Composition with synergistic anti-oxidation effect as well as preparation method and application thereof

By combining linolenic acid and silk fibroin in a specific ratio, a synergistic antioxidant composition is formed, which solves the problems of scarce antioxidant raw materials and insufficient efficacy in existing technologies, and achieves a highly efficient and safe antioxidant effect. It is suitable for scenarios such as post-medical aesthetic care, scar repair and sensitive skin care.

CN121926832APending Publication Date: 2026-04-28SHANGHAI ZHONGYI DAILY CHEM CO LTD +1
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Patent Information

Application Number
CN202610247050.2
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2026-03-02
Publication Date
2026-04-28

AI Technical Summary

Technical Problem

In existing technologies, the application of antioxidant raw materials such as linolenic acid and silk fibroin in Class II medical device products is limited, making it difficult to meet the high-efficiency antioxidant needs in special scenarios such as post-medical aesthetic repair, scar care, and sensitive skin care, and there is a lack of in-depth exploration of the synergistic effects of compound formulations.

Method used

By combining linolenic acid and silk fibroin in a specific ratio, a composition with synergistic antioxidant effects is formed. Through the complementary mechanism of fat-soluble and water-soluble components, a dual complementarity of free radical scavenging and skin barrier protection is achieved, enhancing antioxidant efficiency and improving system stability through intermolecular interactions.

Benefits of technology

It achieves a clear synergistic antioxidant effect with a synergistic index greater than 1, and its antioxidant efficiency is superior to that of a single ingredient. It is suitable for a variety of skin care formulations, meets diverse skin care needs, and has good biocompatibility and safety. It is suitable for Class II medical device products and cosmetics.

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Abstract

The invention relates to the field of antioxidant compositions, in particular to a composition with a synergistic antioxidant effect and a preparation method and application thereof. The core components of the composition are linolenic acid and silk fibroin, the synergistic index is greater than 1 after the linolenic acid and the silk fibroin are compounded, the synergistic effect percentage is up to 9.9%, and the antioxidant effect is obviously superior to that of a single component. The composition is wide in application scene, not only can meet the requirements of post-art nursing, scar repair management, daily skin care of sensitive skin and the like, but also can be matched with various common skin care dosage forms such as cream, facial masks and essence, the system stability and bioavailability are improved through intermolecular interaction, the effect is lasting and stable, and the composition has extremely high practical value.
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Description

Technical Field

[0001] This invention relates to the field of antioxidant compositions, and more particularly to a composition with synergistic antioxidant effects, its preparation method, and its application. Background Technology

[0002] As a core branch of anti-aging skincare, antioxidant skincare products are experiencing continuous growth, driven by evolving consumer skincare needs, ongoing innovation in beauty technology, and increasingly pronounced market segmentation. Today, antioxidant products are no longer limited to traditional cosmetic products. With the rapid development of the medical aesthetics industry, post-treatment skincare following anti-aging procedures such as phototherapy has become a new demand scenario, creating a market gap for medical device-grade antioxidant products and driving the antioxidant skincare field towards a diversified approach combining cosmetic and medical device applications.

[0003] In the research of antioxidant raw materials, the antioxidant value of linolenic acid and silk fibroin has been recognized by the academic community. As a natural component rich in unsaturated fatty acids, linolenic acid's antioxidant mechanism mainly involves directly capturing and scavenging free radicals in the body through its own structure, reducing the damage of free radicals to skin cells. Silk fibroin, derived from natural silk, possesses excellent biocompatibility due to its unique amino acid sequence and molecular configuration. It can also efficiently scavenge free radicals by regulating oxidative stress responses. Both have solid theoretical and practical support for their application in the field of antioxidants, laying a solid foundation for the research and development of compound compositions.

[0004] However, existing technologies have certain limitations. Class II medical device products have extremely high requirements for the safety of raw materials, resulting in a very limited variety of available antioxidant raw materials. This makes it difficult to meet the high-efficiency antioxidant needs in special scenarios such as post-medical aesthetic repair, scar care, and sensitive skin maintenance. While there have been previous applications of single-ingredient antioxidants, there has been a lack of in-depth exploration of the synergistic effects of combining two ingredients. Therefore, providing compositions with synergistic antioxidant effects can compensate for the shortcomings of existing technologies, such as the shortage and insufficient efficacy of antioxidant raw materials registered as medical devices, and provides an innovative direction for developing multifunctional and highly safe antioxidant skincare products. Summary of the Invention

[0005] To address the aforementioned technical problems, the first aspect of this invention provides a composition with synergistic antioxidant effects, wherein the raw materials for its preparation, by mass parts, include 90-100 parts water, 0.001-20 parts unsaturated fatty acids and 0.001-20 parts natural protein, and the synergistic index of the composition is >1.

[0006] Furthermore, the raw materials for preparing the composition with synergistic antioxidant effect include, by mass parts, 90-100 parts water, 0.1-1 parts unsaturated fatty acids and 0.5-1 parts natural protein, and the synergistic index of the composition is >1.

[0007] As an example of implementation, the unsaturated fatty acid in the composition has a mass concentration of 0.001-1 wt%.

[0008] Furthermore, the mass concentration of the unsaturated fatty acid in the composition is 0.1-1 wt%.

[0009] As an example of implementation, the natural protein has a mass concentration of 0.001-1 wt% in the composition.

[0010] Furthermore, the mass concentration of the natural protein in the composition is 0.5-1 wt%.

[0011] As an example of implementation, the raw materials for preparing the composition include, by weight, 95-100 parts water, 0.001-1 parts unsaturated fatty acids and 0.001-1 parts natural protein.

[0012] Furthermore, the raw materials for preparing the composition, by mass parts, include 95-100 parts water, 0.1-1 parts unsaturated fatty acids, and 0.5-1 parts natural protein.

[0013] Furthermore, the raw materials for preparing the composition, by mass parts, include 98.5-99 parts water, 0.1-1 parts unsaturated fatty acids, and 0.5-1 parts natural protein.

[0014] As an implementable example, the unsaturated fatty acids include one or more of linolenic acid, docosahexaenoic acid, eicosapentaenoic acid, oleic acid, linoleic acid, or arachidonic acid.

[0015] Furthermore, the linolenic acid mentioned includes α-linolenic acid and / or γ-linolenic acid.

[0016] As an example of an implementation, the natural protein includes one or more of silk fibroin, collagen, whey protein, soy protein, or sericin.

[0017] The synergistic antioxidant effect of linolenic acid and silk fibroin primarily stems from the dual complementarity of free radical scavenging mechanisms and skin barrier protection functions. As a lipid-soluble "direct quenching" antioxidant, linolenic acid, through its unsaturated bonds, can penetrate the skin's lipid barrier and act on the cell membrane level, directly neutralizing superoxide anions and hydroxyl radicals, blocking the oxidation chain reaction, and reducing lipid peroxidation damage to the cell membrane. Simultaneously, it can replenish intercellular lipids, participate in the synthesis of the stratum corneum lipid membrane, and enhance the integrity of the skin barrier to reduce oxidative triggers. Meanwhile, water-soluble silk fibroin is a "direct scavenging + indirect activating" antioxidant. Its amino acid side chain groups, such as tyrosine and histidine, can capture free radicals and chelate metal ions to inhibit free radical generation in the skin surface and stratum corneum. It can also regulate the activity of endogenous antioxidant enzymes. Furthermore, its excellent biocompatibility and film-forming properties can repair damaged keratinocytes and form a moisturizing protective film, providing a basic platform for antioxidant activity. Both enhance antioxidant efficiency and improve the skin's tolerance to oxidative damage through a free radical scavenging network that covers the entire "surface-to-deep" layer and dual protection of "lipid barrier replenishment + protein structure repair," achieving synergistic effects.

[0018] Meanwhile, the synergistic effect of the two is also enhanced by the improved system stability brought about by intermolecular interactions. The hydrophilic groups such as hydroxyl and amino groups in silk fibroin molecules can form hydrogen bonds or electrostatic interactions with the carboxyl groups of linolenic acid, effectively improving the water solubility and dispersion stability of linolenic acid, preventing its aggregation and failure, and reducing the oxidative degradation of linolenic acid itself; while the film-forming properties of silk fibroin fix linolenic acid at the site of action on the skin, delaying its volatilization and loss, and prolonging the duration of active action. In addition, both have good biocompatibility, no obvious sensitization, and meet the safety requirements of raw materials for medical device products. No toxic products are generated during the synergistic effect. Through the complementary physicochemical properties, the antioxidant system is more stable and the efficacy is more lasting, ultimately achieving a technical effect with a synergy index (SI) > 1.

[0019] A second aspect of the present invention provides a method for preparing a composition with synergistic antioxidant effects, comprising: mixing unsaturated fatty acids, natural proteins and water, and dissolving them completely to obtain a composition with synergistic antioxidant effects.

[0020] A third aspect of the present invention provides the application of a composition having a synergistic antioxidant effect in Class II medical device products and cosmetics.

[0021] Beneficial effects (a) The combination of linolenic acid and silk fibroin produces a clear synergistic effect, with synergy indices greater than 1 and a synergistic effect percentage of up to 9.9%. The antioxidant efficiency is better than that of a single component, and it can more effectively scavenge free radicals and block oxidative damage.

[0022] (ii) Both of the components in the composition, silk fibroin and linolenic acid, have been recorded as Class II medical devices and their safety has been verified. This solves the problem of the scarcity of available antioxidant raw materials for medical device products and can be used in compliance with Class II medical device regulations.

[0023] (III) The composition is suitable for various scenarios such as post-medical aesthetic care, scar repair management, and daily skin care for sensitive skin. It can also be used with a variety of commonly used skin care formulations such as creams, masks, and serums, making it highly practical.

[0024] (iv) The raw materials of the composition are all derived from nature, have no obvious allergenicity, and can be gently applied to the skin. It is suitable for daily anti-aging of healthy skin and can also meet the repair needs of damaged skin. It has a wide range of applicable people.

[0025] (v) Silk fibroin and linolenic acid can be combined through intermolecular hydrogen bonds or electrostatic interactions, which can improve the water solubility and dispersion stability of linolenic acid, reduce its oxidative degradation, and prolong the action time of active ingredients, thus ensuring the long-lasting and stable efficacy of the product. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the composition in Example 1.

[0027] Figure 2 This is a schematic diagram of the composition of Comparative Example 1.

[0028] Figure 3 This is a schematic diagram of the composition in Comparative Example 3. Detailed Implementation

[0029] Example 1 The first aspect of this example provides a composition with synergistic antioxidant effects, the raw materials of which include 98.5g water, 1g α-linolenic acid and 0.5g silk fibroin.

[0030] The second aspect of this example provides a method for preparing a composition with synergistic antioxidant effects, comprising: mixing α-linolenic acid, silk fibroin and water, and dissolving them completely to obtain a composition with synergistic antioxidant effects.

[0031] The third aspect of this example provides an application of a composition with synergistic antioxidant effects in Class II medical device products and cosmetics.

[0032] Example 2 This example provides a composition with synergistic antioxidant effects, the raw materials of which include 98.9g water, 0.1g α-linolenic acid and 1g silk fibroin.

[0033] Example 3 This example provides a composition with synergistic antioxidant effects, the raw materials of which include 99g water, 0.5g α-linolenic acid and 0.5g silk fibroin.

[0034] A schematic diagram of the composition in this example is shown below. Figure 3 As shown.

[0035] Comparative Example 1 This example provides a 0.5wt% aqueous solution of silk fibroin, which is prepared by means of 0.5g silk fibroin and 99.5g water.

[0036] A schematic diagram of the composition in this example is shown below. Figure 2 As shown.

[0037] Comparative Example 2 This example provides a 0.5wt% aqueous solution of alpha-linolenic acid, which is prepared by means of 0.5g of alpha-linolenic acid and 99.5g of water.

[0038] Comparative Example 3 This example provides a 0.5wt% alpha-linolenic acid ethanol solution, which is prepared from 0.5g alpha-linolenic acid and 99.5g ethanol.

[0039] A schematic diagram of the composition in this example is shown below. Figure 3 As shown.

[0040] Comparative Example 4 This example provides a 0.1wt% alpha-linolenic acid ethanol solution, which is prepared from 0.1g alpha-linolenic acid and 99.9g ethanol.

[0041] Comparative Example 5 This example provides a 1wt% alpha-linolenic acid ethanol solution, which is prepared by 1g of alpha-linolenic acid and 99g of ethanol.

[0042] Comparative Example 6 This example provides a 0.1wt% aqueous solution of silk fibroin, which is prepared by means of 0.1g silk fibroin and 99.9g water.

[0043] Comparative Example 7 This example provides a 1wt% aqueous solution of silk fibroin, which is prepared by using 1g of silk fibroin and 99g of water.

[0044] Comparative Example 8 This example provides an antioxidant composition prepared from 98.9g of water, 1g of α-linolenic acid and 0.1g of silk fibroin.

[0045] Antioxidant performance test Take the products from Examples 1-3 and Comparative Examples 1-8, add 10 mL of 3.7 mol / L sulfuric acid solution, mix thoroughly on a magnetic stirrer, and maintain at 55°C and 650 rpm for 3 min. Titrate with a prepared 0.001017 mol / L potassium permanganate solution until a faint pink color appears and does not fade within 30 s, recording the volume (mL) of potassium permanganate titrant consumed. Blank tests were performed simultaneously. All data have been subtracted for blanks: water blank = 0.10 mL, ethanol blank = 1.52 mL.

[0046] For detailed titration results, please refer to Table 1.

[0047] Table 1

[0048] The Synergy Index (SI) = Actual (volume of potassium permanganate solution consumed) / Expected sum; Synergistic effect percentage = [(actual value - expected sum) / expected sum] × 100%.

[0049] (1) Calculate the SI value of Comparative Example 8 The sum of Comparative Example 6 and Comparative Example 5 is used as the expected sum value, and Comparative Example 8 is used as the measured value. The SI of Comparative Example 8 can be calculated as 7.265 / (1.445+6)≈0.98, which means SI<1, indicating that there is no synergistic effect.

[0050] (2) Calculate the SI value of Example 1 The sum of Comparative Example 1 and Comparative Example 5 is used as the expected sum value, and Example 1 is used as the measured value; The SI of Example 1 can be calculated as 11.84 / (5.01+6)≈1.08, i.e. SI>1, indicating that there is a synergistic effect.

[0051] The synergistic effect percentage was calculated to be approximately 7.5% as [(11.84-11.01) / 11.01]×100%.

[0052] (3) Calculate the SI value of Example 2 The sum of Comparative Example 7 and Comparative Example 4 was used as the expected sum value, and Example 2 was used as the measured value; The SI of Example 2 can be calculated as 9.15 / (8.085+0.38)≈1.08, i.e. SI>1, indicating that there is a synergistic effect.

[0053] The synergistic effect percentage was calculated to be approximately 8.1% as [(9.15-8.465) / 8.465]×100%.

[0054] (4) Calculate the SI value of Example 3 The sum of Comparative Example 1 and Comparative Example 3 is used as the expected sum value, and Example 3 is used as the measured value; The SI of Example 3 can be calculated as 9.31 / (5.01+3.465)≈1.1, i.e. SI>1, indicating that there is a synergistic effect.

[0055] The synergistic effect percentage was calculated to be approximately 9.9% as [(9.31-8.475) / 8.475]×100%.

[0056] Based on the antioxidant performance test data and the calculation results of synergistic index and synergistic effect percentage of Examples 1-3 and Comparative Examples 1-8, it can be seen that the single linolenic acid and silk fibroin system did not show a synergistic antioxidant effect; while the composition prepared in Examples 1-3 of the present invention, through the compounding of linolenic acid and silk fibroin in a specific ratio, all showed a synergistic index greater than 1 and a synergistic effect percentage as high as 9.9%, which fully verified the clear synergistic antioxidant effect produced by the compounding of the two.

[0057] Experimental results show that the composition of this invention achieves a synergistic effect of antioxidant efficacy through the complementarity of fat-soluble linolenic acid and water-soluble silk fibroin in terms of free radical scavenging mechanism, skin barrier protection function, and physicochemical properties. Its antioxidant efficiency is significantly better than that of a single-component system. Furthermore, since all raw materials have a safety basis with Class II medical device usage records, this composition not only solves the industry pain points of scarce raw materials and insufficient efficacy in medical device-grade antioxidant products, but also provides an innovative solution that combines safety, effectiveness, and practicality for the development of Class II medical device products and cosmetics, thanks to its stable synergistic effect, wide applicability, and mild action.

Claims

1. A composition having a synergistic antioxidant effect, characterized in that, The raw materials for preparing the composition, by mass parts, include 90-100 parts water, 0.001-20 parts unsaturated fatty acids and 0.001-20 parts natural protein, and the synergistic index of the composition is >1.

2. The composition with synergistic antioxidant effect according to claim 1, characterized in that, The water and the unsaturated fatty acid in the composition have a mass concentration of 0.001-1 wt%.

3. The composition with synergistic antioxidant effect according to claim 1, characterized in that, The water and the natural protein in the composition have a mass concentration of 0.001-1 wt%.

4. The composition with synergistic antioxidant effect according to claim 1, characterized in that, The raw materials for preparing the composition, by mass, include 95-100 parts water, 0.001-1 parts unsaturated fatty acids and 0.001-1 parts natural protein.

5. The composition with synergistic antioxidant effect according to claim 1, characterized in that, The raw materials for preparing the composition, by mass parts, include 98.5-99 parts water, 0.001-1 parts unsaturated fatty acids and 0.001-1 parts natural protein.

6. The composition with synergistic antioxidant effect according to claim 1, characterized in that, The unsaturated fatty acids mentioned include one or more of linolenic acid, docosahexaenoic acid, eicosapentaenoic acid, oleic acid, linoleic acid, or arachidonic acid.

7. The composition with synergistic antioxidant effect according to claim 6, characterized in that, The linolenic acid mentioned includes α-linolenic acid and / or γ-linolenic acid.

8. The composition with synergistic antioxidant effect according to claim 1, characterized in that, The natural proteins mentioned include one or more of silk fibroin, collagen, whey protein, soy protein, or sericin.

9. A method for preparing a composition with synergistic antioxidant effect according to any one of claims 1-8, comprising: By mixing unsaturated fatty acids, natural proteins, and water until completely dissolved, a composition with synergistic antioxidant effects is obtained.

10. The application of a composition with synergistic antioxidant effect according to any one of claims 1-8, characterized in that, It is used in Class II medical devices and cosmetics.