CN110330658A - A kind of sterilization, low bacterial adhesion, the anti-bacterial hydrogel of bacterium release and its preparation method and application - Google Patents
A kind of sterilization, low bacterial adhesion, the anti-bacterial hydrogel of bacterium release and its preparation method and application Download PDFInfo
- Publication number
- CN110330658A CN110330658A CN201910516312.0A CN201910516312A CN110330658A CN 110330658 A CN110330658 A CN 110330658A CN 201910516312 A CN201910516312 A CN 201910516312A CN 110330658 A CN110330658 A CN 110330658A
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- bacterial
- preparation
- bacterium
- sterilization
- 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.)
- Granted
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
- A61L26/0019—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
-
- 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
- A61L2300/21—Acids
- A61L2300/214—Amino acids
-
- 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
- A61L2300/232—Monosaccharides, disaccharides, polysaccharides, lipopolysaccharides
-
- 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
Abstract
The invention belongs to hydrogel fields, specifically disclose a kind of sterilization, low bacterial adhesion, bacterium release anti-bacterial hydrogel preparation method, include: to carry out free radicals copolymerization reaction after 1) mixing response type monomer with epoxy monomer, obtains response type polymer containing epoxy group；2) it epoxy group response type polymer will be contained will be mixed with hydrophilic polymers containing epoxy group and be dissolved in solvent, and amino-containing fungicide is added carried out epoxy ring opening reaction and obtain.The invention also discloses sterilization made from above-mentioned preparation method, low bacterial adhesion, bacterium release anti-bacterial hydrogel and its as the application in wound dressing.The method of the present invention preparation process is simple and efficient, and obtained hydrogel is full-featured and biocompatibility is preferable, is had wide Research Prospects in biomedical, field of tissue engineering technology, is provided new approaches for the preparation of functional material.
Description
Technical field
The invention belongs to hydrogel fields, and in particular to a kind of sterilization, low bacterial adhesion, bacterium release anti-bacterial hydrogel
And its preparation method and application.
Background technique
Bacterium be widely present in nature and part bacterium attachment and breeding seriously threaten the mankind health and just
Often life.According to statistics, the nosocomial infection of about 60-70% is all related with biomaterial associated infection.It is supported by constructing antimicrobial surface
Antibacterial attachment and proliferation growth are of great significance to human health.Antimicrobial mode is broadly divided into three classes at present, is respectively
Sterilization, antibacterium are sticked and bacterium release, and gradually develops to multifunctional antibiotic mode.
Hydrogel is extensive since its inherent transparency, flexibility and biocompatibility have in art of wound dressings
Application prospect.This is because on the one hand, flexibility and high adhesion enable hydrogel tightly to cover wound, provide and fill for wound
The protection divided, avoids mechanical damage；On the other hand, wound fluid can be absorbed in the hydrophily three-dimensional network of hydrogel, protection
The surface of a wound is not dehydrated.
The Patent Application Publication of Publication No. CN107868260A discloses a kind of low bacterial adhesion, sterilization and reproducible
The preparation method of novel hydrogels, including UV polymerization reaction, esterification, ATRP react and load silver reaction, made from this method
Hydrogel poor biocompatibility, being not suitable for application is wound dressing, and the preparation method is very complicated, is not suitable for the big rule of industrialization
Mould production application.
Still there is the problems such as preparation process complexity, poor biocompatibility, have a single function in current anti-bacterial hydrogel, because
This, develops that a kind of preparation method for wound dressing is simple, multifunctional antibiotic hydrogel of good biocompatibility is in biology
Medical domain has broad application prospects and potential value.
Summary of the invention
The object of the present invention is to provide a kind of preparations for the anti-bacterial hydrogel that sterilization, low bacterial adhesion, bacterium discharge
Method not only simplifies preparation process, reduces production cost, also improves the biocompatibility of hydrogel.
Another object of the present invention also resides in and provides sterilization made from the above method, low bacterial adhesion, bacterium discharge
Anti-bacterial hydrogel and its application in wound dressing.
A kind of sterilization, low bacterial adhesion, bacterium release anti-bacterial hydrogel preparation method, comprising the following steps:
(1) free radicals copolymerization reaction is carried out after mixing response type monomer with epoxy monomer, obtains response type containing epoxy group
Polymer；
(2) it epoxy group response type polymer will be contained will be mixed with hydrophilic polymers containing epoxy group and be dissolved in solvent, addition contains
The fungicide of amino carries out epoxy ring opening reaction and obtains the anti-bacterial hydrogel.
Epoxy-functional is introduced stimulus responsive polymers and hydrophilic using free radicals copolymerization reaction by the method for the present invention respectively
On type polymer chain, then by copolymer and amino-containing fungicide progress epoxy ring opening reaction containing epoxy-functional, form
Component containing hydrophilic, response type component and load have the cross-linked network of fungicide, it is excellent that biocompatibility have been made, and collection kills
The multifunctional water gel that bacterium, antifouling and desorption are integrated.
Multifunctional water gel produced by the present invention is that the hydrophilic component as present in system can be reasonably resistant to
Bacterium is sticked；And the fungicide in system can make hydrogel effectively kill the bacterium of adherency on the surface of the material；When sound in system
Answering property polymer content reaches a timing, and hydrogel can respond change of external conditions and change own physical chemical property, thus
So that hydrogel has the characteristics that intelligent response, and then the desorption for being adhered to hydrogel surface killed bacterial is driven, realizes water-setting
The regeneration of glue function of surface.
In step (1), the response type monomer is temperature response type monomer n-isopropyl acrylamide (NIPAM), pH
Response type monomer methacrylic acid (MAA) or salt response type monomer dimethyl-(4- vinyl phenyl) ammonium propane sulfonic acid inner salt
(DVBAPS)。
The epoxy monomer is methyl propenoic acid glycidyl ether (GMA), methacrylic acid (glycidol oxygen) ethyl ester
Or 4- hydroxybutyl acrylate glycidol ether.
In step (2), the hydrophilic polymers containing epoxy group carry out after being mixed by hydrophilic monomer with epoxy monomer
Free radicals copolymerization reaction obtains.
The hydrophilic monomer is hydroxyethyl methacrylate (HEMA), N- hydroxyethyl acrylamide (HEAA), sulfo group
Glycine betaine methacrylate (SBMA) or carboxybetaine methyl methacrylate (CBMA).
In step (2), the hydrophilic polymer containing epoxy group is polyethyleneglycol diglycidylether (PEGDGE) or gathers
Propylene glycol diglycidylether.
In step (2), the solvent is deionized water or/and dimethyl sulfoxide.
The reaction temperature of the Raolical polymerizable is 50~70 DEG C, and the reaction time is 5~7h；Initiator is freely
Base initiator, preferably potassium peroxydisulfate, ammonium persulfate or azo-bis-isobutyl cyanide.
In step (2), the amino-containing fungicide is preferably chitosan, lysine or polyethyleneimine.This be by
It is safe and non-toxic in preferred fungicide, have superior bio compatibility, now widely used nano silver, triclosan can be overcome
The problem of equal fungicide poor biocompatibility, hydrogel obtained can be used as wound dressing and directly act on human body.
In step (2), the reaction temperature of the epoxy ring opening reaction is 70~90 DEG C, and the reaction time is 1~10h.It is excellent
Being selected as reaction temperature is 75~85 DEG C, and the reaction time is 2~4h.Epoxy ring opening reaction under preferred reaction conditions is more abundant,
Load fungicide sufficiently, hydrogel bactericidal property obtained is good.
In step (2), the matter of the fungicide, hydrophilic polymers containing epoxy group and the response type polymer containing epoxy group
Amount is than being 2:1~5:0.5~2.
It is described the invention also discloses the anti-bacterial hydrogel that sterilization made from the above method, low bacterial adhesion, bacterium discharge
Anti-bacterial hydrogel with a thickness of 1~200mm.The too thin mechanical property that will lead to of the multifunctional antibiotic hydrogel is poor, and too thick
Then it is not suitable for being used as wound dressing.
In addition the present invention discloses the anti-bacterial hydrogel of above-mentioned sterilization, low bacterial adhesion, bacterium release deposited as wound
Application in material.
Compared with the prior art, the present invention has the following beneficial effects:
(1) fungicide that the method for the present invention uses is safe and non-toxic, has superior bio compatibility, can overcome at present extensively
The problem of fungicide poor biocompatibility such as nano silver, triclosan for using, it is higher to ensure that anti-bacterial hydrogel obtained has
Biocompatibility, can be used as wound dressing and directly act on human body；
(2) inventive process avoids use conventional free radical initiation methods to prepare hydrogel, but opens using epoxy
Cyclopolymerization one kettle way prepares multifunctional water gel, and preparation method of the present invention is simple and efficient, and cost is lower, and aquogel system will not
Residual initiator and crosslinking agent, therefore there is preferably biocompatibility；
(3) hydrogel made from the method for the present invention, which has, sterilizes-antifouling-release triple functions, compared to single function antibacterial
Hydrogel, antimicrobial mode is more comprehensively.
Detailed description of the invention
Fig. 1 be the present invention in sterilization, low bacterial adhesion, bacterium discharge anti-bacterial hydrogel structure function schematic diagram；
Fig. 2 be embodiment 1 obtained in sterilization, low bacterial adhesion, bacterium release anti-bacterial hydrogel surface fluorescence show
The relational graph of micro- figure and incubation time and bacterial number.
Specific embodiment
The invention is further illustrated by the examples, but the present invention is not limited by following embodiment.
Embodiment 1
(1) 1.18g DVBAPS and 0.08g GMA is taken to be placed in the 25ml round-bottomed flask containing water and each 5ml of trifluoroethanol,
In the case where logical nitrogen after stirring 30min, 0.02g azodiisobutyronitrile is added and continues to stir in the case where logical nitrogen
20min reacts 6h at 60 DEG C, and it is solid to collect poly (DVBAPS-co-GMA) copolymer for freeze-drying after a period of time of then dialysing
Body sample；
(2) it takes 0.25g poly (DVBAPS-co-GMA) and 0.5g PEGDGE to be placed in container, 1ml salt water, salt is added
Water concentration is 0.5M, is sufficiently stirred at 60 DEG C, and 0.5g lysine is added after to be dissolved and continues stirring and dissolving, solution is transferred to
It in spare mold, is placed in 80 DEG C of convection oven and reacts 2h, obtain the anti-bacterial hydrogel with a thickness of 1mm.
Fig. 2 be embodiment 1 obtained in sterilization, low bacterial adhesion, bacterium release anti-bacterial hydrogel surface fluorescence show
The relational graph of micro- figure and incubation time and bacterial number.
As shown in Figure 2, with the continuous extension of incubation time, the bacterial number that hydrogel surface is adhered in 192h is still
Lower than~106/cm2, show that the hydrogel in the incubation of Escherichia coli, has excellent antibacterium Adhering capacity；And
And the bacterium 92% of hydrogel surface attachment is dead bacterium, shows that the hydrogel has excellent sterilizing ability；Pass through the NaCl of 1M
After solution impregnates, the bacterium of 86% surface attachment can be released, and show that the hydrogel has bacterium desorption, function of surface regeneration
Ability.
Embodiment 2
(1) 1.18g DVBAPS and 0.08g GMA is taken to be placed in the 25ml round-bottomed flask containing water and each 5ml of trifluoroethanol,
In the case where logical nitrogen after stirring 30min, 0.02g azodiisobutyronitrile is added and continues to stir in the case where logical nitrogen
20min reacts 6h at 60 DEG C, and it is solid to collect poly (DVBAPS-co-GMA) copolymer for freeze-drying after a period of time of then dialysing
Body sample；
(2) 1.25g HEAA and 0.08g GMA is taken to be placed in the 25ml round-bottomed flask containing water and each 5ml of dimethyl sulfoxide,
In the case where logical nitrogen after stirring 30min, continue to stir 20min in the case where logical nitrogen after 0.02g potassium peroxydisulfate is added,
6h is reacted at 60 DEG C, poly (HEAA-co-GMA) copolymer solids sample is collected in freeze-drying after a period of time of then dialysing；
(3) it takes 0.25g poly (DVBAPS-co-GMA) and 0.5g poly (HEAA-co-GMA) to be placed in container, is added
1ml deionized water is sufficiently stirred at 60 DEG C, and 0.5g lysine is added after to be dissolved and continues stirring and dissolving, solution is transferred to
It in spare mold, is placed in 80 DEG C of convection oven and reacts 2h, obtain the anti-bacterial hydrogel with a thickness of 1mm.
Embodiment 3
(1) 0.47g NIPAM and 0.08g GMA is taken to be placed in the 25ml round-bottomed flask containing water and each 5ml of trifluoroethanol,
After stirring 30min in the case where logical nitrogen, 0.02g azodiisobutyronitrile is added and continues to stir 20min in the case where logical nitrogen,
6h is reacted at 60 DEG C, poly (NIPAM-co-GMA) copolymer solids sample is collected in freeze-drying after a period of time of then dialysing；
(2) GMA of 1.25g HEAA and 0.08g is taken to be placed in the 25ml round-bottomed flask containing water and each 5ml of dimethyl sulfoxide,
In the case where logical nitrogen after stirring 30min, continue to stir in the case where logical nitrogen after 0.02g azo-bis-isobutyl cyanide is added
20min reacts 6h at 60 DEG C, and poly (HEAA-co-GMA) copolymer solids are collected in freeze-drying after a period of time of then dialysing
Sample；
(3) it takes 0.25g poly (DVBAPS-co-GMA) and 0.5g poly (HEAA-co-GMA) to be placed in container, is added
0.5ml deionized water and 0.5ml dimethyl sulfoxide, are sufficiently stirred at 60 DEG C, and 0.5g lysine is added after to be dissolved and continues to stir
Dissolution is mixed, solution is transferred in spare mold, is placed in 80 DEG C of convection oven and reacts 2h, is obtained with a thickness of the anti-of 1mm
Bacterium hydrogel.
Embodiment 4
(1) 0.48g MAA and 0.08g GMA is taken to be placed in the 25ml round-bottomed flask containing water and each 5ml of trifluoroethanol, logical
After stirring 30min in the case where nitrogen, 0.02g azodiisobutyronitrile is added and continues to stir 20min in the case where logical nitrogen, 60
6h is reacted at DEG C, poly (MAA-co-GMA) copolymer solids sample is collected in freeze-drying after a period of time of then dialysing；
(2) GMA of 0.66g SBMA and 0.08g is taken to be placed in the 25ml round-bottomed flask containing water and each 5ml of dimethyl sulfoxide,
In the case where logical nitrogen after stirring 30min, continue to stir in the case where logical nitrogen after 0.02g azo-bis-isobutyl cyanide is added
20min reacts 6h at 60 DEG C, and poly (SBMA-co-GMA) copolymer solids are collected in freeze-drying after a period of time of then dialysing
Sample；
(3) it takes 0.25g poly (MAA-co-GMA) and 0.5g poly (SBMA-co-GMA) to be placed in container, 1ml is added
Deionized water is sufficiently stirred at 60 DEG C, and 0.63g chitosan is added after to be dissolved and continues stirring and dissolving, solution is transferred to standby
It in mold, is placed in 80 DEG C of convection oven and reacts 2h, obtain the anti-bacterial hydrogel with a thickness of 1mm.
Claims (10)
1. a kind of preparation method for the anti-bacterial hydrogel that sterilization, low bacterial adhesion, bacterium discharge, which is characterized in that including following
Step:
(1) free radicals copolymerization reaction is carried out after mixing response type monomer with epoxy monomer, obtains the polymerization of response type containing epoxy group
Object；
(2) it epoxy group response type polymer will be contained will be mixed with hydrophilic polymers containing epoxy group and be dissolved in solvent, and be added and contain amino
Fungicide carry out epoxy ring opening reaction obtain the anti-bacterial hydrogel.
2. the preparation method for the anti-bacterial hydrogel that sterilization according to claim 1, low bacterial adhesion, bacterium discharge, special
Sign is that the hydrophilic polymers containing epoxy group carry out free-radical polymerized anti-after being mixed by hydrophilic monomer with epoxy monomer
It should obtain.
3. the preparation method for the anti-bacterial hydrogel that sterilization according to claim 2, low bacterial adhesion, bacterium discharge, special
Sign is that the hydrophilic monomer is hydroxyethyl methacrylate, N- hydroxyethyl acrylamide, sulfobetaines metering system
Acid esters or carboxybetaine methyl methacrylate.
4. the preparation method for the anti-bacterial hydrogel that sterilization according to claim 1 or 2, low bacterial adhesion, bacterium discharge,
It is characterized in that, the epoxy monomer is methyl propenoic acid glycidyl ether, methacrylic acid (glycidol oxygen) ethyl ester or 4-
Hydroxybutyl acrylate glycidol ether.
5. the preparation method for the anti-bacterial hydrogel that sterilization according to claim 1, low bacterial adhesion, bacterium discharge, special
Sign is that the hydrophilic polymer containing epoxy group is polyethyleneglycol diglycidylether or polypropylene glycol diglycidyl ether.
6. the preparation method for the anti-bacterial hydrogel that sterilization according to claim 1, low bacterial adhesion, bacterium discharge, special
Sign is that the response type monomer is n-isopropyl acrylamide, methacrylic acid or dimethyl-(4- vinyl phenyl) ammonium third
Acid inner salt.
7. the preparation method for the anti-bacterial hydrogel that sterilization according to claim 1, low bacterial adhesion, bacterium discharge, special
Sign is that the amino-containing fungicide is chitosan, lysine or polyethyleneimine.
8. the preparation method for the anti-bacterial hydrogel that sterilization according to claim 1, low bacterial adhesion, bacterium discharge, special
Sign is that the reaction temperature of the epoxy ring opening reaction is 70~90 DEG C, and the reaction time is 1~10h.
9. sterilization made from a kind of methods described in any item according to claim 1~8, low bacterial adhesion, bacterium discharge anti-
Bacterium hydrogel, which is characterized in that the anti-bacterial hydrogel with a thickness of 1~200mm.
10. the anti-bacterial hydrogel that a kind of sterilization according to claim 9, low bacterial adhesion, bacterium discharge is as wound
Application in dressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910516312.0A CN110330658B (en) | 2019-06-14 | 2019-06-14 | Antibacterial hydrogel with functions of sterilization, low bacterial adhesion and bacterial release and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910516312.0A CN110330658B (en) | 2019-06-14 | 2019-06-14 | Antibacterial hydrogel with functions of sterilization, low bacterial adhesion and bacterial release and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110330658A true CN110330658A (en) | 2019-10-15 |
| CN110330658B CN110330658B (en) | 2021-06-22 |
Family
ID=68141040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910516312.0A Active CN110330658B (en) | 2019-06-14 | 2019-06-14 | Antibacterial hydrogel with functions of sterilization, low bacterial adhesion and bacterial release and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110330658B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028614A (en) * | 2019-04-16 | 2019-07-19 | 东华大学 | The micro-nano gel of antibacterial and fiber with protein adsorption function and preparation method thereof |
| CN110743371A (en) * | 2019-11-20 | 2020-02-04 | 哈尔滨工业大学（威海） | Preparation method of grafted hydrophilic polymer bionic ultrafiltration membrane |
| CN111574728A (en) * | 2020-04-26 | 2020-08-25 | 江西省科学院应用化学研究所 | Antibacterial polyurethane hydrogel medical dressing and preparation method thereof |
| CN112007209A (en) * | 2020-04-29 | 2020-12-01 | 浙江大学 | CS/QCS/zwitterion/epoxidized zwitterion antibacterial and release integrated gel dressing and preparation method thereof |
| CN112048223A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Anti-fouling, sterilizing and releasing multifunctional response antibacterial surface and preparation method thereof |
| CN112048224A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Antibacterial surface with dual functions of sterilization and release and preparation method thereof |
| CN113476643A (en) * | 2021-06-08 | 2021-10-08 | 浙江工业大学 | Preparation method of hydrogel dressing capable of quickly gelling and slowly reinforcing after injection |
| CN113801568A (en) * | 2020-06-12 | 2021-12-17 | 威高集团有限公司 | Antibacterial coating with pH response function, functional material with antibacterial coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020193517A1 (en) * | 2001-03-12 | 2002-12-19 | Wang James H. | Water-responsive biodegradable polymer compositions and method of making same |
| CN101649034A (en) * | 2009-08-31 | 2010-02-17 | 苏州大学 | pH/temperature response double hydrophilic block copolymer |
| CN101982202A (en) * | 2010-11-02 | 2011-03-02 | 华东理工大学 | Medical hydrogel dressings and preparation method thereof |
| CN102030861A (en) * | 2010-11-09 | 2011-04-27 | 长春工业大学 | Method for preparing epoxy functional acrylate polymer |
| CN105348434A (en) * | 2015-12-07 | 2016-02-24 | 江南大学 | Responsive copolymer film being controllable in surface appearance and performance |
| CN109232834A (en) * | 2018-08-02 | 2019-01-18 | 浙江工业大学 | It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof |
| CN109731133A (en) * | 2019-02-01 | 2019-05-10 | 浙江大学 | A kind of antibacterial, anti-adhesive, the temperature sensitive chitosan gel rubber dressing of injection type and preparation method thereof |
-
2019
- 2019-06-14 CN CN201910516312.0A patent/CN110330658B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020193517A1 (en) * | 2001-03-12 | 2002-12-19 | Wang James H. | Water-responsive biodegradable polymer compositions and method of making same |
| CN101649034A (en) * | 2009-08-31 | 2010-02-17 | 苏州大学 | pH/temperature response double hydrophilic block copolymer |
| CN101982202A (en) * | 2010-11-02 | 2011-03-02 | 华东理工大学 | Medical hydrogel dressings and preparation method thereof |
| CN102030861A (en) * | 2010-11-09 | 2011-04-27 | 长春工业大学 | Method for preparing epoxy functional acrylate polymer |
| CN105348434A (en) * | 2015-12-07 | 2016-02-24 | 江南大学 | Responsive copolymer film being controllable in surface appearance and performance |
| CN109232834A (en) * | 2018-08-02 | 2019-01-18 | 浙江工业大学 | It is a kind of with anti-pollution-sterilization-release triple functions antibacterial polymer brush and preparation method thereof |
| CN109731133A (en) * | 2019-02-01 | 2019-05-10 | 浙江大学 | A kind of antibacterial, anti-adhesive, the temperature sensitive chitosan gel rubber dressing of injection type and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| JIAHUI WU,ET AL.: ""Electric Assisted Salt-responsive Bacteria Killing and Release of Polyzwitterionic Brushes in Low-concentration Salt Solution"", 《LANGMUIR》 * |
| LEI HUANG，ET AL.: ""Bacteria killing and release of salt-responsive, regenerative, double-layered polyzwitterionic brushes"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| MARISA FARIA，ET AL.: ""Poly(glycidyl methacrylate)/bacterial cellulose nanocomposites:Preparation, characterization and post-modification"", 《INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES》 * |
| 吴家慧，等: ""电场诱导两性离子聚合物刷构象转变及其抗菌性能研究"", 《2018(第3届)抗菌科学与技术论坛论文摘要集》 * |
| 徐晨: ""基于氨基酸两性离子水凝胶库的制备与眼科应用研究"", 《中国博士学位论文全文数据库 工程科技辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028614B (en) * | 2019-04-16 | 2021-05-11 | 东华大学 | Antibacterial micro-nano gel and fiber with protein adsorption function and preparation method thereof |
| CN110028614A (en) * | 2019-04-16 | 2019-07-19 | 东华大学 | The micro-nano gel of antibacterial and fiber with protein adsorption function and preparation method thereof |
| CN110743371A (en) * | 2019-11-20 | 2020-02-04 | 哈尔滨工业大学（威海） | Preparation method of grafted hydrophilic polymer bionic ultrafiltration membrane |
| CN111574728A (en) * | 2020-04-26 | 2020-08-25 | 江西省科学院应用化学研究所 | Antibacterial polyurethane hydrogel medical dressing and preparation method thereof |
| CN111574728B (en) * | 2020-04-26 | 2023-03-31 | 江西省科学院应用化学研究所 | Antibacterial polyurethane hydrogel medical dressing and preparation method thereof |
| CN112007209A (en) * | 2020-04-29 | 2020-12-01 | 浙江大学 | CS/QCS/zwitterion/epoxidized zwitterion antibacterial and release integrated gel dressing and preparation method thereof |
| CN113801568A (en) * | 2020-06-12 | 2021-12-17 | 威高集团有限公司 | Antibacterial coating with pH response function, functional material with antibacterial coating and preparation method thereof |
| CN112048224A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Antibacterial surface with dual functions of sterilization and release and preparation method thereof |
| CN112048224B (en) * | 2020-08-31 | 2021-10-08 | 浙江工业大学 | Antibacterial surface with dual functions of sterilization and release and preparation method thereof |
| CN112048223B (en) * | 2020-08-31 | 2021-10-08 | 浙江工业大学 | Anti-fouling, sterilizing and releasing multifunctional response antibacterial surface and preparation method thereof |
| CN112048223A (en) * | 2020-08-31 | 2020-12-08 | 浙江工业大学 | Anti-fouling, sterilizing and releasing multifunctional response antibacterial surface and preparation method thereof |
| CN113476643A (en) * | 2021-06-08 | 2021-10-08 | 浙江工业大学 | Preparation method of hydrogel dressing capable of quickly gelling and slowly reinforcing after injection |
| CN113476643B (en) * | 2021-06-08 | 2022-07-26 | 浙江工业大学 | Preparation method of hydrogel dressing capable of quickly gelling and slowly reinforcing after injection |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110330658B (en) | 2021-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110330658A (en) | A kind of sterilization, low bacterial adhesion, the anti-bacterial hydrogel of bacterium release and its preparation method and application | |
| CN106565912B (en) | A kind of polyquaternium quasi polymer lotion antibacterial agent and its preparation method and application | |
| AU2004233805B2 (en) | Formation of strong superporous hydrogels | |
| CN110484062B (en) | Method for constructing anti-fouling, sterilizing and releasing surface coating by utilizing dopamine and product thereof | |
| CN108912352A (en) | A kind of antibacterial adherency injection aquagel dressing and its preparation method and application | |
| CN108192020B (en) | Preparation method of intelligent zwitterionic polymer material | |
| CN105153359A (en) | Conductive hydrogel, conductive hydrogel coil and their preparation methods | |
| CN108371728A (en) | A kind of imitative mussel for tissue repair contacts the preparation method of anti-bacterial hydrogel | |
| CN104830135B (en) | A kind of antimicrobial coating | |
| CN109942839B (en) | In-situ free radical polymerization gel with antibacterial and self-adhesive properties, and preparation method and application thereof | |
| CN110055208B (en) | Non-pancreatin digestion cell harvesting culture method based on temperature-sensitive hydrogel material | |
| CN109851716B (en) | Water-soluble chitosan with temperature sensitivity and preparation method thereof | |
| CN113713183A (en) | Biomedical coating with excellent long-acting anticoagulation, antibiosis and anti-fouling performances and preparation method thereof | |
| CN103709309A (en) | Preparation method of salt-resistant water-absorbent resin with high water absorption rate | |
| CN108484936A (en) | A kind of hydrogel and its preparation method and application prepared by graft modification material | |
| CN109731133A (en) | A kind of antibacterial, anti-adhesive, the temperature sensitive chitosan gel rubber dressing of injection type and preparation method thereof | |
| CN105295077A (en) | Temperature sensitive type polyion liquid gel and preparation method thereof | |
| CN113968984A (en) | Preparation method of safe and long-acting multifunctional wound dressing | |
| CN110627976B (en) | Tussah silk fibroin hydrogel and preparation method and application thereof | |
| CN104262880A (en) | High-strength antimicrobial nanometer composite cation double-network hydrogel and preparation method thereof | |
| CN110028614A (en) | The micro-nano gel of antibacterial and fiber with protein adsorption function and preparation method thereof | |
| CN109134715B (en) | Preparation method of antifouling, bactericidal and reproducible long-acting antibacterial mixed polymer brush | |
| CN104693347A (en) | Metal ion cross-linked nanogel with zwitter-ion structure and preparing method thereof | |
| CN103214625A (en) | Thermo-sensitive grafted hydrogel with function of resisting protein adsorption and preparation method thereof | |
| CN109232833A (en) | A kind of preparation method of low bacterial adhesion, bacterium release and reproducible high-strength nano composite hydrogel |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20191015 Assignee: Ningbo Dianshi Building Decoration Engineering Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980035749 Denomination of invention: An antibacterial hydrogel with sterilization, low bacterial adhesion and bacterial release, its preparation method and application Granted publication date: 20210622 License type: Common License Record date: 20230520 Application publication date: 20191015 Assignee: Ningbo Tianye Construction Consulting Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980035744 Denomination of invention: An antibacterial hydrogel with sterilization, low bacterial adhesion and bacterial release, its preparation method and application Granted publication date: 20210622 License type: Common License Record date: 20230520 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20191015 Assignee: Zhejiang Baosheng Plastic Industry Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980037517 Denomination of invention: An antibacterial hydrogel with sterilization, low bacterial adhesion and bacterial release, its preparation method and application Granted publication date: 20210622 License type: Common License Record date: 20230705 |