CN101235204A - Method for preparing nano-phase hydroxyapatite/fimbrin composite material - Google Patents
Method for preparing nano-phase hydroxyapatite/fimbrin composite material Download PDFInfo
- Publication number
- CN101235204A CN101235204A CNA2008100523282A CN200810052328A CN101235204A CN 101235204 A CN101235204 A CN 101235204A CN A2008100523282 A CNA2008100523282 A CN A2008100523282A CN 200810052328 A CN200810052328 A CN 200810052328A CN 101235204 A CN101235204 A CN 101235204A
- Authority
- CN
- China
- Prior art keywords
- hydroxyapatite
- silk fibroin
- reaction
- composite material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a preparation process of nano-hydroxyapatite/ silk fibroin composite material, which comprises choosing CaC1 2-C 2 H5 OH-H2O ternary system with molar ratio of 1:2:8 as solution, adding silk fibroin fiber which has fully been degelatinized according to the proportion that mass fraction is 3-14.68 (w/w) under the temperature of 75+-5 DEG C, dissolving 0.5h to obtain silk fibroin solution whose mass fraction is 3-14.68 (w/w), adding diammonium phosphate in silk fibroin solution according to the molar ration that calcium: phosphorus=10:6 under the condition of uniform stirring, finishing the dripping within 2-5h, then continuing compound reaction for 2-3h, wherein the temperature in former 2-4h is 30-60 DEG C, and the temperature of the latter 2-4h is 60-100 DEG C in the whole 4-8h reaction process, paying attention to the change of pH value of reaction system, regulating the pH value to 9-12 with ammonial solution which is diluted, and obtaining the composite material through filtering, fully repeatedly scouring and filtering after finished reaction.
Description
Technical field
The present invention relates to the Composite Preparation technology, be specially a kind of preparation method of nanophase hydroxyapatite/fibroin albumen composite material, the matrix material that makes can be applicable to the damaged reparation of bone and substitutes, and international Patent classificating number intends being Int.Cl.A61L 27/12 (2006.01).
Background technology
(be called for short HA, chemical formula is Ca to hydroxyapatite
10(OH)
2(PO
4)
6) be a kind of typical biomaterial, have good biocompatibility and biological activity.It can contact with blood and not produce blood coagulation, and slight tissue reaction is only arranged in soft tissue and bone.Contain in the composition of hydroxyapatite and can carry out elements such as metathetical calcium, phosphorus by human body normal metabolic approach; Also contain can with the groups such as hydroxyl of tissue generation bonding, the combination by key reaches affine completely, thereby it is partly or entirely absorbed by tissue and replaces, and is a kind of extremely valuable bone alternate material.
The method for preparing hydroxyapatite mainly contains dry method and synthesizes and synthetic two kinds of wet method.Wherein wet method is synthesized and is comprised hydrothermal synthesis method, chemical precipitation method, microemulsion method and sol-gel processing.But clinic study shows: the artificial bone that uses single hydroxyapatite to make is frangible, intensity is low, poor toughness, has limited its clinical application and usefulness performance.For this reason, the investigator adopts other material and hydroxyapatite to carry out compound use, attempts to improve or improve the mechanical property of the bone shaping spare of being made by single hydroxyapatite.At present, can carry out the compound material with hydroxyapatite and roughly be divided three classes: 1. natural biologic material, as collagen, scleroblast, silk fibroin and scleroproein tamanori etc.; 2. non-natural Biodegradable material is as poly(lactic acid), chitosan etc.; 3. other material is as polyester, polymeric amide, urethane, polyethylene, polyvinyl alcohol etc.Studies confirm that, with hydroxyapatite and above-mentioned substance compound after, formed bone shaping spare improves a lot on mechanical property or even biological property.
But, recombining process commonly used at present is that hydroapatite particles mixes with the mechanical-physical of composite high-molecular thing basically, its mixed-scale and homogeneity are difficult to guarantee, the combination of composite inner two alternate shortage chemical bonds, interface binding power is firm inadequately, be difficult to form orderly microtexture, inorganic particles is still not ideal in the degree of scatter of polymer in mutually, and the degradation rate of material can't be controlled well.Therefore, biocompatibility, processibility and mechanical property etc. for the optimization of composite property, optimization of preparation, raising matrix material also need further research.
On the other hand, medical research shows, must satisfy three basic demands as the hydroxyapatite composite material of bone shaping spare: biocompatibility, biological activity and favorable mechanical performance.Because the kind that fibroin protein (hereinafter to be referred as SF) is amino acid contained and the characteristics of space structure make silk fibroin and tissue have the excellent biological compatibility energy, can be used as and exempt to tear open operating sutures use in the anthropoid body.And silk fibroin belongs to polymer, has certain mechanical strength and adhesion, satisfy fully theoretically and the nanophase hydroxyapatite between compound, be used to develop the bone alternate material of superior performance.This compound existing research about hydroxyapatite and silk fibroin.For example, the someone studied on both complex methods adopt " two-step approach " recombining process (referring to Lu Divine Land, Li Mingzhong etc., silk, 2006.2:7-19).Should " two-step approach " technological process be: the first step be the preparation of silk fibroin protein solution.The preparation method of this solution is, is 1: 2: 8 CaCl with degumed silk cellulose fiber mol ratio
2-C
2H
5OH-H
2The ternary solvent system that O forms in (70 ± 2) ℃ stirring and dissolving, obtains mixing solutions after the filtration, mixing solutions obtains pure silk fibroin solution after the dialysis purification concentrates; Second step was the preparation of hydroxyapatite and fibroin albumen composite material.The concrete grammar of this Composite Preparation is: 1. analytical pure lime carbonate is made calcium oxide in 1050 ℃ of calcining 3h, take by weighing a certain amount of being dissolved in the deionized water, stir the suspension that forms different concns; 2. add 1L water in the there-necked flask, put into ultrasonic oscillator, be heated to certain temperature, (HA: SF=4: 1), gradation adds the above-mentioned suspension that is 1. obtained again by being metered into the pure silk fibroin solution that has made; 3. drip phosphoric acid solution in proportion, control pH value is 8～9, is added dropwise to complete the back and continues to stir 3h, and room temperature is sealed ageing 48h; 4. use deionized water wash, suction filtration 3 times; 5. use absolute ethanol washing, suction filtration 3 times, after the drying, can obtain the composite particles of the two.Result of study shows, the phosphatic rock crystallite has similarity in hydroxyapatite/silk fibroin composite nanoparticle of making of method and the people's bone thus, body material also has degradability and excellent osteoinductive energy, and the potential purposes is being arranged aspect bone reparation or the bone immobilizing material.
Though above-mentioned result of study illustrated hydroxyapatite and silk fibroin carry out compound after, its nanoparticle has good biological property, its recombining process still belongs to both simple physics blend.Whether even to blended, whether that finishes on nano-scale is compound, and it is last that can hydroxyapatite and silk fibroin form combining of key, still existing problems.In addition, this preparation method is in filtration-dialysis that silk fibroin protein solution is carried out-spissated process, and both water consumption was consuming time again, also can bring the discharging of a large amount of salt, and this does not conform to the green processing developing direction with energy-conservation, reduction of discharging.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined provides a kind of preparation method of nanophase hydroxyapatite/fibroin albumen composite material.This preparation method can realize compound on nano-scale of hydroxyapatite and silk fibroin molecular, and compound evenly good, can form the matrix material of nano level network structure; Simultaneously this preparation method have water saving, save time, energy-conservation, the characteristics that reduce discharging, be suitable for actual promoting the use of.
The technical scheme that the present invention solves described composite material and preparation method thereof technical problem is: design a kind of preparation method of nanophase hydroxyapatite/fibroin albumen composite material, this preparation method's technological process is: selecting mol ratio for use is 1: 2: 8 CaCl
2-C
2H
5OH-H
2The O ternary system is made solvent, is the fibroin fiber that the ratio input of 3～15% (w/w) is fully come unstuck in massfraction under 75 ± 5 ℃, behind the dissolving 0.5h, makes the silk fibroin protein solution that massfraction is 3～14.68% (w/w); Under at the uniform velocity stirring, by calcium: the molar ratio of phosphorus=10: 6 adds Secondary ammonium phosphate in silk fibroin protein solution, and at the uniform velocity dropwises in 2～5h, continues complex reaction 2～3h then; In the reaction process of whole 4～8h, homo(io)thermism is 30～60 ℃ in preceding 2～4h, and homo(io)thermism is 60～100 ℃ in the 2～4h of back; And want the pH value of attentive response system to change, and be 9～12 with the ammoniacal liquor conditioned reaction system pH of diluting; After reaction finishes, after filtration, wash fully repeatedly, refilter, can obtain described nanophase hydroxyapatite/fibroin albumen composite material.
Compared with prior art, preparation method of the present invention is the reaction recombining process of " single stage method ", and it is simple to have preparation technology, and equipment requirements is low, and be a kind ofly save time, water saving, energy-conservation, " green production " method of reducing discharging, meet the requirement that modern civilization is produced.The prepared matrix material of the present invention has inner two-phase interface bonding strength height, and hydroxyapatite crystal is evenly distributed, and is compound fully good along c axle oriented growth, is network structure, and advantage such as mechanical mechanics property raising.
Description of drawings
Fig. 1 is the complex reaction schematic flow sheet of a kind of embodiment of preparation method of nanophase hydroxyapatite/fibroin albumen composite material of the present invention;
Fig. 2 is the transmission electron microscope photo figure of nanophase hydroxyapatite/fibroin albumen composite material of being obtained of the embodiment of the invention 1 preparation method;
Fig. 3 is the X-ray diffractogram of nanophase hydroxyapatite/fibroin albumen composite material of being obtained of the embodiment of the invention 1 preparation method;
Fig. 4 is a mistake! It is invalid to link.The infrared spectrogram of nanophase hydroxyapatite/fibroin albumen composite material that embodiment 1 preparation method is obtained.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
The preparation method (hereinafter to be referred as the preparation method, referring to Fig. 1) of the nanophase hydroxyapatite/fibroin albumen composite material (hereinafter to be referred as matrix material) of the present invention design, its technological process is: selecting mol ratio for use is 1: 2: 8 CaCl
2-C
2H
5OH-H
2The O ternary system is made solvent, is the fibroin fiber that the ratio input of 3～15% (w/w) is fully come unstuck in massfraction under 75 ± 5 ℃, behind the dissolving 0.5h, can make the silk fibroin protein solution that massfraction is 3～14.68% (w/w); Under at the uniform velocity stirring, by calcium: the mol ratio of phosphorus=10: 6 is added Secondary ammonium phosphate in prepared silk fibroin protein solution, and at the uniform velocity dropwises in 2～5h, continues complex reaction 2～3h then; In the reaction process process of whole 4～8h, adopt stage temperature control method control reaction, promptly (preceding 2～4h) the inner control homo(io)thermism of reaction are 30～60 ℃ to first half term, and (back 2～4h) the inner control homo(io)thermism of reaction are 60～100 ℃ to the second half; In the total overall reaction technological process, the pH value of attentive response system to change, and be 9～12 with the pH value of the ammoniacal liquor conditioned reaction system of diluting; After reaction finishes, after filtration, wash fully repeatedly, refilter, can obtain described nanophase hydroxyapatite/fibroin albumen composite material.Among the preparation method of the present invention, the degumming technology of described fibroin fiber is a prior art.
" two-step approach " of prior art is nanometer hydroxyapatite and the fibroin pure protein solution for preparing respectively, the compound substance of two kinds of materials that adopt the method preparation of blend and obtain, this method is difficult to realize well compound on the nanoscale, thereby causes the defective of matrix material.The present invention is different from prior art " two-step approach ", its reaction is in a reaction system, both can obtain the hydroxyapatite of nanoscale, can impel silk fibroin (SF) to follow the generation of hydroxyapatite and synchronous precipitation again, realized two kinds of components compound on nanoscale, prepared matrix material is evenly good, is a kind of matrix material of nano level network structure.
" two-step approach " arts demand of prior art requires to have time enough, water and energy to the purge process of protein soln.Because the protein purification method mainly is a dialysis process, and dialysis procedure not only needs a large amount of pure water, and can produce more sewage, also need considerable time, to finish the stripping of calcium chloride material in the protein soln; Simultaneously, in dialysis procedure, because of the effect of solution osmotic pressure makes the concentration of protein soln reduce, therefore with the nanometer hydroxyapatite compound tense, in order to improve the content of protein in matrix material, must the protein soln that obtain be concentrated, complex process is consuming time quite long.Preparation method of the present invention is " single stage method " technology, does not need the purge process to protein soln, thus have water saving, save time, energy-conservation, the characteristics that reduce discharging, meet direction of industry, be suitable for actual promoting the use of.
The prepared matrix material of the present invention proves that through the chemical method test ratio of calcium and phosphorus of gained matrix material is between 1.6692～1.6740; The content of silk fibroin is 10～30% (w/w).What of silk fibroin content are depended on the difference (referring to embodiment 1-5) of compound preparation technology parameter.Transmission electron microscope observing is (referring to Fig. 2) as can be seen, the matrix material that is obtained have inner two-phase interface in conjunction with good, hydroxyapatite crystal is evenly distributed, along C axle oriented growth, compound fully good, be the characteristics of network structure; X-ray diffraction test shows (referring to Fig. 3), diffraction spectrogram is similar to hydroxyapatite, and through the Rietveld analytical method as can be known, the crystal of the material that obtains has good growth characteristics along the C direction of principal axis; Infrared spectra proves (referring to Fig. 4), and the chemical constitution of the matrix material that is obtained has embodied the chromatogram characteristic of protein and hydroxyapatite, does not produce new chemical bond combination between the two.
Matrix material of the present invention is applicable to makes bone shaping spare, perhaps is used for the damaged or reparation that damages of bone or substitutes, and has excellent biological compatibility and mechanical property.
The present invention does not address part and is applicable to prior art.
Below illustrative specific embodiment can to help further to understand this law bright, but claim of the present invention is not subjected to the restriction of embodiment.
Embodiment 1
The degumed silk cellulose fiber that 2.78g is fully come unstuck is dissolved in 27.68g CaCl
2, 35.98g C
2H
5OH, 28.60g H
2In the ternary system solvent that O formed, under 75 ± 2 ℃, carry out stirring and dissolving, obtain weak yellow liquid behind the 0.5h; The gained weak yellow liquid is placed in three mouthfuls of round-bottomed flasks of 1L, more described flask is put into thermostat water bath, load onto agitator, normal pressure dropping funnel and pH telltale; Take by weighing (NH
4) HPO
419.80g, be dissolved in the 500ml water, regulate pH value to 10.5 with ammoniacal liquor, obtain diammonium hydrogen phosphate solution; Start agitator, evenly drip the ammonium dibasic phosphate solution of gained thereupon with the speed of 2.4ml/min, complex reaction 3.5h is controlled at 30 ℃ in the temperature of the preceding 2h of complex reaction, and back 0.5h temperature is controlled at 60 ℃; After reaction finishes, after vacuum filtration, washing, ultra red ray drying, grinding, can obtain pulverous described matrix material.
The matrix material that the present embodiment method makes behind chemical method test, projection electron microscopic observation, X-ray diffraction test and examination of infrared spectrum, draws following feature respectively:
Ratio of calcium and phosphorus is 1.6695, and is consistent with the ratio of calcium and phosphorus in the standard hydroxyapatite;
Inner two-phase compound evenly good, have network structure, be needle-like or columnar grain; The grain-size of calculating gained through the Rietveld analytical method is less than 50nm (referring to Fig. 2, Fig. 3), and belongs to hexagonal system, and unit cell parameters is a=b=9.3383 * 10
-10M, c=6.9011 * 10
-10M is 125.3441 * 10 along c direction of principal axis average grain size
-10M;
Contain hydroxyapatite and silk fibroin functional group separately, and do not contain new chemical functional group (referring to accompanying drawing 4);
Silk fibroin content in the matrix material is 10% (w/w).
Embodiment 2
The fibroin fiber that 4.41g is fully come unstuck is dissolved in 27.68g CaCl
2, 35.98g C
2H
5OH, 28.60gH
2In the ternary system solvent that O formed, under 72 ± 2 ℃, carry out stirring and dissolving, obtain weak yellow liquid behind the 0.5h; The gained weak yellow liquid is placed in three mouthfuls of round-bottomed flasks of 1L, more described flask is put into thermostat water bath, load onto agitator, normal pressure dropping funnel and pH telltale; Take by weighing (NH
4) HPO
419.80g, be dissolved in the 500ml water, regulate pH value to 11 with ammoniacal liquor, obtain diammonium hydrogen phosphate solution; Start agitator, evenly drip the ammonium dibasic phosphate solution of gained thereupon with the speed of 2.4ml/min, complex reaction 4h is controlled at 30 ℃ in the preceding 3h temperature of complex reaction, and back 1h temperature is controlled at 60 ℃; After reaction finishes, after vacuum filtration, washing, ultra red ray drying, grinding, can obtain pulverous described matrix material.
After the detection of matrix material that present embodiment obtains, have following feature through being same as embodiment 1:
Ratio of calcium and phosphorus is 1.6692, and is consistent with the ratio of calcium and phosphorus in the standard hydroxyapatite;
Inner two-phase compound evenly good, have network structure, be needle-like or columnar grain; Grain-size belongs to hexagonal system less than 50nm, and unit cell parameters is a=b=9.0859 * 10
-10M, c=6.9816 * 10
-10M is 168.2896 * 10 along c direction of principal axis average grain size
-10M;
Contain hydroxyapatite and silk fibroin functional group separately, and do not contain new chemical functional group;
Silk fibroin content in the matrix material is 15% (w/w).
Embodiment 3
The difference of present embodiment and embodiment 2 is that the add-on of fibroin fiber is 6.25g.Surplus with embodiment 2.
After the detection of matrix material that this enforcement obtains, have following feature through being same as embodiment 1:
Ratio of calcium and phosphorus is 1.6698, and is consistent with the ratio of calcium and phosphorus in the standard hydroxyapatite;
Inner two-phase compound evenly good, have network structure, be needle-like or columnar grain; Grain-size belongs to hexagonal system less than 50nm, and unit cell parameters is a=b=9.0319 * 10
-10M, c=7.0148 * 10
-10M is 227.7282 * 10 along c direction of principal axis average grain size
-10M;
Contain hydroxyapatite and silk fibroin functional group separately, and do not contain new chemical functional group;
Silk fibroin content in the matrix material is 20% (w/w).
Embodiment 4
The degumed silk cellulose fiber that 8.33g is fully come unstuck is dissolved in 27.68g CaCl
2, 35.98g C
2H
5OH, 28.60g H
2In the ternary system solvent that O formed, under 78 ± 2 ℃, carry out stirring and dissolving, obtain weak yellow liquid behind the 0.5h; The gained weak yellow liquid is placed in three mouthfuls of round-bottomed flasks of 1L, more described flask is put into thermostat water bath, load onto agitator, normal pressure dropping funnel and pH telltale; Take by weighing (NH
4) HPO
419.80g, be dissolved in the 500ml water, regulate pH value to 11.5 with ammoniacal liquor, obtain diammonium hydrogen phosphate solution; Start agitator, evenly drip the ammonium dibasic phosphate solution of gained thereupon with the speed of 2.4ml/min, complex reaction 5.5h is controlled at 30 ℃ in the preceding 3h temperature of complex reaction, and back 2.5h temperature is controlled at 60 ℃; After reaction finishes, after vacuum filtration, washing, ultra red ray drying, grinding, can obtain pulverous described matrix material.
After the detection of matrix material that present embodiment obtains, have following feature through being same as embodiment 1:
Ratio of calcium and phosphorus is 1.6699, and is consistent with the ratio of calcium and phosphorus in the standard hydroxyapatite;
Inner two-phase compound evenly good, have network structure, be needle-like or columnar grain; Grain-size belongs to hexagonal system less than 50nm, and unit cell parameters is a=b=9.0319 * 10
-10M, c=7.0418 * 10
-10M is 230.7645 * 10 along c direction of principal axis average grain size
-10M;
Contain hydroxyapatite and silk fibroin functional group separately, do not contain new chemical functional group;
Silk fibroin content in the matrix material is 25% (w/w).
Embodiment 5
The concrete preparation process of present embodiment is identical with embodiment 4, and difference is that the add-on of fibroin fiber is 10.71g.After the detection of matrix material that present embodiment obtains, have following feature through being same as embodiment 1:
Ratio of calcium and phosphorus is 1.6693, and is consistent with the ratio of calcium and phosphorus in the standard hydroxyapatite;
Inner two-phase compound evenly good, have network structure, be needle-like or columnar grain; Grain-size belongs to hexagonal system less than 50nm, and unit cell parameters is a=b=8.8950 * 10
-10M, c=7.7209 * 10
-10M is 152.4232 * 10 along c direction of principal axis average grain size
-10M;
Contain hydroxyapatite and silk fibroin functional group separately, and do not contain new chemical functional group;
Silk fibroin content in the matrix material is 30% (w/w).
Claims (2)
1. the preparation method of a nanophase hydroxyapatite/fibroin albumen composite material, this preparation method's technological process is: selecting mol ratio for use is 1: 2: 8 CaCl
2-C
2H
5OH-H
2The O ternary system is made solvent, is the fibroin fiber that the ratio input of 3～15% (w/w) is fully come unstuck in massfraction under 75 ± 5 ℃, behind the dissolving 0.5h, makes the silk fibroin protein solution that massfraction is 3～14.68% (w/w); Under at the uniform velocity stirring, by calcium: the mol ratio of phosphorus=10: 6 is added Secondary ammonium phosphate in silk fibroin protein solution, and at the uniform velocity dropwises in 2～5h, continues complex reaction 2～3h then; In the reaction process of whole 4～8h, homo(io)thermism is 30～60 ℃ in preceding 2～4h, and homo(io)thermism is 60～100 ℃ in the 2～4h of back; And want the pH value of attentive response system to change, and be 9～12 with the ammoniacal liquor conditioned reaction system pH of diluting; After reaction finishes, after filtration, wash fully repeatedly, refilter, can obtain described nanophase hydroxyapatite/fibroin albumen composite material.
2. nanophase hydroxyapatite/fibroin albumen composite material is characterized in that the preparation method's preparation according to claim 1 of described matrix material and gets that its ratio of calcium and phosphorus is between 1.6692～1.6740; The content of its silk fibroin is 10～30% (w/w).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100523282A CN101235204B (en) | 2008-02-26 | 2008-02-26 | Method for preparing nano-phase hydroxyapatite/fimbrin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100523282A CN101235204B (en) | 2008-02-26 | 2008-02-26 | Method for preparing nano-phase hydroxyapatite/fimbrin composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101235204A true CN101235204A (en) | 2008-08-06 |
| CN101235204B CN101235204B (en) | 2010-08-11 |
Family
ID=39919126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100523282A Expired - Fee Related CN101235204B (en) | 2008-02-26 | 2008-02-26 | Method for preparing nano-phase hydroxyapatite/fimbrin composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101235204B (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482497A (en) * | 2009-07-31 | 2012-05-30 | 科学与工业研究委员会 | Accelerated Gelation Of Regenerated Fibroin |
| CN102491299A (en) * | 2011-11-14 | 2012-06-13 | 苏州大学 | Preparation method of nano hydroxyapatite |
| CN101474429B (en) * | 2009-01-22 | 2012-10-10 | 浙江理工大学 | Method for preparing hydroxylapatite-silk fibroin compound stent material using two-step method |
| CN103041447A (en) * | 2012-12-14 | 2013-04-17 | 深圳先进技术研究院 | Injectable silk fibroin bone repair filling sustained-release material, and preparation method and application thereof |
| CN103432629A (en) * | 2013-07-22 | 2013-12-11 | 苏州三和开泰花线织造有限公司 | Preparation method for silk fibroin/hydroxyapatite composite material |
| CN103738932A (en) * | 2013-12-13 | 2014-04-23 | 苏州大学 | Nano-hydroxyapatite and preparation method thereof |
| CN104043149A (en) * | 2014-06-20 | 2014-09-17 | 苏州大学 | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof |
| CN105780487A (en) * | 2016-04-21 | 2016-07-20 | 安徽皖翎羽绒制品有限公司 | Waterborne polyurethane coating agent containing superfine down feather fiber-hydroxyapatite composite microsphere |
| CN109806445A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院化学研究所 | Biocompatible materials and preparation method, dual bone tissue reparation or alternative materials and preparation method and application |
| CN109806443A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院化学研究所 | Bone holder material and its preparation method and application |
| CN110227181A (en) * | 2019-05-31 | 2019-09-13 | 武汉大学 | A kind of preparation method and applications of fibroin albumen composite hydroxylapatite material |
| CN110624131A (en) * | 2019-10-14 | 2019-12-31 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of degradable intervertebral fusion device surface bioactive coating and product thereof |
| CN110917400A (en) * | 2019-12-05 | 2020-03-27 | 中山大学 | Nano-hybrid silk fibroin hydrogel and preparation method and application thereof |
| CN111422977A (en) * | 2020-01-19 | 2020-07-17 | 浙江大学 | Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate |
| CN111849013A (en) * | 2020-07-14 | 2020-10-30 | 重庆医科大学附属口腔医院 | Nano-hydroxyapatite-silk fibroin mineralized scaffold and preparation method and application thereof |
| CN113209378A (en) * | 2021-05-25 | 2021-08-06 | 四川大学 | Injectable silk fibroin/nano hydroxyapatite composite hydrogel and preparation method thereof |
-
2008
- 2008-02-26 CN CN2008100523282A patent/CN101235204B/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474429B (en) * | 2009-01-22 | 2012-10-10 | 浙江理工大学 | Method for preparing hydroxylapatite-silk fibroin compound stent material using two-step method |
| CN102482497A (en) * | 2009-07-31 | 2012-05-30 | 科学与工业研究委员会 | Accelerated Gelation Of Regenerated Fibroin |
| CN102482497B (en) * | 2009-07-31 | 2014-07-30 | 科学与工业研究委员会 | Accelerated Gelation Of Regenerated Fibroin |
| CN102491299A (en) * | 2011-11-14 | 2012-06-13 | 苏州大学 | Preparation method of nano hydroxyapatite |
| CN102491299B (en) * | 2011-11-14 | 2013-11-27 | 苏州大学 | Preparation method of nano hydroxyapatite |
| CN103041447B (en) * | 2012-12-14 | 2015-04-22 | 深圳先进技术研究院 | Injectable silk fibroin bone repair filling sustained-release material, and preparation method and application thereof |
| CN103041447A (en) * | 2012-12-14 | 2013-04-17 | 深圳先进技术研究院 | Injectable silk fibroin bone repair filling sustained-release material, and preparation method and application thereof |
| CN103432629A (en) * | 2013-07-22 | 2013-12-11 | 苏州三和开泰花线织造有限公司 | Preparation method for silk fibroin/hydroxyapatite composite material |
| CN103738932B (en) * | 2013-12-13 | 2016-04-20 | 苏州大学 | A kind of nanometer hydroxyapatite and preparation method thereof |
| CN103738932A (en) * | 2013-12-13 | 2014-04-23 | 苏州大学 | Nano-hydroxyapatite and preparation method thereof |
| CN104043149A (en) * | 2014-06-20 | 2014-09-17 | 苏州大学 | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof |
| CN105780487A (en) * | 2016-04-21 | 2016-07-20 | 安徽皖翎羽绒制品有限公司 | Waterborne polyurethane coating agent containing superfine down feather fiber-hydroxyapatite composite microsphere |
| CN109806445A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院化学研究所 | Biocompatible materials and preparation method, dual bone tissue reparation or alternative materials and preparation method and application |
| CN109806443A (en) * | 2017-11-21 | 2019-05-28 | 中国科学院化学研究所 | Bone holder material and its preparation method and application |
| CN110227181A (en) * | 2019-05-31 | 2019-09-13 | 武汉大学 | A kind of preparation method and applications of fibroin albumen composite hydroxylapatite material |
| CN110624131A (en) * | 2019-10-14 | 2019-12-31 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of degradable intervertebral fusion device surface bioactive coating and product thereof |
| CN110917400A (en) * | 2019-12-05 | 2020-03-27 | 中山大学 | Nano-hybrid silk fibroin hydrogel and preparation method and application thereof |
| CN110917400B (en) * | 2019-12-05 | 2022-03-29 | 中山大学 | Nano-hybrid silk fibroin hydrogel and preparation method and application thereof |
| CN111422977A (en) * | 2020-01-19 | 2020-07-17 | 浙江大学 | Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate |
| CN111422977B (en) * | 2020-01-19 | 2021-10-01 | 浙江大学 | Preparation method for constructing multilayer duplex-structure water treatment biological membrane by taking silkworm plane silk as substrate |
| CN111849013A (en) * | 2020-07-14 | 2020-10-30 | 重庆医科大学附属口腔医院 | Nano-hydroxyapatite-silk fibroin mineralized scaffold and preparation method and application thereof |
| CN113209378A (en) * | 2021-05-25 | 2021-08-06 | 四川大学 | Injectable silk fibroin/nano hydroxyapatite composite hydrogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101235204B (en) | 2010-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101235204B (en) | Method for preparing nano-phase hydroxyapatite/fimbrin composite material | |
| Wang et al. | Biomimetic collagen/hydroxyapatite composite scaffolds: fabrication and characterizations | |
| CN107265426B (en) | template-mediated synthesis of silicon-containing hydroxyapatite material and preparation method thereof | |
| CN105536050B (en) | A kind of graphene oxide is modified bone cement and preparation method and application | |
| CN106565974B (en) | Alginate/hydroxyapatite overlong nanowire composite hydrogel | |
| CN103071447B (en) | Method for preparing strontium-doped hydroxyapatite through supersound | |
| CN104961114B (en) | Calcium and magnesium phosphate nano structural material and preparation method thereof | |
| CN109133907A (en) | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor | |
| CN113460986B (en) | Method for preparing hydroxyapatite microsphere with core-shell structure by one-step method and application thereof | |
| CN103028146B (en) | Reinforcement medical composite material and method for preparing same | |
| CN108404203A (en) | A kind of preparation method of redox graphene/bio-vitric nano fiber scaffold | |
| CN102491300B (en) | Preparation method of amphiphilic monodisperse hydroxyapatite monocrystal nanorod | |
| CN103058159B (en) | Hollow hierarchical hydroxyapatite microspheres and preparation method and application thereof | |
| CN101254909A (en) | Method for preparing meso-porous nano hydroxyl phosphorite crystal | |
| CN106927441A (en) | A kind of aperture controllable hollow hydroxyapatite micro-sphere, preparation method and applications | |
| CN110215537A (en) | A kind of nanoscale calcium citrate/hydroxyapatite composite powder of controllable crystallinity and preparation method thereof | |
| Sha et al. | A modified calcium silicate composite bone cement prepared from polyethylene glycol and graphene oxide for biomaterials | |
| Wang et al. | Three-dimensional porous network structure developed in hydroxyapatite-based nanocomposites containing enzyme pretreated silk fibroin | |
| CN103738932B (en) | A kind of nanometer hydroxyapatite and preparation method thereof | |
| CN104909345A (en) | Preparation method for carbonate-doped rod hydroxyapatite powder | |
| CN101905039B (en) | Large-aperture porous hydroxyapatite/chitosan/polyvinylalcohol bone alternate material | |
| CN105457090A (en) | Magnesium partially substituted hydroxyapatite fiber and preparation method and application thereof | |
| CN101401951A (en) | Calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof | |
| CN101214382A (en) | Method for preparing europium-labeled hydroxyapatite nano particle | |
| CN108434523A (en) | A kind of preparation method of strontium doping hydroxyapatite laminated film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100811 Termination date: 20130226 |