CN106512073A - Alginic acid/chitosan mixed sponge and preparation method - Google Patents

Alginic acid/chitosan mixed sponge and preparation method Download PDF

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Publication number
CN106512073A
CN106512073A CN201610881153.0A CN201610881153A CN106512073A CN 106512073 A CN106512073 A CN 106512073A CN 201610881153 A CN201610881153 A CN 201610881153A CN 106512073 A CN106512073 A CN 106512073A
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China
Prior art keywords
alginic acid
chitosan
sponge
preparation
acid
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CN201610881153.0A
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Chinese (zh)
Inventor
李冉冉
杜勇
张亚兰
张仁辉
周艳华
朱红
付金霞
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TIANJIN YUWANG BIOLOGICAL MEDICAL TECHNOLOGY CO LTD
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TIANJIN YUWANG BIOLOGICAL MEDICAL TECHNOLOGY CO LTD
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Priority to CN201610881153.0A priority Critical patent/CN106512073A/en
Publication of CN106512073A publication Critical patent/CN106512073A/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/043—Mixtures of macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A61L24/0036—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/04—Materials for stopping bleeding

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a preparation method for alginic acid/chitosan mixed sponge, and belongs to the field of bio-medical materials. The preparation method comprises the steps of uniformly mixing micron or nano-level indissolvable calcium salt powder and a sodium alginate solution to form a suspension; slowly adding a chitosan acid solution to the suspension, and performing stirring to form alginic acid/chitosan gel; and performing homogenization, defoaming and freeze-drying on the alginic acid/chitosan gel to obtain the alginic acid/chitosan mixed sponge. The alginic acid/chitosan mixed sponge prepared with the method is simple in process and low in energy consumption, and can be prepared only by one freeze-drying step; and the sponge has good water absorptivity and softness, can be folded at will, is nontoxic, good in bio-compatibility and safe to degrade, has anti-adhesion performance and other performance, can be widely applied to wound hemostasis and wound repair, and is especially suitable for nursing of severe exudates or deep wounds.

Description

Alginic acid/chitosan blend sponge and preparation method
Technical field
The invention belongs to biomedical materials field, more particularly to a kind of alginic acid/chitosan blend sponge and preparation side Method
Background technology
Shitosan is unique cationic polysaccharide containing amino in nature, can attract negatively charged blood platelet and it is red carefully Born of the same parents.Due to the hydrophily of amino, the quantity of fibrinogen adsorption can be promoted, so as to increase platelet adhesion reaction and thrombus shape Into.The loose structure of the spongy hemostatic material obtained after freeze-drying can induce infiltration and increasing of the repair cell in dressing Grow, can cover for the surface of a wound long period, and the effect with obvious wound healing.Chitosan-phospholipid complex is to thin The microorganisms such as bacterium, yeast, fungi have good inhibiting effect.Shitosan to burn patient wound infection produce Pseudomonas aeruginosa, Staphylococcus aureus and streptococcus pyogenes, the skin bacterium (such as MRSE) of human epidermal presence, enterobacteria are (as greatly Enterobacteria) and Human Fungi (such as tropical Candida albicans) all there is significant bacteriostasis.
Sodium alginate is the linear anionic natural polysaccharide being present in brown algae marine organisms, by beta-D-mannuronic acid (M) it is polymerized by (1-4) glycosidic bond with α-L- guluronic acids (G).Sodium alginate is meeting Ca2+、Ba2+Etc. divalence sun Ion, the Ca under ionotropic change2+By Na+Displace, form existing strength character resilient calcium alginate gel again.Sea Alginic acid can be made into gel diaphragm or sponge material, for protecting the surface of a wound and treatment burn.Alginic acid dressing with wound on After purulence blood contact, there is ion exchange with the calcium ion in dressing in the sodium ion in human body.When increasing sodium ion is entered After dressing, dressing itself is converted into water-soluble sodium alginate by water-insoluble calcium alginate at leisure, and substantial amounts of moisture is entered Fiber and make dressing formed colloid.Dressing on wound can form one layer of moist hydrogel, so as to provide one to wound Moist environment of healing again.
Shitosan is cationic polymer, complex reaction can occur with the anionic polyelectrolyte such as sodium alginate, be formed Compound polyelectrolyte, so that reach Synergistic and the intermingling material mechanicalness of two kinds of medical macromolecular materials physiological functions The improvement of energy, the raising of water absorption rate.Preparation method one kind of conventional alginic acid/chitosan sponge is shitosan and sodium alginate Compound polyelectrolyte is initially formed, is freezed, then successively in CaCl2Soak with NaOH solution, with distillation water washing, freeze again It is dry；Another kind is first to form sponge by sodium alginate lyophilized, then forms polymer with after chitosan complexes reaction, then passes through It is lyophilized to prepare.Two methods are required for through freezing dry process twice, and time-consuming, high energy consumption, and the sponge flexibility for preparing Poor with water imbibition, clinical practice is limited.
The content of the invention
The present invention is carried for the poor problem of existing alginic acid/chitosan sponge complicated process of preparation, high energy consumption, flexibility A kind of alginic acid/chitosan blend sponge of flexibility and preparation method, alginic acid/chitosan sponge technique prepared by this law are supplied Simply, energy consumption is low, only needs one-step freezing to be dried and can be prepared by；And the sponge has good water imbibition and flexibility, can appoint Meaning folding, nontoxic, good biocompatibility, safe disposal, the performance such as prevent adhesion, and can be widely used in wound hemostasis, wound repair, It is particularly suitable for serious diffusate or has the nursing of the wound of depth.
The present invention realizes that the technical scheme of purpose is as follows：
A kind of alginic acid/chitosan blend sponge and preparation method, comprise the following steps：
(1) it is sodium alginate powder is soluble in water, it is configured to the sodium alginate soln that percentage by weight is 0.1%～6%； Micron or nanoscale slightly solubility calcium salt powder are well mixed with sodium alginate soln, be configured to percentage by weight for 0.01%～ 5% calcium salt/sodium alginate suspension.
(2) Chitosan powder is dissolved in the acid solution that volume fraction is 0.25%～3%, by weight percentage, is prepared Into the shitosan acid solution that concentration is 0.1%～5%, shitosan acid solution is slowly added in above-mentioned suspension, is stirred Mix, form alginic acid/chitosan gel rubber suspension.
(3), by alginic acid/chitosan gel rubber suspension homogenate, deaeration, freeze-drying, alginic acid/chitosan blend sea is obtained final product It is continuous.
And, described slightly solubility calcium salt is calcium carbonate, calcium sulfate, calcium phosphate, at least one in calcium silicates.
And, the acid in described acid solution is acetic acid, hydrochloric acid, sulfuric acid, at least one in phosphoric acid.
And, described shitosan acid solution is 0.01 with the weight ratio of calcium salt/sodium alginate suspension:1～1: 100。
And, the gel particle of described alginic acid/chitosan gel rubber Jing after homogenate is micron or grade.
And, described alginic acid/chitosan gel rubber suspension can also add glycerine, second two in the system Jing after homogenate At least one in alcohol, D-sorbite, maltitol, further increases the flexibility of sponge.
And, the addition of the glycerine, ethylene glycol, D-sorbite or maltitol is sodium alginate powder weight 0.5-2 times.
The advantages of the present invention are：
1st, alginic acid/chitosan blend sponge prepared by the present invention, has had the physiology work(of two kinds of medical macromolecular materials concurrently Can, compared with homogenous material, the ability of hemostasis and wound healing can be remarkably reinforced.
2nd, preparation process is simple of the present invention, energy consumption are low, it is only necessary to which one-step freezing is dried the medical material that can be prepared by superior performance Material.Insoluble calcium phosphate contacts generation dissociation with acid solution, discharges calcium ion, and calcium ion occurs ion with sodium alginate and puts Change, form calcium alginate gel；Calcium alginate with anion passes through electrostatical binding with the shitosan with cation, you can formed Alginic acid/chitosan gel rubber；Alginic acid/chitosan gel rubber Jing homogenate, deaeration, freeze-drying obtain final product alginic acid/chitosan blend Sponge.
3rd, alginic acid/chitosan sponge flexibility that prepared by the present invention is good, arbitrarily can fold, and water suction is rapid to be expanded, and still Good intensity can be kept.Alginic acid/chitosan gel rubber particle is applied between whole sponge, reduces the crystallinity of sponge Can, increased the flexibility of sponge.
4th, alginic acid/chitosan sponge surfacing, smooth prepared by the present invention, pore structure is homogeneous, can quickly absorb big Amount sepage, and it is non-toxic to skin and mucosa, non-stimulated.
Description of the drawings
Alginic acid/shitosan exterior view and table after bending prepared by the respectively conventional two step freeze-dryings of Fig. 1 and Fig. 3 Face figure, sponge degree of crystallinity prepared by the method are higher, and flexibility is poor, cracky after folding.
Fig. 2 and Fig. 4 is respectively alginic acid/chitosan blend sponge surface figure and surface after bending prepared by embodiment 1 Figure, sponge surface are smooth, and homogeneous, flexibility is good, arbitrarily can fold.
Specific embodiment
Below by specific embodiment, the invention will be further described, and following examples are descriptive, is not limit Qualitatively, it is impossible to which protection scope of the present invention is limited with this.
Embodiment 1
A kind of method of alginic acid/chitosan blend sponge, step are as follows：
(1) 1g sodium alginate powders are dissolved in 100mL water, are configured to the sodium alginate soln that percentage by weight is 1%； 0.05g calcium carbonate powders are well mixed with sodium alginate soln, calcium carbonate/marine alga that percentage by weight is 0.05% is configured to Sour sodium suspension.
(2) 1.5g Chitosan powders are dissolved in the acetic acid solution that 100mL volume fractions are 2%, by weight percentage, are matched somebody with somebody The shitosan acid solution that concentration is 1.5% is made, shitosan acid solution is slowly added into into above-mentioned calcium carbonate/sodium alginate In suspension, stirring forms alginic acid/chitosan gel rubber suspension.
(3), by alginic acid/chitosan gel rubber suspension homogenate, vacuum defoamation, precooling, -55 DEG C of freeze-drying 20h are obtained final product Alginic acid/chitosan blend sponge.
Embodiment 2
A kind of method of alginic acid/chitosan blend sponge, step are as follows：
(1) 3g sodium alginate powders are dissolved in 100mL water, are configured to the sodium alginate soln that percentage by weight is 3%； 2g calcium phosphate powders are well mixed with sodium alginate soln, calcium phosphate/sodium alginate that percentage by weight is 2% are configured to and are mixed Suspension.
(2) 1.5g Chitosan powders are dissolved in the hydrochloric acid solution that 50mL volume fractions are 1%, by weight percentage, are prepared Into the shitosan acid solution that concentration is 3%, shitosan acid solution is slowly added into into above-mentioned calcium phosphate/sodium alginate and is suspended In liquid, stirring forms alginic acid/chitosan gel rubber suspension.
(3), by alginic acid/chitosan gel rubber suspension homogenate, 2g glycerine is added, is mixed, vacuum defoamation, precooling, -55 DEG C freeze-drying 15h, obtains final product alginic acid/chitosan blend sponge.
The addition of glycerine can reduce the effect of be combineding with each other of alginic acid and shitosan macromolecule interchain, increase macromolecular chain Between mobility；The process of Jing glycerine the docile property of alginic acid/chitosan blend sponge is more preferable, lubricity is good, adhesion, and have Certain tensile strength, with more comfort.

Claims (7)

1. the preparation method of a kind of alginic acid/chitosan blend sponge, it is characterised in that comprise the following steps：
(1) it is sodium alginate powder is soluble in water, it is configured to the sodium alginate soln that percentage by weight is 0.1%～6%；Will be micro- Rice or nanoscale slightly solubility calcium salt powder are well mixed with sodium alginate soln, are configured to percentage by weight for 0.01%～5% Calcium salt/sodium alginate suspension；
(2) Chitosan powder is dissolved in the acid solution that volume fraction is 0.25%～3%, by weight percentage, is configured to dense The shitosan acid solution for 0.1%～5% is spent, shitosan acid solution is slowly added into into step calcium salt/alginic acid (1) In sodium suspension, stirring forms alginic acid/chitosan gel rubber suspension；
(3), by alginic acid/chitosan gel rubber suspension homogenate, deaeration, freeze-drying obtain final product alginic acid/chitosan blend sponge.
2. the preparation method of alginic acid according to claim 1/chitosan blend sponge, it is characterised in that：The step (1) slightly solubility calcium salt is calcium carbonate, calcium sulfate, calcium phosphate, at least one in calcium silicates.
3. the preparation method of alginic acid according to claim 1/chitosan blend sponge, it is characterised in that：The step (2) the acid in acid solution is acetic acid, hydrochloric acid, sulfuric acid, at least one in phosphoric acid.
4. the preparation method of alginic acid according to claim 1/chitosan blend sponge, it is characterised in that：Described shell Glycan acid solution is 0.01-1 with the weight ratio of calcium salt/sodium alginate suspension：1-100.
5. the preparation method of alginic acid according to claim 1/chitosan blend sponge, it is characterised in that：Described sea Gel particle of the alginic acid/chitosan gel rubber Jing after homogenate is micron or grade.
6. the preparation method of alginic acid according to claim 1/chitosan blend sponge, it is characterised in that：The step (3) glycerine, ethylene glycol, D-sorbite, malt are additionally added in system of the middle alginic acid/chitosan gel rubber suspension Jing after homogenate At least one in sugar alcohol.
7. the preparation method of alginic acid according to claim 6/chitosan blend sponge, it is characterised in that：Described the third three 0.5-2 times for sodium alginate powder weight of the addition of alcohol, ethylene glycol, D-sorbite or maltitol.
CN201610881153.0A 2016-10-10 2016-10-10 Alginic acid/chitosan mixed sponge and preparation method Pending CN106512073A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107320761A (en) * 2017-07-17 2017-11-07 山东陆海蓝圣生物科技股份有限公司 A kind of efficient bleeding-stopping dressing containing high water absorption cored powder ball and preparation method thereof
CN110585474A (en) * 2019-09-29 2019-12-20 青岛大学附属医院 Preparation method of marine organism polysaccharide-based composite sponge, composite sponge and application
CN113736306A (en) * 2021-10-19 2021-12-03 湖北中烟工业有限责任公司 High-stability yellow chitosan edible silk screen printing ink and preparation method thereof
CN113736313A (en) * 2021-10-19 2021-12-03 湖北中烟工业有限责任公司 Chitosan-iron oxide red-based easily-dried water-based ink and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060211972A1 (en) * 2003-03-28 2006-09-21 Brian Nielsen Wound dressing
CN101249275A (en) * 2008-01-10 2008-08-27 中国人民解放军第二军医大学 Wound dressing capable of insulating sea water and method of preparing the same
CN104436278A (en) * 2013-09-25 2015-03-25 山东康力医疗器械科技有限公司 Method for preparing chitosan haemostatic material for arteriovenous puncture points

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060211972A1 (en) * 2003-03-28 2006-09-21 Brian Nielsen Wound dressing
CN101249275A (en) * 2008-01-10 2008-08-27 中国人民解放军第二军医大学 Wound dressing capable of insulating sea water and method of preparing the same
CN104436278A (en) * 2013-09-25 2015-03-25 山东康力医疗器械科技有限公司 Method for preparing chitosan haemostatic material for arteriovenous puncture points

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107320761A (en) * 2017-07-17 2017-11-07 山东陆海蓝圣生物科技股份有限公司 A kind of efficient bleeding-stopping dressing containing high water absorption cored powder ball and preparation method thereof
CN107320761B (en) * 2017-07-17 2020-05-05 山东陆海蓝圣生物科技股份有限公司 Efficient hemostatic dressing containing high-water-absorption core-spun powder balls and preparation method thereof
CN110585474A (en) * 2019-09-29 2019-12-20 青岛大学附属医院 Preparation method of marine organism polysaccharide-based composite sponge, composite sponge and application
CN110585474B (en) * 2019-09-29 2022-01-04 青岛大学附属医院 Preparation method of marine organism polysaccharide-based composite sponge, composite sponge and application
CN113736306A (en) * 2021-10-19 2021-12-03 湖北中烟工业有限责任公司 High-stability yellow chitosan edible silk screen printing ink and preparation method thereof
CN113736313A (en) * 2021-10-19 2021-12-03 湖北中烟工业有限责任公司 Chitosan-iron oxide red-based easily-dried water-based ink and preparation method thereof

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