CN112169006A - Composite dressing with antibacterial function and preparation method thereof - Google Patents

Composite dressing with antibacterial function and preparation method thereof Download PDF

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Publication number
CN112169006A
CN112169006A CN202011033183.9A CN202011033183A CN112169006A CN 112169006 A CN112169006 A CN 112169006A CN 202011033183 A CN202011033183 A CN 202011033183A CN 112169006 A CN112169006 A CN 112169006A
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solution
antibacterial
silk fibroin
sodium alginate
composite dressing
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何立彬
万禁禁
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Guangdong Taibao Medical Science Technology Co Ltd
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Guangdong Taibao Medical Science Technology 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
    • A61L15/22Bandages, 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
    • A61L15/18Bandages, 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
    • A61L15/26Macromolecular compounds obtained otherwise than 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
    • A61L15/32Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
    • 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
    • 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
    • A61L15/62Compostable, hydrosoluble or hydrodegradable materials
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/103Agents inhibiting growth of microorganisms
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • 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
    • A61L2300/216Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • 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
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602Type of release, e.g. controlled, sustained, slow
    • 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

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Abstract

The invention provides a composite dressing with an antibacterial function, which is prepared from sodium alginate, silk fibroin, polyethylene oxide and halloysite nanotubes loaded with antibacterial components by an electrostatic spinning means; the mass ratio of the sodium alginate to the silk fibroin to the polyoxyethylene is 1: (2-4): (1-3); the halloysite nanotube loaded with the antibacterial component accounts for 4-10% of the mass ratio of the silk fibroin; the antibacterial component is one or a combination of curcumin and naringenin. The composite dressing has excellent biocompatibility and safety, and the mechanical property of the antibacterial dressing is effectively improved by compounding the sodium alginate, the silk fibroin and the polyethylene oxide in a proper proportion and adding a certain amount of halloysite nanotubes loaded with antibacterial components; the halloysite nanotube is adopted to load the antibacterial ingredients, so that the release rate of the antibacterial ingredients is slowed down, and the aim of long-acting antibiosis is fulfilled.

Description

Composite dressing with antibacterial function and preparation method thereof
Technical Field
The invention belongs to the technical field of medical dressings, and particularly relates to a composite dressing with an antibacterial function and a preparation method thereof.
Background
The skin is directly contacted with the external environment, and is easily damaged due to injury or diseases. Wound infection is a key factor affecting wound healing, and in order to reduce the probability of wound infection, a dressing is generally used for covering and protecting a wound, providing an environment beneficial to wound healing, and promoting wound healing. Good medical dressings should have excellent antibacterial performance, most medical dressings in the market adopt metal ions such as a certain amount of antibiotics or nano silver with antibacterial performance and the like which are directly added, but the antibiotics can generate drug resistance after long-term use, and the metal ions have potential harm to human bodies; and the release rate of the antibacterial component is high, and the antibacterial effect lasts for a period of time, but generally, in the tissue repair process after major surgery, the infection generally lasts for more than 1 week. Therefore, it is important to develop a dressing that is safe and can slow the release rate of the drug to achieve long-lasting antimicrobial activity.
Sodium alginate (sodium alginate) is a linear anionic natural polysaccharide extracted from seaweed, is polymerized from beta-D-mannuronic acid (M) and alpha-L-guluronic acid (G) through (1-4) glycosidic bonds, and has stability, solubility, viscosity and safety required by pharmaceutical preparation auxiliary materials; however, sodium alginate is an anionic polyelectrolyte, and molecular chains of the polyelectrolyte are rigid and extend like worms in an aqueous solution, so that electrostatic spinning of pure sodium alginate is very difficult. Silk fibroin is a natural protein from silkworms and can be processed into a range of materials with controllable mechanical properties and degradation rates. The silk fibroin is mainly composed of nonpolar amino acid, has excellent characteristics of good biocompatibility, small inflammatory reaction, high degradability, good air and moisture permeability, promotion of wound healing and the like, and is widely applied to the field of medical dressings.
The electrostatic spinning technology is a common simple method for preparing nano-fibers, drugs and biological macromolecules are easily loaded into the fibers and on the surfaces of the fibers in the electrostatic spinning or spinning treatment process, and in addition, the antibacterial elements cannot change in performance after being loaded into the fibers, so that the antibacterial performance of the fibers can be maintained, and bacterial infection can be more effectively prevented.
The halloysite nanotube is tubular aluminosilicate, has a loading rate of about 15-20%, a length-diameter ratio of 20-50, can remarkably enhance the mechanical property of the fiber when oriented in polymer fibers, is natural, does not pollute the environment, has good compatibility, and can be widely applied to the aspects of cosmetics, drug slow release and the like when used as a tubular container.
Disclosure of Invention
The invention aims to provide a safe and continuously effective antibacterial composite dressing for overcoming the defects of the existing medical dressing.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the composite dressing with the antibacterial function is prepared from sodium alginate, silk fibroin, polyethylene oxide and halloysite nanotubes loaded with antibacterial components by an electrostatic spinning method.
Preferably, the mass ratio of the sodium alginate to the silk fibroin to the polyethylene oxide is 1: (2-4): (1-3).
Preferably, the halloysite nanotubes loaded with the antibacterial component account for 4-10% of the mass ratio of the silk fibroin.
Preferably, the antibacterial component is curcumin or naringenin.
Preferably, the antibacterial component is a combination of curcumin and naringenin.
Preferably, the antibacterial component consists of curcumin and naringenin in a mass ratio of 1: 1.
The invention also provides a preparation method of the composite dressing with the antibacterial function, which comprises the following steps:
s1: preparation of sodium alginate solution: dissolving sodium alginate in deionized water, and stirring at normal temperature to obtain sodium alginate solution with mass concentration of 2-3%;
s2: preparing a silk fibroin solution: placing natural silkworm shell or silk into sodium carbonate aqueous solution or sodium bicarbonate aqueous solution or biological enzyme aqueous solution, heating for degumming, dissolving with lithium bromide-formic acid solution, dialyzing, filtering, concentrating, and preparing to obtain silk fibroin solution with mass concentration of 5-8%;
s3: preparation of polyethylene oxide solution: dissolving polyoxyethylene in deionized water, and stirring at normal temperature to prepare a polyoxyethylene solution with the mass concentration of 2-3%;
s4: preparing the halloysite nanotube loaded with the antibacterial component: adding the antibacterial component into ethanol, fully stirring and ultrasonically dissolving to obtain a saturated solution A, fully and uniformly mixing the halloysite nanotube and the saturated solution A to obtain a suspension B, vacuumizing the suspension B for 30min to ensure that the pressure in the halloysite nanotube cavity is negative, repeating the steps twice, centrifuging to remove supernatant, washing the precipitate with deionized water, drying and grinding to obtain the halloysite nanotube loaded with the antibacterial component;
s5: preparing electrostatic mixed spinning solution: preparing a mixed solution from a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution and a halloysite nanotube carrying an antibacterial component, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution;
s6: preparing a nanofiber membrane: injecting the electrostatic mixed spinning solution into an injector of an electrostatic spinning device, adjusting the electrospinning voltage to be 20-30kV, the distance from a jet orifice to a receiver to be 10-20cm, and the spinning speed to be 0.5-2mL/h, starting the spinning device, collecting the electrospun nanofibers on the receiver, and carrying out vacuum drying on the collected fiber membrane in a vacuum drying oven for 2 days to obtain the composite dressing with the antibacterial function.
In the step S2, the lithium bromide-formic acid solution is prepared from a lithium bromide solution with a mass concentration of 20-30% and a formic acid solution with a mass concentration of 90-98% in a volume ratio of 1: 1.
The mass ratio of the antibacterial component to the halloysite nanotubes in the step S4 is (1-1.5): 1.
the invention has the beneficial effects that: 1) the composite dressing has excellent biocompatibility, the adopted raw materials of sodium alginate, silk fibroin and halloysite nanotubes are all natural sources, polyoxyethylene is also a nontoxic, biocompatible and biodegradable synthetic polymer, and the main antibacterial components of curcumin and naringenin are plant components extracted from natural Chinese herbal medicines, so that the dressing has better antibacterial property and better safety compared with antibiotics and metal ion antibacterial agents; 2) polyethylene oxide is added in the raw materials, and the polyethylene oxide and sodium alginate have an intermolecular interaction, so that the flexibility and entanglement degree of a molecular chain segment of the sodium alginate are improved, and the electrostatic spinning capacity of the sodium alginate is improved; 3) according to the invention, sodium alginate, silk fibroin and polyethylene oxide are compounded in a proper proportion, and a certain amount of halloysite nanotubes loaded with antibacterial components are added, so that the mechanical property of the composite dressing is effectively improved; 4) the halloysite nanotube is adopted to load the antibacterial components, so that the release rate of the antibacterial components is slowed down, and the aim of long-acting antibiosis of the composite dressing is fulfilled.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples.
Example 1
A composite dressing with antibacterial function is prepared from sodium alginate, silk fibroin, polyethylene oxide and halloysite nanotubes loaded with curcumin by electrostatic spinning;
wherein the mass ratio of sodium alginate to silk fibroin to polyoxyethylene is 1: 2: 1; the halloysite nanotube loaded with curcumin accounts for 6% of the mass proportion of the silk fibroin.
Example 2
A composite dressing with antibacterial function is prepared from sodium alginate, silk fibroin, polyethylene oxide and a halloysite nanotube carrying naringenin by electrostatic spinning;
wherein the mass ratio of sodium alginate to silk fibroin to polyoxyethylene is 1: 2: 1; the halloysite nanotube carrying naringenin accounts for 6% of the mass proportion of the silk fibroin.
Example 3
A composite dressing with antibacterial function is prepared from sodium alginate, silk fibroin, polyethylene oxide and halloysite nanotubes loaded with antibacterial components by electrostatic spinning;
wherein the mass ratio of sodium alginate to silk fibroin to polyoxyethylene is 1: 2: 1; the halloysite nanotube loaded with the antibacterial component accounts for 6% of the mass ratio of the silk fibroin; the antibacterial component is prepared from curcumin and naringenin according to a mass ratio of 1: 1.
The preparation method of the composite antibacterial dressing of examples 1-3 is as follows:
s1: preparation of sodium alginate solution: dissolving sodium alginate in deionized water, and stirring at normal temperature to obtain a sodium alginate solution with the mass concentration of 2%;
s2: preparing a silk fibroin solution: placing natural silkworm shell or silk into sodium carbonate aqueous solution, heating for degumming, dissolving with lithium bromide-formic acid solution (composed of 20 wt% lithium bromide solution and 98 wt% formic acid solution at volume ratio of 1: 1), dialyzing, filtering, concentrating, and preparing into 5% silk fibroin solution;
s3: preparation of polyethylene oxide solution: dissolving polyoxyethylene into deionized water, and stirring at normal temperature to prepare a polyoxyethylene solution with the mass concentration of 2%;
s4: preparing the halloysite nanotube loaded with the antibacterial component: adding 3g of antibacterial component into ethanol, fully stirring and ultrasonically dissolving to obtain a saturated solution A, fully and uniformly mixing 3g of halloysite nanotube and the saturated solution A to obtain a suspension B, vacuumizing the suspension B for 30min to make the inner cavity of the halloysite nanotube have negative pressure, repeating the steps twice, centrifuging to remove supernatant, washing the precipitate with deionized water, drying and grinding to obtain the halloysite nanotube loaded with the antibacterial component;
s5: preparing electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 2: 1, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding a halloysite nanotube which is 6% of the mass of silk fibroin and carries an antibacterial component, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution;
s6: preparing a nanofiber membrane: and (2) injecting the electrostatic mixed spinning solution into an injector of an electrostatic spinning device, adjusting the electrospinning voltage to be 25kV, adjusting the distance from a jet orifice to a receiver to be 15cm, adjusting the spinning speed to be 1mL/h, starting the spinning device, collecting the electrospun nanofibers on the receiver, and performing vacuum drying on the collected fiber membrane in a vacuum drying oven for 2 days to obtain the composite dressing with the antibacterial function.
Example 4
A composite dressing with antibacterial function is prepared from sodium alginate, silk fibroin, polyethylene oxide and halloysite nanotubes loaded with antibacterial components by electrostatic spinning;
wherein the mass ratio of sodium alginate to silk fibroin to polyoxyethylene is 1: 3: 2; the halloysite nanotube loaded with the antibacterial component accounts for 8% of the mass ratio of the silk fibroin; the antibacterial component is prepared from curcumin and naringenin according to a mass ratio of 1: 1.
The preparation method of the composite antibacterial dressing comprises the following steps:
s1: preparation of sodium alginate solution: dissolving sodium alginate in deionized water, and stirring at normal temperature to obtain a sodium alginate solution with the mass concentration of 2%;
s2: preparing a silk fibroin solution: placing natural silkworm shell or silk into sodium bicarbonate water solution, heating for degumming, dissolving with lithium bromide-formic acid solution (composed of 30 wt% lithium bromide solution and 95 wt% formic acid solution at volume ratio of 1: 1), dialyzing, filtering, concentrating, and preparing to obtain 6% silk fibroin solution;
s3: preparation of polyethylene oxide solution: dissolving polyoxyethylene into deionized water, and stirring at normal temperature to prepare a polyoxyethylene solution with the mass concentration of 3%;
s4: preparing the halloysite nanotube loaded with the antibacterial component: adding 3.5g of antibacterial component into ethanol, fully stirring and ultrasonically dissolving to obtain a saturated solution A, fully and uniformly mixing 2.5g of halloysite nanotube and the saturated solution A to obtain a suspension B, vacuumizing the suspension B for 30min to ensure that the pressure in the tube cavity of the halloysite nanotube is negative, repeating the steps twice, centrifuging to remove supernatant, drying and grinding the precipitate to obtain the halloysite nanotube loaded with the antibacterial component;
s5: preparing electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 3: 2, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding a halloysite nanotube which is 8% of the mass of silk fibroin and carries an antibacterial component, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution;
s6: preparing a nanofiber membrane: and (2) injecting the electrostatic mixed spinning solution into an injector of an electrostatic spinning device, adjusting the electrospinning voltage to be 20kV, adjusting the distance from a jet orifice to a receiver to be 15cm, adjusting the spinning speed to be 1.5mL/h, starting the spinning device, collecting the electrospun nanofibers on the receiver, and performing vacuum drying on the collected fiber membrane in a vacuum drying oven for 2 days to obtain the composite dressing with the antibacterial function.
Example 5
A composite dressing with antibacterial function is prepared from sodium alginate, silk fibroin, polyethylene oxide and halloysite nanotubes loaded with curcumin by electrostatic spinning;
wherein the mass ratio of sodium alginate to silk fibroin to polyoxyethylene is 1: 4: 2; the halloysite nanotube loaded with curcumin accounts for 4% of the mass proportion of the silk fibroin.
The preparation method of the composite antibacterial dressing comprises the following steps:
s1: preparation of sodium alginate solution: dissolving sodium alginate in deionized water, and stirring at normal temperature to obtain a sodium alginate solution with the mass concentration of 3%;
s2: preparing a silk fibroin solution: placing natural silkworm shell or silk into a biological enzyme aqueous solution, heating for degumming, dissolving by a lithium bromide-formic acid solution (comprising a lithium bromide solution with the mass concentration of 20 wt% and a formic acid solution with the mass concentration of 90 wt% according to the volume ratio of 1: 1), dialyzing, filtering, concentrating, and preparing to obtain a silk fibroin solution with the mass concentration of 8%;
s3: preparation of polyethylene oxide solution: dissolving polyoxyethylene into deionized water, and stirring at normal temperature to prepare a polyoxyethylene solution with the mass concentration of 3%;
s4: preparation of the halloysite nanotubes loaded with curcumin: adding 3.6g of curcumin component into ethanol, fully stirring and ultrasonically dissolving to obtain a saturated solution A, fully and uniformly mixing 2.4g of halloysite nanotubes and the saturated solution A to obtain a suspension B, vacuumizing the suspension B for 30min to ensure that the pressure in the tube cavity of the halloysite nanotubes is negative, repeating the steps twice, centrifuging to remove supernatant, washing precipitates with deionized water, drying and grinding to obtain the halloysite nanotubes loaded with curcumin;
s5: preparing electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 4: 2, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding a halloysite nanotube which is 4% of the mass of the silk fibroin and is loaded with curcumin, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution;
s6: preparing a nanofiber membrane: and (2) injecting the electrostatic mixed spinning solution into an injector of an electrostatic spinning device, adjusting the electrospinning voltage to be 30kV, adjusting the distance from a jet orifice to a receiver to be 20cm, and the spinning speed to be 0.5mL/h, starting the spinning device, collecting the electrospun nanofibers on the receiver, and carrying out vacuum drying on the collected fiber membrane in a vacuum drying oven for 2 days to obtain the composite dressing with the antibacterial function.
Example 6
The composite dressing with the antibacterial function is characterized by being prepared from sodium alginate, silk fibroin, polyethylene oxide and a halloysite nanotube carrying naringenin by an electrostatic spinning method.
Wherein the mass ratio of sodium alginate to silk fibroin to polyoxyethylene is 1: 2: 3; the halloysite nanotube carrying naringenin accounts for 10% of the mass proportion of the silk fibroin.
The preparation method of the composite antibacterial dressing comprises the following steps:
s1: preparation of sodium alginate solution: dissolving sodium alginate in deionized water, and stirring at normal temperature to obtain a sodium alginate solution with the mass concentration of 2%;
s2: preparing a silk fibroin solution: placing natural silkworm shell or silk into sodium bicarbonate water solution, heating for degumming, dissolving with lithium bromide-formic acid solution (composed of 25 wt% lithium bromide solution and 95 wt% formic acid solution at volume ratio of 1: 1), dialyzing, filtering, concentrating, and preparing to obtain 7% silk fibroin solution;
s3: preparation of polyethylene oxide solution: dissolving polyoxyethylene into deionized water, and stirring at normal temperature to prepare a polyoxyethylene solution with the mass concentration of 2%;
s4: preparation of the halloysite nanotube loaded with naringenin: adding 3.3g of naringenin component into ethanol, fully stirring and ultrasonically dissolving to obtain a saturated solution A, fully and uniformly mixing 2.7g of halloysite nanotube and the saturated solution A to obtain a suspension B, vacuumizing the suspension B for 30min to ensure that the pressure in the tube cavity of the halloysite nanotube is negative, repeating the steps twice, centrifuging to remove the supernatant, washing the precipitate with deionized water, drying and grinding to obtain the halloysite nanotube carrying the naringenin;
s5: preparing electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 2: 3, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding a halloysite nanotube which is 10% of the mass of silk fibroin and is loaded with naringenin, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution;
s6: preparing a nanofiber membrane: and (2) injecting the electrostatic mixed spinning solution into an injector of an electrostatic spinning device, adjusting the electrospinning voltage to be 30kV, adjusting the distance from a jet orifice to a receiver to be 10cm, adjusting the spinning speed to be 2mL/h, starting the spinning device, collecting the electrospun nanofibers on the receiver, and performing vacuum drying on the collected fiber membrane in a vacuum drying oven for 2 days to obtain the composite dressing with the antibacterial function.
Comparative example 1
A composite dressing in which the halloysite nanotubes loaded with curcumin were directly replaced with nano-silver loaded halloysite nanotubes, compared to the composite dressing of example 1. Other components, contents and preparation method are unchanged.
Comparative example 2
Compared with the composite dressing in the embodiment 4, the halloysite nanotubes loaded with the antibacterial component are directly replaced by the antibacterial component consisting of curcumin and naringenin according to the mass ratio of 1:1, and other components are unchanged.
Step S4 is omitted from the preparation method, and step S5 is preparation of an electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 2: 1, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding an antibacterial component accounting for 6% of the mass of the silk fibroin, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution.
Comparative example 3
Compared with the composite dressing in example 4, the composite dressing has the mass ratio of sodium alginate to silk fibroin to polyethylene oxide of 1: 1: 4, the antibacterial component is unchanged.
The preparation method comprises the following steps of S5 preparation of electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 1: 4, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding a halloysite nanotube which is 8% of the mass of silk fibroin and is loaded with an antibacterial component, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution; the other steps are the same.
Comparative example 4
Compared with the composite dressing in example 5, the halloysite nanotubes loaded with curcumin account for 3% of the mass proportion of silk fibroin, and other components and contents are unchanged.
The preparation method comprises the following steps of S5 preparation of electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 4: 2, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding a halloysite nanotube which is 3% of the mass of the silk fibroin and is loaded with curcumin, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution; the other steps are the same.
Comparative example 5
Compared with the composite dressing in example 6, the halloysite nanotubes loaded with naringenin account for 12% of the mass proportion of silk fibroin, and other components and contents are unchanged.
The preparation method comprises the following steps of S5 preparation of electrostatic mixed spinning solution: according to the solid mass ratio of sodium alginate to silk fibroin to polyoxyethylene of 1: 2: 3, mixing a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution, adding a halloysite nanotube which is 12% of the mass of silk fibroin and is loaded with naringenin, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution; the other steps are the same.
To illustrate the effect of the composite dressing with antibacterial function of the present invention, the following method was used for testing.
First, cytotoxicity test
The composite dressings prepared in examples 1 to 6 and comparative example 1 were subjected to cytotoxicity evaluation test (test according to national standard GB/T16886.5-2003) to compare examples 1 to 6 and comparative example 1.
The cytotoxicity detection results show that after the cells of the examples 1-6 are co-cultured with human fibroblasts for 24 hours and 48 hours, the corresponding relative cell proliferation rate is more than 92%, and the cytotoxicity rating is 0 grade, so that the cells have good cell compatibility. In contrast, comparative example 1, which was co-cultured with human fibroblasts for 24 hours and 48 hours, had a relative cell proliferation rate of about 80% and a cytotoxicity rating of 1, and was slightly cytotoxic. The composite dressing with the antibacterial function has better safety.
Second, tensile mechanical property test
The composite dressings prepared in examples 1, 4, 5 and 6 of the present invention and comparative examples 2, 3, 4 and 5 were cut into test strips of the same size, both ends of the test strips were wrapped with tinfoil paper, and the tensile mechanical properties were measured while leaving the middle 20mm long. And (3) performing mechanical property test on an Instron5967 universal material testing machine, wherein the stretching speed is 5mm/min, and calculating the breaking strength and the breaking elongation by taking the average value after 5 times of measurement. The results are shown in table 1:
table 1 analysis of tensile properties of different dressings
Sample (I) Maximum breaking strength (Mpa) Elongation at Break (%)
Example 1 1.56±0.16 53.07±8.24
Example 4 1.85±0.21 55.80±10.03
Example 5 1.62±0.25 48.65±7.81
Example 6 1.74±0.13 51.50±9.16
Comparative example 2 0.55±0.17 28.95±6.54
Comparative example 3 1.28±0.19 36.54±7.30
Comparative example 4 1.07±0.10 33.78±5.92
Comparative example 5 1.93±0.34 27.06±6.07
As can be seen from the comparison of the mechanical property data in the table, the mechanical property of the composite dressing product of the present invention is significantly improved, and the mechanical property of example 4 is the best. In addition, compared with the comparative example 3 and the example, the maximum breaking strength and the elongation at break of the composite material are lower than the data of the example, which shows that when the mass ratio of the sodium alginate to the silk fibroin to the polyethylene oxide is 1: (2-4): and (1-3), the composite dressing has better mechanical property.
Compared with example 6, the maximum breaking strength of comparative example 5 is higher than that of example 6, but the breaking elongation is obviously lower than that of example 6, the mechanical property data of comparative example 2 is obviously lower than that of example 4, and the mechanical property data of comparative example 4 is obviously lower than that of example 5, which shows that the addition of the halloysite nanotube loaded with the antibacterial component can effectively improve the mechanical property of the electrospinning material, but when the content is not within 4-10% of the mass ratio of silk fibroin, the mechanical property is obviously influenced.
Third, antibacterial effect test
The composite dressings of examples 1 to 6 and comparative example 2 were each sampled, cut into a size of 1.0cm × 1.0cm, placed in a 250ml Erlenmeyer flask, 70ml of PBS and 5ml of bacterial suspension were added, respectively, and the concentration of bacterial suspension in PBS was adjusted to 1 × 104-9×104CFU/ml, the Erlenmeyer flask is fixed on a shaking table, after shaking at 150r/min for 24h, the sample solution of the experimental group (added sample) and the blank group (not added sample) are respectively taken, after being diluted properly by PBS, the plate is inoculated by agar pouring method, and colony counting is carried out. At the same time, a control group should be established, and only PBS and bacterial suspension are added into the control group. The strain is selected from Escherichia coli E.C and Staphylococcus aureus S.a. The bacteriostasis rate is the ratio (in percentage) of the difference of the average colony number of the tested sample before and after oscillation to the average colony number of the sample before oscillation.
The number of colonies of the sample-free group is 1 multiplied by 104-9×104And the difference between the CFU/ml and the average colony number of the group before and after oscillation is within 10 percent, and the difference between the experimental group bacteriostatic rate and the blank group bacteriostatic rate is more than 26 percent, namely the product has the antibacterial effect. The results are shown in tables 2 and 3.
Table 2 antimicrobial testing of composite dressing pairs E.C and S.a
Figure BDA0002704425780000131
Figure BDA0002704425780000141
TABLE 3 antibacterial Effect of composite dressings on E.C and S.a
Figure BDA0002704425780000142
As can be seen from tables 2 and 3, the composite dressing of the present invention has excellent antibacterial effects against both escherichia coli and staphylococcus aureus, and the antibacterial effect gradually decreases with the lapse of time, but still has antibacterial effect on day 7 and antibacterial effect against escherichia coli on day 11. The composite dressing with the antibacterial function has a long-acting antibacterial effect. In addition, the composite dressings of examples 3 and 4 still have antibacterial effects on both bacteria at day 10, which shows that the two components of curcumin and naringenin are loaded through the halloysite nanotube in a compounding manner, so that a synergistic effect is generated, and the antibacterial effect of the composite dressings is enhanced.
The composite dressing of comparative example 2 had no antibacterial effect on escherichia coli on day 7, and had no antibacterial effect on staphylococcus aureus on day 5, and had no long-lasting bacteriostatic effect as compared with examples 1-6. The invention is proved that the release rate of the antibacterial component is slowed down by loading the antibacterial component by using the halloysite nanotube, thereby realizing the aim of long-acting antibiosis.
It should be noted that the specific embodiments are only representative examples of the present invention, and obviously, the technical solutions of the present invention are not limited to the above examples, and technical solutions that are undoubtedly obtained by those skilled in the art according to the disclosure of the present invention all belong to the protection scope of the present invention.

Claims (9)

1. The composite dressing with the antibacterial function is characterized by being prepared from sodium alginate, silk fibroin, polyethylene oxide and halloysite nanotubes loaded with antibacterial components by an electrostatic spinning method.
2. The composite dressing with antibacterial function according to claim 1, wherein the mass ratio of sodium alginate to silk fibroin to polyethylene oxide is 1: (2-4): (1-3).
3. The composite dressing with the antibacterial function according to claim 1, wherein the halloysite nanotubes loaded with the antibacterial component account for 4-10% of the mass proportion of the silk fibroin.
4. The composite dressing with antibacterial function according to claim 1, wherein the antibacterial component is curcumin or naringenin.
5. The composite dressing with antibacterial function according to claim 1, characterized in that the antibacterial component is a combination of curcumin and naringenin.
6. The composite dressing with antibacterial function according to claim 5, wherein the antibacterial component consists of curcumin and naringenin in a mass ratio of 1: 1.
7. The method for preparing a composite dressing having an antibacterial function according to any one of claims 1 to 6, comprising the steps of:
s1: preparation of sodium alginate solution: dissolving sodium alginate in deionized water, and stirring at normal temperature to obtain sodium alginate solution with mass concentration of 2-3%;
s2: preparing a silk fibroin solution: placing natural silkworm shell or silk into sodium carbonate aqueous solution or sodium bicarbonate aqueous solution or biological enzyme aqueous solution, heating for degumming, dissolving with lithium bromide-formic acid solution, dialyzing, filtering, concentrating, and preparing to obtain silk fibroin solution with mass concentration of 5-8%;
s3: preparation of polyethylene oxide solution: dissolving polyoxyethylene in deionized water, and stirring at normal temperature to prepare a polyoxyethylene solution with the mass concentration of 2-3%;
s4: preparing the halloysite nanotube loaded with the antibacterial component: adding the antibacterial component into ethanol, fully stirring and ultrasonically dissolving to obtain a saturated solution A, fully and uniformly mixing the halloysite nanotube and the saturated solution A to obtain a suspension B, vacuumizing the suspension B for 30min to ensure that the pressure in the halloysite nanotube cavity is negative, repeating the steps twice, centrifuging to remove supernatant, washing the precipitate with deionized water, drying and grinding to obtain the halloysite nanotube loaded with the antibacterial component;
s5: preparing electrostatic mixed spinning solution: preparing a mixed solution from a sodium alginate solution and a silk fibroin solution, adding a polyoxyethylene solution and a halloysite nanotube carrying an antibacterial component, magnetically stirring and mixing, and uniformly oscillating by adopting ultrasonic waves to obtain an electrostatic mixed spinning solution;
s6: preparing a nanofiber membrane: injecting the electrostatic mixed spinning solution into an injector of an electrostatic spinning device, adjusting the electrospinning voltage to be 20-30kV, the distance from a jet orifice to a receiver to be 10-20cm, and the spinning speed to be 0.5-2mL/h, starting the spinning device, collecting the electrospun nanofibers on the receiver, and carrying out vacuum drying on the collected fiber membrane in a vacuum drying oven for 2 days to obtain the composite dressing with the antibacterial function.
8. The method for preparing a composite dressing having an antibacterial function according to claim 7, wherein the lithium bromide-formic acid solution in step S2 is prepared from a lithium bromide solution with a mass concentration of 20-30% and a formic acid solution with a mass concentration of 90-98% in a volume ratio of 1: 1.
9. The method for preparing the composite dressing with the antibacterial function according to claim 7, wherein the mass ratio of the antibacterial component to the halloysite nanotubes in the step S4 is (1-1.5): 1.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979999A (en) * 2021-02-25 2021-06-18 南通纺织丝绸产业技术研究院 Biological macromolecule and modified halloysite composite hydrogel and preparation and application thereof
CN113604958A (en) * 2021-08-11 2021-11-05 浙江理工大学 Preparation method and application of anti-infection composite layer medical dressing
CN114984305A (en) * 2022-07-19 2022-09-02 中国人民解放军总医院第一医学中心 Novel antibacterial film-forming liquid medical dressing and preparation method thereof
CN115896979A (en) * 2022-12-30 2023-04-04 东北农业大学 Naringenin cyclodextrin inclusion compound nanofiber and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979999A (en) * 2021-02-25 2021-06-18 南通纺织丝绸产业技术研究院 Biological macromolecule and modified halloysite composite hydrogel and preparation and application thereof
CN112979999B (en) * 2021-02-25 2022-11-11 南通纺织丝绸产业技术研究院 Biological macromolecule and modified halloysite composite hydrogel and preparation and application thereof
CN113604958A (en) * 2021-08-11 2021-11-05 浙江理工大学 Preparation method and application of anti-infection composite layer medical dressing
CN114984305A (en) * 2022-07-19 2022-09-02 中国人民解放军总医院第一医学中心 Novel antibacterial film-forming liquid medical dressing and preparation method thereof
CN115896979A (en) * 2022-12-30 2023-04-04 东北农业大学 Naringenin cyclodextrin inclusion compound nanofiber and preparation method and application thereof
CN115896979B (en) * 2022-12-30 2023-09-29 东北农业大学 Naringenin cyclodextrin inclusion compound nanofiber as well as preparation method and application thereof

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