Collagen supramolecular ionic liquid and preparation method thereof, and cosmetics

Abstract

The present application relates to the field of cosmetics, and relates to a collagen supramolecular ionic liquid, a preparation method thereof, and cosmetics. The collagen supramolecular ionic liquid comprises: collagen molecules and polypeptide molecules; the collagen molecules and the polypeptide molecules self-assemble to form supramolecular molecules under the interaction of non-covalent bonds. The polypeptide molecules have an amphiphilic structure, which is conducive to forming a stable self-assembled structure in water. The collagen supramolecular ionic liquid of the present application utilizes the amphiphilicity of polypeptide molecules to self-assemble them with collagen molecules to form supramolecular molecules, which greatly improves the solubility of collagen; avoids the use of surfactants such as emulsifiers and cosolvents, and applies it to cosmetics, which can greatly reduce the irritation to the skin.

Description

Technical Field

[0001] The present application relates to the field of cosmetics, and in particular, to a collagen supramolecular ionic liquid and a preparation method thereof, and cosmetics. Background Art

[0002] Collagen has a strong stretching ability and is an important substance that makes up ligaments, tendons, and corneas. It can also maintain skin elasticity, promote cell growth, and prevent skin wrinkles. Collagen is easily absorbed by the human body, promotes platelet aggregation, and has a hemostatic effect. It also has very good biodegradability and biocompatibility, and is widely used in medicine, chemicals, health products, food, cosmetics, and feed industries.

[0003] Collagen is known as the "soft gold of skin". It can participate in the growth, division, differentiation, proliferation and migration of skin cells. It can provide the skin with the necessary nutrients and moisture, thereby delaying skin aging and promoting the repair of skin wounds. Collagen also has an antioxidant effect, which can promote cell metabolism, delay cell aging, and make human skin soft, smooth and elastic. Summary of the invention

[0004] The purpose of the embodiments of the present application is to provide a collagen supramolecular ionic liquid and a preparation method and cosmetics thereof.

[0005] The present application provides a collagen supramolecular ionic liquid, the collagen supramolecular ionic liquid comprising: collagen molecules and polypeptide molecules;

[0006] The collagen molecules and the polypeptide molecules self-assemble to form supramolecules under the interaction of non-covalent bonds.

[0007] The inventors have found through research that although collagen has a variety of excellent biological activities, it has low solubility in water due to its own molecular weight, polarity and other reasons. Collagen is difficult to be directly absorbed by the skin when directly applied to cosmetics. The conventional practice is to increase its solubility by using emulsifiers, cosolvents, etc., but the emulsifiers, cosolvents, etc. introduced by these practices greatly increase the irritation to the skin.

[0008] The collagen supramolecular ionic liquid provided in the present application greatly improves the solubility of collagen by self-assembling collagen and polypeptides under the interaction of non-covalent bonds to form supramolecular molecules, and can deliver collagen to the deep layers of the skin to exert its effect, thereby improving the effect of skin absorption. Furthermore, in the scheme of the present application, the polypeptide molecules have an amphiphilic structure, which is conducive to forming a stable self-assembled structure in water. The collagen supramolecular ionic liquid of the present application utilizes the amphiphilicity of polypeptide molecules to self-assemble them with collagen molecules to form supramolecular molecules, which greatly improves the solubility of collagen; it avoids the use of surfactants such as emulsifiers and cosolvents, and its application in cosmetics can greatly reduce irritation to the skin.

[0009] In other embodiments of the present application, the collagen supramolecular ionic liquid has a differential scanning calorimetry graph different from that of collagen, polypeptide molecules, and a mixture of collagen and polypeptide molecules. The differential scanning calorimetry graph of the collagen supramolecular ionic liquid has no melting peak.

[0010] In other embodiments of the present application, collagen molecules are completely dissolved in the collagen supramolecular ionic liquid.

[0011] In other embodiments of the present application, the collagen supramolecular ionic liquid further includes alcohol and water.

[0012] In other embodiments of the present application, the collagen includes: one or more of collagen, collagen amino acids, collagen extracts, soluble collagen or hydrolyzed collagen.

[0013] In other embodiments of the present application, the polypeptide includes: one or more of palmitoyl dipeptide-7, palmitoyl tripeptide-1, palmitoyl tripeptide-5, palmitoyl pentapeptide-4, hexapeptide-9 or palmitoyl pentapeptide-5.

[0014] In other embodiments of the present application, the alcohol includes one or more of 1,2-pentanediol, 1,2-hexanediol, caprylyl glycol, and phenoxyethanol.

[0015] In a second aspect, the present application provides a method for preparing a collagen supramolecular ionic liquid, the preparation method comprising:

[0016] Mix collagen, peptides and water and homogenize until the white precipitate disappears;

[0017] The homogenized solution was heated at 30°C to 70°C with stirring for 5 to 60 minutes;

[0018] After heating, let the solution stand to cool or freeze, then add alcohol and stir evenly.

[0019] In other embodiments of the present application, the homogenization speed is 1000 rpm to 5000 rpm.

[0020] In other embodiments of the present application, the stirring and heating is carried out by water bath heating; the stirring speed is 15 rpm to 1000 rpm.

[0021] In other embodiments of the present application, when preparing collagen supramolecular ionic liquid, each raw material is prepared according to the following ratios;

[0022] In terms of mass fractions, collagen 0.0001-0.5; polypeptide 0.0001-5; alcohol 0.01-5; water 89.5-100.

[0023] In a third aspect, the present application provides a cosmetic comprising the collagen supramolecular ionic liquid provided in the first aspect; or the cosmetic comprising the collagen supramolecular ionic liquid prepared by the preparation method of the collagen supramolecular ionic liquid provided in the second aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 A photo showing the solubility test of the aqueous solution of collagen in Comparative Example 1 is shown;

[0026] Figure 2 The photo of the solubility test of the collagen supramolecular ionic liquid of Example 1 is shown;

[0027] Figure 3 The differential scanning calorimetry diagrams of the collagen aqueous solution provided in Comparative Example 1, the palmitoyl tripeptide-5 aqueous solution provided in Comparative Example 2, the mixture of collagen and palmitoyl tripeptide-5 provided in Comparative Example 3, and the supramolecular collagen provided in Example 1 are shown;

[0028] Figure 4 Differential scanning calorimetry graphs of the soluble collagen provided by Comparative Example 4, the palmitoyl dipeptide-7 provided by Comparative Example 2, the mixture of the soluble collagen and palmitoyl dipeptide-7 provided by Comparative Example 3, and the supramolecular collagen provided by Example 8 are shown. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments.

[0030] Therefore, the following detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0031] The inventors have found through research that although collagen has a variety of excellent biological activities, it is difficult to be directly absorbed by the skin due to its own molecular weight, polarity and other reasons, and its solubility in water is not high, and emulsifiers (myristyl trimethyl ammonium bromide, distearyl dimethyl ammonium chloride, lauryl trimethyl ammonium chloride, etc.) and cosolvents (matrine coconut oil, etc.) are needed to improve its solubility. However, emulsifiers and cosolvents greatly increase the irritation to the skin.

[0032] Therefore, developing a collagen product that can deliver collagen to the deep layers of the skin to exert its effect without causing adverse effects such as irritation to the skin has very important application value.

[0033] Based on this, the embodiment of the present application provides a collagen supramolecular ionic liquid, the collagen supramolecular ionic liquid comprises: collagen molecules and polypeptide molecules;

[0034] Collagen molecules and polypeptide molecules self-assemble to form supramolecules under the interaction of non-covalent bonds.

[0035] In the scheme of the present application, the polypeptide molecule has an amphiphilic structure, which is conducive to forming a stable self-assembled structure in water. The collagen supramolecular ionic liquid of the present application utilizes the amphiphilicity of the polypeptide molecule to self-assemble it with the collagen molecule to form a supramolecular, which greatly improves the solubility of collagen; avoids the use of surfactants such as emulsifiers and cosolvents, and is applied to cosmetics to greatly reduce irritation to the skin.

[0036] Furthermore, supramolecules are molecular aggregates formed by the interaction of two or more molecules. The molecules in the definition of supramolecules are broad and can be molecules or ions.

[0037] Self-assembly refers to the phenomenon that relatively simple or small molecules, starting from a disordered state, aggregate and organize themselves into regular structures through interactions without external intervention. It is an important way to form supramolecular structures.

[0038] Exemplarily, two or more basic structural units spontaneously organize or aggregate into a stable structure with a certain regular geometric appearance under the interaction based on non-covalent bonds.

[0039] The above-mentioned non-covalent bonds include: electrostatic interaction, hydrogen bonding, hydrophobic interaction, π-π stacking interaction, and mechanical bonding.

[0040] The collagen supramolecular ionic liquid provided in the present application greatly improves the solubility of collagen by self-assembling collagen and polypeptides under the interaction of non-covalent bonds to form supramolecular molecules, and can deliver collagen to the deep layers of the skin to exert its effect, thereby improving the effect of skin absorption.

[0041] Further, in some embodiments of the present application, the collagen supramolecular ionic liquid has a differential scanning calorimetry graph different from that of collagen, polypeptide molecules, and a mixture of collagen and polypeptide molecules. The differential scanning calorimetry graph of the collagen supramolecular ionic liquid has no melting peak.

[0042] The differential scanning calorimetry diagram of the collagen supramolecular ionic liquid is different from that of collagen, polypeptide molecules, and a mixture of collagen and polypeptide molecules, forming a supramolecular structure, which greatly improves the solubility of collagen and thus greatly improves the absorption effect on the skin.

[0043] Furthermore, in some embodiments of the present application, collagen molecules are completely dissolved in the collagen supramolecular ionic liquid.

[0044] In the collagen supramolecular ionic liquid, the collagen molecules are completely dissolved, which is beneficial for the delivery of the collagen molecules to the deep layers of the skin to exert their effects.

[0045] Furthermore, in some embodiments of the present application, the collagen supramolecular ionic liquid also includes alcohol and water.

[0046] Furthermore, in some embodiments of the present application, the collagen includes: one or more of collagen, collagen amino acids, collagen extracts, soluble collagen or hydrolyzed collagen.

[0047] Illustratively, in some embodiments of the present application, the collagen is selected from any one of: collagen, collagen amino acids, collagen extracts, soluble collagen or hydrolyzed collagen.

[0048] In some embodiments of the present application, the collagen selected is: a mixture of collagen and collagen amino acids, and the two can be mixed in any proportion; or the collagen selected is: a mixture of collagen extract and soluble collagen, and the two can be mixed in any proportion; or the collagen selected is: a mixture of soluble collagen and hydrolyzed collagen, and the two can be mixed in any proportion.

[0049] Furthermore, in some embodiments of the present application, the polypeptide includes: one or more of palmitoyl dipeptide-7, palmitoyl tripeptide-1, palmitoyl tripeptide-5, palmitoyl pentapeptide-4, hexapeptide-9 or palmitoyl pentapeptide-5.

[0050] The amphiphilic structure of polypeptides is conducive to forming a stable self-assembly structure in water. By utilizing the amphiphilicity of polypeptide molecules, they are self-assembled with collagen molecules to form supramolecules, which greatly improves the solubility of collagen; avoiding the use of surfactants such as emulsifiers and cosolvents, and applying them to cosmetics can greatly reduce irritation to the skin.

[0051] The following is an example of palmitoyl tripeptide-5:

[0052]

[0053] From the structural formula of palmitoyl tripeptide-5, it can be seen that palmitoyl tripeptide-5 has a long carbon chain hydrophobic end and an amino acid hydrophilic end, forming an amphiphilic structure. This amphiphilic structure can form a stable self-assembly structure with collagen molecules in water. This self-assembly structure can improve the transdermal properties of collagen molecules; it helps to dissolve collagen molecules with low solubility, which is equivalent to increasing the amount of collagen molecules added in the supramolecular.

[0054] Palmitoyl tripeptide-5 can be used as an effective ingredient in cosmetics, thereby greatly improving the efficacy of the supramolecular formula and avoiding the addition of surfactants such as emulsifiers, greatly reducing irritation to the skin.

[0055] It should be understood that other polypeptides have similar structures and can thus achieve the same effects.

[0056] Further, exemplarily, in some embodiments of the present application, the polypeptide is selected from: any one of palmitoyl dipeptide-7, palmitoyl tripeptide-1, palmitoyl tripeptide-5, palmitoyl pentapeptide-4, hexapeptide-9 or palmitoyl pentapeptide-5.

[0057] For example, in some embodiments of the present application, the polypeptide selected is: a mixture of palmitoyl dipeptide-7 and palmitoyl tripeptide-1; the two can be mixed in any ratio.

[0058] For example, in some embodiments of the present application, the polypeptide selected is a mixture of palmitoyl tripeptide-5, palmitoyl pentapeptide-4, and hexapeptide-9, and the three can be mixed in any proportion.

[0059] Furthermore, in some embodiments of the present application, the alcohol includes one or more of 1,2-pentanediol, 1,2-hexanediol, caprylyl glycol, and phenoxyethanol.

[0060] For example, in some embodiments of the present application, the alcohol is selected from any one of 1,2-pentanediol, 1,2-hexanediol, caprylyl glycol or phenoxyethanol.

[0061] For example, in some embodiments of the present application, the alcohol selected is: a mixture of 1,2-pentanediol and 1,2-hexanediol; the two can be mixed in any proportion.

[0062] For example, in some embodiments of the present application, the alcohol selected is: a mixture of 1,2-hexanediol, caprylyl glycol, and phenoxyethanol; the three can be mixed in any proportion.

[0063] Some embodiments of the present application provide a method for preparing a collagen supramolecular ionic liquid, the preparation method comprising:

[0064] Mix collagen, peptides and water and homogenize until the white precipitate disappears;

[0065] The homogenized solution was heated at 30°C to 70°C with stirring for 5 to 60 minutes;

[0066] After heating, let the solution stand to cool or freeze, then add alcohol and stir evenly.

[0067] In some embodiments, cooling is cooling at room temperature, such as 20°C to 25°C; freezing is freezing at sub-zero temperatures, such as -30°C to -10°C.

[0068] Furthermore, in some embodiments of the present application, the homogenization speed is 1000 rpm to 5000 rpm.

[0069] Further optionally, the homogenization speed is 1000 rpm to 4000 rpm. For example, in some embodiments of the present application, the homogenization speed is 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm or 4000 rpm.

[0070] Furthermore, in some embodiments of the present application, the stirring heating is carried out by water bath heating; the stirring speed is 15 rpm to 1000 rpm.

[0071] Further optionally, in some embodiments of the present application, the stirring speed is 100 rpm to 1000 rpm.

[0072] Illustratively, in some embodiments of the present application, the stirring speed is 200 rpm, 300 rpm, 400 rpm, 500 rpm, 600 rpm, 700 rpm, 800 rpm or 900 rpm.

[0073] Furthermore, in some embodiments of the present application, when preparing the collagen supramolecular ionic liquid, each raw material is prepared according to the following ratios;

[0074] In terms of mass fractions, collagen 0.0001-0.5; polypeptide 0.0001-5; alcohol 0.01-5; water 89.5-100.

[0075] For example, in some embodiments of the present application, the collagen is 0.0001, 0.001, 0.01, 0.2, 0.3, 0.4 or 0.5 by weight;

[0076] Peptide 0.0001, 0.001, 0.01, 0.5, 1, 2, 3, 4, or 5;

[0077] alcohol 0.01, 0.02, 0.05, 1, 2, 3, 4 or 5;

[0078] Water 89.5, 90, 91, 92, 95, 98, 99 or 100.

[0079] Some embodiments of the present application provide a cosmetic comprising the collagen supramolecular ionic liquid provided by any of the aforementioned embodiments.

[0080] Some embodiments of the present application provide a cosmetic comprising a collagen supramolecular ionic liquid prepared by the method for preparing a collagen supramolecular ionic liquid provided in any of the aforementioned embodiments.

[0081] Some specific embodiments are listed below to better illustrate the present application.

[0082]

Preparation of collagen supramolecular ionic liquid

[0083] Mix collagen, cosolvent and pure water, and homogenize at a low speed of 2000 rpm until large white precipitates disappear; put the homogenized solution into a 50°C hot water bath and stir and heat at a stirring speed of 800 rpm for 30 minutes; after heating, take out the solution and let it stand at room temperature to cool; after the solution cools to room temperature, add alcohol and stir evenly to obtain the final collagen supramolecular ionic liquid.

[0084] Examples 1-6

[0085] Provided is a collagen supramolecular ionic liquid, which is prepared according to the aforementioned preparation steps; the preparation parameters of each embodiment are shown in Table 1.

[0086] Embodiment 7-8

[0087] Provided is a collagen supramolecular, comprising the steps of mixing collagen, a cosolvent and pure water, and homogenizing at a low speed of 2000 rpm until a large white precipitate disappears; placing the homogenized solution in a 50° C. hot water bath, stirring and heating at a stirring speed of 800 rpm, and heating for 30 minutes; taking out the solution after heating and standing it at room temperature to cool; freezing it at -20° C., and then transferring it to a vacuum freeze dryer for freeze drying, and collecting the freeze-dried powder, which is supramolecular collagen; the preparation parameters of each embodiment are shown in Table 2.

[0088] Comparative Example 1

[0089] Provided is a collagen aqueous solution, wherein the collagen content in the collagen aqueous solution is 50 ppm.

[0090] Comparative Example 2

[0091] A polypeptide powder is provided.

[0092] Comparative Example 3

[0093] Provided is a mixture of collagen and polypeptide; the preparation step is to directly mix the collagen and polypeptide at room temperature.

[0094] Comparative Example 4

[0095] A collagen powder is provided.

[0096] Table 1

[0097]

[0098] Table 2

[0099]

[0100]

Performance test

[0101] 1. Detect the dissolution of the solutions of the embodiments and comparative examples;

[0102] Results see instructions Figure 1 and Figure 2 .

[0103] Figure 1 A photo of the solubility test of the aqueous solution of collagen in Comparative Example 1 is shown; Figure 1 It can be seen that the collagen in the aqueous solution of collagen in Comparative Example 1 is not completely dissolved, and white suspended matter is still visible.

[0104] Figure 2 The solubility test photo of collagen supramolecular ionic liquid of Example 1 is shown; Figure 2 It can be seen that the collagen in the collagen supramolecular ionic liquid of Example 1 is completely dissolved, and no white suspended matter is seen.

[0105] This shows that the collagen supramolecular ionic liquid provided in the embodiments of the present application makes collagen have better solubility.

[0106] 2. The examples and comparative examples were subjected to differential scanning calorimetry test.

[0107] Results see instructions Figure 3 . Figure 3 Differential scanning calorimetry graphs of the collagen provided in Comparative Example 4, the palmitoyl tripeptide-5 provided in Comparative Example 2, the mixture of collagen and palmitoyl tripeptide-5 provided in Comparative Example 3, and the supramolecular collagen provided in Example 7 are shown.

[0108] from Figure 3 It can be seen that:

[0109] The spectra of Comparative Example 4, Comparative Example 2 and Comparative Example 3 all show obvious melting peaks.

[0110] The collagen provided in Comparative Example 4 melts at about 162°C; the palmitoyl tripeptide-5 provided in Comparative Example 2 melts at about 220°C.

[0111] The physical mixture of collagen and palmitoyl tripeptide-5 provided in Comparative Example 3 has both melting peaks, indicating that the simple physical mixture of collagen and palmitoyl tripeptide-5 does not change the crystal state of collagen.

[0112] The spectrum of the supramolecular collagen provided in Example 7 has no obvious melting peak. There is a stronger interaction between collagen and palmitoyl tripeptide-5 than in a simple mixture, forming a supramolecular structure.

[0113] 3. Perform differential scanning calorimetry test on the embodiments and comparative examples.

[0114] Results see instructions Figure 4 . Figure 4 Differential scanning calorimetry graphs of the soluble collagen provided by Comparative Example 4, the palmitoyl dipeptide-7 provided by Comparative Example 2, the mixture of the soluble collagen and palmitoyl dipeptide-7 provided by Comparative Example 3, and the supramolecular collagen provided by Example 8 are shown.

[0115] from Figure 4 It can be seen that:

[0116] The spectra of Comparative Example 4, Comparative Example 2 and Comparative Example 3 all show obvious melting peaks.

[0117] The soluble collagen provided in Comparative Example 4 melts at about 226°C; the palmitoyl dipeptide-7 provided in Comparative Example 2 melts at about 129°C.

[0118] The physical mixture of soluble collagen and palmitoyl dipeptide-7 provided in Comparative Example 3 has both melting peaks, indicating that the simple physical mixture of soluble collagen and palmitoyl dipeptide-7 does not change the crystal state of collagen.

[0119] The spectrum of the supramolecular collagen provided in Example 8 has no obvious melting peak. There is a stronger interaction between the soluble collagen and palmitoyl dipeptide-7 than in a simple mixture, thus forming a supramolecular structure.

[0120] This shows that the collagen supramolecular ionic liquid of the present application forms a supramolecular structure, which greatly improves the solubility of collagen and is beneficial to improving skin absorption.

[0121] The embodiments described above are part of the embodiments of the present application, rather than all of the embodiments. The detailed description of the embodiments of the present application is not intended to limit the scope of the present application for protection, but merely represents the selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

Claims

1. A collagen supramolecular ionic liquid, characterized in that: The collagen supramolecular ionic liquid is made of collagen, polypeptide, alcohol and water; By mass fraction, 0.005-0.400 collagen; 0.025-1.320 polypeptide; 1.3-4.0 alcohol; and 94.28-98.652 water; Wherein, the collagen includes any one of soluble collagen, hydrolyzed collagen, collagen amino acids or collagen extracts; the polypeptide includes any one of palmitoyl tripeptide-5, palmitoyl dipeptide-7, palmitoyl tripeptide-1, palmitoyl pentapeptide-5, hexapeptide-9 and palmitoyl pentapeptide-4; the alcohol includes any one of 1,2-pentanediol, caprylyl glycol and phenoxyethanol; Collagen and peptides self-assemble to form supramolecules under non-covalent interactions; The differential scanning calorimetry diagram of the collagen supramolecular ionic liquid has no melting peak; The preparation method of the collagen supramolecular ionic liquid comprises: mixing collagen, polypeptide and water, and homogenizing until the white precipitate disappears; The homogenized solution was heated with stirring at 30°C to 70°C for 5 min to 60 min; After heating, let the solution stand to cool, then add alcohol and stir evenly.

2. The collagen supramolecular ionic liquid according to claim 1, characterized in that: In the collagen supramolecular ionic liquid, the collagen is completely dissolved.

3. The collagen supramolecular ionic liquid according to claim 1, characterized in that: The homogenizing speed is 1000 rpm~5000 rpm.

4. The collagen supramolecular ionic liquid according to claim 1, characterized in that: The stirring and heating is carried out by water bath heating; the stirring speed is 15 rpm ~1000 rpm.

5. A cosmetic, characterized in that: The cosmetic comprises the collagen supramolecular ionic liquid according to any one of claims 1 to 4.

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