CN103908693A - Bionic alginate composite antimicrobial dressing and preparation method thereof - Google Patents

Bionic alginate composite antimicrobial dressing and preparation method thereof Download PDF

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Publication number
CN103908693A
CN103908693A CN201410149677.1A CN201410149677A CN103908693A CN 103908693 A CN103908693 A CN 103908693A CN 201410149677 A CN201410149677 A CN 201410149677A CN 103908693 A CN103908693 A CN 103908693A
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alginic acid
bionic
component
dressing
chitosan
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CN103908693B (en
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位晓娟
顾其胜
奚廷斐
王庆生
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SHANDONG YINUO BIOLOGICAL TECHNOLOGY Co Ltd
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SHANDONG YINUO BIOLOGICAL TECHNOLOGY Co Ltd
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Abstract

The invention belongs to the field of biomedical materials, and particularly relates to bionic alginate composite antimicrobial dressing and a preparation method thereof. The bionic alginate composite antimicrobial dressing is prepared from the following raw materials: alginate components, chitosan components and silver ion components. The method is characterized by comprising the following steps: adding deionized water to agitate a solvent after mixing the raw materials, so as to obtain mixed water gel; repeatedly thawing, freezing and drying the mixed water gel to obtain a product, wherein the product comprises the following raw materials by weight percent: 60-90% of alginate components, 9.8-39% of chitosan components and 0.2-1% of silver ion components. The process system disclosed by the invention is controllable in temperature and condition, the problems of residues such as a toxic cross-linking agent or an assistant and the like do not exist, the safety risk of clinical application is greatly reduced, and the bionic alginate composite antimicrobial dressing has good product transformation feasibility.

Description

A kind of bionic-type alginic acid base composite antibiotic dressing and preparation method thereof
(1) technical field
The invention belongs to biomedical materials field, particularly a kind of bionic-type alginic acid base composite antibiotic dressing and preparation method thereof.
(2) background technology
Along with the raising that people require for medical effect, infection control and healing acceleration more and more become the key factor that is related to all kinds of surgical clinical operation prognosis quality.Especially the damage of special environment as battlefield wound or large wound surface, depth wound first aid in, quick-acting haemostatic powder, effectively antiinflammatory and promote healing can be to save life to provide powerful guarantee.The market value of U.S.'s wound care in 2003 and disposable product has reached 47.6 hundred million U.S. dollars, mainly comprises the wound control products such as biological skin and dressing, the wet wound healing product of alginate, adhesive bandage, and the wound closed product such as sealer.Also there are the multiple Wound care products such as multiple collagen-based, chitosan-based, Sargassum acidic group, cellulose base and fibrin, platelet rich plasma in China, for dissimilar wound healing.
Along with the development of regeneration medicine technology, research and develop advanced Wound care products and always be clinical and hot issue basic research common concern.This field has many Related products, research or patent, but still has many problems constantly to improve, such as penetrating fluid absorption, mechanical performance, anti-microbial property and original position repairing performance etc.
Sargassum acidic group biomaterial early has historical records for wound care, just has people to treat wound with Sargassum at ancient rome era, and Sargassum was once once used for wound hemostasis by sailor.Since nineteen eighty-three, first case alginate casting product put goods on the market, Related product is in the clinical practice history of existing 30 years, and its safety and effectiveness are fully confirmed.Chitosan-based biomaterial had been proved performances such as having good hemostasis, anti, inhibiting bacteria and diminishing inflammation, analgesia, promoting healing already, was widely used in the fields such as organizational project, medicament slow release, health care of food.Silver ion also obtains clinical confirmation as its effectiveness of broad spectrum antimicrobicide and safety.So far, existing many alginic acid research report, product patent and product relevant with chitosan-based antiseptic dressing, becomes one of focus of achievements conversion in bio-medical material.
Current existing patent and product are to adopt the materials such as alginic acid/chitosan/active carbon by spraying or the mode such as immersion is prepared the antiseptic dressing of silver ion mostly, and technique is simple effective but long-acting releasing effect is not good.Patent CN102406957, CN1935268A, CN102505461A, CN10450222A etc. also disclose the method for preparing in several ways Sargassum acidic group antiseptic dressing, but all there is some difference with the method for patent of the present invention.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides bionic-type alginic acid base composite antibiotic dressing that a kind of preparation technology is simple, feasibility is good and preparation method thereof.
The present invention is achieved through the following technical solutions:
The dressing of a kind of bionic-type alginic acid base composite antibiotic, taking alginic acid component, chitosan component and silver ion component as raw material, it is characterized in that: after raw material is mixed, add deionized water and stirring solvent, obtain mixing water gel, mixing water gel obtains product through multigelation, lyophilization; The percentage by weight of each raw material is, alginic acid component 60-90%, chitosan component 9.8-39%, silver ion component 0.2-1%.
The present invention's use Sargassum acidic group and chitosan-based material are as the slow-released carrier of silver ion, be cross-linked the bionic-type adjuvant that obtains again satisfactory mechanical property through lyophilization by secondary physical, and can discharge gradually silver ion along with swelling, the degraded of dressing matrix, reach the effect of long acting antibiotic.Sargassum acidic group biomaterial in dressing matrix material has good mechanical performance, fluid absorbent and gelling performance, chitosan material has good antibacterial activity, anthemorrhagic performance, easing pain and diminishing inflammation and promotes the effects such as healing, after the two and silver ion chelating, form good crosslinked stable three dimensional structure through multigelation, can realize the long-acting slow-release of silver ion, thereby reach the object of long acting antibiotic.In addition, because this kind of silver ion mode of loading is reliable and stable, therefore can alleviate due to prominent and release the toxicity causing, the breadth of the concentration of silver ions of loading with is higher than traditional approach.
More excellent technical scheme of the present invention is:
The weight proportion of described each raw material is, alginic acid component 75-90%, chitosan component 9.8-38.7%, silver ion component 0.5-1%.
Described alginic acid component is grouped into by two kinds of one-tenth: the salt that salt, alginic acid and the bivalent metal ion that alginic acid and valent metal ion form forms, and wherein, the former is one or more in sodium alginate, potassium alginate and ammonium alginate, the latter is calcium alginate; The mass ratio of the two is 10-3:1, preferably 5-8:1.
Alginic acid component is made up of the alginic acid Base Metal salt of two kinds of different prices, can form gradually the stable hydrogel network of metal ion crosslinked between the two, and cross-linking process is slow, controllability good, and the hydrogel network mechanical performance of formation significantly strengthens.
Described chitosan component is water solublity, is one or more in carboxymethyl chitin, carboxymethyl chitosan, Chitofilmer, hydroxypropyl chitosan, ethoxyl chitin and hydroxyethyl chitosan.Owing to having introduced chitosan component, there is good anthemorrhagic performance and have antibacterial, antiinflammatory, analgesia function concurrently and can promote wound healing, also can form chelate structure with silver ion, make in the three-dimensional net structure that is present in material that silver ion component is stable, long-acting, can disengage gradually the fungistatic effect that reaches long-acting, stable after being applied to wound surface.
Described silver ion component is one or more in nitrate, silver chloride, silver sulfate, nanometer silver and silver sulfadiazine.Silver ion compositional range is wider, as silver nitrate, is also applicable to water-insoluble silver ion donor as silver sulfadiazine etc. applicable to water-soluble silver ionic compound.
The preparation method of bionic-type alginic acid base composite antibiotic of the present invention dressing, is characterized in that: alginic acid component, chitosan component are mixed with silver ion component, add deionized water, stirring at room temperature 0.5-5h, obtains mixing water gel; Mixing water gel is placed in to freezing 12h at-20 DEG C, take out thaw after stirring and evenly mixing, then be placed in freezing 12h at-20 DEG C, so multigelation 1-5 time, lyophilization obtains product.
Preferred version is: described raw material adds after deionized water, stirring at room temperature 0.5-4h; Described mixing water gel multigelation number of times is 2-4 time.
For further improving hygrometric state mechanical performance and the fluid absorbent of dressing, the present invention adopts multigelation method to carry out secondary physical to dressing and is cross-linked.Be cross-linked for related twice and all do not introduce other chemical substances or inorganic ions, do not relate to the residual equivalent risk control problem of cross-linking agent, there is good safety and operability.In addition, technique of the present invention is simply controlled, has significantly reduced the difficulty of preparation process risk management, has good product and transforms feasibility.
Product of the present invention except as conventional dressing for clinical, mechanical strength, antibiotic property, haemostatic effect and healing quality are also strengthened, not only greatly improve the repairing effect of common wound, the wound more for chronic ulcer, diabetic foot, decubital ulcer and the hemorrhage amount of coming to a head also has good therapeutical effect, significantly improve patient's compliance, expanded clinical application range.
(4) detailed description of the invention
Adopt specific embodiment to be used for elaborating compound antiseptic dressing of the present invention and preparation process thereof below.
Embodiment 1:
The preparation process of a kind of bionic-type alginic acid of the present invention base composite antibiotic dressing is as follows:
Adopt alginic acid component to be formed by sodium alginate and calcium alginate; Chitosan component is carboxymethyl chitosan; Silver ion component is silver nitrate.Wherein, the molecular weight of sodium alginate, calcium alginate and carboxymethyl chitosan is respectively 80,000,30,000,200,000 dalton.
Take alginic acid component 9g(sodium alginate: the mass ratio of calcium alginate is 8:1), carboxymethyl chitosan 0.9g, silver nitrate 0.1g, after above-mentioned three kinds of powder are mixed, add deionized water 300ml, stirring at room temperature 3h fully mixes, and silver ion is fully sequestered on polysaccharide molecule chain; The mixing water gel of gained is placed in to-20 DEG C of multigelations 3 times; Last lyophilization obtains bionic-type alginic acid base composite antibiotic dressing sponge.
Embodiment 2:
The preparation process of a kind of bionic-type alginic acid of the present invention base composite antibiotic dressing is as follows:
Adopt alginic acid component to be formed by potassium alginate and calcium alginate; Chitosan component is carboxymethyl chitin; Silver ion component is nanometer silver.Wherein, the molecular weight of potassium alginate, calcium alginate and carboxymethyl chitin is respectively 100,000,20,000,150,000 dalton.
Take alginic acid component 8g(potassium alginate: the mass ratio of calcium alginate is 5:1), carboxymethyl chitin 1.5g, silver nitrate 0.5g, after above-mentioned three kinds of powder are mixed, add deionized water 300ml, stirring at room temperature 2h fully mixes, and silver ion is fully sequestered on polysaccharide molecule chain; The mixing water gel of gained is placed in to-20 DEG C of multigelations 2 times; Last lyophilization obtains bionic-type alginic acid base composite antibiotic dressing sponge.
Embodiment 3:
The preparation process of a kind of bionic-type alginic acid of the present invention base composite antibiotic dressing is as follows:
Adopt alginic acid component to be formed by sodium alginate and calcium alginate; Chitosan component is hydroxypropyl chitosan; Silver ion component is silver sulfadiazine.Wherein, the molecular weight of sodium alginate, calcium alginate and hydroxypropyl chitosan is respectively 80,000,30,000,100,000 dalton.
Take alginic acid component 7.5g(sodium alginate: the mass ratio of calcium alginate is 5:1), hydroxypropyl chitosan 1.5g, silver nitrate 1.0g, after above-mentioned three kinds of powder are mixed, add deionized water 300ml, stirring at room temperature 4h fully mixes, and silver ion is fully sequestered on polysaccharide molecule chain; The mixing water gel of gained is placed in to-20 DEG C of multigelations 4 times; Last lyophilization obtains bionic-type alginic acid base composite antibiotic dressing sponge.
Embodiment 4:
The preparation process of a kind of bionic-type alginic acid of the present invention base composite antibiotic dressing is as follows:
Adopt alginic acid component to be formed by sodium alginate and calcium alginate; Chitosan component is carboxymethyl chitosan; Silver ion component is the two components of silver sulfadiazine and silver nitrate.Wherein, the molecular weight of sodium alginate, calcium alginate and carboxymethyl chitosan is respectively 120,000,30,000,200,000 dalton.
Take alginic acid component 8.4g(sodium alginate: the mass ratio of calcium alginate is 6:1), carboxymethyl chitosan 0.9g, silver nitrate 0.2g, silver sulfadiazine 0.5g, after above-mentioned several powder are mixed, add deionized water 300ml, stirring at room temperature 3h fully mixes, and silver ion is fully sequestered on polysaccharide molecule chain; The mixing water gel of gained is placed in to-20 DEG C of multigelations 3 times; Last lyophilization obtains bionic-type alginic acid base composite antibiotic dressing sponge.
The above; it is only preferred embodiment of the present invention; not that the present invention is done to other forms of restriction; any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations; but do not depart from technical solution of the present invention content; any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.

Claims (9)

1. bionic-type alginic acid base composite antibiotic dressing, taking alginic acid component, chitosan component and silver ion component as raw material, it is characterized in that: after raw material is mixed, add deionized water and stirring solvent, obtain mixing water gel, mixing water gel obtains product through multigelation, lyophilization; The percentage by weight of each raw material is, alginic acid component 60-90%, chitosan component 9.8-39%, silver ion component 0.2-1%.
2. bionic-type alginic acid base composite antibiotic according to claim 1 dressing, is characterized in that: the weight proportion of described each raw material is, alginic acid component 75-90%, chitosan component 9.8-38.7%, silver ion component 0.5-1%.
3. bionic-type alginic acid base composite antibiotic according to claim 1 dressing, it is characterized in that: described alginic acid component is grouped into by two kinds of one-tenth: the salt that salt, alginic acid and the bivalent metal ion that alginic acid and valent metal ion form forms, wherein, the former is one or more in sodium alginate, potassium alginate and ammonium alginate, and the latter is calcium alginate; The mass ratio of the two is 10-3:1.
4. bionic-type alginic acid base composite antibiotic according to claim 1 dressing, it is characterized in that: described chitosan component is water solublity, is one or more in carboxymethyl chitin, carboxymethyl chitosan, Chitofilmer, hydroxypropyl chitosan, ethoxyl chitin and hydroxyethyl chitosan.
5. bionic-type alginic acid base composite antibiotic adjuvant according to claim 1, is characterized in that: described silver ion component is one or more in nitrate, silver chloride, silver sulfate, nanometer silver and silver sulfadiazine.
6. bionic-type alginic acid base composite antibiotic according to claim 3 dressing, is characterized in that: the mass ratio of described alginic acid monovalent salt and divalent salts is 5-8:1.
7. the preparation method of bionic-type alginic acid base composite antibiotic according to claim 1 dressing, is characterized in that: alginic acid component, chitosan component are mixed with silver ion component, add deionized water, stirring at room temperature 0.5-5h, obtains mixing water gel; Mixing water gel is placed in to freezing 12h at-20 DEG C, take out thaw after stirring and evenly mixing, then be placed in freezing 12h at-20 DEG C, so multigelation 1-5 time, lyophilization obtains product.
8. the preparation method of bionic-type alginic acid base composite antibiotic according to claim 7 dressing, is characterized in that: described raw material adds after deionized water, stirring at room temperature 0.5-4h.
9. the preparation method of bionic-type alginic acid base composite antibiotic according to claim 7 dressing, is characterized in that: described mixing water gel multigelation number of times is 2-4 time.
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CN107714299A (en) * 2017-12-04 2018-02-23 广东泰宝医疗科技股份有限公司 A kind of medical dressing is dispelled pain patch
CN108478874A (en) * 2018-04-25 2018-09-04 信阳师范学院 A kind of preparation method of the nano combined bone holder material of hydroxyethyl chitosan
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CN104474535A (en) * 2014-12-10 2015-04-01 成都新际生物活性胶原开发有限公司 Water-soluble gel for treating diabetic foot
CN105107008A (en) * 2015-09-16 2015-12-02 中南民族大学 Hydroxybutyl chitosan/oxidized sodium alginate/nano-silver composite hydrogel dressing plaster
CN105288698A (en) * 2015-11-19 2016-02-03 广东泰宝医疗科技股份有限公司 Calcium alginate composite medical surgical dressing and preparation method thereof
CN106380609A (en) * 2016-09-19 2017-02-08 天津科技大学 Antibacterial carboxymethyl chitosan hydrogel and preparation method thereof
CN107714299A (en) * 2017-12-04 2018-02-23 广东泰宝医疗科技股份有限公司 A kind of medical dressing is dispelled pain patch
CN108478874A (en) * 2018-04-25 2018-09-04 信阳师范学院 A kind of preparation method of the nano combined bone holder material of hydroxyethyl chitosan
TWI693929B (en) * 2018-06-27 2020-05-21 南六企業股份有限公司 Antibacterial wound dressing
CN109847097A (en) * 2018-12-10 2019-06-07 安徽徽科生物工程技术有限公司 Intrinsic bioremediation film, preparation method and application
WO2021237094A1 (en) * 2020-05-22 2021-11-25 Mig Usa, Llc Antimicrobial compositions and methods of use and for making same
CN112295008A (en) * 2020-11-10 2021-02-02 北京深核智能科技有限公司 Bioactive dressing with anti-inflammatory and hemostatic functions
CN112295008B (en) * 2020-11-10 2021-08-10 广州图微科创生物科技有限公司 Bioactive dressing with anti-inflammatory and hemostatic functions
CN112451738A (en) * 2020-11-30 2021-03-09 西安交通大学 Silver ion polysaccharide polymer antibacterial dressing and preparation method and application thereof
CN115591008A (en) * 2021-12-31 2023-01-13 上海炫鑫医药科技有限公司(Cn) Spray-type liquid wound-protecting dressing and preparation method thereof
CN114409973A (en) * 2022-02-23 2022-04-29 北京工业大学 Bio-based blending material and preparation method thereof

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