Mussel mucoprotein composite hydrocolloid, preparation method thereof and application of mussel mucoprotein composite hydrocolloid in anti-acne paste

Abstract

The invention provides a mussel mucoprotein composite hydrocolloid which comprises 0.5-3 wt% of mussel mucoprotein, 60-85 wt% of a hydrocolloid matrix, 5-15 wt% of polyvinylpyrrolidone, 2-8 wt% of chitosan quaternary ammonium salt and 3-10 wt% of glycerin, and the mussel mucoprotein is covalently grafted with the hydrocolloid matrix through an amido bond. The preparation method comprises the following steps: (1) dispersing the hydrocolloid matrix in a buffer solution, and adding 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, (2) adding a mussel mucoprotein solution, (3) sequentially adding polyvinylpyrrolidone K30, chitosan quaternary ammonium salt and glycerol, homogenizing, and carrying out vacuum defoaming, and (4) forming a film by a tape casting method, drying and sterilizing. The adhesive strength, the antibacterial property and the stability of the high-strength adhesive are remarkably superior to those of the prior art, and the high-strength adhesive is particularly suitable for the high-strength adhesive requirement of a facial activity area.

Description

Technical Field

[0001] The invention belongs to the technical field of daily necessities, and particularly relates to a mussel mucin composite hydrocolloid, a preparation method thereof, and application thereof in an anti-acne patch. Background Art

[0002] Mussel mucin, a natural adhesive protein secreted by marine mussels, has attracted considerable attention in the biomedical field in recent years due to its excellent biocompatibility and wet adhesion. Containing a high proportion of dopa residues, this protein can form a strong adhesive interface underwater and promote cell migration and angiogenesis. Currently, commercially available mussel mucin is primarily extracted from natural mussel byssus threads, but suffers from low yields, large batch variability, and potential pathogen risks. While there have been reports of producing mussel mucin using genetic recombination techniques, maintaining the stability and activity of the recombinant protein remains a technical challenge.

[0003] Hydrocolloid dressings, a representative product of moist healing, are typically composed of hydrophilic polymers such as sodium carboxymethylcellulose and gelatin, capable of absorbing exudate to form a gel environment. However, existing hydrocolloid dressings generally suffer from deficiencies such as insufficient adhesion, poor antimicrobial properties, and an inability to actively promote tissue regeneration. Some studies have attempted to simply mix natural mussel mucin into a hydrocolloid matrix, but the effectiveness has been limited due to the ease with which physically mixed proteins can be lost and the oxidative inactivation of dopa groups.

[0004] In the prior art, CN105477674A discloses a hemostatic composite material of chitosan and mussel mucin. Although the coexistence of two bioactive substances is achieved through physical mixing, the protein and the hydrogel matrix are mainly bound by weak interactions such as hydrogen bonds and electrostatic adsorption. This binding mode is very prone to dissociation under the environment of body fluid flushing, and experimental data show that the protein loss rate can reach more than 30%. More importantly, the free amino groups on the chitosan molecular chain are not directionally modified, resulting in the inability of the dopa residues of mussel mucin to form a stable covalent cross-linked network with it. When the material is applied to a moist wound, the interfacial bonding strength will rapidly drop from the initial 15kPa to below 5kPa, which is significantly weaker than the 20kPa threshold required clinically. CN202411153079A adopts silk fibroin microsphere encapsulation technology. Although it achieves the sustained release of mussel mucin through the β-pleated structure, this design has two major defects: first, there is a lack of chemical bonding between the microspheres and the hydrocolloid matrix, and the carrier escapes in the swollen state. Animal experiments show that 28% of the microspheres detach from the matrix within 24 hours. Second, the hydrophobic properties of silk fibroin will hinder the direct contact between mussel mucin and wound tissue. In vitro tests show that its cell adhesion efficiency is 40% lower than that of the direct grafting system. In addition, most existing products use naturally extracted mussel mucin, which has batch instability and potential immunogenicity risks. Affected by differences in the breeding environment, the dopa content of natural protein in different batches fluctuates by 30%, and the molecular weight distribution range is wide. Clinical data show that the wound healing time of dressings prepared with raw materials from different batches can differ by up to 3.5 days; it is difficult to completely remove endotoxins during the extraction process, far exceeding the recombinant protein standard of less than 10EU / mg. The impurities contained in natural protein may trigger IgE-mediated allergic reactions. In clinical trials, about 8% of patients experienced local redness and swelling.

[0005] These technical defects seriously restrict the clinical application of mussel mucin materials. Therefore, it is necessary to design a mussel mucin composite hydrocolloid and its preparation method and application in anti-acne patches. Summary of the Invention

[0006] In order to overcome the defects in the prior art, a mussel mucin composite hydrocolloid, a preparation method thereof, and an application thereof in an anti-acne patch are provided.

[0007] In order to achieve the above object, the present invention provides the following technical solutions: A mussel mucin composite hydrocolloid comprises the following components: 0.5-3wt% of mussel mucin, 60-85wt% of a hydrocolloid matrix, 5-15wt% of polyvinyl pyrrolidone, 2-8wt% of chitosan quaternary ammonium salt, and 3-10wt% of glycerol. The mussel mucin is covalently grafted to the hydrocolloid matrix via an amide bond.

[0008] The hydrocolloid matrix comprises sodium carboxymethyl cellulose, gelatin and sodium polyacrylate, and the mass ratio of the sodium carboxymethyl cellulose, gelatin and sodium polyacrylate is 3-5:1-2:3.

[0009] The mussel mucin is a fusion protein of type III mussel mucin and byssal fiber skeleton protein. The mussel mucin has a DOPA content of ≥1.5wt%, a molecular weight of 30-50kDa, and an isoelectric point of 8.5-9.5.

[0010] The mussel mucin composite hydrocolloid further comprises the following components: 0.1-0.5 wt % of sodium metabisulfite and 0.05-0.2 wt % of butylated hydroxytoluene as antioxidants.

[0011] A method for preparing a mussel mucin composite hydrocolloid, the method comprising the following steps: (1) Disperse the hydrocolloid matrix in a phosphate buffer solution at pH 7.4, add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, and activate the carboxyl groups for 30-60 minutes. The activation temperature is controlled at 25-35°C. (2) Add mussel mucin solution and react under nitrogen protection for 4-8 hours, maintaining the reaction temperature at 35-45°C; (3) Polyvinylpyrrolidone K30, chitosan quaternary ammonium salt and glycerol are added in sequence, homogenized and then vacuum degassed to obtain a homogeneous gel precursor; (4) The homogeneous gel precursor is formed into a film by a casting method, and the dried film material is sterilized to obtain the mussel mucin composite hydrocolloid.

[0012] The hydrocolloid matrix includes sodium carboxymethyl cellulose, gelatin and sodium polyacrylate, and the mass ratio of sodium carboxymethyl cellulose, gelatin and sodium polyacrylate is 3-5:1-2:3; the hydrocolloid matrix needs to be preheated at 60-80°C for 10-20 minutes before dispersion; The molar ratio of the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide to N-hydroxysuccinimide is 2-3:1, and the total added amount of the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 1.2-1.8 times the molar number of the sodium carboxymethyl cellulose in the hydrocolloid matrix.

[0013] The concentration of mussel mucin in the mussel mucin solution is 5-15 mg / mL. The mussel mucin is dissolved in a Tris-HCl buffer solution containing 0.1-0.3 M sodium chloride. The pH value of the mussel mucin solution is 8.0-8.5.

[0014] The chitosan quaternary ammonium salt has a substitution degree of 60-80%, a deacetylation degree of ≥90%, and a molecular weight of 50-100 kDa.

[0015] The preparation method of the chitosan quaternary ammonium salt comprises the following steps: dissolving chitosan in a 1-2 wt% acetic acid solution, adding 2,3-epoxypropyltrimethylammonium chloride, wherein the molar ratio of the chitosan to the 2,3-epoxypropyltrimethylammonium chloride is 1:1.5-1:2.5, performing a microwave-assisted reaction for 40-80 minutes, a microwave power of 300-500 W, and a reaction temperature of 70-80° C.; precipitating and purifying the reaction product, and freeze-drying the reaction product to obtain the chitosan quaternary ammonium salt.

[0016] An application of a mussel mucin composite hydrocolloid, wherein the mussel mucin composite hydrocolloid is used for preparing an anti-acne patch.

[0017] Compared with the prior art, the advantages and beneficial effects of the present invention are: 1. The fusion protein obtained by genetic recombination technology in this application has a stable DOPA content and molecular weight distribution, which solves the problem of large differences in batches of naturally extracted proteins. The covalent cross-linked network formed by DOPA residues and sodium carboxymethyl cellulose enables the material to maintain an adhesion strength of more than 15kPa in a humid environment, far exceeding the 5-8kPa level of commercially available anti-acne patches. This strong adhesion is particularly suitable for use in active areas of the face. At the same time, the introduction of chitosan quaternary ammonium salt not only gives the material broad-spectrum antibacterial properties, but its positive charge characteristics can also neutralize the negatively charged metabolites produced by Propionibacterium acnes, thereby enhancing the antibacterial effect from the electrical interaction level.

[0018] 2. The gel environment formed after the hydrocolloid matrix of the present application absorbs sebum can keep the wound surface moderately moist and control the water activity within the ideal range of 0.85-0.92, which not only avoids scabs caused by excessive dryness, but also prevents bacterial growth caused by excessive moisture. Mussel mucin forms ionic bonds with the skin's stratum corneum through its rich basic amino acid residues. This bonding method is more durable than the physical adsorption of traditional pressure-sensitive adhesives. Clinical data show that its nighttime shedding rate is reduced to less than 3%. More importantly, the byssus skeleton domain in the fusion protein can directionally guide the migration of keratinocytes, and combined with the osmotic pressure regulation provided by glycerol, it can shorten the resolution time of inflammatory acne by more than 30%.

[0019] 3. This application controls the free protein content below 0.5% through a covalent grafting process, significantly reducing the risk of sensitization. The antioxidant system extends the half-life of dopa residues in the sebum environment to 72 hours, preventing oxidation products from irritating the skin. The microporous structure formed by the cast film technology ensures breathability while reducing the amount of irritating antibacterial agents such as silver ions by 80%, making it particularly suitable for use on sensitive skin. Actual tests show that after 28 days of continuous use, there was no damage to the skin barrier function, and the transepidermal water loss value remained within the normal fluctuation range.

[0020] 4. The preheating of the hydrocolloid matrix used in this application improves viscosity stability and ensures a consistent coating process. The microwave-assisted synthesis of chitosan quaternary ammonium salts exhibits minimal variation in degree of substitution, significantly reducing batch-to-batch performance variability. These properties offer broad application prospects in consumer anti-acne products, meeting medical-grade efficacy requirements while maintaining the price advantage of daily chemical products. DETAILED DESCRIPTION

[0021] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0022] In this application, the sources of various raw materials are briefly described as follows: Polyvinylpyrrolidone K30: purchased from Shanghai Qifuqing Material Technology Co., Ltd., product model PVPK30, in line with the Chinese Pharmacopoeia and USP standards.

[0023] Chitosan quaternary ammonium salt: HACC-102 type produced by Wuhan Kemik Biopharmaceutical Technology Co., Ltd., packaging specification 20kg cardboard barrel.

[0024] Glycerol: purchased from Sinopharm Chemical Reagent Co., Ltd., food grade, CAS 56-81-5, purity ≥99%.

[0025] Sodium carboxymethyl cellulose: Use CMC-Na produced by Ashland Company of the United States, medium to high viscosity type.

[0026] Gelatin: MX0911 series type A gelatin from Shanghai Maokang Biotechnology Co., Ltd.

[0027] Sodium polyacrylate: AQUALIC series produced by Nippon Shokubai Co., Ltd.

[0028] 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide: Shanghai MacLean Biochemical Pharmaceutical Grade EDC, purity ≥98%.

[0029] N-Hydroxysuccinimide: Beijing J&K Technology Pharmaceutical Grade NHS, purity ≥97%.

[0030] Sodium metabisulfite: analytical grade, Sigma-Aldrich.

[0031] Butylated hydroxytoluene: Tokyo Chemical Industry Food Grade BHT, used as an antioxidant.

[0032] 2,3-Epoxypropyltrimethylammonium chloride: reagent grade product from Sigma-Aldrich.

[0033] A mussel mucin composite hydrocolloid comprises the following components: 0.5-3wt% of mussel mucin, 60-85wt% of a hydrocolloid matrix, 5-15wt% of polyvinyl pyrrolidone, 2-8wt% of chitosan quaternary ammonium salt, and 3-10wt% of glycerol. The mussel mucin is covalently grafted to the hydrocolloid matrix via an amide bond.

[0034] The hydrocolloid matrix comprises sodium carboxymethyl cellulose, gelatin and sodium polyacrylate, and the mass ratio of the sodium carboxymethyl cellulose, gelatin and sodium polyacrylate is 3-5:1-2:3.

[0035] The mussel mucin is a fusion protein of type III mussel mucin and byssal fiber skeleton protein. The mussel mucin has a DOPA content of ≥1.5wt%, a molecular weight of 30-50kDa, and an isoelectric point of 8.5-9.5.

[0036] The mussel mucin composite hydrocolloid further comprises the following components: 0.1-0.5 wt % of sodium metabisulfite and 0.05-0.2 wt % of butylated hydroxytoluene as antioxidants.

[0037] A method for preparing a mussel mucin composite hydrocolloid, the method comprising the following steps: (1) Disperse the hydrocolloid matrix in a phosphate buffer solution at pH 7.4, add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, and activate the carboxyl groups for 30-60 minutes. The activation temperature is controlled at 25-35°C. (2) Add mussel mucin solution and react under nitrogen protection for 4-8 hours, maintaining the reaction temperature at 35-45°C; (3) Polyvinylpyrrolidone K30, chitosan quaternary ammonium salt and glycerol are added in sequence, homogenized and then vacuum degassed to obtain a homogeneous gel precursor; (4) The homogeneous gel precursor is formed into a film by a casting method, and the dried film material is sterilized to obtain the mussel mucin composite hydrocolloid.

[0038] The hydrocolloid matrix includes sodium carboxymethyl cellulose, gelatin and sodium polyacrylate, and the mass ratio of sodium carboxymethyl cellulose, gelatin and sodium polyacrylate is 3-5:1-2:3; the hydrocolloid matrix needs to be preheated at 60-80°C for 10-20 minutes before dispersion; The molar ratio of the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide to N-hydroxysuccinimide is 2-3:1, and the total added amount of the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 1.2-1.8 times the molar number of the sodium carboxymethyl cellulose in the hydrocolloid matrix.

[0039] The concentration of mussel mucin in the mussel mucin solution is 5-15 mg / mL. The mussel mucin is dissolved in a Tris-HCl buffer solution containing 0.1-0.3 M sodium chloride. The pH value of the mussel mucin solution is 8.0-8.5.

[0040] The chitosan quaternary ammonium salt has a substitution degree of 60-80%, a deacetylation degree of ≥90%, and a molecular weight of 50-100 kDa.

[0041] The preparation method of the chitosan quaternary ammonium salt comprises the following steps: dissolving chitosan in a 1-2 wt% acetic acid solution, adding 2,3-epoxypropyltrimethylammonium chloride, wherein the molar ratio of the chitosan to the 2,3-epoxypropyltrimethylammonium chloride is 1:1.5-1:2.5, performing a microwave-assisted reaction for 40-80 minutes, a microwave power of 300-500 W, and a reaction temperature of 70-80° C.; precipitating and purifying the reaction product, and freeze-drying the reaction product to obtain the chitosan quaternary ammonium salt.

[0042] An application of a mussel mucin composite hydrocolloid, wherein the mussel mucin composite hydrocolloid is used for preparing an anti-acne patch.

[0043] The technical solution of the present invention is further illustrated below by examples and comparative examples, but the protection scope of the present invention is not limited thereto.

[0044] Example 1 To prepare the mussel mucin composite hydrocolloid, the mussel mucin was added at a 3wt% concentration, the total hydrocolloid matrix was 72.5wt% (the mass ratio of sodium carboxymethylcellulose, gelatin, and sodium polyacrylate was 4:1.5:3), polyvinyl pyrrolidone was 10wt%, chitosan quaternary ammonium salt was 5wt%, and the glycerol content was 6.5wt%. The antioxidant system contained 0.5wt% sodium metabisulfite and 0.12wt% butylated hydroxytoluene. The hydrocolloid matrix was dispersed in phosphate buffer at a temperature of 35°C and activated for 60 minutes. A 10mg / mL mussel mucin solution was dissolved in Tris-HCl buffer (pH 8.3) containing 0.2M sodium chloride and reacted with the activated hydrocolloid matrix under nitrogen for 6 hours at 45°C. Chitosan quaternary ammonium salt has a degree of substitution of 70% and a molecular weight of 75 kDa. The chitosan and 2,3-epoxypropyltrimethylammonium chloride molar ratio was 1:2, and the reaction was microwaved for 60 minutes (400 W power, 75°C). After film casting, the dried film was sterilized with ethylene oxide.

[0045] Example 2 In this embodiment, the same points as in Example 1 are not described in detail, and the differences are as follows: The mussel mucin content was 0.5 wt% in the hydrocolloid matrix (sodium carboxymethylcellulose, gelatin, and sodium polyacrylate in a mass ratio of 3:2:3), along with 15 wt% polyvinylpyrrolidone, 8 wt% chitosan quaternary ammonium salt, and 10 wt% glycerol. Antioxidants included 0.1 wt% sodium metabisulfite and 0.05 wt% butylated hydroxytoluene. The hydrocolloid matrix was preheated to 80°C and activated for 30 minutes. The mussel mucin solution was prepared at a concentration of 5 mg / mL (0.1 M NaCl, pH 8.0) and the reaction time was 4 hours at 35°C. The chitosan quaternary ammonium salt had a degree of substitution of 80% and a molecular weight of 100 kDa. The chitosan quaternary ammonium salt was prepared in a molar ratio of 1:1.5 to 2,3-epoxypropyltrimethylammonium chloride. Microwave reaction was performed for 40 minutes (power 300 W, temperature 70°C).

[0046] Example 3 In this embodiment, the same points as in Example 1 are not described in detail, and the differences are as follows: Mussel mucin was used at a concentration of 1.75 wt% in a hydrocolloid matrix (sodium carboxymethylcellulose, gelatin, and sodium polyacrylate in a mass ratio of 5:1:3). Polyvinyl pyrrolidone (5 wt%), chitosan quaternary ammonium salt (2 wt%), and glycerol (3 wt%) were also added. Sodium metabisulfite (0.3 wt%) and butylated hydroxytoluene (BHT) were also added. The hydrocolloid matrix was preheated to 60°C and activated for 45 minutes. The mussel mucin solution was prepared at a concentration of 15 mg / mL (0.3 M NaCl, pH 8.5) and the reaction time was 8 hours at 40°C. The chitosan quaternary ammonium salt had a degree of substitution of 60% and a molecular weight of 50 kDa. The reaction was microwaved for 80 minutes (500 W power, 80°C).

[0047] Comparative Example 1

[0048] In this comparative example, the same points as Example 1 are not repeated here, and the differences are as follows: sodium metabisulfite and butylated hydroxytoluene are omitted, and the other components and processes are the same.

[0049] Comparative Example 2

[0050] In this comparative example, the similarities with Example 2 are not repeated here, and the differences are as follows: the mussel mucin and the hydrocolloid matrix are physically mixed rather than covalently grafted, and the other parameters are the same.

[0051] Comparative Example 3

[0052] In this comparative example, the similarities with Example 3 are not repeated here, and the differences are as follows: natural mussel mucin (DOPA content fluctuation ±30%, molecular weight distribution 30-100 kDa) was used instead of the recombinant fusion protein.

[0053] Comparative Example 4

[0054] In this comparative example, the same points as those in Example 1 are not repeated here, and the differences are as follows: the degree of substitution of chitosan quaternary ammonium salt is 40%, the molecular weight is 30 kDa, and other parameters remain unchanged.

[0055] Comparative Example 5

[0056] In this comparative example, the similarities with Example 2 are not repeated here, and the differences are as follows: the hydrocolloid matrix is ​​not preheated but directly dispersed in a normal temperature buffer solution.

[0057] Performance test results and analysis

[0058] The mussel mucin composite hydrocolloids obtained in the examples and comparative examples were subjected to performance tests, and the results are shown in Table 1.

[0059] Table 1 Performance test results

[0060] As can be seen from Table 1, the adhesion strengths of Examples 1-3 all exceeded 15 kPa, significantly better than the physical mixing in Comparative Example 2 and the case of the unpreheated matrix in Comparative Example 5. The amide bond network formed by covalent grafting in Example 1 achieved a strength of 18.7 kPa, while the physical mixing in Comparative Example 2 resulted in a 65% decrease in adhesion due to protein loss. The insufficient degree of substitution of the chitosan quaternary ammonium salt in Comparative Example 4 weakened the electrical neutralization effect with Propionibacterium acnes, and the antibacterial rate was reduced to 87.4%. In Example 1, 0.5 wt% sodium metabisulfite and an antioxidant system reduced the oxidation rate of dopa, and the 24-hour protein retention rate reached 98.5%; however, due to the lack of antioxidants in Comparative Example 1, the protein cross-linking network was destroyed, and the retention rate was only 92.3%. In Comparative Example 3, the natural protein had a wide molecular weight distribution and was not tightly bound to the matrix, and the retention rate dropped to 85.4%. In Example 1, the chitosan quaternary ammonium salt substitution degree was 80%, and the positive charge neutralized the negative charge of the bacterial membrane, resulting in an antibacterial rate of 99.9%. At a substitution degree of 40% (Comparative Example 4), insufficient charge density resulted in a 12.5% ​​decrease in antibacterial rate. In Comparative Example 5, the lack of preheating resulted in uneven dispersion of the hydrocolloid matrix and a poor distribution of antibacterial components.

[0061] The byssus skeleton in the fusion protein of Example 1 guided keratinocyte migration, and with the help of glycerol osmotic pressure regulation, the disappearance time was only 4.2 days. Comparative Example 3 used natural protein, which had large batch differences and significant fluctuations in efficacy. The synergistic effect of grafting and antioxidants in Example 1 extended the half-life of DOPA to 74 hours, significantly longer than that of the physical mixing system, compared to only 28 hours in Comparative Example 2. The half-life of the natural protein in Comparative Example 3 was shortened to 45 hours due to catalytic oxidation by impurities.

[0062] This application anchors mussel mucin in a hydrocolloid matrix through amide bonds, addressing the protein loss problem associated with physical mixing. Compared to Comparative Example 2, the retention rate is increased by over 30%, while also avoiding batch variability associated with naturally extracted proteins. Compared to Comparative Example 3, the adhesion strength fluctuates by ±25%. Chitosan quaternary ammonium salt optimization: When the degree of substitution is ≥60%, the density of quaternary ammonium groups is sufficient to disrupt bacterial membrane integrity; however, the insufficient degree of substitution in Comparative Example 4 results in reduced charge neutralization efficiency.

[0063] Preheating treatment and antioxidant system: The hydrocolloid matrix is ​​preheated to 60-80°C to fully swell the sodium carboxymethyl cellulose and improve viscosity stability; sodium metabisulfite and butylated hydroxytoluene synergistically inhibit DOPA oxidation, extending the half-life to 68-74 hours.

[0064] The technical solution of the present invention is significantly superior to the existing technology in terms of adhesion strength, antibacterial properties and stability. It is particularly suitable for the high-strength bonding requirements of the active areas of the face, while taking into account the safety requirements of sensitive skin.

[0065] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A mussel mucin composite hydrocolloid, characterized in that: The mussel mucin composite hydrocolloid comprises the following components: 0.5-3wt% of mussel mucin, 60-85wt% of a hydrocolloid matrix, 5-15wt% of polyvinyl pyrrolidone, 2-8wt% of chitosan quaternary ammonium salt, and 3-10wt% of glycerol. The mussel mucin is covalently grafted to the hydrocolloid matrix via an amide bond.

2. A mussel mucin composite hydrocolloid according to claim 1, characterized in that: The hydrocolloid matrix comprises sodium carboxymethyl cellulose, gelatin and sodium polyacrylate, and the mass ratio of the sodium carboxymethyl cellulose, gelatin and sodium polyacrylate is 3-5:1-2:

3.

3. The mussel mucin composite hydrocolloid according to claim 1, characterized in that: The mussel mucin is a fusion protein of type III mussel mucin and byssal fiber skeleton protein. The mussel mucin has a DOPA content of ≥1.5wt%, a molecular weight of 30-50kDa, and an isoelectric point of 8.5-9.

5.

4. A mussel mucin composite hydrocolloid according to claim 1, characterized in that, The mussel mucin composite hydrocolloid further comprises the following components: 0.1-0.5 wt % of sodium metabisulfite and 0.05-0.2 wt % of butylated hydroxytoluene as antioxidants.

5. A method for preparing the mussel mucin composite hydrocolloid according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: (1) Disperse the hydrocolloid matrix in a phosphate buffer solution at pH 7.4, add 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide, and activate the carboxyl groups for 30-60 minutes. The activation temperature is controlled at 25-35°C. (2) Add mussel mucin solution and react under nitrogen protection for 4-8 hours, maintaining the reaction temperature at 35-45°C; (3) Polyvinylpyrrolidone K30, chitosan quaternary ammonium salt and glycerol are added in sequence, homogenized and then vacuum degassed to obtain a homogeneous gel precursor; (4) The homogeneous gel precursor is formed into a film by a casting method, and the dried film material is sterilized to obtain the mussel mucin composite hydrocolloid.

6. The method for preparing a mussel mucin composite hydrocolloid according to claim 5, wherein: The hydrocolloid matrix includes sodium carboxymethyl cellulose, gelatin and sodium polyacrylate, and the mass ratio of sodium carboxymethyl cellulose, gelatin and sodium polyacrylate is 3-5:1-2:3; the hydrocolloid matrix needs to be preheated at 60-80°C for 10-20 minutes before dispersion; The molar ratio of the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide to N-hydroxysuccinimide is 2-3:1, and the total added amount of the 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N-hydroxysuccinimide is 1.2-1.8 times the molar number of the sodium carboxymethyl cellulose in the hydrocolloid matrix.

7. The method for preparing a mussel mucin composite hydrocolloid according to claim 5, wherein: The concentration of mussel mucin in the mussel mucin solution is 5-15 mg / mL. The mussel mucin is dissolved in a Tris-HCl buffer solution containing 0.1-0.3 M sodium chloride. The pH value of the mussel mucin solution is 8.0-8.

5.

8. The method for preparing a mussel mucin composite hydrocolloid according to claim 5, wherein: The chitosan quaternary ammonium salt has a substitution degree of 60-80%, a deacetylation degree of ≥90%, and a molecular weight of 50-100 kDa.

9. The method for preparing a mussel mucin composite hydrocolloid according to claim 8, characterized in that: The preparation method of the chitosan quaternary ammonium salt comprises the following steps: dissolving chitosan in a 1-2 wt% acetic acid solution, adding 2,3-epoxypropyltrimethylammonium chloride, wherein the molar ratio of the chitosan to the 2,3-epoxypropyltrimethylammonium chloride is 1:1.5-1:2.5, performing a microwave-assisted reaction for 40-80 minutes, a microwave power of 300-500 W, and a reaction temperature of 70-80° C.; precipitating and purifying the reaction product, and freeze-drying the reaction product to obtain the chitosan quaternary ammonium salt.

10. A use of the mussel mucin composite hydrocolloid according to any one of claims 1 to 4, characterized in that: The mussel mucin composite hydrocolloid is used for preparing an anti-acne patch.

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