π electrons of the benzene ring partially fill the empty orbital of the sulfur atom, reducing the oxidation activity of the sulfhydryl group; the conjugation effect restricts the rotational freedom of the sulfhydryl group and prevents it from being exposed to the oxidative microenvironment. This hyperconjugated system significantly increases the oxidation activation energy of the sulfhydryl group, thereby preventing the oxidation of the sulfhydryl group in ergothioneine.

[0020] The catechol structure of tannic acid forms a five-membered ring chelate with transition metal ions. The chelation prevents the metal ions from catalyzing the generation of hydroxyl radicals from H2O2, effectively blocking the Fenton reaction. The chelation of tannic acid with transition metal ions effectively inhibits the coordination of sulfur and metal, avoiding the direct binding of metal ions to sulfhydryl groups and triggering electron transfer, and significantly reducing the oxidation rate of sulfhydryl groups.

[0021] In addition, the carboxylic acid group of tannic acid and the imidazole ring of ergothioneine form a buffer system, stabilizing the solution pH within the range of 5.0 - 6.5. At this pH, the sulfhydryl group exists in the form of -SH rather than the easily oxidized -S-, and its oxidation half-life is extended to 4.3 times that under neutral conditions. Meanwhile, the acidic environment also prevents the nucleophilic substitution reaction of the sulfhydryl group with water molecules, effectively inhibiting the occurrence of hydrolysis side reactions and further protecting the stability of the ergothioneine molecule.

[0022] The compounding of tannin substances and ergothioneine can further enhance the role of ergothioneine as an antioxidant. Both tannin substances and ergothioneine have excellent antioxidant properties. They can scavenge free radicals through different mechanisms and reduce the damage of oxidative stress to cells. When these two components are compounded in a certain proportion, tannin substances and ergothioneine can cooperate with each other to enhance each other's antioxidant effect, thus providing more comprehensive antioxidant protection. In addition to the antioxidant effect, tannin substances and ergothioneine can also protect cells from damage by inhibiting inflammatory reactions and reducing apoptosis, thus maintaining the normal function and structure of cells.

[0023] The beneficial effects of the present invention:

[0024] (1) Through the preparation method of the present invention, ergothioneine and tannin substances form a stable structure. Under the conditions of 60 °C or sunlight irradiation, the odor stability of ergothioneine can be maintained for more than one month, far exceeding the prior art (for example, the compounding scheme of licorice extract only maintains for two weeks), fully meeting the stringent requirements of the cosmetics industry for the stability of raw materials.

[0025] (2) Tannic acid has a wide source and can be obtained by natural extraction or chemical synthesis. Compared with other compounding raw materials (such as hyaluronic acid, licorice extract, polyphenols, ginsenosides, etc.), the cost is lower, without complex compounding or high-precision control, greatly reducing the production cost and facilitating large-scale commercial promotion.

[0026] (3) Tannin substances stabilize the structure of ergothioneine through multiple mechanisms, effectively reducing degradation by-products, avoiding interference with its antioxidant activity, and ensuring the full play of the core efficacy of ergothioneine. At the same time, after the compounding of tannin substances and ergothioneine, they also act synergistically through their respective unique antioxidant mechanisms. Not only is the ability to scavenge free radicals enhanced, but also oxidative stress damage can be alleviated, providing more comprehensive antioxidant protection. In addition, this combination also exhibits the ability to inhibit inflammatory responses and reduce apoptosis, achieving multiple cell protections.

[0027] (4) There are many choices of tannin substances, and natural sources such as persimmon tannin meet the safety standards of cosmetic raw materials, have no irritation or sensitization risks, and are suitable for the development of sensitive skin products. Detailed implementation method

[0028] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following combines examples to detail the specific implementation method, structure, characteristics, and effects according to the present invention as follows.

[0029] Example 1

[0030] A preparation method of an odor-improving composition of ergothioneine and tannin substances, the specific steps of the preparation method are as follows,

[0031] Add tannin substances to a PBS buffer solution with a pH of 6.5, ultrasonicate for 45 min, add ergothioneine, the ultrasonic power is 7 kHz, stir in the dark at 33 °C at a rotation speed of 500 r / min for 8 h, wash with deionized water and measure the Zeta potential of the solution in the range of -10 to 10 mV, centrifuge at a rotation speed of 7000 r / min for 15 min, and then freeze-dry at -30 °C for 12 h to obtain the odor-improving composition.

[0032] In this example, the compounding mass ratio of ergothioneine to chemically synthesized tannic acid is 10:1.

[0033] Example 2

[0034] A preparation method of an odor-improving composition of ergothioneine and tannin substances, the specific steps of the preparation method are as follows,

[0035] Add tannin substances to a PBS buffer solution with a pH of 6, ultrasonicate for 30 min, add ergothioneine, the ultrasonic power is 6 kHz, stir in the dark at 25 °C at a rotation speed of 450 r / min for 6 h, wash with deionized water and measure the Zeta potential of the solution in the range of -10 to 10 mV, centrifuge at a rotation speed of 6000 r / min for 10 min, and then freeze-dry at -30 °C for 12 h to obtain the odor-improving composition.

[0036] In this example, the compounding mass ratio of ergothioneine to chemically synthesized tannic acid is 20:1.

[0037] Example 3

[0038] A method for preparing an odor-improving composition of ergothioneine and tannin substances, the specific steps of the preparation method are as follows,

[0039] Add the tannin substances to a PBS buffer solution with a pH of 6.8, ultrasonicate for 60 min, add ergothioneine, the ultrasonic power is 8 kHz, stir in the dark at 37 °C at a rotation speed of 550 r / min for 10 h, wash with deionized water and measure that the Zeta potential of the solution is in the range of -10 to 10 mV, centrifuge at a rotation speed of 8000 r / min for 20 min, and then freeze-dry at -30 °C for 12 h to obtain the odor-improving composition.

[0040] In this example, the compounding mass ratio of ergothioneine to chemically synthesized tannic acid is 50:1.

[0041] Example 4

[0042] In this example, the compounding mass ratio of ergothioneine to chemically synthesized tannic acid is 70:1, and the remaining steps are the same as those in Example 1.

[0043] Example 5

[0044] In this example, the compounding mass ratio of ergothioneine to chemically synthesized tannic acid is 100:1, and the remaining steps are the same as those in Example 1.

[0045] Example 6

[0046] In this example, the compounding mass ratio of ergothioneine to chemically synthesized tannic acid is 1:1, and the remaining steps are the same as those in Example 1.

[0047] Example 7

[0048] In this example, chemically synthesized tannic acid is replaced with persimmon tannin, and the remaining steps are the same as those in Example 1.

[0049] Example 8

[0050] In this example, chemically synthesized tannic acid is replaced with Chinese gallnut tannin, and the remaining steps are the same as those in Example 1.

[0051] Example 9

[0052] In this example, chemically synthesized tannic acid is replaced with witch hazel tannin, and the remaining steps are the same as those in Example 1.

[0053] Example 10

[0054] In this embodiment, chemically synthesized tannic acid is replaced with tannic acid, and the remaining steps are the same as those in Example 1.

[0055] Comparative Example 1

[0056] In this comparative example, chemically synthesized tannic acid is replaced with citric acid, and the remaining steps are the same as those in Example 1.

[0057] Comparative Example 2

[0058] In this comparative example, chemically synthesized tannic acid is replaced with zinc PCA, and the remaining steps are the same as those in Example 1.

[0059] Comparative Example 3

[0060] In this comparative example, chemically synthesized tannic acid is replaced with disodium EDTA, and the remaining steps are the same as those in Example 1.

[0061] Comparative Example 4

[0062] In this comparative example, chemically synthesized tannic acid is replaced with sodium phytate, and the remaining steps are the same as those in Example 1.

[0063] Comparative Example 5

[0064] In this comparative example, chemically synthesized tannic acid is replaced with sodium gluconate, and the remaining steps are the same as those in Example 1.

[0065] Comparative Example 6

[0066] In this comparative example, no chemically synthesized tannic acid is added, and the remaining steps are the same as those in Example 1.

[0067] Comparative Example 7

[0068] Only ergothioneine and chemically synthesized tannic acid are mechanically mixed, and the remaining steps are the same as those in Example 1.

[0069] The examples and comparative examples are mixed with deionized water at a mass ratio of 1:99, placed for one month under light conditions and at a high temperature of 60 °C, and tested for the generation of peculiar smell. The experimental data are sorted out in the following table.

[0070] One month of light exposure One month at a high temperature of 60°C Example 1 No obvious change in smell No obvious change in smell Example 2 No obvious change in smell No obvious change in smell Example 3 No obvious change in smell No obvious change in smell Example 4 No obvious change in smell No obvious change in smell Example 5 No obvious change in smell No obvious change in smell Example 6 No obvious change in smell No obvious change in smell Example 7 No obvious change in smell No obvious change in smell Example 8 No obvious change in smell No obvious change in smell Example 9 No obvious change in smell No obvious change in smell Example 10 No obvious change in smell No obvious change in smell Comparative example 1 A fishy smell is produced A fishy smell is produced Comparative example 2 A fishy smell is produced A fishy smell is produced Comparative example 3 A fishy smell is produced A fishy smell is produced Comparative example 4 A fishy smell is produced A fishy smell is produced Comparative example 5 A fishy smell is produced A fishy smell is produced Comparative example 6 A distinct fishy smell is produced A distinct fishy smell is produced Comparative example 7 A slight fishy smell is produced A slight fishy smell is produced

[0071] From the data of the examples and comparative examples, it can be seen that the compounding of ergothioneine and tannin substances in a certain proportion significantly improves their stability under extreme conditions and effectively inhibits the generation of peculiar smell.

[0072] The above are only the preferred embodiments of the present invention and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above in the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments by using the disclosed technical content without departing from the technical solution of the present invention. However, as long as it does not depart from the technical solution content of the present invention, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. An odor-improving composition of ergothioneine and tannins, characterized in that, The composition is a compound of ergothioneine and tannin substances in a mass ratio of 1 to 120:

1.

2. The improved odor composition of ergothioneine and tannin substances according to claim 1, wherein The tannin substances are selected from tannins of plant origin or tannic acid substances synthesized chemically.

3. The composition for improving odor containing ergothioneine and tannin substances according to claim 1, wherein, The ergothioneine and tannin substances are preferably compounded in a mass ratio of 1 to 100:

1.

4. A method for preparing an odor-improving composition of ergothioneine and tannins as described in any one of claims 1 to 3, characterized in that, The specific steps of the preparation method are as follows. Add the tannin substances to PBS buffer, ultrasonicate for 30 to 60 min, add ergothioneine, stir in the dark at a rotation speed of 450 to 550 r / min at 25 to 37 °C for 6 to 10 h, wash with deionized water and measure the Zeta potential of the solution within the range of -10 to 10 mV, centrifuge for 10 to 20 min, and then freeze-dry at -30 °C for 12 h to obtain the odor-improving composition.

5. The preparation method of an odor-improving composition of ergothioneine and tannins according to claim 4, characterized in that, The tannin substances and PBS buffer are mixed in a mass ratio of (3 to 5):(95 to 97).

6. The preparation method of an odor-improving composition of ergothioneine and tannin substances according to claim 4, characterized in that, The pH of the PBS buffer is 6 to 6.

8.

7. The preparation method of an odor-improving composition of ergothioneine and tannin substances according to claim 4, characterized in that, The ultrasonic power is 6 to 8 kHz.

8. The preparation method of an odor-improving composition of ergothioneine and tannins according to claim 4, characterized in that, The centrifugation speed is 6000 to 8000 r / min.

9. Use of an odor-improving composition of ergothioneine and tannin substances according to any one of claims 1 to 3 in the preparation of cosmetics, pharmaceuticals and the food field.