CN105816919B - A kind of composite material and preparation method containing natural nano hydroxyapatite - Google Patents
A kind of composite material and preparation method containing natural nano hydroxyapatite Download PDFInfo
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- CN105816919B CN105816919B CN201610345291.7A CN201610345291A CN105816919B CN 105816919 B CN105816919 B CN 105816919B CN 201610345291 A CN201610345291 A CN 201610345291A CN 105816919 B CN105816919 B CN 105816919B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention discloses a kind of composite material and preparation methods containing natural nano hydroxyapatite.The preparation method of the composite material includes the following steps: that the aqueous solution of formulation vehicle obtains carrier aqueous solution, and the carrier aqueous solution is mixed with the native hydroxyl apatite, is irradiated sterilizing to get the composite material is arrived；The carrier is collagen, carboxymethyl chitosan or hyaluronic acid.There are mainly two types of forms for the composite material that the method for the present invention is prepared: injection-type and sponge-type, wherein injection-type composite material and the sponge-type composite material main distinction are used for sponge-type composite material and be lyophilized, and preserving type is simple, easy to use；And injection-type composite material has the advantages that injectable, can be applied to the filling in irregular defect site.
Description
Technical field
The present invention relates to a kind of composite material and preparation methods containing native hydroxyl apatite.
Background technique
Hydroxyapatite (Hydroxyapatite, abbreviation HA) is the main inorganic composition of human body and animal skeleton, tooth,
Content is about 60wt% in sclerotin, and basic unit is needle-shaped phosphorite crystal.HA has good bioactivity and life
Object compatibility can combine closely with the formation of the hard and soft tissue of human body in a short time after being implanted into human body, be that a kind of performance is very excellent
Good bone renovating material.
In animal body hard tissue material, HA exists in the form of composite material.Body bone tissue be exactly by crystallite HA with
The collagen fabric mutually twisted solid being wound, formation of this composite material on three-dimensional space experienced complexity
, very long biochemical reaction.Data show that although people's bone growth ability has very big difference in different age brackets,
People still has power of regeneration to old bone, and sclerotin can change.
And currently, prepare the wet chemistry methods such as sol-gel method, hydro-thermal reaction method, the Hydrolyze method that HA is mostly used greatly, synthesized
Journey is more complicated, and impurity is easily introduced in preparation process, and technological parameter is more difficult to control, and cannot replicate the natural knot of HA completely
Structure is easy to cause the ingredient of HA and structure to change.The industrialized production of these preparation methods is also faced with many simultaneously
It is difficult.Up to the present, (meet that component is uniform, particle is thin, particle diameter distribution is narrow, without group simultaneously to acquisition " ideal powder "
The harsh conditions such as poly-, large specific surface area) it is still very difficult；Although importantly, preparing wherein certain characteristic or several spies
The nano-powder of property high quality more outstanding is not too much difficult, but its cost is often relatively high.Therefore, receiving for low cost is industrialized
Rice hydroxyapatite preparation method requires study.
Simultaneously as single hydroxyapatite material toughness is low, inconsistent phenomenon and biodegrade can be occurred by implanting
Property it is poor, density of material is big, easily accumulate, be unfavorable for cellular infiltration and grow into.Accordingly, it is desirable to provide a kind of contain native hydroxyl apatite
Composite material, for the bone tissue reparations such as bone defect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of composite material containing native hydroxyl apatite, specially one
Preparation method of the kind by the purification of hydroxy apatite plural gel for retaining natural structure or sponge material that are extracted in bone, the present invention
The preparation method of provided native hydroxyl apatite is easy to operate, from a wealth of sources, and maintains the natural needle of hydroxyapatite
Shape structure.Provided composite material has variform, and easy to use, the later period can be applied to the bone tissues such as bone defect and repair
It is multiple.
The preparation method of composite material provided by the present invention containing native hydroxyl apatite, includes the following steps:
(1) native hydroxyl apatite is prepared, is included the following steps:
1) animal skeleton in vitro using the aqueous solution soaking of surfactant；
2) use alkali treatment 1) product；
3) using the product of the aqueous solution soaking step 2) of surfactant；
4) use hot water, alkali, organic solvent or enzymatic treatment step 3) product；
5) use buffer soaking step 4) product, it is then freeze-dried to get the native hydroxyl apatite；
(2) composite material is prepared, is included the following steps:
The aqueous solution of formulation vehicle mixes the carrier aqueous solution with the native hydroxyl apatite, is irradiated
It sterilizes to get the composite material is arrived；
The carrier is collagen, carboxymethyl chitosan or hyaluronic acid.
In above-mentioned preparation method, the in vitro animal skeleton is in vitro mammal, birds or marine organisms
The cortex bone or cancellous bone of ox, horse or pig, the bone of the birds such as fish or bird specifically can be used in bone；
The in vitro animal skeleton is cut into the bulk that length is 0~20cm, concretely 3~10cm.
In above-mentioned preparation method, step (1) 1) and 3) in, quality-volume of the aqueous solution of the surfactant is dense
Degree can be 0.5~3g/100ml；
The surfactant can be TritonX-100, Tween-80 or Tween-40；
Step (1) 1) in, the temperature of the immersion can be 4~100 DEG C, and the time of the immersion can be 0~72 hour, but
It is not zero；
Step (1) 3) in, the temperature of the immersion can be 4~60 DEG C, and the time of the immersion can be 0~72 hour, but
It is not zero.
In above-mentioned preparation method, step (1) 2) and 4) in, the alkali can be NaOH, Ca (OH)2、KOH、Na2CO3、
K2CO3、NaHCO3, ammonium hydroxide and KHCO3At least one of；
It is handled using the aqueous solution of the alkali, the concentration of the aqueous solution of alkali described in step 2) can be 0.5~6mol/
L, the concentration of the aqueous solution of alkali described in step 4) can be 2~6mol/L；
Step (1) 2) in, the temperature of the alkali process can be 4~150 DEG C, and the time of the alkali process can be small for 1~24
When；
Step (1) 4) in, the temperature of the alkali process can be 30~150 DEG C, and the time of the alkali process can be 5~120
Hour.
In above-mentioned preparation method, step (1) 4) in, the temperature of the hot water treatment can be 30~150 DEG C, the hot water
The time of processing can be 0.5~5 day；
The organic solvent can be at least one of ethyl acetate, tetrahydrofuran, toluene and hexafluoroisopropanol, described to have
The time of solvent processing can be 10~240h, and the treatment process can cooperate the aid in treatment such as ultrasound, concussion, broken.
The temperature of the enzymatic treatment can be 4~30 DEG C, and the time of the enzymatic treatment can be 10~120 hours；
The enzymatic treatment can carry out under conditions of pH value is 7.0~7.4；
The enzymatic treatment is using in trypsase, cradin, papain, bromelain and clostridiopetidase A at least one
The aqueous solution of kind, the mass percentage of the aqueous solution can be 0.05~4%；
The enzyme activity for the enzyme that the enzymatic treatment uses can be >=250units/mg.
In above-mentioned preparation method, step (1) 5) in, the buffer can be PBS buffer solution, the pH value of the buffer
It is 6.5~7.8,；
It is impregnated under conditions of 4~30 DEG C using the buffer；
It the use of the pH value that the buffer is repeatedly dipped to the buffer is 7.0~7.4, the time impregnated every time
It can be 30min.
In above-mentioned preparation method, step (1) 5) in, the time of the freeze-drying is 8~48h.
In above-mentioned preparation method, step (1) 1) -4) after, it is all made of clear water and is cleaned.
In above-mentioned preparation method, in step (2), the mass percentage of the carrier aqueous solution can for 0.5%~
6%；
In the mixture of the carrier aqueous solution and the native hydroxyl apatite, the quality of the native hydroxyl apatite
Percentage composition is 1~90%, such as 60%~70%.
In above-mentioned preparation method, in step (2), cobalt -60 can be used and carry out irradiation sterilization；
The irradiation dose of the irradiation sterilization can be 15~25kGy, concretely 15kGy or 25kGy.
In above-mentioned preparation method, after the irradiation sterilization, the method also includes to the carrier aqueous solution and institute
The step of mixture of native hydroxyl apatite is freeze-dried is stated, is obtained in spongiform composite material.
When the mixture of the carrier aqueous solution and the native hydroxyl apatite is without the freeze-drying process
Step may be used as preparing injection-type artificial bone, as injectable type gel complex material.
Material without the freeze-drying process needs after the irradiation sterilization using stored refrigerated, and protects
It is shorter to deposit the time limit；Coarse crushing process need to be passed through by the freeze-drying process, grinding particle size is 0~2mm, optimal granularity
For 0.5mm~1mm.
Invention further provides the composite material of above method preparation, the quality percentages of the native hydroxyl apatite
Content is 1~90%, but is not zero.
Preparation method provided by the invention removes organic matter preparation by heat treatment, alkali process or method of enzymatically treating first
Native hydroxyl Apatite materials then use collagen, hyaluronic acid, carboxymethyl chitosan etc. to prepare native hydroxyl for bracket
Apatite composite material.The present invention prepares hydroxyapatite, and prepared hydroxyapatite material tool using new way
Have nanostructure, can human simulation people's bone hydroxyapatite structure, native hydroxyl apatite can be observed under transmission electron microscope
Specific acicular texture.And due to single hydroxyapatite material poor mechanical property, hydroxy-apatite is being made in the present invention
It is on the basis of stone, the progress of the carriers such as itself and collagen, chitosan, hyaluronic acid is compound, prepare composite hydroxylapatite material
Material.Wherein the flowing carriers such as collagen provide supporting structure, play toughening effect, can effectively improve the mechanical property of bracket
Can, and its porous structure is conducive to cell and grows into, guide tissue regeneration；Hydroxyapatite can be bonded with new bone formation bone, be drawn
Lead skeletonization.
There are mainly two types of forms for the composite material that the method for the present invention is prepared: injection-type and sponge-type, wherein injection
Type composite material and the sponge-type composite material main distinction are that sponge-type composite material uses freeze-drying, and preserving type is simple,
It is easy to use；And injection-type composite material has the advantages that injectable, can be applied to the filling in irregular defect site.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of the native hydroxyl apatite prepared in the embodiment of the present invention 1.
Fig. 2 is XRD diagram of the step (3) in the embodiment of the present invention 1 (before calcining and after calcining) with material obtained by step (8)
Spectrum.
Fig. 3 is the stereoscan photograph of the composite material prepared in the embodiment of the present invention 2.
Fig. 4 is the stereoscan photograph of the composite material prepared in the embodiment of the present invention 3.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Quantitative test in following embodiment, is respectively provided with three repeated experiments, and results are averaged.
The preparation of embodiment 1, native hydroxyl apatite/carboxymethyl chitosan injectable type composite material
(1) the fresh pig long bone for just completing to butcher is collected from the slaughterhouse of standardized management by special messenger, avoids connecing as far as possible
Pollutant is touched, stored frozen immediately after collection.
(2) it will sufficiently be cleaned after the material thaws of freezing, is then cut into 5cm long, washes off surface
Attachment.
(3) the sample 10h of 15 ± 2 DEG C of immersion treatment steps (2) of 1g/100ml TritonX-100 aqueous solution is used, then
It is washed with clear water.
(4) the sample 1h for using 15 ± 2 DEG C of immersion treatment steps (3) of 1mol/L NaOH solution aqueous solution, then uses clear water
It rinses.
(5) the sample 10h of 15 ± 2 DEG C of immersion treatment steps (4) of 1g/100ml TritonX-100 aqueous solution is used, then
It is washed with clear water.
(6) for 24 hours using the sample of 98 ± 2 DEG C of immersion treatment steps (5) of 3mol/L NaOH solution aqueous solution, then with clear
Water rinses.
(7) 15 ± 2 DEG C of PBS buffer solution immersion treatment step (6) products therefrom repeatedly for the use of pH being 6.5, impregnates every time
30min makes its final pH 7.0.
(8) step (7) products therefrom is subjected to freeze-drying 8h, obtains native hydroxyl Apatite materials.
In order to confirm that obtained material is hydroxyapatite, obtained dusty material is subjected to XRD analysis.Meanwhile
Material after step (3) is subjected to XRD analysis, and carries out XRD analysis after calcining to it, actual conditions: uses GSL
The calcining of 1400X type carries out calcination processing to the sample after step (3) with high-temperature atmosphere furnace.Sample quilt in calcination process in order to prevent
Oxidation needs to lead to nitrogen, after 800 DEG C of 3 hours of heat preservation, furnace cooling in calcination process.When taking out sample from furnace, hair
Existing sample becomes powder by bulk.
As shown in Fig. 2, the bone sample diffraction peak after the step of without any processing (3) is in Dispersed precipitate, illustrate sample
Crystallinity is lower, is the diffraction packet for having a widthization between 30-35 ° in 2 θ, is the main diffraction peak of hydroxyapatite, shows its master
Wanting inorganic constituents is hydroxyapatite.And the diffraction maximum of sample becomes sharply after calcination processing, diffraction peak intensity increases, explanation
Calcination processing keeps the crystallinity of sample significantly raised.The diffraction maximum of sample and the diffraction maximum of hydroxyapatite are basic after calcination processing
Unanimously, the main component for illustrating post-calcination sample is still hydroxyapatite.But also go out outside the diffraction maximum of hydroxyapatite in figure
Stronger β-Ca is showed3(PO4)2Diffraction maximum, illustrate in bone material original hydroxyapatite by calcining part convert in order to
β-Ca3(PO4)2.And it is complete by the diffraction maximum of hydroxyapatite sample obtained by step (8) and the diffraction maximum of hydroxyapatite
It is complete consistent, it is mainly hydroxyapatite which demonstrate material made from this kind of method removing organic matter.
Hydroxyapatite material obtained is placed under transmission electron microscope and is observed, if Fig. 1 shows, fractions distribution is uniform, particle
Carefully, particle diameter distribution is narrow, soilless sticking, large specific surface area, has typical club shaped structure, and average-size size is 20nm.And this kind
The natural bone material of preparation method materials, from a wealth of sources, preparation method is simple, and industrialization difficulty is low, solves current hydroxyl phosphorus
The big difficulty of lime stone preparation industrialization difficulty.
Obtained hydroxyapatite material DNA residue detection is subjected to, test result is (0.15 ± 0.05) ng/
Mg illustrates that inhereditary material removes completely.
Obtained hydroxyapatite material has been subjected to kjeldahl determination analysis, test result is (1.01 ± 0.53) ‰,
Illustrate that organic principle removes completely, only retains hydroxyapatite material.
Configuring carboxymethyl chitosan sugar aqueous solution, (wherein carboxymethyl chitosan is purchased from Zhejiang golden shell pharmaceutcal corporation, Ltd, molecule
Amount is 3 × 105), mass fraction 3%, at the same be added above-mentioned preparation native hydroxyl Apatite materials (its additional amount be carboxylic first
The 70% of the gross mass of base enclosure water solution and native hydroxyl Apatite materials), it is uniformly mixed.It is injected into pre-designed
Syringe in；Obtained sample carries out irradiation sterilization, and sterilizing can be -60 radiation sterilization of cobalt, irradiation dose 25KGy.
Injection material form prepared by the present embodiment is gel, can be injected into wound location, has easy to operate, side
Just the advantages that plastotype.
Embodiment 2, the preparation of native hydroxyl apatite/carboxymerhyl chitosan sponge material
Injection-type composite material prepared by embodiment 1 is lyophilized, native hydroxyl apatite/carboxymethyl chitosan is made
Sponge material, wherein carboxymethyl chitosan provides toughness support, and native hydroxyl apatite is attached to rack surface, plays bone guided
Effect.
Obtained sponge material is observed under scanning electron microscope, as shown in figure 3, obtained sponge material has
Porous structure is conducive to cell and grows into, guide tissue regeneration；Hydroxyapatite uniform adsorption provides mechanics branch in rack surface
Support guides skeletonization.
Embodiment 3, the preparation of native hydroxyl apatite/collagen protein sponge material
(1) the fresh long bone of pig for just completing to butcher is collected from the slaughterhouse of standardized management by special messenger, avoids connecing as far as possible
Pollutant is touched, stored frozen immediately after collection；
(2) it will sufficiently be cleaned after the material thaws of freezing, is then cut into 5cm long, washes off surface
Attachment.
(3) the sample 10h of 15 ± 2 DEG C of immersion treatment steps (2) of 1g/100ml TritonX-100 aqueous solution is used, then
It is washed with clear water.
(4) the sample 1h for using 45 ± 2 DEG C of immersion treatment steps (3) of 1mol/L NaOH solution aqueous solution, then uses clear water
It rinses；
(5) the sample 10h of 15 ± 2 DEG C of immersion treatment steps (4) of 1g/100ml TritonX-100 aqueous solution is used, then
It is washed with clear water.
(6) 1% 25 ± 2 DEG C of immersion treatments of trypsin solution (enzyme activity of trypsase is 300units/mg) are used
The sample 48h of step (5), is then rinsed with clear water；
(7) 15 ± 2 DEG C of PBS buffer solution immersion treatment step (6) products therefrom repeatedly for the use of pH being 6.5, impregnates every time
30min makes its final pH 7.2.
(8) step (7) products therefrom is subjected to freeze-drying 12h, obtains native hydroxyl Apatite materials.
The above-mentioned native hydroxyl Apatite materials being prepared are placed under transmission electron microscope and are observed, form and Fig. 1
It is similar, it is evenly distributed, has typical club shaped structure.
The kjeldahl determination analysis result of the native hydroxyl Apatite materials of above-mentioned preparation is (1.35 ± 0.25) ‰, and explanation has
Machine ingredient removes completely, has only retained hydroxyapatite material.
The hydroxyapatite material of above-mentioned preparation has carried out DNA residue detection, and test result is (0.21 ± 0.07) ng/
Mg illustrates that inhereditary material substantially completely removes.
Collagen aqueous solution (wherein the molecular weight of collagen is 30KDa) is configured, concentration 4wt% is added simultaneously
(its additional amount is the total of collagen aqueous solution and native hydroxyl Apatite materials to the native hydroxyl Apatite materials of above-mentioned preparation
The 60% of quality), it is uniformly mixed.
Uniformly mixed sample is freeze-dried for 24 hours, hydroxyapatite/collagen protein sponge material is made；It obtains
Sample carry out irradiation sterilization, sterilizing can be -60 radiation sterilization of cobalt, irradiation dose is specially 15KGy.
Obtained sponge material is observed under scanning electron microscope, as shown in figure 4, obtained sponge material has
Porous structure is conducive to cell and grows into, guide tissue regeneration；Hydroxyapatite uniform adsorption provides mechanics branch in rack surface
Support guides skeletonization.
Claims (5)
1. a kind of preparation method of the composite material containing native hydroxyl apatite, includes the following steps:
The aqueous solution of formulation vehicle obtains carrier aqueous solution, and the carrier aqueous solution is mixed with native hydroxyl apatite, warp
Irradiation sterilization to get arrive the composite material；
The carrier is collagen, carboxymethyl chitosan or hyaluronic acid；
The native hydroxyl apatite is prepared by the method included the following steps:
1) animal skeleton in vitro using the aqueous solution soaking of surfactant；
2) use alkali treatment 1) product；
3) using the product of the aqueous solution soaking step 2 of surfactant；
4) alkali or enzymatic treatment step 3 are used) product；
5) use buffer soaking step 4) product, it is then freeze-dried to get the native hydroxyl apatite；
Step 1) and 3) in, quality-volumetric concentration of the aqueous solution of the surfactant is 0.5 ~ 3g/100ml；
The surfactant is TritonX-100, Tween-80 or Tween-40；
In step 1), the temperature of the immersion is 4 ~ 100 DEG C, and the time of the immersion is 0 ~ 72 hour, but is not zero；
In step 3), the temperature of the immersion is 4 ~ 60 DEG C, and the time of the immersion is 0 ~ 72 hour, but is not zero；
Step 2 and 4) in, the alkali be NaOH, Ca (OH)2, at least one of KOH and ammonium hydroxide；
It is handled using the aqueous solution of the alkali；
In step 2, the temperature of the alkali process is 4 ~ 150 DEG C, and the time of the alkali process is 1 ~ 24 hour；
In step 4), when using alkali process: for the temperature of the alkali process for 98 ~ 150 DEG C, the time of the alkali process is 24 ~ 120
Hour；
In step 4), when using enzymatic treatment: for the temperature of the enzymatic treatment for 4 ~ 30 DEG C, the time of the enzymatic treatment is 10 ~ 120 small
When；
The enzymatic treatment carries out under conditions of pH value is 7.0 ~ 7.4；
The enzymatic treatment is using at least one of trypsase, cradin, papain, bromelain and clostridiopetidase A
Aqueous solution, the mass percentage of the aqueous solution are 0.05 ~ 4%；
In step 5), the buffer is PBS buffer solution, and the pH value of the buffer is 6.5 ~ 7.8,；
It is impregnated under conditions of 4 ~ 30 DEG C using the buffer；
It the use of the pH value that the buffer is repeatedly dipped to the buffer is 7.0 ~ 7.4.
2. preparation method according to claim 1, it is characterised in that: the in vitro animal skeleton is dynamic in vitro lactation
Object, birds or the bone of marine organisms.
3. preparation method according to claim 1 or 2, it is characterised in that: the mass percentage of the carrier aqueous solution
It is 0.5% ~ 3%；
In the mixture of the carrier aqueous solution and the native hydroxyl apatite, the quality percentage of the native hydroxyl apatite
Content is 1 ~ 90%；
Irradiation sterilization is carried out using cobalt -60；
The irradiation dose of the irradiation sterilization is 15 ~ 25kGy；
After the irradiation sterilization, the method also includes the mixing to the carrier aqueous solution and the native hydroxyl apatite
The step of object is freeze-dried.
It is described natural in the composite material 4. the composite material that any preparation method is prepared in claim 1-3
The mass percentage of hydroxyapatite is 1 ~ 90%.
5. composite material described in claim 4 is preparing the application in bone renovating material.
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| CN106421929B (en) * | 2016-09-22 | 2019-11-15 | 四川大学 | A kind of injectable calcium phosphate/natural high molecular composite material and its preparation method and application |
| CN107261215B (en) * | 2017-06-28 | 2020-04-21 | 海口市人民医院 | Nano pearl powder/C-HA composite stent and application thereof |
| CN107281547A (en) * | 2017-07-03 | 2017-10-24 | 扬州大学 | A kind of preparation method of injection bone renovating material |
| KR102330140B1 (en) | 2017-12-14 | 2021-11-23 | 가이스틀리히 파마 아게 | Dried implant composition and injectable aqueous implant formulation |
| CN108543115B (en) * | 2018-04-02 | 2020-06-09 | 华中农业大学 | Osteoinductive collagen-based composite hydrogel and preparation method thereof |
| CN110606477A (en) * | 2018-06-14 | 2019-12-24 | 诺一迈尔（苏州）医学科技有限公司 | Preparation method of hydroxyapatite, composite material containing hydroxyapatite and application of composite material |
| CN108992708A (en) * | 2018-07-02 | 2018-12-14 | 西安巨子生物基因技术股份有限公司 | Modified bone meal in surface and preparation method thereof |
| CN109954167B (en) * | 2019-02-28 | 2021-09-21 | 天新福（北京）医疗器材股份有限公司 | Bone repair material and application thereof |
| CA3141985C (en) * | 2019-06-14 | 2023-12-05 | Geistlich Pharma Ag | Injectable aqueous implant formulation containing ascorbic acid |
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