Gynecological antibacterial repair gel and preparation method thereof
By introducing modified MOF and nanosilver into gynecological hydrogels to form a chemical crosslinking network structure, the problem of insufficient antibacterial performance of existing gynecological hydrogels is solved, and efficient antibacterial repair and mechanical strength improvement is achieved.
Patent Information
- Application Number
- CN202510446445.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-10
- Publication Date
- 2025-07-08
AI Technical Summary
The antibacterial properties of existing gynecological hydrogels are limited and it is difficult to achieve excellent antibacterial effects.
Modified MOF is used as an antibacterial agent, and the copper-zinc bimetallic organic framework of modified thiol-polyethylene glycol-carboxyl and cystine-modified copper-zinc bimetallic skeleton is introduced into the hydrogel matrix, combining oxidized sodium alginate and chitosan derivatives to form a chemical crosslinking network structure, improving mechanical properties and antibacterial ability.
The prepared gynecological antibacterial repair gel has excellent antibacterial properties, self-repair properties and mechanical properties, which significantly improves wound healing efficiency and antibacterial durability.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of biomedical polymer materials, and particularly relates to an antibacterial repair gel for gynecology and a preparation method thereof. Background Art
[0002] The skin plays a crucial role in maintaining dynamic balance and preventing the invasion of microorganisms and chemicals, and is the first line of defense against human injury, infection, and dehydration. However, the skin with limited healing ability is also extremely vulnerable to injuries such as burns and bruises. Generally, the preferred method for skin regeneration is autologous skin transplantation, but the shortage of donor skin and the inevitable new wounds at the donor site limit its wide application. Therefore, wound dressings have now become the mainstream therapy for skin repair to cope with the high annual incidence of skin injuries.
[0003] A wound dressing with excellent performance should contain components that promote tissue regeneration, and at the same time, it should also have anti-inflammatory, antibacterial, and pro-angiogenic components. Among various types of wound dressings, hydrogels have unique advantages, such as maintaining a moist wound environment and accelerating wound healing. Therefore, compared with other materials, hydrogels are considered the most promising candidates. However, the mechanical strength of hydrogels is too low, which limits the application of hydrogel dressings.
[0004] Patent CN114685919B provides a low-swelling, highly water-absorbent hydrogel and its preparation method and application. In this patent, a metal-organic framework material MOF is added to the hydrogel system. This additive can use hydrophilic groups in the hydrogel matrix, such as carboxyl groups, hydroxyl groups, and ionic groups, as fixed metal nodes, and then adhere well to the network structure of the hydrogel. It can tightly adsorb and combine the physical cross-linked network structure and the chemical cross-linked network structure of polyvinyl alcohol-glycerol together, and at the same time, it has a relatively high porosity, which can alleviate the volume expansion of the hydrogel after water absorption. However, the antibacterial substance added in this patent is mainly chitosan, and the antibacterial performance of chitosan itself is limited, making it difficult to achieve excellent antibacterial effects. Summary of the Invention
[0005] The present invention provides an antibacterial repair gel for gynecology and a preparation method thereof, which can solve the problem that the antibacterial performance of chitosan itself in the background art is limited and it is difficult to achieve excellent antibacterial effects.
[0006] The object of the present invention can be achieved by the following technical solutions:
[0007] An antibacterial repair gel for gynecology, comprising components calculated by weight percentage as follows: 3-9% polyvinyl alcohol, 20-26% glycerol, 2-7% oxidized sodium alginate, 4-9% carboxymethyl chitosan, 1-4% modified MOF, and the balance is water; the modified MOF is nano silver loaded on copper-zinc bimetallic organic framework modified by mercapto-polyethylene glycol-carboxyl and cystine.
[0008] The well-dispersed modified MOF can use hydrophilic groups in the hydrogel matrix, such as carboxyl groups, hydroxyl groups, and ionic groups, as fixed metal nodes, and thus can be well attached to the network structure of the hydrogel, tightly combining the physical cross-linked network structure of polyvinyl alcohol-glycerol with the chemical cross-linked network structure formed by the Schiff base chemical cross-linking of oxidized sodium alginate and chitosan derivatives, improving the overall mechanical properties of the hydrogel.
[0009] Further, the preparation method of oxidized sodium alginate is as follows:
[0010] Dissolve sodium alginate in deionized water to prepare a sodium alginate solution; add sodium periodate to the sodium alginate solution in the dark and stir in the dark for 2-4 h; then add ethylene glycol and continue to stir in the dark for 0.5-2 h; add ethanol for precipitation, and filter out the precipitate; dissolve the precipitate in deionized water, perform dialysis treatment with a cellulose dialysis bag with a molecular weight cut-off of 7000, and freeze-dry the obtained product to obtain oxidized sodium alginate.
[0011] Among them, the mass fraction of the sodium alginate solution is 1%-5%; the mass ratio of sodium periodate to sodium alginate is (0.5-1):1; the addition amount of ethylene glycol is 2-5 mL / g sodium alginate.
[0012] Further, the preparation method of the modified MOF is as follows:
[0013] A1: Ultrasonically dissolve a copper salt and 2-aminoterephthalic acid in methanol to obtain a mixed solution, then add a zinc salt, ultrasonically dissolve for 20-30 min, then add it to a reaction kettle, heat at 120 °C for 12-24 h, cool to room temperature, centrifuge, wash, and vacuum dry to obtain a copper-zinc bimetallic organic framework;
[0014] Among them, the molar ratio of the copper salt, 2-aminoterephthalic acid, and zinc salt is 1:1:(0.2-0.4); the concentration of the copper salt in the mixed solution is 4 g / L.
[0015] In the above steps, using 2-aminoterephthalic acid as the organic ligand, a copper-zinc bimetallic organic framework was prepared. This metal-organic framework contains two metals, copper and zinc, as well as amino groups. Copper ions and zinc ions are well-known antibacterial agents, and both have broad antibacterial activities against a variety of bacteria (such as viruses, fungi, and Gram-positive bacteria). The antibacterial ability can be enhanced through the synergistic effect between copper and zinc ions, and wound healing can be promoted by reducing the possibility of wound infection. Loading the copper-zinc bimetallic organic framework into a hydrogel can be a strategy to alleviate its degradation and prevent the premature release of copper ions and zinc ions, thereby improving the antibacterial persistence of the hydrogel. However, the copper-zinc bimetallic organic framework has a high specific surface area, and the particles are prone to attracting and aggregating with each other to form aggregates, thus affecting its antibacterial ability.
[0016] A2: Add the copper-zinc bimetallic organic framework to a 5 wt% aqueous DMF solution to form a MOF solution, and add mercapto-polyethylene glycol-carboxylic acid to a 5 wt% aqueous DMF solution to form a mercapto-polyethylene glycol-carboxylic acid solution; dissolve cystine in a 5 wt% aqueous dimethyl sulfoxide solution to form a cystine solution; mix the MOF solution, the mercapto-polyethylene glycol-carboxylic acid solution, and the cystine solution, ultrasonicate for 5 - 10 min, and then stir at room temperature for 12 h to obtain a mixed solution a;
[0017] Among them, the dosage ratio of the copper-zinc bimetallic organic framework to the aqueous DMF solution is 5 g: 140 mL; the dosage ratio of mercapto-polyethylene glycol-carboxylic acid to the aqueous DMF solution is 0.4 g: 100 mL; the dosage ratio of cystine to the aqueous dimethyl sulfoxide solution is 0.34 g: 100 mL; in the mixed solution a, the MOF solution, the mercapto-polyethylene glycol-carboxylic acid solution, and the cystine solution are mixed according to the mass ratio of the copper-zinc bimetallic organic framework, mercapto-polyethylene glycol-carboxylic acid, and cystine of 10: (1 - 2): (0.5 - 1).
[0018] In the above steps, the carboxyl groups of mercapto-polyethylene glycol-carboxylic acid and cystine react with the amino groups of the copper-zinc bimetallic organic framework to form amide bonds, thereby obtaining a metal-organic framework containing mercapto groups and disulfide bonds. The introduction of these two substances can improve the dispersibility of the copper-zinc bimetallic organic framework through steric hindrance effects, and enhance the antibacterial and repair abilities of the hydrogel. The bond energy of the disulfide bond is relatively low, which can improve the self-healing ability of the hydrogel, help maintain the structural integrity of the hydrogel, and thus better exert its antibacterial function.
[0019] A3: Add silver nanoparticles to the mixed solution a, ultrasonicate for 1 - 5 h, and then centrifuge, wash, and dry the solution to obtain a modified MOF.
[0020] Among them, the concentration of silver nanoparticles in the mixed solution a is 4 - 6 g / L.
[0021] The mixed solution a contains a mercapto group and an amino group. The mercapto group can form a covalent bond with Ag. At the same time, the amino group further improves the dispersibility and stability of the silver nanoparticles, reduces the possibility of silver nanoparticle aggregation, and improves the antibacterial property of the hydrogel.
[0022] Further, in step A1, the zinc salt is any one of zinc nitrate hexahydrate, zinc acetate, and zinc chloride.
[0023] Further, in step A1, the copper salt is any one of copper nitrate trihydrate, copper sulfate pentahydrate, and copper chloride dihydrate.
[0024] A preparation method of an antibacterial and repair gel for gynecology, comprising the following steps:
[0025] S1: Glycerol, polyvinyl alcohol and water are mixed evenly and then sealed and refluxed at 100 - 120 °C for 1 - 2 h to obtain a polyvinyl alcohol - glycerol precursor solution;
[0026] S2: Sodium alginate oxide, carboxymethyl chitosan, and modified MOF are added to the polyvinyl alcohol - glycerol precursor solution obtained in S1 and mixed evenly, and then reacted at 80 - 90 °C for 10 - 12 h to obtain a hydrogel precursor solution;
[0027] S3: The hydrogel precursor solution is cooled to 20 - 30 °C to obtain an antibacterial and repair gel for gynecology.
[0028] Further, in step S3, the cooling rate is 2 - 10 °C / min.
[0029] Advantages of the present invention:
[0030] The gel prepared by the present invention has excellent antibacterial properties, repair properties, self - repair properties, and mechanical properties. In the process of preparing the gel of the present invention, modified MOF is added. The well - dispersed modified MOF can improve the overall mechanical properties of the gel. The modified MOF contains silver nanoparticles. The well - dispersed silver nanoparticles have excellent antibacterial properties and can endow the hydrogel with excellent antibacterial ability. Moreover, the copper and zinc ions in the copper - zinc bimetallic organic framework can improve the antibacterial ability through synergistic action, and promote wound healing by reducing the possibility of wound infection. The disulfide bond can improve the self - repair ability of the gel. Specific embodiments
[0031] The following describes the specific embodiments of the present invention in detail, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.
[0032] The silver nanoparticles in the present invention are purchased from Ningbo Jinlei Nanomaterials Technology Co., Ltd.
[0033] Example 1
[0034] This example provides an antibacterial repair gel for gynecology, and its preparation method is as follows:
[0035] S1: Mix 3 g of polyvinyl alcohol, 20 g of glycerol and 20 g of water evenly, and then carry out closed reflux at 100 °C for 1 h to obtain a polyvinyl alcohol-glycerol precursor solution;
[0036] S2: Add 2 g of oxidized sodium alginate, 4 g of carboxymethyl chitosan, and 1 g of modified MOF into the polyvinyl alcohol-glycerol precursor solution obtained in S1, mix evenly, add water to 100 g, and react at 80 °C for 10 h to obtain a hydrogel precursor solution;
[0037] S3: Cool the hydrogel precursor solution to 20 °C at a cooling rate of 2 °C / min to obtain the antibacterial repair gel for gynecology.
[0038] The preparation method of oxidized sodium alginate is as follows:
[0039] Dissolve sodium alginate in deionized water to prepare a sodium alginate solution with a mass fraction of 3%; add sodium periodate to the sodium alginate solution in a light-shielded manner according to the mass ratio of 0.7:1 to sodium alginate, and stir in the dark for 4 h; then add ethylene glycol, and the addition amount of ethylene glycol is 3 mL / g of sodium alginate, and continue to stir in the dark for 2 h; add ethanol for precipitation, and the addition amount of ethanol is 80 mg / L of sodium alginate, filter out the precipitate; dissolve the precipitate in deionized water, carry out dialysis treatment with a cellulose dialysis bag with a molecular weight cut-off of 7000, and freeze-dry the obtained product to obtain oxidized sodium alginate.
[0040] The preparation method of modified MOF is as follows:
[0041] A1: Ultrasonically dissolve 1.4 g of copper nitrate trihydrate and 1.8 g of 2-aminoterephthalic acid in 350 mL of methanol to obtain a mixed solution, then add 0.4 g of zinc acetate, ultrasonically dissolve for 20 min, and then add it to a reaction kettle, heat at 120 °C for 12 h, cool to room temperature, centrifuge, wash, and vacuum dry to obtain a copper-zinc bimetallic organic framework;
[0042] A2: Add 5 g of copper-zinc bimetallic organic framework into 140 mL of DMF aqueous solution with a mass fraction of 5 wt% to form a MOF solution. Add 0.4 g of mercapto-polyethylene glycol-carboxyl into 100 mL of DMF aqueous solution with a mass fraction of 5 wt% to form a mercapto-polyethylene glycol-carboxyl solution. Dissolve 0.34 g of cystine in 100 mL of dimethyl sulfoxide aqueous solution with a mass fraction of 5 wt% to form a cystine solution. Mix the MOF solution, mercapto-polyethylene glycol-carboxyl solution and cystine solution, ultrasonicate for 5 min, and then stir at room temperature for 12 h to obtain a mixed solution a. In the mixed solution a, the MOF solution, mercapto-polyethylene glycol-carboxyl solution and cystine solution are mixed according to the mass ratio of copper-zinc bimetallic organic framework, mercapto-polyethylene glycol-carboxyl, and cystine of 10:1:0.5.
[0043] A3: Add silver nanoparticles into the mixed solution a, the concentration of silver nanoparticles in the mixed solution a is 4 g / L. After ultrasonication for 1 h, the solution is centrifuged, washed and dried to obtain the modified MOF.
[0044] Example 2
[0045] This example provides an antibacterial repair gel for gynecology, and its preparation method is as follows:
[0046] S1: Mix 3 g of polyvinyl alcohol, 20 g of glycerol and 20 g of water evenly, and then carry out closed reflux at 110 °C for 1.5 h to obtain a polyvinyl alcohol-glycerol precursor solution.
[0047] S2: Add 2 g of oxidized sodium alginate, 4 g of carboxymethyl chitosan, and 1 g of modified MOF into the polyvinyl alcohol-glycerol precursor solution obtained in S1, mix evenly, add water to 100 g, and react at 90 °C for 11 h to obtain a hydrogel precursor solution.
[0048] S3: Cool the hydrogel precursor solution to 25 °C at a cooling rate of 2 °C / min to obtain the antibacterial repair gel for gynecology.
[0049] The preparation method of oxidized sodium alginate is the same as that in Example 1.
[0050] The preparation method of the modified MOF is as follows:
[0051] A1: Ultrasonically dissolve 1.4 g of copper nitrate trihydrate and 1.8 g of 2-aminoterephthalic acid in 350 mL of methanol to obtain a mixed solution. Then add 0.6 g of zinc acetate, ultrasonically dissolve for 30 min, and then add it to a reaction kettle. Heat at 120 °C for 20 h. After cooling to room temperature, centrifuge, wash and vacuum dry to obtain the copper-zinc bimetallic organic framework.
[0052] A2: Add 5 g of copper-zinc bimetallic organic framework into 140 mL of DMF aqueous solution with a mass fraction of 5 wt% to form a MOF solution. Add 0.4 g of mercapto-polyethylene glycol-carboxyl into 100 mL of DMF aqueous solution with a mass fraction of 5 wt% to form a mercapto-polyethylene glycol-carboxyl solution. Dissolve 0.34 g of cystine in 100 mL of dimethyl sulfoxide aqueous solution with a mass fraction of 5 wt% to form a cystine solution. Mix the MOF solution, mercapto-polyethylene glycol-carboxyl solution and cystine solution, ultrasonicate for 10 min, and then stir at room temperature for 12 h to obtain a mixed solution a. In the mixed solution a, the MOF solution, mercapto-polyethylene glycol-carboxyl solution and cystine solution are mixed according to the mass ratio of copper-zinc bimetallic organic framework, mercapto-polyethylene glycol-carboxyl, and cystine of 10:1.5:0.8.
[0053] A3: Add silver nanoparticles into the mixed solution a. The concentration of silver nanoparticles in the mixed solution a is 5 g / L. After ultrasonication for 3 h, the solution is centrifuged, washed, and dried to obtain the modified MOF.
[0054] Example 3
[0055] This example provides an antibacterial repair gel for gynecology, and its preparation method is as follows:
[0056] S1: Mix 3 g of polyvinyl alcohol, 20 g of glycerol and 20 g of water evenly, and then carry out closed reflux at 120 °C for 2 h to obtain a polyvinyl alcohol-glycerol precursor solution.
[0057] S2: Add 2 g of oxidized sodium alginate, 4 g of carboxymethyl chitosan, and 1 g of modified MOF into the polyvinyl alcohol-glycerol precursor solution obtained in S1, mix evenly, add water to 100 g, and react at 90 °C for 12 h to obtain a hydrogel precursor solution.
[0058] S3: Cool the hydrogel precursor solution to 30 °C at a cooling rate of 2 °C / min to obtain the antibacterial repair gel for gynecology.
[0059] The preparation method of oxidized sodium alginate is the same as that in Example 1.
[0060] The preparation method of the modified MOF is as follows:
[0061] A1: Ultrasonically dissolve 1.4 g of copper nitrate trihydrate and 1.8 g of 2-aminoterephthalic acid in 350 mL of methanol to obtain a mixed solution. Then add 0.7 g of zinc acetate, ultrasonicate for 30 min to dissolve, and then add it to a reaction kettle. Heat at 120 °C for 24 h. After cooling to room temperature, centrifuge, wash, and vacuum dry to obtain a copper-zinc bimetallic organic framework.
[0062] A2: Add 5 g of copper-zinc bimetallic organic framework into 140 mL of DMF aqueous solution with a mass fraction of 5 wt% to form a MOF solution. Add 0.4 g of mercapto-polyethylene glycol-carboxyl into 100 mL of DMF aqueous solution with a mass fraction of 5 wt% to form a mercapto-polyethylene glycol-carboxyl solution. Dissolve 0.34 g of cystine in 100 mL of dimethyl sulfoxide aqueous solution with a mass fraction of 5 wt% to form a cystine solution. Mix the MOF solution, the mercapto-polyethylene glycol-carboxyl solution, and the cystine solution, and ultrasonicate for 5 - 10 min, then stir at room temperature for 12 h to obtain a mixed solution a. In the mixed solution a, the MOF solution, the mercapto-polyethylene glycol-carboxyl solution, and the cystine solution are mixed according to the mass ratio of copper-zinc bimetallic organic framework, mercapto-polyethylene glycol-carboxyl, and cystine of 10:2:1.
[0063] A3: Add silver nanoparticles into the mixed solution a, and the concentration of silver nanoparticles in the mixed solution a is 6 g / L. After ultrasonication for 5 h, centrifuge, wash, and dry the solution to obtain the modified MOF.
[0064] Example 4
[0065] The difference between this example and Example 3 is as follows:
[0066] An antibacterial and repair gel for gynecology, and its preparation method is as follows:
[0067] S1: Mix 6 g of polyvinyl alcohol, 23 g of glycerol, and 23 g of water evenly, and carry out closed reflux at 120 °C for 2 h to obtain a polyvinyl alcohol-glycerol precursor solution.
[0068] S2: Add 4.5 g of oxidized sodium alginate, 6.5 g of carboxymethyl chitosan, and 2.5 g of modified MOF into the polyvinyl alcohol-glycerol precursor solution obtained in S1, mix evenly, add water to 100 g, and react at 90 °C for 12 h to obtain a hydrogel precursor solution.
[0069] S3: Cool the hydrogel precursor solution to 30 °C at a cooling rate of 2 °C / min to obtain the antibacterial and repair gel for gynecology.
[0070] The remaining raw materials and steps are the same as those in Example 3.
[0071] Example 5
[0072] The difference between this example and Example 3 is as follows:
[0073] An antibacterial and repair gel for gynecology, and its preparation method is as follows:
[0074] S1: Mix 9 g of polyvinyl alcohol, 26 g of glycerol, and 26 g of water evenly, and carry out closed reflux at 120 °C for 2 h to obtain a polyvinyl alcohol-glycerol precursor solution.
[0075] S2: Add 7 g of oxidized sodium alginate, 9 g of carboxymethyl chitosan, and 4 g of modified MOF into the polyvinyl alcohol-glycerol precursor solution obtained in S1. After mixing evenly, add water to make up to 100 g, and react at 90 °C for 12 h to obtain a hydrogel precursor solution.
[0076] S3: Cool the hydrogel precursor solution to 30 °C at a cooling rate of 2 °C / min to obtain the antibacterial repair gel for gynecology.
[0077] The remaining raw materials and steps are the same as those in Example 3.
[0078] Comparative Example 1
[0079] Compared with Example 1, the difference in this comparative example is that silver nanoparticles are omitted. The specific steps are as follows:
[0080] The preparation method of the modified MOF is as follows:
[0081] A1: Ultrasonically dissolve 1.4 g of copper nitrate trihydrate and 1.8 g of 2-aminoterephthalic acid in 350 mL of methanol to obtain a mixed solution. Then add 0.4 g of zinc acetate, ultrasonically dissolve for 20 min, and then add it to a reaction kettle. Heat at 120 °C for 12 h. After cooling to room temperature, centrifuge, wash, and vacuum dry to obtain a copper-zinc bimetallic organic framework.
[0082] A2: Add 5 g of the copper-zinc bimetallic organic framework into 140 mL of a DMF aqueous solution with a mass fraction of 5 wt% to form a MOF solution. Add 0.4 g of mercapto-polyethylene glycol-carboxyl into 100 mL of a DMF aqueous solution with a mass fraction of 5 wt% to form a mercapto-polyethylene glycol-carboxyl solution; dissolve 0.34 g of cystine in 100 mL of a dimethyl sulfoxide aqueous solution with a mass fraction of 5 wt% to form a cystine solution; mix the MOF solution, the mercapto-polyethylene glycol-carboxyl solution, and the cystine solution, ultrasonically for 5 min, and then stir at room temperature for 12 h to obtain a mixed solution a. Centrifuge, wash, and dry to obtain the modified MOF. In the mixed solution a, the MOF solution, the mercapto-polyethylene glycol-carboxyl solution, and the cystine solution are mixed according to the mass ratio of the copper-zinc bimetallic organic framework, mercapto-polyethylene glycol-carboxyl, and cystine of 10:1:0.5.
[0083] The remaining raw materials and steps are the same as those in Example 1.
[0084] Comparative Example 2
[0085] Compared with Example 1, the difference in this comparative example is that mercapto-polyethylene glycol-carboxyl and cystine are omitted. The specific steps are as follows:
[0086] The preparation method of the modified MOF is as follows:
[0087] A1: 1.4 g of copper nitrate trihydrate and 1.8 g of 2-aminoterephthalic acid were ultrasonically dissolved in 350 mL of methanol to obtain a mixed solution. Then, 0.4 g of zinc acetate was added and dissolved by ultrasonic treatment for 20 min. After that, it was added to a reaction kettle and heated at 120 °C for 12 h. After cooling to room temperature, it was centrifuged, washed, and dried under vacuum to obtain a copper-zinc bimetallic organic framework;
[0088] A2: 5 g of the copper-zinc bimetallic organic framework was added to 140 mL of a DMF aqueous solution with a mass fraction of 5 wt% to form a MOF solution. Nanoscale silver particles were added to the MOF solution, and the concentration of nanoscale silver in the MOF solution was 4 g / L. After ultrasonic treatment for 1 h, the solution was centrifuged, separated, washed, and dried to obtain a modified MOF.
[0089] The remaining raw materials and steps were the same as those in Example 1.
[0090] Comparative Example 3
[0091] Compared with Example 1, the difference in this comparative example was that the zinc salt was omitted, and the specific steps were as follows:
[0092] The preparation method of the modified MOF was as follows:
[0093] A1: 1.4 g of copper nitrate trihydrate and 1.8 g of 2-aminoterephthalic acid were ultrasonically dissolved in 350 mL of methanol to obtain a mixed solution, which was dissolved by ultrasonic treatment for 20 min. After that, it was added to a reaction kettle and heated at 120 °C for 12 h. After cooling to room temperature, it was centrifuged, washed, and dried under vacuum to obtain a copper-based metallic organic framework;
[0094] A2: 5 g of the copper-based metallic organic framework was added to 140 mL of a DMF aqueous solution with a mass fraction of 5 wt% to form a MOF solution; 0.4 g of mercapto-polyethylene glycol-carboxyl was added to 100 mL of a DMF aqueous solution with a mass fraction of 5 wt% to form a mercapto-polyethylene glycol-carboxyl solution; 0.34 g of cystine was dissolved in 100 mL of a dimethyl sulfoxide aqueous solution with a mass fraction of 5 wt% to form a cystine solution; the MOF solution, the mercapto-polyethylene glycol-carboxyl solution, and the cystine solution were mixed and ultrasonically treated for 5 min, and then stirred at room temperature for 12 h to obtain a mixed solution a. In the mixed solution a, the MOF solution, the mercapto-polyethylene glycol-carboxyl solution, and the cystine solution were mixed according to the mass ratio of the copper-based metallic organic framework, mercapto-polyethylene glycol-carboxyl, and cystine of 10:1:0.5;
[0095] A3: Nanoscale silver particles were added to the mixed solution a, and the concentration of nanoscale silver in the mixed solution a was 4 g / L. After ultrasonic treatment for 1 h, the solution was centrifuged, separated, washed, and dried to obtain a modified MOF.
[0096] The remaining raw materials and steps were the same as those in Example 1.
[0097] Comparative Example 4
[0098] Compared with Example 1, the difference in this comparative example is that the modified MOF is replaced by ZIF-8, and the other raw materials and steps are the same as those in Example 1.
[0099] Comparative Example 5
[0100] Compared with Example 1, the difference in this comparative example is that the addition amount of the modified MOF is 0.5 g, and the other raw materials and steps are the same as those in Example 1.
[0101] Comparative Example 6
[0102] Compared with Example 5, the difference in this comparative example is that the addition amount of the modified MOF is 4.5 g, and the other raw materials and steps are the same as those in Example 5.
[0103] The gels prepared in Examples 1 - 5 and Comparative Examples 1 - 6 were subjected to performance tests. The test items are as follows, and the test results are shown in Table 1:
[0104] I. Antibacterial performance test: The single colonies of Staphylococcus aureus and Escherichia coli on the solid LB agar plate were immersed in 40 mL of fresh LB solution at a fixed temperature (37°C) with gentle shaking (75 rpm) for 24 h. Then, the obtained bacterial suspension was diluted to 105 CFU / mL. The sample was added to 2 mL of the bacterial suspension, and then the suspension was incubated at 37°C with a shaking speed of 75 rpm. After 24 h of incubation, the number of colonies was counted and the antibacterial rate was evaluated using the following equation: Antibacterial rate (%) = (number of bacteria in the control group - number of bacteria in the experimental group) / number of bacteria in the control group × 100%.
[0105] II. Wound healing rate test: Eleven adult male mice weighing 18 - 22 g were prepared, and a skin wound with a diameter of 8 mm was made on the back of each mouse. The wound was tightly covered with the sample gel. After 10 days, the wound size of the mice was measured. The wound healing rate was calculated using the following formula: Wound healing rate (%) = (S0 - S10) / S0 × 100%, where S0 represents the initial wound area size and S10 represents the wound area size on the 10th day.
[0106] III. Mechanical strength test: The sample was prepared into a dumbbell-shaped tensile test specimen spline, and the test was carried out according to the method of the standard "GB / T 1040.3 - 2006". Specifically, a 2 kN clamp was selected, the inlet force was 0.1 N, the tensile rate was 30 mm / min, and 6 spline specimens were stretched in each group to take the average value.
[0107] IV. Self-healing performance test: Cut the gel in the middle with a blade and then splice it together. Keep the interface aligned. After repairing at room temperature for 1 h, conduct a tensile performance test. Observe the two curves and the maximum tensile strength to evaluate the self-healing efficiency. The maximum tensile strength before repair is Pa0, and the maximum tensile strength after repair is Pa1. The calculation formula for the repair efficiency is as follows: Repair efficiency (%) = Pa1 / Pa0 × 100%.
[0108] Table 1
[0109]
[0110]
[0111] As can be seen from Table 1, the properties of the gels prepared in Examples 1 - 5 are superior to those in Comparative Examples 1 - 6. In Comparative Example 1, no silver nanoparticles are contained, and its antibacterial performance is significantly reduced compared with that in Example 1; in Comparative Example 2, no mercapto-polyethylene glycol-carboxyl and cystine are contained, the dispersibility of the modified MOF decreases, and the self-healing groups decrease, so its antibacterial performance and other properties are lower than those in Example 1; in Comparative Example 3, no zinc salt is contained, and the antibacterial performance decreases, indicating that copper and zinc ions can improve the antibacterial ability through synergistic effects and promote wound healing by reducing the possibility of wound infection. In Comparative Example 4, the modified MOF is replaced with ZIF-8, and the dispersibility is poor, and the comprehensive performance is the worst; the addition amounts of the modified MOF in Comparative Examples 5 and 6 are lower than that in Example 1 and higher than that in Example 5 respectively, but their properties are lower than those in Example 1 and Example 5 respectively, indicating that too high or too low addition amounts of the modified MOF are not conducive to preparing gels with excellent properties, and the addition amount of the modified MOF in the present invention is the optimal amount.
[0112] The above discloses only several specific embodiments of the present invention. However, the embodiments of the present invention are not limited thereto, and any changes that can be thought of by those skilled in the art should fall within the protection scope of the present invention.
Claims
1. An antibacterial repair gel for gynecology, characterized in that, It comprises components calculated according to the following weight percentages: 3-9% polyvinyl alcohol, 20-26% glycerol, 2-7% oxidized sodium alginate, 4-9% carboxymethyl chitosan, 1-4% modified MOF, and the balance is water; the modified MOF is nano-silver loaded on copper-zinc bimetallic organic framework modified by mercapto-polyethylene glycol-carboxyl and cystine.
2. The antibacterial repair gel for gynecology according to claim 1, characterized in that, The preparation method of oxidized sodium alginate is as follows: Dissolve sodium alginate in deionized water to prepare a sodium alginate solution; add sodium periodate to the sodium alginate solution in the dark and stir in the dark for 2-4 h; then add ethylene glycol and continue to stir in the dark for 0.5-2 h; add ethanol for precipitation, and filter out the precipitate; dissolve the precipitate in deionized water, dialyze, and freeze-dry to obtain oxidized sodium alginate; Among them, the mass fraction of the sodium alginate solution is 1%-5%; the mass ratio of sodium periodate to sodium alginate is (0.5-1):1; the addition amount of ethylene glycol is 2-5 mL / g sodium alginate.
3. The antibacterial repair gel for gynecology according to claim 1, characterized in that, The preparation method of modified MOF is as follows: A1: Ultrasonically dissolve a copper salt and 2-aminoterephthalic acid in methanol to obtain a mixed solution, then add a zinc salt, ultrasonically dissolve for 20-30 min, then add it to a reaction kettle, heat at 120 °C for 12-24 h, cool to room temperature, centrifuge, wash, and vacuum dry to obtain a copper-zinc bimetallic organic framework; A2: Add the copper-zinc bimetallic organic framework to a 5 wt% DMF aqueous solution to form a MOF solution, and add mercapto-polyethylene glycol-carboxyl to a 5 wt% DMF aqueous solution of DMF to form a mercapto-polyethylene glycol-carboxyl solution; dissolve cystine in a 5 wt% dimethyl sulfoxide aqueous solution to form a cystine solution; mix the MOF solution, mercapto-polyethylene glycol-carboxyl solution, and cystine solution, ultrasonically for 5-10 min, and then stir at room temperature for 12 h to obtain a mixed solution a; A3: Add nano-silver particles to the mixed solution a, ultrasonically for 1-5 h, then centrifuge, wash, and dry the solution to obtain the modified MOF.
4. The antibacterial repair gel for gynecology according to claim 3, characterized in that, In step A1, the molar ratio of the copper salt, 2-aminoterephthalic acid, and zinc salt is 1:1:(0.2-0.4); the concentration of the copper salt in the mixed solution is 4 g / L.
5. The antibacterial repair gel for gynecology according to claim 3, characterized in that, In step A1, the zinc salt is any one of zinc nitrate hexahydrate, zinc acetate, and zinc chloride.
6. The antibacterial repair gel for gynecology according to claim 3, characterized in that, In step A1, the copper salt is any one of copper nitrate trihydrate, copper sulfate pentahydrate, and copper chloride dihydrate.
7. The antibacterial repair gel for gynecology according to claim 3, characterized in that, In step A2, the dosage ratio of the copper-zinc bimetallic organic framework to the DMF aqueous solution is 5 g:140 mL; the dosage ratio of mercapto-polyethylene glycol-carboxyl to the DMF aqueous solution is 0.4 g:100 mL; the dosage ratio of cystine to the dimethyl sulfoxide aqueous solution is 0.34 g:100 mL; in the mixed solution a, the MOF solution, mercapto-polyethylene glycol-carboxyl solution, and cystine solution are mixed according to the mass ratio of the copper-zinc bimetallic organic framework, mercapto-polyethylene glycol-carboxyl, and cystine of 10:(1-2):(0.5-1).
8. The antibacterial repair gel for gynecology according to claim 3, characterized in that, In step A3, the concentration of nano-silver in the mixed solution a is 4-6 g / L.
9. The preparation method of a gynecological antibacterial repair gel according to any one of claims 1-8, characterized in that, It includes the following steps: S1: Mix glycerol, polyvinyl alcohol and water evenly, and then carry out closed reflux at 100 - 120 °C for 1 - 2 h to obtain a polyvinyl alcohol - glycerol precursor solution; S2: Add sodium alginate oxide, carboxymethyl chitosan, and modified MOF into the polyvinyl alcohol - glycerol precursor solution obtained in S1, mix evenly, and then react at 80 - 90 °C for 10 - 12 h to obtain a hydrogel precursor solution; S3: Cool the hydrogel precursor solution to 20 - 30 °C to obtain an antibacterial repair gel for gynecology.
10. The preparation method of a gynecological antibacterial repair gel according to claim 9, characterized in that, In step S3, the cooling rate is 2 - 10 °C / min.