Antibacterial gel dressing beneficial to treatment of gynecological diseases and preparation method thereof
By combining silver-copper bimetallic MOF materials, gold nanorod hybrid MXene nanosheet composite carriers and licorice polysaccharide-based hydrogels, a dense porous structure is formed, which solves the stability problem of hydrogel dressings under the influence of the external environment and achieves efficient treatment of gynecological diseases.
Patent Information
- Application Number
- CN202510826078.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-19
- Publication Date
- 2025-09-12
AI Technical Summary
Existing hydrogel dressings have poor structural stability under the influence of the external environment, which affects the antibacterial effect. The antibacterial effect is not ideal and it is difficult to effectively treat gynecological diseases.
A combination of silver-copper bimetallic loaded MOF material, gold nanorod hybrid MXene nanosheet composite carrier and licorice polysaccharide-based hydrogel is used, which is attached to the hydrogel through a preparation method to form a dense porous structure. Combined with photothermal properties and traditional Chinese medicine composition, multi-pathway antibacterial treatment is achieved.
It significantly improves the stability of the gel structure and the antibacterial effect, enhances the ability to kill bacteria, can effectively treat gynecological diseases, and has excellent drug loading capacity and stability.
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Figure CN120617606A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of medical dressings, and in particular relates to an antibacterial gel dressing beneficial for treating gynecological diseases and a preparation method thereof. Background Art
[0002] Among all women of childbearing age, the number of patients suffering from gynecological diseases is increasing. Such diseases are mainly caused by group infections such as Escherichia coli, Staphylococcus aureus, Lactobacillus, Candida albicans and Trichomonas, which can cause vaginitis, cervical diseases, and even lead to serious consequences such as tumors and miscarriage. Most women fail to pay enough attention to gynecological diseases, and insufficient daily prevention has also led to a substantial increase in the number of patients, and even brought great inconvenience to normal life and work. Even if cured, it will lead to recurrence if it is not taken seriously in the later stage.
[0003] In recent years, with the abuse of antibiotics and the development of drug resistance in the human body, people have paid more and more attention to the application of safe natural medicines. Among them, natural hydrogels not only have adhesion properties and can fit tightly to biological tissues, but can also be used as drug carriers to achieve sustained and controlled release of drugs, thereby improving the antibacterial effect of drugs. They have broad application prospects in the field of medical dressings for gynecological diseases.
[0004] The existing technology currently has the following problems:
[0005] Common hydrogels have certain water absorption and are easily affected by the external environment, which has an adverse effect on the stability of the gel structure and further restricts the antibacterial effect. Summary of the Invention
[0006] In view of the above situation, in order to overcome the defects of the prior art, the present invention proposes an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases, comprising the following components in parts by weight: 30-40 parts of MOF material loaded with silver-copper bimetallic, 20-30 parts of licorice polysaccharide-based hydrogel, 10-20 parts of gold nanorod hybrid MXene nanosheet composite carrier, and 20-30 parts of traditional Chinese medicine composition.
[0007] The silver-copper bimetallic MOF material comprises the following components in parts by weight: 6-8 parts of silver nitrate, 10-12 parts of copper nitrate trihydrate, and 5-8 parts of pyridine-3,5-dicarboxylic acid.
[0008] The gold nanorod hybrid MXene nanosheet composite carrier comprises the following components in parts by weight: 10-20 parts of MXene nanosheets, 8-10 parts of gold nanorods, and 3-4 parts of thiol-polyethylene glycol-methoxyl groups.
[0009] The raw materials of the traditional Chinese medicine composition include the following components in parts by weight: 3-5 parts of honeysuckle, 3-5 parts of dandelions, 3-5 parts of viola yedoensis, 3-5 parts of gardenia, 3-5 parts of plantain seeds, 3-5 parts of phellodendron, 3-5 parts of angelica dahurica, and 3-5 parts of liquorice.
[0010] The preparation method of the gold nanorod hybrid MXene nanosheet composite carrier specifically comprises the following steps:
[0011] (1) Add 1.6 g of lithium fluoride to 20 mL of 30% hydrochloric acid solution, then slowly add 1.0 g of titanium aluminum carbide, stir at 40-50 ° C for 20-30 h, centrifuge at 3000-4000 rpm for 5 min, wash with deionized water until the pH is 6.0, collect the supernatant containing MXene flakes, centrifuge at 3000-4000 rpm for 1 h, repeat this process until the supernatant becomes clear, stop collecting, and concentrate the collected MXene solution under reduced pressure to 15-20 mL. As a new type of two-dimensional material, MXene nanosheets have a large specific surface area and high photothermal conversion efficiency. They can be used as drug carriers and combined with photodynamic therapy to introduce antibacterial treatment, which can effectively kill bacteria and treat gynecological diseases caused by bacterial infection to obtain MXene nanosheets;
[0012] (2) Add 100 μL of 1% chloroauric acid solution to 10 mL of 8-10% hexadecyltrimethylammonium bromide solution, then add 600 μL of 0.05% sodium borohydride ice water solution, stir at 8000-10000 rpm for 2-3 min, take 1-2 mL of the prepared seed solution, add it to the MXene nanosheets described in step (1), stir in a constant temperature water bath at 28 ° C in the dark for 1-2 h, and stir at a speed of 60-80 rpm. , and then immediately add the growth solution after it becomes colorless after stirring. The mixture is placed in a constant temperature water bath at 28°C and protected from light for 12 hours. The negatively charged MXene nanosheets are combined with the positively charged gold nanorod seed solution by electrostatic interaction, so that the gold nanorods grow in situ on the surface of the MXene nanosheets, which not only effectively prevents the stacking of nanosheets, but also increases the drug loading capacity. At the same time, it can also synergistically enhance the photothermal performance, which is beneficial to enhance the killing effect of bacteria, and obtain a gold nanorod hybrid MXene nanosheet solution;
[0013] (3) The gold nanorod hybrid MXene nanosheet solution described in step (2) is centrifuged at a speed of 10000-12000 rpm for 1-2 times, and the precipitate is dispersed in 2 mL of deionized water and stored in a constant temperature water bath at 28°C for use. 30-40 mg of thiol-polyethylene glycol-methoxy powder is weighed and dissolved in 18 mL of deionized water. The precipitate dispersion is slowly added while stirring at a speed of 800-1000 rpm, and then stirred at a speed of 200-300 rpm in the dark for 5-6 hours, centrifuged, and the product is collected. A tight Au-S bond is formed between the gold nanorod hybrid MXene nanosheet and the thiol-polyethylene glycol-methoxy group, which can replace the hexadecyltrimethylammonium bromide on the surface of the gold nanorod to improve biocompatibility and enhance the stability of the structure. It can be used as a nanocarrier with good application effect in photothermal treatment of bacterial infections of gynecological diseases, and a gold nanorod hybrid MXene nanosheet composite carrier is obtained;
[0014] Preferably, in step (2), the growth solution is prepared by first weighing 4.0 g of hexadecyltrimethylammonium bromide and dissolving it in 98 mL of deionized water, then adding 2 mL of a 1% chloroauric acid solution and stirring evenly, then adding 1-2 mg of silver nitrate and stirring for 30 min, adding 0.1 mg of ascorbic acid, and stirring at a speed of 6000-8000 rpm. By adding the growth solution, gold ions can be reduced to gold atoms, and crystals can be grown in a specific direction, with a high specific surface area and a high loading capacity, and good dispersibility and stability.
[0015] The preparation method of the silver-copper bimetallic MOF material specifically comprises the following steps:
[0016] Dissolve 0.06-0.08g of silver nitrate and 0.10-0.12g of copper nitrate trihydrate in 5mL of water and stir until completely dissolved to prepare a metal ion solution for use. Then weigh 0.05-0.08g of pyridine-3,5-dicarboxylic acid and dissolve it in 5mL of water. Stir in an ultrasonic water bath at 40-50°C for 20-30min. The obtained pyridine-3,5-dicarboxylic acid suspension is mixed with the metal ion solution. The mixture is magnetically stirred at a speed of 100-200rpm at 20°C for 10-15min. The mixed solution is transferred to a 25mL polytetrafluoroethylene liner. The reactor is placed in an oven and heated to 100-120°C. The reaction is carried out for 18-24h. The product is vacuum filtered and collected and washed with deionized water and water. The mixture was washed alternately with water and ethanol three times and then vacuum dried. Zinc nitrate, copper nitrate trihydrate and pyridine-3,5-dicarboxylic acid were used as raw materials to synthesize a bimetallic MOF loaded with silver ions and copper ions under hydrothermal conditions. The antibacterial effect was achieved based on the direct interaction between the active sites on its surface and the bacterial surface and the released metal ions destroying the permeability of the bacterial cell membrane. Among them, MOF, as a storage depot for silver ions and copper ions, can slowly and steadily release metal ions, which can not only reduce the toxicity of metal ions to cells, but also maintain long-term antibacterial properties. The loading of silver ions and copper ions also increases the high specific surface area of MOF and increases the contact area between the active sites and bacteria, thereby obtaining a MOF material loaded with silver-copper bimetallic.
[0017] The present invention also provides a method for preparing an antibacterial gel dressing useful for treating gynecological diseases, which specifically comprises the following steps:
[0018] S1. The honeysuckle, dandelion, viola yedong ding, gardenia, plantain seed, phellodendron, angelica dahurica and licorice were dried and pretreated and then crushed, mixed evenly, 500g of Chinese medicine powder was weighed and placed in 6-8 times the amount by mass fraction of 80% ethanol solution, soaked overnight, and then heated and pressurized in a reflux condenser and a rotary evaporator for 1-3 times, the extracts were combined, filtered, and the total extract was concentrated under reduced pressure. The honeysuckle, dandelion and viola yedong can clear away heat and detoxify, gardenia and plantain seed can be lightly infiltrated and diuretic, so that the damp-heat evil is discharged from the urine, phellodendron has the effect of clearing heat, purging fire and detoxifying, angelica dahurica has the effect of dispelling disease and dampness, discharging pus and promoting tissue regeneration, and promoting blood circulation and relieving pain. Licorice coordinates the synergistic effect of the components, thereby being able to safely and effectively treat gynecological diseases caused by bacterial infection to obtain a Chinese medicine composition;
[0019] S2. Dissolve carboxymethyl chitosan in 100 mL of water, vanillin in 50 mL of anhydrous ethanol, and glycyrrhizic acid polysaccharide in 50 mL of water, stir them separately, then add the MOF material loaded with silver-copper bimetallic to the glycyrrhizic acid solution, stir magnetically for 10-30 min, mix it with the carboxymethyl chitosan solution and the vanillin alcohol solution, let it stand at room temperature for 5-6 h, and distribute the MOF material loaded with silver-copper bimetallic on the glycyrrhizic acid-based hydrogel to form a connected and dense porous gel. The addition of the MOF material loaded with silver-copper bimetallic can be combined with The amino and hydroxyl chelation on carboxymethyl chitosan significantly reduced the pore size of the gel network, enhanced the cross-linking density, and improved the structural stability. The hydrogel's network structure and surface metal active sites interacted with the bacterial cell membrane. The slow collapse of the gel structure and MOF structure led to the release of a small amount of metal ions and organic ligands, which triggered bacterial cell membrane damage and achieved excellent bactericidal and antibacterial effects. At the same time, the network structure also reduced the adverse reactions caused by the rapid release of metal ions, resulting in a MOF material-modified licorice polysaccharide-based hydrogel loaded with silver and copper bimetallics.
[0020] S3, the gold nanorod hybrid MXene nanosheet composite carrier and the silver-copper bimetallic MOF material modified licorice polysaccharide-based hydrogel described in step S2 are placed in the traditional Chinese medicine composition described in step S1 in sequence, ultrasonically treated for 20-30 minutes, taken out, and then the drug-loaded gold nanorod hybrid MXene nanosheet composite carrier is placed in a polytetrafluoroethylene mold, and then the drug-loaded hydrogel is cast in the polytetrafluoroethylene mold. After four freeze-thaw cycles, the gold nanorod hybrid MXene nanosheet composite carrier can be evenly dispersed in the gel structure, further reducing the The network pore size reduces water absorption and penetration, improves structural stability, and also gives the gel excellent photothermal properties, which can be combined with photothermal therapy to achieve an antibacterial effect. The MOF material modified licorice polysaccharide-based hydrogel loaded with silver and copper bimetallic also improves the drug loading limitation problem of the gold nanorod hybrid MXene nanosheet composite carrier. Through the synergistic cooperation of the gel network, surface active sites, photothermal properties and traditional Chinese medicine composition, the bacteria that cause gynecological diseases are killed in multiple ways, from multiple angles and methods, with significant antibacterial therapeutic effects, and an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases is obtained;
[0021] Preferably, in step S2, the amount of carboxymethyl chitosan added is 4.0-5.0 g, the amount of vanillin added is 1.5-2.5 g, and the amount of glycyrrhizic acid polysaccharide added is 2.0-3.0 g. Biocompatible carboxymethyl chitosan and non-toxic vanillin are used as the matrix for forming the hydrogel, and the active substance glycyrrhizic acid polysaccharide is added to give the hydrogel certain antibacterial properties, thereby preparing a hydrogel material with excellent biocompatibility, self-healing and adhesion properties, which has excellent advantages in use as a dressing for gynecological diseases.
[0022] The beneficial effects achieved by the present invention are as follows:
[0023] The present invention enhances the stability of the gel structure and reduces the adverse effects of external moisture by attaching and dispersing a silver-copper bimetallic MOF material and a gold nanorod hybrid MXene nanosheet composite carrier on a glycyrrhizic acid-based hydrogel. At the same time, it significantly increases the loading capacity of the traditional Chinese medicine composition. Furthermore, under the synergistic effect of the gel network, surface active sites, and photothermal properties in the dressing, the bacteria that cause gynecological diseases are effectively killed, achieving an excellent antibacterial therapeutic effect. In the glycyrrhizic acid-based hydrogel modified with the silver-copper bimetallic MOF material, the silver-copper bimetallic MOF material is distributed in the glycyrrhizic acid-based hydrogel. On the gel, a dense porous gel is formed, which reduces the pore size of the gel network, enhances the cross-linking density, reduces the water absorption, and thus improves the stability. The network structure of the hydrogel is conducive to the contact between the metal active sites on the MOF surface and the bacterial cell membrane. As the gel structure and the MOF structure slowly collapse, a small amount of metal ions and organic ligands are released, which triggers the damage of the bacterial cell membrane and achieves excellent bactericidal and antibacterial effects. Among them, the MOF material loaded with silver-copper bimetallic destroys the permeability of the bacterial cell membrane based on the direct interaction between its surface active sites and the bacterial surface and the released metal ions, thereby achieving antibacterial effect. Bacterial effect; in the gold nanorod hybrid MXene nanosheet composite carrier, the gold nanorods are in situ grown on the surface of the MXene nanosheet, which not only prevents the stacking of the nanosheets, but also increases the drug loading of the nanosheets. At the same time, the two can synergistically enhance the photothermal performance and strengthen the killing effect on bacteria. In addition, the addition of thiol-polyethylene glycol-methoxy groups improves the biocompatibility and structural stability. The gold nanorod hybrid MXene nanosheet composite carrier and the MOF material modified licorice polysaccharide-based hydrogel loaded with silver-copper bimetallic are respectively loaded with the antibacterial component traditional Chinese medicine composition, and then freeze-thaw combination is performed to prepare a gel dressing Among them, the gold nanorod hybrid MXene nanosheet composite carrier further reduces the network pore size of the gel structure, reduces the absorption and penetration of water, and reduces the adverse effects of the external environment on the stability of the gel. At the same time, it also gives the gel excellent photothermal properties, so that it can be combined with photothermal therapy to achieve an antibacterial effect; the present invention uses MOF materials loaded with silver-copper bimetallic, licorice polysaccharide-based hydrogel, gold nanorod hybrid MXene nanosheet composite carrier and traditional Chinese medicine composition to prepare an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases. It has excellent drug loading capacity and stability, can effectively reduce bacterial infection, and is beneficial for the treatment of gynecological diseases. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1 This is a scanning electron micrograph of the antibacterial gel dressing for treating gynecological diseases prepared in Example 1 of the present invention;
[0025] Figure 2 The drug loading results of Examples 1-4 and Comparative Examples 1-3 of the present invention are shown;
[0026] Figure 3 The water absorption results of Examples 1-4 and Comparative Examples 1-3 of the present invention are shown in FIG.
[0027] Figure 4 The graph shows the antibacterial rates of Examples 1-4 and Comparative Examples 1-3 of the present invention. DETAILED DESCRIPTION
[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.
[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described herein can be applied to the present invention. The preferred embodiments and materials described herein are for illustrative purposes only and are not intended to limit the scope of this application.
[0030] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.
[0031] Example 1
[0032] This embodiment proposes an antibacterial gel dressing that is beneficial for treating gynecological diseases, comprising the following components in parts by weight: 40 parts of a silver-copper bimetallic MOF material, 30 parts of a licorice polysaccharide-based hydrogel, 20 parts of a gold nanorod hybrid MXene nanosheet composite carrier, and 30 parts of a traditional Chinese medicine composition.
[0033] The MOF material loaded with silver-copper bimetallic includes the following components in parts by weight: 8 parts of silver nitrate, 12 parts of copper nitrate trihydrate, and 8 parts of pyridine-3,5-dicarboxylic acid.
[0034] The gold nanorod hybrid MXene nanosheet composite carrier includes the following components in parts by weight: 20 parts of MXene nanosheets, 10 parts of gold nanorods, and 4 parts of thiol-polyethylene glycol-methoxy.
[0035] The Chinese medicine composition comprises the following components in parts by weight: 5 parts of honeysuckle, 5 parts of dandelion, 5 parts of viola yedoensis, 5 parts of gardenia, 5 parts of plantain seeds, 5 parts of phellodendron, 5 parts of angelica dahurica and 5 parts of liquorice.
[0036] The preparation method of the gold nanorod hybrid MXene nanosheet composite carrier specifically comprises the following steps:
[0037] (1) Add 1.6 g of lithium fluoride to 20 mL of 30% hydrochloric acid solution, then slowly add 1.0 g of titanium aluminum carbide, stir at 50 ° C for 30 h, centrifuge at 4000 rpm for 5 min, wash with deionized water until pH 6.0, collect the supernatant containing MXene flakes, centrifuge at 4000 rpm for 1 h, repeat this process until the supernatant becomes clear, stop collecting, and concentrate the collected MXene solution under reduced pressure to 20 mL. As a new type of two-dimensional material, MXene nanosheets have a large specific surface area and high photothermal conversion efficiency. They can be used as drug carriers and combined with photodynamic therapy to introduce antibacterial treatment, which can effectively kill bacteria and treat gynecological diseases caused by bacterial infection, thereby obtaining MXene nanosheets;
[0038] (2) Add 100 μL of 1% chloroauric acid solution to 10 mL of 10% hexadecyltrimethylammonium bromide solution, then add 600 μL of 0.05% sodium borohydride ice water solution, stir at 10,000 rpm for 3 min, take 2 mL of the prepared seed solution, add it to the MXene nanosheets described in step (1), stir in a constant temperature water bath at 28°C in the dark for 2 h, stirring at 80 rpm, and then add it immediately after the growth solution becomes colorless. The growth solution is to first weigh 4.0 g of hexadecyltrimethylammonium bromide and dissolve it in 98 mL of deionized water, then add 2 mL of 1% chloroauric acid solution, stir evenly, and then add 2 mg of silver nitrate. After stirring for 30 minutes, 0.1 mg of ascorbic acid was added and stirred at 8000 rpm. The addition of the growth solution can reduce gold ions to gold atoms and cause crystal growth along a specific direction, with a high specific surface area and a high loading capacity, as well as good dispersibility and stability. The mixed solution was placed in a 28°C constant temperature water bath and stored away from light for 12 hours. The negatively charged MXene nanosheets were combined with the positively charged gold nanorod seed solution by electrostatic action, so that the gold nanorods were in situ grown on the surface of the MXene nanosheets, which not only effectively prevented the stacking of the nanosheets, but also increased the drug loading capacity. At the same time, it can synergistically enhance the photothermal performance, which is beneficial to enhance the killing effect on bacteria, and obtain a gold nanorod hybrid MXene nanosheet solution;
[0039] (3) The gold nanorod hybrid MXene nanosheet solution described in step (2) was centrifuged twice at 12000 rpm, the precipitate was dispersed in 2 mL of deionized water, and stored in a constant temperature water bath at 28°C for use. 40 mg of thiol-polyethylene glycol-methoxy powder was weighed and dissolved in 18 mL of deionized water. The precipitate dispersion was slowly added under stirring at 1000 rpm, and then stirred at 300 rpm in the dark for 6 h. The product was centrifuged and collected. A tight Au-S bond was formed between the gold nanorod hybrid MXene nanosheet and the thiol-polyethylene glycol-methoxy group, which could not only replace the hexadecyltrimethylammonium bromide on the surface of the gold nanorods to improve biocompatibility, but also enhance the stability of the structure. It can be used as a nanocarrier with good application effect in photothermal treatment of bacterial infections of gynecological diseases, and a gold nanorod hybrid MXene nanosheet composite carrier was obtained.
[0040] The preparation method of the MOF material loaded with silver-copper bimetallic material specifically comprises the following steps:
[0041] 0.08 g of silver nitrate and 0.12 g of copper nitrate trihydrate were dissolved in 5 mL of water and stirred until completely dissolved to prepare a metal ion solution for use. 0.08 g of pyridine-3,5-dicarboxylic acid was weighed and dissolved in 5 mL of water. The solution was stirred in an ultrasonic water bath at 50 ° C for 30 min. The obtained pyridine-3,5-dicarboxylic acid suspension was mixed with the metal ion solution and magnetically stirred at 200 rpm for 15 min at 20 ° C. The mixed solution was transferred to a 25 mL polytetrafluoroethylene liner. The reactor was placed in an oven and heated to 120 ° C. The reaction was carried out for 24 h. The product was vacuum filtered and collected and washed alternately with deionized water and anhydrous ethanol for 3 times, and then vacuum dried. Using zinc nitrate, copper nitrate trihydrate and pyridine-3,5-dicarboxylic acid as raw materials, a bimetallic MOF loaded with silver ions and copper ions was synthesized under hydrothermal conditions. The antibacterial effect was achieved based on the direct interaction between the active sites on its surface and the bacterial surface and the released metal ions destroying the permeability of the bacterial cell membrane. Among them, MOF, as a storage depot for silver ions and copper ions, can slowly and stably release metal ions, which can not only reduce the toxicity of metal ions to cells, but also maintain long-term antibacterial properties. The loading of silver ions and copper ions also increases the high specific surface area of MOF and increases the contact area between the active sites and bacteria, thereby obtaining a MOF material loaded with silver-copper bimetallic.
[0042] This embodiment provides a method for preparing an antibacterial gel dressing that is beneficial for treating gynecological diseases, which specifically includes the following steps:
[0043] S1. The honeysuckle, dandelion, viola yedong ding, gardenia, plantain seed, phellodendron, angelica dahurica and licorice were dried and pretreated and then crushed, mixed evenly, 500g of Chinese medicine powder was weighed and placed in 8 times the amount by mass of 80% ethanol solution, soaked overnight, and then heated and pressurized in a reflux condenser and a rotary evaporator for extraction 3 times, the extracts were combined, filtered, and the total extract was concentrated under reduced pressure. The honeysuckle, dandelion and viola yedong can clear away heat and detoxify, gardenia and plantain seed can be lightly infiltrated and diuretic, so that the damp-heat evil is discharged from the urine, phellodendron has the effect of clearing heat, purging fire and detoxifying, angelica dahurica has the effect of dispelling disease and dampness, discharging pus and promoting tissue regeneration, and promoting blood circulation and relieving pain. Licorice coordinates the synergistic synergy of the components, thereby being able to safely and effectively treat gynecological diseases caused by bacterial infection to obtain a Chinese medicine composition;
[0044] S2. Dissolve carboxymethyl chitosan in 100 mL of water, dissolve vanillin in 50 mL of anhydrous ethanol, and dissolve glycyrrhizic acid polysaccharide in 50 mL of water, and stir them evenly. The amount of carboxymethyl chitosan added is 5.0 g, the amount of vanillin added is 2.5 g, and the amount of glycyrrhizic acid polysaccharide added is 3.0 g. Biocompatible carboxymethyl chitosan and non-toxic vanillin are used as matrices to form a hydrogel. The active substance glycyrrhizic acid polysaccharide is added to give the hydrogel certain antibacterial properties. A hydrogel material with excellent biocompatibility, self-healing and adhesion properties is prepared, which has excellent advantages in use as a dressing for gynecological diseases. Then, the MOF material loaded with silver-copper bimetallic is added to the glycyrrhizic acid polysaccharide solution, and magnetic stirring is performed for 30 min. Then, the MOF material is mixed with the carboxymethyl chitosan solution and the vanillin alcohol solution. The liquid was mixed evenly and allowed to stand at room temperature for 6 hours. The silver-copper bimetallic MOF material was distributed on the licorice polysaccharide-based hydrogel to form a connected and dense porous gel. The addition of the silver-copper bimetallic MOF material can chelate with the amino and hydroxyl groups on the carboxymethyl chitosan, significantly reducing the pore size of the gel network, enhancing the cross-linking density, and improving the structural stability. The network structure and surface metal active sites of the hydrogel interacted with the bacterial cell membrane. With the slow collapse of the gel structure and the MOF structure, a small amount of metal ions and organic ligands were released, thereby causing damage to the bacterial cell membrane and achieving excellent bactericidal and antibacterial effects. At the same time, the network structure also reduced the adverse reactions caused by the rapid release of metal ions, and obtained a licorice polysaccharide-based hydrogel modified with a silver-copper bimetallic MOF material.
[0045] S3, the gold nanorod hybrid MXene nanosheet composite carrier and the silver-copper bimetallic MOF material modified licorice polysaccharide-based hydrogel described in step S2 are placed in the traditional Chinese medicine composition described in step S1 in sequence, ultrasonically treated for 30 minutes, taken out, and then the drug-loaded gold nanorod hybrid MXene nanosheet composite carrier is placed in a polytetrafluoroethylene mold, and then the drug-loaded hydrogel is cast in the polytetrafluoroethylene mold. After four freeze-thaw cycles, the gold nanorod hybrid MXene nanosheet composite carrier can be evenly dispersed in the gel structure, further reducing the network The pore size reduces the absorption and penetration of water, improves the stability of the structure, and also gives the gel excellent photothermal properties, which can be combined with photothermal therapy to achieve an antibacterial effect. The MOF material modified licorice polysaccharide-based hydrogel loaded with silver-copper bimetallic also improves the drug loading limitation problem of the gold nanorod hybrid MXene nanosheet composite carrier. Through the synergistic cooperation of the gel network, surface active sites, photothermal properties and traditional Chinese medicine compositions, the bacteria that cause gynecological diseases are killed in multiple ways, from multiple angles and by multiple methods, with significant antibacterial therapeutic effects, and an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases is obtained.
[0046] In this embodiment, the antibacterial gel dressing prepared for treating gynecological diseases was subjected to scanning electron microscopy to observe its microscopic morphology. Figure 1 This is a 10,000-fold magnified SEM image of the antibacterial gel dressing for treating gynecological diseases prepared in Example 1. Figure 1 The antibacterial gel dressing prepared in this embodiment, which is beneficial for treating gynecological diseases, presents a dense network structure.
[0047] Example 2
[0048] This embodiment proposes an antibacterial gel dressing that is beneficial for treating gynecological diseases, comprising the following components in parts by weight: 30 parts of a silver-copper bimetallic MOF material, 20 parts of a licorice polysaccharide-based hydrogel, 10 parts of a gold nanorod hybrid MXene nanosheet composite carrier, and 20 parts of a traditional Chinese medicine composition.
[0049] The MOF material loaded with silver-copper bimetallic includes the following components in parts by weight: 6 parts of silver nitrate, 10 parts of copper nitrate trihydrate, and 5 parts of pyridine-3,5-dicarboxylic acid.
[0050] The gold nanorod hybrid MXene nanosheet composite carrier includes the following components in parts by weight: 10 parts of MXene nanosheets, 8 parts of gold nanorods, and 3 parts of mercapto-polyethylene glycol-methoxy.
[0051] The Chinese medicine composition comprises the following components in parts by weight: 3 parts of honeysuckle, 3 parts of dandelion, 3 parts of viola yedoensis, 3 parts of gardenia, 3 parts of plantain seeds, 3 parts of phellodendron, 3 parts of angelica dahurica and 3 parts of liquorice.
[0052] The preparation method of the gold nanorod hybrid MXene nanosheet composite carrier specifically comprises the following steps:
[0053] (1) Add 1.6 g of lithium fluoride to 20 mL of 30% hydrochloric acid solution, then slowly add 1.0 g of titanium aluminum carbide, stir at 40 ° C for 20 h, centrifuge at 3000 rpm for 5 min, wash with deionized water until pH 6.0, collect the supernatant containing MXene flakes, centrifuge at 3000 rpm for 1 h, repeat this process until the supernatant becomes clear, stop collecting, and concentrate the collected MXene solution under reduced pressure to 15 mL. As a new type of two-dimensional material, MXene nanosheets have a large specific surface area and high photothermal conversion efficiency. They can be used as drug carriers and combined with photodynamic therapy to introduce antibacterial treatment, which can effectively kill bacteria and treat gynecological diseases caused by bacterial infection, thereby obtaining MXene nanosheets;
[0054] (2) Add 100 μL of 1% chloroauric acid solution to 10 mL of 8% hexadecyltrimethylammonium bromide solution, then add 600 μL of 0.05% sodium borohydride ice water solution, stir at 8000 rpm for 2 min, take 1 mL of the prepared seed solution, add it to the MXene nanosheets described in step (1), stir in a constant temperature water bath at 28 ° C in the dark for 1 h, stirring at 60 rpm, and then wait until the growth solution becomes colorless and immediately add it to the growth solution. First, weigh 4.0 g of hexadecyltrimethylammonium bromide and dissolve it in 98 mL of deionized water, then add 2 mL of 1% chloroauric acid solution and stir evenly, then add 1 mg of silver nitrate and stir. Stir for 30 minutes, add 0.1 mg of ascorbic acid, and stir at 6000 rpm. By adding the growth solution, gold ions can be reduced to gold atoms, and crystals can grow along a specific direction, with high specific surface area and high loading capacity, good dispersibility and stability. The mixed solution is placed in a constant temperature water bath at 28°C and stored away from light for 12 hours. The negatively charged MXene nanosheets are combined with the positively charged gold nanorod seed solution by electrostatic action, so that the gold nanorods are in situ grown on the surface of the MXene nanosheets, which not only effectively prevents the stacking of the nanosheets, but also increases the drug loading capacity. At the same time, it can synergistically enhance the photothermal performance, which is beneficial to enhance the killing effect of bacteria, and obtain a gold nanorod hybrid MXene nanosheet solution;
[0055] (3) The gold nanorod hybrid MXene nanosheet solution described in step (2) was centrifuged once at a speed of 10,000 rpm, and the precipitate was dispersed in 2 mL of deionized water and stored in a constant temperature water bath at 28°C for use. 30 mg of thiol-polyethylene glycol-methoxy powder was weighed and dissolved in 18 mL of deionized water. The precipitate dispersion was slowly added under stirring at a speed of 800 rpm, and then stirred at a speed of 200 rpm in the dark for 5 h. The product was centrifuged and collected. A tight Au-S bond was formed between the gold nanorod hybrid MXene nanosheet and the thiol-polyethylene glycol-methoxy group, which could not only replace the hexadecyltrimethylammonium bromide on the surface of the gold nanorods to improve biocompatibility, but also enhance the stability of the structure. It can be used as a nanocarrier with good application effect in photothermal treatment of bacterial infections of gynecological diseases, and a gold nanorod hybrid MXene nanosheet composite carrier was obtained.
[0056] The preparation method of the MOF material loaded with silver-copper bimetallic material specifically comprises the following steps:
[0057] 0.06 g of silver nitrate and 0.10 g of copper nitrate trihydrate were dissolved in 5 mL of water and stirred until completely dissolved to prepare a metal ion solution for use. 0.05 g of pyridine-3,5-dicarboxylic acid was weighed and dissolved in 5 mL of water. The solution was stirred in an ultrasonic water bath at 40°C for 20 min. The obtained pyridine-3,5-dicarboxylic acid suspension was mixed with the metal ion solution and magnetically stirred at 100 rpm for 10 min at 20°C. The mixed solution was transferred to a 25 mL polytetrafluoroethylene liner. The reactor was placed in an oven and heated to 100°C. The reaction was carried out for 18 h. The product was vacuum filtered and collected and washed alternately with deionized water and anhydrous ethanol for 3 times, and then vacuum dried. Using zinc nitrate, copper nitrate trihydrate and pyridine-3,5-dicarboxylic acid as raw materials, a bimetallic MOF loaded with silver ions and copper ions was synthesized under hydrothermal conditions. The antibacterial effect was achieved based on the direct interaction between the active sites on its surface and the bacterial surface and the released metal ions destroying the permeability of the bacterial cell membrane. Among them, MOF, as a storage depot for silver ions and copper ions, can slowly and stably release metal ions, which can not only reduce the toxicity of metal ions to cells, but also maintain long-term antibacterial properties. The loading of silver ions and copper ions also increases the high specific surface area of MOF and increases the contact area between the active sites and bacteria, thereby obtaining a MOF material loaded with silver-copper bimetallic.
[0058] This embodiment provides a method for preparing an antibacterial gel dressing that is beneficial for treating gynecological diseases, which specifically includes the following steps:
[0059] S1. The honeysuckle, dandelion, viola yedong ding, gardenia, plantain seed, phellodendron, angelica dahurica and licorice were dried and pretreated and then crushed, mixed evenly, 500g of Chinese medicine powder was weighed and placed in 6 times the amount by mass of 80% ethanol solution, soaked overnight, and then heated and pressurized in a reflux condenser and a rotary evaporator for extraction once, the extracts were combined and filtered, and the total extract obtained was concentrated under reduced pressure. The honeysuckle, dandelion and viola yedong can clear away heat and detoxify, the gardenia and plantain seed can be lightly infiltrated and diuretic, and the damp-heat evil can be discharged from the urine, the phellodendron has the effect of clearing heat, purging fire and detoxifying, and the angelica dahurica has the effect of dispelling disease and dampness, discharging pus and promoting tissue regeneration, and promoting blood circulation and relieving pain. The licorice harmonizes the components synergistically, thereby being able to safely and effectively treat gynecological diseases caused by bacterial infection to obtain a Chinese medicine composition;
[0060] S2. Dissolve carboxymethyl chitosan in 100 mL of water, dissolve vanillin in 50 mL of anhydrous ethanol, and dissolve glycyrrhizic acid polysaccharide in 50 mL of water, and stir them evenly. The amount of carboxymethyl chitosan added is 4.0 g, the amount of vanillin added is 1.5 g, and the amount of glycyrrhizic acid polysaccharide added is 2.0 g. Biocompatible carboxymethyl chitosan and non-toxic vanillin are used as the matrix to form the hydrogel. The active substance glycyrrhizic acid polysaccharide is added to give the hydrogel certain antibacterial properties. A hydrogel material with excellent biocompatibility, self-healing and adhesion properties is prepared, which has excellent advantages in use as a dressing for gynecological diseases. Then, the MOF material loaded with silver-copper bimetallic is added to the glycyrrhizic acid polysaccharide solution, and magnetic stirring is performed for 10 min. Then, the MOF material is mixed with the carboxymethyl chitosan solution and the vanillin alcohol solution. The liquid was mixed evenly and allowed to stand at room temperature for 5 hours. The silver-copper bimetallic MOF material was distributed on the licorice polysaccharide-based hydrogel to form a connected and dense porous gel. The addition of the silver-copper bimetallic MOF material can chelate with the amino and hydroxyl groups on the carboxymethyl chitosan, significantly reducing the pore size of the gel network, enhancing the cross-linking density, and improving the structural stability. The network structure and surface metal active sites of the hydrogel interacted with the bacterial cell membrane. With the slow collapse of the gel structure and the MOF structure, a small amount of metal ions and organic ligands were released, thereby causing damage to the bacterial cell membrane and achieving excellent bactericidal and antibacterial effects. At the same time, the network structure also reduced the adverse reactions caused by the rapid release of metal ions, and obtained a licorice polysaccharide-based hydrogel modified with a silver-copper bimetallic MOF material.
[0061] S3, the gold nanorod hybrid MXene nanosheet composite carrier and the silver-copper bimetallic MOF material modified licorice polysaccharide-based hydrogel described in step S2 are placed in the traditional Chinese medicine composition described in step S1 in sequence, ultrasonically treated for 20 minutes, taken out, and then the drug-loaded gold nanorod hybrid MXene nanosheet composite carrier is placed in a polytetrafluoroethylene mold, and then the drug-loaded hydrogel is cast in the polytetrafluoroethylene mold. After four freeze-thaw cycles, the gold nanorod hybrid MXene nanosheet composite carrier can be evenly dispersed in the gel structure, further reducing the network The pore size reduces the absorption and penetration of water, improves the stability of the structure, and also gives the gel excellent photothermal properties, which can be combined with photothermal therapy to achieve an antibacterial effect. The MOF material modified licorice polysaccharide-based hydrogel loaded with silver-copper bimetallic also improves the drug loading limitation problem of the gold nanorod hybrid MXene nanosheet composite carrier. Through the synergistic cooperation of the gel network, surface active sites, photothermal properties and traditional Chinese medicine compositions, the bacteria that cause gynecological diseases are killed in multiple ways, from multiple angles and by multiple methods, with significant antibacterial therapeutic effects, and an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases is obtained.
[0062] Example 3
[0063] This embodiment proposes an antibacterial gel dressing that is beneficial for treating gynecological diseases, comprising the following components in parts by weight: 35 parts of a silver-copper bimetallic MOF material, 25 parts of a licorice polysaccharide-based hydrogel, 15 parts of a gold nanorod hybrid MXene nanosheet composite carrier, and 25 parts of a traditional Chinese medicine composition.
[0064] The MOF material loaded with silver-copper bimetallic includes the following components in parts by weight: 7 parts of silver nitrate, 11 parts of copper nitrate trihydrate, and 6.5 parts of pyridine-3,5-dicarboxylic acid.
[0065] The gold nanorod hybrid MXene nanosheet composite carrier includes the following components in parts by weight: 15 parts of MXene nanosheets, 9 parts of gold nanorods, and 3.5 parts of mercapto-polyethylene glycol-methoxy.
[0066] The Chinese medicine composition comprises the following components in parts by weight: 4 parts of honeysuckle, 4 parts of dandelion, 4 parts of viola yedoensis, 4 parts of gardenia, 4 parts of plantain seeds, 4 parts of phellodendron, 4 parts of angelica dahurica and 4 parts of liquorice.
[0067] The preparation method of the gold nanorod hybrid MXene nanosheet composite carrier specifically comprises the following steps:
[0068] (1) Add 1.6 g of lithium fluoride to 20 mL of 30% hydrochloric acid solution, then slowly add 1.0 g of titanium aluminum carbide, stir at 45 ° C for 25 h, centrifuge at 3500 rpm for 5 min, wash with deionized water until pH 6.0, collect the supernatant containing MXene flakes, centrifuge at 3500 rpm for 1 h, repeat this process until the supernatant becomes clear, stop collecting, and concentrate the collected MXene solution under reduced pressure to 17.5 mL. As a new type of two-dimensional material, MXene nanosheets have a large specific surface area and high photothermal conversion efficiency. They can be used as drug carriers and combined with photodynamic therapy to introduce antibacterial treatment, which can effectively kill bacteria and treat gynecological diseases caused by bacterial infection, thereby obtaining MXene nanosheets;
[0069] (2) Add 100 μL of 1% chloroauric acid solution to 10 mL of 9% hexadecyltrimethylammonium bromide solution, then add 600 μL of 0.05% sodium borohydride ice water solution, stir at 9000 rpm for 2.5 min, take 1.5 mL of the prepared seed solution, add it to the MXene nanosheets described in step (1), stir in a constant temperature water bath at 28°C in the dark for 1.5 h, stirring at 70 rpm, and then immediately add the growth solution after it becomes colorless. The growth solution is to first weigh 4.0 g of hexadecyltrimethylammonium bromide and dissolve it in 98 mL of deionized water, then add 2 mL of 1% chloroauric acid solution, stir evenly, and then add 1.5 mg of nitric acid. Silver acid, stirred for 30 minutes, 0.1 mg of ascorbic acid was added, and stirred at a speed of 7000 rpm. By adding the growth solution, gold ions can be reduced to gold atoms, and crystals can be grown along a specific direction, with high specific surface area and high loading capacity, good dispersibility and stability. The mixed solution was placed in a constant temperature water bath at 28 ° C and stored away from light for 12 hours. The negatively charged MXene nanosheets and the positively charged gold nanorod seed solution were combined by electrostatic action, so that the gold nanorods were in situ grown on the surface of the MXene nanosheets, which not only effectively prevented the stacking of the nanosheets, but also increased the drug loading capacity. At the same time, it can also synergistically enhance the photothermal performance, which is beneficial to enhance the killing effect of bacteria, and obtain a gold nanorod hybrid MXene nanosheet solution;
[0070] (3) The gold nanorod hybrid MXene nanosheet solution described in step (2) was centrifuged once at a speed of 11000 rpm, and the precipitate was dispersed in 2 mL of deionized water and stored in a constant temperature water bath at 28 ° C for use. 35 mg of thiol-polyethylene glycol-methoxy powder was weighed and dissolved in 18 mL of deionized water. The precipitate dispersion was slowly added under stirring at a speed of 900 rpm, and then stirred in the dark at a speed of 250 rpm for 5.5 h. The product was centrifuged and collected. A tight Au-S bond was formed between the gold nanorod hybrid MXene nanosheet and the thiol-polyethylene glycol-methoxy group, which could not only replace the hexadecyltrimethylammonium bromide on the surface of the gold nanorods to improve biocompatibility, but also enhance the stability of the structure. It can be used as a nanocarrier with good application effect in photothermal treatment of bacterial infections of gynecological diseases, and a gold nanorod hybrid MXene nanosheet composite carrier was obtained.
[0071] The preparation method of the MOF material loaded with silver-copper bimetallic material specifically comprises the following steps:
[0072] 0.07 g of silver nitrate and 0.11 g of copper nitrate trihydrate were dissolved in 5 mL of water and stirred until completely dissolved to prepare a metal ion solution for use. Then 0.065 g of pyridine-3,5-dicarboxylic acid was weighed and dissolved in 5 mL of water. The mixture was stirred in an ultrasonic water bath at 45 ° C for 25 min. The obtained pyridine-3,5-dicarboxylic acid suspension was mixed with the metal ion solution and magnetically stirred at 150 rpm for 12.5 min at 20 ° C. The mixed solution was transferred to a 25 mL polytetrafluoroethylene liner. The reactor was placed in an oven, heated to 110 ° C, reacted for 21 h, vacuum filtered, and the product was collected and washed alternately with deionized water and anhydrous ethanol for 3 times, and then vacuum dried. Using zinc nitrate, copper nitrate trihydrate and pyridine-3,5-dicarboxylic acid as raw materials, a bimetallic MOF loaded with silver ions and copper ions was synthesized under hydrothermal conditions. The antibacterial effect was achieved based on the direct interaction between the active sites on its surface and the bacterial surface and the released metal ions destroying the permeability of the bacterial cell membrane. Among them, MOF, as a storage reservoir for silver ions and copper ions, can slowly and steadily release metal ions, which can not only reduce the toxicity of metal ions to cells, but also maintain long-term antibacterial properties. The loading of silver ions and copper ions also increases the high specific surface area of MOF and increases the contact area between the active sites and bacteria, thereby obtaining a MOF material loaded with silver-copper bimetallic.
[0073] This embodiment provides a method for preparing an antibacterial gel dressing that is beneficial for treating gynecological diseases, which specifically includes the following steps:
[0074] S1. The honeysuckle, dandelion, viola yedong ding, gardenia, plantain seed, phellodendron, angelica dahurica and licorice were dried and pretreated and then crushed, mixed evenly, 500g of Chinese medicine powder was weighed and placed in 7 times the amount by mass fraction of 80% ethanol solution, soaked overnight, and then heated and pressurized in a reflux condenser and a rotary evaporator for 2 times, the extracts were combined and filtered, and the total extract was concentrated under reduced pressure. The honeysuckle, dandelion and viola yedong can clear away heat and detoxify, gardenia and plantain seed can be lightly infiltrated and diuretic, so that the damp-heat evil is discharged from the urine, phellodendron has the effect of clearing heat, purging fire and detoxifying, angelica dahurica has the effect of dispelling disease and dampness, discharging pus and promoting tissue regeneration, and promoting blood circulation and relieving pain. Licorice coordinates the synergistic effect of the components, thereby being able to safely and effectively treat gynecological diseases caused by bacterial infection to obtain a Chinese medicine composition;
[0075] S2. Dissolve carboxymethyl chitosan in 100 mL of water, dissolve vanillin in 50 mL of anhydrous ethanol, and dissolve glycyrrhizic acid polysaccharide in 50 mL of water, and stir them evenly. The amount of carboxymethyl chitosan added is 4.5 g, the amount of vanillin added is 2.0 g, and the amount of glycyrrhizic acid polysaccharide added is 2.5 g. Biocompatible carboxymethyl chitosan and non-toxic vanillin are used as the matrix for forming the hydrogel. The active substance glycyrrhizic acid polysaccharide is added to give the hydrogel certain antibacterial properties. A hydrogel material with excellent biocompatibility, self-healing and adhesion properties is prepared. It has excellent advantages in use as a dressing for gynecological diseases. Then, the MOF material loaded with silver-copper bimetallic is added to the glycyrrhizic acid polysaccharide solution, and magnetic stirring is performed for 20 min. Then, the MOF material is mixed with the carboxymethyl chitosan solution and the vanillin alcohol solution. The mixture was mixed evenly and allowed to stand at room temperature for 5.5 hours. The silver-copper bimetallic MOF material was distributed on the licorice polysaccharide-based hydrogel to form a dense and interconnected porous gel. The addition of the silver-copper bimetallic MOF material can chelate with the amino and hydroxyl groups on the carboxymethyl chitosan, significantly reducing the pore size of the gel network, enhancing the cross-linking density, and improving the structural stability. The network structure and surface metal active sites of the hydrogel interacted with the bacterial cell membrane. As the gel structure and MOF structure slowly collapsed, a small amount of metal ions and organic ligands were released, thereby causing damage to the bacterial cell membrane and achieving excellent bactericidal and antibacterial effects. At the same time, the network structure also reduced the adverse reactions caused by the rapid release of metal ions, thereby obtaining a licorice polysaccharide-based hydrogel modified with a silver-copper bimetallic MOF material.
[0076] S3, the gold nanorod hybrid MXene nanosheet composite carrier and the silver-copper bimetallic MOF material modified licorice polysaccharide-based hydrogel described in step S2 are placed in the traditional Chinese medicine composition described in step S1 in sequence, ultrasonically treated for 25 minutes, taken out, and then the drug-loaded gold nanorod hybrid MXene nanosheet composite carrier is placed in a polytetrafluoroethylene mold, and then the drug-loaded hydrogel is cast in the polytetrafluoroethylene mold. After four freeze-thaw cycles, the gold nanorod hybrid MXene nanosheet composite carrier can be evenly dispersed in the gel structure, further reducing the network The pore size reduces the absorption and penetration of water, improves the stability of the structure, and also gives the gel excellent photothermal properties, which can be combined with photothermal therapy to achieve an antibacterial effect. The MOF material modified licorice polysaccharide-based hydrogel loaded with silver-copper bimetallic also improves the drug loading limitation problem of the gold nanorod hybrid MXene nanosheet composite carrier. Through the synergistic cooperation of the gel network, surface active sites, photothermal properties and traditional Chinese medicine compositions, the bacteria that cause gynecological diseases are killed in multiple ways, from multiple angles and by multiple methods, with significant antibacterial therapeutic effects, and an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases is obtained.
[0077] Example 4
[0078] This embodiment proposes an antibacterial gel dressing that is beneficial for treating gynecological diseases, comprising the following components in parts by weight: 30 parts of a silver-copper bimetallic MOF material, 30 parts of a licorice polysaccharide-based hydrogel, 10 parts of a gold nanorod hybrid MXene nanosheet composite carrier, and 30 parts of a traditional Chinese medicine composition.
[0079] The MOF material loaded with silver-copper bimetallic includes the following components in parts by weight: 6 parts of silver nitrate, 12 parts of copper nitrate trihydrate, and 8 parts of pyridine-3,5-dicarboxylic acid.
[0080] The gold nanorod hybrid MXene nanosheet composite carrier includes the following components in parts by weight: 20 parts of MXene nanosheets, 8 parts of gold nanorods, and 3 parts of mercapto-polyethylene glycol-methoxy.
[0081] The Chinese medicine composition comprises the following components in parts by weight: 5 parts of honeysuckle, 5 parts of dandelion, 5 parts of viola yedoensis, 5 parts of gardenia, 5 parts of plantain seeds, 5 parts of phellodendron, 5 parts of angelica dahurica and 5 parts of liquorice.
[0082] The preparation method of the gold nanorod hybrid MXene nanosheet composite carrier specifically comprises the following steps:
[0083] (1) Add 1.6 g of lithium fluoride to 20 mL of 30% hydrochloric acid solution, then slowly add 1.0 g of titanium aluminum carbide, stir at 50 ° C for 20 h, centrifuge at 4000 rpm for 5 min, wash with deionized water until pH 6.0, collect the supernatant containing MXene flakes, centrifuge at 4000 rpm for 1 h, repeat this process until the supernatant becomes clear, stop collecting, and concentrate the collected MXene solution under reduced pressure to 20 mL. As a new type of two-dimensional material, MXene nanosheets have a large specific surface area and high photothermal conversion efficiency. They can be used as drug carriers and combined with photodynamic therapy to introduce antibacterial treatment, which can effectively kill bacteria and treat gynecological diseases caused by bacterial infection, thereby obtaining MXene nanosheets;
[0084] (2) Add 100 μL of 1% chloroauric acid solution to 10 mL of 10% hexadecyltrimethylammonium bromide solution, then add 600 μL of 0.05% sodium borohydride ice water solution, stir at 10,000 rpm for 2 min, take 1 mL of the prepared seed solution, add it to the MXene nanosheets described in step (1), stir in a constant temperature water bath at 28°C in the dark for 1 h, stirring at 80 rpm, and then immediately add the growth solution after it becomes colorless. The growth solution is to first weigh 4.0 g of hexadecyltrimethylammonium bromide and dissolve it in 98 mL of deionized water, then add 2 mL of 1% chloroauric acid solution, stir evenly, and then add 2 mg of silver nitrate. After stirring for 30 minutes, 0.1 mg of ascorbic acid was added and stirred at 8000 rpm. The addition of the growth solution can reduce gold ions to gold atoms and cause crystal growth along a specific direction, with a high specific surface area and a high loading capacity, as well as good dispersibility and stability. The mixed solution was placed in a 28°C constant temperature water bath and stored away from light for 12 hours. The negatively charged MXene nanosheets were combined with the positively charged gold nanorod seed solution by electrostatic action, so that the gold nanorods were in situ grown on the surface of the MXene nanosheets, which not only effectively prevented the stacking of the nanosheets, but also increased the drug loading capacity. At the same time, it can synergistically enhance the photothermal performance, which is beneficial to enhance the killing effect on bacteria, and obtain a gold nanorod hybrid MXene nanosheet solution;
[0085] (3) The gold nanorod hybrid MXene nanosheet solution described in step (2) was centrifuged twice at 12000 rpm, the precipitate was dispersed in 2 mL of deionized water, and stored in a constant temperature water bath at 28°C for use. 30 mg of thiol-polyethylene glycol-methoxy powder was weighed and dissolved in 18 mL of deionized water. The precipitate dispersion was slowly added under stirring at 1000 rpm, and then stirred at 300 rpm in the dark for 5 h. The product was centrifuged and collected. A tight Au-S bond was formed between the gold nanorod hybrid MXene nanosheet and the thiol-polyethylene glycol-methoxy group, which could not only replace the hexadecyltrimethylammonium bromide on the surface of the gold nanorods to improve biocompatibility, but also enhance the stability of the structure. It can be used as a nanocarrier with good application effect in photothermal treatment of bacterial infections of gynecological diseases, and a gold nanorod hybrid MXene nanosheet composite carrier was obtained.
[0086] The preparation method of the MOF material loaded with silver-copper bimetallic material specifically comprises the following steps:
[0087] 0.06 g of silver nitrate and 0.12 g of copper nitrate trihydrate were dissolved in 5 mL of water and stirred until completely dissolved to prepare a metal ion solution for use. 0.08 g of pyridine-3,5-dicarboxylic acid was weighed and dissolved in 5 mL of water. The mixture was stirred in an ultrasonic water bath at 50 ° C for 20 min. The obtained pyridine-3,5-dicarboxylic acid suspension was mixed with the metal ion solution and magnetically stirred at 200 rpm for 10 min at 20 ° C. The mixed solution was transferred to a 25 mL polytetrafluoroethylene liner. The reactor was placed in an oven and heated to 120 ° C. The reaction was carried out for 18 h. The product was vacuum filtered and collected and washed alternately with deionized water and anhydrous ethanol for 3 times, and then vacuum dried. Using zinc nitrate, copper nitrate trihydrate and pyridine-3,5-dicarboxylic acid as raw materials, a bimetallic MOF loaded with silver ions and copper ions was synthesized under hydrothermal conditions. The antibacterial effect was achieved based on the direct interaction between the active sites on its surface and the bacterial surface and the released metal ions destroying the permeability of the bacterial cell membrane. Among them, MOF, as a storage depot for silver ions and copper ions, can slowly and stably release metal ions, which can not only reduce the toxicity of metal ions to cells, but also maintain long-term antibacterial properties. The loading of silver ions and copper ions also increases the high specific surface area of MOF and increases the contact area between the active sites and bacteria, thereby obtaining a MOF material loaded with silver-copper bimetallic.
[0088] This embodiment provides a method for preparing an antibacterial gel dressing that is beneficial for treating gynecological diseases, which specifically includes the following steps:
[0089] S1. The honeysuckle, dandelion, viola yedong ding, gardenia, plantain seed, phellodendron, angelica dahurica and licorice were dried and pretreated and then crushed, mixed evenly, 500g of Chinese medicine powder was weighed and placed in 8 times the amount by mass of 80% ethanol solution, soaked overnight, and then heated and pressurized in a reflux condenser and a rotary evaporator for extraction 3 times, the extracts were combined, filtered, and the total extract was concentrated under reduced pressure. The honeysuckle, dandelion and viola yedong can clear away heat and detoxify, gardenia and plantain seed can be lightly infiltrated and diuretic, so that the damp-heat evil is discharged from the urine, phellodendron has the effect of clearing heat, purging fire and detoxifying, angelica dahurica has the effect of dispelling disease and dampness, discharging pus and promoting tissue regeneration, and promoting blood circulation and relieving pain. Licorice coordinates the synergistic synergy of the components, thereby being able to safely and effectively treat gynecological diseases caused by bacterial infection to obtain a Chinese medicine composition;
[0090] S2. Dissolve carboxymethyl chitosan in 100 mL of water, dissolve vanillin in 50 mL of anhydrous ethanol, and dissolve glycyrrhizic acid polysaccharide in 50 mL of water, and stir them evenly. The amount of carboxymethyl chitosan added is 5.0 g, the amount of vanillin added is 1.5 g, and the amount of glycyrrhizic acid polysaccharide added is 2.0 g. Biocompatible carboxymethyl chitosan and non-toxic vanillin are used as matrices to form a hydrogel. The active substance glycyrrhizic acid polysaccharide is added to give the hydrogel certain antibacterial properties. A hydrogel material with excellent biocompatibility, self-healing and adhesion properties is prepared, which has excellent advantages in use as a dressing for gynecological diseases. Then, the MOF material loaded with silver-copper bimetallic is added to the glycyrrhizic acid polysaccharide solution, and magnetic stirring is performed for 10 min. Then, the MOF material is mixed with the carboxymethyl chitosan solution and the vanillin alcohol solution. The liquid was mixed evenly and allowed to stand at room temperature for 5 hours. The silver-copper bimetallic MOF material was distributed on the licorice polysaccharide-based hydrogel to form a connected and dense porous gel. The addition of the silver-copper bimetallic MOF material can chelate with the amino and hydroxyl groups on the carboxymethyl chitosan, significantly reducing the pore size of the gel network, enhancing the cross-linking density, and improving the structural stability. The network structure and surface metal active sites of the hydrogel interacted with the bacterial cell membrane. With the slow collapse of the gel structure and the MOF structure, a small amount of metal ions and organic ligands were released, thereby causing damage to the bacterial cell membrane and achieving excellent bactericidal and antibacterial effects. At the same time, the network structure also reduced the adverse reactions caused by the rapid release of metal ions, and obtained a licorice polysaccharide-based hydrogel modified with a silver-copper bimetallic MOF material.
[0091] S3, the gold nanorod hybrid MXene nanosheet composite carrier and the silver-copper bimetallic MOF material modified licorice polysaccharide-based hydrogel described in step S2 are placed in the traditional Chinese medicine composition described in step S1 in sequence, ultrasonically treated for 20 minutes, taken out, and then the drug-loaded gold nanorod hybrid MXene nanosheet composite carrier is placed in a polytetrafluoroethylene mold, and then the drug-loaded hydrogel is cast in the polytetrafluoroethylene mold. After four freeze-thaw cycles, the gold nanorod hybrid MXene nanosheet composite carrier can be evenly dispersed in the gel structure, further reducing the network The pore size reduces the absorption and penetration of water, improves the stability of the structure, and also gives the gel excellent photothermal properties, which can be combined with photothermal therapy to achieve an antibacterial effect. The MOF material modified licorice polysaccharide-based hydrogel loaded with silver-copper bimetallic also improves the drug loading limitation problem of the gold nanorod hybrid MXene nanosheet composite carrier. Through the synergistic cooperation of the gel network, surface active sites, photothermal properties and traditional Chinese medicine compositions, the bacteria that cause gynecological diseases are killed in multiple ways, from multiple angles and by multiple methods, with significant antibacterial therapeutic effects, and an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases is obtained.
[0092] Comparative Example 1
[0093] This comparative example provides an antibacterial gel dressing that is beneficial for treating gynecological diseases. The difference between it and Example 1 is that the antibacterial gel dressing that is beneficial for treating gynecological diseases does not contain a silver-copper bimetallic MOF material; the preparation method of the gold nanorod hybrid MXene nanosheet composite carrier is the same as that in Example 1; the preparation method of the antibacterial gel dressing that is beneficial for treating gynecological diseases is the same as that in Example 1.
[0094] Comparative Example 2
[0095] This comparative example provides an antibacterial gel dressing that is beneficial for treating gynecological diseases. The difference between it and Example 1 is that the antibacterial gel dressing that is beneficial for treating gynecological diseases does not contain a gold nanorod hybrid MXene nanosheet composite carrier; the preparation method of the silver-copper bimetallic loaded MOF material is the same as that in Example 1; the preparation method of the antibacterial gel dressing that is beneficial for treating gynecological diseases is the same as that in Example 1.
[0096] Comparative Example 3
[0097] This comparative example provides an antibacterial gel dressing that is beneficial for treating gynecological diseases. The difference between the comparative example and Example 1 is that the MOF material loaded with silver-copper bimetallic does not contain silver nitrate and copper nitrate trihydrate, the gold nanorod hybrid MXene nanosheet composite carrier does not contain gold nanorods, and the glycyrrhizic acid-based hydrogel does not contain vanillin; the preparation method of the gold nanorod hybrid MXene nanosheet composite carrier does not include step (2); silver nitrate and copper nitrate trihydrate are not added in the preparation method of the MOF material loaded with silver-copper bimetallic; and vanillin is not added in step S2 of the preparation method of the antibacterial gel dressing that is beneficial for treating gynecological diseases.
[0098] Experimental Example 1
[0099] Drug loading experiment
[0100] Test sample: antibacterial gel dressing for treating gynecological diseases prepared in Examples 1-4 and Comparative Examples 1-3.
[0101] Test method: Accurately weigh 1g / mL of the Chinese herbal composition and dilute it to 20mg / mL. Using distilled water as a blank, scan with an ultraviolet spectrophotometer in the wavelength range of 330-500nm, with maximum absorption at 350nm. Then dilute the Chinese herbal composition to a drug solution of 0-20mg / mL, measure the absorbance A at 350nm, and obtain the standard curve equation A=0.1087C+0.0238 by regression, r 2 =0.9946, the optimal linear range is 2-8 mg / mL; weigh 1 mL of the test sample and dissolve it in 1 mL of methanol solution, vortex for 20 minutes and stir to ensure sufficient extraction of the drug. After standing for 1 hour, centrifuge at 10,000 rpm for 5 minutes, take 1 mL of the supernatant and make it up to the volume in a 50 mL volumetric flask. Measure the absorbance with distilled water as a blank, and calculate the drug loading (%).
[0102] Figure 2The drug loading results of Examples 1-4 and Comparative Examples 1-3 are shown in FIG. As shown in the figure, the drug loading of Examples 1-4 is 36.4-38.5%, indicating that the drug loading is relatively high; the drug loading of Comparative Examples 1-3 is 22.7-26.3%, indicating that the drug loading is relatively low; the antibacterial gel dressing for treating gynecological diseases of Comparative Example 1 does not contain the MOF material loaded with silver-copper bimetallic, and the loading effect of MOF on the traditional Chinese medicine composition cannot be exerted, resulting in a relatively low drug loading; the antibacterial gel dressing for treating gynecological diseases of Comparative Example 2 does not contain The gold nanorod hybrid MXene nanosheet composite carrier lacks the nanosheet structure to load the traditional Chinese medicine composition, resulting in a small drug loading capacity; the antibacterial gel dressing for the treatment of gynecological diseases in comparative example 3 does not contain silver nitrate, copper nitrate trihydrate, gold nanorods and vanillin, which is not conducive to increasing the specific surface area of the silver-copper bimetallic MOF material and the gold nanorod hybrid MXene nanosheet composite carrier. At the same time, the cross-linking effect of the licorice polysaccharide-based hydrogel is weakened, which is not conducive to better loading the traditional Chinese medicine composition, resulting in a small drug loading capacity.
[0103] Experimental Example 2
[0104] Stability test
[0105] Test sample: antibacterial gel dressing for treating gynecological diseases prepared in Examples 1-4 and Comparative Examples 1-3.
[0106] Test method: freeze-dry the test sample to obtain the initial mass W0, then soak it in phosphate buffer (pH 7.4) and let it stand at 37°C. Use filter paper to absorb the excess liquid on the surface and weigh it every 3 hours until the sample mass reaches equilibrium. Stop the experiment and record the post-test mass W t , water absorption is calculated according to the following formula;
[0107] Water absorption (%) = (W t -W0) / W0×100%
[0108] Among them, W0 is the initial mass before testing, W t Balance the sample mass after testing.
[0109] Figure 3The water absorption results of Examples 1-4 and Comparative Examples 1-3 are shown in FIG. As shown in the figure, the water absorption of Examples 1-4 is 16.3-17.9%, which is not easily affected by external moisture, indicating that the stability is good; the water absorption of Comparative Examples 1-3 is 26.5-30.9%, which is easily affected by external moisture, indicating that the stability is poor; the antibacterial gel dressing for treating gynecological diseases of Comparative Example 1 does not contain the MOF material loaded with silver-copper bimetallic, and cannot increase the cross-linking density of the licorice polysaccharide-based hydrogel, which is not conducive to reducing the water absorption, resulting in poor stability; the antibacterial gel dressing for treating gynecological diseases of Comparative Example 2 does not contain The gold nanorod hybrid MXene nanosheet composite carrier cannot further reduce the network pore size of the gel structure, which is not conducive to reducing the absorption and penetration of water, resulting in poor stability; the antibacterial gel dressing for the treatment of gynecological diseases in Comparative Example 3 does not contain silver nitrate, copper nitrate trihydrate, gold nanorods and vanillin, and cannot exert the chelating effect of silver ions and copper ions on amino and hydroxyl groups in the gel, cannot reduce the stacking of MXene nanosheets, and cannot exert the cross-linking effect of vanillin, thereby adversely affecting the connectivity and density of the gel pore size, and cannot reduce the absorption of external water with a uniform small pore size, resulting in poor stability.
[0110] Experimental Example 3
[0111] Antibacterial test
[0112] Test sample: antibacterial gel dressing for treating gynecological diseases prepared in Examples 1-4 and Comparative Examples 1-3.
[0113] Test method: Before the test, the environment was sterilized with ultraviolet light. All test operations were performed next to the flame of an alcohol lamp. Escherichia coli and Staphylococcus aureus that had been activated and cultured in advance were picked up separately and added to 1 mL of sterile water. After sufficient shaking and dilution, 100 μL of the diluted bacterial solution was taken with a pipette and added to the culture dish. The bacterial solution was immediately spread with a spreader, and the sterilized tweezers were passed over the flame of the alcohol lamp. The sterilized test sample that had been irradiated with 808 nm near-infrared light for 20 minutes was then clamped with tweezers and attached to the culture medium. The tweezers were gently pressed down, and the culture dish was immediately closed. The temperature was set to 37°C in a constant temperature incubator and inverted for 24 hours. After the end, the number of viable bacteria was determined by the pouring method, and the antibacterial rate (%) was calculated.
[0114] Figure 4The antibacterial rate results of Examples 1-4 and Comparative Examples 1-3 are shown in FIG. As shown in the figure, the antibacterial rates of Escherichia coli and Staphylococcus aureus of Examples 1-4 are 99.99-99.99% and 99.98-99.99% respectively, which are basically close to 100%, indicating that the antibacterial property is strong; the antibacterial rates of Escherichia coli and Staphylococcus aureus of Comparative Examples 1-3 are 65.49-85.35% and 62.63-82.23% respectively, indicating that the antibacterial property is weak; the antibacterial gel dressing for treating gynecological diseases of Comparative Example 1 does not contain the MOF material loaded with silver-copper bimetallic, and cannot use its surface active sites and release The released metal ions destroy the permeability of the bacterial cell membrane and reduce the drug loading, resulting in weak antibacterial activity; the antibacterial gel dressing for the treatment of gynecological diseases in comparative example 2 does not contain a gold nanorod hybrid MXene nanosheet composite carrier, and cannot release the loaded Chinese medicine composition through photothermal performance response, resulting in weak antibacterial activity; the antibacterial gel dressing for the treatment of gynecological diseases in comparative example 3 does not contain silver nitrate, copper nitrate trihydrate, gold nanorods and vanillin, and can neither exert the bactericidal effect of silver ions and copper ions, nor weaken the photothermal performance response release, nor is it conducive to the stability of the licorice polysaccharide-based hydrogel, resulting in weak antibacterial activity.
[0115] The above experimental results show that the drug loading capacity, stability and antibacterial properties of Examples 1-4 of the present invention are significantly better than those of the samples of Comparative Examples 1-3. Among them, Example 1 using the MOF material loaded with silver-copper bimetallic and the gold nanorod hybrid MXene nanosheet composite carrier has a higher drug loading capacity, better stability and better antibacterial properties. The MOF material loaded with silver-copper bimetallic and the gold nanorod hybrid MXene nanosheet composite carrier are attached and dispersed on the licorice polysaccharide-based hydrogel, which enhances the stability of the gel structure and reduces the adverse effects of external moisture. At the same time, it also significantly increases the loading capacity of the traditional Chinese medicine composition. Under the synergistic effect of the gel network, surface active sites and photothermal properties in the dressing, the bacteria that cause gynecological diseases are effectively killed, achieving excellent antibacterial treatment effects.
[0116] While the embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various changes, modifications, substitutions, and alterations can be made to the embodiments without departing from the principles and spirit of the invention.
[0117] The present invention and its embodiments are described above. Such description is not restrictive. The drawings show only one embodiment of the present invention, and actual applications are not limited thereto. In short, if a person skilled in the art is inspired by the above, and does not deviate from the purpose of the present invention, any method and embodiment similar to the technical solution without creative design shall fall within the scope of protection of the present invention.
Claims
1. An antibacterial gel dressing for treating gynecological diseases, characterized by: The antibacterial gel dressing for treating gynecological diseases comprises the following components in parts by weight: 30-40 parts of a silver-copper bimetallic MOF material, 20-30 parts of a licorice polysaccharide-based hydrogel, 10-20 parts of a gold nanorod hybridized MXene nanosheet composite carrier, and 20-30 parts of a traditional Chinese medicine composition; the silver-copper bimetallic MOF material comprises the following components in parts by weight: 6-8 parts of silver nitrate, 10-12 parts of copper nitrate trihydrate, 5 parts of pyridine-3,5-dicarboxylic acid, and 10-20 parts of a hydroxyl group-containing ... -8 parts; the gold nanorod hybrid MXene nanosheet composite carrier includes the following components in parts by weight: 10-20 parts of MXene nanosheets, 8-10 parts of gold nanorods, and 3-4 parts of thiol-polyethylene glycol-methoxy; the raw materials of the traditional Chinese medicine composition include the following components in parts by weight: 3-5 parts of honeysuckle, 3-5 parts of dandelion, 3-5 parts of Viola yedoensis, 3-5 parts of Gardenia jasminoides, 3-5 parts of Plantago seeds, 3-5 parts of Phellodendron amurense, 3-5 parts of Angelica dahurica, and 3-5 parts of Licorice.
2. A method for preparing the antibacterial gel dressing for treating gynecological diseases according to claim 1, characterized in that: The specific steps include: S1. Dry and pre-treat honeysuckle, dandelion, Viola yedoensis, gardenia, plantago, phellodendron, angelica dahurica, and liquorice, then crush and mix them evenly. Weigh 500 g of the Chinese medicine powder and place it in 6-8 times the amount of 80% ethanol solution by mass, soak overnight, and then heat and pressurize and extract 1-3 times in a reflux condenser and a rotary evaporator. Combine the extracts, filter, and concentrate the obtained total extract under reduced pressure to obtain a Chinese medicine composition. S2. Dissolve carboxymethyl chitosan in 100 mL of water, dissolve vanillin in 50 mL of anhydrous ethanol, and dissolve glycyrrhizic acid in 50 mL of water, and stir them separately. Then, add the MOF material loaded with silver-copper bimetallic to the glycyrrhizic acid solution, stir magnetically for 10-30 min, and then mix evenly with the carboxymethyl chitosan solution and the vanillin alcohol solution. Let it stand at room temperature for 5-6 h to obtain a MOF material-modified glycyrrhizic acid-based hydrogel loaded with silver-copper bimetallic. S3. Place the gold nanorod hybrid MXene nanosheet composite carrier and the silver-copper bimetallic MOF material modified licorice polysaccharide-based hydrogel described in step S2 in the traditional Chinese medicine composition described in step S1 in sequence, ultrasonically treat for 20-30 minutes, take out, and then place the drug-loaded gold nanorod hybrid MXene nanosheet composite carrier into a polytetrafluoroethylene mold, and then cast the drug-loaded hydrogel in the polytetrafluoroethylene mold. After four freeze-thaw cycles, an antibacterial gel dressing that is beneficial for the treatment of gynecological diseases is obtained.
3. The method for preparing the antibacterial gel dressing for treating gynecological diseases according to claim 2, characterized in that: In step S2, the amount of carboxymethyl chitosan added is 4.0-5.0 g, the amount of vanillin added is 1.5-2.5 g, and the amount of glycyrrhizic polysaccharide added is 2.0-3.0 g.
4. The method for preparing the antibacterial gel dressing for treating gynecological diseases according to claim 3, characterized in that: The preparation method of the gold nanorod hybrid MXene nanosheet composite carrier specifically comprises the following steps: (1) Add 1.6 g of lithium fluoride to 20 mL of 30% hydrochloric acid solution, then slowly add 1.0 g of titanium aluminum carbide, stir at 40-50 ° C for 20-30 h, centrifuge at 3000-4000 rpm for 5 min, wash with deionized water until the pH is 6.0, collect the supernatant containing MXene flakes, centrifuge at 3000-4000 rpm for 1 h, repeat this process until the supernatant becomes clear, stop collecting, and concentrate the collected MXene solution under reduced pressure to 15-20 mL to obtain MXene nanosheets; (2) Add 100 μL of 1% chloroauric acid solution to 10 mL of 8-10% hexadecyltrimethylammonium bromide solution, then add 600 μL of 0.05% sodium borohydride ice water solution, stir at 8000-10000 rpm for 2-3 min, take 1-2 mL of the prepared seed solution, add it to the MXene nanosheets described in step (1), stir in a constant temperature water bath at 28°C in the dark for 1-2 h, and stir at a speed of 60-80 rpm. Then, wait until the growth solution becomes colorless after stirring, and immediately add it thereto. The mixed solution is placed in a constant temperature water bath at 28°C in the dark for 12 h to obtain a gold nanorod hybrid MXene nanosheet solution; (3) The gold nanorod hybrid MXene nanosheet solution described in step (2) was centrifuged at a speed of 10000-12000 rpm for 1-2 times, and the precipitate was dispersed in 2 mL of deionized water and stored in a constant temperature water bath at 28°C for use. 30-40 mg of thiol-polyethylene glycol-methoxy powder was weighed and dissolved in 18 mL of deionized water. The precipitate dispersion was slowly added while stirring at a speed of 800-1000 rpm, and then stirred at a speed of 200-300 rpm in the dark for 5-6 hours. The mixture was centrifuged and the product was collected to obtain a gold nanorod hybrid MXene nanosheet composite carrier.
5. The method for preparing the antibacterial gel dressing for treating gynecological diseases according to claim 4, characterized in that: In step (2), the growth solution is prepared by first weighing 4.0 g of hexadecyltrimethylammonium bromide and dissolving it in 98 mL of deionized water, then adding 2 mL of a 1% chloroauric acid solution and stirring evenly, then adding 1-2 mg of silver nitrate and stirring for 30 min, adding 0.1 mg of ascorbic acid, and stirring at a speed of 6000-8000 rpm.
6. The method for preparing the antibacterial gel dressing for treating gynecological diseases according to claim 5, characterized in that: The preparation method of the silver-copper bimetallic MOF material specifically comprises the following steps: 0.06-0.08 g of silver nitrate and 0.10-0.12 g of copper nitrate trihydrate were dissolved in 5 mL of water and stirred until completely dissolved to prepare a metal ion solution for use. Then 0.05-0.08 g of pyridine-3,5-dicarboxylic acid was weighed and dissolved in 5 mL of water. The mixture was stirred in an ultrasonic water bath at 40-50 ° C for 20-30 min. The obtained pyridine-3,5-dicarboxylic acid suspension was mixed with the metal ion solution and magnetically stirred at 100-200 rpm for 10-15 min at 20 ° C. The mixed solution was transferred to a 25 mL polytetrafluoroethylene liner. The reactor was placed in an oven, heated to 100-120 ° C, reacted for 18-24 h, vacuum filtered, the product was collected and washed alternately with deionized water and anhydrous ethanol for 3 times, and then vacuum dried to obtain a silver-copper bimetallic MOF material.
Citation Information
Patent Citations
Solution processable metal-organic frameworks via surface functionalization
WO2021001727A1