CN100341588C - Method for preparing porous collagen composite nano hydroox apatite artificial bone - Google Patents
Method for preparing porous collagen composite nano hydroox apatite artificial bone Download PDFInfo
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- CN100341588C CN100341588C CNB2005101079420A CN200510107942A CN100341588C CN 100341588 C CN100341588 C CN 100341588C CN B2005101079420 A CNB2005101079420 A CN B2005101079420A CN 200510107942 A CN200510107942 A CN 200510107942A CN 100341588 C CN100341588 C CN 100341588C
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Abstract
The present invention relates to a preparation method of porous collagen composite nano hydroxyapatite artificial bones, which belongs to the scientific field of biological engineering and materials. The present invention comprises the following steps: firstly, preparing nano diameter granule hydroxyapatite; then preparing collagen solution and adding the collagen solution into hydroxyapatite powder; finally, freezing and drying the mixed pasty material of the hydroxyapatite powder and the collagen to obtain porous collagen composite nano hydroxyapatite artificial bones. The components of the artificial bones prepared by the method are similar to the components of natural bones, and the artificial bones have the advantages of strong conduction effect, high porosity, good porosity communication, etc., and the artificial bones are favorable to the growth of bone cells. The nano hydroxyapatite with low crystallinity is favorable to the degradation absorption of artificial bones and the rebuilding of autogenous bones; the artificial bones have good biocompatibility, the pH value is neutral, no acid reaction occurs during the degradation process, non-infective inflammation or rejection is eliminated, collagen in the artificial bones continuously vacates space for bone cells in the process of the degradation absorption by a body, and a good osteology surgery implantation material is provided for the clinical osteology surgery.
Description
Technical field
The present invention relates to a kind of preparation method of porous collagen composite nano hydroox apatite artificial bone, be used for repairing bone defect and bone splits, belong to biological engineering and materials science field.
Background technology
It is the graft that has the call that is only second to blood transfusion that skeleton is transplanted, and is the common clinical example because accident or disease cause bone damaged.Repair materials commonly used at present has from body bone, allograph bone and synthetic material, and these materials all there being deficiency in varying degrees, can not meet clinical needs.Though do not have immunological rejection as autologous bone transplanting, repairing effect is good, and it is very limited to draw materials, and causes for the bone in district damaged; Homogeneous allogenic bone transplantation causes immunological rejection easily, and repairing effect is poor, and the danger of infectious disease toxicity disease is arranged, and the cost height of taking a sample, handling, storing, and considerable restraint is received in its application; Synthetic material all is non-degradable material as poly-polymethacrylic acid methyl ester, sulphurated siliastic etc., can not the repair deficiency district.At present the emphasis of research be devoted to find out have good physicochemical property, biological characteristics biomaterial as bone graft.Utilize the calcium phosphate material as the history of bone grafting material through last 100 years, still have wide practical use at present, but traditional calcium phosphate material such as hydroxyapatite (HA), tricalcium phosphate atresias such as (TCP) or aperture are little, the hole traffic does not reach the ingrown structural requirement of osteon, and clinical practice is subjected to certain limitation.The bioactivity calcium phosphate pottery has excellent biological compatibility, bone conductibility, osteoinductive, thereby is widely used in orthopaedics and the reparation of dentistry bone.But because hydroxyapatite has shortcomings such as the inherent fragility of ceramic material is big, toughness is low, the damaged reparation of position bone can not be used to bear a heavy burden.Though coral hydroxyapatite commonly used clinically at present has hole traffic preferably and enough mechanical strengths, but still has shortcomings such as fragility is big, toughness is low, degradability is poor, repair ability is weak, can only be as the packing material of orthopaedics.
Organic component in the osseous tissue is mainly hydroxyapatite (HA) and collagen.Biological hydroxyapatite belongs to bioactive ceramics, and it contains and can carry out elements such as metathetical calcium, phosphorus by human body normal metabolic approach in forming, also contain can with the hydroxyl (OH) group of tissue generation bonding.HA has the chemical analysis similar to osseous tissue, crystal structure, coefficient of friction, proportion, heat conductivity and absolute intensity.Collagen has the function of excellent biological compatibility, reduced immunogenicity, promotion cell adhesion, growth, breeding, thereby as a kind of clinical biomaterial many biomedical applications is arranged.In order to imitate the The Nomenclature Composition and Structure of Complexes of nature bone, many calcium phosphate ceramic/collagen composite materials that bone is repaired that are used for have been developed.Yet agglomerating high-crystallinity calcium phosphate ceramic granule is degraded and absorbed hardly in vivo and rebuilds in the composite, thereby, influenced the bone repair ability of composite.Nature bone is made up of the nanometer hydroxyapatite of low-crystallinity and collagen, therefore composition, structure and characteristic in order to imitate nature bone, and preparation nano hydroxyapatite/collagen compound support frame material is one of focus of biomaterial research.It is reported, the high-molecular bone compounded material of nanometer phase calcium-phosphorus salt collagen of Tsing-Hua University's development has bone repairing effect preferably, but from its production technology and product, have still that mechanical strength is not enough, fragility is big, toughness is low, porosity is low, connect pore structure defectives such as (the hole traffic are poor) in not having.In connect pore structure help the growing into blood vessel in material deep and communicate with each other, with the nutrition supply of the material deep tissue that guarantees to grow into.Except that the combining of material and recipient bed, loose structure is growing into, form the mechanicalness internal lock, strengthening the combination of embedded material, for maintenance has been created condition of body osseous tissue.Porous surface is beneficial to blood vessel and soft tissue is grown into, and to interconnect be the ingrown prerequisite of bone in the aperture, interconnect and help that cell and body fluid flow in vivo, tissue metabolism, sclerotin is grown into, and micropore and a large amount of external callus are common to constitute firm " biological fixing ", micropore constitutes huge surface area, for bone apposition provides good substrate.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of porous collagen composite nano hydroox apatite artificial bone, animal collagen is combined with the hydroxyapatite of nanometer particle size, lyophilization is made high porosity, is had the cmposite artificial bone of good hole traffic, to meet clinical needs better.
The preparation method of the porous collagen composite nano hydroox apatite artificial bone that the present invention proposes may further comprise the steps:
(1) preparation nanometer footpath grain hydroxyapatite:
To contain Ca
2+Chemical compound be dissolved in the deionized water, the preparation Ca
2+Concentration is the solution of 0.2～0.8mol/L, adds while stirring and contains PO
4 3-Chemical compound, the mol ratio that makes Ca and P is 1～1.67, adding NaOH solution to pH value then while stirring is 7～8, the sucking filtration collecting precipitation, with deionized water wash 3 times, sucking filtration, filter cake placed 90～150 ℃ of following dryings of drying baker 48～96 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding;
(2) preparation collagen solution:
Get the tendon of the leg of pork, bracket or horse lower limb, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon after pulverizing is soaked in 0.1% the phosphoric acid solution, and the adding pepsin, making the pepsin in every milliliter of phosphoric acid solution is 10～15 international active units, fully mixing, at room temperature soaked 50～100 hours, with the soak filter cleaner, obtain collagen solution, concentration is 1～1.2 * 10
-2G/ml;
(3) in the hydroxy apatite powder of above-mentioned preparation, add collagen solution, add 0.25～0.3g hydroxy apatite powder in every milliliter of collagen solution, abundant stirring and evenly mixing, transferring to pH value with NaOH solution is 7～8;
(4) the mixing paste lyophilization with above-mentioned hydroxyapatite and collagen becomes porous collagen composite nano hydroox apatite artificial bone.
With the porous collagen composite nano hydroox apatite artificial bone of method preparation of the present invention, composition with similar nature bone; The nanometer hydroxyapatite of low-crystallinity wherein helps the degraded and absorbed of artificial bone and from the reconstruction of body bone; Conduction is strong; The porosity height of artificial bone, the hole traffic is good, helps the osteocyte growth; The good biocompatibility of this artificial bone, pH value is neutral, does not have acid reaction in the degradation process, therefore can not cause postoperative non-infectious inflammation or rejection, and collagen wherein is the continuous vacating space of growing into of osteocyte in by the process of body degraded and absorbed.
The specific embodiment
The preparation method of the porous collagen composite nano hydroox apatite artificial bone that the present invention proposes in the preparation of nanometer footpath grain hydroxyapatite, will contain Ca
2+Chemical compound be dissolved in the deionized water, be made into the Ca of 0.2～0.8mol/L
2+Solution adds while stirring and contains phosphonium ion (PO
4 3-) chemical compound, the mol ratio that makes Ca/P is 1～1.67.Adding NaOH solution to pH value then while stirring is 7～8, begins precipitation to occur when pH value is 6, and along with the rising of pH value, precipitation is more and more, and solution is more and more muddy, treats that pH value rises to 7～8 and promptly stops to splash into of NaOH.The sucking filtration collecting precipitation is used deionized water wash 3 times, and sucking filtration, filter cake place 90～150 ℃ in drying baker dry down, obtain the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding.The above-mentioned Ca that contains
2+Chemical compound comprise calcium chloride (CaCl
2), lime nitrate (Ca (NO
3)
24H
2O) etc.; Above-mentioned phosphonium ion (the PO that contains
4 3-) chemical compound comprise DAP ((NH
4)
2HPO
4), sodium hydrogen phosphate (Na
2HPO
4), phosphoric acid (H
3PO
4) etc.The preparation process of collagen solution is, get the tendon of the leg of pork, bracket or horse lower limb, remove the oils and fats on tendon surface with the liquid detergent washing after careful rejecting fat and the muscular tissue, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, the tendon after pulverizing is soaked in 0.1% phosphoric acid (analytical pure) solution, and adds pepsin (10～15U/ml), abundant mixing, at room temperature soaked 50～100 hours, with the soak filter cleaner, the concentration requirement of filtrate reaches 1～1.2 * 10
-2G/ml.In hydroxy apatite powder, add collagen solution (adding 0.25～0.3g hydroxyapatite dry powder in every ml collagen solution) then, abundant stirring and evenly mixing, transferring to pH value with NaOH solution is 7～8.The mixing paste precipitate lyophilizing of hydroxyapatite and collagen is become porous collagen composite nano hydroox apatite artificial bone.Cryodesiccated temperature control flow is: reduced to-40 ℃ through 3 hours from room temperature, be incubated 2 hours, freeze real back evacuation distillation 10 hours, be warming up to 0 ℃ through 4 hours, per hour heat up 10 ℃, 0 ℃ is incubated 4 hours, is warming up to 15 ℃ through 1 hour, and 15 ℃ are incubated 1 hour, be warming up to 25 ℃ through 1 hour, and then be warming up to 35 ℃ through 1 hour, be incubated 5 hours, go vacuum.
Introduce embodiments of the invention below:
Embodiment one
(1) preparation of nanometer particle size hydroxyapatite
Take by weighing 44g CaCl
2.2H
2O is dissolved in the 1000ml deionized water, stirs it is fully dissolved, and adds 17mlH while stirring
3PO
4, NaOH solution to the pH value that adds 1mol/L then while stirring is 7.5.Sucking filtration collecting precipitation, usefulness deionized water wash 3 times, sucking filtration, filter cake placed 100 ℃ of following dryings of drying baker 48 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding.
(2) preparation of collagen solution
The learn from else's experience tendon of the qualified leg of pork in quarantine back, remove the oils and fats on tendon surface with the liquid detergent washing after careful rejecting fat and the muscular tissue, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon 25g after pulverizing is soaked in phosphoric acid (analytical pure) solution of 1000ml 0.1%, and the pepsin of adding 1200U (iu), fully mixing at room temperature soaked 70～80 hours, filter cleaner makes the concentration of filtrate reach 1.08 * 10
-2G/ml.
(3) take by weighing 250g hydroxyapatite dry powder and add the 1000ml collagen solution, abundant stirring and evenly mixing, transferring to pH value with the NaOH solution of 3mol/L is 7.3.
(4) pour the mixing paste of above-mentioned hydroxyapatite and collagen into 20 * 10 * 3cm
3The rustless steel pallet in, floating, lyophilizing becomes porous solid and is the hydroxyapatite/collagen cmposite artificial bone.
(5) above-mentioned artificial bone is cut into 2 * 1 * 3cm
3Block, pack cobalt-60 radiosterilize sterilization.
Embodiment two
(1) preparation of nanometer particle size hydroxyapatite
Take by weighing 50g CaCl
2.2H
2O is dissolved in the 1000ml deionized water, stirs it is fully dissolved, and adds 26g DAP ((NH while stirring
4)
2HPO
4), NaOH solution to the pH value that adds 1mol/L then while stirring is 8.0.Sucking filtration collecting precipitation, usefulness deionized water wash 3 times, sucking filtration, filter cake placed 98 ℃ of following dryings of drying baker 48 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding.
(2) preparation of collagen solution
The learn from else's experience tendon of the qualified bracket in quarantine back, remove the oils and fats on tendon surface with the liquid detergent washing after careful rejecting fat and the muscular tissue, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon 25g after pulverizing is soaked in phosphoric acid (analytical pure) solution of 1000ml 0.1%, and the pepsin of adding 1000U (iu), fully mixing at room temperature soaked 70～80 hours, filter cleaner makes the concentration of filtrate reach 1.18 * 10
-2G/ml.
(3) take by weighing 280g hydroxyapatite dry powder and add the 1000ml collagen solution, abundant stirring and evenly mixing, transferring to pH value with the NaOH solution of 3mol/L is 7.5.
(4) pour the mixing paste of above-mentioned hydroxyapatite and collagen into 20 * 10 * 3cm
3The rustless steel pallet in, floating, lyophilizing becomes porous solid and is the hydroxyapatite/collagen cmposite artificial bone.
(5) above-mentioned artificial bone is cut into 2 * 1 * 3.5cm
3Block, pack cobalt-60 radiosterilize sterilization.
Embodiment three
(1) preparation of nanometer particle size hydroxyapatite
Take by weighing 189g lime nitrate (Ca (NO
3)
24H
2O) be dissolved in the 1000ml deionized water, stirring is fully dissolved it, adds 68g sodium hydrogen phosphate (Na while stirring
2HPO
4), NaOH solution to the pH value that adds 1mol/L then while stirring is 7.4.Sucking filtration collecting precipitation, usefulness deionized water wash 3 times, sucking filtration, filter cake placed 95 ℃ of following dryings of drying baker 48 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding.
(2) preparation of collagen solution
The back qualified horse leg tendon of the quarantine of learning from else's experience, remove the oils and fats on tendon surface with the liquid detergent washing after careful rejecting fat and the muscular tissue, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon 25g after pulverizing is soaked in phosphoric acid (analytical pure) solution of 1000ml 0.1%, and the pepsin of adding 1500U (iu), fully mixing at room temperature soaked 70～80 hours, filter cleaner makes the concentration of filtrate reach 1.2 * 10
-2G/ml.
(3) take by weighing 260g hydroxyapatite dry powder and add the 1000ml collagen solution, abundant stirring and evenly mixing, transferring to pH value with the NaOH solution of 3mol/L is 7.0.
(4) pour the mixing paste of above-mentioned hydroxyapatite and collagen into 20 * 10 * 3cm
3The rustless steel pallet in, floating, lyophilizing becomes porous solid and is the hydroxyapatite/collagen cmposite artificial bone.
(5) above-mentioned artificial bone is cut into 2 * 1 * 3cm
3Block, pack cobalt-60 radiosterilize sterilization.
Embodiment four
(1) preparation of nanometer particle size hydroxyapatite
Take by weighing 189g lime nitrate (Ca (NO
3)
24H
2O) be dissolved in the 1000ml deionized water, stirring is fully dissolved it, adds 63g DAP ((NH while stirring
4)
2HPO
4), NaOH solution to the pH value that adds 1mol/L then while stirring is 7.2.Sucking filtration collecting precipitation, usefulness deionized water wash 3 times, sucking filtration, filter cake placed 98 ℃ of following dryings of drying baker 48 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding.
(2) preparation of collagen solution
The back qualified leg of pork tendon of the quarantine of learning from else's experience, remove the oils and fats on tendon surface with the liquid detergent washing after careful rejecting fat and the muscular tissue, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon 25g after pulverizing is soaked in phosphoric acid (analytical pure) solution of 1000ml 0.1%, and the pepsin of adding 1100U (iu), fully mixing at room temperature soaked 70～80 hours, filter cleaner makes the concentration of filtrate reach 1.18 * 10
-2G/ml.
(3) take by weighing 300g hydroxyapatite dry powder and add the 1000ml collagen solution, abundant stirring and evenly mixing, transferring to pH value with the NaOH solution of 3mol/L is 8.0.
(4) pour the mixing paste of above-mentioned hydroxyapatite and collagen into 20 * 10 * 3cm
3The rustless steel pallet in, floating, lyophilizing becomes porous solid and is the hydroxyapatite/collagen cmposite artificial bone.
(5) above-mentioned artificial bone is cut into 2 * 1 * 2.5cm
3Block, pack cobalt-60 radiosterilize sterilization.
Embodiment five
(1) preparation of nanometer particle size hydroxyapatite
Take by weighing 29.4g CaCl
2.2H
2O is dissolved in the 1000ml deionized water, stirs it is fully dissolved, and adds 16g DAP ((NH while stirring
4)
2HPO
4), NaOH solution to the pH value that adds 1mol/L then while stirring is 7.9.Sucking filtration collecting precipitation, usefulness deionized water wash 3 times, sucking filtration, filter cake placed 100 ℃ of following dryings of drying baker 48 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding.
(2) preparation of collagen solution
The back qualified bracket tendon of the quarantine of learning from else's experience, remove the oils and fats on tendon surface with the liquid detergent washing after careful rejecting fat and the muscular tissue, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon 25g after pulverizing is soaked in phosphoric acid (analytical pure) solution of 1000ml 0.1%, and add the pepsin of 1200 U (iu), fully mixing at room temperature soaked 70～80 hours, filter cleaner makes the concentration of filtrate reach 1.08 * 10
-2G/ml.
(3) take by weighing 270g hydroxyapatite dry powder and add the 1000ml collagen solution, abundant stirring and evenly mixing, transferring to pH value with the NaOH solution of 3mol/L is 7.2.
(4) pour the mixing paste of above-mentioned hydroxyapatite and collagen into 20 * 10 * 3cm
3The rustless steel pallet in, floating, lyophilizing becomes porous solid and is the hydroxyapatite/collagen cmposite artificial bone.
(5) above-mentioned artificial bone is cut into 2 * 1 * 3cm
3Block, pack cobalt-60 radiosterilize sterilization.
Embodiment six
(1) preparation of nanometer particle size hydroxyapatite
Take by weighing 118g lime nitrate (Ca (NO
3)
24H
2O) be dissolved in the 1000ml deionized water, stirring is fully dissolved it, adds 29ml H while stirring
3PO
4, NaOH solution to the pH value that adds 1mol/L then while stirring is 7.2.Sucking filtration collecting precipitation, usefulness deionized water wash 3 times, sucking filtration, filter cake placed 98 ℃ of following dryings of drying baker 48 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding.
(2) preparation of collagen solution
The back qualified horse leg tendon of the quarantine of learning from else's experience, remove the oils and fats on tendon surface with the liquid detergent washing after careful rejecting fat and the muscular tissue, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon 25g after pulverizing is soaked in phosphoric acid (analytical pure) solution of 1000ml 0.1%, and add the pepsin of 1100 U (iu), fully mixing at room temperature soaked 70～80 hours, filter cleaner makes the concentration of filtrate reach 1.18 * 10
-2G/ml.
(3) take by weighing 275g hydroxyapatite dry powder and add the 1000ml collagen solution, abundant stirring and evenly mixing, transferring to pH value with the NaOH solution of 3mol/L is 8.0.
(4) pour the mixing paste of above-mentioned hydroxyapatite and collagen into 20 * 10 * 3cm
3The rustless steel pallet in, floating, lyophilizing becomes porous solid and is the hydroxyapatite/collagen cmposite artificial bone.
(5) above-mentioned artificial bone is cut into 2 * 1 * 2.5cm
3Block, pack cobalt-60 radiosterilize sterilization.
Claims (4)
1, a kind of preparation method of porous collagen composite nano hydroox apatite artificial bone is characterized in that this method may further comprise the steps:
(1) preparation nanometer hydroxyapatite:
To contain Ca
2+Chemical compound be dissolved in the deionized water, the preparation Ca
2+Concentration is the solution of 0.2～0.8mol/L, adds while stirring and contains PO
4 3-Chemical compound, the mol ratio that makes Ca and P is 1～1.67, adding NaOH solution to pH value then while stirring is 7～8, the sucking filtration collecting precipitation, with deionized water wash 3 times, sucking filtration, filter cake placed 90～150 ℃ of following dryings of drying baker 48～96 hours, obtained the hydroxy apatite powder that particle diameter is a nanometer scale after the grinding;
(2) preparation collagen solution:
Get the tendon of the leg of pork, bracket or horse lower limb, with after the rinsed with deionized water tendon being crushed to granularity is 3～6 millimeters, tendon after pulverizing is soaked in the phosphoric acid solution, ratio is: 0.1 part of mass percent concentration of adding is 85% phosphoric acid solution in per 100 parts of deionized waters, and adding pepsin, making the pepsin in every milliliter of phosphoric acid solution is 10～15 international active units, abundant mixing, at room temperature soaked 50～100 hours, with the soak filter cleaner, obtain collagen solution, concentration is 1～1.2 * 10
-2G/ml;
(3) in the hydroxy apatite powder of above-mentioned preparation, add collagen solution, add 0.25～0.3g hydroxy apatite powder in every milliliter of collagen solution, abundant stirring and evenly mixing, transferring to pH value with NaOH solution is 7～8;
(4) the mixing paste lyophilization with above-mentioned hydroxyapatite and collagen becomes porous collagen composite nano hydroox apatite artificial bone.
2, the method for claim 1 is characterized in that the wherein said Ca of containing
2+Chemical compound be CaCl
2Or lime nitrate.
3, the method for claim 1 is characterized in that the wherein said PO of containing
4 3-Chemical compound be (NH
4)
2HPO
4, Na
2HPO
4Or H
3PO
4In any.
4, the method for claim 1 is characterized in that the cryodesiccated temperature control flow of wherein said porous collagen composite nano hydroox apatite artificial bone is: reduced to-40 ℃ through 3 hours from room temperature, be incubated 2 hours, freeze real back evacuation distillation 10 hours, be warming up to 0 ℃ through 4 hours, per hour heat up 10 ℃, 0 ℃ is incubated 4 hours, be warming up to 15 ℃ through 1 hour, 15 ℃ are incubated 1 hour, are warming up to 25 ℃ through 1 hour, and then are warming up to 35 ℃ through 1 hour, be incubated 5 hours, go vacuum.
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| CN101229392B (en) * | 2007-01-24 | 2013-05-22 | 张立海 | Inversely crystallized collagen-hydroxyl apatite bone repairing material and preparing method thereof |
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| CN101693774B (en) * | 2009-09-28 | 2011-05-25 | 暨南大学 | Nanometer hydroxyapatite/natural polymer composite, preparation method and application thereof |
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| CN102133426A (en) * | 2011-03-07 | 2011-07-27 | 胡庆柳 | Artificial bone imitating bioactivity of cancellous bone and preparation method thereof |
| CN103285427B (en) * | 2013-04-26 | 2014-11-05 | 中国国旅贸易有限责任公司 | Artificial bone material and preparation method thereof |
| CN103705976B (en) * | 2014-01-09 | 2016-01-13 | 山东省淡水渔业研究院 | A kind of composite bone repairing material and preparation method thereof |
| CN105013002B (en) * | 2014-04-25 | 2018-06-01 | 胡庆柳 | Absorbable biological activity bone induction material and preparation method thereof |
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| CN107837425B (en) * | 2016-09-18 | 2021-08-06 | 浙江蓝怡医药有限公司 | Novel porous biological ceramic bone material and preparation method thereof |
| CN107952115B (en) * | 2016-10-17 | 2021-10-26 | 北京湃生生物科技有限公司 | Bionic biomineralization artificial bone repair material and preparation method and application thereof |
| CN106620869A (en) * | 2016-11-10 | 2017-05-10 | 武汉医佳宝生物材料有限公司 | Collagen/hydroxyapatite composite artificial bone and preparation method thereof |
| CN106860916B (en) * | 2017-04-06 | 2020-06-12 | 福州大学 | GO/nHA/collagen composite bone repair material and preparation method thereof |
| CN107158480A (en) * | 2017-04-21 | 2017-09-15 | 陈建峰 | A kind of preparation method of bone internal fixation material |
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| CN109381745B (en) * | 2018-09-21 | 2021-03-19 | 北京市意华健科贸有限责任公司 | Collagen coral hydroxyapatite composite bone filling scaffold material and preparation method thereof |
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