CN100584390C - Material for bone tissue engineering scaffold - Google Patents
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- CN100584390C CN100584390C CN200610045990A CN200610045990A CN100584390C CN 100584390 C CN100584390 C CN 100584390C CN 200610045990 A CN200610045990 A CN 200610045990A CN 200610045990 A CN200610045990 A CN 200610045990A CN 100584390 C CN100584390 C CN 100584390C
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Abstract
The present invention relates to biological material technology, and is especially porous magnesium, magnesium alloy and composite magnesium material used as high strength biomedicine rack material for human body hard tissue defection and its preparation process. The porous magnesium, magnesium alloy and composite magnesium material used in bone tissue engineering rack has porosity of 5-99 % and pore diameter of 50-900 microns. Owing to easy degradation and absorption of magnesium inside body, the bone tissue engineering rack of porous magnesium, magnesium alloy and composite magnesium material has excellent mechanical performance and excellent biocompatibility and can provide 3D space for cell to grow.
Description
Technical field
The present invention relates to technical field of biological materials, be specially adapted to the damaged biomedical engineering timbering material technical field of human body hard tissue; Be specially porous metals magnesium, magnesium alloy and magnesium base composite material as bone tissue engineering stent material and preparation method thereof.
Background technology
At present, more to the research of tissue engineering bracket material, mainly comprise macromolecular material, bioceramic material and composite etc.Wherein the macromolecular material class comprises PLA, PGA and PLA/PGA copolymer etc. again, research is more at present, be U.S. FDA approved listing and be used for clinical biodegradable medical macromolecular material to have excellent biological compatibility, degradability and absorbability.Its shortcoming is that hydrophilic is relatively poor, and the acid product that the degraded back produces can reduce the pH value around the polymer, the mechanical strength deficiency, and the mechanical strength loss is too fast in degradation process, can not fully play the effect of support during bone tissue restoration.The bioceramic class then mainly comprises hydroxyapatite and tricalcium phosphate etc.Hydroxyapatite has the inorganic constituents identical with skeleton, has excellent biological compatibility, and implantable bone broken ends of fractured bone place easily forms synostosis, can be processed into multi-pore structure, is beneficial to that histiocyte is grown into and the discrepancy of metabolite and nutrient substance.Shortcoming is that fragility is big, and pliability is not enough, the degraded difficulty.Tricalcium phosphate has excellent biological compatibility and bone conductibility.Its shortcoming is that fragility is big, and degradation rate is too fast, and can not change degradation rate according to the needs of cell, does not therefore now also have real medical practical value.At present, also a lot of to the used in tissue engineering composite study, mainly be for overcome homogenous material the defective that can't overcome, improve the combination property of material, mainly concentrate on compound between macromolecular material and the bioceramic material.
Metal material is considered to have biological stability all the time, does not possess the degradable absorbent properties in vivo, thereby is not subjected to the attention of researcher in the field of tissue engineering technology.And the corrosion electrochemistry reaction because it has higher negative electrode current potential, can take place with water in the magnesium in the metal material (Mg), generates water soluble and material absorbed by the body.Simultaneously, magnesium belongs to macroelement in human body, and its content accounts for the 4th in all elements in vivo, and the human body metabolism is played important effect.Body weight is the adult of 70kg, and its intravital content of magnesium is about 1mol, and half is distributed in the osseous tissue approximately, thereby magnesium also has excellent biological compatibility.Porous magnesium can provide the three dimensional growth space to cell as a kind of degradable biological (organizational project) material, itself biologically active, but the growing into of inducing cell differentiation, growth and blood vessel.In the process of its degraded and absorbed, the cell of plantation continues propagation, breeding, forms new respective organization with original specific function and form and organ, to reach the purpose of repairing wound and rebuilding function, can be used as tissue engineering bracket material.
It should be noted that magnesium has the mechanical property that is far superior to macromolecular material and bioceramic material.According to bibliographical information, the porous magnesium of powder metallurgic method preparation, its intensity can reach 17MPa, surpasses existing macromolecule
(undercapacity is to play the support effect), bioceramic material (bending strength 4.4MPa) and the composite of the two (＜15MPa) intensity.
Summary of the invention
The present invention is intended to solve the strength problem of bone tissue engineering stent material, proposed a kind of metal structure engineering scaffold material-porous magnesium and alloy and composite and preparation method thereof, porous metals magnesium, magnesium alloy and magnesium base composite material have been applied to the bone tissue engineering scaffold field.
Technical scheme of the present invention is:
Magnesium metal, magnesium alloy and magnesium base composite material are prepared into loose structure, are applied to the tissue engineering bracket field.Described magnesium metal is pure magnesium.Magnesium alloy comprises: existing magnesium alloy, and as Mg-Mn, Mg-Al-Zn, Mg-Al-Mn, Mg-Al-Si, Mg-Al-RE, Mg-Al-Ca, Mg-Al-Ca-RE, Mg-Al-Sr, Mg-Zn-Zr, Mg-Zn-Al, Mg-Zn-Al-Ca, Mg-Zn-Mn, Mg-RE-Zr, Mg-RE, Mg-RE-Mn, magnesium alloys such as Mg-RE-Zn system; And the new magnesium alloy system that designs in order to improve the magnesium alloy performance.Magnesium base composite material comprises that with pure magnesium or magnesium alloy be main component, the composite that is composited with other materials (as macromolecular material, hydroxyapatite, calcium phosphate biological ceramic material, bio-vitric, biomedical metal material etc.) in order to improve its performance.
The preparation method of described porous material comprises that powder metallurgic method, melt solidifying method, metaliding, self propagating high temperature synthesize, corrode port-creating method, solid-state sintering, weave, welding, bonding etc.
The preparation method of described composite comprises: powder metallurgic method, solid dispersion method, spray deposition, liquid infiltration, in-situ compositing etc.
Porous metals magnesium disclosed in this invention, magnesium alloy and magnesium base composite material, its porosity are 5-99%, and the aperture is 50-900 μ m.The character of utilizing magnesium easily to be degraded and absorbed in vivo, porous magnesium of preparing and alloy thereof, composite have good mechanical performance, biocompatibility, and compressive strength is 10MPa-100MPa, and provides the three dimensional growth space for cell.
The metal porous tissue engineering bracket material of the present invention can be handled on the surface, to control its degradation speed, improves biocompatibility.Surface treatment method comprises alkali treatment, alkali treatment and subsequent heat treatment, surface preparation bioactivity coatings, thermal spraying, surface laser cladding, chemical composition coating, anodic oxidation, plasma micro-arc oxidation, surperficial infiltration layer processing, electroplating surface, Crow face coat and synergism coat etc. change.Described bone tissue engineering stent material carries out the surface layer that obtains after the surface treatment, comprise: hydroxyapatite layer, the calcium phosphate layer has the polymeric coating layer of good biocompatibility, carry and discharge polymeric coating layer of somatomedin etc., its surface layer thickness is 1 μ m-800 μ m.The coating that is generated can make the degradation speed of described material reduce, thereby reduces the rate of release of the hydrogen that the degraded because of magnesium produces, and helps the adhesion of cell at material surface.Simultaneously, the surface layer biologically active effect that is generated can increase the adhesion of cell at material surface, and helps growth, the differentiation of cell.
Described porous material is the implant damage position directly, also can cultivate through cell in vitro, at the required cell of surface adhesion, is implanted to damaged part then.After described porous material implanted, following reaction took place under humoral effect:
Mg+H
2O＝MgO+H
2
Mg
2++H
2O＝MgO+2H
-
Mg＝Mg
2++2e
Final generation material absorbed by the body, its surface adhesion cell and cells in vivo in the loose structure of progressively growing into, along with the degraded of porous support materials, finally reach the purpose of tissue reconstruction by growth and breeding.
The invention has the beneficial effects as follows:
1, the present invention proposes a kind of metal structure engineering scaffold material-porous magnesium and alloy and composite.Metal material is applied to the bone tissue engineering scaffold field, the character of utilizing magnesium easily to be degraded and absorbed in vivo, porous magnesium of preparing and alloy thereof, composite have good mechanical performance, biocompatibility, and provide the three dimensional growth space for cell.
2, porous metals magnesium, magnesium alloy and magnesium base composite material are applied to the bone tissue engineering scaffold field, have excellent biological compatibility.The corrosion electrochemistry reaction because it has higher negative electrode current potential, can take place with water in the magnesium in the metal material (Mg), generates water soluble and material absorbed by the body.Simultaneously, magnesium belongs to macroelement in human body, and its content accounts for the 4th in all elements in vivo, and the human body metabolism is played important effect.Body weight is the adult of 70kg, and its intravital content of magnesium is about 1mol, and half is distributed in the osseous tissue approximately, thereby magnesium also has excellent biological compatibility.
3, porous magnesium can provide the three dimensional growth space to cell as a kind of degradable biological (organizational project) material, itself biologically active, but the growing into of inducing cell differentiation, growth and blood vessel.In the process of its degraded and absorbed, the cell of plantation continues propagation, breeding, forms new respective organization with original specific function and form and organ, to reach the purpose of repairing wound and rebuilding function, can be used as tissue engineering bracket material.
4, porous metals magnesium, magnesium alloy and magnesium base composite material are applied to the bone tissue engineering scaffold field, magnesium has the mechanical property that is far superior to macromolecular material and bioceramic material.
Description of drawings
Fig. 1 carries out the rectangular histogram of In vitro culture for porous magnesium alloy material among the embodiment 3 with osteoblast.Wherein, abscissa and osteoblast incubation time (d, day); Vertical coordinate is represented absorbance.
The specific embodiment
Embodiment 1
Adopting powder metallurgy process, is that the carbamide of 200-500 μ m is pore creating material with the particle diameter, fully mixes with magnesium powder (particle diameter is 100 μ m), and die cast under 100MPa and the room temperature is at Ar
2Protection is removed pore creating material in 473K, then 10 down
-8Sintering is prepared the porous magnesium material under Pa, the 773K, and the aperture is 250 μ m, and porosity is 35%, and recording its Young's modulus is 1.8GPa, and compressive strength is 17MPa.The Young's modulus and the compressive strength of people's bone are respectively 0.01-2GPa, 0.2-80MPa.This shows that the Young's modulus of prepared porous magnesium and compressive strength all in the required scope of people's bone, can be used as bone tissue engineering stent material.
Embodiment 2
The porous magnesium material that embodiment 1 is prepared is put into 37 ℃ simulated body fluid, corrodes degradation experiment.Regularly take out sample, utilize weight method, study its degraded situation.The result shows that porous magnesium is degraded gradually under the effect of simulated body fluid, and its degradation speed is about 0.001mm/.Hence one can see that, and the porous magnesium material can be degraded in human body, is finally absorbed fully by human body, is applied to tissue engineering bracket material, can be the cell growth space is provided.
Embodiment 3
Adopt the prepared porous AZ31 magnesium alloy materials of seepage flow casting, the aperture is 400 μ m, and porosity is 50%, and compressive strength is 20MPa, through behind the Different Alkali heat treatment (respectively at saturated NaHCO
3With saturated NaHPO
4In soak 3h, and under 773K heat treatment 10h), with the osteoblast In vitro culture, respectively cultivation back 1 day and 2 days, with mtt assay test sample surface cell adhesion amount (representing), as a comparison with blank group cell growing state with absorbance.Result such as Fig. 1.
As seen from Figure 1, cell can adhere at prepared porous magnesium material surface.Find that with the contrast of blank group the porous magnesium material does not only have the normal growth of pair cell to produce destruction, and helps the growth of cell through after the surface treatment, blank group cell quantity increases to some extent.This shows that prepared porous magnesium alloy material has excellent biological compatibility through after the surface treatment, cell can be realized adhesion, growth etc.
Adopt the corrosion port-creating method to prepare porous AZ91 magnesium alloy materials, the aperture is 300 μ m, and porosity is 45%, and compressive strength is 22MPa, and by sputter, in its surface preparation calcium phosphate coating, coating layer thickness is 20 μ m.To prepare sample and implant in the mice Thigh bone tissue, after 10 weeks, section and dyeing are done in sampling, observe and implant sample surrounding tissue upgrowth situation.Found that around sample, have osseous tissue to generate.
Embodiment 5
Adopt the self propagating high temperature synthetic method to prepare porous WE2 magnesium alloy, the aperture is 500 μ m, and porosity is 30%, and compressive strength is 19MPa, and by sol-gel process, at its surface preparation hydroxyapatite coating layer, coating layer thickness is 18 μ m.To prepare sample and implant in the mice Thigh bone tissue, after 12 weeks, section and dyeing are done in sampling, observe and implant sample surrounding tissue upgrowth situation.Found that around sample, have osseous tissue to generate.
Embodiment 6
Adopt magnesium fibrage to become the porous magnesium structure, the aperture is 500 μ m, and porosity is 60%, and compressive strength is 25MPa, through being prepared into required form after the heat treatment 12h under the 773K, it is carried out anodization.Material after handling was soaked in simulated body fluid 1 day, analyze surface composition, have calcium phosphate to generate, show that material surface has the biological action that is suitable for the osseous tissue growth.
Embodiment 7
Adopt metaliding to prepare the porous magnesium material, the aperture is 460 μ m, porosity is 38%, and compressive strength is 20MPa, utilizes dip coating, porous magnesium is dipped in 0.5h in the tetrahydrofuran solution of 5% (w/w) polylactic acid-cell growth factor, from solution, lift out, and, go out the polylactic acid coating in the porous magnesium surface preparation through drying at room temperature 24h, and in the polylactic acid coating, carrying cell growth factor, coating layer thickness is 10 μ m.Prepared material was carried out cell culture 1 day external, implant then in the mice body, polymeric coating layer inner cell somatomedin discharges in body, promotes the continuous Growth and Differentiation of adherent cell of material surface and mice autologous tissue cell.
Embodiment 8
Polylactic acid is added into 30% volume fraction (weight ratio of magnesium fiber and pore creating material is 1: 1 in the mixture of magnesium metal fiber and pore creating material, the magnesium fiber dimensious is: diameter is 50um, draw ratio is 20: 1, pore creating material is an ammonium bicarbonate, and its granularity is 300 μ m), and stir, (pressure is 100MPa to adopt mold pressing, time is 30min) compound preparation in bulk, remove pore creating material down through 373K, make composite porous.The aperture is 300 μ m, and porosity is 30%, and compressive strength is 30MPa, will prepare sample and implant in the mice Thigh bone tissue, and after 12 weeks, section and dyeing are done in sampling, observe and implant sample surrounding tissue upgrowth situation.Found that around sample, have osseous tissue to generate.
Claims (2)
1, a kind of bone tissue engineering stent material is characterized in that: described bone tissue engineering stent material is porous metals magnesium alloy or magnesium base composite material; Described porous metals magnesium alloy or magnesium base composite material, its porosity are 5-99%, and the aperture is 50-900 μ m; Above-mentioned material is applied to the bone tissue engineering scaffold field, the character of utilizing magnesium easily to be degraded and absorbed in vivo, porous magnesium alloy or the magnesium base composite material prepared have good mechanical performance, biocompatibility, and compressive strength is 10MPa-100MPa, and provide the three dimensional growth space for cell;
Magnesium alloy is meant Mg-Mn, Mg-Al-Zn, Mg-Al-Mn, Mg-Al-Si, Mg-Al-RE, Mg-Al-Ca, Mg-Al-Ca-RE, Mg-Al-Sr, Mg-Zn-Zr, Mg-Zn-Al, Mg-Zn-Al-Ca, Mg-Zn-Mn, Mg-RE-Zr, Mg-RE, Mg-RE-Mn or Mg-RE-Zn magnesium alloy system;
Magnesium base composite material is meant that with pure magnesium or above-mentioned magnesium alloy be main component, the composite that is composited with macromolecular material, hydroxyapatite, calcium phosphate biological ceramic material or bio-vitric.
2, bone tissue engineering stent material as claimed in claim 1, it is characterized in that: described bone tissue engineering stent material also has for controlling its degradation speed, improving biocompatibility and carry out the surface layer that obtains after the surface treatment, be meant: hydroxyapatite layer, calcium phosphate layer, have the polymeric coating layer of good biocompatibility or carry and discharge the polymeric coating layer of somatomedin, its surface layer thickness is 1 μ m-800 μ m.
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|---|---|---|---|
| CN200610045990A CN100584390C (en) | 2006-03-08 | 2006-03-08 | Material for bone tissue engineering scaffold |
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|---|---|---|---|
| CN200610045990A CN100584390C (en) | 2006-03-08 | 2006-03-08 | Material for bone tissue engineering scaffold |
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| CN100584390C true CN100584390C (en) | 2010-01-27 |
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Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101461964B (en) * | 2007-12-19 | 2013-03-13 | 中国科学院金属研究所 | Bioactivity surface modification method of biological medical degradable magnesium alloy |
| US8172908B2 (en) * | 2008-01-17 | 2012-05-08 | The University Of Hong Kong | Implant for tissue engineering |
| KR101289122B1 (en) * | 2008-03-18 | 2013-07-23 | 한국보건산업진흥원 | COMPLEX IMPLANTS INFILTERATED WITH BIODEGRADABLE Mg(ALLOYS) INSIDE POROUS STRUCTURAL MATERIALS AND METHOD FOR MANUFACTURING THE SAME |
| US20110166251A1 (en) * | 2009-07-14 | 2011-07-07 | Karen Hoi Man Wong | Polymeric based and surface treated metallic hybrid materials and fabrication methods thereof |
| CN101797400A (en) * | 2010-04-12 | 2010-08-11 | 李扬德 | Porous degradable magnesium alloy bone scaffold material containing HA nano-powder |
| CN102648986A (en) * | 2011-02-24 | 2012-08-29 | 中国科学院金属研究所 | Application of magnesium-based material used as material for adjuvant therapy of osteoporosis |
| CN102206819B (en) * | 2011-04-07 | 2013-05-01 | 上海交通大学 | Method for preparing bioactive calcium phosphate coating on magnesium alloy surface for endosseous implant |
| CN102397589A (en) * | 2011-11-15 | 2012-04-04 | 东南大学 | Bio-absorbable medical compound material and preparation method thereof |
| CN102397588B (en) * | 2011-11-15 | 2014-02-12 | 东南大学 | Porous magnesium alloy three-dimensional reinforced absorbable medical compound material and preparation method thereof |
| CN102552993B (en) * | 2011-11-15 | 2014-02-12 | 东南大学 | Magnesium alloy sheet-reinforced absorbable intrabony fixing composite material and preparation method thereof |
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