Supermolecular composition for resisting sunlight damage as well as preparation process and application of supramolecular composition

Abstract

The invention discloses a supramolecular composition for resisting sunlight damage as well as a preparation method and application of the supramolecular composition, and belongs to the technical field of cosmetics. The supramolecular composition disclosed by the invention is prepared from nicotinamide, 4-hydroxyethylpiperazine ethanesulfonic acid and riboflavin. The invention also provides a preparation method of the supramolecular composition, which comprises the following steps: S1, mixing the nicotinamide, the 4-hydroxyethylpiperazine ethanesulfonic acid and the riboflavin according to the proportion, heating in inert gas, and assembling the components into the liquid supramolecular composition by using a microwave-assisted method after the components are completely molten; and S2, cooling the supramolecular composition obtained in the step S1, performing vacuum drying, and crushing into powder to obtain the supramolecular composition. The supramolecular composition is constructed through specific component combination, and the photoresponse characteristic is changed to inhibit generation of photosensitive by-products; all the components have a synergistic effect, so that respective light protection characteristics can be retained, a stable structure can be formed through intermolecular interaction, and the technical limitations that a traditional single component is easy to inactivate and single in function are overcome.

Description

Technical Field

[0001] The present invention relates to the technical field of skin light damage protection, and provides a supramolecular composition for resisting sunlight damage, a preparation process and an application thereof. Background Art

[0002] While traditional anti-photodamage ingredients like vitamin C and coenzyme Q10 offer some light protection, they suffer from significant drawbacks in practical application. Furthermore, these ingredients are easily degraded and inactivated by UV rays, causing their protective effects to rapidly diminish. Furthermore, these traditional ingredients are insufficiently targeted at photodamage issues like skin dulling and erythema, making them inadequate for comprehensively addressing the myriad skin issues caused by UV rays and effectively preventing sun damage.

[0003] Riboflavin (RF), also known as vitamin B2, is a naturally occurring compound found in both free and conjugated forms throughout human tissues and is essential for normal life. While riboflavin possesses potential photoprotective properties, it is easily converted into photosensitive products under light exposure, leading to skin darkening and erythema. This not only reduces its protective effects but can also have adverse effects on the skin. Effectively addressing the critical issue of balancing riboflavin's photostability and efficacy is crucial.

[0004] HEPES, a commonly used buffer, is currently used primarily for pH regulation and cosmetic formulation stability. Its potential for scavenging light-induced free radicals and protecting cells has remained largely untapped. Therefore, effectively utilizing HEPES's ability to protect skin cells and mitigate UV damage is crucial for photoprotective products.

[0005] While niacinamide possesses numerous skincare benefits, when used alone, it cannot effectively block the complex multi-pathway damage induced by UV rays, including DNA oxidative damage and the release of inflammatory factors. These technical limitations severely limit the effectiveness of existing photoprotection products.

[0006] Therefore, it is of great significance to develop a supramolecular composition that can effectively resist sun damage and make it have more efficient and comprehensive photoprotection effect. Summary of the Invention

[0007] To address the problems of the prior art, the present invention provides a supramolecular composition for protecting against sun damage, its preparation process, and its application. The supramolecular composition is constructed by combining specific components to modify the light response characteristics to inhibit the formation of photosensitizing byproducts. Riboflavin's efficacy in photoprotection can be utilized to inhibit non-target photochemical reactions. The buffering and free radical scavenging properties of HEPES synergize with nicotinamide to neutralize acidic metabolites, while nicotinamide's antioxidant properties compensate for riboflavin's photostability, thereby constructing the supramolecular composition. The synergistic effects of the components in the supramolecular composition provided by the present invention not only retain their respective photoprotective properties but also form a stable structure through intermolecular interactions, overcoming the technical limitations of traditional single-component inactivation and single-function formulations.

[0008] In a first aspect, the present invention provides a supramolecular composition for protecting against sun damage, which is prepared from nicotinamide, 4-hydroxyethylpiperazineethanesulfonic acid and riboflavin.

[0009] Furthermore, in the supramolecular composition, by weight percentage, nicotinamide accounts for 20%-80%, 4-hydroxyethylpiperazineethanesulfonic acid accounts for 20%-80%, and riboflavin accounts for 0.001%-5%.

[0010] Furthermore, the supramolecular composition comprises 20%-80% nicotinamide by weight, preferably 20%, 30%, 40%, 45%, 50%, 55%, 60%, 70%, or 80%. Compared to using nicotinamide alone, the addition of nicotinamide to HEPES forms a hydrogen bond network, significantly increasing the antioxidant efficiency of nicotinamide by at least three times.

[0011] Furthermore, in the supramolecular composition, 4-hydroxyethylpiperazineethanesulfonic acid accounts for 20%-80% by weight, preferably 20%, 30%, 40%, 45%, 50%, 55%, 60%, 70%, or 80%. Prior art often uses HEPES as a pH buffer, and the addition amount is less than 5%. The present invention adds HEPES at a level of 20-80%, and also utilizes its synergistic antioxidant properties with niacinamide, as well as its own free radical scavenging ability.

[0012] Furthermore, in the supramolecular composition, riboflavin accounts for 0.001%-5% by weight, preferably 0.001%, 0.005%, 0.008%, 0.01%, 0.02%, 0.03%, 0.05%, 0.07%, 0.08%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, or 5%. Compared to the prior art where riboflavin is added in an amount of 1-10% to maintain photorepair activity, the small amount of riboflavin added in the present invention not only effectively inhibits photosensitivity through intermolecular intercalation, but also maintains photorepair activity.

[0013] Furthermore, in the supramolecular composition, by weight percentage, nicotinamide accounts for 40% to 60%; 4-hydroxyethylpiperazineethanesulfonic acid accounts for 40% to 60%; and riboflavin accounts for 0.001% to 0.5%.

[0014] Preferably, nicotinamide accounts for 49.98% to 50%; 4-hydroxyethylpiperazineethanesulfonic acid accounts for 49.95% to 49.999%; and riboflavin accounts for 0.001% to 0.02%.

[0015] Preferably, nicotinamide accounts for 50%; 4-hydroxyethylpiperazineethanesulfonic acid accounts for 49.98%; and riboflavin accounts for 0.02%.

[0016] By limiting the synergistic ratio of nicotinamide and HEPES to a high percentage, while ensuring a supramolecular backbone structure, the high proportion of HEPES fully unleashes its free radical scavenging potential, while the high proportion of nicotinamide enhances its ability to block DNA oxidation and inflammatory pathways. The trace addition of riboflavin, at 0.001-5%, inhibits its photosensitivity through supramolecular encapsulation while retaining its photoinduced repair function. The defined ratios of the three enable HEPES and nicotinamide to form an intermolecular hydrogen bond network, into which riboflavin is embedded through π-π bonding, forming a stable three-dimensional supramolecular structure. Ultimately, this achieves a synergistic effect of enhanced photostability and multi-target protection against photodamage.

[0017] In a second aspect, the present invention provides a method for preparing a supramolecular composition for protecting against sun damage, the specific steps comprising: Step S1: Nicotinamide, 4-hydroxyethylpiperazineethanesulfonic acid, and riboflavin are mixed in proportion, heated under an inert gas atmosphere, and after complete melting, microwave-assisted assembly of the components is performed to form a liquid supramolecular composition; Step S2: The supramolecular composition obtained in step S1 is cooled, vacuum-dried, and then crushed into powder.

[0018] Furthermore, the inert gas refers to a gas environment that does not chemically react with the raw materials, and specifically at least one of helium, neon, argon, krypton, xenon, and nitrogen can be used to prevent oxidative decomposition of photosensitive components such as riboflavin under high temperature conditions.

[0019] Furthermore, the heating temperature is 100-150°C, preferably 100°C, 110°C, 115°C, 120°C, 125°C, 130°C, 140°C, or 150°C. Nicotinamide has a melting point of 131-132°C, 4-hydroxyethylpiperazineethanesulfonic acid has a melting point of 234-238°C, and riboflavin begins to decompose at 282-290°C. When nicotinamide, 4-hydroxyethylpiperazineethanesulfonic acid, and riboflavin are mixed in appropriate proportions, each component readily liquefies within the preferred temperature range to form a supramolecular composition.

[0020] Furthermore, the microwave-assisted method utilizes electromagnetic waves to induce molecular vibrations to promote the formation of non-covalent bonds between components. Specifically, microwave radiation power can be set at 100-500W, microwave reaction temperature at 80-120°C, and microwave reaction time at 1-120 seconds. This method shortens the assembly time of the components, not only promoting the formation of non-covalent bonds between nicotinamide and 4-hydroxyethylpiperazineethanesulfonic acid molecules but also uniformly embedding riboflavin into the framework formed by nicotinamide and 4-hydroxyethylpiperazineethanesulfonic acid. This allows the components to be tightly bound together through supramolecular assembly, thereby enhancing riboflavin's photostability, releasing the free radical scavenging potential of HEPES, and improving nicotinamide's effectiveness in blocking multi-pathway damage. The rate of supramolecular structure formation can be precisely controlled by regulating microwave power and irradiation time. Conventional heating methods make it difficult to precisely control molecular orientation and form a stable hydrogen bond network, and riboflavin will still undergo photosensitivity reactions with ultraviolet rays. By matching microwave energy with a specific frequency of molecular structure, directional molecular arrangement and stable coating can be achieved. Microwave radiation is used to accelerate the process of intermolecular interactions, which can be achieved by adjusting microwave power and irradiation time. This method can directionally induce HEPES and riboflavin to form a stable supramolecular structure while retaining the active conformation of nicotinamide.

[0021] Furthermore, the radiation power of the microwave is 100W, 150W, 200W, 250W, 300W, 350W, 400W, 450W or 500W.

[0022] Furthermore, the microwave reaction temperature is 80°C, 90°C, 100°C, 105°C, 110°C, or 120°C.

[0023] Furthermore, the microwave reaction time is 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 105s, 110s, 115s, or 120s.

[0024] Furthermore, the cooling process refers to rapidly cooling the molten composition using liquid nitrogen for 1 to 10 seconds and then cooling it to room temperature. In the present invention, room temperature refers to 10 to 40°C, preferably 20 to 30°C, and more preferably 25°C. Conventional melt cooling processes do not control the crystallization rate, resulting in the active ingredient being enriched at the grain boundaries to form light-sensitive areas.

[0025] Furthermore, the cold pulverization process produces a supramolecular composition powder having a particle size of 10 to 50 μm, preferably 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm. Cold pulverization refers to the rapid cooling of a molten material to a glassy state followed by mechanical crushing. This can be achieved by combining liquid nitrogen quenching with a grinding process, ensuring that the supramolecular structure remains stable during the phase transition, fixing the intermolecular hydrogen bond network, and maintaining the integrity of the supramolecular structure.

[0026] During the preparation of the supramolecular composition of the present invention: Inert gas forms an inert atmosphere, which can prevent the oxidative decomposition of heat-sensitive ingredients such as nicotinamide and riboflavin during the heating and melting process of the components, and avoid the oxidative degradation and loss of active ingredients caused by high-temperature oxidation. At the same time, it can promote the formation of weak interactions such as hydrogen bonds between molecules, ensuring the integrity of the main structure formed by nicotinamide and HEPES, and also ensuring the structural stability of riboflavin after dispersion; Microwave-assisted molecular assembly to form a three-dimensional supramolecular structure also accelerates the self-assembly process, resulting in a stable supramolecular network. This not only protects riboflavin from photodegradation and inhibits its photosensitized conversion, but also enhances the free radical scavenging ability of HEPES and effectively maintains the multi-pathway blocking function of nicotinamide. Specifically, the electromagnetic field-directed energy input drives the formation of a hydrogen-bonded network between the amide groups of nicotinamide and the sulfonic acid groups of HEPES, building a stable supramolecular structure with intermolecular hydrogen bonds, forming a spatial network backbone and enhancing its ability to capture reactive oxygen species. Riboflavin's isoalloxazine rings are embedded in this network through π-π stacking, with its photoresponsive active sites spatially blocked by the piperazine rings of HEPES, limiting its photoinduced isomerization reaction pathway. Upon exposure to ultraviolet light, riboflavin's excited electrons are transferred to HEPES via a charge transfer mechanism, resulting in free radical scavenging reactions. Nicotinamide neutralizes the acidic species generated during the free radical scavenging process. The three components work synergistically through non-covalent bonds to form a photostable protective barrier.

[0027] The cooling process solidifies the supramolecular assembly; the pulverization process controls the product particle size to form a light-stable powder form; the powder form is conducive to improving the subsequent dispersion uniformity and transdermal absorption efficiency of the supramolecular composition in the cosmetic matrix, and avoiding irritation caused by excessive local concentration.

[0028] The present invention achieves supramolecular assembly in a solvent-free environment through the synergistic effect of an inert atmosphere and microwaves, thus avoiding the problem of component degradation. Through staged physical and chemical control, the present invention assembles the components into a unified system. The buffering function and free radical scavenging ability of HEPES are simultaneously activated, the photosensitized conversion pathway of riboflavin is blocked by the intermolecular charge transfer mechanism, and the antioxidant and DNA repair functions of nicotinamide are enhanced in the synergistic system, thus solving the problems of traditional components such as easy inactivation, single function, and poor compatibility stability.

[0029] In the present invention, the three active ingredients are heated and melted in an inert environment to form a homogeneous liquid phase. The alternating electromagnetic field generated by microwaves then aligns the polar molecules. The amino groups of niacinamide and the sulfonic acid groups of 4-hydroxyethylpiperazineethanesulfonic acid form a three-dimensional framework through hydrogen bonding, within which the riboflavin molecules are encapsulated. This inclusion structure shields the riboflavin from external light while enhancing the spatial exposure of the free radical-trapping groups in the 4-hydroxyethylpiperazineethanesulfonic acid molecules. During rapid cooling, the molecular motion is instantly frozen, forming a stable glassy supramolecular system. The resulting powder form facilitates uniform dispersion of the active ingredients within the cosmetic matrix.

[0030] In a third aspect, the present invention provides a cosmetic comprising the supramolecular composition of the present invention or the supramolecular composition prepared by the method of the present invention.

[0031] In a fourth aspect, the present invention provides a use of the supramolecular composition of the present invention in preparing cosmetics for protecting against sun damage.

[0032] Furthermore, the cosmetics may be daytime protective essence, after-sun repair mask, anti-photoaging cream, etc.

[0033] It can be seen from the above technical solutions that compared with the prior art, the present invention has the following beneficial effects: This solution utilizes supramolecular encapsulation technology to maintain riboflavin's photoresponsive properties while suppressing its side effects. This application addresses the skin irritation caused by riboflavin's photosensitive byproducts, enhances the sustained neutralization of UV-induced free radicals by 4-hydroxyethylpiperazineethanesulfonic acid, and establishes a synergistic pathway for niacinamide to block the release of inflammatory factors. The supramolecular assembly structure enables the components to form a dynamic protective barrier under light irradiation, enhancing the stability of the composition across a wide spectrum of UV light.

[0034] Under direct sunlight, nicotinamide, as an antioxidant, competitively binds to key sites of the nicotinamide adenine dinucleotide pathway in the supramolecular composition of the present invention, simultaneously blocking the release of inflammatory factors, oxidative stress response, UV-induced DNA oxidative damage and inflammatory response, and forming a hydrogen bond network with HEPES to maintain the pH stability of the system and inhibit UV-induced tyrosinase activation; HEPES captures semiquinone free radicals generated by riboflavin photoactivation (especially the piperazine ring structure that can capture free radical intermediates), enhancing the charge balance ability of the molecular chain, enabling it to preferentially capture hydroxyl free radicals (such as singlet oxygen free radicals) under UV irradiation, blocking lipid peroxidation chains. Riboflavin modifies the photoresponsiveness of HEPES molecules through molecular assembly, inhibiting the formation of photosensitized byproducts. Riboflavin undergoes conformational changes under UV excitation, triggering charge transfer with HEPES, converting UV energy into free radical scavenging reactions. Riboflavin also embeds into the niacinamide-HEPES supramolecular framework through π-π stacking, creating a steric hindrance that prevents its own photolysis while continuously inhibiting melanin precursor production and photoisomerization. Nicotinamide inhibits the PARP enzyme that repairs UV-damaged DNA, neutralizes the acidic substances produced during free radical scavenging, and promotes cellular repair by regulating NAD+ metabolism. The three components work synergistically through non-covalent bonds to form a photostable protective barrier. Their synergistic action addresses the multi-dimensional damage pathways triggered by UVA / B wavelengths, including oxidative stress, inflammation, and pigmentation.

[0035] The supramolecular composition described in this invention enhances the effectiveness of photodamage through the synergistic action of three components. Niacinamide blocks UV-induced DNA oxidation and the release of inflammatory factors, forming a hydrogen-bonding network with HEPES to block multiple pathways of damage and reduce skin redness. 4-Hydroxyethylpiperazineethanesulfonic acid exerts its photoinduced free radical scavenging ability, forming an immediate protective barrier before UV exposure. It forms a charge-transfer complex with riboflavin to maintain pH stability and scavenge UV-generated reactive oxygen species. Riboflavin reduces photosensitivity while maintaining photosensitivity within the supramolecular structure, forming a π-π stacking interaction with niacinamide to enhance photostability while retaining its anti-yellowing properties. This supramolecular assembly enhances the stability of each component, preventing degradation associated with individual use. It also addresses multiple UV-induced damage mechanisms, ultimately providing comprehensive protection against yellowing and erythema, inhibiting redness, dullness, and collagen loss caused by sun exposure, while also reducing UV-induced reactive oxygen species (ROS) accumulation.

[0036] The supramolecular composition of the present invention utilizes the synergistic effect of riboflavin and niacinamide to inhibit the photosensitization conversion of riboflavin through the supramolecular structure, thereby enhancing the repair of post-sun erythema and inflammation; through the stable compatibility of the three components in the supramolecular composition, it continuously fights against DNA oxidative damage and blocks the multi-pathway damage mechanism caused by ultraviolet rays.

[0037] The supramolecular composition of the present invention forms a stable supramolecular system through the synergistic effect of each component, which has the advantages of improving photostability and comprehensive protection effect, reducing skin damage caused by ultraviolet rays, and can achieve a synergistic effect of multi-dimensional light damage protection in terms of ultraviolet blocking, light damage repair and long-term photoaging protection. The present application achieves a stable combination of anti-photodamage ingredients, significantly reduces the amount of photosensitizing byproducts of riboflavin, improves the free radical scavenging efficiency of HEPES, and sustains the cell repair function of nicotinamide. UV-induced DNA oxidative damage and inflammatory responses are inhibited by multiple pathways, and skin erythema and pigmentation problems are simultaneously improved.

[0038] Compared with Comparative Example 1 (a mixture prepared by directly mixing the three components) and Comparative Example 2 (a composition prepared with different proportions of the three components), the supramolecular composition prepared by the present invention has significantly improved the photostability of riboflavin, the retention rate of the active ingredient riboflavin is the highest after ultraviolet irradiation, and no phototoxic products are detected.

[0039] Compared with Comparative Example 1, the supramolecular composition prepared by the present invention increases the repair rate of DNA cross-linking damage caused by ultraviolet rays from 43% in Comparative Example 1 to 91%, and the erythema index can be reduced by 82% within 24 hours after sun exposure.

[0040] Terminology Certain embodiments of the present invention are now described in detail, examples of which are illustrated by the accompanying structural formulas and chemical formulae. The present invention is intended to encompass all substitutions, modifications, and equivalent technical solutions, which are all included within the scope of the invention as defined in the claims. Those skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used to practice the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the combined documents, patents, and similar materials differ from or contradict the present application (including but not limited to defined terms, term applications, described technologies, etc.), the present application shall prevail.

[0041] It will be further appreciated that certain features of the invention, which, for clarity, are described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which, for brevity, are described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.

[0042] Unless otherwise specified, all technical terms used in the present invention have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. All patents and publications related to the present invention are incorporated herein by reference in their entirety.

[0043] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0044] In the following description, all numbers disclosed herein are approximate, regardless of whether the word "about" or "approximately" is used. The numerical value of each number may vary by 1%, 2%, 5%, 7%, 8%, 10%, 15%, or 20%. Whenever a number having a value of N is disclosed, any number having a value of N+ / -1%, N+ / -2%, N+ / -3%, N+ / -5%, N+ / -7%, N+ / -8%, N+ / -10%, N+ / -15%, or N+ / -20% is expressly disclosed, where "+ / -" means plus or minus. DETAILED DESCRIPTION

[0045] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the following examples. The specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention in any way. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessary confusion about the concepts of the present disclosure. Such structures and technologies are also described in many publications.

[0046] The reagents used in the present invention can be purchased from the market or prepared by the method described in the present invention.

[0047] Examples 1 to 8 The supramolecular composition comprises, by weight percentage, nicotinamide accounting for 20%-80%, 4-hydroxyethylpiperazineethanesulfonic acid accounting for 20%-80%, and riboflavin accounting for 0.001%-5%. The specific composition is shown in Table 1:

[0048]

[0049] Preparation process: The components of Examples 1-9 were mixed according to the formulation in Table 1, and heated to 120° C. under a nitrogen atmosphere. After the components were completely melted, they were assembled into a liquid supramolecular composition using a microwave-assisted method. The microwave radiation power was 100-500 W, the microwave reaction temperature was 80-120° C., and the microwave reaction time was 1-120 s. The liquefied supramolecular composition was rapidly cooled using liquid nitrogen for 5 seconds to room temperature, vacuum dried, and then pulverized into powder.

[0050] Comparative Example 1 The components of Example 1 in Table 1 were mixed in the proportions shown and then pulverized into powder to obtain a mixture.

[0051] Comparative Example 2 The difference from Example 1 is that the proportions of the components are different. By weight, nicotinamide accounts for 92%, 4-hydroxyethylpiperazineethanesulfonic acid accounts for 3%, and riboflavin accounts for 5%. The remaining operations are the same as in Example 1.

[0052] Effect Example 1 Experimental purpose: To evaluate the changes in skin glossiness and tan index after subjects used the product for 28 consecutive days.

[0053] Experimental Materials: Test product: Skin care product to be evaluated: The supramolecular composition prepared in the embodiment of the present invention, glycerin, and water are prepared in a weight ratio of 1:10:80 to prepare solutions 1 to 9.

[0054] Control product 1: glycerol and water are used in a weight ratio of 10:80 to prepare a blank solution; the mixture of comparative example 1, glycerol and water are used in a weight ratio of 1:10:80 to prepare a control solution 1.

[0055] Control product 2: glycerol and water are used in a weight ratio of 10:80 to prepare a blank solution; the composition of comparative example 2, glycerol, and water are used in a weight ratio of 1:10:80 to prepare a control solution 2.

[0056] Testing Method: Use daily after cleansing. Apply cream to the entire face. In the morning, apply the test product or control product to the entire face. Testing is conducted in a room at 20-22°C and 40-60% relative humidity. Subjects must first acclimate to the same environment for 15 minutes.

[0057] The test results were collected at the following four time periods: before using the sample (D0), 7 days after using the sample (D7), 14 days after using the sample (D14), and 28 days after using the sample (D28).

[0058] The test item is: Skin gloss meter GL200 is used to test skin gloss. (The larger the measured value, the better the skin gloss).

[0059] The results are shown in the following table: Table 2 Skin glossiness test results

[0060] As shown in Table 2, after 28 days of using the solution prepared in this embodiment of the present invention, the skin brightness test value of the experimental group reached approximately 13. The skin brightness test values ​​of the two control solution groups showed almost no significant change over the 28 days. While the control solutions showed some improvement, the skin brightness enhancement effect was not as strong as that of solutions 1-9. This demonstrates that the prepared supramolecular composition has the ability to significantly enhance skin glossiness. This is due to the fact that the active ingredients used can effectively reduce the production and deposition of melanin in the skin, leaving the skin soft, translucent, elastic, and fairer-looking.

[0061] Furthermore, after 28 days of continuous use of solutions 1-9, subjects showed an average 15% improvement in their sallowness index (ITA° measurement). In particular, the supramolecular composition prepared in Example 1, formulated as Solution 1, significantly improved the subjects' sallowness index. The supramolecular composition of the present invention effectively reduces pigmentation and exhibits benefits such as damage repair, inflammation suppression, and barrier protection. Riboflavin, while potentially protective against UV light, can also induce sallowness. By encapsulating riboflavin within the molecule, the supramolecular composition reduces pigmentation, effectively reducing sallowness and suppressing negative effects. It also increases non-sunscreen indicators such as the sallowness index and inflammatory factors, while weakening the SPE value test. This addresses the issues of traditional anti-photodamage ingredients, which are prone to inactivation and have limited efficacy.

[0062] Effect Example 2 Light Stability Comparison The photostability of each formulation was evaluated. The ingredients were mixed evenly to obtain the corresponding formulation (as shown in Table 3). The formulation was coated on a transparent glass plate (5 mg / cm2) and subjected to a certain dose of UVA radiation (5 J / cm 2 ) for 6 hours. Repeat three times. Irradiate at a distance of 120 cm from the light source.

[0063] The residual amount of the composition or riboflavin after exposure to UVA radiation was determined by HPLC using a C18 column (4.6 × 250 mm, 5 μm) with a mobile phase of methanol:0.1% formic acid in water (25:75) at a flow rate of 1.0 mL / min and detection at 267 nm. The percentage of riboflavin was determined by comparing the residual amount of the composition or riboflavin after exposure to UVA radiation with the residual amount of the composition or riboflavin obtained under the same conditions but without UVA radiation. Phototoxic products were detected using Q-TOF mass spectrometry (ESI+ mode).

[0064] To avoid the effects of differences from different UV lamps and different studies, the data were normalized by the photostability of the composition or riboflavin alone for each study. The results are provided in Table 4 below, Table 3: Ratio of preparations (unit: g)

[0065] Table 4: Photostability results

[0066] Results and Discussion: Formulations B and C exhibited >90% retention after 6 hours of UVB irradiation, with no detectable degradation impurities. In contrast, the retention of a single riboflavin solution was only 35%, with the detection of leucoflavin. Formulation D, a mixture of riboflavin, HEPES, and niacinamide at room temperature, also exhibited a significant decrease in retention after 6 hours of UVB irradiation, reaching only 42%, with the detection of leucoflavin and niacin. Formulation E also exhibited a significant decrease in retention after 6 hours of UVB irradiation, reaching only 49%, with the detection of degradation impurities. This demonstrates that the supramolecular compositions prepared using the present invention exhibit excellent photostability and sustained photostability. Compared to Formulation A, which utilizes only the photocatalytic activity of riboflavin, the supramolecular compositions prepared in the present invention exhibit synergistic effects, particularly through the real-time free radical interception of HEPES and the damage repair of niacinamide, converting UV energy into a protective effect. The encapsulation of riboflavin within the supramolecular composition also ensures its stability.

[0067] Effect Example 3 Experimental group: supramolecular composition of Example 1 of the present invention; comparative group: mixture of Comparative Example 1; positive control group: containing 10% panthenol (a known repair agent); negative control group: untreated group (only UV irradiation).

[0068] UV-induced skin damage model Subject: Human skin equivalent model (EpiDermTM 3D epidermal tissue); Irradiation conditions: ① Light source: Solar Simulator (UVA 320-400 nm + UVB 290-320 nm), total irradiation dose 2 MED (Minimum Erythema Dose). ② Parameter: Irradiance 1.5 mW / cm 2 , exposure time 40 minutes (simulating summer noon sunlight exposure).

[0069] Experimental Procedure: Subjects were divided into experimental, control, positive, and negative control groups, and the surface of the subjects was smeared with the solution. Epidermal cells were collected 0, 6, and 24 hours after UV irradiation, and single-cell suspensions were prepared. Cells were mixed with 1% low-melting-point agarose, plated on glass slides, and treated with lysis buffer (2.5 M NaCl, 0.1 M EDTA, 10 mM Tris, 1% Triton X-100) for 1 hour. After electrophoresis (25 V, 30 minutes), the cells were stained with SYBR Gold, and DNA tailing was observed under fluorescence microscopy (Tail Moment value quantifies the degree of damage). The repair rate was calculated as (1 - (treated group / negative control group)) × 100%.

[0070] The erythema index of the subjects was measured using a Mexameter MX18 (probe wavelength 568 nm / 660 nm).

[0071] EI = log (melanin absorbance (660 nm) / hemoglobin absorbance (568 nm)).

[0072] The results are shown in Table 5 below: Table 5

[0073] Compared to Comparative Example 1, the supramolecular composition prepared in the present invention increased the repair rate of DNA crosslink damage caused by UV radiation from 43% in Comparative Example 1 to 91%, and the erythema index was reduced by 82% within 24 hours after sun exposure. This demonstrates that the supramolecular composition prepared in the present invention converts UV energy into a protective effect through the real-time free radical interception of HEPES and the damage repair of niacinamide.

[0074] The methods of the present invention have been described through preferred embodiments. It is apparent that those skilled in the art will be able to modify or appropriately alter and combine the methods and applications described herein within the scope, spirit, and spirit of the present invention to implement and apply the technology of the present invention. Those skilled in the art may refer to the disclosure herein and appropriately modify the process parameters to achieve the desired effect. It is particularly important to note that all similar substitutions and modifications apparent to those skilled in the art are considered encompassed by the present invention.

Claims

1. A supramolecular composition for protecting against sun damage, characterized in that: Made from niacinamide, 4-hydroxyethylpiperazineethanesulfonic acid, and riboflavin; In the supramolecular composition, by weight percentage, nicotinamide accounts for 20%-80%, 4-hydroxyethylpiperazineethanesulfonic acid accounts for 20%-80%, and riboflavin accounts for 0.001%-5%.

2. The supramolecular composition according to claim 1, characterized in that By weight percentage, nicotinamide accounts for 40% to 60%; 4-hydroxyethylpiperazineethanesulfonic acid accounts for 40% to 60%; and riboflavin accounts for 0.001% to 0.5%. Preferably, nicotinamide accounts for 49.98% to 50%; 4-hydroxyethylpiperazineethanesulfonic acid accounts for 49.95% to 49.999%; and riboflavin accounts for 0.001% to 0.02%.

3. A method for preparing a supramolecular composition for protecting against sun damage, characterized in that: The specific steps include: Step S1: Nicotinamide, 4-hydroxyethylpiperazineethanesulfonic acid, and riboflavin are mixed in proportion, heated under an inert gas atmosphere, and after complete melting, microwave-assisted assembly of the components is performed to form a liquid supramolecular composition; Step S2: The supramolecular composition obtained in step S1 is cooled, vacuum-dried, and then crushed into powder.

4. The preparation method according to claim 3, characterized in that The inert gas is selected from at least one of helium, neon, argon, krypton, xenon and nitrogen. The heating temperature is 100°C to 150°C.

5. The preparation method according to claim 3, characterized in that: The microwave-assisted method adopts a microwave radiation power of 100-500W, a microwave reaction temperature of 80-120°C, and a microwave reaction time of 1-120s.

6. The preparation method according to claim 3, characterized in that: The radiation power of the microwave is 100W, 150W, 200W, 250W, 300W, 350W, 400W, 450W or 500W; The microwave reaction temperature is 80°C, 90°C, 100°C, 105°C, 110°C or 120°C; The microwave reaction time is 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 105s, 110s, 115s or 120s.

7. The preparation method according to claim 3, characterized in that: The cooling refers to rapidly cooling the molten composition using liquid nitrogen for 1 to 10 seconds and then cooling it to room temperature; room temperature refers to 10 to 40°C.

8. A cosmetic, characterized in that: The invention comprises the supramolecular composition according to claims 1 to 2 or the supramolecular composition prepared by the method according to any one of claims 4 to 8.

9. Use of the supramolecular composition according to claims 1 to 2 or the supramolecular composition prepared by the method according to any one of claims 4 to 8 in preparing cosmetics for protecting against sun damage.

10. The use according to claim 9, characterized in that: The cosmetic is a daytime protective essence, an after-sun repair mask or an anti-photoaging cream.

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