CN113577363A - Composite wound dressing and preparation method thereof - Google Patents

Composite wound dressing and preparation method thereof Download PDF

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Publication number
CN113577363A
CN113577363A CN202110938732.5A CN202110938732A CN113577363A CN 113577363 A CN113577363 A CN 113577363A CN 202110938732 A CN202110938732 A CN 202110938732A CN 113577363 A CN113577363 A CN 113577363A
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graphene oxide
silver
chitosan
nano
wound dressing
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刘果
李杰玲
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Guilin Qingyan Haolong New Material Co ltd
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Guilin Qingyan Haolong New Material Co ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/20Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28Polysaccharides or their derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/40Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing ingredients of undetermined constitution or reaction products thereof, e.g. plant or animal extracts
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/46Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104Silver, e.g. silver sulfadiazine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/23Carbohydrates
    • A61L2300/236Glycosaminoglycans, e.g. heparin, hyaluronic acid, chondroitin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/12Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces

Abstract

The application provides a preparation method of a composite wound dressing, which comprises the following steps: dispersing graphene oxide and a surfactant in water to obtain a graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the surfactant is (125-: 1; adding a silver nitrate solution into the graphene oxide dispersion liquid to obtain a mixed solution, wherein the volume ratio of the graphene oxide dispersion liquid to the silver nitrate solution is 1: 1; performing microwave treatment on the mixed solution to obtain a nano silver/graphene oxide composite material; adding chitosan into a solvent, then adding the nano-silver/graphene oxide composite material, and performing ultrasonic dispersion to obtain a reaction solution, wherein the mass ratio of the chitosan to the nano-silver/graphene oxide composite material is (5-20): 6; adding a cross-linking agent to obtain the chitosan/nano silver/graphene oxide composite material. The present application also provides a composite wound dressing.

Description

Composite wound dressing and preparation method thereof
Technical Field
The application relates to the technical field of antibacterial materials, in particular to a composite wound dressing and a preparation method thereof.
Background
The wound dressing is a medical material which is in direct contact with the surface of a wound and has wide clinical application. Has the function of preventing wound surface and systemic infection in the clinical treatment process. The antibacterial materials adopted by the existing traditional wound dressing are mainly divided into organic antibacterial agents, inorganic antibacterial agents and natural antibacterial agents.
The organic antibacterial agent mainly comprises guanidine salts and quaternary ammonium salts, is commonly used in polyethylene food packaging films to play an antibacterial role, but has poor thermal stability and generates certain cytotoxicity to human beings. The natural antibacterial agent is mainly extracted from natural plants, such as chitin, mustard, castor oil, horseradish, and the like, is simple and convenient to use, but has limited antibacterial action, poor heat resistance, low sterilization rate, no broad-spectrum long-acting use and small quantity. The inorganic antibacterial agent utilizes the antibacterial capacity of metals such as silver, copper, zinc and the like, and the metals (or ions thereof) such as silver, copper, zinc and the like are fixed on the surface of porous materials such as fluorite, silica gel and the like by methods such as physical adsorption ion exchange and the like to prepare the antibacterial agent, and then the antibacterial agent is added into a corresponding product to obtain the material with the antibacterial capacity, wherein the metals such as mercury, cadmium, lead and the like also have the antibacterial capacity but are harmful to human bodies; and ions such as copper, nickel, lead and the like have colors, which affect the appearance of the product, and zinc has certain antibacterial property, but the antibacterial strength of zinc is only 1/1000 of silver ions. Silver ion antibacterial agents have become common antibacterial agents because of their high antibacterial strength. However, in actual production, since silver is a noble metal, the production cost for preparing the antibacterial agent containing silver ions is high.
Disclosure of Invention
In view of the above, the present application provides a method for preparing a composite wound dressing to solve the above problems.
In addition, the composite wound dressing prepared by the preparation method of the composite wound dressing is also necessary to be provided.
In order to achieve the above object, the present application provides a method for preparing a composite wound dressing, comprising the following steps:
dispersing graphene oxide and a surfactant in water to obtain a graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the surfactant is (125) -300: 1;
adding a silver nitrate solution into the graphene oxide dispersion liquid to obtain a mixed solution, wherein the volume ratio of the graphene oxide dispersion liquid to the silver nitrate solution is 1: 1;
performing microwave treatment on the mixed solution, performing ultrasonic treatment, and finally performing centrifugal cleaning to obtain a nano silver/graphene oxide composite material;
adding chitosan into a solvent, dropwise adding acetic acid until the chitosan is completely dissolved, then adding the nano-silver/graphene oxide composite material, and performing ultrasonic dispersion to obtain a reaction solution, wherein the mass ratio of the chitosan to the nano-silver/graphene oxide composite material is (5-20): 6;
adding a cross-linking agent into the reaction solution, performing cross-linking on the nano-silver/graphene oxide composite material and the chitosan, removing the solvent, washing, and drying to obtain a chitosan/nano-silver/graphene oxide composite material;
mixing the chitosan/nano-silver/graphene oxide composite material with polypropylene, and processing to obtain chitosan/nano-silver/graphene oxide master batches;
dissolving a reinforcer in a hydrochloric acid solution, and adding the chitosan/nano silver/graphene oxide master batch and an additive to obtain a prefabricated product, wherein the additive is one of alginate or fibroin; and
and spraying the prefabricated product to a fiber net through high pressure to obtain the composite wound dressing with the bacteriostasis rate of more than 99.99%.
The application also provides a composite wound dressing prepared by the preparation method of the composite wound dressing.
According to the preparation method of the composite wound dressing, the graphene is used as the carrier, the high-efficiency antibacterial property of silver, the biocompatibility of the graphene and the antibacterial property of chitosan are utilized, the antibacterial rate of the composite wound dressing prepared by the preparation method is greater than 99.99%, the using amount of silver can be reduced, and the production cost is saved.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples, given by way of illustration, are intended to illustrate the invention and are not to be construed as limiting the invention.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The chitosan is a product of natural polysaccharide chitin with partial acetyl removed, has various physiological functions of biodegradability, biocompatibility, nontoxicity, bacteriostasis, cancer resistance, lipid reduction, immunity enhancement and the like, and is widely applied to a plurality of fields of antibacterial agents, medical fibers, medical dressings, biomedical fields, medical absorbable materials and the like. The basic unit of the chitosan is glucosamine which is a substance existing in a human body, so the chitosan has good affinity with human body cells, has no rejection reaction, and can form cation clusters and induce the aggregation of red blood cells and platelets by carrying positive charges to promote blood coagulation, thereby achieving the effect of hemostasis. In addition, the chitosan can promote the growth of vascular endothelium, and has antibacterial property.
The main component of alginate is calcium alginate, which is a water insoluble substance. When the alginate meets liquid (such as seepage, blood and the like) rich in sodium ions, calcium ions and sodium ions are exchanged, calcium ions are released, and the sodium ions are combined with the alginic acid to form a hydrophilic gelatinous substance, so that the wound can be helped to maintain a wet environment, enhance autolytic debridement and promote the growth of granulation tissues, and meanwhile, the alginate has strong liquid absorption capacity and can absorb liquid which is 20 times of the weight of the alginate. Wherein, the autolysis debridement is to use a wet dressing to hydrate the wound, soften necrotic crust, dissolve necrotic tissue by the lysin produced by phagocytes and neutrophils in the exudate and absorb the exudate.
The application provides a preparation method of a composite wound dressing, which comprises the following steps:
step one, weighing 0.5-1.0 part by mass of graphite powder and 0.5-1.0 part by mass of sodium nitrate, adding the graphite powder and the sodium nitrate into a reaction bottle containing 4.6-5.6 parts by mass of concentrated sulfuric acid under ice bath, and adding 1.0-1.5 parts by mass of potassium permanganate (or phosphoric acid or sodium nitrate) while stirring to prepare a mixed solution;
keeping the temperature of the mixed solution at less than 15 ℃ for 1-3 h, taking out, stirring at room temperature for 3-4 days, adding deionized water for dilution, adding 1.0-2.0 parts by mass of 20-50% hydrogen peroxide, continuously stirring for 2-3h, and performing centrifugal separation to obtain a bright yellow precipitate;
washing the bright yellow precipitate for multiple times by using 0.05-1 mol/L dilute hydrochloric acid and distilled water until the pH value is 7, adding the distilled water into the bright yellow precipitate, performing ultrasonic treatment for 2-3h, centrifuging again, removing insoluble precipitate at the lower layer to obtain a suspension, filtering the suspension to obtain a solid product, and performing vacuum freeze drying on the solid product to obtain the graphene oxide. In some embodiments, the graphene oxide is a single layer or multiple layers.
And step two, mixing the graphene oxide prepared in the step one with a surfactant, dispersing the mixture in water, and performing ultrasonic treatment to obtain a graphene oxide dispersion liquid. The mass ratio of the graphene oxide to the surfactant is (125) -300) 1. In some embodiments, the surfactant is one of N, N-dimethylformamide, polyvinylpyrrolidone, or sodium dodecyl sulfate.
And adding a silver nitrate solution into the graphene oxide dispersion liquid, and carrying out ultrasonic treatment for 10min to obtain a mixed solution. Wherein the volume ratio of the graphene oxide dispersion liquid to the silver nitrate solution is 1: 1. And carrying out microwave treatment on the mixed solution. In some embodiments, the microwave treatment power is 100W-200W and the treatment time is 1min-5 min. The N, N-dimethylformamide is decomposed under the condition of microwave high temperature to generate reducing gas (such as carbon monoxide), and anions in the silver nitrate solution can be reduced to silver simple substance, so that other reducing reagents are reduced from being introduced into the mixed solution, and the operation is simple. And (3) carrying out ultrasonic treatment for 2-3h after microwave treatment, and carrying out centrifugal cleaning to obtain the nano silver/graphene oxide composite material.
And step three, adding 5-10 parts of chitosan into a solvent, dropwise adding 5-10 parts of acetic acid (glacial acetic acid) until the chitosan is completely dissolved, then adding the nano-silver/graphene oxide composite material, and performing ultrasonic dispersion to obtain a reaction solution. Wherein the mass ratio of the chitosan to the nano silver/graphene oxide composite material is (5-20): 6. when the mass ratio of the chitosan to the nano-silver/graphene oxide composite material is less than 5:6, the chitosan is less in content in the prepared chitosan/nano-silver/graphene oxide composite material, the hemostatic effect of the chitosan is not obvious, and the bacteriostatic effect of the chitosan is not obvious. When the mass ratio of the chitosan to the nano-silver/graphene oxide composite material is greater than 20:6, the antibacterial effect of the obtained chitosan/nano-silver/graphene oxide composite material is reduced due to the excessive content of the chitosan.
And adding a cross-linking agent into the reaction solution, carrying out cross-linking condensation reaction on the nano-silver/graphene oxide composite material and the chitosan to obtain a solution, removing the solvent in the solution, washing, and drying to obtain the chitosan/nano-silver/graphene oxide composite material.
In some embodiments, the crosslinking agent is glutaraldehyde. The mass ratio of the cross-linking agent in the solution is 2-7%. When the mass ratio of the cross-linking agent in the solution is less than 2%, the content of the cross-linking agent is low, which may result in incomplete cross-linking of the nano silver/graphene oxide composite material and the chitosan. When the mass ratio of the cross-linking agent in the solution is more than 7%, the content of the cross-linking agent is too large, and the excessive cross-linking agent can be removed by washing for many times, so that the preparation process is increased.
In some embodiments, the solvent is one of acetone or disodium edetate.
And step four, mixing the chitosan/nano-silver/graphene oxide composite material with polypropylene, adding the mixture into a double-screw extruder, mixing and extruding the mixture, and granulating the mixture to obtain the chitosan/nano-silver/graphene oxide master batch. In some embodiments, the chitosan/nano-silver/graphene oxide composite material accounts for 5% or more of the mass ratio of the chitosan/nano-silver/graphene oxide master batch. When the ratio is less than 5%, the chitosan/nano silver/graphene oxide composite material in the prepared composite wound dressing is low, and the bacteriostasis rate of the composite wound dressing is less than 99.99%.
Dissolving a reinforcer in a hydrochloric acid solution, and adding the chitosan/nano-silver/graphene oxide master batch and an additive to obtain a prefabricated product, wherein the additive is one of alginate or fibroin. In some embodiments, the enhancer is one of glutaraldehyde, glyoxal, or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride/N-hydroxysuccinimide [ EDC/NHS for short ].
And spraying the prefabricated product to a fiber net through high pressure to obtain the composite wound dressing with the bacteriostasis rate of more than 99.99%. In some embodiments, the fiber mesh is one of alginate or fibroin.
According to the preparation method of the composite wound dressing, the graphene is used as the carrier, the high-efficiency antibacterial property of silver, the biocompatibility of the graphene and the antibacterial property of chitosan are utilized, the antibacterial rate of the prepared composite wound dressing is greater than 99.99%, and the chitosan is used for replacing part of silver in the composite wound dressing, so that the usage amount of silver in the wound dressing can be reduced, and the production cost is saved.
The application also provides a composite wound dressing prepared by the preparation method of the composite wound dressing.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by persons skilled in the art that the following examples are illustrative only and are not to be construed as limiting the invention. Reagents, software and equipment not specifically submitted to the following examples are conventional commercial products or open sources unless otherwise submitted.
Example 1
(1) Preparation of graphene oxide
Respectively weighing 1.0 part by mass of graphite powder and sodium nitrate, adding the graphite powder and the sodium nitrate into a reaction bottle containing 5.6 parts by mass of concentrated sulfuric acid in an ice bath, adding 1.5 parts by mass of potassium permanganate while stirring, and carrying out constant-temperature reaction at about 10 ℃ for 3 hours to obtain a mixed solution. And taking out the mixed solution, stirring the mixed solution for 3 days at 37 ℃, then diluting the mixed solution by using deionized water, adding 2.0 parts of 25% hydrogen peroxide, continuously stirring the mixed solution for 2 hours, and performing centrifugal separation to obtain a bright yellow precipitate.
The bright yellow precipitate was washed several times with 0.1moL/L dilute hydrochloric acid and distilled water successively to a pH of approximately 7. Adding the distilled water into the bright yellow precipitate, performing ultrasonic treatment for 3 hours, centrifuging again, removing insoluble precipitate at the lower layer to obtain a suspension, filtering the suspension to obtain a solid product, and performing vacuum freeze drying on the solid product to obtain the graphene oxide.
(2) Preparation of nano-silver/graphene oxide composite material
1.25 parts by mass of the graphene oxide prepared above and 0.006 part of N, N-Dimethylformamide (DMF) were dispersed in 20mL of an aqueous solution, wherein the DMF served as both a solvent and a reducing agent, and the dispersion was homogenized by sonication for 1 hour to obtain a graphene oxide dispersion.
Adding AgNO into graphene oxide dispersion liquid3Solution of graphene oxide dispersion with AgNO3The volume ratio of the solution was 1:1, and after 10 minutes of ultrasonic treatment, a mixed solution was obtained. And (3) irradiating the mixed solution for 1min by using microwaves (high fire 100W), continuing performing ultrasonic treatment for 3h, and then performing centrifugal cleaning to obtain the nano silver/graphene oxide composite material.
(3) Preparation of chitosan/nano silver/graphene oxide composite material
Adding 10 parts of chitosan into 5 parts by mass of disodium ethylene diamine tetraacetate solution, dropwise adding 6 parts of acetic acid to dissolve the chitosan, adding the prepared 6 parts of nano silver/graphene oxide composite material, and performing ultrasonic dispersion uniformly to obtain a reaction solution. Adding glutaraldehyde into the reaction liquid, wherein the mass of the glutaraldehyde accounts for 3% of that of the reaction liquid, so that the nano-silver/graphene oxide and chitosan are subjected to condensation reaction, and then removing the solvent, washing and drying to obtain the chitosan/nano-silver/graphene oxide material.
(4) Preparation of chitosan/nano-silver/graphene oxide composite wound dressing
Mixing the prepared chitosan/nano-silver/graphene oxide material with polypropylene, and processing to obtain the chitosan/nano-silver/graphene oxide master batch. Wherein the chitosan/nano-silver/graphene oxide material accounts for 5% of the mass of the chitosan/nano-silver/graphene oxide master batch.
Dissolving 2 parts by mass of enhancer EDC/NHS in 0.2% hydrochloric acid solution, and adding 90 parts of chitosan/nano-silver/graphene oxide master batch and 8 parts of alginate for dissolution. And then spraying high-pressure micro water flow onto one layer of fiber mesh or a plurality of layers of fiber meshes to enable the fiber meshes to be attached with chitosan/nano silver/graphene oxide materials, thus obtaining the chitosan/nano silver/graphene oxide composite wound dressing used for the wound.
To further verify the effectiveness of the composite wound dressing prepared in the above examples, the following tests were also performed.
1. Instruments and materials used for testing:
nutrient agar, a culture dish, a vertical pressure steam sterilizer, an electric heating blast drying box, a biochemical incubator, an electric heating constant temperature incubator, a graduated suction pipe and the like; staphylococcus aureus (ATCC6538), escherichia coli (ATCC25922), candida albicans (ATCC10231), all passage 4; 4 batches of chitosan/nano silver/graphene oxide dressing have the following batch numbers: a. b, c and d.
2. The test method comprises the following steps:
flask oscillation method for detecting antibacterial performance of chitosan/nano-silver/graphene oxide composite wound dressing
The antibacterial performance (such as staphylococcus aureus, escherichia coli and candida albicans) of 4 batches of chitosan/nano silver/graphene oxide composite wound dressings was tested by adopting a flask oscillation method with optimized conditions.
The specific method comprises the following steps: the chitosan/nano-silver/graphene oxide composite wound dressing is cut into a size of 1cm multiplied by 1cm, accurately weighed (0.75g), and then placed in a sterile conical flask to serve as a sample piece group. The web material was used as a control panel set, while an unspiked panel set was prepared and set as f. 70mL of phosphate buffer solution (0.03moL/L, PBS) and 5mL of staphylococcus aureus bacteria solution/escherichia coli bacteria solution/candida albicans bacteria solution are respectively added into the three groups of sample slice groups, and shaking culture is carried out for 1h at 37 ℃ and 200 rpm/min. Samples were taken at 0h and 1h, respectively, and the change in bacterial count was calculated. Each batch of product test was repeated 3 times and the average inhibition rate was calculated.
Calculating the bacteriostatic rate: according to the formula, X is (A-B)/A X100 percent, and X is the bacteriostasis rate; a is the average colony number of the sample before oscillation; b is the average colony number of the sample after oscillation. And (4) judging the standard: the difference value of the number of bacterial colonies before and after the oscillation of the sample-free group is within 10 percent, the difference value between the bacteriostatic rate of the test sample and the bacteriostatic rate of the control sample is more than 26 percent, and the product can be judged to have the antibacterial effect.
TABLE 1 Difference (%)% before and after the shaking culture of the three bacteria
Figure BDA0003214155210000081
Figure BDA0003214155210000091
As can be seen from Table 1, the differences of the numbers of the colonies of Staphylococcus aureus, Escherichia coli and Candida albicans before and after 1h of oscillation at 37 ℃ and 200rpm/min are within 10%, which indicates that the test is effective.
TABLE 2 test 4 dressing groups (a, b, c, d) and web (f) for S.aureus inhibition (%)
Figure BDA0003214155210000092
According to the data in table 2, 4 batches of chitosan/nano silver/graphene oxide composite wound dressings have an effect on staphylococcus aureus for 1 hour, the bacteriostasis rates are all greater than or equal to 99.99% and far exceed the judgment standard (the product can be judged to have an antibacterial effect if the difference between the bacteriostasis rate of a test sample and the bacteriostasis rate of a control sample is greater than 26% according to the standard specification), and this shows that 4 batches of chitosan/nano silver/graphene oxide composite wound dressings have an excellent bacteriostasis effect on staphylococcus aureus.
Table 3 test 4 groups of dressings (a, b, c, d) and fiber net (f) for their respective inhibition rates for Escherichia coli (%)
Figure BDA0003214155210000093
Figure BDA0003214155210000101
According to the data in table 3, 4 batches of chitosan/nano silver/graphene oxide composite wound dressing have an effect on coliform bacteria for 1 hour, the inhibition rates are all greater than or equal to 99.99%, and far exceed the judgment standard (the difference between the inhibition rate of a test sample and the inhibition rate of a control sample is greater than 26%, the product can be judged to have an antibacterial effect), which indicates that 4 batches of chitosan/nano silver/graphene oxide composite wound dressing have an excellent antibacterial effect on the coliform bacteria.
TABLE 4 test of inhibition (%), respectively, of Candida albicans by 4 groups of dressings (a, b, c, d) and fibrous web (f)
Figure BDA0003214155210000102
According to the data in table 4, 4 batches of chitosan/nano silver/graphene oxide composite wound dressing have an effect on candida albicans for 1 hour, the bacteriostasis rates are all greater than or equal to 99.99% and far exceed the judgment standard (the product can be judged to have an antibacterial effect if the difference between the bacteriostasis rate of the test sample and the bacteriostasis rate of the control sample is greater than 26% specified by the standard), which indicates that 4 batches of chitosan/nano silver/graphene oxide composite wound dressing have an excellent bacteriostasis effect on candida albicans.
Although the present invention has been described in detail with reference to the above embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.

Claims (9)

1. A preparation method of the composite wound dressing is characterized by comprising the following steps:
dispersing graphene oxide and a surfactant in water to obtain a graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the surfactant is (125) -300: 1;
adding a silver nitrate solution into the graphene oxide dispersion liquid to obtain a mixed solution, wherein the volume ratio of the graphene oxide dispersion liquid to the silver nitrate solution is 1: 1;
performing microwave treatment on the mixed solution, performing ultrasonic treatment, and finally performing centrifugal cleaning to obtain a nano silver/graphene oxide composite material;
adding chitosan into a solvent, dropwise adding acetic acid until the chitosan is completely dissolved, then adding the nano-silver/graphene oxide composite material, and performing ultrasonic dispersion to obtain a reaction solution, wherein the mass ratio of the chitosan to the nano-silver/graphene oxide composite material is (5-20): 6;
adding a cross-linking agent into the reaction solution, performing cross-linking on the nano-silver/graphene oxide composite material and the chitosan, removing the solvent, washing, and drying to obtain a chitosan/nano-silver/graphene oxide composite material;
mixing the chitosan/nano-silver/graphene oxide composite material with polypropylene, and processing to obtain chitosan/nano-silver/graphene oxide master batches;
dissolving a reinforcer in a hydrochloric acid solution, and adding the chitosan/nano silver/graphene oxide master batch and an additive to obtain a prefabricated product, wherein the additive is one of alginate or fibroin; and
and spraying the prefabricated product to a fiber net through high pressure to obtain the composite wound dressing with the bacteriostasis rate of more than 99.99%.
2. The method for preparing a composite wound dressing according to claim 1, wherein the chitosan/nano silver/graphene oxide composite material accounts for 5% or more of the chitosan/nano silver/graphene oxide master batch by mass.
3. A method of preparing a composite wound dressing as claimed in claim 1, wherein the power of the microwave treatment is 100W-200W for 1min-5 min.
4. A method of preparing a composite wound dressing as claimed in claim 1, in which the fortifier is one of glutaraldehyde, glyoxal or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride/N-hydroxysuccinimide.
5. A method of preparing a composite wound dressing as claimed in claim 1, in which the surfactant is one of N, N-dimethylformamide, polyvinylpyrrolidone or sodium dodecylsulphonate.
6. A method of preparing a composite wound dressing as claimed in claim 1, in which the solvent is one of acetone or disodium edetate.
7. A method of preparing a composite wound dressing according to claim 1, wherein the cross-linking agent is glutaraldehyde.
8. A method of preparing a composite wound dressing according to claim 1, wherein the preparation of graphene oxide comprises the steps of:
adding 0.5-1.0 part by mass of graphite powder and 0.5-1.0 part by mass of sodium nitrate into a reaction bottle containing 4.6-5.6 parts by mass of concentrated sulfuric acid under ice bath, and adding 1.0-1.5 parts by mass of one of potassium permanganate, phosphoric acid or sodium nitrate while stirring to prepare a mixed solution;
keeping the temperature of the mixed solution at less than 15 ℃ for reaction for 1-3 h, taking out the mixed solution, stirring the mixed solution at room temperature for 3-4 days, adding deionized water for dilution, adding 1.0-2.0 parts of 20-50% hydrogen peroxide, continuously stirring the mixed solution for 2-3h, and performing centrifugal separation to obtain a bright yellow precipitate;
washing the bright yellow precipitate for multiple times by using 0.05-1 mol/L diluted hydrochloric acid and distilled water until the pH value is 7, adding the distilled water into the bright yellow precipitate, performing ultrasonic treatment for 2-3h, centrifuging again, removing insoluble precipitate at the lower layer to obtain a suspension, filtering the suspension to obtain a solid product, and performing vacuum freeze drying on the product to obtain the graphene oxide.
9. A composite wound dressing prepared by the method of making a composite wound dressing according to any one of claims 1 to 8.
CN202110938732.5A 2021-08-16 2021-08-16 Composite wound dressing and preparation method thereof Pending CN113577363A (en)

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