CN104043149A - Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof - Google Patents
Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof Download PDFInfo
- Publication number
- CN104043149A CN104043149A CN201410280003.5A CN201410280003A CN104043149A CN 104043149 A CN104043149 A CN 104043149A CN 201410280003 A CN201410280003 A CN 201410280003A CN 104043149 A CN104043149 A CN 104043149A
- Authority
- CN
- China
- Prior art keywords
- silk fibroin
- bone cement
- calcium phosphate
- hydroxylapatite
- 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.)
- Pending
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a hydroxyapatite-silk fibroin (HA-SP) composite reinforced calcium phosphate bone cement and a preparation method thereof. The preparation method comprises the following steps: doping the calcium phosphate bone cement powder with 1-4wt.% of hydroxyapatite-silk fibroin composite, taking a silk fibroin solution as a blending solution and carrying out blending in a liquid-solid ratio L/P=0.33-0.4mL/g, and solidifying to obtain the hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement. The hydroxyapatite-silk fibroin composite adopted in the preparation of the calcium phosphate bone cement is capable of effectively improving the interface compatibility of organic and inorganic phases and increasing the interface bonding force in the calcium phosphate bone cement/silk fibroin (CPC/SF) system, and thus capable of improving the mechanical properties of the calcium phosphate bone cement; the silk fibroin solution is taken as the solidifying solution so that the collapse resistance of the calcium phosphate bone cement can be effectively improved; the mechanical properties of the bone cement are improved to meet the basic requirements of clinical application.
Description
Technical field
The present invention relates to medical technical field, be specifically related to the packing material that the most often adopts in operation, particularly a kind of hydroxylapatite-silk fibroin strengthens calcium phosphate bone cement and preparation method thereof.
Background technology
Osteoporotic or traumatic fracture are very common.In the U.S., approximately there are every year 1500000 routine osteoporotic fractures, wherein betiding spinal column is 750,000 examples, far above Other diseases such as heart diseases, medical nursing cost exceedes 13,800,000,000 dollars in nineteen ninety-five, estimates that the year two thousand thirty will be greater than 60,000,000,000 dollars.Vertebral compression fracture (Vertebral Compression Fractures, VCF) not only incidence rate is high, and consequence is serious, the deformity of spine that vertebral compression fracture causes progressively affects lung, gastrointestinal function, also may cause chronic back pain, insomnia, movable minimizing etc., cause quality of life sharply to decline, report shows that the mortality rate in 5 years reaches 34%.
Minimally-invasive treatment day by day prevailing, as percutaneous vertebroplasty (Percutaneous vertebroplasty, and percutaneous balloon kyphoplasty (Percutaneous kyphoplasty PVP), PKP), reduction of patient pain rapidly, fractured vertebral body is resetted, improve pulmonary function, demonstrate great superiority.
At present, the packing material that PVP/PKP the most often adopts in performing the operation is clinically polymethyl methacrylate (Polymethylmethacrylate, PMMA).But there is a lot of shortcomings in PMMA: polymerization with monomer have certain toxicity and the polymer biological compatibility poor, a large amount of heat releases of polymerization process damage surrounding tissue, its mechanical strength easily forms stress shielding far above natural bone around simultaneously.These shortcomings have caused PMMA that some serious complication usually can occur in the time of clinical practice.
And calcium phosphate bone cement (Calcium phosphate cement, CPC) solidifying end-product is hydroxyapatite (Hydroxyapatite, HA), extremely similar to the inorganic constituents of body bone tissue, show excellent biocompatibility, good bone conduction ability, in addition, CPC energy self-curing and heat release are few, injectable is moulding, energy slow degradation, and the energy various medicines of load and somatomedin [Zhang J, Liu W, Schnitzler V, Tancret F, Bouler J-M.Calcium phosphate cements for bone substitution:Chemistry, handling and mechanical properties.Acta Biomaterialia.2013].Therefore, attracted increasing researcher and orthopedist's concern.But CPC mechanical strength is lower, fragility is large, has the shortcoming of length hardening time, bad adhesion simultaneously, and these have all limited its range of application, cannot meet the requirement of PVP/PKP.
At present, the main method addressing the above problem is that CPC and degradable high polymer are carried out compound.A large amount of organic synthesis high polymers is all attempted being applied to the mechanical property of improving CPC.Now existing by Poly(D,L-lactide-co-glycolide (poly (lactic-co-glycolic acid), PLGA) microparticle is compound in CPC having no significant effect hardening time and end-product, when PLGA ratio reaches 30wt%, compressive strength is brought up to 24MPa by 12MPa, and elastic modelling quantity is brought up to 8GPa by 2GPa.But the acid compound that degradable macromolecule degraded produces has certain side effect to surrounding tissue.And the contained albumen of many natural high polymers, polysaccharide are similar to tissue, thereby possesses unique advantage.
Fibroin albumen (Silk fibroin, SF) be a kind of native protein, contain 18 seed amino acids including the necessary aminoacid of human body, as: glycine (Gly), alanine (Ala), serine (Ser).Large quantity research shows that fibroin albumen has mechanical property and the modifiability of good biocompatibility, degradability, excellence, thereby has a wide range of applications.The people such as Xie Ruijuan carry out silk fibroin powder and CPC compound, and research finds, fibroin ratio is in 0～3% scope, and setting time shortens along with the increase of fibroin ratio; In the time that fibroin ratio is increased to 4% by 3%, CPC/SF composite modulation is irregular, does not have an injectivity; Composite S F can improve the bending strength of CPC, brings up to 5.3MPa (2%) [Xie Ruijuan, Deng Qiming, the preparation of Zhan Hong continent .CPC/SF composite from 0.9MPa.Textile journal .2009; 30:5-9].But because the interface compatibility between inorganic phase and organic facies is poor, biphase adhesion is poor, is difficult to significantly improve the mechanical strength of CPC.
Summary of the invention
Technical problem to be solved by this invention is to provide calcium phosphate bone cement of a kind of hydroxylapatite-silk fibroin complex enhancing and preparation method thereof, to meet the application requirements of PVP/PKP.
For addressing the above problem, the technical scheme that first aspect present invention provides is: the preparation method of the calcium phosphate bone cement that a kind of hydroxylapatite-silk fibroin complex strengthens,
It is characterized in that, comprise the steps:
In calcium phoshate bone cement powder, mix the hydroxylapatite-silk fibroin complex of 1～4wt.%, using silk fibroin protein solution as distiller liquor, be in harmonious proportion by the liquid-solid ratio of L/P=0.33～0.4mL/g, solidify and obtain the calcium phosphate bone cement that hydroxylapatite-silk fibroin strengthens.
Preferably, described silk fibroin protein solution concentration is 4～10wt.%.
Preferably, described hydroxylapatite-silk fibroin complex is to prepare by coprecipitation, wherein hydroxyapatite: fibroin albumen weight ratio=8:2～6:4.
Preferably, described in be cured as the demoulding after 0.5h, be then placed in 37 DEG C, 100% relative humidity environment and solidify.
The calcium phosphate bone cement compositions that second aspect present invention provides a kind of hydroxylapatite-silk fibroin to strengthen, it is characterized in that, its composition and weight ratio are that the weight ratio of calcium phoshate bone cement powder and hydroxylapatite-silk fibroin complex is 96-99% ︰ 1-4%.
The calcium phosphate bone cement that third aspect present invention provides a kind of hydroxylapatite-silk fibroin to strengthen, its for weight ratio be calcium phoshate bone cement powder and the hydroxylapatite-silk fibroin complex of 96-99% ︰ 1-4%, reconcile into pasty state with L/P=0.33～0.4mL/g liquid-solid ratio with silk fibroin protein solution, solidify and obtain.
Fourth aspect present invention provides a kind of purposes of calcium phosphate bone cement of hydroxylapatite-silk fibroin enhancing, the bone cement that it is used for the preparation of vertebroplasty.
Preferably, described vertebroplasty comprises percutaneous vertebroplasty PVP and percutaneous balloon kyphoplasty PKP.
Compared with prior art, the present invention has the following advantages:
1. the hydroxylapatite-silk fibroin complex using in calcium phosphate bone cement preparation of the present invention is a kind of organic-inorganic composite body, in CPC/SF system, can effectively improve the interface compatibility of organic-inorganic between biphase, thereby improve interface binding power and improve the mechanical property of calcium phosphate bone cement.
2. this natural polymer good biocompatibility of fibroin albumen, and its molecule connects and is rich in the group such as great amount of hydroxy group, carboxyl, can induce hydroxyapatite deposition, improves bone cement mechanical property.
3. make consolidation liquid and can effectively improve the anti-collapsibility performance of calcium phosphate bone cement with silk fibroin protein solution, to meet the basic demand of clinical practice.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is the scanning electron microscope (SEM) photograph of hydroxylapatite-silk fibroin complex in the embodiment of the present invention.
Fig. 2 is that each group of bone cement comprcssive strength is relatively analyzed.
Fig. 3 A is the scanning electron microscope (SEM) photograph of the bone cement of CPC/SF group; Fig. 3 B is the scanning electron microscope (SEM) photograph that adds 3wt.% hydroxylapatite-silk fibroin complex in embodiment 4.
Fig. 4 is the comparative analysis of each group of bone cement setting time
Fig. 5 is the injectivity diagram of adding 3wt.% hydroxylapatite-silk fibroin complex in embodiment 4.
Fig. 6 A and Fig. 6 B add the anti-collapsibility comparison of 3wt.% hydroxylapatite-silk fibroin complex with different consolidation liquids in embodiment 4.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the invention is described.
Embodiment 1
(1) preparation of fibroin albumen
By silkworm silk in the Na of 0.02mol/L
2cO
3in solution, boil 20min, repeatedly wash to eliminate sericin by rubbing with the hands with deionized water.After oven dry, be dissolved in 9.3mol/L LiBr solution, dissolve after 4 hours at 60 DEG C, deionized water dialysis 48h, high speed centrifugation is removed fibroin condensation product, through concentrated or dilute after make the silk fibroin protein solution that concentration is 5wt.% and 20wt.%.
(2) preparation of hydroxylapatite-silk fibroin complex
Take 7.37g Ca (OH)
2be dissolved in the Ca (OH) that is mixed with 16wt.% in 38mL water
2solution adds the SF solution of 12.5mL 20wt.%, mix homogeneously after it dissolves.Measure 4mLH
3pO
4dilute a little with 6mL water, in high-speed stirred, it is slowly splashed in aforementioned mixed solution, find solution gradual change muddiness.Finally with NH
3h
2o is adjusted to 9.0 by pH, continues to stir after 3h.Product is through sucking filtration, washing, dry, for subsequent use after grinding.
(3) hydroxylapatite-silk fibroin complex strengthens the preparation of calcium phosphate bone cement
In CPC powder, mix 0wt.%, 1wt.%, 2wt.%, 3wt.% and 4wt.%HA-SF complex, using the SF solution of 5wt.% as distiller liquor, press the liquid-solid ratio of L/P=0.33mL/g, measure and be in harmonious proportion and two coordinate after uniform pasty state and insert mould (φ 4.6mm × 10.0mm).The demoulding after 0.5h, is then placed in 37 DEG C, 100% relative humidity environment and solidifies.
Embodiment 2
(1) preparation of fibroin albumen
By silkworm silk in the Na of 0.02mol/L
2cO
3in solution, boil 40min, repeatedly wash to eliminate sericin by rubbing with the hands with deionized water.After oven dry, be dissolved in 9.3mol/L LiBr solution, dissolve after 4 hours at 60 DEG C, deionized water dialysis 48h, high speed centrifugation is removed fibroin condensation product, makes the silk fibroin protein solution that concentration is 5wt.%.
(2) preparation of hydroxylapatite-silk fibroin complex
Take 5.16g Ca (OH)
2be dissolved in and in 30mL water, be mixed with Ca (OH)
2solution adds the SF solution of 60mL5wt.%, mix homogeneously after it dissolves.Measure 3.0mL H
3pO
4dilute a little with 5mL water, in high-speed stirred, it is slowly splashed in aforementioned mixed solution, find solution gradual change muddiness.Finally with NH
3h
2o is adjusted to 9.0 by pH, continues to stir after 3h.Product is through sucking filtration, washing, dry, for subsequent use after grinding.
(3) hydroxylapatite-silk fibroin complex strengthens the preparation of calcium phosphate bone cement
In CPC powder, mix 0wt.%, 1wt.%, 2wt.%, 3wt.% and 4wt.% hydroxylapatite-silk fibroin complex, using SF solution as distiller liquor, press the liquid-solid ratio of L/P=0.35mL/g, measure and be in harmonious proportion and two coordinate after uniform pasty state and insert mould (φ 4.6mm × 10.0mm).The demoulding after 0.5h, is then placed in 37 DEG C, 100% relative humidity environment and solidifies.
Embodiment 3
(1) preparation of fibroin albumen
By mulberry silk in the Na of 0.02mol/L
2cO
3in solution, boil 30min, repeatedly wash to eliminate sericin by rubbing with the hands with deionized water.After oven dry, be dissolved in 9.3mol/L LiBr solution, dissolve after 4 hours at 60 DEG C, deionized water dialysis 48h, high speed centrifugation is removed fibroin condensation product, makes the silk fibroin protein solution that concentration is 5wt.% and 10wt.%.
(2) preparation of hydroxylapatite-silk fibroin complex
Take 4.45g Ca (OH)
2be dissolved in and in 25mL water, be mixed with Ca (OH)
2solution adds the SF solution of 40mL10wt.%, mix homogeneously after it dissolves.Measure 2.5mL H
3pO
4dilute a little with 5mL water, in high-speed stirred, it is slowly splashed in aforementioned mixed solution, find solution gradual change muddiness.Finally with NH
3h
2o is adjusted to 9.0 by pH, continues to stir after 3h.Product is through sucking filtration, washing, dry, for subsequent use after grinding.
(3) hydroxylapatite-silk fibroin complex strengthens the preparation of calcium phosphate bone cement
In CPC powder, mix 0wt.%, 1wt.%, 2wt.%, 3wt.% and 4wt.% hydroxylapatite-silk fibroin complex, using SF solution as distiller liquor, press the liquid-solid ratio of L/P=0.4mL/g, measure and be in harmonious proportion and two coordinate after uniform pasty state and insert mould (φ 4.6mm × 10.0mm).The demoulding after 0.5h, is then placed in 37 DEG C, 100% relative humidity environment and solidifies.
Embodiment 4
Pattern and the performance measurement of hydroxylapatite-silk fibroin complex and enhancing calcium phosphate bone cement.
(1) surface topography of hydroxylapatite-silk fibroin complex and CPC is observed
The metal spraying 2min sample preparation under 20mA by hydroxylapatite-silk fibroin complex and CPC sample section, with its surface topography of Quanta250 type scanning electron microscopic observation.
Fig. 1 is the microstructure photo of hydroxylapatite-silk fibroin complex.Between mineral crystal granule and organic facies, in conjunction with good, do not occur being obviously separated.It is slender rod shaped that hydroapatite particles is, size homogeneous, and granule is about 250nm, diameter 50nm, and is evenly distributed.
Fig. 3 is the section microstructure of bone cement.From 3A, CPC/SF organizes a large amount of sheet-shaped hydroxyapatites and concentrates on respectively independently region, has formed sheet-shaped hydroxyapatite microcell, and these microcells are around the bar-shaped hydroxyapatites of some random arrangement.CPC/HA-SF/SF (Fig. 3 B) group and CPC/SF group structural similarity, exist many have bar-shaped hydroxyapatite around sheet-shaped hydroxyapatite microcell, but different is, microcell bar-shaped hydroxyapatite is around orientation texture more, these orientation textures be because hydroxyapatite taking the hydroxylapatite-silk fibroin complex introduced as template formation of deposits gradually.
(2) compressive strength determination
Bone cement sample upper and lower surface after solidifying is polished flat (Φ 4.6mm × 9.2mm), be placed on universal testing machine (HY-1080) and carry out compression verification.Loading speed is 1mm/min, records load-displacement curves.Every group of 6 samples, calculate the compression strength value of sample according to following formula (1):
In formula, P represents the comprcssive strength of sample, and N represents load peaks, and D represents the diameter of sample.
From Fig. 2, can clearly find, hydroxylapatite-silk fibroin complex is added in proportion in CPC and with SF solution and makes consolidation liquid, compressive strength improves with the increase of hydroxylapatite-silk fibroin complex ratio, in the time that addition reaches 3%, intensity reaches maximum 50.2 ± 1.9MPa; And continuation increases complex content, intensity decreases to 42.9 ± 3.3MPa (* p<0.05).
(3) setting time
Use iso standard method Vicat apparatus to measure.Initial set test point is cylindrical fine needle, and final set test point for installing an annular adnexa (Needle with ring) on columniform head; Syringe needle diameter is 1.13 ± 0.05mm, and annular adnexa diameter is 4.93 ± 0.05mm; Syringe needle quality is 33.4 ± 0.2g, and slipper gross mass is 300 ± 1g., fill in diameter 12.5mm after the modulation evenly of CPC/HA-SF powder and consolidation liquid according to certain liquid-solid ratio, in the mould of plastics of high 5mm, be placed on maintenance in 37 DEG C, the environment of 100% relative humidity.Taking out at regular intervals sample, place it on testboard, first select initial set test point, from the surface of syringe needle contact sample, allow slide bar freely fall to test point and insert sample apart from base plate 1.5mm, is now initial set state.Use final set test point instead, the surface to sample by syringe needle vertical landing, until circular impression can not be observed in surface, is recorded as final setting time carefully, and each sample so repeats 3 times.
Fig. 4 is the setting time result of CPC/HA-SF/SF bone cement.Make consolidation liquid with SF solution, while not adding hydroxylapatite-silk fibroin complex, the presetting period shortens to 29.6 ± 0.4min, and final setting time shortens to 36.1 ± 0.7min.Continue in solid phase, to add after hydroxylapatite-silk fibroin complex, setting time further shortens to some extent, and final setting time foreshortens to 31.7 ± 0.3min.
(4) injection property
Use bone cement push rod (internal diameter is 2.74mm) for balloon kyphoplasty, by inserting in push rod after 7.5gCPC/HA-SF powder and consolidation liquid mixing, mix after 3min, slowly release.Record whole process.
Process as shown in Figure 5, can be like a cork all release from apparatus by bone cement, and have good bond performance and substantially keep shape, shows that this system has good injectivity.
(5) anti-collapsibility
By after CPC/HA-SF powder and consolidation liquid mediation evenly, insert mould of plastics, room temperature is placed the 10min demoulding, after the demoulding, directly immerses in phosphate buffer (PBS), observes and records sample and just immersed PBS and 37 DEG C of defeated and dispersed situations of placing after 24 hours.
Fig. 6 is anti-collapsibility result of the test, and CPC/HA-SF group (Fig. 6 A) is using water as consolidation liquid, immerses in PBS solution after the demoulding, and the rapid part of bone cement is defeated and dispersed, substantially completely defeated and dispersed after 10min.And make CPC/HA-SF/SF (Fig. 6 B) group of consolidation liquid with SF solution, the demoulding has no obviously defeated and dispersed after immersing PBS solution, still can keep well shape after 24h.Result shows, can effectively improve the anti-collapsibility of CPC using SF solution as consolidation liquid.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not subject to the restriction of above-mentioned example; that in above-mentioned example and description, describes just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. the preparation method of the calcium phosphate bone cement of a hydroxylapatite-silk fibroin complex enhancing, it is characterized in that, in calcium phoshate bone cement powder, mix the hydroxylapatite-silk fibroin complex of 1～4wt.%, using silk fibroin protein solution as distiller liquor, be in harmonious proportion by the liquid-solid ratio of L/P=0.33～0.4mL/g, solidify and obtain the calcium phosphate bone cement that hydroxylapatite-silk fibroin strengthens.
2. preparation method according to claim 1, is characterized in that, described hydroxylapatite-silk fibroin complex is to prepare by coprecipitation, wherein hydroxyapatite: fibroin albumen weight ratio=8:2～6:4.
3. preparation method according to claim 1, is characterized in that, described silk fibroin protein solution concentration is 4～10wt.%.
4. preparation method according to claim 1, is characterized in that, described in be cured as the demoulding after 0.5h, be then placed in 37 DEG C, 100% relative humidity environment and solidify.
5. the calcium phosphate bone cement compositions that hydroxylapatite-silk fibroin strengthens, is characterized in that, its composition and weight ratio be, calcium phoshate bone cement powder is 96-99%, and hydroxylapatite-silk fibroin complex is 1-4%.
6. the calcium phosphate bone cement that hydroxylapatite-silk fibroin strengthens, it is characterized in that, its for weight ratio be calcium phoshate bone cement powder and the hydroxylapatite-silk fibroin complex of 96-99% ︰ 1-4%, reconcile into pasty state with L/P=0.33～0.4mL/g liquid-solid ratio with silk fibroin protein solution, solidify and obtain.
7. a purposes for the calcium phosphate bone cement that the calcium phosphate bone cement that the hydroxylapatite-silk fibroin of claim 6 strengthens, the method for claim 1 obtain, the bone cement of using for the preparation of vertebroplasty.
8. purposes according to claim 7, is characterized in that, described vertebroplasty comprises percutaneous vertebroplasty PVP and percutaneous balloon kyphoplasty PKP.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410280003.5A CN104043149A (en) | 2014-06-20 | 2014-06-20 | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410280003.5A CN104043149A (en) | 2014-06-20 | 2014-06-20 | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104043149A true CN104043149A (en) | 2014-09-17 |
Family
ID=51496864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410280003.5A Pending CN104043149A (en) | 2014-06-20 | 2014-06-20 | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104043149A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688283A (en) * | 2016-02-01 | 2016-06-22 | 苏州大学 | Modified silk fibroin-calcium phosphate composite bone cement and preparation method thereof |
| CN108283730A (en) * | 2018-04-20 | 2018-07-17 | 袁杰 | A kind of preparation method of brushite bone cement |
| CN109260523A (en) * | 2018-09-14 | 2019-01-25 | 广州润虹医药科技股份有限公司 | A kind of calcium phosphate bone cement complex microsphere and its preparation method and application |
| DE102019211781A1 (en) * | 2019-08-06 | 2021-02-11 | Gebr. Brasseler Gmbh & Co. Kg | Preparation and ready-mix for use in medical or dental applications, medical or dental product and its use and its manufacture |
| CN114377213A (en) * | 2022-02-25 | 2022-04-22 | 苏州大学附属第一医院 | Novel selenium-enhanced bioactive bone cement and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235204A (en) * | 2008-02-26 | 2008-08-06 | 天津工业大学 | Method for preparing nano-phase hydroxyapatite/fimbrin composite material |
| CN101961509A (en) * | 2010-09-21 | 2011-02-02 | 苏州大学 | Silk fibroin/calcium phosphate bone cement composite material and preparation method thereof |
| CN102058907A (en) * | 2010-12-31 | 2011-05-18 | 苏州大学 | Hydroxyapatite/silk fibroin composite material and preparation method thereof |
| CN102552985A (en) * | 2012-01-20 | 2012-07-11 | 苏州大学 | Silk fibroin/calcium phosphate bone cement-based porous composite material and preparation method thereof |
-
2014
- 2014-06-20 CN CN201410280003.5A patent/CN104043149A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235204A (en) * | 2008-02-26 | 2008-08-06 | 天津工业大学 | Method for preparing nano-phase hydroxyapatite/fimbrin composite material |
| CN101961509A (en) * | 2010-09-21 | 2011-02-02 | 苏州大学 | Silk fibroin/calcium phosphate bone cement composite material and preparation method thereof |
| CN102058907A (en) * | 2010-12-31 | 2011-05-18 | 苏州大学 | Hydroxyapatite/silk fibroin composite material and preparation method thereof |
| CN102552985A (en) * | 2012-01-20 | 2012-07-11 | 苏州大学 | Silk fibroin/calcium phosphate bone cement-based porous composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李浩: "丝素蛋白/羟基磷灰石复合物对磷酸钙骨水泥的影响", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688283A (en) * | 2016-02-01 | 2016-06-22 | 苏州大学 | Modified silk fibroin-calcium phosphate composite bone cement and preparation method thereof |
| CN105688283B (en) * | 2016-02-01 | 2019-01-25 | 苏州大学 | A kind of modified fibroin albumen-compound bone cement of calcium phosphate and preparation method thereof |
| CN108283730A (en) * | 2018-04-20 | 2018-07-17 | 袁杰 | A kind of preparation method of brushite bone cement |
| CN109260523A (en) * | 2018-09-14 | 2019-01-25 | 广州润虹医药科技股份有限公司 | A kind of calcium phosphate bone cement complex microsphere and its preparation method and application |
| DE102019211781A1 (en) * | 2019-08-06 | 2021-02-11 | Gebr. Brasseler Gmbh & Co. Kg | Preparation and ready-mix for use in medical or dental applications, medical or dental product and its use and its manufacture |
| CN114377213A (en) * | 2022-02-25 | 2022-04-22 | 苏州大学附属第一医院 | Novel selenium-enhanced bioactive bone cement and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104043149A (en) | Hydroxyapatite-silk fibroin composite reinforced calcium phosphate bone cement and preparation method thereof | |
| Ghosh et al. | Arginine-presenting peptide hydrogels decorated with hydroxyapatite as biomimetic scaffolds for bone regeneration | |
| JP7054954B2 (en) | Polycaprolactone fine granule sphere filler containing collagen peptide and its production method | |
| Wang et al. | Synthesis and characterization of a chitosan based nanocomposite injectable hydrogel | |
| CN105288741B (en) | A kind of acrylic compounds composite bone cement and preparation method thereof with Partial digestion function | |
| CN103463678A (en) | Multifunctional medical biological bone cement | |
| CN102886075B (en) | Human hard tissue repair material and preparation method thereof | |
| CN101698117B (en) | Bone-repairing composite material and method for preparing the same | |
| EP3067074A1 (en) | Biomaterial having enhanced rubber properties through natural cross-linkage of collagen and hyaluronic acid, preparing method thereof, and using method thereof | |
| JP4932992B2 (en) | Biodegradable ceramic fibers from silica sol | |
| CN106860916A (en) | A kind of GO/nHA/ collagen composites bone renovating material and preparation method thereof | |
| CN110237301A (en) | A kind of sodium alginate base can induce Bone Defect Repari gel and its preparation method and application | |
| CN109331223B (en) | Medicine-carrying bioactive glass composite calcium phosphate bone cement and application thereof | |
| Sha et al. | A modified calcium silicate composite bone cement prepared from polyethylene glycol and graphene oxide for biomaterials | |
| CN109106986B (en) | Medicine controlled-release calcium phosphate bone cement composite microsphere, preparation method and application thereof | |
| CN110087697A (en) | Stop blooding flowable object | |
| US20020128725A1 (en) | Process and composition for medical use | |
| CN110746516B (en) | Natural polymer hydrogel based on collagen and preparation method thereof | |
| Ma et al. | Effect of polyaspartic acid on hydroxyapatite deposition in silk fibroin blend films | |
| CN109806443A (en) | Bone holder material and its preparation method and application | |
| CN112156227A (en) | Composition and preparation of bone filling material, and preparation method and application thereof | |
| Wang et al. | The effect of magnetic poly (lactic-co-glycolic acid) microsphere-gelatin hydrogel on the growth of pre-osteoblasts under static magnetic field | |
| CN106581771B (en) | A kind of sericin composite hydrogel and preparation method thereof | |
| CN107459662B (en) | Preparation method of nano composite hydrogel | |
| CN105688283B (en) | A kind of modified fibroin albumen-compound bone cement of calcium phosphate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140917 |