CN108815587A - A kind of hydrogel coating and preparation method thereof with long-term antibacterial functions - Google Patents

A kind of hydrogel coating and preparation method thereof with long-term antibacterial functions Download PDF

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Publication number
CN108815587A
CN108815587A CN201810732892.2A CN201810732892A CN108815587A CN 108815587 A CN108815587 A CN 108815587A CN 201810732892 A CN201810732892 A CN 201810732892A CN 108815587 A CN108815587 A CN 108815587A
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hydrogel coating
long
preparation
antibacterial functions
poly
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CN108815587B (en
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王云兵
罗日方
张博
李高参
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Jilin Qiming Haoyue Biotechnology Co.,Ltd.
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Sichuan University
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    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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Abstract

The invention discloses a kind of hydrogel coating and preparation method thereof with long-term antibacterial functions.This approach includes the following steps:(1) base material is pre-processed;(2) pretreated base material is sequentially placed into poly- positive electricity electrolyte solution and polyphenolic substance and the mixed solution of antibacterials at room temperature, after reacting 5~20min in poly- negative electricity electrolyte solution, is cleaned 3~5 times;(3) step (2) described operation 5~20 times is repeated, hydrogel coating is obtained.The method of the present invention is easy to operate, raw material is cheap, and the hydrogel coating being prepared has good biocompatibility and excellent anti-microbial property;The hydrogel coating has good drug load and stable medicine-releasing performance, can be used for the preparation and modification of cardiovascular implantation instrument, orthopaedics packing material and antibacterial wound dressing.

Description

A kind of hydrogel coating and preparation method thereof with long-term antibacterial functions
Technical field
The invention belongs to medical material tech fields, and in particular to a kind of hydrogel coating with long-term antibacterial functions and Preparation method, the coating can be widely used in surface modification, the modification of orthopaedics packing material of cardiovascular implantation instrument And wound dressing materials.
Background technique
Intrusion due to bacterium to materials such as intervention medical device, surgical instrument, wound gauze, sutures, usually causes The failure of wound infection and operation, life and health are seriously threatened.It is each that preparation at present, which has the material of good antibacterial functions, The problem of a industry is paid close attention to jointly.For example, the contact lenses with antimicrobial coating have the ability for preferably preventing germ contamination; Catheter with antimicrobial coating can more preferably avoid patient in ground immunity by secondary injury (bacterium infection) etc..
Existing anti-biotic material is primarily present following problems:1) antimicrobial medical device often quick quilt after being implanted into human body Body internal protein wraps up, and easily causes the adherency of microorganism, and adhesion protein hinders the release of antibacterials, easily causes Bacterium infection;2) implant is infected by bacterial in order to prevent, and implanted device is immersed in drug solution before surgical, but by Smaller in the medication amount of absorption, drug is easy to fall off and operating time is long, and patient's immunity is low etc. can cause antibacterial effect Difference, implant are usually needed to perform the operation again by body rejection;3) coating deposited by noncovalent interaction in surfaces of medical devices Material, has that load medication amount limited, influences vulnerable to environmental stimulus, the defects of stability is poor;4) document report passes through poly- electricity The covalence graft antibacterials of matter molecule are solved, the coating structure stability of preparation is good, but this method preparation process is complicated, drug is living Property is lower to be difficult to promote.Therefore, prepare it is a kind of it is simple with sample preparation, be clinically using the material that the period is long, antibacterial activity is good Urgent problem to be solved.
Summary of the invention
For above-mentioned deficiency in the prior art, the present invention provide a kind of hydrogel coating with long-term antibacterial functions and A kind of hydrogel coating with interlayer structure can be prepared in preparation method.
To achieve the above object, the technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) base material is pre-processed;
(2) pretreated base material is placed in 0.01~1mM, the poly- positive electricity electrolyte solution that pH value is 5.5~8.5 In, after reacting 1~20min at room temperature, deionized water is cleaned 3~5 times;
(3) step (2) products therefrom is placed in 0.01~20mM, the polyphenolic substance and antimicrobial that pH value is 5.5~9.5 In the mixed solution of object, after reacting 5~20min at room temperature, deionized water is cleaned 3~5 times;Wherein, the polyphenolic substance Molar ratio with antibacterials is 1~2:1~2;
(4) step (3) products therefrom is placed in 0.01~1mM, in the poly- negative electrolyte that pH value is 5.5~8.5, in room temperature After 1~20min of lower reaction, deionized water is cleaned 3~5 times;The poly- negative electrolyte is phosphoric acid base class, sulfonic acid base class, polysaccharide Or carboxyl class molecule;
(5) at room temperature, using step (4) products therefrom as substrate, step (2)~(4) operation 5~20 times, warp are repeated After nitrogen is dry, hydrogel coating is obtained.
Further, base material is metal base material, ceramic substrate material or polymer-based material in step (1).
Wherein, metal base material is stainless steel, cobalt-base alloys, titanium and its alloy, gold, kirsite or pure iron and its conjunction Gold.
Ceramic based material is TiO2Film, isotropic pyrolytic carbon LTIC, silicon, SiO2, hydroxyapatite, calcium phosphate, Buddha's warrior attendant Stone or diamond-like.
Polymer-based material is terylene, polytetrafluoroethylene (PTFE), polyurethane, polyformaldehyde, silicon rubber, polylactic acid, the friendship of glycolide-the third Ester copolymer, polytrimethylene carbonate or polycaprolactone.
Further, in step (2) gather sun electrolyte be poly-L-Lysine hydrobromate, polyallylamine hydrochloride, Poly-L-arginine hydrochloride, polyethyleneimine, chitosan or poly- hexyl purple nitrile.
Further, the molar ratio of polyphenolic substance and antibacterials is 1 in step (3):1.
Further, polyphenolic substance is epicatechin, epigallocatechin, epigallocatechin in step (3) Gallate, L-Epicatechin gallate, gallic acid, catechol, theaflavin or tannic acid.
Further, antibacterials are molecular weight less than 1000 in step (3), have benzene ring structure, can inhibit gram The aromatic series drug of positive bacteria or Gram-negative bacteria;
Wherein, the drug for inhibiting gram-positive bacteria is penicillin (G), procaine penicillin, benzyl because of penicillin, mould Plain V, ampicillin, Amoxicillin, celebrating ampicillin or Amoxicillin;
The drug for inhibiting Gram-negative bacteria is Kanamycin Sulfate, Piperacillin, azlocillin, mezlocillin, chain Mycin, kalamycin, tobramycin, Netilmicin, Etimicin, Piperacillin, azlocillin, mezlocillin or big mycin sulphur Hydrochlorate.
Further, it is that kayexalate salt, sulfuric acid are soft that the sulfonic acid base class molecule in yin electrolyte is gathered in step (4) Ossein, dermatan sulfate, keratan sulfate, heparin or Heparan sulfate;Phosphoric acid base class molecule is DNA;Polysaccharide Class molecule is glucan;Carboxyl class molecule is polyacrylic acid, polyglutamic acid, sodium alginate or hyaluronic acid.
Further, the concentration for gathering positive electrolyte is 0.1mM, pH value 7.5;The concentration of the mixed solution is 0.1mM, PH value is 7.4;The concentration of the poly- negative electrolyte is 0.2mM, pH value 6.8.
The hydrogel coating with long-term antibacterial functions that the above method is prepared.
Beneficial effects of the present invention are:
1, it using polyphenol compound as sandwich of layers, cooperates with and makees by electrostatic interaction, π-π effect and a small amount of covalent bond With polyelectrolyte compounds are carried out layer assembly in biomaterial surface, and can be loaded not in the assembling process of material With antibacterials molecule, and adjust the thickness of hydrogel thin film by adjusting the concentration of material constituent element, pH, the assembling number of plies.
2, compared to traditional anti-biotic material, polyphenol sandwich structure hydrogel coating have Superhydrophilic, compact structure, The advantages that stability is good, the material provide possibility, and Polyphenols for drug molecule diffusion steady in a long-term and sustained anti-microbial Closing object has good interface binding power, and the binding force of hydrogel coating and substrate can be improved, can be widely used in anticoagulant Blood material surface.
3, the present invention has good structural stability by the hydrogel coating of a variety of valence links synergistic effect preparation.It is poly- Electrolyte molecule has good regulating power, can effectively inhibit the burst release of drug.
4, the method for the present invention is easy to operate, raw material is cheap, easily promotes, the hydrogel coating being prepared, and has excellent Anti- albumen adhesive capacity, the stable release antibacterials of energy, meanwhile, polyphenol has the healing for promoting wound, adjusts cell function The effects of.
Detailed description of the invention
Fig. 1 is anti-bacterial hydrogel coating electron microscope (SEM) scanning figure that the present invention is prepared;
Fig. 2 is the anti-bacterial hydrogel coating material antibacterial effect detection figure that the present invention is prepared.
Specific embodiment
A specific embodiment of the invention is described below, in order to facilitate understanding by those skilled in the art this hair It is bright, it should be apparent that the present invention is not limited to the ranges of specific embodiment, for those skilled in the art, As long as various change is in the spirit and scope of the present invention that the attached claims limit and determine, these variations are aobvious and easy See, all are using the innovation and creation of present inventive concept in the column of protection.
Embodiment 1
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) stainless steel material cleaned, dried;
(2) stainless steel after cleaning is placed in concentration for 0.1mM, in the polyethylenimine solution that pH value is 7.5, in room temperature Lower reaction 2min, stainless steel is taken out, and is cleaned 3 times with deionized water;
(3) step (2) products therefrom is placed in concentration is 0.1mM, and the tannic acid that pH value is 7.4 is mixed with penicillin (G) In solution, 2min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Wherein, mole of tannic acid and penicillin Than being 1:1;
(4) step (3) products therefrom is placed in concentration for 0.2mM, in the polyacrylic acid solution that pH value is 6.8, in room temperature Lower reaction 3min then takes out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Embodiment 2
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) titanium alloy material cleaned, dried;
(2) titanium alloy after cleaning is placed in concentration as 0.1mM, in the chitosan solution that pH value is 5, reacted at room temperature 2min takes out titanium alloy, and is cleaned 3 times with deionized water;
(3) step (2) products therefrom is placed in concentration is 0.1mM, the epigallocatechin gallic acid that pH value is 7.4 In ester and procaine penicillin mixed solution, 2min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Its In, the molar ratio of Epigallo-catechin gallate (EGCG) and procaine penicillin is 2:1;
(4) step (3) products therefrom is placed in concentration is 0.2mM, the kayexalate salting liquid that pH value is 7.8 In, 7min is reacted at room temperature, is then taken out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Embodiment 3
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) polytetrafluoroethylene PTFE material cleaned, dried;
(2) polytetrafluoroethylene (PTFE) after cleaning is placed in concentration is 0.1mM, the poly-L-Lysine hydrobromate that pH value is 7.8 In solution, 1min is reacted at room temperature, is taken out and is cleaned 3 times with deionized water;
(3) step (2) products therefrom is placed in concentration is 0.1mM, and the epigallocatechin and benzyl that pH value is 7.4 are because of blueness In mycin mixed solution, 1min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Wherein, epi-nutgall catechu Plain and benzyl is 1 because of the molar ratio of penicillin:2;
(4) step (3) products therefrom is placed in concentration for 0.2mM, in the chondroitin sulfate solution that pH value is 7.2, in room Temperature is lower to react 5min, then takes out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Embodiment 4
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) the pure iron material modified to needs is polished, is cleaned, is dried;
(2) the pure iron material after cleaning is placed in concentration is 0.1mM, and the poly-L-Lysine hydrobromate that pH value is 7.5 is molten In liquid, 2min is reacted at room temperature, pure iron material is taken out, and is cleaned 3 times with deionized water;
(3) by step (2) products therefrom be placed in concentration be 0.1mM, pH value be 7.5 L-Epicatechin gallate and Ah In Amdinocillin mixed solution, 2min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Wherein, epicatechin does not have The molar ratio of infanticide acid esters and Amoxicillin is 1.5:1;
(4) step (3) products therefrom is placed in concentration for 0.2mM, in the sodium alginate soln that pH value is 7.0, in room temperature Lower reaction 3min then takes out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Embodiment 5
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) quartz plate modified to needs is cleaned, is dried;
(2) quartz plate after cleaning is placed in concentration is 0.1mM, the poly-L-Lysine hydrobromate solution that pH value is 7.8 In, 5min is reacted at room temperature, quartz plate is taken out, and is cleaned 3 times with deionized water;
(3) step (2) products therefrom is placed in concentration is 0.1mM, the epicatechin and kanamycins sulfuric acid that pH value is 7.5 In mixed salt solution, 2min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Wherein, epicatechin and block that The molar ratio of doxycycline sulfate is 1:1;
(4) step (3) products therefrom is placed in concentration for 0.2mM, in the collagen solution that pH value is 8.8, in room temperature Lower reaction 5min then takes out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Embodiment 6
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) the isotropic pyrolytic carbon LTIC material modified to needs is cleaned, is dried;
(2) the isotropic pyrolytic carbon LTIC material after cleaning is placed in concentration is 0.1mM, the polyene third that pH value is 7.5 In base amide hydrochloride, after reacting 5min at room temperature, isotropic pyrolytic carbon LTIC material is taken out, and use deionized water Cleaning 3 times;
(3) step (2) products therefrom is placed in concentration is 0.1mM, and the epicatechin that pH value is 7.5 mixes molten with streptomysin In liquid, 1min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Wherein, mole of epicatechin and streptomysin Than being 1:1;
(4) step (3) products therefrom is placed in concentration for 0.2mM, in the hyaluronic acid solution that pH value is 7.8, in room temperature Lower reaction 1min then takes out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Embodiment 7
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) polyester material modified to needs is cleaned, is dried;
(2) by the terylene after cleaning be placed in concentration be 0.1mM, pH value be 7.5 polyallylamine hydrochloride solution in, in After reacting 3min at room temperature, terylene is taken out, and is cleaned 3 times with deionized water;
(3) step (2) products therefrom is placed in concentration is 0.1mM, and the gallic acid that pH value is 7.8 is mixed with Netilmicin In solution, 1min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Wherein, gallic acid and Netilmicin Molar ratio is 1:1;
(4) step (3) products therefrom is placed in concentration for 0.2mM, in the dextran solution that pH value is 6.8, at room temperature 3min is reacted, then takes out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Embodiment 8
A kind of preparation method of the hydrogel coating with long-term antibacterial functions, includes the following steps:
(1) to needing the nickel-titanium alloy material of modifying and decorating to be cleaned, dried;
(2) Nitinol after cleaning is placed in concentration is 0.1mM, the poly-L-arginine HCI solution that pH value is 7.5 In, after reacting 2min at room temperature, Nitinol is taken out, and is cleaned 3 times with deionized water;
(3) step (2) products therefrom is placed in concentration is 0.1mM, and the curcumin that pH value is 6.8 mixes molten with Piperacillin In liquid, 3min is reacted at room temperature, then takes out and is cleaned 3 times with deionized water;Wherein, mole of curcumin and Piperacillin Than being 1:1;
(4) step (3) products therefrom is placed in concentration for 0.2mM, in the keratan sulfate solution that pH value is 6.8, in room Temperature is lower to react 1min, then takes out and is cleaned 3 times with deionized water;
(5) using step (4) products therefrom as substrate, operation 3 times, 5 times, 10 times and 20 times of step (2)~(4) are repeated, It is prepared with different useful loads, and the hydrogel coating with long-term antibacterial functions, is then dried and is put with nitrogen Enter in vacuum oven and saves.
Detection
Electron microscope scanning and anti-Staphylococcus aureus are carried out to the gel coat that embodiment 1 is prepared respectively Bacterium effect detection, result are shown in Fig. 1 and Fig. 2 respectively;As can be known from Fig. 1, the tannic acid in gel coat and penicillin are at pre- group Uniform microballoon is formd after dress, which forms crosslink sites in macromolecule polyalcohol coating, and seine is formed Fine and close 3D hydrogel antimicrobial coating, ensure that the stability of gel coat structure;As can be known from Fig. 2, there is no bacterium in Fig. 2 Appearance, illustrate the coating have good anti-bacterial attachment and bactericidal effect.
The gel coat and conventional coatings that embodiment 1 is prepared respectively again carry out destruction and length under resistance to extreme condition The test of phase stability, detailed process is as follows:
1, extreme condition stability inferior is tested
By the coating prepared after pretreatment, weighs the quality of sample and observe sample SEM pattern.Then by coating Respectively pH value be 1 hydrochloric acid solution, the sodium hydroxide solution that pH value is 12,4M NaCl solution in impregnate 2 hours, take out use A large amount of deionized water cleanings, weigh the quality of sample after nitrogen is dry, and measure SEM pattern.Pass through quality retaining ratio and sample Product pattern changes to compare the difference of modified coating and conventional coatings.
2, long term stability tests
The sample prepared is immersed in 37 DEG C, long period of soaking is carried out in the PBS solution that pH value is 7.4, changed one every 7 days Secondary liquid, every the variation of 15 days observation sample topographies.
3, drug release rate detects
Drug release rate is tested in coating:It places it in the PBS solution that pH value is 7.4 and impregnates, at regular intervals A certain amount of solution is taken, and supplements isometric PBS solution, by the collection and detection of certain time, by ultrasound by coating It destroys and collects wherein total medicament contg, calculate the total content of drug in coating, and calculate the release medicine of various time points The percentage of object.
The gel coat that the embodiment of the present invention 1 is prepared is compared with conventional coatings by above-mentioned detection, it is possible to find For the gel coat that the embodiment of the present invention 1 is prepared either in terms of stability or drug release rate, performance is remote It is much better than conventional coatings.

Claims (9)

1. a kind of preparation method of the hydrogel coating with long-term antibacterial functions, which is characterized in that include the following steps:
(1) base material is pre-processed;
(2) pretreated base material is placed in 0.01~1mM, in the poly- positive electricity electrolyte solution that pH value is 5.5~8.5, in After reacting 1~20min at room temperature, deionized water is cleaned 3~5 times;
(3) step (2) products therefrom is placed in 0.01~20mM, polyphenolic substance that pH value is 5.5~9.5 and antibacterials In mixed solution, after reacting 5~20min at room temperature, deionized water is cleaned 3~5 times;Wherein, the polyphenolic substance and anti- The molar ratio of bacterium drug is 1~2:1~2;
(4) step (3) products therefrom is placed in 0.01~1mM, in the poly- negative electrolyte that pH value is 5.5~8.5, at room temperature instead After answering 1~20min, deionized water is cleaned 3~5 times;The poly- negative electrolyte is phosphoric acid base class, sulfonic acid base class, polysaccharide or carboxylic Base class molecule;
(5) at room temperature, using step (4) products therefrom as substrate, step (2)~(4) operation 5~20 times is repeated, through nitrogen After drying, hydrogel coating is obtained.
2. the preparation method of the hydrogel coating according to claim 1 with long-term antibacterial functions, which is characterized in that step Suddenly base material described in (1) is metal base material, ceramic substrate material or polymer-based material.
3. according to the preparation method of the hydrogel coating described in claim 1 with long-term antibacterial functions, which is characterized in that step (2) described in gather sun electrolyte be poly-L-Lysine hydrobromate, polyallylamine hydrochloride, poly-L-arginine hydrochloride, Polyethyleneimine, chitosan or poly- hexyl purple nitrile.
4. according to the preparation method of the hydrogel coating described in claim 1 with long-term antibacterial functions, which is characterized in that step (3) molar ratio of polyphenolic substance described in and antibacterials is 1:1.
5. according to the preparation method of the hydrogel coating described in claim 1 or 4 with long-term antibacterial functions, which is characterized in that Polyphenolic substance described in step (3) is epicatechin, epigallocatechin, Epigallo-catechin gallate (EGCG), table Catechin and gallate, gallic acid, catechol, theaflavin or tannic acid.
6. according to the preparation method of the hydrogel coating described in claim 1 or 4 with long-term antibacterial functions, which is characterized in that Antibacterials described in step (3) are molecular weight less than 1000, have benzene ring structure, can inhibit gram-positive bacteria, or leather orchid The aromatic series drug of family name's negative bacterium.
7. according to the preparation method of the hydrogel coating described in claim 1 with long-term antibacterial functions, which is characterized in that step (4) described in gather yin electrolyte in sulfonic acid base class molecule be kayexalate salt, chondroitin sulfate, dermatan sulfate, Keratan sulfate, heparin or Heparan sulfate;Phosphoric acid base class molecule is DNA;Polysaccharide molecule is glucan; Carboxyl class molecule is polyacrylic acid, polyglutamic acid, sodium alginate or hyaluronic acid.
8. according to the preparation method of the hydrogel coating described in claim 1 with long-term antibacterial functions, which is characterized in that described The concentration of poly- sun electrolyte is 0.1mM, pH value 7.5;The concentration of the mixed solution is 0.1mM, pH value 7.4;It is described poly- The concentration of negative electrolyte is 0.2mM, pH value 6.8.
9. the hydrogel coating with long-term antibacterial functions that any one of claim 1~8 the method is prepared.
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CN112870442A (en) * 2021-01-19 2021-06-01 中国地质大学(北京) Double-sided guiding bone repair membrane and preparation method and application thereof
CN112915251A (en) * 2021-01-27 2021-06-08 四川大学 Biological polymer fiber wound dressing and preparation method thereof
CN111529752B (en) * 2020-04-15 2021-07-16 东华大学 Variable cross-section porous strip suture for promoting tendon healing and preparation method thereof
CN113244436A (en) * 2021-03-23 2021-08-13 安徽医科大学 Chlorhexidine and catecholamine copolymerized antibacterial coating and preparation method and application thereof
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CN110898250A (en) * 2019-11-28 2020-03-24 浙江大学 Self-degradable hydrogel adhesive material for skin transplantation and preparation method thereof
CN111150880A (en) * 2020-01-08 2020-05-15 广州贝奥吉因生物科技股份有限公司 Antibacterial composite hydrogel and preparation method thereof
CN111529752B (en) * 2020-04-15 2021-07-16 东华大学 Variable cross-section porous strip suture for promoting tendon healing and preparation method thereof
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CN112500528A (en) * 2020-12-03 2021-03-16 山东省眼科研究所 Drug-loaded contact lens with antibacterial effect and preparation method thereof
CN112870442A (en) * 2021-01-19 2021-06-01 中国地质大学(北京) Double-sided guiding bone repair membrane and preparation method and application thereof
CN112915251A (en) * 2021-01-27 2021-06-08 四川大学 Biological polymer fiber wound dressing and preparation method thereof
CN113244436A (en) * 2021-03-23 2021-08-13 安徽医科大学 Chlorhexidine and catecholamine copolymerized antibacterial coating and preparation method and application thereof
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WO2023045591A1 (en) * 2021-09-27 2023-03-30 中国农业科学院都市农业研究所 Algae inhibition material and application thereof in agricultural greenhouse films
CN113908812A (en) * 2021-10-15 2022-01-11 成都工业学院 Spherical hydrogel filler based on fly ash and preparation method thereof
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CN117567790B (en) * 2024-01-15 2024-03-26 四川大学 Medical polyurethane foam with procoagulant inner surface and anticoagulant outer surface and preparation method thereof

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