CN110128690A - A kind of preparation method based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer - Google Patents
A kind of preparation method based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer Download PDFInfo
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- CN110128690A CN110128690A CN201810126630.1A CN201810126630A CN110128690A CN 110128690 A CN110128690 A CN 110128690A CN 201810126630 A CN201810126630 A CN 201810126630A CN 110128690 A CN110128690 A CN 110128690A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Abstract
The present invention relates to antimicrobial surface technical field, especially a kind of preparation method based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer；Include the following steps: that (1) substrate surface pre-processes；(2) preparation of polyimidazole salt；(3) using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface layer by layer；The present invention is acted on using surface charge, has good inhibiting effect to the breeding of bacterium；The method of the present invention is easy to operate, and using the method for polycondensation reaction and layer upon layer electrostatic self assembly, surface texture is controllable, and antibacterial ability is lasting；Antimicrobial surface prepared by the present invention has good biocompatibility.
Description
Technical field
The present invention relates to antimicrobial surface technical fields, especially a kind of to be based on polyimidazole salt and hyaluronic acid self assembly layer by layer
The preparation method of antimicrobial surface.
Background technique
Bacterium is prevalent in each corner of life, it is easy to be adhered to a variety of surfaces, such as wound surface, medical treatment
Instrument, implantable biomaterial surface etc..Once successfully adhering to, quick breeding is just started, and generate biomembrane, has been exempted from resisting
The effect of epidemic disease system and antibiotic.The adherency of bacterium will lead to bacterium infection problem, causes a series of disease, brings to sufferer
Pain and disaster.For a long time, the use of antibiotic results in the generation of bacterial drug resistance, this is to solve the problems, such as bacterium infection
Increase difficulty.
The premise of bacterium infection is to be adhered to material surface, and therefore, the effective ways for solving bacterium infection are to allow carefully
Bacterium is not adhere to surface or bacterium and kills once adherency.The some antibiotic methods applied at present have antibiotic, silver ion
Antibacterial etc., but the problem of due to drug resistance and antibacterial timeliness, antibacterial cannot be realized well.
Summary of the invention
The object of the present invention is to provide a kind of preparations based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer
Method is the method using polycondensation reaction and layer upon layer electrostatic self assembly, can effectively kill the bacterium for being adhered to surface, and have
Good biocompatibility reduces the risk of bacterium infection, this is that can be used for clinical antibacterial for medical and health care system
Agent.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of preparation method based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer, includes the following steps:
(1) substrate surface pre-processes；(2) preparation of polyimidazole salt；(3) hyaluronic acid and polyimidazole salt electrostatic self-assembled structure layer by layer are utilized
Build antimicrobial surface.
Preferably, the substrate in the step (1) is dimethyl silicone polymer, and substrate surface pre-treatment step is as follows:
The first step is cleaned 2-4 times under ultrasound condition with deionized water and ethyl alcohol, is placed in 35~40 DEG C of oven dryings for 24 hours；
Second step, preparing the mixed solution of the concentrated sulfuric acid and hydrogen peroxide, that substrate dried in step 1 is placed in mixing is molten
30~60s in liquid takes out, is cleaned 2~4 times with deionized water；
Third step prepares the dopamine of different proportion and three (methylol) aminomethane solution of polyethyleneimine, by
The substrate that two steps obtain is added, and the reaction 18 that heats while stirring~for 24 hours, heating temperature is 40 DEG C, obtains surface preparation
Substrate.
Preferably, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1 in the second step.
Preferably, more in three (methylol) aminomethane solution of the dopamine of the different proportion and polyethyleneimine
The mass ratio of bar amine and polyethyleneimine is 3:1,2:1,1:1,0.5:1 and 0.25:1.
Preferably, the raw material that the preparation of polyimidazole salt is selected in the step (2) has bis- (2- amino ethoxy) second of 1,2-
Alkane solution, the formaldehyde of 35~40wt% of concentration is water-soluble, glyoxal water solution and glacial acetic acid of 35~45wt% of concentration；1,2- is bis-
(2- amino ethoxy) ethane: formaldehyde: glyoxal: the molar ratio of glacial acetic acid is 1:1:1:2.
Preferably, in the step (2) polyimidazole salt preparation the following steps are included:
The first step, 1,2- bis- (2- amino ethoxy) ethane solution and deionized water are mixed under conditions of ice-water bath and are stirred
It mixes；
Second step, is added glacial acetic acid and deionized water is mixed；
The mixed solution of formaldehyde, glyoxal and deionized water is added dropwise in third step, and in 70~90 DEG C of heating stirring
Under the conditions of react 20~25h.
Preferably, using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface layer by layer in the step (3)
The step of it is as follows:
Firstly, the substrate obtained after step (1) processing, after immersing 15~20min of aqueous solution of hyaluronic acid, takes out and uses
Deionized water is cleaned 2~3 times,
After substrate by above-mentioned with hyaluronic acid immerses 15~20min of aqueous solution of polyimidazole salt again, taking-up spend from
The step of sub- water cleans 2~4 times, reuses hyaluronic acid and polyimidazole salt electrostatic self-assembled constructs antimicrobial surface layer by layer, obtains
Obtain the multilayer complex films of polyanion hyaluronic acid and polycation imidazole salts.
Preferably, the number of plies of the multilayer complex films is 10~100 layers.
Preferably, the molecular weight of polyimidazole salt is 104~105, the molecular weight of hyaluronic acid is 104~105；Polyimidazole salt
The concentration of aqueous solution and hyaluronic acid aqueous solution is 1~5mg/mL.
Preferably, the antimicrobial surface has 90% or more for the sterilizing rate of bacterium, bacterial species include Escherichia coli,
Staphylococcus aureus, Candida albicans, pneumococcus.
It is using the beneficial effect of technical solution of the present invention:
1, the present invention is acted on using surface charge, has good inhibiting effect to the breeding of bacterium.
2, the method for the present invention is easy to operate, and using the method for polycondensation reaction and layer upon layer electrostatic self assembly, surface texture is controllable,
Antibacterial ability is lasting.
3, antimicrobial surface prepared by the present invention has good biocompatibility.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the survival condition of the not bacteria on surfaces of the dimethyl silicone polymer containing antimicrobial surface；
Fig. 2 is the survival condition of the bacteria on surfaces of the dimethyl silicone polymer containing antimicrobial surface.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.These attached drawings are simplified schematic diagram, only with
Illustration illustrates basic structure of the invention, therefore it only shows the composition relevant to the invention.
Embodiment 1
In the present embodiment, substrate antimicrobial surface preparation method, the specific steps are as follows:
(1) substrate surface pre-processes
Substrate is dimethyl silicone polymer, and substrate surface pre-treatment step is as follows:
Firstly, being cleaned 2 times under ultrasound condition with deionized water and ethyl alcohol, it is placed in 40 DEG C of baking ovens and dries for 24 hours；
The volume ratio of second step, the mixed solution of the preparation concentrated sulfuric acid and hydrogen peroxide, the concentrated sulfuric acid and hydrogen peroxide is 3:1,
Dried substrate is placed in 60s in mixed solution, takes out, is cleaned 2 times with deionized water；
Third step prepares dopamine and polyethyleneimine mass ratio as three (methylol) aminomethane solution (pH=of 1:1
8.5) substrate that, second step is obtained is added, and is placed under 40 DEG C of condition of heating and stirring and reacts 18h.
(2) preparation of polyimidazole salt
The raw material of selection has bis- (2- amino ethoxy) the ethane solution of 1,2-, the formaldehyde of 35~40wt% of concentration water-soluble, dense
Spend the glyoxal water solution and glacial acetic acid of 35~45wt%.The preparation step of polyimidazole salt is as follows: firstly, 1, the 2- of 10mL is bis-
The deionized water of (2- amino ethoxy) ethane solution and 10mL are mixed under conditions of ice-water bath；Second step is added
The glacial acetic acid of 3.8mL and the deionized water of 6.2mL are mixed；The formaldehyde of 6.7mL, the second two of 7.7mL is added dropwise in third step
The mixed solution of aldehyde and 5mL deionized water, and reacted for 24 hours under 80 DEG C of condition of heating and stirring.Bis- (the 2- amino ethoxies of 1,2-
Base) ethane: formaldehyde: glyoxal: the molar ratio of glacial acetic acid is 1:1:1:2.
(3) using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface layer by layer
Using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface steps are as follows layer by layer: firstly, through step
(1) substrate obtained after handling, after immersing the aqueous solution 15min of hyaluronic acid, taking-up is cleaned 2 times with deionized water, then will be upper
After the aqueous solution 15min for stating the substrate immersion polyimidazole salt with hyaluronic acid, taking-up is cleaned 2 times, in repetition with deionized water
Step is stated, the multilayer complex films of polyanion hyaluronic acid and polycation imidazole salts can be obtained.
The molecular weight of the polyimidazole salt is 104~105Between；The molecular weight of hyaluronic acid is 104~105Between；Poly- miaow
The concentration of azoles saline solution and hyaluronic acid aqueous solution is 2mg/mL；The number of plies of obtained multilayer complex films is 15 layers.
Embodiment the result shows that, using the method for the present invention prepare substrate antimicrobial surface, the antimicrobial surface, for bacterium
Sterilizing rate has 90% or more, and bacterial species include Escherichia coli, staphylococcus aureus, Candida albicans, pneumococcus.
Embodiment 2
In the present embodiment, substrate antimicrobial surface preparation method, the specific steps are as follows:
(1) substrate surface pre-processes
Substrate is dimethyl silicone polymer, and substrate surface pre-treatment step is as follows:
Firstly, being cleaned 3 times under ultrasound condition with deionized water and ethyl alcohol, it is placed in 38 DEG C of baking ovens and dries for 24 hours；
The volume ratio of second step, the mixed solution of the preparation concentrated sulfuric acid and hydrogen peroxide, the concentrated sulfuric acid and hydrogen peroxide is 3:1,
Dried substrate is placed in 45s in mixed solution, takes out, is cleaned 3 times with deionized water；
Third step prepares dopamine and polyethyleneimine mass ratio as three (methylol) aminomethane solution (pH=of 3:1
8.5) substrate that, second step is obtained is added, and is placed under 40 DEG C of condition of heating and stirring and reacts 20h.
(2) preparation of polyimidazole salt
The raw material of selection has bis- (2- amino ethoxy) the ethane solution of 1,2-, the formaldehyde of 35~40wt% of concentration water-soluble, dense
Spend the glyoxal water solution and glacial acetic acid of 35~45wt%.The preparation step of polyimidazole salt is as follows: firstly, 1, the 2- of 10mL is bis-
The deionized water of (2- amino ethoxy) ethane solution and 10mL are mixed under conditions of ice-water bath；Second step is added
The glacial acetic acid of 3.8mL and the deionized water of 6.2mL are mixed；The formaldehyde of 6.7mL, the second two of 7.7mL is added dropwise in third step
The mixed solution of aldehyde and 5mL deionized water, and 20h is reacted under 90 DEG C of condition of heating and stirring.Bis- (the 2- amino ethoxies of 1,2-
Base) ethane: formaldehyde: glyoxal: the molar ratio of glacial acetic acid is 1:1:1:2.
(3) using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface layer by layer
Using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface steps are as follows layer by layer: firstly, through step
(1) substrate obtained after handling, after immersing the aqueous solution 18min of hyaluronic acid, taking-up is cleaned 3 times with deionized water, then will be upper
After the aqueous solution 18min for stating the substrate immersion polyimidazole salt with hyaluronic acid, taking-up is cleaned 3 times, in repetition with deionized water
Step is stated, the multilayer complex films of polyanion hyaluronic acid and polycation imidazole salts can be obtained.
The molecular weight of the polyimidazole salt is 104~105Between；The molecular weight of hyaluronic acid is 104~105Between；Poly- miaow
The concentration of azoles saline solution and hyaluronic acid aqueous solution is 1mg/mL；The number of plies of obtained multilayer complex films is 30 layers.
Embodiment the result shows that, using the method for the present invention prepare substrate antimicrobial surface, the antimicrobial surface, for bacterium
Sterilizing rate has 90% or more, and bacterial species include Escherichia coli, staphylococcus aureus, Candida albicans, pneumococcus.
Embodiment 3
In the present embodiment, substrate antimicrobial surface preparation method, the specific steps are as follows:
(1) substrate surface pre-processes
Substrate is dimethyl silicone polymer, and substrate surface pre-treatment step is as follows:
Firstly, being cleaned 4 times under ultrasound condition with deionized water and ethyl alcohol, it is placed in 35 DEG C of baking ovens and dries for 24 hours；
The volume ratio of second step, the mixed solution of the preparation concentrated sulfuric acid and hydrogen peroxide, the concentrated sulfuric acid and hydrogen peroxide is 3:1,
Dried substrate is placed in 30s in mixed solution, takes out, is cleaned 4 times with deionized water；
Third step prepares dopamine and polyethyleneimine mass ratio as three (methylol) aminomethane solution (pH=of 2:1
8.5) substrate that, second step is obtained is added, and is placed under 40 DEG C of condition of heating and stirring and reacts for 24 hours.
(2) preparation of polyimidazole salt
The raw material of selection has bis- (2- amino ethoxy) the ethane solution of 1,2-, the formaldehyde of 35~40wt% of concentration water-soluble, dense
Spend the glyoxal water solution and glacial acetic acid of 35~45wt%.The preparation step of polyimidazole salt is as follows: firstly, 1, the 2- of 10mL is bis-
The deionized water of (2- amino ethoxy) ethane solution and 10mL are mixed under conditions of ice-water bath；Second step is added
The glacial acetic acid of 3.8mL and the deionized water of 6.2mL are mixed；The formaldehyde of 6.7mL, the second two of 7.7mL is added dropwise in third step
The mixed solution of aldehyde and 5mL deionized water, and reacted for 24 hours under 80 DEG C of condition of heating and stirring.Bis- (the 2- amino ethoxies of 1,2-
Base) ethane: formaldehyde: glyoxal: the molar ratio of glacial acetic acid is 1:1:1:2.
(3) using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface layer by layer
Using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface steps are as follows layer by layer: firstly, through step
(1) substrate obtained after handling, after immersing the aqueous solution 20min of hyaluronic acid, taking-up is cleaned 3 times with deionized water, then will be upper
After the aqueous solution 20min for stating the substrate immersion polyimidazole salt with hyaluronic acid, taking-up is cleaned 4 times, in repetition with deionized water
Step is stated, the multilayer complex films of polyanion hyaluronic acid and polycation imidazole salts can be obtained.
The molecular weight of the polyimidazole salt is 104~105Between；The molecular weight of hyaluronic acid is 104~105Between；Poly- miaow
The concentration of azoles saline solution and hyaluronic acid aqueous solution is 1mg/mL；The number of plies of obtained multilayer complex films is 10 layers.
Embodiment the result shows that, using the method for the present invention prepare substrate antimicrobial surface, the antimicrobial surface, for bacterium
Sterilizing rate has 90% or more, and bacterial species include Escherichia coli, staphylococcus aureus, Candida albicans, pneumococcus.
Embodiment 4
In the present embodiment, substrate antimicrobial surface preparation method, the specific steps are as follows:
(1) substrate surface pre-processes
Substrate is dimethyl silicone polymer, and substrate surface pre-treatment step is as follows:
Firstly, being cleaned 2 times under ultrasound condition with deionized water and ethyl alcohol, it is placed in 40 DEG C of baking ovens and dries for 24 hours；
The volume ratio of second step, the mixed solution of the preparation concentrated sulfuric acid and hydrogen peroxide, the concentrated sulfuric acid and hydrogen peroxide is 3:1,
Dried substrate is placed in 60s in mixed solution, takes out, is cleaned 2 times with deionized water；
Third step prepares dopamine and polyethyleneimine mass ratio as three (methylol) aminomethane solution (pH of 0.5:1
=8.5) substrate that, second step is obtained is added, and is placed under 40 DEG C of condition of heating and stirring and reacts 18h.
(2) preparation of polyimidazole salt
The raw material of selection has bis- (2- amino ethoxy) the ethane solution of 1,2-, the formaldehyde of 35~40wt% of concentration water-soluble, dense
Spend the glyoxal water solution and glacial acetic acid of 35~45wt%.The preparation step of polyimidazole salt is as follows: firstly, 1, the 2- of 10mL is bis-
The deionized water of (2- amino ethoxy) ethane solution and 10mL are mixed under conditions of ice-water bath；Second step is added
The glacial acetic acid of 3.8mL and the deionized water of 6.2mL are mixed；The formaldehyde of 6.7mL, the second two of 7.7mL is added dropwise in third step
The mixed solution of aldehyde and 5mL deionized water, and reacted for 24 hours under 80 DEG C of condition of heating and stirring.Bis- (the 2- amino ethoxies of 1,2-
Base) ethane: formaldehyde: glyoxal: the molar ratio of glacial acetic acid is 1:1:1:2.
(3) using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface layer by layer
Using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface steps are as follows layer by layer: firstly, through step
(1) substrate obtained after handling, after immersing the aqueous solution 15min of hyaluronic acid, taking-up is cleaned 2 times with deionized water, then will be upper
After the aqueous solution 15min for stating the substrate immersion polyimidazole salt with hyaluronic acid, taking-up is cleaned 2 times, in repetition with deionized water
Step is stated, the multilayer complex films of polyanion hyaluronic acid and polycation imidazole salts can be obtained.
The molecular weight of the polyimidazole salt is 104~105Between；The molecular weight of hyaluronic acid is 104~105Between；Poly- miaow
The concentration of azoles saline solution and hyaluronic acid aqueous solution is 2mg/mL；The number of plies of obtained multilayer complex films is 10 layers.
Embodiment the result shows that, using the method for the present invention prepare substrate antimicrobial surface, the antimicrobial surface, for bacterium
Sterilizing rate has 90% or more, and bacterial species include Escherichia coli, staphylococcus aureus, Candida albicans, pneumococcus.
Embodiment 5
In the present embodiment, substrate antimicrobial surface preparation method, the specific steps are as follows:
(1) substrate surface pre-processes
Substrate is dimethyl silicone polymer, and substrate surface pre-treatment step is as follows:
Firstly, being cleaned 2 times under ultrasound condition with deionized water and ethyl alcohol, it is placed in 40 DEG C of baking ovens and dries for 24 hours；
The volume ratio of second step, the mixed solution of the preparation concentrated sulfuric acid and hydrogen peroxide, the concentrated sulfuric acid and hydrogen peroxide is 3:1,
Dried substrate is placed in 60s in mixed solution, takes out, is cleaned 2 times with deionized water；Third step is prepared dopamine and is gathered
Aziridine mass ratio is three (methylol) the aminomethane solution (pH=8.5) of 0.25:1, and the substrate that second step obtains is added
Enter, is placed under 40 DEG C of condition of heating and stirring and reacts 18h.
(2) preparation of polyimidazole salt
The raw material of selection has bis- (2- amino ethoxy) the ethane solution of 1,2-, the formaldehyde of 35~40wt% of concentration water-soluble, dense
Spend the glyoxal water solution and glacial acetic acid of 35~45wt%.The preparation step of polyimidazole salt is as follows: firstly, 1, the 2- of 10mL is bis-
The deionized water of (2- amino ethoxy) ethane solution and 10mL are mixed under conditions of ice-water bath；Second step is added
The glacial acetic acid of 3.8mL and the deionized water of 6.2mL are mixed；The formaldehyde of 6.7mL, the second two of 7.7mL is added dropwise in third step
The mixed solution of aldehyde and 5mL deionized water, and reacted for 24 hours under 80 DEG C of condition of heating and stirring.Bis- (the 2- amino ethoxies of 1,2-
Base) ethane: formaldehyde: glyoxal: the molar ratio of glacial acetic acid is 1:1:1:2.
(3) using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface layer by layer
Using hyaluronic acid and polyimidazole salt, electrostatic self-assembled constructs antimicrobial surface steps are as follows layer by layer: firstly, through step
(1) substrate obtained after handling, after immersing the aqueous solution 15min of hyaluronic acid, taking-up is cleaned 2 times with deionized water, then will be upper
After the aqueous solution 15min for stating the substrate immersion polyimidazole salt with hyaluronic acid, taking-up is cleaned 2 times, in repetition with deionized water
Step is stated, the multilayer complex films of polyanion hyaluronic acid and polycation imidazole salts can be obtained.
The molecular weight of the polyimidazole salt is 104~105Between；The molecular weight of hyaluronic acid is 104~105Between；Poly- miaow
The concentration of azoles saline solution and hyaluronic acid aqueous solution is 3mg/mL；The number of plies of obtained multilayer complex films is 20 layers.
Embodiment the result shows that, using the method for the present invention prepare substrate antimicrobial surface, the antimicrobial surface, for bacterium
Sterilizing rate has 90% or more, and bacterial species include Escherichia coli, staphylococcus aureus, Candida albicans, pneumococcus.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of preparation method based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer, which is characterized in that including
Following steps: (1) substrate surface pre-processes；(2) preparation of polyimidazole salt；(3) quiet layer by layer using hyaluronic acid and polyimidazole salt
Antimicrobial surface is constructed in electric self assembly.
2. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: the substrate in the step (1) is dimethyl silicone polymer, and substrate surface pre-treatment step is as follows:
The first step is cleaned 2-4 times under ultrasound condition with deionized water and ethyl alcohol, is placed in 35~40 DEG C of oven dryings for 24 hours；
Substrate dried in step 1 is placed in mixed solution by second step, the mixed solution for preparing the concentrated sulfuric acid and hydrogen peroxide
30~60s takes out, is cleaned 2~4 times with deionized water；
Third step prepares the dopamine of different proportion and three (methylol) aminomethane solution of polyethyleneimine, by second step
The substrate of acquisition is added, and the reaction 18 that heats while stirring~for 24 hours, heating temperature is 40 DEG C, obtains the substrate of surface preparation.
3. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 2
Method, it is characterised in that: the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 3:1 in the second step.
4. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: in the dopamine of the different proportion and three (methylol) aminomethane solution of polyethyleneimine, DOPA
The mass ratio of amine and polyethyleneimine is 3:1,2:1,1:1,0.5:1 and 0.25:1.
5. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: the raw material that the preparation of polyimidazole salt is selected in the step (2) has bis- (2- amino ethoxy) ethane of 1,2-
Solution, the formaldehyde of 35~40wt% of concentration is water-soluble, glyoxal water solution and glacial acetic acid of 35~45wt% of concentration；Bis- (the 2- of 1,2-
Amino ethoxy) ethane: formaldehyde: glyoxal: the molar ratio of glacial acetic acid is 1:1:1:2.
6. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: in the step (2) polyimidazole salt preparation the following steps are included:
The first step, 1,2- bis- (2- amino ethoxy) ethane solution and deionized water are mixed under conditions of ice-water bath；
Second step, is added glacial acetic acid and deionized water is mixed；
The mixed solution of formaldehyde, glyoxal and deionized water is added dropwise in third step, and in 70~90 DEG C of condition of heating and stirring
20~25h of lower reaction.
7. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: electrostatic self-assembled constructs antimicrobial surface layer by layer using hyaluronic acid and polyimidazole salt in the step (3)
Steps are as follows:
Firstly, the obtained substrate after step (1) processing, after immersing 15~20min of aqueous solution of hyaluronic acid, taking-up spend from
Sub- water cleans 2~3 times,
After the substrate by above-mentioned with hyaluronic acid immerses 15~20min of aqueous solution of polyimidazole salt again, deionized water is used in taking-up
Cleaning 2~4 times is gathered the step of reusing hyaluronic acid and polyimidazole salt electrostatic self-assembled constructs antimicrobial surface layer by layer
The multilayer complex films of anion hyaluronic acid and polycation imidazole salts.
8. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: the number of plies of the multilayer complex films is 10~100 layers.
9. a kind of preparation side based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: the molecular weight of polyimidazole salt is 104~105, the molecular weight of hyaluronic acid is 104~105；Polyimidazole salt water
The concentration of solution and hyaluronic acid aqueous solution is 1~5mg/mL.
10. a kind of preparation based on polyimidazole salt and hyaluronic acid self assembly antimicrobial surface layer by layer according to claim 1
Method, it is characterised in that: the antimicrobial surface has 90% or more for the sterilizing rate of bacterium, bacterial species include Escherichia coli,
Staphylococcus aureus, Candida albicans, pneumococcus.
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| CN113235187A (en) * | 2021-04-22 | 2021-08-10 | 常州大学 | Hyaluronic acid electrostatic spinning fiber containing polyion liquid and preparation method thereof |
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Application publication date: 20190816 |