CN109821066A - A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support - Google Patents
A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support Download PDFInfo
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- CN109821066A CN109821066A CN201910158830.XA CN201910158830A CN109821066A CN 109821066 A CN109821066 A CN 109821066A CN 201910158830 A CN201910158830 A CN 201910158830A CN 109821066 A CN109821066 A CN 109821066A
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- gelatin
- dihydrate
- calcium sulphate
- dicalcium phosphate
- porous support
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- RBLGLDWTCZMLRW-UHFFFAOYSA-K dicalcium phosphate dihydrate Substances O.O.[Ca+2].[Ca+2].[O-]P([O-])([O-])=O RBLGLDWTCZMLRW-UHFFFAOYSA-K 0.000 title claims abstract description 57
- 239000008273 gelatin Substances 0.000 title claims abstract description 53
- 229920000159 gelatin Polymers 0.000 title claims abstract description 53
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 53
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 53
- 108010010803 Gelatin Proteins 0.000 title claims abstract description 52
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 title description 40
- 239000000463 material Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 230000003013 cytotoxicity Effects 0.000 abstract description 5
- 231100000135 cytotoxicity Toxicity 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000007767 bonding agent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 description 22
- 239000000523 sample Substances 0.000 description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 20
- 235000011132 calcium sulphate Nutrition 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 239000012798 spherical particle Substances 0.000 description 10
- 239000001175 calcium sulphate Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229960005069 calcium Drugs 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000035876 healing Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 231100001083 no cytotoxicity Toxicity 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 229940123373 Adenovirus E1A gene Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007541 cellular toxicity Effects 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 210000002919 epithelial cell Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
- 238000001890 transfection Methods 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The present invention discloses a kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support, belongs to biomedical materials field.The method of the invention is using dicalcium phosphate dihydrate and calcium sulphate dihydrate as raw material, using gelatin as bonding agent, finally obtains porous support by stacking in a mold, this method has the advantages such as simple controllable, the cost of material economy of process, with short production cycle；Gelatin/dicalcium phosphate dihydrate that this method is prepared/calcium sulphate dihydrate biological stephanoporate bracket material has 61% porosity, and cytotoxicity is qualified, and bracket has good degradation property, and has certain bioactivity；So being expected to realize industrialized production, into clinical application.
Description
Technical field
The present invention relates to a kind of preparation methods of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support, are mainly used for
Bone Defect Repari belongs to biomedical materials field.
Background technique
As the important component of bone tissue engineer research, the preparation of bone tissue engineering scaffold attracts always researcher
Sight.In bone tissue engineer reparation field, organic and/or inorganic materials main for the selection of repair materials, synthetic material,
Natural biological derived material etc..Dicalcium phosphate dihydrate is prone to hydration in human body, is easy degradation, but hydrogen phosphate dihydrate
Calcium no clear superiority compared with people's bone in mechanical properties, a kind of successful bone renovating material must solve following mainly to ask
Topic: can significantly reduce the degradation speed of timbering material, guarantee that bone renovating material can discharge a large amount of calcium in degradation process
Ion, the transport of nutriment in bone tissue is conducive to certain porosity, and is met on this basis for cytotoxicity
And cell compatibility experiment probe into.Therefore, the weight that a kind of bone renovating material of good performance is scientific research personnel's research and development is found
Point.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support,
Prepare the porosity for meeting bone tissue engineer needs, mechanical strength, no cytotoxicity multiporous biological timbering material, and have
Have the advantages that good cost economy, simple process, biocompatibility, bioactivity and biological degradability are good, specifically includes step
It is rapid following:
(1) it is prepared by stirring dry spray-on process using dicalcium phosphate dihydrate as core, calcium sulphate dihydrate is the core-shell structure sample of shell
Product A, wherein the mass percent of dicalcium phosphate dihydrate is 30%-60%, and the mass percent of calcium sulphate dihydrate is 40-70%.
(2) sample A is put in mold and stacking is carried out by gelatin bonds to obtain the additional amount of sample B(gelatin for sample B
Wetting), it is cooled to room temperature to the gelatin gel solution in sample B, then timbering material is put into alcohol and solidifies 2-6h,
Timbering material takes out from alcohol and is dried, and is then removed from the molds material, obtains sample C.
(3) the sample C prepared is crosslinked with glutaraldehyde.
(4) by crosslinked sample C 5-8 times wash with distilled water, gelatin/bis- water phosphorus are obtained after sample C is dried
Sour hydrogen calcium/calcium sulphate dihydrate porous support.
Preferably, the mass percent concentration of step (2) gelatin gel solution of the present invention is 10% ~ 30%.
Preferably, the drying condition in step (2) of the present invention and (4) is that drying box temperature is 30-60 DEG C, drying time
For 24-48 h.
Preferably, the crosslinking condition in step (3) of the present invention: the glutaraldehyde cross-linking for being 1% ~ 5% with mass percent concentration
12~24h。
Beneficial effects of the present invention:
(1) gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials of the present invention, in the degradation of timbering material
Cheng Zhong, the cementation of gelatin can allow bracket to keep complete pattern system at degradation initial stage, when gelatin degradation a part
Later, calcium sulfate can provide a large amount of calcium sources, enhance the bioactivity of timbering material, after calcium sulfate is degradable, two water
Calcium monohydrogen phosphate can continue slowly to degrade up to the complete formation of new bone.
(2) present invention prepares spherical particle material using stirring spray drying process and in a mold prepared by stacking using gelatin
Porous support materials out, preparation process is simple, low in cost；It is carried out by gelatin compound, can prepare and meet mechanical property
Composite material；The porosity of composite porous support material is 61% or so；Calcium sulphate dihydrate and dicalcium phosphate dihydrate have excellent
Biocompatibility, no biotoxicity, have good osteoconductive；Three's material, which combines, has property more better than homogenous material
Can, this composite material finally can be with autologous bone tissue fusion and gradually by autologous bone tissue substitute.
(3) material toxicity test the result shows that, toxicity material non-toxic or has micro- poison when measuring big but meets doctor at 0-1 grade
Available condition is learned, therefore this material is expected the reparation for bone defect, further verifying will be examined by zoopery.
Detailed description of the invention
Fig. 1 is the porous support shape appearance figure that the embodiment of the present invention 1 obtains.
Fig. 2 is the porous support XRD diagram that the embodiment of the present invention 1 obtains.
Fig. 3 is the porous support scanning analysis figure that the embodiment of the present invention 1 obtains.
Specific embodiment
Below with reference to specific example, invention is further described in detail, but the protection scope of this civilization is not limited to institute
State content.
Embodiment 1
A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support, specifically includes step or less:
(1) Bone Defect Repari spherical particle material is prepared by stirring dry spray-on process, by α type half-H 2 O calcium sulphate and phosphate dihydrate
Hydrogen calcium composition, using dicalcium phosphate dihydrate as core, calcium sulphate dihydrate is calculated in mass percent as shell, dicalcium phosphate dihydrate
Content is 60%, remaining is α type half-H 2 O calcium sulphate.
(2) the spherical particle material being prepared is put in homemade mold through mass percent concentration is 10% bright
Glue carries out stacking bonding.
(3) sample after stacking being bonded is placed on filter paper until the gelatin gel solution being compounded in timbering material is cold
But to room temperature, then timbering material is put into alcohol and solidifies 2h, the temperature of drying box is set in 30 DEG C, timbering material from wine
It takes out and is put into drying box after drying for 24 hours in essence, material is removed from the molds.
It (4) is that 1% glutaraldehyde carries out crosslinking 12h with mass percent concentration by the sample after drying.
(5) by crosslinked sample 5 times wash with distilled water, dry 24 h are placed again into 30 DEG C of drying box, it is dry
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support is obtained after processing, looks figure is as shown in Figure 1.
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials size that the present embodiment is prepared is 10cm
× 10cm, compression strength are (6.1 ± 0.05) Mpa, and porosity 59%, degradation property is to degrade 80% in 120 days, comprehensive analysis
Afterwards, which can be applied in bone defect healing.
According to standard GB/T/T14233.3-2005, using the people's renal epithelial cell for choosing transfection Adenovirus E1A gene
(293T cell) tests gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials cytotoxicity of preparation, real
Test that the results are shown in Table 1:
The relative growth rate of 1 bracket of table
In conjunction with standard GB/T/T14233.3-2005 relevant regulations, cytotoxicity result show gelatin/dicalcium phosphate dihydrate/
For calcium sulphate dihydrate porous support materials concentration in 0.5-2.0mg/ml, relative growth rate (RGR) is between 81-98, cell
Toxicity is 1 grade；Thus illustrate gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate biological support no cytotoxicity.
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate biological support primary color that the present embodiment prepares is Huang
Color；Reason is that gelatin solution is yellow and the surface for being attached to composite pellets particle, so that whole timbering material is in Huang
Color.Fig. 2 is gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate biologic bracket material XRD diagram, it can be seen that is existed in compound rest
Calcium sulphate dihydrate and dicalcium phosphate dihydrate two-phase, and since gelatin is amorphous substance, so there is the disperse of gelatin suctions
Receive peak；Fig. 3 is gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate biologic bracket material scanning analysis figure, it can be seen that timbering material
There is apparent holes between middle spherical particle and particle.
Embodiment 2
A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support, specifically includes step or less:
(1) Bone Defect Repari spherical particle material is prepared by stirring dry spray-on process, by α type half-H 2 O calcium sulphate and phosphate dihydrate
Hydrogen calcium composition, using dicalcium phosphate dihydrate as core, calcium sulphate dihydrate is calculated in mass percent as shell, dicalcium phosphate dihydrate
Content is 50%, remaining is α type half-H 2 O calcium sulphate.
(2) the spherical particle material being prepared is put in homemade mold through mass percent concentration is 20% bright
Glue carries out stacking bonding.
(3) sample after stacking being bonded is placed on filter paper until the gelatin gel solution being compounded in timbering material is cold
But to room temperature, then timbering material is put into alcohol and solidifies 3h, the temperature of drying box is set in 40 DEG C, timbering material from wine
It is taken out in essence after being put into drying box dry 36h, material is removed from the molds.
It (4) is that 2% glutaraldehyde is crosslinked for 24 hours with mass percent concentration by the sample after drying.
(5) it by crosslinked sample 6 times wash with distilled water, is placed again into 40 DEG C of drying box and dries 36h, at drying
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support is obtained after reason.
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials size that the present embodiment is prepared is 10cm
× 10cm, compression strength are (5.9 ± 0.05) Mpa, and porosity 60%, degradation property is to degrade 80% in 115 days, comprehensive analysis
Afterwards, which can be applied in bone defect healing.
It is porous to gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate of preparation according to standard GB/T/T14233.3-2005
Timbering material cytotoxicity is tested (method is with embodiment 1), the experimental results showed that the toxicity of resulting materials is at 0-1 grades, material
Expect nontoxic or has micro- poison when measuring big but meet the available condition of medicine.
Embodiment 3
A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support, specifically includes step or less:
(1) Bone Defect Repari spherical particle material is prepared by stirring dry spray-on process, by α type half-H 2 O calcium sulphate and phosphate dihydrate
Hydrogen calcium composition, using dicalcium phosphate dihydrate as core, calcium sulphate dihydrate is calculated in mass percent as shell, dicalcium phosphate dihydrate
Content is 40%, remaining is α type half-H 2 O calcium sulphate.
(2) the spherical particle material being prepared is put in homemade mold through mass percent concentration is 30% bright
Glue carries out stacking bonding.
(3) sample after stacking being bonded is placed on filter paper until the gelatin gel solution being compounded in timbering material is cold
But to room temperature, then timbering material is put into alcohol and solidifies 5h, the temperature of drying box is set in 30 DEG C, timbering material from wine
It is taken out in essence after being put into drying box dry 48h, material is removed from the molds.
It (4) is that 4% glutaraldehyde is crosslinked for 24 hours with mass percent concentration by the sample after drying.
(5) by crosslinked sample 6 times wash with distilled water, dry 24 h are placed again into 50 DEG C of drying box, it is dry
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support is obtained after processing.
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials size that the present embodiment is prepared is 10cm
× 10cm, compression strength are (6.0 ± 0.05) Mpa, and porosity 61%, degradation property is to degrade 80% in 124 days, comprehensive analysis
Afterwards, which can be applied in bone defect healing.According to state
Family standard GB/T14233.3-2005, to gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials cell toxicant of preparation
Property tested (method is with embodiment 1), the experimental results showed that the toxicity of resulting materials is at 0-1 grades, material non-toxic or big in amount
Shi Youwei is malicious but meets the available condition of medicine.
Embodiment 4
A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support, specifically includes step or less:
(1) Bone Defect Repari spherical particle material is prepared by stirring dry spray-on process, by α type half-H 2 O calcium sulphate and phosphate dihydrate
Hydrogen calcium composition, using dicalcium phosphate dihydrate as core, calcium sulphate dihydrate is calculated in mass percent as shell, dicalcium phosphate dihydrate
Content is 30%, remaining is α type half-H 2 O calcium sulphate.
(2) the spherical particle material being prepared is put in homemade mold through mass percent concentration is 20% bright
Glue carries out stacking bonding.
(3) sample after stacking being bonded is placed on filter paper until the gelatin gel solution being compounded in timbering material is cold
But to room temperature, then timbering material is put into alcohol and solidifies 6h, the temperature of drying box is set in 60 DEG C, timbering material from wine
It is taken out in essence after being put into drying box dry 48h, material is removed from the molds.
It (4) is that 5% glutaraldehyde is crosslinked for 24 hours with mass percent concentration by the sample after drying.
(5) it by crosslinked sample 8 times wash with distilled water, is placed again into 50 DEG C of drying box and dries 48h, at drying
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support is obtained after reason.
Gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials size that the present embodiment is prepared is 10cm
× 10cm, compression strength are (5.8 ± 0.05) Mpa, and porosity 60%, degradation property is to degrade 80% in 123 days, comprehensive analysis
Afterwards, which can be applied in bone defect healing.According to state
Family standard GB/T14233.3-2005, to gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support materials cell toxicant of preparation
Property tested (method is with embodiment 1), the experimental results showed that the toxicity of resulting materials is at 0-1 grades, material non-toxic or big in amount
Shi Youwei is malicious but meets the available condition of medicine.
Claims (4)
1. a kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support, which is characterized in that specifically include
Below step:
(1) it is prepared by stirring dry spray-on process using dicalcium phosphate dihydrate as core, calcium sulphate dihydrate is the core-shell structure sample of shell
Product A, wherein the mass percent of dicalcium phosphate dihydrate is 30%-60%, and the mass percent of calcium sulphate dihydrate is 40-70%；
(2) sample A is put in mold and bonds to obtain sample B by gelatin progress stacking, to the gelatin gel solution in sample B
It is cooled to room temperature, then timbering material is put into alcohol and solidifies 2-6h, timbering material is taken out from alcohol and is dried, then
Material is removed from the molds, sample C is obtained；
(3) the sample C prepared is crosslinked with glutaraldehyde；
(4) by crosslinked sample C 5-8 times wash with distilled water, gelatin/hydrogen phosphate dihydrate is obtained after sample C is dried
Calcium/calcium sulphate dihydrate porous support.
2. gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support preparation method according to claim 1, feature
Be: the mass percent concentration of gelatin gel solution is 10% ~ 30%.
3. gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support preparation method according to claim 1, feature
Be: the drying condition in step (2) and (4) is that drying box temperature is 30-60 DEG C, and drying time is 24-48 h.
4. gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support preparation method according to claim 1, feature
Be: crosslinking condition be with mass percent concentration be 1% ~ 5% glutaraldehyde cross-linking 12 ~ for 24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020085A (en) * | 2007-02-14 | 2007-08-22 | 中国人民解放军总医院 | New-type of inorganic bone grafting material and its prepn and use |
| CN102488920A (en) * | 2011-12-14 | 2012-06-13 | 浙江大学 | Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof |
| US20140294913A1 (en) * | 2013-03-28 | 2014-10-02 | Nesrin Hasirci | Biodegradable bone fillers, membranes and scaffolds containing composite particles |
| CN106377794A (en) * | 2016-08-31 | 2017-02-08 | 昆明理工大学 | Preparation method of strontium-doped beta-TCP/calcium sulfate composite support |
-
2019
- 2019-03-04 CN CN201910158830.XA patent/CN109821066A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020085A (en) * | 2007-02-14 | 2007-08-22 | 中国人民解放军总医院 | New-type of inorganic bone grafting material and its prepn and use |
| CN102488920A (en) * | 2011-12-14 | 2012-06-13 | 浙江大学 | Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof |
| US20140294913A1 (en) * | 2013-03-28 | 2014-10-02 | Nesrin Hasirci | Biodegradable bone fillers, membranes and scaffolds containing composite particles |
| CN106377794A (en) * | 2016-08-31 | 2017-02-08 | 昆明理工大学 | Preparation method of strontium-doped beta-TCP/calcium sulfate composite support |
Non-Patent Citations (1)
| Title |
|---|
| 黄洁: ""骨修复用球状硫酸钙基复合材料制备及其性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20190531 |