CN102406963A - Multi-component bone tissue engineering scaffold material and preparation method thereof - Google Patents
Multi-component bone tissue engineering scaffold material and preparation method thereof Download PDFInfo
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- CN102406963A CN102406963A CN2011103414414A CN201110341441A CN102406963A CN 102406963 A CN102406963 A CN 102406963A CN 2011103414414 A CN2011103414414 A CN 2011103414414A CN 201110341441 A CN201110341441 A CN 201110341441A CN 102406963 A CN102406963 A CN 102406963A
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Abstract
The invention discloses a multi-component bone tissue engineering scaffold and a preparation method thereof. The multi-component bone tissue engineering scaffold is prepared from chitosan, gelatin, pectin and nano hydroxyapatite by weight percent. The preparation method comprises the following steps of: selecting the chitosan and the pectin to prepare a hydroxyapatite/chitosan-pectin compound by virtue of a codeposition technology, wherein the particle diameter of the hydroxyapatite is 10-100nm; and dispersing nHCP into a chitosan-gelatin solution, crosslinking with glutaric dialdehyde and then freeze-drying to obtain the multi-component bone tissue engineering scaffold. In the scaffold prepared by the preparation method disclosed by the invention, nHCP can be uniformly dispersed in the scaffold and is difficult to agglomerate; the pore diameter of the scaffold is 100-300 mu m, and the porosity of the scaffold is greater than 80%; and the scaffold disclosed by the invention can be used for promoting the adhersion and growth of skeletogenous cells, has good biocompatibility and is expected to be used as a novel bone tissue engineering biological material.
Description
Technical field
The present invention relates to a kind of multi-component bone tissue engineering bracket material and preparation method thereof, belong to the bone reparing biological material technology.
Background technology
At present, all kinds of orthopaedic diseases are more and more serious, and bone reparation and regeneration are general and complicated clinical problems.Many people death owing to lack ideal substitution material.Present bone-grafting material mainly contains from body bone, homogeneous allogenic bone, through the xenogenesis bone of special handling, but all there is certain limitation in these strategies, and use is restricted.Support base bone tissue engineer strategy is to solve the damaged effective way of bone.Ideal engineering material of bone tissue should have suitable biological degradability, mechanical property and biocompatibility.Suitable microenvironment should be provided for the growth of cell and tissue, and it not only will provide support effect for the growth of cell, and the more important thing is to provide inducing properties for the growth of cell, promotes the regeneration of new osseous tissue.
Hydroxyapatite/high polymer composite material can be simulated the structure and the composition of nature bone well, is a kind of ideal bone tissue engineering stent material.The HA/ high polymer can obtain through directly mixing hydroxyapatite (HA) crystal and high polymer, but in the complex of this method preparation, the HA Dispersion of Particles is inhomogeneous, and agglomeration takes place easily.And the HA granule possibly spin off from timbering material in the material degradation process, thus the tissue around the damage.Composite through the biomineralization preparation; Its Polymer Surface forms the HA coating; This method for preparing can be regulated and control crystalline size of HA and pattern through the characteristic of high polymer well; Simultaneously this material has good biocompatibility, but because cell and material directly contact is the HA coating, thus high polymer component wherein in use role be very little.This with in a short time to greatest extent the requirement of the The Nomenclature Composition and Structure of Complexes of simulation nature bone also have certain difference.
Summary of the invention
The object of the present invention is to provide a kind of multi-component bone tissue engineering bracket material and preparation method thereof; The bone tissue engineering stent material that makes with this method has structure similar with nature bone and excellent mechanical property; Overcome HA Dispersion of Particles heterogeneity in the conventional stent; The shortcoming of reuniting easily can be brought into play simultaneously the effect of each component, in bone tissue engineer, has good application prospects.
The present invention realizes through following technical scheme; A kind of multi-component bone tissue engineering bracket material; It is characterized in that this multi-component bone tissue engineering bracket material is made up of following component and mass content percentage ratio thereof, and each constituent mass degree sum is 100%:
Chitosan: 3.6%～63%,
Gelatin: 3%～56.7%,
Pectin: 0.6%～56.7%,
Nanometer hydroxyapatite: 10%～72%.
The method for preparing of above-mentioned multi-component bone tissue engineering bracket material is characterized in that comprising following process:
(1) pectin is dissolved in the deionized water, being prepared into concentration is every milliliter of pectin solution that contains 1～4 milligram; Chitosan is dissolved in 1%～3% the acetic acid solution, being prepared into concentration is every milliliter of acetic acid solution that contains 2～4 milligrams of chitosans;
(2) lime nitrate is dissolved in the prepared pectin solution of step (1), is mixed with the mixed solution that calcium ions concentration is 0.05～0.5mol/L, be designated as A solution; Sodium dihydrogen phosphate is dissolved in step (1) the prepared chitosan acetic acid solution, is mixed with the mixed solution that phosphorus-containing acid ion concentration is 0.30～0.3mol/L, be designated as B solution;
(3) ratio by calcium ion and phosphate radical amount is 1.67:1, and the B drips of solution of step (2) preparation is added in the A solution; And use NaOH solution adjusting pH value to be 3.0-13.0; Stirred 6～20 hours, and obtained mixed liquor;
(4) mixed liquor that step (3) is obtained; Left standstill 6 to 48 hours; Through centrifugalize, collecting solids and using deionized water wash is 7 to cleaning mixture pH, and it is nanometer hydroxyapatite/chitosan-pectin complex (nHCP) of 10-100 nm that last lyophilization obtains particle diameter;
(5) with every milliliter of aqueous gelatin solution and every milliliter of acetic acid solution that contains 2～4 milligrams of chitosans that contains 2 ~ 4 milligrams, be (3～7) in the chitosan in two kinds of solution with the mass ratio of gelatin: the ratio of (7～3) stirs mixed in 10～12 hours; Form chitosan-gelatin (CG) solution;
(6) mass content by nanometer hydroxyapatite/chitosan-pectin complex (nHCP) is 10%～90%; Nanometer hydroxyapatite/chitosan that step (4) is prepared-pectin complex (nHCP); Add in step (5) prepared chitosan-gelatin solution; Ultra-sonic dispersion 5 ~ 20 min make it form the dispersion liquid of homogeneous;
(7) dispersion liquid that step (6) is obtained and mass content are that 0.25% glutaraldehyde solution is (10～2) by volume: 1; Stir down its mixing is obtained mold liquid; Mold liquid is added in the mould; In temperature is-20 ℃～-60 ℃ following pre-freezes more than 8 hours, and the gel that obtains lyophilization in vacuum freeze drier obtains timbering material;
(8) timbering material that step (7) is obtained soaked 3～8 hours in mass concentration is 1%～5% sodium hydroxide solution; Remove residual acetic acid; Be placed on mass concentration again and be in 2%～5% the sodium borohydride solution and soaked 3～8 hours; Remove free glutaraldehyde, wash, be dipped to solution repeatedly with deionized water and be neutral, and then be that-20 ℃～-60 ℃ following pre-freezes are more than 8 hours in temperature; Lyophilization in vacuum freeze drier once more finally obtains multi-component bone tissue engineering bracket material (nHCP/CG).
The invention has the advantages that procedure is simple, hydroxyapatite size that is obtained and pattern can be by controls such as the concentration of the forming of chitosan-pectic matrix, calcium ion and reaction pH value.The nanometer hydroxyapatite size homogeneous (like Fig. 1) that forms; The porosity of the multicomponent porous support of preparation is greater than 80% on this basis, and the aperture with a large amount of connections is the micropore that is suitable for the cell growth of 100～300 μ m, and the size in aperture is determined by the pre-freeze temperature.The nHCG complex disperses homogeneous (like Fig. 2) in support.The mechanical property of this support can be controlled by the content of the degree of cross linking and nHCG, and compressive strength can reach 13.45MPa, and is very approaching with the compressive strength of spongy bone.This timbering material can be and promotes osteoblastic adhesion and growth simultaneously, has excellent biological compatibility, and zoopery is found to promote the reparation that bone is damaged fast, had good application prospects in the bone tissue engineer field.
Description of drawings
Fig. 1 is the transmission electron microscope photo with the embodiment of the invention one prepared nanometer hydroxyapatite/chitosan-pectin complex (nHCP).
Fig. 2 is the stereoscan photograph of the multi-component bone tissue engineering bracket material of the embodiment of the invention one gained.
The specific embodiment
The used primary raw material of embodiment is: chitosan (deacetylation 95%, relative molecular mass 200,000, Qingdao Hai Hui biological product company limited), pectin, gelatin (Sigma company, the U.S.).Other reagent are acetic acid (CH for example
3COOH), lime nitrate (Ca (NO
3)
24H
2O), sodium dihydrogen phosphate ((NaH
2PO
42H
2O) glutaraldehyde (OHC (CH
2)
3CHO), sodium hydroxide (NaOH), sodium borohydride (NaBH
4) wait and be analytical pure.
Embodiment one:
1g pectin is dissolved in the 100mL deionized water, is prepared into the pectin solution that concentration is 1% (w/v); The 1g chitosan is dissolved in the acetic acid solution of 100mL 1%, being prepared into concentration is the acetic acid solution of 1% (w/v) chitosan; With 4.723g lime nitrate (Ca (NO
3)
24H
2O) be dissolved in the pectin solution 1.653g sodium dihydrogen phosphate (NaH
2PO
42H
2O) be dissolved in the chitosan solution; Contain phosphatic chitosan solution and be added drop-wise in the pectin solution that contains calcium ion above-mentioned; Calcium ion wherein is 1.67 with the ratio of phosphate radical amount, and use mass concentration be 5% NaOH solution to regulate pH value be 9, stirred 6 hours; Left standstill 48 hours, keeping pH is 9.Solids is collected in centrifugalize, and to use deionized water rinsing be 7 until the solution pH value, be-20 ℃ of following pre-freezes in temperature, again through lyophilization acquisition nanometer hydroxyapatite/chitosan-pectin complex (nHCP).
It is that being mixed with concentration is 2% (w/v) chitosan solution in 2% the 50mL acetic acid that the 1g chitosan is dissolved in mass concentration; The 1g gelatin is dissolved in it in 50mL deionized water under 50 ℃ temperature, and being mixed with concentration is 2% (w/v) aqueous gelatin solution; Above-mentioned chitosan solution is mixed with gelatin solution, stirred 10 hours; 2g nHCP complex is added in the chitosan-gelatin mixed solution of 100 mL, ultrasonic (600W) disperses 10 min, makes it form the dispersion liquid of homogeneous; In dispersion liquid, add mass concentration then and be 0.25% glutaraldehyde solution 10mL, stir 50s, pour into rapidly in the mould, put under-50 ℃ the low temperature pre-freeze more than 8 hours, gel lyophilization in vacuum freeze drier that pre-freeze is good; Is to soak 8 hours in 5% the sodium hydroxide solution the support after the lyophilizing in mass concentration, removes residual acetic acid.Be placed on mass concentration again and be in 2% the sodium borohydride solution and soaked 8 hours; Remove free glutaraldehyde; Wash, be dipped to solution repeatedly with deionized water and be neutral; Put into once more that pre-freeze is more than 8 hours under-50 ℃ the low temperature, gel lyophilization in vacuum freeze drier that pre-freeze is good obtains multi-component bone tissue engineering bracket material (nHCP/CG).
Embodiment two:
1g pectin is dissolved in the 100mL deionized water, is prepared into the pectin solution that concentration is 1% (w/v); The 1g chitosan is dissolved in the acetic acid solution of 100mL 1%, being prepared into concentration is the acetic acid solution of 1% (w/v) chitosan; With 2.362g lime nitrate (Ca (NO
3)
24H
2O) be dissolved in the pectin solution 0.827g sodium dihydrogen phosphate (NaH
2PO
42H
2O) be dissolved in the chitosan solution; Contain phosphatic chitosan solution and be added drop-wise in the pectin solution that contains calcium ion above-mentioned; Wherein calcium ion is 1.67 with the ratio of phosphate radical amount, and use mass concentration be 5% NaOH solution to regulate pH value be 9, stirred 6 hours; Left standstill 48 hours, keeping pH is 9.Centrifugal, and to use deionized water rinsing be 7 until the solution pH value, be-20 ℃ of following pre-freezes in temperature, again through lyophilization acquisition nanometer hydroxyapatite/chitosan-pectin complex (nHCP).
It is that being mixed with concentration is 2% (w/v) chitosan solution in 2% the 50mL acetic acid that the 1g chitosan is dissolved in mass concentration; The 1g gelatin is dissolved in it in 50mL deionized water under 50 ℃ temperature, and being mixed with concentration is 2% (w/v) aqueous gelatin solution; Above-mentioned chitosan solution is mixed with gelatin solution, stirred 10 hours; 1g nHCP complex is added in the chitosan-gelatin mixed solution of 100 mL, ultrasonic (600W) disperses 10 min, makes it form the dispersion liquid of homogeneous; In dispersion liquid, add mass concentration then and be 0.25% glutaraldehyde solution 10mL, stir 50s, pour into rapidly in the mould, put under-50 ℃ the low temperature pre-freeze more than 8 hours, gel lyophilization in vacuum freeze drier that pre-freeze is good; Is to soak 8 hours in 5% the sodium hydroxide solution the support after the lyophilizing in mass concentration, removes residual acetic acid.Be placed on mass concentration again and be in 2% the sodium borohydride solution and soaked 8 hours; Remove free glutaraldehyde; Wash, be dipped to solution repeatedly with deionized water and be neutral; Put into once more that pre-freeze is more than 8 hours under-50 ℃ the low temperature, gel lyophilization in vacuum freeze drier that pre-freeze is good obtains multi-component bone tissue engineering bracket material (nHCP/CG).
Embodiment three:
1g pectin is dissolved in the 100mL deionized water, is prepared into the pectin solution that concentration is 1% (w/v); The 0.5g chitosan is dissolved in the acetic acid solution of 100mL 1%, being prepared into concentration is the acetic acid solution of 0.5% (w/v) chitosan; With 4.723g lime nitrate (Ca (NO
3)
24H
2O) be dissolved in the pectin solution 1.653g sodium dihydrogen phosphate (NaH
2PO
42H
2O) be dissolved in the chitosan solution; Contain phosphatic chitosan solution and be added drop-wise in the pectin solution that contains calcium ion above-mentioned; Wherein calcium ion is 1.67 with the ratio of phosphate radical amount, and use mass concentration be 5% NaOH solution to regulate pH value be 9, stirred 6 hours; Left standstill 48 hours, keeping pH is 9.Centrifugal, and to use deionized water rinsing be 7 until the solution pH value, be-20 ℃ of following pre-freezes in temperature, again through lyophilization acquisition nanometer hydroxyapatite/chitosan-pectin complex (nHCP).
It is that being mixed with concentration is 2% (w/v) chitosan solution in 2% the 50mL acetic acid that the 1g chitosan is dissolved in mass concentration; The 1g gelatin is dissolved in it in 50mL deionized water under 50 ℃ temperature, and being mixed with concentration is 2% (w/v) aqueous gelatin solution; Above-mentioned chitosan solution is mixed with gelatin solution, stirred 10 hours; 1g nHCP complex is added in the 100 mL chitosan-gelatin mixed solutions, and large power supersonic (600W) disperses 10 min, makes it form the dispersion liquid of homogeneous; In dispersion liquid, add mass concentration then and be 0.25% glutaraldehyde solution 20mL, stir 50s, pour into rapidly in the mould, put under-50 ℃ the low temperature pre-freeze more than 8 hours, gel lyophilization in vacuum freeze drier that pre-freeze is good; Is to soak 8 hours in 5% the sodium hydroxide solution the support after the lyophilizing in mass concentration, removes residual acetic acid.Be placed on mass concentration again and be in 2% the sodium borohydride solution and soaked 8 hours; Remove free glutaraldehyde; Wash, be dipped to solution repeatedly with deionized water and be neutral; Put into once more that pre-freeze is more than 8 hours under-50 ℃ the low temperature, gel lyophilization in vacuum freeze drier that pre-freeze is good obtains multi-component bone tissue engineering bracket material (nHCP/CG).
Claims (2)
1. a multi-component bone tissue engineering bracket material is characterized in that, this multi-component bone tissue engineering bracket material is made up of following component and mass content percentage ratio thereof, and each constituent mass degree sum is 100%:
Chitosan: 3.6%～63%,
Gelatin: 3%～56.7%,
Pectin: 0.6%～56.7%,
Nanometer hydroxyapatite: 10%～72%.
2. method for preparing the described multi-component bone tissue engineering bracket material of claim 1 is characterized in that comprising following process:
(1) pectin is dissolved in the deionized water, being prepared into concentration is every milliliter of pectin solution that contains 1～4 milligram; Chitosan is dissolved in 1%～3% the acetic acid solution, being prepared into concentration is every milliliter of acetic acid solution that contains 2～4 milligrams of chitosans;
(2) lime nitrate is dissolved in the prepared pectin solution of step (1), is mixed with the mixed solution that calcium ions concentration is 0.05～0.5mol/L, be designated as A solution; Sodium dihydrogen phosphate is dissolved in step (1) the prepared chitosan acetic acid solution, is mixed with the mixed solution that phosphorus-containing acid ion concentration is 0.30～0.3mol/L, be designated as B solution;
(3) ratio by calcium ion and phosphate radical amount is 1.67:1, and the B drips of solution of step (2) preparation is added in the A solution; And use NaOH solution adjusting pH value to be 3.0-13.0; Stirred 6～20 hours, and obtained mixed liquor;
(4) mixed liquor that step (3) is obtained; Left standstill 6 to 48 hours; Through centrifugalize, collecting solids and using deionized water wash is 7 to cleaning mixture pH, and it is nanometer hydroxyapatite/chitosan-pectin complex of 10-100 nm that last lyophilization obtains particle diameter;
(5) with every milliliter of aqueous gelatin solution and every milliliter of acetic acid solution that contains 2～4 milligrams of chitosans that contains 2 ~ 4 milligrams, be (3～7) in the chitosan in two kinds of solution with the mass ratio of gelatin: the ratio of (7～3) stirs mixed in 10～12 hours; Form chitosan-gelatin solution;
(6) mass content by nanometer hydroxyapatite/chitosan-pectin complex is 10%～90%; Nanometer hydroxyapatite/chitosan that step (4) is prepared-pectin complex; Add in step (5) prepared chitosan-gelatin solution; Ultra-sonic dispersion 5 ~ 20 min make it form the dispersion liquid of homogeneous;
(7) dispersion liquid that step (6) is obtained and mass content are that 0.25% glutaraldehyde solution is (10～2) by volume: 1; Stir down its mixing is obtained mold liquid; Mold liquid is added in the mould; In temperature is-20 ℃～-60 ℃ following pre-freezes more than 8 hours, and the gel that obtains lyophilization in vacuum freeze drier obtains timbering material;
(8) timbering material that step (7) is obtained soaked 3～8 hours in mass concentration is 1%～5% sodium hydroxide solution; Remove residual acetic acid; Be placed on mass concentration again and be in 2%～5% the sodium borohydride solution and soaked 3～8 hours; Remove free glutaraldehyde, wash, be dipped to solution repeatedly with deionized water and be neutral, and then be that-20 ℃～-60 ℃ following pre-freezes are more than 8 hours in temperature; Lyophilization in vacuum freeze drier once more finally obtains the multi-component bone tissue engineering bracket material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105963789A (en) * | 2016-06-03 | 2016-09-28 | 昆明理工大学 | Method for preparing bone tissue engineering scaffold material |
| CN107412849A (en) * | 2017-07-31 | 2017-12-01 | 赵娜 | A kind of bionic scaffold material of excellent bonding performance and preparation method thereof |
| CN110075360A (en) * | 2019-05-21 | 2019-08-02 | 福建吉特瑞生物科技有限公司 | A kind of chitosan/HA base personalization cranium, jaw face, vertebra bone renovating material and preparation method thereof |
| CN115105639A (en) * | 2022-06-08 | 2022-09-27 | 厦门大学 | Composite membrane for periodontal tissue repair and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105963789A (en) * | 2016-06-03 | 2016-09-28 | 昆明理工大学 | Method for preparing bone tissue engineering scaffold material |
| CN105963789B (en) * | 2016-06-03 | 2019-09-27 | 昆明理工大学 | A kind of preparation method of bone tissue engineering stent material |
| CN107412849A (en) * | 2017-07-31 | 2017-12-01 | 赵娜 | A kind of bionic scaffold material of excellent bonding performance and preparation method thereof |
| CN110075360A (en) * | 2019-05-21 | 2019-08-02 | 福建吉特瑞生物科技有限公司 | A kind of chitosan/HA base personalization cranium, jaw face, vertebra bone renovating material and preparation method thereof |
| CN110075360B (en) * | 2019-05-21 | 2021-12-07 | 福建吉特瑞生物科技有限公司 | Chitosan/HA-based personalized cranio-maxillofacial and spinal bone repair material and preparation method thereof |
| CN115105639A (en) * | 2022-06-08 | 2022-09-27 | 厦门大学 | Composite membrane for periodontal tissue repair and preparation method thereof |
| CN115105639B (en) * | 2022-06-08 | 2023-09-05 | 厦门大学 | Composite membrane for periodontal tissue repair and preparation method thereof |
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Application publication date: 20120411 |