CN103705982A - Method for preparing chitosan/hyaluronic acid/gelatin crosslinked composite porous stent - Google Patents
Method for preparing chitosan/hyaluronic acid/gelatin crosslinked composite porous stent Download PDFInfo
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- CN103705982A CN103705982A CN201310733239.5A CN201310733239A CN103705982A CN 103705982 A CN103705982 A CN 103705982A CN 201310733239 A CN201310733239 A CN 201310733239A CN 103705982 A CN103705982 A CN 103705982A
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Abstract
The invention relates to the technical field of novel materials, and in particular relates to a method for preparing a chitosan/hyaluronic acid/gelatin crosslinked composite porous stent. The method uses chitosan, hyaluronic acid, gelatin and other natural biological materials as raw materials and dialdehyde starch as a crosslinking agent, and combines a lyophilisation method and a particulate leaching method to prepare the chitosan/hyaluronic acid/gelatin crosslinked composite porous stent, which is excellent in mechanical performance and made of a pure natural biological material. The chitosan/hyaluronic acid/gelatin crosslinked composite porous stent prepared by the method has the characteristics of high porosity, high pore strength, large pore diameter and the like, the pore diameter is 100-300 mu m, and the porosity is more than 90 percent. The stent is of an opening pore structure with small pores in large pores, and is suitable for cell implanting on the surface of the composite stent. Compared with a chitosan stent, the crosslinked composite porous stent has a better mechanical performance, proliferation and differentiation of cells on the surface of the composite stent can be more favored, and the compatibility of the composite stent to biological cells is excellent.
Description
Technical field
the invention belongs to new material technology field, be specifically related to the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin.
Background technology
appear as human health and the life of organizational project extend and have brought fine prospect, utilize biomedical material to prepare artificial substituent and treat disease, can solve a human organ difficult problem limited because damaged or afunction need to change, draw materials.When people invest artificial tissue or organ energy, one of its key is to utilize the preparation of the organizational project three-dimensional porous rack material of cell culture.
at present, tissue engineered porous scaffold material is mainly from some natural polymers and synthetic macromolecule.Natural polymer mainly contains collagen, chitin, chitosan, hyaluronic acid, gelatin, alginate, chondroitin sulfate etc.; Synthetic macromolecule mainly has polylactic acid, polyglycolic acid, polyhydroxybutyrate, polycaprolactone, poe etc.In line with facilitating, be easy to get, take from nature to be used for nature, utilize the close and similar advantage of holding altogether of natural biologic material and tissue, many researcheres have all selected natural biologic material to prepare tissue engineering bracket material, but natural biologic material ubiquity the weak problem of mechanical strength, this just needs people to select suitable natural biologic material to carry out composite, and select effective cross-linking agent to improve its mechanical property, and this cross-linking agent must be also no cytotoxicity.
secondly, as effective tissue engineering bracket, it is inadequate that light has material itself, also biomaterial will be made to the three-dimensional porous rack with given shape and pore structure.For cell can enter support, require support to there is loose structure, and there is a certain size aperture and the opening structure of hole strength, and the aperture of different directions is identical.Therefore, the preparation method of tissue engineered porous scaffold and technology are also most important.Pore method mainly contains particle leaching, phase separation method/freeze-drying, gas foaming method, sintering microsphere method etc. at present.But how, select suitable pore method, the organizational project three-dimensional porous rack that preparation meets certain requirements, make rack surface there is cellular affinity, and surface micro-structure as large aperture (100 ~ 300 μ m), high porosity (>90%), hole, hole communicates and certain hole strength etc. is conducive to adhesion, propagation and the differentiation of cell, remains a technical barrier.
Summary of the invention
problem to be solved by this invention is to provide the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin, thereby reach, make rack surface there is cellular affinity, and surface micro-structure as large aperture (100 ~ 300 μ m), high porosity (>90%), hole, hole communicates and certain hole strength etc. is conducive to the objects such as adhesion, propagation and differentiation of cell.
the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin that the present invention proposes, concrete steps are as follows:
(1) chitosan aqueous solution that configuration quality percentage ratio is 1 ~ 10% respectively, 1 ~ 10% hyaluronic acid aqueous solution, 1 ~ 10% aqueous gelatin solution and 1 ~ 10% dialdehyde starch aqueous solution;
(2) chitosan aqueous solution, hyaluronic acid aqueous solution and aqueous gelatin solution step (1) being obtained be take mass ratio as 40 ~ 80:5 ~ 15:20 ~ 40 blend, add again dialdehyde starch aqueous solution, wherein, the gross mass of chitosan, hyaluronic acid and gelatin and the mass ratio of dialdehyde starch are 25 ~ 75:1, after stirring, react 6 ~ 24 hours, deaeration, obtains the crosslinked composite solution of chitosan/hyaluronic acid/gelatin after deaeration;
(3) grind silica gel particle, and screen granularity at 100 ~ 150 object silica gel particles with screen cloth;
(4) take the crosslinked composite solution of chitosan/hyaluronic acid/gelatin after the deaeration that step (2) obtains, the silica gel particle that step (3) obtains, the gross weight of polysaccharide/hyaluronic acid/gelatin and the weight ratio of silica gel are 1:5 ~ 15, after being uniformly mixed, pour in container, wait prolonging that levelling is whole and be placed in-120 ~-20 ℃ of refrigerating chambers after freezing 12 ~ 48 hours, move into again in freezer dryer lyophilization 6 ~ 36 hours, obtain (chitosan+hyaluronic acid+gelatin)/silica gel after lyophilization;
(5) (chitosan+hyaluronic acid+gelatin)/silica gel after lyophilization step (4) being obtained takes out from micro-container, be immersed in mass concentration and be in 1 ~ 10% NaOH aqueous solution and boil 1 ~ 3 hour, repeat to change NaOH aqueous solution 5 ~ 10 times, until the silica gel particle in complete sample dissolution, finally with deionized water, repeatedly clean, until eluate is neutrality, last lyophilization is processed 6 ~ 36 hours, obtains the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin.
in an optimal technical scheme of the present invention, described hyaluronic molecular weight ranges is 5000 ~ 200000.
in the present invention, described hyaluronic acid, claims again alduronic acid, hyaluronic acid, glass sugar carbylic acid, HA, the senior polysaccharide that its basic structure Shi You disaccharidase unit's D-Glucose aldehydic acid and N-acetyl-glucosamine form, and its chemical structural formula is as follows:
in an optimal technical scheme of the present invention, the aldehyde group content value range of dialdehyde starch is 35% ~ 95%, preferably 65% ~ 85%.
in the present invention, the primary structure of technical term dialdehyde starch is in hydration half aldehyde alcohol and molecule and intermolecular hemiacetal, normally use periodic acid as oxidant, by controlling the mol ratio of periodic acid and starch, can prepare the dialdehyde starch of any aldehyde group content, in course of reaction, periodic acid (HIO
4
) starch oxidation is become to aldehyde, itself be reduced into iodic acid (HIO
3
).
Advantage of the present invention is: 1. the present invention is the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin, the present invention is that to take the natural biologic materials such as chitosan, hyaluronic acid and gelatin be raw material, take dialdehyde starch as cross-linking agent, adopt freeze-drying and particle leaching to combine, make the crosslinked complex stephanoporate bracket of the chitosan/hyaluronic acid/gelatin being formed by natural biologic material of good mechanical performance; The advantage such as 2. preparation method of the present invention has that technique is simple and convenient, product quality is high, can reduce production and construction cost, application prospect is extensive, utilizing product prepared by the present invention is high-performance organizational project three-dimensional porous rack of new generation, the pore morphology that there is porous, high porosity and be connected, possess suitable mechanical strength, be conducive to the advantages such as adhesion, propagation and differentiation of cell; 3. the crosslinked complex stephanoporate bracket of chitosan/hyaluronic acid/gelatin that prepared by the present invention has aperture large (100～300 μ m), porosity high (>90%), and macropore, containing the opening pore structure of aperture, is adapted at rack surface repopulating cell; 4. compare chitosan crosslinked porous support, this chitosan/hyaluronic acid/gelatine composite crosslinked porous support has better mechanical property, adding of hyaluronic acid and gelatin, is more conducive to cell in propagation and the differentiation on compound rest surface, good to the affinity of biological cell.
accompanying drawing explanation
below in conjunction with drawings and Examples, the invention will be further described:
fig. 1 is the preparation flow figure of the crosslinked complex stephanoporate bracket of chitosan/hyaluronic acid/gelatin.
fig. 2 is the scanning electron microscope (SEM) photograph of the crosslinked complex stephanoporate bracket of chitosan/hyaluronic acid/gelatin; Fig. 2 a enlargement ratio is that 100, Fig. 2 b enlargement ratio is 400.
The specific embodiment
below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for the present invention is described.The implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.The raw material that the present invention adopts is common commercially available prod.
below in conjunction with embodiment, describe the present invention in detail, should be appreciated that described herein giving an example only in order to explain the present invention, be not intended to limit the present invention.
embodiment 1
the chitosan aqueous solution that configuration quality percentage ratio is 2% respectively, 2% hyaluronic acid aqueous solution, 2% aqueous gelatin solution and 2% dialdehyde starch aqueous solution;
above-mentioned chitosan aqueous solution, hyaluronic acid aqueous solution and aqueous gelatin solution be take to mass ratio as 60:10:30 blend, add again dialdehyde starch aqueous solution, wherein, the gross mass of chitosan, hyaluronic acid and gelatin and the mass ratio of dialdehyde starch are 50:1, after stirring, cross-linking reaction is 12 hours, deaeration, obtains the crosslinked composite solution of chitosan/hyaluronic acid/gelatin after deaeration;
grind silica gel particle, and screen granularity at 120 ~ 150 object silica gel particles with screen cloth;
take the crosslinked composite solution of chitosan/hyaluronic acid/gelatin after the above-mentioned deaeration of 5 g, the above-mentioned silica gel particle of 1 g, the gross weight of polysaccharide/hyaluronic acid/gelatin and the weight ratio of silica gel are 1:10, after being uniformly mixed, pour in micro-container of 10 mL, wait prolonging that levelling is whole and be placed in-30 ℃ of refrigerating chambers after freezing 12 hours, then move in freezer dryer lyophilization 24 hours, obtain (chitosan+hyaluronic acid+gelatin)/silica gel after lyophilization.
(chitosan+hyaluronic acid+gelatin)/silica gel after above-mentioned lyophilization is taken out from micro-container, be immersed in mass concentration and be in 5% NaOH aqueous solution and boil 2 hours, repeat to change NaOH aqueous solution repeatedly, until the silica gel particle in complete sample dissolution, finally with deionized water, repeatedly clean, until eluate is neutrality, lyophilization is processed 24 hours, obtains the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin.
embodiment 2
identical with embodiment 1, but in step (1), the concentration of chitosan solution, hyaluronic acid solution, gelatin solution and dialdehyde starch solution becomes 3% by 2%, and other are constant.
embodiment 3
identical with embodiment 1, but in step (1), the concentration of chitosan solution, hyaluronic acid solution, gelatin solution and dialdehyde starch solution becomes 1% by 2%, and other are constant.
embodiment 4
identical with embodiment 1, but in step (2), the mass ratio of chitosan solution, hyaluronic acid solution and gelatin solution becomes 50:15:35 from 60:10:30, and other are constant.
embodiment 5
identical with embodiment 1, but in step (2), the mass ratio of chitosan solution, hyaluronic acid solution and gelatin solution becomes 70:5:25 from 60:10:30, and other are constant.
embodiment 6
identical with embodiment 1, but the middle polysaccharide of step (2), hyaluronic acid and the gross mass of gelatin and the mass ratio of dialdehyde starch become 60:1 from 50:1, and other are constant.
embodiment 7
identical with embodiment 1, but the middle polysaccharide of step (2), hyaluronic acid and the gross mass of gelatin and the mass ratio of dialdehyde starch become 70:1 from 50:1, and other are constant.
embodiment 8
identical with embodiment 1, but in step (4) in refrigerating chamber cryogenic temperature become-50 ℃ from-30 ℃, other are constant.
embodiment 9
identical with embodiment 1, but in step (4) in refrigerating chamber cryogenic temperature become-100 ℃ from-30 ℃, other are constant.
the crosslinked complex stephanoporate bracket of prepared chitosan/hyaluronic acid/gelatin in above-described embodiment is all used to its surface of sem observation and cross-section morphology, and it and chitosan stent are compared to research, the crosslinked complex stephanoporate bracket of chitosan/hyaluronic acid/gelatin simultaneously embodiment being made has carried out cytocompatibility Journal of Sex Research.Fig. 1 be the crosslinked compound rest of chitosan/hyaluronic acid/gelatin preparation flow figure, Fig. 2 is the scanning electron microscope (SEM) photograph of the crosslinked compound rest of chitosan/hyaluronic acid/gelatin.
above-mentioned example is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that spirit is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (6)
1. chitosan/hyaluronic acid/gelatin is cross-linked a preparation method for complex stephanoporate bracket, and concrete steps are as follows:
(1) chitosan aqueous solution that configuration quality percentage ratio is 1 ~ 10% respectively, 1 ~ 10% hyaluronic acid aqueous solution, 1 ~ 10% aqueous gelatin solution and 1 ~ 10% dialdehyde starch aqueous solution;
(2) chitosan aqueous solution, hyaluronic acid aqueous solution and aqueous gelatin solution step (1) being obtained be take mass ratio as 40 ~ 80:5 ~ 15:20 ~ 40 blend, add again dialdehyde starch aqueous solution, wherein, the gross mass of chitosan, hyaluronic acid and gelatin and the mass ratio of dialdehyde starch are 25 ~ 75:1, after stirring, react 6 ~ 24 hours, deaeration, obtains the crosslinked composite solution of chitosan/hyaluronic acid/gelatin after deaeration;
(3) grind silica gel particle, and screen granularity at 100 ~ 150 object silica gel particles with screen cloth;
(4) take the crosslinked composite solution of chitosan/hyaluronic acid/gelatin after the deaeration that step (2) obtains, the silica gel particle that step (3) obtains, the gross weight of polysaccharide/hyaluronic acid/gelatin and the weight ratio of silica gel are 1:5 ~ 15, after being uniformly mixed, pour in container, wait prolonging that levelling is whole and be placed in-120 ~-20 ℃ of refrigerating chambers after freezing 12 ~ 48 hours, move into again in freezer dryer lyophilization 6 ~ 36 hours, obtain (chitosan+hyaluronic acid+gelatin)/silica gel after lyophilization;
(5) (chitosan+hyaluronic acid+gelatin)/silica gel after lyophilization step (4) being obtained takes out from micro-container, be immersed in mass concentration and be in 1 ~ 10% NaOH aqueous solution and boil 1 ~ 3 hour, repeat to change NaOH aqueous solution 5 ~ 10 times, until the silica gel particle in complete sample dissolution, finally with deionized water, repeatedly clean, until eluate is neutrality, last lyophilization is processed 6 ~ 36 hours, obtains the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin.
2. the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin according to claim 1, is characterized in that, described hyaluronic molecular weight is 5000 ~ 200000.
3. the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin according to claim 1, is characterized in that, wherein in step (4), levelling to be prolonged is whole is placed in-100 ~-50 ℃ of refrigerating chambers freezing 24 hours.
4. the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin according to claim 1, is characterized in that, described hyaluronic acid chemical structural formula is as follows:
5. the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin according to claim 1, is characterized in that, in described dialdehyde starch, aldehyde group content is 35% ~ 95%.
6. the preparation method of the crosslinked complex stephanoporate bracket of a kind of chitosan/hyaluronic acid/gelatin according to claim 1, is characterized in that, in described dialdehyde starch, aldehyde group content is 65% ~ 85%.
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| CN103977412A (en) * | 2014-04-23 | 2014-08-13 | 湖南尔康正阳药用胶囊有限公司 | Enteric-coated capsule material composition |
| CN107519531A (en) * | 2017-08-24 | 2017-12-29 | 张阳 | A kind of titanium alloy bone implant of biological coating structure and preparation method thereof |
| CN109793934A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院大连化学物理研究所 | The engineered myocardium sticking patch of one kind and its preparation and application |
| CN111304916A (en) * | 2020-03-23 | 2020-06-19 | 动之医学技术(上海)有限公司 | Chitosan-based composite fiber |
| CN112370437A (en) * | 2020-10-20 | 2021-02-19 | 好医生药业集团有限公司 | Amoxicillin capsule and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103977412A (en) * | 2014-04-23 | 2014-08-13 | 湖南尔康正阳药用胶囊有限公司 | Enteric-coated capsule material composition |
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| CN107519531A (en) * | 2017-08-24 | 2017-12-29 | 张阳 | A kind of titanium alloy bone implant of biological coating structure and preparation method thereof |
| CN109793934A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院大连化学物理研究所 | The engineered myocardium sticking patch of one kind and its preparation and application |
| CN109793934B (en) * | 2017-11-17 | 2021-06-29 | 中国科学院大连化学物理研究所 | Tissue-engineered myocardial patch and preparation and application thereof |
| CN111304916A (en) * | 2020-03-23 | 2020-06-19 | 动之医学技术(上海)有限公司 | Chitosan-based composite fiber |
| CN112370437A (en) * | 2020-10-20 | 2021-02-19 | 好医生药业集团有限公司 | Amoxicillin capsule and preparation method thereof |
| CN112370437B (en) * | 2020-10-20 | 2022-10-21 | 好医生药业集团有限公司 | Amoxicillin capsule and preparation method thereof |
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