CN108042839A - A kind of chitosan complexes bandage and preparation method thereof - Google Patents

A kind of chitosan complexes bandage and preparation method thereof Download PDF

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Publication number
CN108042839A
CN108042839A CN201711392479.8A CN201711392479A CN108042839A CN 108042839 A CN108042839 A CN 108042839A CN 201711392479 A CN201711392479 A CN 201711392479A CN 108042839 A CN108042839 A CN 108042839A
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chitosan
solution
complexes
preparation
bandage
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覃彩芹
郑科旺
李伟
黄超凡
陈蔚
付梅芳
郭海
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Hubei Engineering University
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Hubei Engineering University
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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
    • A61L15/22Bandages, 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
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/44Medicaments
    • 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
    • A61L2300/106Halogens or compounds thereof, e.g. iodine, chlorite
    • 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
    • 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
    • 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
    • A61L2300/41Anti-inflammatory agents, e.g. NSAIDs
    • 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
    • A61L2300/418Agents promoting blood coagulation, blood-clotting agents, embolising 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
    • 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
    • A61L2300/604Biodegradation

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Abstract

The present invention relates to a kind of chitosan complexes bandages and preparation method thereof, belong to pharmaceutical technology field.Preparation method includes:Chitosan and polyvinylpyrrolidone are dissolved respectively, obtain chitosan solution and polyvinylpyrrolidonesolution solution;Chitosan solution and polyvinylpyrrolidonesolution solution are mixed, obtains chitosan polyvinylpyrrolidone mixed liquor;It is added in after additive is dissolved in water into chitosan polyvinylpyrrolidone mixed liquor, obtains spinning solution.Spinning solution is spun to chitosan complexes layer, is then bonded with water suction cushion layer, baseband layer.The preparation method is simple for process, simple operation, production cost are low, is suitble to produce and prepare chitosan complexes bandage on a large scale.Not only production cost is low, safe and harmless for the chitosan complexes bandage being prepared by the above method, while also has the characteristics that air permeable humidity retaining is good, hemostasis clotting ability is strong, inhibiting bacteria and diminishing inflammation ability is excellent, can effectively facilitate the healing of the surface of a wound.

Description

A kind of chitosan complexes bandage and preparation method thereof
Technical field
The present invention relates to field of medicaments, and more particularly to a kind of chitosan complexes bandage and preparation method thereof.
Background technology
Bandage is since its absorbability is good, can protect the surface of a wound, cheap, easy to use, it has also become vast family and One of first-aid applicance of business unit's indispensability.However, the shortcomings that current bandage, is also fairly obvious, such as:It cannot keep the surface of a wound Moistening;Do not possess antibiotic property;It cannot promote the healing of wound.
Chitosan is in alkaline conditions by a kind of derivative formed after deacetylation, deacetylation by chitin It is unique a large amount of existing alkaline polysaccharides in nature generally between 65%-90%.Chitosan is a kind of natural macromolecule Compound has the characteristics that nontoxic, antibacterial, anti-inflammatory, hemostasis, immune, good biocompatibility and biological degradability, no Chitosan with molecular weight has the activity of blood different influences.
Chinese invention patent application (publication number CN105126150A) discloses a kind of bandage of chitosan-containing mixture And preparation method thereof, it is the mixture formed with the chitosan of the chitosan of high molecular weight and low molecular weight, passes through infusion process It is made to be dispersed in bed course, but the chitosan compound bandage that this method is used to prepare, the attachment portion shell only on bed course Glycan substance and attachment it is uneven, easy to fall off, the effect of wound healing cannot be played completely.
Chinese invention patent application (publication number CN102552964A) discloses a kind of nano silver chitosan composite antibacterial group Object, bandage and preparation method thereof are closed, it is by dispersed nano-silver particles in high molecular weight chitosan, passes through dry-wet spinning Nano silver chitosan fibrous layer is prepared, is finally assembled into nano silver chitosan bandage.Infusion process makes it be dispersed in bed course, but It is the chitosan compound bandage prepared using this method, attachment portion chitosan material and attachment unevenness only on bed course It is even, easy to fall off, the effect of wound healing cannot be played completely.This wound sticking dressing can play antibacterial, wound is promoted to be cured The effects that conjunction, but nano silver belongs to heavy metal, has certain harm to human body, nano silver is with high costs in addition, is unsuitable for Mass production and application.
It is, thus, sought for a kind of be beneficial to large-scale production and finished product bandage can be made to have preferable hemostatic bacteriostatic effect Preparation method.
The content of the invention
One of the objects of the present invention is to provide a kind of preparation method of chitosan complexes bandage, the preparation method works Skill is simple, simple operation, production cost are low, is suitble to produce and prepare chitosan complexes bandage on a large scale.
Another object of the present invention is to provide a kind of chitosan complexes bandage, it is prepared by above-mentioned preparation method , which also has in addition to having preferable air permeable humidity retaining and stronger hemostasis, clotting ability There is good inhibiting bacteria and diminishing inflammation ability, the healing of the surface of a wound can be effectively facilitated.Also, the chitosan complexes bandage production cost It is low, safe and harmless.
The present invention is solved its technical problem and is realized using following technical scheme:
The present invention proposes a kind of preparation method of chitosan complexes bandage, comprises the following steps:Dissolving shell gathers respectively Sugar and polyvinylpyrrolidone, obtain chitosan solution and polyvinylpyrrolidonesolution solution;Mix chitosan solution and polyethylene pyrrole Pyrrolidone solution obtains chitosan-polyvinylpyrrolidone mixed liquor;It is added in after additive is dissolved in water to chitosan-polyethylene In pyrrolidones mixed liquor, spinning solution is obtained.
Spinning solution is spun to chitosan complexes layer, is then bonded with water suction cushion layer, baseband layer, it is compound to obtain chitosan Object bandage.
The present invention also proposes a kind of chitosan complexes bandage, by the preparation method of above-mentioned chitosan complexes bandage It is prepared.
The advantageous effect for the chitosan complexes bandage and preparation method thereof that present pre-ferred embodiments provide is:
Not only production cost is low, safe and harmless for the chitosan complexes bandage that present pre-ferred embodiments provide, simultaneously Also have the characteristics that air permeable humidity retaining is good, hemostasis clotting ability is strong, inhibiting bacteria and diminishing inflammation ability is excellent, being cured for the surface of a wound can be effectively facilitated It closes.
Its preparation method is simple for process, simple operation, production cost are low, is suitble to large-scale produce and prepare chitosan and answer Close object bandage.
Description of the drawings
It in order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of scope, for those of ordinary skill in the art, without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.
Fig. 1 is different samples in test example 1 of the present invention to the antibacterial test result figure of Escherichia coli;
Fig. 2 is different samples in test example 1 of the present invention to the antibacterial test result figure of staphylococcus aureus;
Fig. 3 is the electron-microscope scanning figure of the chitosan complexes layer that embodiment 3 provides in test example 2 of the present invention;
Fig. 4 is the electron-microscope scanning figure of the chitosan complexes layer that control group 1 provides in test example 2 of the present invention;
Fig. 5 is the electron-microscope scanning figure of the chitosan complexes layer that control group 2 provides in test example 2 of the present invention.
Specific embodiment
It, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.
Chitosan complexes bandage of the embodiment of the present invention and preparation method thereof is specifically described below.
The preparation method of chitosan complexes bandage provided in an embodiment of the present invention may include following steps:It dissolves respectively Chitosan and polyvinylpyrrolidone, obtain chitosan solution and polyvinylpyrrolidonesolution solution.
Wherein, chitosan solution is that chitosan is dissolved in acid solution so that chitosan is abundant, release activity into Point.It is preferred that concentration of the chitosan in chitosan solution is 0.5-3wt% in the embodiment of the present invention.
Optionally, above-mentioned acid solution can for example include aqueous acetic acid, aqueous hydrochloric acid solution and aqueous citric acid solution In any one, be preferably acetic acid.When selecting acetic acid as acid solution, acetic acid is preferably formulated to mass concentration as 1-5% Aqueous acetic acid for use namely aqueous acetic acid in acetic acid concentration be 1-5wt%.
Since the chitosan of high molecular weight has, good mechanical performance, rush are hemagglutinin, but its biocidal property is poor, and in The chitosan of molecular weight has good inhibiting bacteria and diminishing inflammation, but its bad mechanical property.Therefore, the shell in the embodiment of the present invention gathers For glycogen material by the way that the chitosan of high molecular weight is combined with the chitosan of middle-molecular-weihydroxyethyl, the machinery that can have both reached certain is strong Degree, and can improve its inhibiting bacteria and diminishing inflammation, cause inhibiting bacteria and diminishing inflammation poor to avoid the chitosan only with high molecular weight or only The defects of causing chitosan composite bed mechanical strength inadequate using the chitosan of middle-molecular-weihydroxyethyl or low molecular weight.
Optionally, the deacetylation of the high molecular weight chitosan in the embodiment of the present invention is preferably greater than 80%, weight Average molecular weight is preferably greater than 100kDa;The deacetylation of middle-molecular-weihydroxyethyl chitosan is preferably greater than 80%, and weight average molecular weight is excellent Elect 10-50kDa as.
It is preferred that the mass ratio of above-mentioned high molecular weight chitosan and middle-molecular-weihydroxyethyl chitosan is (80:20)-(90:10).More Goodly, the mass ratio of above-mentioned high molecular weight chitosan and middle-molecular-weihydroxyethyl chitosan is 85:15.Under this ratio, with reference to chitosan Deacetylation and weight average molecular weight in possessed above range can effectively improve the mechanical strength of bandage finished product and antibacterial It is anti-inflammatory.
Polyvinylpyrrolidonesolution solution is that polyvinylpyrrolidone is soluble in water, it is preferred that gathering in the embodiment of the present invention Concentration of the vinylpyrrolidone in polyvinylpyrrolidonesolution solution is 1-5wt%.The weight average molecular weight of polyvinylpyrrolidone Preferably greater than 1,300,000, so that the spinning solution that the later stage obtains can easily be spun into porous fiber film.
Chitosan solution and polyvinylpyrrolidonesolution solution are mixed, obtains chitosan-polyvinylpyrrolidone mixed liquor.Preferably Ground, chitosan-polyvinylpyrrolidone mixed liquor is by chitosan solution and polyvinylpyrrolidonesolution solution using volume ratio as (50: 50)-(70:30) it is obtained by mixing.
What deserves to be explained is if only with chitosan solution or the molecule of polyvinylpyrrolidone in the embodiment of the present invention Amount is less than 1,300,000, then is not easy that spinning solution spinning is made to form a film;If only with polyvinylpyrrolidonesolution solution, it is unable to reach Anti-inflammatory, promoting healing effect of the chitosan to the surface of a wound.
Further, added in after additive being dissolved in water into above-mentioned chitosan-polyvinylpyrrolidone mixed liquor, you can Obtain spinning solution.It is preferred that the volume ratio of the aqueous solution of chitosan-polyvinylpyrrolidone mixed liquor and additive is (80: 20)-(90:10).Wherein, 0.01-0.1g additives are contained in the aqueous solution of every mL additives.
Above-mentioned additive includes vitamin C, vitamin B2, Iodophor and glycerine.Wherein, vitamin C and vitamin B2 can promote Into wound healing, Iodophor can be wound bactericidal antiphlogistic.
Optionally, the mass ratio of said vitamin C, vitamin B2, glycerine and chitosan can be respectively 0.1-0.5: 0.1-0.5:10-20:100, the amount ratio of Iodophor and chitosan can be 5mL:1-2g.Preferably, vitamin C, vitamin B2, The mass ratio of glycerine and chitosan is respectively 0.3:0.3:15:100, the amount ratio of Iodophor and chitosan is 5mL:1.5g.
It is preferred that before adding in chitosan-polyvinylpyrrolidone mixed liquor, the mixture of additive and water is carried out Ultrasonic disperse so that each additive component is more scattered, in favor of being mixed with chitosan-polyvinylpyrrolidone mixed liquor, obtains To the preferable spinning solution of property.Specifically, ultrasonic disperse can carry out 5- in supersonic frequency under conditions of 45-120KHz 20min。
Further, spinning solution is spun to chitosan complexes layer.It specifically, can be by the object after spinning solution spinning Matter is defined as porous fiber layer, chitosan complexes layer be then porous fiber layer is cut into appropriate size according to actual needs and .
Optionally, electrospinning device processing can be used in spinning, and spinning voltage may be configured as 10-25KV.Spinning nozzle to receive The distance between collection net could be provided as 6-35cm;Spinning-nozzle internal diameter could be provided as 0.9-1.2mm.
It holds, spinning solution is spun to by porous fiber film using electrospinning device, the fiber so not only made Film has many advantages, such as porous, large specific surface area, stable structure, avoids and be easy to cause vitamin using conventional heated drying membrane formation process The active principles such as C lose drug effect due to being aoxidized;And thickness, size of hole of tunica fibrosa etc. can be by adjusting electrostatic The parameter of spinning equipment is controlled, and is further improved the antibacterial of bandage, anti-inflammatory, promoting healing effect, is avoided conventional wound Mouthful patch poor air permeability easily accumulates tissue fluid, the shortcomings of biocidal property is poor.In addition, it is additionally favorable for making vitamin C, vitamin B2 and Iodophor Be evenly distributed on porous fiber film, avoid be additionally required oral vitamin C, vitamin B2 wound healing or Iodophor is embrocated at the surface of a wound and reaches anti-inflammatory purpose.
Further, above-mentioned chitosan composite bed and water suction cushion layer, baseband layer are bonded, you can obtain chitosan complexes Bandage.
Not only production cost is low, safe and harmless for thus obtained chitosan complexes bandage, while also has ventilative protect The characteristics of moist good, hemostasis clotting ability is strong, inhibiting bacteria and diminishing inflammation ability is excellent, the healing of the surface of a wound can be effectively facilitated.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
Chitosan is dissolved in the aqueous acetic acid that mass fraction is 2wt% and is configured to the shell that mass fraction is 0.5wt% Glycan solution.Wherein, chitosan is made of the high molecular weight chitosan of 85wt% and the middle-molecular-weihydroxyethyl chitosan of 15wt%.It is high The deacetylation of molecular weight chitosan is 90%, weight average molecular weight 110kDa;The deacetylation of middle-molecular-weihydroxyethyl chitosan is 85%, weight average molecular weight 20kDa.
Weight average molecular weight is soluble in water for 1,350,000 polyvinylpyrrolidone, and it is the poly- of 2wt% to be configured to mass concentration Vinylpyrrolidone solution.
It is 50 by volume by above-mentioned chitosan solution and above-mentioned polyvinylpyrrolidonesolution solution:50 mixing, obtain shell and gather Sugar-polyvinylpyrrolidone mixed liquor.
It is 0.01g in proportion by the additive of vitamin C, vitamin B2, Iodophor and glycerine composition:1mL be dispersed in from In sub- water, then ultrasonic disperse 10 minutes under the frequency of 45KHz.Wherein ascorbic quality is chitosan mass 0.1%, the quality of vitamin B2 is the 0.1% of chitosan mass, and the quality of glycerine is the 10% of chitosan mass, Iodophor dosage It is 5mL with chitosan mass ratio:1g.
It is 20 by volume by the aqueous solution of additive:80 are slowly added dropwise to chitosan-polyvinylpyrrolidone mixed liquor In, it stirs evenly, obtains spinning solution.
Spinning solution is spun into porous fiber layer by electrospinning device.Wherein, electrospinning parameters condition is:Spinning Voltage is that the distance between 15KV, spinning nozzle to collecting net is 10cm, and spinning-nozzle internal diameter is 0.9mm.
The porous fiber film that will be obtained obtains chitosan complexes layer by cutting, then successively with water suction cushion layer, base band Layer bonding, is made bandage.
Embodiment 2
Chitosan is dissolved in the aqueous acetic acid that mass fraction is 2wt% and is configured to the shell that mass fraction is 1.5wt% Glycan solution.Wherein, chitosan is made of the high molecular weight chitosan of 85wt% and the middle-molecular-weihydroxyethyl chitosan of 15wt%.It is high The deacetylation of molecular weight chitosan is 90%, weight average molecular weight 110kDa;The deacetylation of middle-molecular-weihydroxyethyl chitosan is 85%, weight average molecular weight 15kDa.
Weight average molecular weight is soluble in water for 1,400,000 polyvinylpyrrolidone, and it is the poly- of 3wt% to be configured to mass concentration Vinylpyrrolidone solution.
It is 70 by volume by above-mentioned chitosan solution and above-mentioned polyvinylpyrrolidonesolution solution:30 mixing, obtain shell and gather Sugar-polyvinylpyrrolidone mixed liquor.
It is 0.1g in proportion by the additive of vitamin C, vitamin B2, Iodophor and glycerine composition:1mL is dispersed in deionization In water, then ultrasonic disperse 5 minutes under the frequency of 80KHz.Wherein ascorbic quality is the 0.2% of chitosan mass, is tieed up The quality of raw element B2 is the 0.3% of chitosan mass, and the quality of glycerine is the 15% of chitosan mass, Iodophor dosage and chitosan Mass ratio is 5mL:1.5g.
It is 10 by volume by the aqueous solution of additive:90 are slowly dropped to chitosan-polyvinylpyrrolidone mixed liquor In, it stirs evenly, obtains spinning solution.
Spinning solution is spun into porous fiber layer by electrospinning device.Wherein, electrospinning parameters condition is:Spinning Voltage is that the distance between 20KV, spinning nozzle to collecting net is 18cm, and spinning-nozzle internal diameter is 1.0mm.
The porous fiber film that will be obtained obtains chitosan complexes layer by cutting, then successively with water suction cushion layer, base band Layer bonding, is made bandage.
Embodiment 3
Chitosan is dissolved in the aqueous acetic acid that mass fraction is 2wt% and is configured to the shell that mass fraction is 2wt% and gathers Sugar juice.Wherein, chitosan is made of the high molecular weight chitosan of 85wt% and the middle-molecular-weihydroxyethyl chitosan of 15wt%.High score The deacetylation of son amount chitosan is 90%, weight average molecular weight 110kDa;The deacetylation of middle-molecular-weihydroxyethyl chitosan is 85%, Weight average molecular weight is 15kDa.
Weight average molecular weight is soluble in water for 1,400,000 polyvinylpyrrolidone, and it is the poly- of 4wt% to be configured to mass concentration Vinylpyrrolidone solution.
It is 60 by volume by above-mentioned chitosan solution and above-mentioned polyvinylpyrrolidonesolution solution:40 mixing, obtain shell and gather Sugar-polyvinylpyrrolidone mixed liquor.
It is 0.05g in proportion by the additive of vitamin C, vitamin B2, Iodophor and glycerine composition:1mL be dispersed in from In sub- water, then ultrasonic disperse 5 minutes under the frequency of 100KHz.Wherein ascorbic quality is chitosan mass 0.4%, the quality of vitamin B2 is the 0.5% of chitosan mass, and the quality of glycerine is the 18% of chitosan mass, Iodophor dosage It is 5mL with chitosan mass ratio:1g.
It is 15 by volume by the aqueous solution of additive:85 are slowly dropped to chitosan-polyvinylpyrrolidone mixed liquor In, it stirs evenly, obtains spinning solution.
Spinning solution is spun into porous fiber layer by electrospinning device.Wherein, electrospinning parameters condition is:Spinning Voltage is that the distance between 25KV, spinning nozzle to collecting net is 30cm, and spinning-nozzle internal diameter is 1.0mm.
The porous fiber film that will be obtained obtains chitosan complexes layer by cutting, then successively with water suction cushion layer, base band Layer bonding, is made bandage.
Embodiment 4
Chitosan is dissolved in the aqueous acetic acid that mass fraction is 1wt% and is configured to the shell that mass fraction is 3wt% and gathers Sugar juice.Wherein, chitosan is made of the high molecular weight chitosan of 80wt% and the middle-molecular-weihydroxyethyl chitosan of 20wt%.High score The deacetylation of son amount chitosan is 100%, weight average molecular weight 120kDa;The deacetylation of middle-molecular-weihydroxyethyl chitosan is 85%, weight average molecular weight 10kDa.
Weight average molecular weight is soluble in water for 1,500,000 polyvinylpyrrolidone, and it is the poly- of 1wt% to be configured to mass concentration Vinylpyrrolidone solution.
It is 55 by volume by above-mentioned chitosan solution and above-mentioned polyvinylpyrrolidonesolution solution:45 mixing, obtain shell and gather Sugar-polyvinylpyrrolidone mixed liquor.
It is 0.04g in proportion by the additive of vitamin C, vitamin B2, Iodophor and glycerine composition:1mL be dispersed in from In sub- water, then ultrasonic disperse 10 minutes under the frequency of 120KHz.Wherein ascorbic quality is chitosan mass 0.5%, the quality of vitamin B2 is the 0.5% of chitosan mass, and the quality of glycerine is the 20% of chitosan mass, Iodophor dosage It is 5mL with chitosan mass ratio:2g.
It is 12.5 by volume by the aqueous solution of additive:87.5, which are slowly dropped to chitosan-polyvinylpyrrolidone, mixes It closes in liquid, stirs evenly, obtain spinning solution.
Spinning solution is spun into porous fiber layer by electrospinning device.Wherein, electrospinning parameters condition is:Spinning Voltage is that the distance between 10KV, spinning nozzle to collecting net is 6cm, and spinning-nozzle internal diameter is 1.1mm.
The porous fiber film that will be obtained obtains chitosan complexes layer by cutting, then successively with water suction cushion layer, base band Layer bonding, is made bandage.
Embodiment 5
Chitosan is dissolved in the aqueous acetic acid that mass fraction is 5wt% and is configured to the shell that mass fraction is 1.5wt% Glycan solution.Wherein, chitosan is made of the high molecular weight chitosan of 90wt% and the middle-molecular-weihydroxyethyl chitosan of 10wt%.It is high The deacetylation of molecular weight chitosan is 100%, weight average molecular weight 120kDa;The deacetylation of middle-molecular-weihydroxyethyl chitosan is 85%, weight average molecular weight 10kDa.
Weight average molecular weight is soluble in water for 1,500,000 polyvinylpyrrolidone, and it is the poly- of 5wt% to be configured to mass concentration Vinylpyrrolidone solution.
It is 65 by volume by above-mentioned chitosan solution and above-mentioned polyvinylpyrrolidonesolution solution:35 mixing, obtain shell and gather Sugar-polyvinylpyrrolidone mixed liquor.
It is 0.08g in proportion by the additive of vitamin C, vitamin B2, Iodophor and glycerine composition:1mL be dispersed in from In sub- water, then ultrasonic disperse 20 minutes under the frequency of 80KHz.Wherein ascorbic quality is chitosan mass 0.3%, the quality of vitamin B2 is the 0.3% of chitosan mass, and the quality of glycerine is the 15% of chitosan mass, Iodophor dosage It is 5mL with chitosan mass ratio:1.5g.
It is 17.5 by volume by the aqueous solution of additive:82.5, which are slowly dropped to chitosan-polyvinylpyrrolidone, mixes It closes in liquid, stirs evenly, obtain spinning solution.
Spinning solution is spun into porous fiber layer by electrospinning device.Wherein, electrospinning parameters condition is:Spinning Voltage is that the distance between 15KV, spinning nozzle to collecting net is 35cm, and spinning-nozzle internal diameter is 1.2mm.
The porous fiber film that will be obtained obtains chitosan complexes layer by cutting, then successively with water suction cushion layer, base band Layer bonding, is made bandage.
Embodiment 6
The present embodiment and embodiment 3 difference lies in:Acid solution in the present embodiment is aqueous hydrochloric acid solution.
Embodiment 7
The present embodiment and embodiment 3 difference lies in:Acid solution in the present embodiment is aqueous citric acid solution.
Test example 1
It repeats to implement above-described embodiment 1-7, obtains enough chitosan complexes bandages.By taking embodiment 3 as an example, if Control group 1 and control group 2 are put, wherein, above-mentioned 2 groups of control groups and the difference of embodiment 3 are respectively:Control group 1 does not add dimension The additive that raw element C, vitamin B2, Iodophor and glycerine form, control group 2 do not use electrospinning process, but spinning is former Liquid is poured into mold, using heated drying method drying and forming-film.
Tests below is carried out to embodiment 3, control group 1 and control group 2:
(1), bacteriostatic test:Reference《Drug Micro biological Tests handbook》In method, measure embodiment 3,1 and of control group Chitosan complexes film in the bandage of the gained of control group 2 is to the inhibition of Escherichia coli and staphylococcus aureus.
(2), haemostatic effect is tested:With reference to the method in Chinese invention patent application (CN102552964.4), measure real Apply effect of the chitosan complexes film in the bandage of 2 gained of example 3, control group 1 and control group to blood coagulation time.
(3), water absorption test:Reference《The performance study of Chitosan/Quaternized Chitosan Composite Membranes》In method, survey Determine the water imbibition effect of the chitosan complexes film in the bandage of 2 gained of embodiment 3, control group 1 and control group.
Result of the test is as shown in table 1 and Fig. 1-2.
Table 1 is antibacterial, stops blooding, water absorption rate result
As can be seen from Table 1, embodiment 3 prepares the chitosan complexes porous fibre of gained compared with control group 1 and control group 2 Film layer has better water imbibition, fungistatic effect and haemostatic effect.
The chitosan complexes layer that embodiment 3, control group 1 and control group 2 provide is to Escherichia coli and Staphylococcus aureus The bacteriostatic test result figure of bacterium is as depicted in figs. 1 and 2.Fig. 1 represents different samples from Fig. 2 to Escherichia coli and golden yellow Portugal respectively The antibacterial test result figure of grape coccus, wherein, a represents control group 1, and b represents control group 2, and c represents embodiment 3.
The chitosan complexes porous fibre film layer that embodiment 3 prepares gained it can be seen from Fig. 1 and Fig. 2 has preferably Biocidal property, control group 2 takes second place, and control group 1 is worst, but shows certain biocidal property, this shows added in shell Glycan has certain antibiotic property.
For control group 1, fungistatic effect gets a promotion control group 2, this additive for showing to add in enhances The biocidal property of chitosan complexes film layer.
For control group 2, biocidal property is further promoted embodiment 3, this shows its porous fiber Structure is more advantageous to the release of additive materials, so as to obtain more fungistatic effect.
Test example 2
Binding tests example 1 carries out Electronic Speculum to the chitosan complexes layer that embodiment 3, control group 1 and control group 2 provide and sweeps It retouches, result is as shown in Figures 3 to 5.Fig. 3 is the chitosan complexes porous fibre film layer that embodiment 3 prepares gained, it is seen that is added Add agent that can preferably be attached on Chitosan/PolyvinylpyrrolidoneHybrid Hybrid Film fiber, fibre structure is complete;Fig. 4 is prepared for control group 1 The porous fibre film layer of gained, it is seen that fiber surface and additive-free attachment;Fig. 5 is the porous fibre that control group 2 prepares gained Film layer, it is seen that its compact structure, specific surface area are small.
It can thus be seen that the porous fibre film layer that embodiment 3 prepares gained compared with control group 1 and control group 2 is more suitable for adding Add the attachment of agent, structure and mechanical performance are more preferably.
In addition, the chitosan obtained by embodiment 1-2 and embodiment 4-7 is answered according to the method for test example 1 and test example 2 It closes object bandage and carries out identical test, result of the test is consistent with the result of the test of embodiment 3.What deserves to be explained is herein As a result unanimously refer to that trend is consistent, and it is nonumeric equal with effect.
To sum up, the preparation method of chitosan complexes bandage provided by the invention is simple for process, simple operation, is produced into This is low, is suitble to produce and prepare chitosan complexes bandage on a large scale.The chitosan that the method for being prepared as described above is prepared Not only production cost is low, safe and harmless for compound bandage, while also with air permeable humidity retaining is good, hemostasis clotting ability is strong, suppression The characteristics of bacterium anti-inflammatory activity is excellent can effectively facilitate the healing of the surface of a wound.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts Every other embodiment, belongs to the scope of protection of the invention.

Claims (10)

1. a kind of preparation method of chitosan complexes bandage, which is characterized in that comprise the following steps:Chitosan is dissolved respectively And polyvinylpyrrolidone, obtain chitosan solution and polyvinylpyrrolidonesolution solution;Mix the chitosan solution and described poly- Vinylpyrrolidone solution obtains chitosan-polyvinylpyrrolidone mixed liquor;Additive is dissolved in add in the shell after water and is gathered In sugar-polyvinylpyrrolidone mixed liquor, spinning solution is obtained;
The spinning solution is spun to chitosan complexes layer, is then bonded with water suction cushion layer, baseband layer, it is compound to obtain chitosan Object bandage.
2. the preparation method of chitosan complexes bandage according to claim 1, which is characterized in that the chitosan- Polyvinylpyrrolidone mixed liquor is using volume ratio as (50 through the chitosan solution and the polyvinylpyrrolidonesolution solution: 50)-(70:30) it is obtained by mixing;
Preferably, concentration of the chitosan in the chitosan solution is 0.5-3wt%;
Preferably, concentration of the polyvinylpyrrolidone in the polyvinylpyrrolidonesolution solution is 1-5wt%.
3. the preparation method of chitosan complexes bandage according to claim 1, which is characterized in that the chitosan bag Include high molecular weight chitosan and middle-molecular-weihydroxyethyl chitosan;
Preferably, the mass ratio of the high molecular weight chitosan and the middle-molecular-weihydroxyethyl chitosan is (80:20)-(90:10);
More preferably, the mass ratio of the high molecular weight chitosan and the middle-molecular-weihydroxyethyl chitosan is 85:15;
Preferably, the deacetylation of the high molecular weight chitosan is more than 80%, and weight average molecular weight is more than 100kDa;
Preferably, the deacetylation of the middle-molecular-weihydroxyethyl chitosan is more than 80%, weight average molecular weight 10-50kDa.
4. the preparation method of chitosan complexes bandage according to claim 1, which is characterized in that the polyethylene pyrrole The weight average molecular weight of pyrrolidone is more than 1,300,000.
5. the preparation method of chitosan complexes bandage according to claim 1, which is characterized in that the additive bag Include vitamin C, vitamin B2, Iodophor and glycerine;
Preferably, the vitamin C, the vitamin B2, the mass ratio of the glycerine and the chitosan are respectively 0.1- 0.5:0.1-0.5:10-20:100, the amount ratio of the Iodophor and the chitosan is 5mL:1-2g.
6. the preparation method of chitosan complexes bandage according to claim 1, which is characterized in that the chitosan- The volume ratio of polyvinylpyrrolidone mixed liquor and the aqueous solution of the additive is (80:20)-(90:10);
Preferably, additive described in 0.01-0.1g is contained in the aqueous solution of additive described in every mL.
7. the preparation method of chitosan complexes bandage according to claim 1, which is characterized in that add in the shell Before glycan-polyvinylpyrrolidone mixed liquor, ultrasonic disperse is carried out to the mixture of the additive and water.
8. the preparation method of chitosan complexes bandage according to claim 7, which is characterized in that ultrasonic disperse be in Supersonic frequency carries out 5-20min under conditions of being 45-120KHz.
9. the preparation method of chitosan complexes bandage according to claim 1, which is characterized in that spinning is in voltage To be carried out under conditions of 10-25KV;
Preferably, spinning nozzle to the distance between collecting net be 6-35cm;
Preferably, spinning-nozzle internal diameter is 0.9-1.2mm.
10. a kind of chitosan complexes bandage, which is characterized in that the chitosan complexes bandage is by such as claim 1- The preparation method of 9 any one of them chitosan complexes bandages is prepared.
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Application publication date: 20180518