CN101474429B - Method for preparing hydroxylapatite-silk fibroin compound stent material using two-step method - Google Patents
Method for preparing hydroxylapatite-silk fibroin compound stent material using two-step method Download PDFInfo
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- CN101474429B CN101474429B CN200910095563A CN200910095563A CN101474429B CN 101474429 B CN101474429 B CN 101474429B CN 200910095563 A CN200910095563 A CN 200910095563A CN 200910095563 A CN200910095563 A CN 200910095563A CN 101474429 B CN101474429 B CN 101474429B
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- silk fibroin
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Abstract
The invention discloses a two-step method for preparing hydroxyapatite-silk fibroin composite stent material, comprising the following steps: (1) under the environment of alkaline solution, chemical bonding is formed by carboxyl on silk fibroin molecular and Ca<2+> ions in the solution; when PO4<3-> irons are dripped, the Ca<2+> ions react with the PO4<3-> irons to generate the hydroxyapatite, therefore, hydroxyapatite-silk fibroin composite slurry is prepared; (2) after silk fibroin solution is added in the hydroxyapatite-silk fibroin composite slurry, the intermolecular hydrogen bonding is formed between silk fibroin molecular in the composite and silk fibroin molecular in the solution, then, the mixed solution is poured in a die to obtain the porous hydroxyapatite-silk fibroin composite stent material after freezing-freeze drying. Compared with hydroxyapatite-silk fibroin composite stent material which is directly prepared by a prior blending method, the stent material prepared by the invention has perfect mechanical property.
Description
Technical field
The present invention relates to technical field of material, relate in particular to the method that a kind of two-step method prepares hydroxylapatite-silk fibroin compound stent material.
Background technology
Osseous tissue is that the biomineralization that formed by cell altitude mixture control control growing is organized in the body, is made up of the two large divisions---organic matter and inanimate matter.Organic (mainly being the bone collagen fiber bundle) given the elasticity and the toughness of bone as the network of bone; And the hardness and the rigidity characteristic of inanimate matter (mainly being hydroxylapatite crystal) decision skeleton.Simultaneously, hydroxyapatite (HAP) has excellent biological compatibility and bone conduction effect, is one of well behaved bone reparation/substitution material.But low, the poor toughness of the strength of materials by single hydroxyapatite preparation can not be widely used in bone reparation/substitution material.Therefore, the field of tissue engineering technology that is prepared in hydroxyapatite-polymer composite of good mechanical property and biocompatibility is of great immediate significance, and has become domestic and international research focus.
Silk fibroin protein source is abundant, except being used to traditional textile raw material, because its superior mechanical property and good relatively living body adaptability, in recent years, is that the grow research of timbering materials of the various cells of base material is arisen at the historic moment with it.With the fibroin albumen is substrate, and the preparation hydroxylapatite-silk fibroin compound stent material also has report at home and abroad.As: hydroxyapatite colloidal sols and silk fibroin solution have been mixed with compound rest; With silk fibroin powder and hydroxyapatite powder is raw material, is perforating agent with NaCl, and compression molding has prepared SF/HA composite porous material etc.But according to relevant bibliographical information; The interface binding power of hydroxyapatite and organic matrix is relatively poor; In physiological environment, the boundary layer of hydroxyapatite and macromolecule matrix is damaged easily, thereby causes composite not wait damaged the reparation fully just to lose its active strength prematurely.Therefore, improving hydroxyapatite and high molecular interface binding power, is one of key factor of preparation high-performance hydroxyapatite-polymer composite.
Summary of the invention
The purpose of this invention is to provide the method that technology is simple, cost is low, easy to operate a kind of two-step method prepares hydroxylapatite-silk fibroin compound stent material, this method comprises the following steps:
(1) aqueous solution that in concentration is the silk fibroin protein solution of 0.5~2.5% (w/v), drips calcium ions and phosphate anion successively reacts and constantly stirs, and regulation and control solution pH value is 9 in the course of reaction; Calcium-phosphorus ratio is 10: 6 in the reaction system, and fibroin albumen is 1: 10 with the mass ratio that reaction generates hydroxyapatite; After being added dropwise to complete with reactant liquor ageing 24h, wash after centrifugal the hydroxylapatite-silk fibroin composite sludge;
(2) in step (1) gained hydroxylapatite-silk fibroin composite sludge, add silk fibroin protein solution and the constantly stirring that concentration is 2~10% (w/v); The mass ratio of composite sludge dry weight and fibroin albumen is 4: 1, and the regulation and control pH value is 9; After stirring 20~30min, mixed liquor is injected mould ,-20 ℃ of precooling 12h, behind-80 ℃ of freezing processing 2h, obtained by freeze drying porous hydroxyapatite-silk fibroin compound stent material.
The solution of the calcium ions in the said step (1) is calcium chloride solution or calcium nitrate solution.
The aqueous solution of the phosphorus-containing acid ion in the said step (1) is sodium dihydrogen phosphate, disodium phosphate soln, dipotassium hydrogen phosphate solution or potassium dihydrogen phosphate.
Usefulness of the present invention is:
(1) step (1) is a coprecipitation: under the alkaline solution environment, and the Ca on the silk fibroin molecular in carboxyl and the solution
2+Ion forms chemical bonding; Drip PO
4 3-During ion, Ca
2+Ion again with PO
4 3-Ionic reaction generates hydroxyapatite, thereby has prepared the complex of hydroxylapatite-silk fibroin.
(2) step (2) is a blending method: after in the hydroxylapatite-silk fibroin composite sludge, adding silk fibroin protein solution; Silk fibroin molecular forms intermolecular hydrogen bonding and combines in silk fibroin molecular in the complex and the solution, and the injection mould has also prepared porous hydroxylapatite-silk fibroin compound stent material after freezing-lyophilization.
The timbering material of the present invention's preparation is compared with the hydroxylapatite-silk fibroin compound stent material that existing blending method directly prepares, and has the good mechanical performance.
Description of drawings
Fig. 1 is the dried TEM figure of the hydroxylapatite-silk fibroin complex of preparation in the embodiment of the invention 1;
Fig. 2 is the SEM figure of the hydroxylapatite-silk fibroin compound stent material of preparation in the embodiment of the invention 1;
Fig. 3 is respectively the compressive strength comparison diagram of the hydroxylapatite-silk fibroin compound stent material for preparing in the embodiment of the invention 1 and the reference examples;
Fig. 4 is respectively the modulus of compressibility comparison diagram of the hydroxylapatite-silk fibroin compound stent material for preparing in the embodiment of the invention 1 and the reference examples.
The specific embodiment
Specify technical scheme of the present invention below in conjunction with embodiment.
Embodiment 1
(1), 10mL concentration drips the CaCl that 100mL concentration is 0.25mol/L successively in being the silk fibroin protein solution of 2.5% (w/v)
2Solution and 100mL concentration are the NaH of 0.15mol/L
2PO
4Solution also constantly stirs, and regulation and control solution pH value is 9 in the course of reaction.After being added dropwise to complete with reactant liquor ageing 24h, wash centrifugal (8000rpm, 5min) after three times the hydroxylapatite-silk fibroin composite sludge;
(2) in the hydroxylapatite-silk fibroin composite sludge, add silk fibroin protein solution and the constantly stirring that concentration is 5% (w/v), the mass ratio of composite sludge dry weight and fibroin albumen is 4: 1, and the regulation and control pH value is 9; After stirring 20~30min, mixed liquor is injected mould ,-20 ℃ of precooling 12h, behind-80 ℃ of freezing processing 2h, obtained by freeze drying porous hydroxyapatite-silk fibroin compound stent material.
Embodiment 2
(1), 25mL concentration drips the Ca (NO that 100mL concentration is 0.25mol/L successively in being the silk fibroin protein solution of 1% (w/v)
3)
2Solution and 100mL concentration are the Na of 0.15mol/L
2HPO
4Solution also constantly stirs, and regulation and control solution pH value is 9 in the course of reaction.After being added dropwise to complete with reactant liquor ageing 24h, wash centrifugal (8000rpm, 5min) after three times the hydroxylapatite-silk fibroin composite sludge;
(2) in the hydroxylapatite-silk fibroin composite sludge, add silk fibroin protein solution and the constantly stirring that concentration is 2% (w/v), the mass ratio of composite sludge dry weight and fibroin albumen is 4: 1, and the regulation and control pH value is 9; After stirring 20~30min, mixed liquor is injected mould ,-20 ℃ of precooling 12h, behind-80 ℃ of freezing processing 2h, obtained by freeze drying porous hydroxyapatite-silk fibroin compound stent material.
(1), 50mL concentration drips the Ca (NO that 100mL concentration is 0.25mol/L successively in being the silk fibroin protein solution of 0.5% (w/v)
3)
2Solution and 100mL concentration are the K of 0.15mol/L
2HPO
4Solution also constantly stirs, and regulation and control solution pH value is 9 in the course of reaction.After being added dropwise to complete with reactant liquor ageing 24h, wash centrifugal (8000rpm, 5min) after three times the hydroxylapatite-silk fibroin composite sludge;
(2) in the hydroxylapatite-silk fibroin composite sludge, add silk fibroin protein solution and the constantly stirring that concentration is 8% (w/v), the mass ratio of composite sludge dry weight and fibroin albumen is 4: 1, and the regulation and control pH value is 9; After stirring 20~30min, mixed liquor is injected mould ,-20 ℃ of precooling 12h, behind-80 ℃ of freezing processing 2h, obtained by freeze drying porous hydroxyapatite-silk fibroin compound stent material.
Embodiment 4
(1), 10mL concentration drips the CaCl that 100mL concentration is 0.25mol/L successively in being the silk fibroin protein solution of 2.5% (w/v)
2Solution and 100mL concentration are the KH of 0.15mol/L
2PO
4Solution also constantly stirs, and regulation and control solution pH value is 9 in the course of reaction.After being added dropwise to complete with reactant liquor ageing 24h, wash centrifugal (8000rpm, 5min) after three times the hydroxylapatite-silk fibroin composite sludge;
(2) in the hydroxylapatite-silk fibroin composite sludge, add silk fibroin protein solution and the constantly stirring that concentration is 10% (w/v), the mass ratio of composite sludge dry weight and fibroin albumen is 4: 1, and the regulation and control pH value is 9; After stirring 20~30min, mixed liquor is injected mould ,-20 ℃ of precooling 12h, behind-80 ℃ of freezing processing 2h, obtained by freeze drying porous hydroxyapatite-silk fibroin compound stent material.
Reference examples
(1) in 100mL concentration is the CaCl of 0.25mol/L
2Dripping 100mL concentration in the solution is the NaH of 0.15mol/L
2PO
4Solution also constantly stirs, and regulation and control solution pH value is 9 in the course of reaction.After being added dropwise to complete with reactant liquor ageing 24h, wash centrifugal (8000rpm, 5min) after three times hydroxyapatite mud;
(2) in hydroxyapatite mud, add silk fibroin protein solution and the constantly stirring that concentration is 5% (w/v), the mass ratio of composite sludge dry weight and fibroin albumen is 7: 3, and the regulation and control pH value is 9; After stirring 20~30min, mixed liquor is injected mould ,-20 ℃ of precooling 12h, behind-80 ℃ of freezing processing 2h, obtained by freeze drying porous hydroxyapatite-silk fibroin compound stent material.
Embodiment combines Fig. 1: Fig. 1 is the dried TEM figure of the hydroxylapatite-silk fibroin complex of preparation in the embodiment of the invention 1.Form is a nanoscale needle-like complex.
Embodiment combines Fig. 2: Fig. 2 is the SEM figure of the hydroxylapatite-silk fibroin compound stent material of preparation in the embodiment of the invention 1.Pattern is a three-dimensional porous structure, and the aperture is 150~200 microns, and it is more even to distribute.
Embodiment combines Fig. 3: Fig. 3 is respectively the compressive strength comparison diagram of the hydroxylapatite-silk fibroin compound stent material for preparing in the embodiment of the invention 1 and the reference examples.The compound support frame material of embodiment 1 two-step method preparation, compressive strength obviously increases.
Embodiment combines Fig. 4: Fig. 4 is respectively the modulus of compressibility comparison diagram of the hydroxylapatite-silk fibroin compound stent material for preparing in the embodiment of the invention 1 and the reference examples.The compound support frame material of embodiment 1 two-step method preparation, modulus of compressibility obviously increases.
The hydroxylapatite-silk fibroin compound stent material of embodiment 2,3,4 preparations also has the good mechanical performance with embodiment 1.
At last, it is also to be noted that what more than enumerate only is practical implementation example of the present invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (3)
1. a two-step method prepares the method for hydroxylapatite-silk fibroin compound stent material, it is characterized in that the step of this method is following:
(1) aqueous solution that in concentration is the silk fibroin protein solution of 0.5~2.5%w/v, drips calcium ions and phosphate anion successively reacts and constantly stirs, and the pH value of regulation and control solution is 9 in the course of reaction; Calcium-phosphorus ratio is 10: 6 in the reaction system, and fibroin albumen is 1: 10 with the mass ratio that reaction generates hydroxyapatite; After being added dropwise to complete with reactant liquor ageing 24h, wash after centrifugal the hydroxylapatite-silk fibroin composite sludge;
(2) in step (1) gained hydroxylapatite-silk fibroin composite sludge, add silk fibroin protein solution and the constantly stirring that concentration is 2~10%w/v; The mass ratio of composite sludge dry weight and fibroin albumen is 4: 1, and the regulation and control pH value is 9; After stirring 20~30min, mixed liquor is injected mould ,-20 ℃ of precooling 12h, behind-80 ℃ of freezing processing 2h, obtained by freeze drying porous hydroxyapatite-silk fibroin compound stent material.
2. a kind of two-step method according to claim 1 prepares the method for hydroxylapatite-silk fibroin compound stent material, it is characterized in that: the solution of calcium ions is calcium chloride solution or calcium nitrate solution described in the step (1).
3. a kind of two-step method according to claim 1 prepares the method for hydroxylapatite-silk fibroin compound stent material, it is characterized in that: the aqueous solution of phosphorus-containing acid ion is sodium dihydrogen phosphate, disodium phosphate soln, dipotassium hydrogen phosphate solution or potassium dihydrogen phosphate described in the step (1).
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EP2459650B1 (en) * | 2009-07-31 | 2013-06-05 | Council of Scientific & Industrial Research | Accelerated gelation of regenerated fibroin |
CN101628130B (en) * | 2009-08-20 | 2013-04-03 | 华中科技大学 | Nanometer bionic scaffold material and preparation method thereof |
CN101703798B (en) * | 2009-11-05 | 2013-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano hydroxyapatite coating and preparation method thereof and electrostatic atomization device |
CN101856510B (en) * | 2010-05-14 | 2012-11-21 | 浙江理工大学 | Preparation method of composite nano-fiber support material of silk fibroin and calcium silicate |
CN102491298B (en) * | 2011-11-14 | 2013-11-27 | 苏州大学 | Preparation method for linear nanometre hydroxylapatite |
CN103738932B (en) * | 2013-12-13 | 2016-04-20 | 苏州大学 | A kind of nanometer hydroxyapatite and preparation method thereof |
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CN110227181A (en) * | 2019-05-31 | 2019-09-13 | 武汉大学 | A kind of preparation method and applications of fibroin albumen composite hydroxylapatite material |
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Cited By (2)
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