CN105920659A - Bacteriostatic hydrogel dressing for wound repair and preparation method thereof - Google Patents

Bacteriostatic hydrogel dressing for wound repair and preparation method thereof Download PDF

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Publication number
CN105920659A
CN105920659A CN201610329358.8A CN201610329358A CN105920659A CN 105920659 A CN105920659 A CN 105920659A CN 201610329358 A CN201610329358 A CN 201610329358A CN 105920659 A CN105920659 A CN 105920659A
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dressing
preparation
wound repair
polyglutamic acid
gel
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Inventor
徐荷林
赵应征
肖健
范子梁
杨靖靖
许洁
陈翩翩
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Wenzhou Medical University
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Wenzhou Medical University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0019Chemical 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0057Ingredients of undetermined constitution or reaction products thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • A61L26/0066Medicaments; Biocides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • A61L26/008Hydrogels or hydrocolloids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0061Use of materials characterised by their function or physical properties
    • A61L26/009Materials resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents

Abstract

The invention provides a bacteriostatic hydrogel dressing material for wound repair and a preparation method thereof. The bacteriostatic hydrogel dressing material provided by the invention is solid-state fine powder consisting of epsilon-polylysine, gamma-polyglutamic acid, acellularized scaffold powder and cross-linking agents; and the bacteriostatic hydrogel dressing can be directly spread on the wound surface or can be pasted onto the wound surface after absorbing certain water to become gel. According to composition ingredients, the mass ratio of the epsilon-polylysine to the gamma-polyglutamic acid is (100:1) to (1:10); the acellularized scaffold powder is 0.01 to 20 percent of the total mass of the epsilon-polylysine and the gamma-polyglutamic acid; and the cross-linking agents account for 0.01 percent to 40 percent of the weight of the hydrogel dry powder dressing. The wound repair material has good hygroscopicity; the water absorption capability reaches 200 times of the self weight; the wound repair material also has good bacteriostatic capability, so that the additional addition of antibiotics or silver-containing bacteriostatic ingredients is not needed; and meanwhile, good mechanical performance is also realized. In addition, the bacteriostatic hydrogel dressing material has the advantages that the preparation method is simple; the repeatability is good; and the large-scale production can be easily realized.

Description

The bacteriostatic water gel dressing of a kind of wound repair and preparation method
Technical field
The present invention relates to a kind of bacteriostatic water gel dressing for wound repair and preparation method, specifically by γ-many polyglutamics The aquogel type wound repair material of acid rear preparation crosslinked with ε-poly-l-lysine complex and preparation method.
Background technology
The hemostasis being applied to clinic at present is mainly gelfoam and water miscible cellulose family with wound repair material.Water-setting Glue is a kind of novel biomaterial, and it has important using value in terms of repair in trauma.Clinical practice hydrogel at present Dressing is mainly composed of carboxymethyl cellulose and some other supplementary element, such as pectin, Xanthan gum, propyleneglycoles etc.. Such dressing is provided that the moist environment needed for wound healing, beneficially cell proliferation, epithelial migration and granulation growth, energy Pain relieving, more will not damage wound during change dressings, and can fill the deep dead space of wound, the glue in wound self transudate Former protein degradation enzyme decomposes downright bad material, to reach the effect of autolytic debridement.Such aerogel dressing is a large amount of at absorption wound surface After exudate, the expansion of colloid and cause dressing and wound separation, make antibacterial amount reproduction, easily cause traumatic infection. In processes of wound repair, traumatic infection and the complication that causes are the weights faced in the current clinical practice of Hydrogels dressing Want problem.
ε-the poly-D-lysine of heterogeneous, by fermentable, is generally made up of 25-30 bad amino acid residue Polycation polymerized peptides, such polyamino acid material has good water solublity, and side chain contains substantial amounts of amino, can be thin Cellular surface negative charge effect, has superpower cell adhesion ability.ε-poly-D-lysine antimicrobial spectrum is wide, in acid and subacidity Environment all there is certain fungistatic effect to gram positive bacteria, gram negative bacteria, yeast, mycete, especially to it His natural antiseptic agent be difficult to suppression gram-negative escherichia coli, Salmonella fungistatic effect the best, be current sky Preservative so has the microbiology class food preservative of superior antiseptic property and huge business potential.Chinese patent (patent Application number: CN201410571048.8) disclose the system of a kind of epsilon-polylysine-vitamin e succinate amide complex Standby and be used as the application in terms of food fresh keeping, improve the fat-soluble of epsilon-polylysine, improve the fresh-keeping effect to meat product. At present, yet there are no ε-poly-D-lysine is used for the antibacterial aspect of wound surface document report.
γ-polyglutamic acid (γ-PGA) is that one is synthesized by multiple bacillus and is secreted into extracellular water soluble polymer amount Amino acid polymer, is polymerized by gamma-glutamyl key by D-Glu and Pidolidone.γ-polyglutamic acid is hydrophilic Polymer network, there is high-hydroscopicity, higher mechanical strength, controlled degradation and biocompatibility, be a kind of system Standby wound dressing and the ideal material of tissue engineering bracket.But because of the water solublity that it is strong, it is difficult to form gel, such material Separately as Wound dressing, it is difficult to be formed stable gel state after absorbing wound fluid, thus impact is stopped blooding and repairs Effect.Wang Jing etc. report with γ-polyglutamic acid as raw material, and allyl bromide, bromoallylene and bromination of n-butane make esterifying agent, prepare ester Changing γ-polyglutamic acid, continue to be esterified γ-polyglutamic acid as monomer, azodiisobutyronitrile makees initiator, methacrylic acid Hydroxyl ethyl ester makees cross-linking agent, and preparation γ-polyglutamic acid hydrogel (China's Tissue Engineering Study and clinical rehabilitation, 2008 years the Volume 12 the 1st phase).This gel shows obvious absorbability, such as γ-polyglutamic acid hydrogel that esterification degree is 40% Water absorption rate can reach 44 times of own wt, but the method prepares the synthesis technique that hydrogel needs are complicated, water-setting colloidality Matter poor reproducibility.Chinese patent (Publication No. CN105268015A) discloses a kind of anti-bacterial hydrogel composite, It is prepared by mixing into hydrogel by chitosan and gamma-polyglutamic acid-with certain mass proportioning, after by polyvinylpyrrolidone (PVP) nanometer silver loaded is dispersed in above-mentioned hydrogel and is prepared from.This patent use nanometer silver as antimicrobial component, Though anti-microbial property is relatively strong, but has serious zest, poor biocompatibility to wound surface, it is impossible to degraded, environment is caused Pollute.
Acellularized valve is derived from the extracellular matrix after organism normal structure, de-cell, and it is mainly by structural protein Form with functional protein, the multiple somatomedin the most also comprised, in tissue repair and reconstruction, have important facilitation. The biologic bracket material of Acellularized valve composition is widely used in the regenerative medicine neck of surgical reconstruction and tissue and organ Territory such as cardiac valve, blood vessel, skin, nerve, tendon and small intestinal submucosa etc..
The present invention will have the cation ε-poly-D-lysine of broad-spectrum antibacterial effect, remove cell in conjunction with can promote wound healing Support powder, is first combined through electrostatic with anion γ-polyglutamic acid of strong water absorbing capacity and prepares complex, continue with low concentration Cross-linking agents complex, preparation has the hydrogel of certain mechanical performance, by washing, is dried, pulverizes and be prepared into To having the medical aquogel powder dressing of bacteriostasis, can directly be sprinkling upon wound surface or absorb certain water in advance and become gel Stick on wound surface, wound healing.
Summary of the invention
It is desirable to provide one is without outer added with antibiotic or silver class antipathogenic composition, can be used for wound repair self has The aerogel dressing of bacteriostasis.This dressing can directly be sprinkling upon wound surface or absorb certain water in advance and become gel to stick on wound Face.The present invention will have the cation ε-poly-D-lysine of broad-spectrum antibacterial effect, remove cell in conjunction with can promote wound healing Support composition, is first combined through electrostatic with anion γ-polyglutamic acid of strong water absorbing capacity and prepares complex, continue with low concentration Cross-linking agents complex, preparation has the hydrogel of certain mechanical performance, by washing, is dried, pulverizes and be prepared into To the medical aquogel powder dressing with bacteriostasis.
The present invention can be realized by following technical proposal:
The bacteriostatic water gel dressing of a kind of wound repair is by ε-poly-D-lysine, γ-polyglutamic acid, Acellularized valve powder End and the solid fines of cross-linking agent composition.
The bacteriostatic water gel solids fine powder dressing of above-mentioned wound repair, it can cross the 40 medicinal sieves of mesh.
Above-mentioned ε-poly-D-lysine is 100: 1~1: 10 with the ratio of the quality of γ-polyglutamic acid, and the ratio of preferred mass is 100: 1~1: 1;Acellularized valve powder accounts for the 0.01~20% of the ε-poly-D-lysine gross mass with γ-polyglutamic acid, preferably 0.1~15%;Cross-linking agent accounts for the 0.01%~30% of hydrogel dry powder dressing weight, preferably 0.01%~20%.
Above-mentioned ε-poly-D-lysine is selected from molecular weight 1000~6000Da ε-poly-D-lysine, and preferred molecular weight exists ε-the poly-D-lysine of 2000~5000Da;γ-polyglutamic acid is selected from molecular weight at 500,000~1,200,000 Da γ-many polyglutamics Acid, preferred molecular weight is at 700,000~1,000,000 Da γ-polyglutamic acid;Acellularized valve powder derives from the viscera tissue of pig; Cross-linking agent is selected from paraformaldehyde, glutaraldehyde, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC), N, N- One or more in DIC (DIC).
The preparation method of the bacteriostatic water gel dressing of above-mentioned wound repair, it is characterised in that: this preparation method include with Lower step:
(1) weigh ε-poly-D-lysine to be dissolved in respectively in deionized water with certain concentration with γ-polyglutamic acid, preparation Two phase liquid, equal-volume mixing, stir after, Acellularized valve powder is directly dispersing in pluralgel, stirring Uniformly prepare complex gel;
(2) taking appropriate cross-linking agent to add in complex gel prepared by (1), reaction 3h is stirred at room temperature, preparation is stable Cross-linked gel;
(3) cross-linked gel prepared by (2) is dispersed in the dehydrated alcohol of appropriate volume, stirring dehydration 30min, takes out Filter, wash, dry, prepare gel lump, be ground into fine powder, prepare aerogel dressing powder.
The concentration that in above-mentioned steps (1), ε-poly-D-lysine is dissolved in deionized water is 0.1~50% (w/v), preferably 5~50% (w/v);It is 0.01~50% (w/v) that γ-polyglutamic acid is dissolved in concentration in deionized water, preferably 1~40% (w/v).
Amount is system 0.01~15% (w/v) of addition cross-linking agent in above-mentioned steps (2), preferably 0.05~10% (w/v), Being dissolved in a small amount of deionized water by cross-linking agent and add system, thus cross-linking agent mixes evenly in system, reacts more fast Efficiently, prepared gel structure is tight, mechanical strength is more excellent for speed.
In above-mentioned steps (3), addition dehydrated alcohol volume is 5~100 times of gel rubber system volume, for cost-effective, excellent Select 5~60 times.
The present invention compares similar aerogel dressing and there is following advantage: 1) dressing itself is containing natural antipathogenic composition ε-many Polylysine, it is not necessary to add antibiotic or silver class antipathogenic composition, effectively reduce the stimulation to wound surface;2) dressing is by sky So polyamino acid class material forms with Acellularized valve, has good biocompatibility, biodegradability, and degraded is produced Thing has Nutrition to wound surface;3) comparing the dressing of Clinical practice, dressing materials prepared by the present invention has super-strong moisture absorbing Ability.
Accompanying drawing explanation
Accompanying drawing 1 is the gel dressing powder SEM figure organizing 1 preparation in embodiment 4
Accompanying drawing 2 is the gel dressing powder SEM figure organizing 4 preparations in embodiment 4
Accompanying drawing 3 is the gel dressing powder SEM figure organizing 10 preparations in embodiment 4
Accompanying drawing 4 is the gel dressing powder SEM figure organizing 17 preparations in embodiment 4
Accompanying drawing 5 embodiment 4 is organized 1, organizes 4, group 10 and group 17 Young's modulus measurement results
Specific embodiment
Embodiment 1 water absorption rate measures
By prepared hydrogel pressed powder, weigh to obtain W0Value is placed in the weighing botle filling deionized water, the most swelling, Blot surface moisture with filter paper, weigh to obtain WnValue.Sample water absorption rate calculates according to following equation: water absorption rate (%)=100 × (Wn-W0)/W0
Embodiment 2 bacteriostatic experiment
(1) preparation for examination bacteria suspension takes E.coli K88, strains of streptococcus is inoculated in LB culture medium, Cultivate 24h for 37 DEG C, choose single bacterium in 3ml LB fluid medium with inoculating loop, 37 DEG C, 200r/min concussion cultivate system Standby bacteria suspension.
(2) take 100 μ L bacteria suspensions and be spread evenly across LB/SS flat board, after placing about 30min, a diameter of 7mm Wound dressing be placed on flat board, the drug susceptability test paper after antibacterials are soaked simultaneously is placed on flat board as positive control, steams Reagent paper after distilled water is soaked is put as negative control, cultivates 24h, measures the diameter of each inhibition zone with slide gauge, often for 37 DEG C Kind sample is repeated 3 times and takes its meansigma methods, observes the size of inhibition zone.This experiment uses 0.2g/L lincomycin and 0.5g/L Piperacillin as positive control.
The preparation of embodiment 3 Acellularized valve powder
Weigh pig heart 100g, be cut into the fragment of 1-3cm, to the container filling 300mL 1% sodium lauryl sulphate Shake (SDS) de-cell to process, processing procedure is changed fresh SDS treatment fluid often, until heart fragment becomes half Transparent network structure, incline SDS treatment fluid, continues to remove SDS 5-8 time with 300mL distilled water flushing, prepares wet Profit support, can be prepared Acellularized valve powder by following treatments, and (1) is freeze-dried, pulverization process prepares support Powder;Or (2) moistening support is first dispersed in 0.1M hydrochloric acid, the pepsin digestion adding weight support frame 10% processes 48h, sodium hydroxide regulation pH to 7.4, obtained by freeze drying support powder.
The preparation of embodiment 4 bacteriostatic water gel dressing
According to table 1 prescription, weigh ε-poly-D-lysine and put in two 100ml beakers respectively with γ-polyglutamic acid, point Jia Ru not be stirred at room temperature and make it be completely dissolved by 10ml distilled water, prepare two-phase polymer solution;By ε-Poly-L-Lysine Solution It is slowly added to the γ being stirred continuously-polyglutamic acid solution, prepares complex gel;According to table 1 prescription, weigh carbon Diimine class cross-linking agent is dissolved in 5mL distilled water or directly with pressed powder or be heated to be steam, is slowly added to or is passed through State in complex gel, reaction 3h is stirred at room temperature, prepares stable cross-linked gel;By gel dispersion after above-mentioned crosslinking such as In the dehydrated alcohol of volume shown in table 1, stirring dehydration 30min, sucking filtration, dehydrated alcohol 30ml wash three times, 80 DEG C Dry, prepare gel lump, pulverize, cross the 40 medicinal sieves of mesh, prepare aerogel dressing powder.Prepared hydrogel Dressing is according to embodiment 1, and embodiment 2 carries out water absorption rate experiment and bacteriostatic experiment, and result is summed up and table 1.
Embodiment 5 bacteriostatic water gel dressing surface morphologic observation
Taking bacteriostatic water gel solid state prepared by different prescription and be dried fine materials, be fixed on sample stage, surface metal spraying is placed on to be swept Retouch electricity Microscopic observation.Hydrogel internal structure is carried out electron-microscope scanning result show: the ε-poly-D-lysine/γ-poly of different proportion Glutamic acid, after the cross-linking agents of variable concentrations, the hydrogel material of formation has the structure of three-dimensional, porous, and accompanying drawing 1 is Organizing the gel dressing SEM figure of 1 preparation in embodiment 3, accompanying drawing 2 is the gel dressing SEM figure organizing 4 preparations in embodiment 3, Accompanying drawing 3 is the gel dressing SEM figure organizing 10 preparations in embodiment 3, and accompanying drawing 4 is that the gel organizing 17 preparations in embodiment 3 applies Material SEM figure.
Embodiment 6 bacteriostatic water gel dressing mechanics properties testing
Take bacteriostatic water gel solid state prepared by different prescription and be dried fine materials, PBS soaks 24h, the thickness of measuring samples, Sample is placed on the platform of biomaterial dynamic test machine, is compressed test according to the speed of 1mm/min.By answering Force-strain curve calculates the fracture strength of sample, extension at break and Young's modulus (n=3).Embodiment 3 is organized 1, organizes 4, organize 10 With organize 17 Young's modulus measurement results such as accompanying drawing 5, be all higher than 2kPa, show that there is good mechanical strength.

Claims (8)

1. the bacteriostatic water gel dressing of a wound repair and preparation method, it is characterised in that: by γ-polyglutamic acid, ε- Poly-D-lysine, Acellularized valve powder and the solid fines of cross-linking agent composition.
The bacteriostatic water gel dressing of wound repair the most according to claim 1, it is characterised in that: described solid fines The 40 medicinal sieves of mesh can be crossed.
3. according to the bacteriostatic water gel dressing of the wound repair described in claim 1 or claim 2, it is characterised in that: institute ε-the poly-D-lysine stated is 100: 1~1: 10 with the ratio of the quality of γ-polyglutamic acid, and Acellularized valve powder accounts for ε-poly and relies ammonia The 0.01-20% of the gross mass of acid and γ-polyglutamic acid, cross-linking agent accounts for the 0.01%~40% of hydrogel dry powder dressing weight.
4. according to the bacteriostatic water gel dressing of the wound repair described in claim 1 or claim 2 or claim 3, its It is characterised by: described ε-poly-D-lysine is selected from molecular weight 1000~6000Da ε-poly-D-lysine, and γ-polyglutamic acid is selected from Molecular weight is at 500,000~1,200,000 Da γ-polyglutamic acid, and Acellularized valve powder derives from the viscera tissue of pig;Cross-linking agent is selected from Paraformaldehyde, glutaraldehyde, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, N, N-DIC.
5., according to the preparation method of the bacteriostatic water gel dressing of the wound repair described in claim 1 or claim 2, it is special Levy and be: this preparation method comprises the following steps:
(1) weigh ε-poly-D-lysine to be dissolved in respectively in deionized water with certain concentration with γ-polyglutamic acid, prepare biphase Solution, equal-volume mixing, stir after, Acellularized valve powder is directly dispersing in pluralgel, stir preparation Complex gel;
(2) take appropriate cross-linking agent to add in complex gel prepared by (1), reaction 3h is stirred at room temperature, prepares stable friendship Connection gel;
(3) cross-linked gel prepared by (2) is dispersed in the dehydrated alcohol of appropriate volume, stirring dehydration 30min, sucking filtration, Washing, drying, prepare gel lump, be ground into fine powder, prepare aerogel dressing powder.
The preparation method of the bacteriostatic water gel dressing of wound repair the most according to claim 5, it is characterised in that: described The concentration that in step (1), ε-poly-D-lysine is dissolved in deionized water is 0.1~50% (w/v), γ-polyglutamic acid be dissolved in from In sub-water, concentration is 0.01~50% (w/v).
The preparation method of the bacteriostatic water gel dressing of wound repair the most according to claim 5, it is characterised in that: described Adding amount is system 0.01~15% (w/v) of cross-linking agent in step (2), the mode of addition has: 1. pressed powder directly adds Enter, the most first cross-linking agent is dissolved in a small amount of deionized water and adds system, 3. cross-linking agent is flashed to steam and be passed through system.
The preparation method of the bacteriostatic water gel dressing of wound repair the most according to claim 5, it is characterised in that: described In step (3), addition dehydrated alcohol volume is 5~100 times of gel rubber system volume.
CN201610329358.8A 2016-05-11 2016-05-11 Bacteriostatic hydrogel dressing for wound repair and preparation method thereof Pending CN105920659A (en)

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CN112480470A (en) * 2020-11-25 2021-03-12 南京双威生物医学科技有限公司 Preparation method of medical polyurethane sponge for wound surface sealing negative pressure drainage
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CN107412854A (en) * 2017-07-05 2017-12-01 北京大清生物技术股份有限公司 A kind of tissue engineering bracket material for CO2 laser weld and preparation method thereof
CN109432490A (en) * 2018-10-17 2019-03-08 苏州汇涵医用科技发展有限公司 A kind of transparent aquagel and its preparation method and application
CN110878145A (en) * 2019-11-29 2020-03-13 浙江树人学院(浙江树人大学) Preparation method of okra extract gamma-polyglutamic acid gel nanoparticles
CN112480470A (en) * 2020-11-25 2021-03-12 南京双威生物医学科技有限公司 Preparation method of medical polyurethane sponge for wound surface sealing negative pressure drainage
CN113398064A (en) * 2021-07-07 2021-09-17 福建宸润生物科技有限公司 Medical copper oxide spray and manufacturing method thereof
CN114984300A (en) * 2022-05-30 2022-09-02 浙江大学 Tough antibacterial hydrogel dressing and preparation method thereof

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