CN101474429A - 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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- CN101474429A CN101474429A CNA2009100955632A CN200910095563A CN101474429A CN 101474429 A CN101474429 A CN 101474429A CN A2009100955632 A CNA2009100955632 A CN A2009100955632A CN 200910095563 A CN200910095563 A CN 200910095563A CN 101474429 A CN101474429 A CN 101474429A
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- hydroxyapatite
- 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 hydroxyapatite-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 of the two large divisions---organic matter and inanimate matter.Organic (mainly being the bone collagen fiber bundle) gives 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 preparation with hydroxyapatite-polymer composite of good mechanical property and biocompatibility is of great immediate significance in field of tissue engineering technology, 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 relative good 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 preparation hydroxyapatite-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 hydroxyapatite-silk fibroin compound stent material, this method comprises the following steps:
(1) aqueous solution that drips calcium ions and phosphate anion in concentration is the silk fibroin protein solution of 0.5～2.5% (w/v) 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 hydroxyapatite-fibroin albumen composite sludge;
(2) in step (1) gained hydroxyapatite-fibroin albumen 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 described step (1) is calcium chloride solution or calcium nitrate solution.
The aqueous solution of the phosphorus-containing acid ion in the described 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 hydroxyapatite-fibroin albumen.
(2) step (2) is a blending method: add silk fibroin protein solution in hydroxyapatite-fibroin albumen composite sludge after, silk fibroin molecular in the complex combines with silk fibroin molecular formation intermolecular hydrogen bonding in the solution, injects mould and has also prepared porous hydroxyapatite-silk fibroin compound stent material after freezing-lyophilization.
The timbering material of the present invention's preparation is compared with hydroxyapatite-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 hydroxyapatite-fibroin albumen complex of preparation in the embodiment of the invention 1;
Fig. 2 is the SEM figure of the hydroxyapatite-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 hydroxyapatite-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 hydroxyapatite-silk fibroin compound stent material for preparing in the embodiment of the invention 1 and the reference examples.
The specific embodiment
Describe technical scheme of the present invention in detail below in conjunction with embodiment.
Embodiment 1
(1) in being the silk fibroin protein solution of 2.5% (w/v), 10mL concentration drips the CaCl that 100mL concentration is 0.25mol/L successively
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 hydroxyapatite-fibroin albumen composite sludge;
(2) add silk fibroin protein solution and the constantly stirring that concentration is 5% (w/v) in hydroxyapatite-fibroin albumen composite sludge, 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) in being the silk fibroin protein solution of 1% (w/v), 25mL concentration drips the Ca (NO that 100mL concentration is 0.25mol/L successively
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 hydroxyapatite-fibroin albumen composite sludge;
(2) add silk fibroin protein solution and the constantly stirring that concentration is 2% (w/v) in hydroxyapatite-fibroin albumen composite sludge, 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) in being the silk fibroin protein solution of 0.5% (w/v), 50mL concentration drips the Ca (NO that 100mL concentration is 0.25mol/L successively
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 hydroxyapatite-fibroin albumen composite sludge;
(2) add silk fibroin protein solution and the constantly stirring that concentration is 8% (w/v) in hydroxyapatite-fibroin albumen composite sludge, 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) in being the silk fibroin protein solution of 2.5% (w/v), 10mL concentration drips the CaCl that 100mL concentration is 0.25mol/L successively
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 hydroxyapatite-fibroin albumen composite sludge;
(2) add silk fibroin protein solution and the constantly stirring that concentration is 10% (w/v) in hydroxyapatite-fibroin albumen composite sludge, 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) add silk fibroin protein solution and the constantly stirring that concentration is 5% (w/v) in hydroxyapatite mud, 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 is the dried TEM figure of hydroxyapatite-fibroin albumen complex of preparation in the embodiment of the invention 1 in conjunction with Fig. 1: Fig. 1.Form is a nanoscale needle-like complex.
Embodiment is the SEM figure of the hydroxyapatite-silk fibroin compound stent material of preparation in the embodiment of the invention 1 in conjunction with Fig. 2: Fig. 2.Pattern is a three-dimensional porous structure, and the aperture is 150～200 microns, and it is more even to distribute.
Embodiment is respectively the compressive strength comparison diagram of the hydroxyapatite-silk fibroin compound stent material for preparing in the embodiment of the invention 1 and the reference examples in conjunction with Fig. 3: Fig. 3.The compound support frame material of embodiment 1 two-step method preparation, compressive strength obviously increases.
Embodiment is respectively the modulus of compressibility comparison diagram of the hydroxyapatite-silk fibroin compound stent material for preparing in the embodiment of the invention 1 and the reference examples in conjunction with Fig. 4: Fig. 4.The compound support frame material of embodiment 1 two-step method preparation, modulus of compressibility obviously increases.
Hydroxyapatite-the 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 specific embodiments of the 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 kind of two-step method prepares the method for hydroxyapatite-silk fibroin compound stent material, it is characterized in that the step of this method is as follows:
(1) aqueous solution that drips calcium ions and phosphate anion in concentration is the silk fibroin protein solution of 0.5～2.5% (w/v) 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 hydroxyapatite-fibroin albumen composite sludge;
(2) in step (1) gained hydroxyapatite-fibroin albumen 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 hydroxyapatite-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 hydroxyapatite-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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| CN101856510A (en) * | 2010-05-14 | 2010-10-13 | 浙江理工大学 | Preparation method of composite nano-fiber support material of silk fibroin and calcium silicate |
| CN102482497A (en) * | 2009-07-31 | 2012-05-30 | 科学与工业研究委员会 | Accelerated Gelation Of Regenerated Fibroin |
| CN102491298A (en) * | 2011-11-14 | 2012-06-13 | 苏州大学 | Preparation method for linear nanometre hydroxylapatite |
| 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 |
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| CN103738932A (en) * | 2013-12-13 | 2014-04-23 | 苏州大学 | Nano-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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| 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 |
| CN101856510A (en) * | 2010-05-14 | 2010-10-13 | 浙江理工大学 | Preparation method of composite nano-fiber support material of silk fibroin and calcium silicate |
| 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 |
| CN102491298A (en) * | 2011-11-14 | 2012-06-13 | 苏州大学 | Preparation method for linear nanometre hydroxylapatite |
| CN103738932A (en) * | 2013-12-13 | 2014-04-23 | 苏州大学 | Nano-hydroxyapatite and preparation method thereof |
| CN103738932B (en) * | 2013-12-13 | 2016-04-20 | 苏州大学 | A kind of nanometer hydroxyapatite and preparation method thereof |
| CN106567151A (en) * | 2016-11-03 | 2017-04-19 | 武汉理工大学 | Calcium fluoride collagen micro-fiber composite and preparation method thereof |
| CN109806445A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院化学研究所 | Biocompatible materials and preparation method, dual bone tissue reparation or alternative materials and preparation method and application |
| CN109806443A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院化学研究所 | Bone holder material and its preparation method and application |
| 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 |
| CN111422977A (en) * | 2020-01-19 | 2020-07-17 | 浙江大学 | Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate |
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