CN101181642B - Method for preparing unsymmetrical compound sponge - Google Patents
Method for preparing unsymmetrical compound sponge Download PDFInfo
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- CN101181642B CN101181642B CN200710031328XA CN200710031328A CN101181642B CN 101181642 B CN101181642 B CN 101181642B CN 200710031328X A CN200710031328X A CN 200710031328XA CN 200710031328 A CN200710031328 A CN 200710031328A CN 101181642 B CN101181642 B CN 101181642B
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Abstract
The invention discloses a preparing method for asymmetric compound sponge. The method comprises that: distilled water is used for preparing the sodium carboxymethyl cellulose into liquor with a content of 1 percent; watery acetic acid is used for preparing the chitosan into liquor with a content of 1 percent; warm water is used for preparing glutin into liquor with a content of 1 percent. The sodium carboxymethyl cellulose, glutin and chitosan are measured according to the proportion of the volume ratio: 1:0.5 to 3:0.5 to 3 so as to be stood for froth breaking and then are poured into a molding device for freezing and drying through vacuum so as to get the sponge product; the sponge product is put into a watch glass with carbodiimide liquid so as to be put on a decolor rocking bed after being sealed by using preservative film to be vibrated for 24 hours; then distilled water is added; the opening is sealed again by the preservative film; after that, the watch glass is put on the rocking bed to be rocked for an hour; the operation can be operated for three times. The cross bonding treated sponge is treated by secondarily freezing and drying to get the asymmetric compound sponge. The product prepared by the invention is strong in stanching effect and convenient in clinical use, which has favorable sopping moisture retention and drug-loading performance.
Description
Technical field
The present invention relates to a kind of preparation method of asymmetric composite sponge, specifically be meant adopt freeze-drying method that carboxymethyl cellulose, chitosan and gelatin are mixed and made into to have porous, the sponge product of flexible, hemostasis, medicine carrying function.
Background technology
Need skin-grafting after the large area skin damage debridement that burn, ulcer etc. cause or, cause electrolyte and protein loss, stop antibacterial to be invaded and cause infection, and promote healing up of traumatic tissues to prevent tissue fluid, a large amount of losses of body fluid with the artificial skin flap coverage.Clinical artificial skin commonly used mainly comprises Corii Sus domestica, collagem membrane or collagen sponge polyurethane film etc. both at home and abroad at present.Because Corii Sus domestica is easy and the skin layering, and is poor with the wound tissue compatibility, is unfavorable for the regeneration of epidermal tissue's cell; The poor stability of collagem membrane, to adhere to the ability of body fluid low and have an antigenicity; Collagen sponge can cause the demoulding difficulty; Polyurethane film easily produces hydrops under the film, brings out traumatic infection.Therefore, the research with artificial skin of good histocompatibility remains one of focus of present tissue engineering material scientific research.
Ideal skin substitute products should have pliable and tough and can absorb characteristics such as transudate, bacteriological protection intrusion and loss of moist.Asymmetric sponge with compacted zone and spongy porous layer is one of developing direction of skin tissue engineering research.Its compacted zone can be resisted the intrusion of antibacterial, the control steam permeating rate, and spongy porous layer helps the discharge of wound exudate, and the growth of cell can promote the healing of wound tissue.The macromolecular material that is used for preparing sponge has multiple, wherein chitosan, gelatin, its special performances of carboxymethyl cellulose procatarxis and noticeable.Chitosan can quicken the regeneration and the recovery of skin, and certain fungistatic effect is arranged; Gelatin is the soluble mixtures of polypeptides of a kind of hot water, and certain hemostatic function is arranged; Sodium carboxymethyl cellulose is nontoxic, nonirritant, can degrade fully, has the remarkable triple haemostatic effects of physics, chemistry and physiology.The three has biodegradability and reaches and the good affinity of biological tissue, is extensive use of and be used as bio-medical material.
Present most of medical sponge all is the composite sponge of being made by homogenous material, and this product is owing to the defective of material itself, and functional character is subjected to certain restriction.Also have researcher that chitosan, gelatin are mixed and made into asymmetric sponge or add polyvinyl alcohol again and make asymmetric sponge on both bases, these its effects of so-called asymmetric sponge depend on chitosan and gelatin substantially, and haemostatic effect is limited.The present invention adopts pre-freeze and the freeze-drying can better asymmetric sponge with chitosan, gelatin and carboxymethyl cellulose blend available.
Summary of the invention
The objective of the invention is to the weak point that exists at existing sthptic sponge, adopt pre-freeze---will originate sodium carboxymethyl cellulose, chitosan and the gelatin etc. that enrich of Freeze Drying Technique are made foam product.With respect to single sponge and other asymmetric sponge, this product haemostatic effect is good, clinical easy to use.
The preparation method of asymmetric composite sponge of the present invention comprises the steps:
(1) sodium carboxymethyl cellulose being mixed with concentration with distilled water is 1% solution, and it is 1% solution that chitosan is mixed with concentration with acetic acid,diluted, and it is 1% solution that gelatin is made into concentration with warm water;
(2) be that 1: 0.5～3: 0.5～3 ratio is measured by volume with carboxymethylcellulose sodium solution, gelatin solution and chitosan solution in the step (1), mix homogeneously leaves standstill froth breaking;
(3) mixed liquor that step (2) is obtained is poured in the film formation device, obtains the sponge product through pre-freeze and lyophilization;
(4) the sponge product that step (3) is obtained is put into and is filled the surface plate that mass percent is 0.05～0.2% carbodiimides solution, and the volume ratio of the mixed liquor that carbodiimides and step (2) obtain is 1～3: 1; After sealing with preservative film, place on the decolorization swinging table, vibration 24h after solution in the surface plate all poured out, adds the distilled water with the carbodiimides equal volume, use the preservative film seal, is placed on the shaking table, shakes 1h, repeats this and operates three times;
(5) with the sponge of crosslinking Treatment in (4), carry out secondary pre-freeze and lyophilization and get asymmetric composite sponge.
In order to realize the present invention better, the substitution value of described sodium carboxymethyl cellulose is preferably 0.75～1.2.
Described gelatin isoelectric point, IP is preferably 4.8, weight average molecular weight is preferably 5.0 * 10
5
Described deacetylating degree of chitosan is preferably 60～95%.
Described (2) step should be left standstill froth breaking after stirring; Described used film formation device of (4) step is preferably polystyrene material and makes; Described (3) and (5) step is at-18 ℃ of pre-freeze 12h, at-40 ℃ of vacuum lyophilization 24h.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) the present invention and existing asymmetric composite sponge product contrast, raw material sources are abundant, and properties of product improve greatly, and particularly haemostatic effect and medicine carrying performance are improved significantly.
(2) used chitosan, gelatin and the sodium carboxymethyl cellulose of asymmetric composite sponge product of the present invention preparation all have biodegradability and with the good affinity of biological tissue, the compacted zone of its formation and spongy layer structure can absorb transudate apace, the collaborative participation of three stopped blooding, and this makes the sponge product have powerful haemostatic effect, good biocompatibility.Compare with other like product, more convenient in clinical use.Simultaneously, because very big antibacterial bacteriostatic effect has been played in the adding of chitosan.
(3) the present invention has expanded the application of sodium carboxymethyl cellulose, has driven the economic benefit of relevant enterprise, and also meets the developing direction of international biological hemostatic material.
The specific embodiment
Below in conjunction with embodiment, the present invention is done detailed description further.The inventor has carried out in depth creative research and test to the present invention, and many successful embodiment are arranged, and enumerates six specific embodiments below, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
First step water is that 1.0 sodium carboxymethyl cellulose is mixed with 1% solution with substitution value, and spirit of vinegar is that 60% chitosan is mixed with 1% solution with deacetylation, and it is 1% solution that gelatin is made into concentration with warm water.
Second step was that 1: 2: 2 ratio is measured with sodium carboxymethyl cellulose, gelatin and three kinds of solution of chitosan by volume, and its cumulative volume keeps 30mL.
The 3rd step was mixed above-mentioned three kinds of solution, stirred, and left standstill froth breaking.
The 4th step poured above-mentioned solution in the polystyrene film formation device into, became the sponge product through-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h lyophilizations.
The 5th step put into 50mL with all above-mentioned sponge products and fills the surface plate that mass percent is 0.1% carbodiimides solution, after sealing with preservative film, place on the decolorization swinging table, vibrate 24h, after solution in the surface plate is all poured out, add distilled water with the carbodiimides equal volume, use the preservative film seal, be placed on the shaking table, shake 1h, repeat this operation three times.
The 6th the step with sponge carry out-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h get asymmetric composite sponge.After testing, products obtained therefrom has porous, elasticity preferably, water absorption rate and the water retention of the sponge of 1cm * 1cm specification in distilled water is respectively 2181% and 46.3%, drug loading to ciprofloxacin is 6.19%, drug release rate during 80h is 47.1%, is 50s to rabbit ear portion venous bleeding stopping period.
Embodiment 2
First step water is that 0.75 sodium carboxymethyl cellulose is mixed with 1% solution with substitution value, and spirit of vinegar is that 80% chitosan is mixed with 1% solution with deacetylation, and it is 1% solution that gelatin is made into concentration with warm water.
Second step was that 1: 0.5: 3 ratio is measured with sodium carboxymethyl cellulose, gelatin and three kinds of solution of chitosan by volume, and its cumulative volume keeps 30mL.
The 3rd step was mixed above-mentioned three kinds of solution, stirred, and left standstill froth breaking.
The 4th step poured above-mentioned solution in the polystyrene film formation device into, became the sponge product through-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h lyophilizations.
The 5th step put into 40mL with all above-mentioned sponge products and fills the surface plate that mass percent is 0.05% carbodiimides solution, after sealing with preservative film, place on the decolorization swinging table, vibrate 24h, after solution in the surface plate is all poured out, add distilled water with the carbodiimides equal volume, use the preservative film seal, be placed on the shaking table, shake 1h, repeat this operation three times.
The 6th the step with sponge carry out-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h get asymmetric composite sponge.After testing, products obtained therefrom has porous, elasticity preferably, water absorption rate and the water retention of the sponge of 1cm * 1cm specification in distilled water is respectively 1825% and 38.7%, drug loading to ciprofloxacin is 632%, drug release rate during 80h is 45.2%, is 58s to rabbit ear portion venous bleeding stopping period.
Embodiment 3
First step water is that 1.2 sodium carboxymethyl cellulose is mixed with 1% solution with substitution value, and spirit of vinegar is that 75% chitosan is mixed with 1% solution with deacetylation, and it is 1% solution that gelatin is made into concentration with warm water.
Second step was that 1: 2: 1 ratio is measured with sodium carboxymethyl cellulose, gelatin and three kinds of solution of chitosan by volume, and its cumulative volume keeps 30mL.
The 3rd step was mixed above-mentioned three kinds of solution, stirred, and left standstill froth breaking.
The 4th step poured above-mentioned solution in the polystyrene film formation device into, became the sponge product through-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h lyophilizations.
The 5th step put into 30mL with above-mentioned all sponge products and fills the surface plate that mass percent is 0.2% carbodiimides solution, after sealing with preservative film, place on the decolorization swinging table, vibrate 24h, after solution in the surface plate is all poured out, add distilled water with the carbodiimides equal volume, use the preservative film seal, be placed on the shaking table, shake 1h, repeat this operation three times.
The 6th the step with sponge carry out-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h get asymmetric composite sponge.After testing, products obtained therefrom has porous, elasticity preferably, water absorption rate and the water retention of the sponge of 1cm * 1cm specification in distilled water is respectively 2236% and 41.9%, drug loading to ciprofloxacin is 5.98%, drug release rate during 80h is 43.2%, is 52s to rabbit ear portion venous bleeding stopping period.
Embodiment 4
First step water is that 1.0 sodium carboxymethyl cellulose is mixed with 1% solution with substitution value, and spirit of vinegar is that 95% chitosan is mixed with 1% solution with deacetylation, and it is 1% solution that gelatin is made into concentration with warm water.
Second step was that 1: 1: 0.5 ratio is measured with sodium carboxymethyl cellulose, gelatin and three kinds of solution of chitosan by volume, and its cumulative volume keeps 30mL.
The 3rd step was mixed above-mentioned three kinds of solution, stirred, and left standstill froth breaking.
The 4th step poured above-mentioned solution in the polystyrene film formation device into, became the sponge product through-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h lyophilizations.
The 5th step put into 70mL with above-mentioned all sponge products and fills the surface plate that mass percent is 0.15% carbodiimides solution, after sealing with preservative film, place on the decolorization swinging table, vibrate 24h, after solution in the surface plate is all poured out, add distilled water with the carbodiimides equal volume, use the preservative film seal, be placed on the shaking table, shake 1h, repeat this operation three times.
The 6th the step with sponge carry out-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h get asymmetric composite sponge.After testing, products obtained therefrom has porous, elasticity preferably, water absorption rate and the water retention of the sponge of 1cm * 1cm specification in distilled water is respectively 4639% and 55.2%, drug loading to ciprofloxacin is 10.2%, drug release rate during 80h is 77.1%, is 42s to rabbit ear portion venous bleeding stopping period.
Embodiment 5
First step water is that 1.1 sodium carboxymethyl cellulose is mixed with 1% solution with substitution value, and spirit of vinegar is that 85% chitosan is mixed with 1% solution with deacetylation, and it is 1% solution that gelatin is made into concentration with warm water.
Second step was that 1: 3: 2 ratio is measured with sodium carboxymethyl cellulose, gelatin and three kinds of solution of chitosan by volume, and its cumulative volume keeps 30mL.
The 3rd step was mixed above-mentioned three kinds of solution, stirred, and left standstill froth breaking.
The 4th step poured above-mentioned solution in the polystyrene film formation device into, became the sponge product through-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h lyophilizations.
The 5th step put into 90mL with above-mentioned all sponge products and fills the surface plate that mass percent is 0.1% carbodiimides solution, after sealing with preservative film, place on the decolorization swinging table, vibrate 24h, after solution in the surface plate is all poured out, add distilled water with the carbodiimides equal volume, use the preservative film seal, be placed on the shaking table, shake 1h, repeat this operation three times.
The 6th the step with sponge carry out-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h get asymmetric composite sponge.After testing, products obtained therefrom has porous, elasticity preferably, water absorption rate and the water retention of the sponge of 1cm * 1cm specification in distilled water is respectively 3169% and 44.6%, drug loading to ciprofloxacin is 7.6%, drug release rate during 80h is 68.3%, is 46s to rabbit ear portion venous bleeding stopping period.
Embodiment 6
First step water is that 0.9 sodium carboxymethyl cellulose is mixed with 1% solution with substitution value, and spirit of vinegar is that 70% chitosan is mixed with 1% solution with deacetylation, and it is 1% solution that gelatin is made into concentration with warm water.
Second step was that 1: 0.5: 1.5 ratio is measured with sodium carboxymethyl cellulose, gelatin and three kinds of solution of chitosan by volume, and its cumulative volume keeps 30mL.
The 3rd step was mixed above-mentioned three kinds of solution, stirred, and left standstill froth breaking.
The 4th step poured above-mentioned solution in the polystyrene film formation device into, became the sponge product through-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h lyophilizations.
The 5th step put into 40mL with above-mentioned all sponge products and fills the surface plate that mass percent is 0.2% carbodiimides solution, after sealing with preservative film, place on the decolorization swinging table, vibrate 24h, after solution in the surface plate is all poured out, add distilled water with the carbodiimides equal volume, use the preservative film seal, be placed on the shaking table, shake 1h, repeat this operation three times.
The 6th the step with sponge carry out-18 ℃ of pre-freeze 12h ,-40 ℃ of vacuum lyophilization 24h get asymmetric composite sponge.After testing, products obtained therefrom has porous, elasticity preferably, water absorption rate and the water retention of the sponge of 1cm * 1cm specification in distilled water is respectively 3786% and 43.6%, drug loading to ciprofloxacin is 8.21%, drug release rate during 80h is 71.2%, is 40s to rabbit ear portion venous bleeding stopping period.
Claims (7)
1. the preparation method of an asymmetric composite sponge is characterized in that comprising the steps:
(1) sodium carboxymethyl cellulose being mixed with concentration with distilled water is 1% solution, and it is 1% solution that chitosan is mixed with concentration with acetic acid,diluted, and it is 1% solution that gelatin is made into concentration with warm water;
(2) be that 1: 0.5～3: 0.5～3 ratio is measured by volume with carboxymethylcellulose sodium solution, gelatin solution and chitosan solution in the step (1), mix homogeneously leaves standstill froth breaking;
(3) mixed liquor that step (2) is obtained is poured in the film formation device, obtains the sponge product through pre-freeze and lyophilization;
(4) the sponge product that step (3) is obtained is put into and is filled the surface plate that mass percent is 0.05～0.2% carbodiimides solution, and the volume ratio of the mixed liquor that carbodiimides solution and step (2) obtain is 1～3: 1; After sealing with preservative film, place on the decolorization swinging table, vibration 24h after solution in the surface plate all poured out, adds the distilled water with carbodiimides solution equal volume, use the preservative film seal, is placed on the shaking table, shakes 1h, repeats this and operates three times;
(5) with the sponge of crosslinking Treatment in (4), carry out secondary pre-freeze and lyophilization and get asymmetric composite sponge.
2. the preparation method of asymmetric composite sponge according to claim 1 is characterized in that described sodium carboxymethyl cellulose is the sodium carboxymethyl cellulose of 0.75～1.2 substitution value.
3. the preparation method of asymmetric composite sponge according to claim 1 is characterized in that described chitosan is the chitosan of 60～95% deacetylations.
4. the preparation method of asymmetric composite sponge according to claim 1 is characterized in that described gelatin selects that isoelectric point, IP is 4.8, weight average molecular weight is 5.0 * 10 for use
5Gelatin.
5. the preparation method of asymmetric composite sponge according to claim 1 is characterized in that the cumulative volume of described (2) step carboxymethylcellulose sodium solution, gelatin solution and chitosan solution is 30mL.
6. the preparation method of asymmetric composite sponge according to claim 1 is characterized in that described used film formation device of (3) step is that polystyrene material is made.
7. the preparation method of asymmetric composite sponge according to claim 1, it is characterized in that described (3) step and (5) pre-freeze that goes on foot and freezing be at-18 ℃ of pre-freeze 12h, at-40 ℃ of vacuum lyophilization 24h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710031328XA CN101181642B (en) | 2007-11-09 | 2007-11-09 | Method for preparing unsymmetrical compound sponge |
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| CN200710031328XA CN101181642B (en) | 2007-11-09 | 2007-11-09 | Method for preparing unsymmetrical compound sponge |
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| CN101181642B true CN101181642B (en) | 2011-07-20 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101347637B (en) * | 2008-07-08 | 2011-12-07 | 深圳大学 | Method for preparing crosslinked carboxymethyl chitin tissue engineering stent |
| CN104208742B (en) * | 2013-05-31 | 2016-08-24 | 成都吉泰医疗器械有限公司 | A kind of hemostasis cross-linked composition, Preparation Method And The Use, and by the bleeding stopping and adherence preventing material of its gained |
| CN104740676B (en) * | 2015-03-23 | 2017-09-08 | 常州大学 | A kind of preparation method of taking proanthocyanidins crosslinked gelatin antiseptic dressing |
| CN106390591A (en) * | 2016-09-26 | 2017-02-15 | 海信集团有限公司 | Filtering sponge and preparation thereof, filtering device and laser projection equipment |
| CN106693041A (en) * | 2016-12-16 | 2017-05-24 | 武汉工程大学 | Asymmetric wettable chitosan/starch compound sponge and preparation method thereof |
| CN109401338A (en) * | 2018-10-10 | 2019-03-01 | 江苏银杏湖生物科技有限公司 | A kind of preparation method of gelatine-chitosan-carboxymethyl cellulose biomaterial |
| WO2020155041A1 (en) * | 2019-01-31 | 2020-08-06 | 西北大学 | Polyvinyl alcohol hydrogel having asymmetric pore size |
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