CN109260509A - A kind of self assembly contact-type anti-bacterial hydrogel dressing and preparation method thereof based on poly-dopamine and chitosan oligosaccharide - Google Patents
A kind of self assembly contact-type anti-bacterial hydrogel dressing and preparation method thereof based on poly-dopamine and chitosan oligosaccharide Download PDFInfo
- Publication number
- CN109260509A CN109260509A CN201811426211.6A CN201811426211A CN109260509A CN 109260509 A CN109260509 A CN 109260509A CN 201811426211 A CN201811426211 A CN 201811426211A CN 109260509 A CN109260509 A CN 109260509A
- Authority
- CN
- China
- Prior art keywords
- dopamine
- chitosan oligosaccharide
- poly
- added
- self assembly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0023—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0014—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0019—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/0066—Medicaments; Biocides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/216—Biologically 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/23—Carbohydrates
- A61L2300/236—Glycosaminoglycans, e.g. heparin, hyaluronic acid, chondroitin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
Abstract
The present invention provides a kind of self assembly contact-type anti-bacterial hydrogel dressing and preparation method thereof based on poly-dopamine and chitosan oligosaccharide, the preparation method comprises the following steps: chitosan enzyme hydrolysis will be added in chitosan solution, chitosan oligosaccharide solution is prepared, glycidyl trimethyl ammonium chloride is added, after mixing, heating stirring is reacted, filtration washing, freeze-drying, obtains quaternary ammoniated chitosan oligosaccharide powder；Quaternary ammoniated chitosan oligosaccharide powder is added in dopamine solution, is stirred under weak acid environment, methacrylic acid 2- (dimethylamino) ethyl ester is added, regulation system to alkalinity continues to stir, and obtains the antiseptic solution of poly-dopamine modified lithium；Under the protection of inert gas; acrylic acid will be added in the antiseptic solution of poly-dopamine modified lithium; after heating reaction; cooling; potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is added; the reaction was continued for heating, and washing extraction obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
Description
Technical field
The invention belongs to medical material field of material technology, and in particular to it is a kind of based on poly-dopamine and chitosan oligosaccharide from group
Fill contact-type anti-bacterial hydrogel dressing and preparation method thereof.
Background technique
Chitosan is white or amorphous, translucent, slightly pearly luster the solid of canescence, is by chitin molecule
The position C2 on acetyl group hydrolysis or enzymatic hydrolysis slough product obtained from 60-70% or more, be also chitin, deacetylation crust
Matter, soluble chitin, chitosamine, chitose, chitosan etc..Chitosan is passed through by 2- amino -2- deoxidation-β-D glucose
A kind of Natural polycations biological polyoses of β-Isosorbide-5-Nitrae glycosidic bond polymerization, have excellent biocompatibility and biodegradability,
It is widely used in biomaterial for medical purpose field, but the effect of strong type hydrogen bond causes chitosan neither molten in chitosan molecule
Melt, water, alkali (pH value > 6.5) and common organic solvents is also insoluble in, to limit its application range.
Chitosan oligosaccharide is also known as chitin oligo saccharide, chitooligosaccharide- etc., by 2- acetylaminohydroxyphenylarsonic acid 2- deoxidation-β-D glucose residue and 2- ammonia
Base -2- deoxidation-β-D glucose residue passes through linear polymer made of β-Isosorbide-5-Nitrae glucosides key connection, polymerization in different proportions
Degree is 2-20, there are also hydroxyl abundant, amino and N- acetylamino on strand, therefore the intramolecular of chitosan oligosaccharide and intermolecular
Active force is very big, water-soluble more preferable, has good market prospects in biomaterial for medical purpose field.
It is more and more as the biomaterial of main material using chitosan oligosaccharide with deepening continuously for scientific research, wherein with shell
The hot spot that composite material prepared by oligosaccharides and graphene and its derivative is especially studied.Chinese patent CN108329496A is disclosed
A kind of chitosan oligosaccharide nano silver/graphene oxide modification medical grade rubber material and preparation method thereof, by silver nitrate solution and shell
Oligosaccharide solution is stirred at room temperature, and logical nitrogen eliminates air and seals, and after the ultraviolet light irradiation of 240-290nm, anhydrous second is added
It is centrifuged in alcohol, takes precipitating, and twice and be freeze-dried with ethyl alcohol centrifuge washing, chitosan oligosaccharide is then wrapped up into nano silver composite antibacterial
Agent powder is dissolved in water, and ultrasonic disperse obtains chitosan oligosaccharide package nano silver dispersion, natural rubber film is pre-processed through the concentrated sulfuric acid
Afterwards, it is added in graphene oxide solution and impregnates, isolate diaphragm and washed with ultra-pure water solution, then chitosan oligosaccharide packet is added in diaphragm
It wraps up in nano silver dispersion and impregnates, isolate diaphragm and washed with ultra-pure water solution, complete first bilayer of substrate surface
Self assembly repeats the above process, and is self-assembled modified medical of outermost surface layer obtaining chitosan oligosaccharide package nano silver
Rubber material.This method combines closely conduit and antibacterial agent to form antimicrobial coating with chemical bond, hydrogen bond or electrostatic force, prepares
Journey is simple, easily controllable, and preparation condition is mild, low in cost, but have ignored the bioactivity of chitosan oligosaccharide, improve it is immune and
The effects of antitumor.
Summary of the invention
It is anti-that the technical problem to be solved in the present invention is to provide a kind of self assembly contact-types based on poly-dopamine and chitosan oligosaccharide
Bacterium aerogel dressing and preparation method thereof, the present invention is using chitosan oligosaccharide and methacrylic acid 2- (dimethylamino) ethyl ester as antibacterial
Agent, using dopamine to the adsorptivity of bacterium, make preparation aerogel dressing can be autonomous antibacterial, and it is poly-dopamine, quaternary ammoniated
Chitosan oligosaccharide, methacrylic acid 2- (dimethylamino) can be spontaneously formed between ethyl ester and polyacrylic acid covalent bond, hydrogen bond or
Strong electrostatic force keeps the aerogel dressing mechanical property of preparation and antibiotic property all good.
In order to solve the above technical problems, the technical scheme is that
A kind of preparation method of the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide, feature
It is, the preparation method of the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide includes poly- DOPA
Amine, quaternary ammoniated chitosan oligosaccharide, methacrylic acid 2- (dimethylamino) ethyl ester and polyacrylic acid.
The present invention provides a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide
Preparation method, it is characterised in that: the following steps are included:
(1) chitosan enzyme hydrolysis will be added in chitosan solution, chitosan oligosaccharide solution is prepared, dehydration glyceryl three is added
Ammonio methacrylate, after mixing, heating stirring reaction, filtration washing are freeze-dried, obtain quaternary ammoniated chitosan oligosaccharide powder；
(2) quaternary ammoniated chitosan oligosaccharide powder prepared by step (1) is added in dopamine solution, is stirred under weak acid environment
It mixes, methacrylic acid 2- (dimethylamino) ethyl ester is added, regulation system to alkalinity continues to stir, obtains poly-dopamine modified lithium
Antiseptic solution；
(3) under the protection of inert gas, propylene will be added in the antiseptic solution of the poly-dopamine modified lithium of step (2) preparation
Acid, after heating reaction, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is added in cooling, and heating continues anti-
It answers, washing extraction obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
As a preferred embodiment of the above technical solution, in the step (1), the temperature of hydrolysis is 50-55 DEG C, time 2-4h,
The frequency of oscillation of hydrolysis is 200-300r/min.
As a preferred embodiment of the above technical solution, in the step (1), the materials of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride
Than for 1g:1.5-2mL.
As a preferred embodiment of the above technical solution, in the step (1), the temperature of heating stirring reaction is 50-55 DEG C, the time
For 6-12h.
As a preferred embodiment of the above technical solution, in the step (2), amination chitosan oligosaccharide powder, dopamine and metering system
The mass ratio of sour 2- (dimethylamino) ethyl ester is 1:0.8-0.9:0.3-0.4.
As a preferred embodiment of the above technical solution, in the step (2), the pH value stirred under weak acid environment is 6-6.5, is stirred
Mixing rate is 750-1000r/min, time 10-15min.
As a preferred embodiment of the above technical solution, in the step (2), the pH value most 8.5 of system to alkalinity.
As a preferred embodiment of the above technical solution, in the step (3), acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N '
The mass ratio of N- methylene-bisacrylamide is 4-6:0.1-0.12:0.005-0.008.
As a preferred embodiment of the above technical solution, in the step (3), the variation of reaction temperature are as follows: acrylic acid is added,
At 60-65 DEG C after heating reaction 10-15min, it is cooled to 30-40 DEG C with the rate of 1-3 DEG C/min, potassium peroxydisulfate initiator is added
With crosslinking agent N ' N- methylene-bisacrylamide, 70-75 DEG C is warming up to the reaction was continued 2-3h with the rate of 5-10 DEG C/min.
Compared with prior art, the invention has the following advantages:
(1) include in the self assembly contact-type anti-bacterial hydrogel dressing prepared by the present invention based on poly-dopamine and chitosan oligosaccharide
Poly-dopamine, quaternary ammoniated chitosan oligosaccharide, methacrylic acid 2- (dimethylamino) ethyl ester and polyacrylic acid, wherein dopamine is a kind of
Substance with biological viscosity can occur to aoxidize auto polymerization reaction under weak basic condition, and the poly-dopamine of auto polymerization also contains
There are catechol and amino group abundant, the interaction that ionic bond can be passed through with groups such as the carboxyls on polyacrylic acid surface
Be self-assembly of supermolecule state, in addition, quaternary ammoniated chitosan oligosaccharide belong to cation polymer, can also with anion
By the interaction of ionic bond between polyacrylic acid, it is self-assembly of supermolecule state, therefore, hydrogel prepared by the present invention
It mutually entwines between each component in dressing, keeps the binding force between the inside of aerogel dressing big, because having very high mechanics
Performance and elasticity.
(2) contain in the self assembly contact-type anti-bacterial hydrogel dressing prepared by the present invention based on poly-dopamine and chitosan oligosaccharide
Dopamine have natural affine performance to bacterium, make contacting with bacterium for hydrogel active, then utilize the shell in hydrogel
Oligosaccharides and methacrylic acid 2- (dimethylamino) ethyl ester kill bacterium, play the function of actively sterilization, and metering system
Catechu phenol functional group possessed by sour 2- (dimethylamino) ethyl ester is affinity to cell tissue, further improves water-setting
The promotion wound healing of glue dressing acts on.
(3) the self assembly contact-type anti-bacterial hydrogel dressing prepared by the present invention based on poly-dopamine and chitosan oligosaccharide not only power
Function admirable is learned, also there is active antibiotic property and promotes wound healing effect, before biologic medical field has good market
Scape.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1:
(1) chitosan enzyme solution will be added in chitosan solution, at 50 DEG C, is hydrolyzed with the frequency of oscillation of 200r/min
Chitosan oligosaccharide solution is prepared in 2h, is 1g:1.5mL according to the materials ratio of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride, is added and loses
Water glyceryl trimethyl ammonium chloride, after mixing, heating stirring reacts 6h, filtration washing at 50 DEG C, and freeze-drying obtains
Quaternary ammoniated chitosan oligosaccharide powder.
(2) it is according to the mass ratio of amination chitosan oligosaccharide powder, dopamine and methacrylic acid 2- (dimethylamino) ethyl ester
Quaternary ammoniated chitosan oligosaccharide powder is added in dopamine solution by 1:0.8:0.3, in the case where pH value is 6 weak acid environment, with
The rate of 750r/min stirs 10min, and methacrylic acid 2- (dimethylamino) ethyl ester is added, and regulation system pH value is 8.5, after
The continuous rate with 750r/min stirs 30min, obtains the antiseptic solution of poly-dopamine modified lithium.
It (3) is that 1:3 changes poly-dopamine under the protection of inert gas according to the mass ratio of poly-dopamine and acrylic acid
Property antiseptic solution in acrylic acid is added, at 60 DEG C heating reaction 10min after, be cooled to 30 DEG C with the rate of 1 DEG C/min, press
Mass ratio according to acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is 4:0.1:0.005, is added
Potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide, being warming up to 70 DEG C with the rate of 5 DEG C/min, the reaction was continued
2h, washing extraction, obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
Embodiment 2:
(1) chitosan enzyme solution will be added in chitosan solution, at 55 DEG C, is hydrolyzed with the frequency of oscillation of 300r/min
Chitosan oligosaccharide solution is prepared in 4h, is 1g:2mL according to the materials ratio of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride, dehydration is added
Glyceryl trimethyl ammonium chloride, after mixing, heating stirring reacts 12h, filtration washing at 55 DEG C, and freeze-drying obtains
Quaternary ammoniated chitosan oligosaccharide powder.
(2) it is according to the mass ratio of amination chitosan oligosaccharide powder, dopamine and methacrylic acid 2- (dimethylamino) ethyl ester
Quaternary ammoniated chitosan oligosaccharide powder is added in dopamine solution by 1:0.9:0.4, in the case where pH value is 6.5 weak acid environment, with
The rate of 1000r/min stirs 15min, and methacrylic acid 2- (dimethylamino) ethyl ester is added, and regulation system pH value is 8.5,
Continue to stir 60min with the rate of 1000r/min, obtains the antiseptic solution of poly-dopamine modified lithium.
It (3) is that 1:6 changes poly-dopamine under the protection of inert gas according to the mass ratio of poly-dopamine and acrylic acid
Property antiseptic solution in acrylic acid is added, at 65 DEG C heating reaction 15min after, be cooled to 40 DEG C with the rate of 3 DEG C/min, press
Mass ratio according to acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is 6:0.12:0.008, is added
Enter potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide, is warming up to 75 DEG C with the rate of 10 DEG C/min and continues instead
3h is answered, washing extraction obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
Embodiment 3:
(1) chitosan enzyme solution will be added in chitosan solution, at 53 DEG C, is hydrolyzed with the frequency of oscillation of 250r/min
Chitosan oligosaccharide solution is prepared in 3h, is 1g:1.6mL according to the materials ratio of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride, is added and loses
Water glyceryl trimethyl ammonium chloride, after mixing, heating stirring reacts 8h, filtration washing at 52 DEG C, and freeze-drying obtains
Quaternary ammoniated chitosan oligosaccharide powder.
(2) it is according to the mass ratio of amination chitosan oligosaccharide powder, dopamine and methacrylic acid 2- (dimethylamino) ethyl ester
Quaternary ammoniated chitosan oligosaccharide powder is added in dopamine solution by 1:0.85:0.35, in the case where pH value is 6.2 weak acid environment, with
The rate of 800r/min stirs 13min, and methacrylic acid 2- (dimethylamino) ethyl ester is added, and regulation system pH value is 8.5, after
The continuous rate with 800r/min stirs 40min, obtains the antiseptic solution of poly-dopamine modified lithium.
It (3) is 1:4.5 according to the mass ratio of poly-dopamine and acrylic acid, under the protection of inert gas, by poly-dopamine
Acrylic acid is added in modified antiseptic solution, at 64 DEG C after heating reaction 12min, is cooled to 35 DEG C with the rate of 2 DEG C/min,
Mass ratio according to acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is 5:0.11:0.006,
Potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is added, 73 DEG C of continuation are warming up to the rate of 7 DEG C/min
2.5h is reacted, washing extraction obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
Embodiment 4:
(1) chitosan enzyme solution will be added in chitosan solution, at 54 DEG C, is hydrolyzed with the frequency of oscillation of 270r/min
Chitosan oligosaccharide solution is prepared in 3.5h, is 1g:1.9mL according to the materials ratio of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride, is added
Glycidyl trimethyl ammonium chloride, after mixing, heating stirring reacts 10h at 54 DEG C, and filtration washing is freeze-dried,
Obtain quaternary ammoniated chitosan oligosaccharide powder.
(2) it is according to the mass ratio of amination chitosan oligosaccharide powder, dopamine and methacrylic acid 2- (dimethylamino) ethyl ester
Quaternary ammoniated chitosan oligosaccharide powder is added in dopamine solution by 1:0.83:0.33, in the case where pH value is 6.3 weak acid environment, with
The rate of 850r/min stirs 13min, and methacrylic acid 2- (dimethylamino) ethyl ester is added, and regulation system pH value is 8.5, after
The continuous rate with 950r/min stirs 40min, obtains the antiseptic solution of poly-dopamine modified lithium.
It (3) is 1:5.5 according to the mass ratio of poly-dopamine and acrylic acid, under the protection of inert gas, by poly-dopamine
Acrylic acid is added in modified antiseptic solution, at 63 DEG C after heating reaction 13min, is cooled to 36 with the rate of 2.5 DEG C/min
DEG C, it is 4.5:0.12 according to the mass ratio of acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide:
0.007, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is added, is warming up to 74 with the rate of 8 DEG C/min
DEG C the reaction was continued 2.5h, washing extraction obtain the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
Embodiment 5:
(1) chitosan enzyme solution will be added in chitosan solution, at 54 DEG C, is hydrolyzed with the frequency of oscillation of 270r/min
Chitosan oligosaccharide solution is prepared in 3.5h, is 1g:1.9mL according to the materials ratio of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride, is added
Glycidyl trimethyl ammonium chloride, after mixing, heating stirring reacts 11h at 53 DEG C, and filtration washing is freeze-dried,
Obtain quaternary ammoniated chitosan oligosaccharide powder.
(2) it is according to the mass ratio of amination chitosan oligosaccharide powder, dopamine and methacrylic acid 2- (dimethylamino) ethyl ester
Quaternary ammoniated chitosan oligosaccharide powder is added in dopamine solution by 1:0.87:0.37, in the case where pH value is 6.2 weak acid environment, with
The rate of 800r/min stirs 14min, and methacrylic acid 2- (dimethylamino) ethyl ester is added, and regulation system pH value is 8.5, after
The continuous rate with 900r/min stirs 50min, obtains the antiseptic solution of poly-dopamine modified lithium.
It (3) is that 1:5 changes poly-dopamine under the protection of inert gas according to the mass ratio of poly-dopamine and acrylic acid
Property antiseptic solution in acrylic acid is added, at 63 DEG C heating reaction 14min after, be cooled to 36 DEG C with the rate of 3 DEG C/min, press
Mass ratio according to acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is 5.5:0.11:0.005,
Potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is added, 75 DEG C of continuation are warming up to the rate of 5 DEG C/min
2h is reacted, washing extraction obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
Embodiment 6:
(1) chitosan enzyme solution will be added in chitosan solution, at 55 DEG C, is hydrolyzed with the frequency of oscillation of 200r/min
Chitosan oligosaccharide solution is prepared in 4h, is 1g:1.5mL according to the materials ratio of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride, is added and loses
Water glyceryl trimethyl ammonium chloride, after mixing, heating stirring reacts 6h, filtration washing at 55 DEG C, and freeze-drying obtains
Quaternary ammoniated chitosan oligosaccharide powder.
(2) it is according to the mass ratio of amination chitosan oligosaccharide powder, dopamine and methacrylic acid 2- (dimethylamino) ethyl ester
Quaternary ammoniated chitosan oligosaccharide powder is added in dopamine solution by 1:0.9:0.3, in the case where pH value is 6.5 weak acid environment, with
The rate of 750r/min stirs 15min, and methacrylic acid 2- (dimethylamino) ethyl ester is added, and regulation system pH value is 8.5, after
The continuous rate with 750r/min stirs 60min, obtains the antiseptic solution of poly-dopamine modified lithium.
It (3) is that 1:3 changes poly-dopamine under the protection of inert gas according to the mass ratio of poly-dopamine and acrylic acid
Property antiseptic solution in acrylic acid is added, at 65 DEG C heating reaction 10min after, be cooled to 30 DEG C with the rate of 3 DEG C/min, press
Mass ratio according to acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is 6:0.1:0.008, is added
Potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide, being warming up to 75 DEG C with the rate of 5 DEG C/min, the reaction was continued
2h, washing extraction, obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
Through detecting, the self assembly contact-type anti-bacterial hydrogel based on poly-dopamine and chitosan oligosaccharide of embodiment 1-6 preparation is applied
The antibiotic property of material and the result of mechanical property are as follows:
As seen from the above table, the self assembly contact-type anti-bacterial hydrogel prepared by the present invention based on poly-dopamine and chitosan oligosaccharide applies
Expect that anti-microbial property is good and stablizes, preferable antibiotic property, and excellent in mechanical performance can be kept for a long time.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide, which is characterized in that the base
In the self assembly contact-type anti-bacterial hydrogel dressing of poly-dopamine and chitosan oligosaccharide include poly-dopamine, quaternary ammoniated chitosan oligosaccharide, methyl
Acrylic acid 2- (dimethylamino) ethyl ester and polyacrylic acid.
2. a kind of system of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide described in claim 1
Preparation Method, it is characterised in that: the following steps are included:
(1) chitosan enzyme hydrolysis will be added in chitosan solution, chitosan oligosaccharide solution is prepared, dehydration glyceryl trimethyl is added
Ammonium chloride, after mixing, heating stirring reaction, filtration washing are freeze-dried, obtain quaternary ammoniated chitosan oligosaccharide powder；
(2) quaternary ammoniated chitosan oligosaccharide powder prepared by step (1) is added in dopamine solution, is stirred under weak acid environment,
Methacrylic acid 2- (dimethylamino) ethyl ester is added, regulation system to alkalinity continues to stir, and obtains the anti-of poly-dopamine modified lithium
Bacterium solution；
(3) under the protection of inert gas, acrylic acid will be added in the antiseptic solution of the poly-dopamine modified lithium of step (2) preparation,
After heating reaction, potassium peroxydisulfate initiator and crosslinking agent N ' N- methylene-bisacrylamide is added in cooling, and the reaction was continued for heating,
Washing extraction, obtains the self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide.
3. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide according to claim 2
Preparation method, it is characterised in that: in the step (1), the temperature of hydrolysis is 50-55 DEG C, time 2-4h, the oscillation of hydrolysis
Frequency is 200-300r/min.
4. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide according to claim 2
Preparation method, it is characterised in that: in the step (1), the materials ratio of chitosan oligosaccharide and glyceryl trimethyl ammonium chloride is 1g:
1.5-2mL。
5. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide according to claim 2
Preparation method, it is characterised in that: in the step (1), heating stirring reaction temperature be 50-55 DEG C, time 6-12h.
6. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide according to claim 2
Preparation method, it is characterised in that: in the step (2), amination chitosan oligosaccharide powder, dopamine and methacrylic acid 2- (diformazan
Base amino) ethyl ester mass ratio be 1:0.8-0.9:0.3-0.4.
7. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide according to claim 2
Preparation method, it is characterised in that: in the step (2), the pH value that stirs under weak acid environment is 6-6.5, and stirring rate is
750-1000r/min, time 10-15min.
8. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide according to claim 2
Preparation method, it is characterised in that: in the step (2), system to alkalinity pH value most 8.5.
9. a kind of self assembly contact-type anti-bacterial hydrogel dressing based on poly-dopamine and chitosan oligosaccharide according to claim 2
Preparation method, it is characterised in that: in the step (3), acrylic acid, potassium peroxydisulfate initiator and crosslinking agent N ' N- di-2-ethylhexylphosphine oxide
The mass ratio of acrylamide is 4-6:0.1-0.12:0.005-0.008.
10. a kind of self assembly contact-type anti-bacterial hydrogel based on poly-dopamine and chitosan oligosaccharide according to claim 2 applies
The preparation method of material, it is characterised in that: in the step (3), the variation of reaction temperature are as follows: acrylic acid is added, at 60-65 DEG C
After heating reaction 10-15min, it is cooled to 30-40 DEG C with the rate of 1-3 DEG C/min, potassium peroxydisulfate initiator and crosslinking agent is added
N ' N- methylene-bisacrylamide is warming up to 70-75 DEG C the reaction was continued 2-3h with the rate of 5-10 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811426211.6A CN109260509A (en) | 2018-11-27 | 2018-11-27 | A kind of self assembly contact-type anti-bacterial hydrogel dressing and preparation method thereof based on poly-dopamine and chitosan oligosaccharide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811426211.6A CN109260509A (en) | 2018-11-27 | 2018-11-27 | A kind of self assembly contact-type anti-bacterial hydrogel dressing and preparation method thereof based on poly-dopamine and chitosan oligosaccharide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109260509A true CN109260509A (en) | 2019-01-25 |
Family
ID=65185899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811426211.6A Pending CN109260509A (en) | 2018-11-27 | 2018-11-27 | A kind of self assembly contact-type anti-bacterial hydrogel dressing and preparation method thereof based on poly-dopamine and chitosan oligosaccharide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109260509A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663146A (en) * | 2019-02-01 | 2019-04-23 | 浙江大学 | A kind of antibacterial, the temperature sensitive chitosan gel rubber dressing of injection type and preparation method thereof |
| CN112618785A (en) * | 2020-12-15 | 2021-04-09 | 广东省微生物研究所（广东省微生物分析检测中心） | Porous antibacterial hydrogel dressing and preparation method thereof |
| CN113402781A (en) * | 2021-08-07 | 2021-09-17 | 苏州市德赫亚新纺织科技有限公司 | Preparation method of oxidized chitosan polydopamine composite cross-linking agent |
| CN113662911A (en) * | 2021-08-02 | 2021-11-19 | 郑州大学第一附属医院 | High-adhesion pain-relieving hydrogel patch and preparation method thereof |
| CN113975458A (en) * | 2021-11-19 | 2022-01-28 | 浙江大学 | Nano-silver/double-modified chitosan antibacterial hydrogel dressing for indicating wound infection condition through color-changing effect and preparation method thereof |
| CN114392245A (en) * | 2022-01-10 | 2022-04-26 | 自然资源部第三海洋研究所 | Dopamine-embedded nano-selenium assembly compound and preparation method thereof |
| CN115500222A (en) * | 2022-11-17 | 2022-12-23 | 潍坊学院 | Cultivation method of high-quality tomatoes |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319448A (en) * | 2011-09-16 | 2012-01-18 | 华中科技大学 | Antibacterial aquagel material for preparing medical wound dressing and preparation method thereof |
| CN102596275A (en) * | 2009-09-04 | 2012-07-18 | 亚洲大学校产学协力团 | In situ-forming hydrogel for tissue adhesives and biomedical use thereof |
| CN105664239A (en) * | 2016-03-23 | 2016-06-15 | 成都交大麦迪克科技有限公司 | Preparation method of self-adhesive skin repairing hydrogel |
| CN107583049A (en) * | 2017-10-30 | 2018-01-16 | 江南大学 | A kind of preparation method of the syringeability hydrogel with light thermal property |
| WO2018093943A1 (en) * | 2016-11-16 | 2018-05-24 | The Regents Of The University Of California | Identification and optimization of carbon radicals on hydrated graphene oxide for ubiquitous antibacterial coatings |
| CN108371728A (en) * | 2018-03-09 | 2018-08-07 | 西南交通大学 | A kind of imitative mussel for tissue repair contacts the preparation method of anti-bacterial hydrogel |
| CN108384742A (en) * | 2018-02-11 | 2018-08-10 | 大连金玛健康产业发展有限公司 | A kind of novel activated dose and preparation method thereof for immune cell expansion |
| CN108815567A (en) * | 2018-06-05 | 2018-11-16 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of antiseptic dressing aquagel |
-
2018
- 2018-11-27 CN CN201811426211.6A patent/CN109260509A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596275A (en) * | 2009-09-04 | 2012-07-18 | 亚洲大学校产学协力团 | In situ-forming hydrogel for tissue adhesives and biomedical use thereof |
| CN102319448A (en) * | 2011-09-16 | 2012-01-18 | 华中科技大学 | Antibacterial aquagel material for preparing medical wound dressing and preparation method thereof |
| CN105664239A (en) * | 2016-03-23 | 2016-06-15 | 成都交大麦迪克科技有限公司 | Preparation method of self-adhesive skin repairing hydrogel |
| WO2018093943A1 (en) * | 2016-11-16 | 2018-05-24 | The Regents Of The University Of California | Identification and optimization of carbon radicals on hydrated graphene oxide for ubiquitous antibacterial coatings |
| CN107583049A (en) * | 2017-10-30 | 2018-01-16 | 江南大学 | A kind of preparation method of the syringeability hydrogel with light thermal property |
| CN108384742A (en) * | 2018-02-11 | 2018-08-10 | 大连金玛健康产业发展有限公司 | A kind of novel activated dose and preparation method thereof for immune cell expansion |
| CN108371728A (en) * | 2018-03-09 | 2018-08-07 | 西南交通大学 | A kind of imitative mussel for tissue repair contacts the preparation method of anti-bacterial hydrogel |
| CN108815567A (en) * | 2018-06-05 | 2018-11-16 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of antiseptic dressing aquagel |
Non-Patent Citations (4)
| Title |
|---|
| LIU, LY等: "Polydopamine-Assisted Silver Nanoparticle Self-Assembly on Sericin/Agar Film for Potential Wound Dressing Application", 《INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES》 * |
| LUO, C等: "Antibacterial activity and cytocompatibility of chitooligosaccharide-modified polyurethane membrane via polydopamine adhesive layer", 《CARBOHYDRATE POLYMERS》 * |
| 刘源: "壳聚糖季铵盐的制备及其在促进伤口愈合中的应用", 《中国优秀硕士学位论文全文数据库 医药卫生科技辑》 * |
| 韩璐: "仿贻贝多功能水凝胶及其生物医学应用的研究", 《中国博士学位论文全文数据库 医药卫生科技辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663146A (en) * | 2019-02-01 | 2019-04-23 | 浙江大学 | A kind of antibacterial, the temperature sensitive chitosan gel rubber dressing of injection type and preparation method thereof |
| CN112618785A (en) * | 2020-12-15 | 2021-04-09 | 广东省微生物研究所（广东省微生物分析检测中心） | Porous antibacterial hydrogel dressing and preparation method thereof |
| CN113662911A (en) * | 2021-08-02 | 2021-11-19 | 郑州大学第一附属医院 | High-adhesion pain-relieving hydrogel patch and preparation method thereof |
| CN113402781A (en) * | 2021-08-07 | 2021-09-17 | 苏州市德赫亚新纺织科技有限公司 | Preparation method of oxidized chitosan polydopamine composite cross-linking agent |
| CN113975458A (en) * | 2021-11-19 | 2022-01-28 | 浙江大学 | Nano-silver/double-modified chitosan antibacterial hydrogel dressing for indicating wound infection condition through color-changing effect and preparation method thereof |
| WO2023087864A1 (en) * | 2021-11-19 | 2023-05-25 | 浙江大学 | Nano-silver/double-modified chitosan antibacterial hydrogel dressing indicating wound infection condition by means of color-changing effect and preparation method therefor |
| CN114392245A (en) * | 2022-01-10 | 2022-04-26 | 自然资源部第三海洋研究所 | Dopamine-embedded nano-selenium assembly compound and preparation method thereof |
| CN114392245B (en) * | 2022-01-10 | 2023-10-10 | 自然资源部第三海洋研究所 | Dopamine-embedded nano-selenium assembled compound and preparation method thereof |
| CN115500222A (en) * | 2022-11-17 | 2022-12-23 | 潍坊学院 | Cultivation method of high-quality tomatoes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109260509A (en) | A kind of self assembly contact-type anti-bacterial hydrogel dressing and preparation method thereof based on poly-dopamine and chitosan oligosaccharide | |
| Dave et al. | Natural polysaccharide-based hydrogels and nanomaterials: Recent trends and their applications | |
| Kundu et al. | Cellulose hydrogels: Green and sustainable soft biomaterials | |
| CN109293948B (en) | Hydrogel and preparation method and application thereof | |
| CN102942660B (en) | Natural biological crosslinking nanocomposite three-dimensional gel bracket and preparation method | |
| CN106866998B (en) | A kind of chitosan quaternary ammonium salt/carboxymethyl cellulose superabsorbent hydrogel and its preparation method and application | |
| CN109796606B (en) | Self-healing hydrogel based on multiple dynamic chemical bonds and preparation method thereof | |
| CN101665576B (en) | Microgel based on cyclodextrins and preparation method thereof | |
| CN1954817A (en) | Preparation method of injection type pH and glucose sensitive hydrogel | |
| CN101899171A (en) | Method for preparing chitosan/cellulose composite material | |
| WO2012105685A1 (en) | Hydrogel produced from chitosan derivative | |
| CN102060939B (en) | Preparation method of water-soluble 2'-hydroxylpropylchitosan | |
| WO2003085001A1 (en) | Polysaccharide containing phosphorylcholine group and process for producing the same | |
| CN103834033A (en) | Preparation method of polysialic acid-chitosan derivative hydrogel | |
| CN101798403A (en) | Method for preparing chitosan/polyving alcohol/polylactic acid blended dense membrane | |
| CN113583257A (en) | Electroadhesive hydrogel and preparation method thereof | |
| CN114263068B (en) | Soft antibacterial finishing agent, preparation method and application process thereof | |
| CN108383945B (en) | Agricultural water-retaining agent and preparation method thereof | |
| CN110483810A (en) | A kind of preparation method of nano-cellulose anti-bacterial hydrogel | |
| CN101215383B (en) | Method for preparing acid and base amphiprotic dissoluble chitosan | |
| CN100567375C (en) | PH sensitive aqueous gel and preparation method thereof | |
| WO2022108018A1 (en) | Hydrogel patch comprising syneresis pattern control filling solution, and method for manufacturing same | |
| CN104356404A (en) | Hyaluronic acid microbubble and preparation method thereof | |
| CN114702607A (en) | Water-soluble hydroxymethyl propyl chitosan and preparation method thereof | |
| CN101972489A (en) | Novel wound self-healing biological material, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190125 |
|
| RJ01 | Rejection of invention patent application after publication |