CN1836740A - Composite tri-dimensional porous bone tissue engineering stent material and its preparation method and uses - Google Patents
Composite tri-dimensional porous bone tissue engineering stent material and its preparation method and uses Download PDFInfo
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- CN1836740A CN1836740A CN 200610035107 CN200610035107A CN1836740A CN 1836740 A CN1836740 A CN 1836740A CN 200610035107 CN200610035107 CN 200610035107 CN 200610035107 A CN200610035107 A CN 200610035107A CN 1836740 A CN1836740 A CN 1836740A
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Abstract
The bionic composite 3D bone tissue engineering rack material has pores of 200-500 microns and porosity over 80 %, and contains bioactive nanometer CaO-P2O5-SiO2 glass powder 50-80 wt%, type-I collagen 10-35 wt%, hyaluronic acid 2-8 wt% and phosphatidylserine 2-8 wt%. Its preparation process includes mixing the above said components homogeneously, adding buffering agent and cross-linking agent for cross-linking treatment, freezing, freeze drying to dewater completely, soaking in Na2HPO4 solution, washing, dewatering and vacuum drying. The material is used as bone substituting material for repairing damaged bone tissue in medical field.
Description
Technical field
The present invention relates to biomedical material, particularly the preparation method of bionic-type composite three-dimensional porous bone tissue engineering scaffold material.
The invention still further relates to the material of described method preparation.
The invention still further relates to the application of described material.
Background technology
Organizational project provides a kind of emerging approach for impaired bone tissue restoration, with hydroxyapatite (hydroxyapatite, HA) for the calcium phosphate of representative pottery because of with the close bone alternate material that is widely used in of inorganic phase chemistry composition of bone, weak point is to be difficult to use at weight bearing area owing to its fragility and lower flexural strength, the higher body that is difficult to of the ceramic degree of crystallinity in calcining back is degraded, and the stress shielding of generation is to knitting and moulding very unfavorable.Therefore, the bioceramic of representative that at present commonly used with the hydroxyapatite is can only simply imitate the inorganic constituents of nature bone substrate, has limited it greatly in Clinical Application.
Type i collagen is the main organic principle of nature bone substrate, have excellent biological compatibility and biological degradability through suitably extracting the collagen of handling, just bring into use the fifties as far back as twentieth century, be widely used as soft tissue substitute and drug sustained release system thereafter.Collagen has inherent defective as bone graft substitute: mechanical strength is low, can not better satisfy the requirement of strength that bone renovating material need possess, and clinical operability is relatively poor.
Composite study obtains paying attention in recent years, the research report of existing synthetic Ca-P ceramic/collagen composite.Present most calcium phosphate/collagen complex is actually both mechanical impurities, normally will make with the collagen solution mixing behind agglomerating HA or other ceramic grindings, its weak point is can't form bonding closely between pottery and the collagen matrix, ceramic particle can only be loose branch in the collagen framework, can not solve the existing problem of bioceramic.In addition, need the effect through high temperature and high pressure in the Ca-P ceramic forming processes such as traditional hydroxyapatite usually, compacting, thermal sintering have further destroyed the degradation property of Ca-P ceramic.Collagen in the composite also can lose its inherent biological structure and function under violent condition such as High Temperature High Pressure.
Summary of the invention
The present invention has overcome the deficiencies in the prior art, and a kind of bionic-type composite three-dimensional porous bone tissue engineering scaffold material is provided, and this material is repaired impaired osseous tissue as bone alternate material.
The preparation method and the application thereof of above-mentioned bionic-type composite three-dimensional porous bone tissue engineering scaffold material have been the present invention also aims to provide.
The preparation method of composite three-dimensional porous bone tissue engineering scaffold material of the present invention comprises the steps:
(1) mixes: CaO-P
2O
5-SiO
2System biological activity glass nano-powder, type i collagen albumen, hyaluronic acid, Phosphatidylserine mix, and stir, and make mixed liquor;
(2) crosslinked: add buffer agent in above-mentioned mixed liquor, regulating pH value is 5～6, adds cross-linking agent 3～6mg/ml again and carries out crosslinking Treatment;
(3) mixed liquor that will obtain after step (2) crosslinking Treatment descended the Na of usefulness 0.1mol/l freezing 10～20 hours in-60～80 ℃
2HPO
4Solution soaking 1～3 hour, reuse washed with de-ionized water 30～50 minutes is cleaned after dewater vacuum drying;
The weight portion consumption of above-mentioned each component is as follows:
CaO-P
2O
5-SiO
2System biological activity glass nano-powder 50～80
Type i collagen protein 10～35
Hyaluronic acid 2～8
Phosphatidylserine 2～8
Described CaO-P
2O
5-SiO
2CaO accounts for 36%～16% weight, P in the system biological activity glass nano-powder
2O
5Account for 4% weight, SiO
260%～80% weight.
Preferred version is as follows:
In the step (2), buffer agent is ethylene sulfonic acid (MES) or acetic acid, and cross-linking agent is 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC), N-hydroxy-succinamide (NHS) or glutaraldehyde.
In the step (1), described CaO-P
2O
5-SiO
2System biological activity glass nano-powder can be prepared by following step:
(1) preparation microemulsion: adding octyl phenolic group polyoxyethylene ether (TritonX-100), cosurfactant and concentration are that the ammonium hydroxide aqueous solution or the concentration of 12.5% weight are the calcium nitrate aqueous solution of 0.6M in cyclohexane extraction, the microemulsion of preparation Ammonia and the microemulsion of calcium nitrate solution; In the microemulsion of Ammonia, each component mol ratio is cyclohexane extraction: TritonX-100: cosurfactant: ammonium hydroxide aqueous solution=30: 1: 5～10: 0.5～1.5; In the microemulsion of calcium nitrate solution, each component mol ratio is cyclohexane extraction: TritonX-100: cosurfactant: calcium nitrate aqueous solution=30: 1: 5～10: 0.5～1.5, described cosurfactant are one or more mixture in n-butyl alcohol, n-amyl alcohol, hexanol, the n-octyl alcohol;
(2) hydrolysis: add tetraethoxysilance (TEOS) and tricresyl phosphate second fat (TEP) in the microemulsion of the Ammonia that step (1) obtains hydrolysis takes place, hydrolysis time is 30～60 minutes, and each components by weight is tetraethoxysilance (TEOS): tricresyl phosphate second fat (TEP): the microemulsion of Ammonia=9～13: 1: 50～100;
(4) ageing: above-mentioned mixed liquor was at room temperature placed 3-4 days;
(5) demoulding: adding concentration in above-mentioned mixed liquor is the acetone soln of 70%-80% weight, flocculates, and isolates flocculated colloid, is the acetone soln of 70%-80% weight or dehydrated alcohol cleaning 3-4 time with concentration;
(6) drying: behind above-mentioned flocculated colloid vacuum drying, under 600 ℃ of-700 ℃ of temperature heat treatment 2-3 hour.
The composite three-dimensional porous bone tissue engineering scaffold material aperture of the present invention's preparation is 200 μ m～500 μ m, and porosity is 80%～90%.
The composite three-dimensional porous bone tissue engineering scaffold material of the present invention's preparation can be used and prepare the bone alternate material that is used to repair impaired osseous tissue.
The collagen protein that bionic-type composite three-dimensional porous bone tissue engineering scaffold material of the present invention uses, hyaluronic acid is the main organic principle of natural bone tissue, Phosphatidylserine is a kind of component of cell membrane, effect with modulation mineralising, bio-vitric is highly active nano-powder, therefore material of the present invention has good synosteosis power and cellular affinity, can impel implant to form firm biology with osseous tissue in a short time combines, can be used in the medical field and repair impaired osseous tissue, have very high biological activity and biocompatibility as bone alternate material.
The present invention compared with prior art has following advantage:
(1) material composition of the present invention and structure more approach natural bone tissue, have higher biological activity and biocompatibility.
(2) collagen protein, the hyaluronic acid of the present invention's use are the main organic principles of natural bone tissue, Phosphatidylserine is a kind of component of cell membrane, effect with modulation mineralising, bio-vitric is highly active nano-powder, therefore material of the present invention has good synosteosis power and cellular affinity, can impel implant to form firm biology with osseous tissue in a short time and combine.
(3) the present invention adopts bionic method, utilizes Freeze Drying Technique, has avoided the destruction of High Temperature High Pressure to material property, and has saved cost.
(4) the present invention can change the structure and the mechanical strength of timbering material by regulating the content and the technological parameter of each composition of timbering material.
Description of drawings
Fig. 1 is the sem photograph of the composite three-dimensional porous bone tissue engineering scaffold material of embodiment 1 preparation;
Fig. 2 is the sem photograph of the composite three-dimensional porous bone tissue engineering scaffold material of embodiment 2 preparations.
The specific embodiment
The invention will be further described below in conjunction with the specific embodiment, and the present invention is not limited to this.
(1) preparation CaO-P
2O
5-SiO
2System biological activity glass nano-powder
(1) preparation microemulsion organic formwork: in cyclohexane extraction, add octyl phenolic group polyoxyethylene ether (TritonX-100), cosurfactant and ammonium hydroxide aqueous solution (concentration 12.5%) or calcium nitrate aqueous solution (concentration 0.6M), the microemulsion of preparation Ammonia and the microemulsion of calcium nitrate solution;
(2) hydrolysis: add tetraethoxysilance (TEOS) and tricresyl phosphate second fat (TEP) in the microemulsion of Ammonia, hydrolysis takes place, hydrolysis time is 30～60 minutes, tetraethoxysilance (TEOS): tricresyl phosphate second fat (TEP): the weight ratio of ammonium hydroxide aqueous solution is 9: 1: 50;
(3) mix: the microemulsion of the calcium nitrate solution of step (1) configuration was joined in the microemulsion that step (2) obtains in 1: 1 by volume, stirred 60 minutes, obtain mixed liquor;
(4) ageing: above-mentioned mixed liquor was at room temperature placed 3 days;
(5) demoulding: in above-mentioned mixed liquor, add the acetone soln of 80% (concentration), flocculate, isolate flocculated colloid, clean 3 times with the acetone soln of 80% (concentration) or dehydrated alcohol;
(6) drying: behind above-mentioned flocculated colloid vacuum drying, heat treatment is 3 hours under 600 ℃ of temperature.
In the step (1), each component molar ratio range is cyclohexane extraction: TritonX-100 in the microemulsion of described calcium nitrate solution: cosurfactant: calcium nitrate aqueous solution (mol ratio)=30: 1: 6: 0.75, and each component molar ratio range is cyclohexane extraction: TritonX-100 in the microemulsion of described Ammonia: cosurfactant: ammonium hydroxide aqueous solution (mol ratio)=30: 1: 6: 0.75.Described cosurfactant hexanol.
(2) preparation bionic-type composite three-dimensional porous bone tissue engineering scaffold material
With CaO-P
2O
5-SiO
2System biological activity glass nano-powder 45～55g, type i collagen albumen 35～40g, hyaluronic acid 4～6g, Phosphatidylserine 4～6g mixes, the back that stirs adds buffer agent ethylene sulfonic acid (MES), and regulating pH value is 5～6, is that cross-linking agent carries out crosslinking Treatment with 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) of 3～6mg/ml, after the crosslinking Treatment in-60 ℃ of fridges freezing 20h, then lyophilization to fully the dehydration.Na with 0.1mol/l
2HPO
4Soak 1h, the reuse deionized water washes 30min repeatedly.Clean the back and dewater repeatedly with ethanol, dry under vacuum state again, the acquisition diameter is 6mm, the cylindric block of long 15mm.Pore diameter range is 185～235 μ m, and porosity ranges is 86～89%, and its form as shown in Figure 1.
Embodiment 2
(1) preparation CaO-P
2O
5-SiO
2System biological activity glass nano-powder
(1) preparation microemulsion organic formwork: in cyclohexane extraction, add octyl phenolic group polyoxyethylene ether (TritonX-100), cosurfactant and ammonium hydroxide aqueous solution (concentration 12.5%) or calcium nitrate aqueous solution (concentration 0.6M), the microemulsion of preparation Ammonia and the microemulsion of calcium nitrate solution;
(2) hydrolysis: add tetraethoxysilance (TEOS) and tricresyl phosphate second fat (TEP) in the microemulsion of Ammonia, hydrolysis takes place, hydrolysis time is 30 minutes, tetraethoxysilance (TEOS): tricresyl phosphate second fat (TEP): the weight ratio of ammonium hydroxide aqueous solution is 13: 1: 100;
(3) mix: the microemulsion of the calcium nitrate solution of step (1) configuration was joined in the microemulsion that step (2) obtains in 1: 1 by volume, stirred 80 minutes, obtain mixed liquor;
(4) ageing: above-mentioned mixed liquor was at room temperature placed 4 days;
(5) demoulding: in above-mentioned mixed liquor, add the acetone soln of 75% (concentration), flocculate, isolate flocculated colloid, clean 4 times with the acetone soln of 75% (concentration) or dehydrated alcohol;
(6) drying: behind above-mentioned flocculated colloid vacuum drying, heat treatment is 2 hours under 700 ℃ of temperature.
In the step (1), each component molar ratio range is cyclohexane extraction: TritonX-100 in the microemulsion of described calcium nitrate solution: cosurfactant: calcium nitrate aqueous solution (mol ratio)=30: 1: 9: 1.25, and each component molar ratio range is cyclohexane extraction: TritonX-100 in the microemulsion of described Ammonia: cosurfactant: ammonium hydroxide aqueous solution (mol ratio)=30: 1: 9: 1.25.Described cosurfactant is the mixture (mol ratio 1: 1) of hexanol, n-octyl alcohol, and its form as shown in Figure 2.
(2) preparation bionic-type composite three-dimensional porous bone tissue engineering scaffold material
With CaO-P
2O
5-SiO
2System biological activity glass nano-powder 55～65g, type i collagen protein 25～30g, hyaluronic acid 2～4g, Phosphatidylserine 2～4g mixes, the back that stirs adds buffer agent acetic acid, and regulating pH value is 5～6, is that cross-linking agent carries out crosslinking Treatment with the N-hydroxy-succinamide (NHS) of 3～6mg/ml, after the crosslinking Treatment in-80 ℃ of fridges freezing 10h, then lyophilization to fully the dehydration.Na with 0.1mol/l
2HPO
4Soak 1h, the reuse deionized water washes 30min repeatedly.Clean the back and dewater repeatedly with ethanol, dry under vacuum state again, the acquisition diameter is 5mm, the cylindric block of long 20mm.Pore diameter range is 165～205 μ m, and porosity ranges is 84～87%.
(1) preparation CaO-P
2O
5-SiO
2System biological activity glass nano-powder
(1) preparation microemulsion organic formwork: in cyclohexane extraction, add octyl phenolic group polyoxyethylene ether (TritonX-100), cosurfactant and ammonium hydroxide aqueous solution (concentration 12.5%) or calcium nitrate aqueous solution (concentration 0.6M), the microemulsion of preparation Ammonia and the microemulsion of calcium nitrate solution;
(2) hydrolysis: add tetraethoxysilance (TEOS) and tricresyl phosphate second fat (TEP) in the microemulsion of Ammonia, hydrolysis takes place, hydrolysis time is 30～60 minutes, tetraethoxysilance (TEOS): tricresyl phosphate second fat (TEP): the weight ratio of ammonium hydroxide aqueous solution is 9: 1: 50;
(3) mix: the microemulsion of the calcium nitrate solution of step (1) configuration was joined in the microemulsion that step (2) obtains in 1: 1 by volume, stirred 60 minutes, obtain mixed liquor;
(4) ageing: above-mentioned mixed liquor was at room temperature placed 3 days;
(5) demoulding: in above-mentioned mixed liquor, add the acetone soln of 70% (concentration), flocculate, isolate flocculated colloid, clean 4 times with the acetone soln of 70% (concentration) or dehydrated alcohol;
(6) drying: behind above-mentioned flocculated colloid vacuum drying, heat treatment is 3 hours under 600 ℃ of temperature.
In the step (1), each component molar ratio range is cyclohexane extraction: TritonX-100 in the microemulsion of described calcium nitrate solution: cosurfactant: calcium nitrate aqueous solution (mol ratio)=30: 1: 6: 1.5, and each component molar ratio range is cyclohexane extraction: TritonX-100 in the microemulsion of described Ammonia: cosurfactant: ammonium hydroxide aqueous solution (mol ratio)=30: 1: 6: 1.5.Described cosurfactant is a n-amyl alcohol.
(2) preparation bionic-type composite three-dimensional porous bone tissue engineering scaffold material
With CaO-P
2O
5-SiO
2System biological activity glass nano-powder 55～65g, type i collagen protein 25～30g, hyaluronic acid 2～4g, Phosphatidylserine 2～4g mixes, the back that stirs adds buffer agent acetic acid, and regulating pH value is 5～6, carries out crosslinking Treatment with the glutaraldehyde as cross linker of 3～6mg/ml, after the crosslinking Treatment in-80 ℃ of fridges freezing 10h, then lyophilization to fully the dehydration.Na with 0.1mol/l
2HPO
4Soak 1h, the reuse deionized water washes 30min repeatedly.Clean the back and dewater repeatedly with ethanol, dry under vacuum state again, the acquisition diameter is 5mm, the cylindric block of long 20mm.Pore diameter range is 165～205 μ m, and porosity ranges is 84～87%.
Claims (5)
1, a kind of preparation method of composite three-dimensional porous bone tissue engineering scaffold material is characterized in that comprising the steps:
(1) mixes: CaO-P
2O
5-SiO
2System biological activity glass nano-powder, type i collagen albumen, hyaluronic acid, Phosphatidylserine mix, and stir, and make mixed liquor;
(2) crosslinked: add buffer agent in above-mentioned mixed liquor, regulating pH value is 5～6, adds cross-linking agent 3～6mg/ml again and carries out crosslinking Treatment;
(3) mixed liquor that will obtain after step (2) crosslinking Treatment descended the Na of usefulness 0.1mol/l freezing 10～20 hours in-60～80 ℃
2HPO
4Solution soaking 1～3 hour, reuse washed with de-ionized water 30～50 minutes is cleaned after dewater vacuum drying;
The weight portion consumption of above-mentioned each component is as follows:
CaO-P
2O
5-SiO
2System biological activity glass nano-powder 50～80
Type i collagen protein 10～35
Hyaluronic acid 2～8
Phosphatidylserine 2～8
Described CaO-P
2O
5-SiO
2CaO accounts for 36%～16% weight, P in the system biological activity glass nano-powder
2O
5Account for 4% weight, SiO
260%～80% weight.
2, method according to claim 1, it is characterized in that in the step (2), buffer agent is ethylene sulfonic acid (MES) or acetic acid, and cross-linking agent is 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC), N-hydroxy-succinamide (NHS) or glutaraldehyde.
3, method according to claim 1 and 2 is characterized in that in the step (1) described CaO-P
2O
5-SiO
2System biological activity glass nano-powder is prepared by following step:
(1) preparation microemulsion: adding octyl phenolic group polyoxyethylene ether (TritonX-100), cosurfactant and concentration are that the ammonium hydroxide aqueous solution or the concentration of 12.5% weight are the calcium nitrate aqueous solution of 0.6M in cyclohexane extraction, the microemulsion of preparation Ammonia and the microemulsion of calcium nitrate solution; In the microemulsion of Ammonia, each component mol ratio is cyclohexane extraction: TritonX-100: cosurfactant: ammonium hydroxide aqueous solution=30: 1: 5～10: 0.5～1.5; In the microemulsion of calcium nitrate solution, each component mol ratio is cyclohexane extraction: TritonX-100: cosurfactant: calcium nitrate aqueous solution=30: 1: 5～10: 0.5～1.5, described cosurfactant are one or more mixture in n-butyl alcohol, n-amyl alcohol, hexanol, the n-octyl alcohol;
(2) hydrolysis: add tetraethoxysilance (TEOS) and tricresyl phosphate second fat (TEP) in the microemulsion of the Ammonia that step (1) obtains hydrolysis takes place, hydrolysis time is 30～60 minutes, and each components by weight is tetraethoxysilance (TEOS): tricresyl phosphate second fat (TEP): the microemulsion of Ammonia=9～13: 1: 50～100;
(3) mix: the microemulsion of the calcium nitrate solution that step (1) was obtained in 1: 1 by volume joins in the hydrolyzed solution that step (2) obtains, and stirs 60-80 minute, obtains mixed liquor;
(4) ageing: above-mentioned mixed liquor was at room temperature placed 3-4 days;
(5) demoulding: adding concentration in above-mentioned mixed liquor is the acetone soln of 70%-80% weight, flocculates, and isolates flocculated colloid, is the acetone soln of 70%-80% weight or dehydrated alcohol cleaning 3-4 time with concentration;
(6) drying: behind above-mentioned flocculated colloid vacuum drying, under 600 ℃ of-700 ℃ of temperature heat treatment 2-3 hour.
4, the composite three-dimensional porous bone tissue engineering scaffold material of the described method preparation of one of claim 1-3 is characterized in that described material aperture is 200 μ m～500 μ m, and porosity is 80%～90%.
5, the described material of one of claim 1-3 is used for repairing the application of the bone alternate material of impaired osseous tissue in preparation.
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| CN102580148A (en) * | 2012-03-12 | 2012-07-18 | 华南理工大学 | Preparation method of composite stent for repairing bone defect |
| CN101690830B (en) * | 2009-09-29 | 2012-12-05 | 中国人民解放军第三军医大学第一附属医院 | Preparation method of bionic cartilage extracellular matrix for tissue engineering |
| CN102973982A (en) * | 2011-09-07 | 2013-03-20 | 财团法人工业技术研究院 | Biomedical material applied to soft and hard tissue repair and regeneration |
| CN101601869B (en) * | 2009-06-23 | 2013-04-10 | 华南理工大学 | Method for preparing collagen/bioglass/hyaluronic acid tissue repairing materials |
| CN107308499A (en) * | 2017-04-19 | 2017-11-03 | 上海师范大学 | Nanometer biological glass/polymer three-dimensional porous material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9717433D0 (en) * | 1997-08-19 | 1997-10-22 | Univ Nottingham | Biodegradable composites |
| WO2002087647A1 (en) * | 2001-04-26 | 2002-11-07 | Eija Pirhonen | Bone grafting materials |
| AU2002358639A1 (en) * | 2001-12-10 | 2003-06-23 | Tech-Medical S.R.L. | Biocompatible composite material with an osteotropic action |
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2006
- 2006-04-21 CN CNB2006100351075A patent/CN100356992C/en not_active Expired - Fee Related
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| CN102973982A (en) * | 2011-09-07 | 2013-03-20 | 财团法人工业技术研究院 | Biomedical material applied to soft and hard tissue repair and regeneration |
| CN102973982B (en) * | 2011-09-07 | 2014-12-10 | 财团法人工业技术研究院 | Biomedical material applied to soft and hard tissue repair and regeneration |
| CN102580148A (en) * | 2012-03-12 | 2012-07-18 | 华南理工大学 | Preparation method of composite stent for repairing bone defect |
| CN107308499A (en) * | 2017-04-19 | 2017-11-03 | 上海师范大学 | Nanometer biological glass/polymer three-dimensional porous material and its preparation method and application |
| CN108245711A (en) * | 2018-02-26 | 2018-07-06 | 王由 | A kind of collagen compound 45S5 bioactivity glass and its preparation method and application |
| CN109364307A (en) * | 2018-10-15 | 2019-02-22 | 福建工程学院 | A kind of gradient porous bone holder material and preparation method thereof |
| CN110124110A (en) * | 2019-06-13 | 2019-08-16 | 北京大学口腔医学院 | A kind of shaping bone renovating material and preparation method thereof |
| CN112853623A (en) * | 2021-01-07 | 2021-05-28 | 昆明理工大学 | Preparation method of electrospun kaolinite reinforced natural polysaccharide porous fiber membrane |
| CN112853623B (en) * | 2021-01-07 | 2023-08-25 | 昆明理工大学 | Preparation method of electrostatic spinning kaolinite reinforced natural polysaccharide porous fiber membrane |
| CN114588313A (en) * | 2022-04-13 | 2022-06-07 | 北京纳通医疗科技控股有限公司 | Novel collagen and bioactive ceramic composite bone grafting material and preparation method thereof |
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