CN101897994A - Biological composite scaffold for repairing bone defect and preparation method thereof - Google Patents
Biological composite scaffold for repairing bone defect and preparation method thereof Download PDFInfo
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- CN101897994A CN101897994A CN2010102346608A CN201010234660A CN101897994A CN 101897994 A CN101897994 A CN 101897994A CN 2010102346608 A CN2010102346608 A CN 2010102346608A CN 201010234660 A CN201010234660 A CN 201010234660A CN 101897994 A CN101897994 A CN 101897994A
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Abstract
The invention discloses a biological composite scaffold for repairing bone defect. The composite scaffold is prepared from nano hydroxyapatite and silk fibroin, wherein the mass ratio of the nano hydroxyapatite to the silk fibroin is 90:10-60:40. The composite scaffold is porous, the porosity is 70 to 95 percent, the aperture size is 100 to 600 microns, pores are mainly circular, and the pores are mutually communicated. Aqueous solution of the de-gummed silk fibroin is used as a carrier, silk fibroin/nano hydroxyapatite composite sol is prepared by a co-precipitation method, the silk fibroin/nano hydroxyapatite composite scaffold is prepared by combining ion percolation and freeze drying process, and the distribution of aperture in the composite scaffold is controlled by adjusting the radius of NaCl particles and freezing parameters. Compared with the prior art, the scaffold has the advantages of easily-controlled porosity and the aperture distribution, and good mechanical property.
Description
Technical field
The present invention relates to a kind of biological composite scaffold and preparation method thereof, relate in particular to a kind of fibroin albumen/nanometer hydroxyapatite compound rest and preparation method thereof, belong to biomedical materials field.
Background technology
Because the osseous tissue that factors such as wound, tumor, congenital malformation, infection, pathology cause is damaged to be one of clinical difficult problem that faces.At present, clinical used bone renovating material cuts both ways, and can not reach ideal requirement.Development has biocompatibility, degradable three-dimensional porous rack material is the key issue that addresses this problem.
(hydroxyapatite is the main inanimate matter composition of natural bone tissue HA) to hydroxyapatite, has excellent biological compatibility, has been widely used in the damaged reparation of diverse bone types.But by the material of micron order hydroxy apatite powder preparation, the crisp intensity of matter is low, and the bio-mechanical poor-performing can not be alternative fully by new bone after the implantation, forms occupy-place in the part.Early-stage Study shows the hydroapatite particles that can obtain different shape by the control experimental condition, and its particle size and form have considerable influence to its biocompatibility.But the tissue engineered bone of this distance structure function integration falls far short, and also has some unsurmountable shortcoming, as lacks connection, uniform pore structure, is unfavorable for the growth of osseous tissue; It is inharmonious that its degradation speed and natural bone tissue growth substitute speed; The mechanical property of mechanical strength and natural bone tissue does not match etc.; And pure hydroxyapatite only has bone conduction effect, do not have bone-inducting active.Therefore oneself becomes current research tendency with nano-grade hydroxy apatite and the compound structure of organic macromolecule with bone-inducting active and the similar composite bone substitution timbering material of nature bone.
The mulberry silk dietary protein origin is abundant, and except being used for traditional textile raw material, because its superior mechanical property and relative good organism adaptability, people attempt several different methods, and it is prepared into different structures and composite, apply to bone tissue engineer.Silkworm silk is mainly by sericin and fibroin (silk fibroin, SF) two kinds of albumen formations.As embedded material, the sensitization of sericin has limited its utilization scope.On the contrary, fibroin albumen but has excellent biological compatibility, and water and oxygen are had good permeability.In recent years, be that the research of the various cells growth timbering materials of host material is arisen at the historic moment with it, become a popular research field of tissue engineering.The group study that David L.Kaplan leads RGD, PTH and mPTH covalent modification fibroin albumen and induce the bone formation effect, find that osteoblast can adhere to, breed on fibroin albumen; Prepared three-dimensional porous fibroin support respectively by lyophilization, particle leaching and gas foaming, investigated the influence of preparation method and condition support form and function; Explore a kind of new full water conservancy project skill legal system and be equipped with the fibroin support, studied the inside and outside osteogenic ability behind this support load BMP-2; Studied the deposition of hydroxyapatite on this basis at the fibroin support.People such as Li Wang prepare the SF/HA Nano sol by wet method-mechanochemistry synthetic route, have studied the influence of chemical modification to microstructure of SF/HA pluralgel and gel behavior.People such as the Zhao Yong of Sichuan University, Wang Jiang adopt the biomimetic mineralization method to make up three-dimensional porous fibroin albumen/hydroxyapatite compound rest, and it is carried out external proteasome degradation and osteoblast cultivation.Above-mentioned timbering material has the three-dimensional porous structure of connection, demonstrates excellent biological compatibility and can promote osteoblastic growth and differentiation, thereby be expected to become novel organic/inorganic composite biological material.But preparation and relevant experiment in vivo and vitro thereof for the SF/HA compound rest still are in the starting stage, lack systematic research.
Summary of the invention
At above-mentioned prior art, the invention provides biological composite scaffold of a kind of repairing bone defect and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of biological composite scaffold of repairing bone defect is made by nanometer hydroxyapatite and fibroin albumen, wherein, the mass ratio of nanometer hydroxyapatite and fibroin albumen is 90: 10～60: 40, compound rest is cellular, porosity 70%～95%, aperture size 100～600 μ m based on circle, connect between the aperture mutually.
The preparation method of the biological composite scaffold of described repairing bone defect may further comprise the steps:
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30～90min, use deionized water wash, drying then, remove the sericin that tissue is had sensitivity response;
(2) the above-mentioned fibroin albumen that comes unstuck after handling is dissolved in the 9.3mol/L LiBr solution carries out dialysis treatment under the room temperature, obtain silk fibroin water solution;
(3) be 90: 10～60: 40 according to hydroxyapatite with fibroin albumen quality ratio, calculate required Ca (NO respectively
3)
2And (NH
4)
2HPO
4Quality; Take by weighing the Ca (NO of required quality
3)
2, it is added above-mentioned silk fibroin water solution mixing obtains SF-Ca (NO
3)
2Solution;
(4) take by weighing (NH of respective quality
4)
2HPO
4, be mixed with the aqueous solution that concentration is 2mol/L; Constantly under the stirring condition it is dropwise being added above-mentioned SF-Ca (NO
3)
2In the mixed solution, in this process, add ammonia and regulate pH value, make it remain on 9～10;
(5) above-mentioned gained washing of precipitate is extremely neutral, filter and obtain SF/ nanometer HA complex sol; The NaCl granule of different grain size (particle diameter 150～250 μ m) is joined in the above-mentioned complex sol, stir, injection molding leaves standstill 2～8h with its sealing and in room temperature; The demoulding, and be placed in the methanol 10～90min to produce water-fast beta sheet structure;
(6) will place deionized water to soak 24h under the gained composite room temperature, leaching NaCl granule;-10～-80 ℃ of lyophilization 10～24h promptly obtain the SF/HA compound rest.
The present invention has following outstanding beneficial effect:
The present invention is a carrier with the silk fibroin water solution by the processing of coming unstuck, prepare fibroin albumen/nanometer hydroxyapatite complex sol by coprecipitation, utilize the ion leaching to prepare fibroin albumen/nanometer hydroxyapatite compound rest, the radius by regulating the NaCl particle and the distribution of freezing parameter control compound rest internal orifice dimension in conjunction with freeze drying process.Compared with prior art, adopt the gained support porosity of the present invention and pore-size distribution more easy to control, and have the good mechanical performance.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, use deionized water wash, drying then, remove the sericin that tissue is had sensitivity response;
(2) the above-mentioned fibroin albumen that comes unstuck after handling is dissolved in carries out dialysis treatment in the 9.3mol/LLiBr solution under the room temperature, obtain silk fibroin water solution;
(3) be 70: 30 according to nanometer hydroxyapatite with fibroin albumen quality ratio, calculate required Ca (NO respectively
3)
2And (NH
4)
2HPO
4Quality; Take by weighing the Ca (NO of required quality
3)
2, it is added above-mentioned silk fibroin water solution mixing obtains SF-Ca (NO
3)
2Solution;
(4) take by weighing (NH of respective quality
4)
2HPO
4, be mixed with the aqueous solution that concentration is 2mol/L; Constantly under the stirring condition it is dropwise being added above-mentioned SF-Ca (NO
3)
2In the mixed solution, in this process, add ammonia and regulate pH value, make it remain on 10;
(5) above-mentioned gained washing of precipitate is extremely neutral, filter and obtain SF/ nanometer HA complex sol; With mean diameter is that the NaCl granule of 150 μ m joins in the above-mentioned complex sol, stirs, and injection molding leaves standstill 2h with its sealing and in room temperature; The demoulding, and be placed in the methanol 30min to produce water-fast beta sheet structure;
(6) will place deionized water to soak 24h under the gained composite room temperature, leaching NaCl granule;-20 ℃ of lyophilization 24h promptly obtain SF/ nanometer HA compound rest.
Embodiment 2
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, use deionized water wash, drying then, remove the sericin that tissue is had sensitivity response;
(2) the above-mentioned fibroin albumen that comes unstuck after handling is dissolved in the 9.3mol/L LiBr solution carries out dialysis treatment under the room temperature, obtain silk fibroin water solution;
(3) be 80: 20 according to hydroxyapatite with fibroin albumen quality ratio, calculate required Ca (NO respectively
3)
2And (NH
4)
2HPO
4Quality; Take by weighing the Ca (NO of required quality
3)
2, it is added above-mentioned silk fibroin water solution mixing obtains SF-Ca (NO
3)
2Solution;
(4) take by weighing (NH of respective quality
4)
2HPO
4, be mixed with the aqueous solution that concentration is 2mol/L; Constantly under the stirring condition it is dropwise being added above-mentioned SF-Ca (NO
3)
2In the mixed solution, in this process, add ammonia and regulate pH value, make it remain on 10;
(5) above-mentioned gained washing of precipitate is extremely neutral, filter and obtain SF/ nanometer HA complex sol; With mean diameter is that the NaCl granule of 180 μ m joins in the above-mentioned complex sol, stirs, and injection molding leaves standstill 2h with its sealing and in room temperature; The demoulding, and be placed in the methanol 30min to produce water-fast beta sheet structure;
(6) will place deionized water to soak 24h under the gained composite room temperature, leaching NaCl granule;-20 ℃ of lyophilization 24h promptly obtain SF/ nanometer HA compound rest.
Embodiment 3
(1) mulberry silk is placed the 0.02mol/L sodium carbonate liquor handle and boil 30min, use deionized water wash, drying then, remove the sericin that tissue is had sensitivity response;
(2) the above-mentioned fibroin albumen that comes unstuck after handling is dissolved in the 9.3mol/L LiBr solution carries out dialysis treatment under the room temperature, obtain silk fibroin water solution;
(3) be 60: 40 according to nanometer hydroxyapatite with fibroin albumen quality ratio, calculate required Ca (NO respectively
3)
2And (NH
4)
2HPO
4Quality; Take by weighing the Ca (NO of required quality
3)
2, it is added above-mentioned silk fibroin water solution mixing obtains SF-Ca (NO
3)
2Solution;
(4) take by weighing (NH of respective quality
4)
2HPO
4, be mixed with the aqueous solution that concentration is 2mol/L; Constantly under the stirring condition it is dropwise being added above-mentioned SF-Ca (NO
3)
2In the mixed solution, in this process, add ammonia and regulate pH value, make it remain on 10;
(5) above-mentioned gained washing of precipitate is extremely neutral, filter and obtain SF/ nanometer HA complex sol; With mean diameter is that the NaCl granule of 150 μ m joins in the above-mentioned complex sol, stirs, and injection molding leaves standstill 2h with its sealing and in room temperature; The demoulding, and be placed in the methanol 30min to produce water-fast beta sheet structure;
(6) will place deionized water to soak 24h under the gained composite room temperature, leaching NaCl granule;-20 ℃ of lyophilization 24h promptly obtain SF/ nanometer HA compound rest.
Above-mentioned 3 embodiment gained fibroin albumen/nanometer hydroxyapatite compound rests carry out following detection:
Confirm through Nicolet AVATR360FT-IR: compound rest is by fibroin albumen and nanometer hydroxyapatite is biphase constitutes;
Confirm through JEM-100Cx II sem analysis: hole is interconnected in the compound rest, and the porosity is all above 80%, and average pore size is at 150～200 μ m.
Think carefully that through Shenzhen universal testing machine detects: compound rest comprcssive strength is all above 150MPa.
Claims (2)
1. the biological composite scaffold of a repairing bone defect, it is characterized in that: make by nanometer hydroxyapatite and fibroin albumen, wherein, the mass ratio of nanometer hydroxyapatite and fibroin albumen is 90: 10～60: 40, compound rest is how empty shape, porosity 70%～95%, aperture size 100～600 μ m, based on circle, connect between the aperture.
2. the preparation method of the biological composite scaffold of repairing bone defect as claimed in claim 1 is characterized in that may further comprise the steps:
(1) mulberry silk is placed O.02mol/L sodium carbonate liquor processing boil 30～90min, use deionized water wash, drying then, remove the sericin that tissue is had sensitivity response;
(2) the above-mentioned fibroin albumen that comes unstuck after handling is dissolved in the 9.3mol/L LiBr solution carries out dialysis treatment under the room temperature, obtain silk fibroin water solution;
(3) be 90: 10～60: 40 according to nanometer hydroxyapatite with fibroin albumen quality ratio, calculate required Ca (NO respectively
3)
2And (NH
4)
2HPO
4Quality; Take by weighing the Ca (NO of required quality then
3)
2, it is added above-mentioned silk fibroin water solution mixing obtains SF-Ca (NO
3)
2Solution;
(4) take by weighing (NH of respective quality
4)
2HPO
4, be mixed with the aqueous solution that concentration is 2mol/L; Constantly under the stirring condition it is dropwise being added above-mentioned SF-Ca (NO
3)
2In the mixed solution, in this process, add ammonia and regulate pH value, make it remain on 9～10;
(5) above-mentioned gained washing of precipitate is extremely neutral, filter and obtain SF/ nanometer HA complex sol; The NaCl granule of particle diameter 150～250 μ m is joined in the above-mentioned complex sol, stir, injection molding leaves standstill 2～8h with its sealing and in room temperature; The demoulding, and be placed on 10～90min in the methanol, to produce water-fast beta sheet structure;
(6) will place deionized water to soak 24h under the gained composite room temperature, leaching NaCl granule;-10～-80 ℃ of lyophilization 10～24h promptly obtain SF/ nanometer HA compound rest.
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|---|---|---|---|
| CN 201010234660 CN101897994B (en) | 2010-07-23 | 2010-07-23 | Biological composite scaffold for repairing bone defect and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010234660 CN101897994B (en) | 2010-07-23 | 2010-07-23 | Biological composite scaffold for repairing bone defect and preparation method thereof |
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| CN101897994A true CN101897994A (en) | 2010-12-01 |
| CN101897994B CN101897994B (en) | 2013-01-09 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102028972A (en) * | 2010-12-23 | 2011-04-27 | 西安交通大学 | Honeycomb polymer-based bionic porous scaffold 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 |
| CN102188753A (en) * | 2011-05-10 | 2011-09-21 | 中原工学院 | Nano bone biomimetic material containing tussah silk fibroin, and preparation method thereof |
| CN102302804A (en) * | 2011-09-05 | 2012-01-04 | 济宁学院 | Hydroxyapatite-based biological composite scaffold and tissue engineered bone |
| CN102321270A (en) * | 2011-08-22 | 2012-01-18 | 陕西师范大学 | Preparation method of silk fibroin/hydroxyapatite/collagen composite porous stent |
| CN102430155A (en) * | 2011-12-08 | 2012-05-02 | 西安交通大学 | Cellular silk fibroin porous scaffold, and preparation method thereof |
| CN105327401A (en) * | 2015-11-17 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of silk fibroin two-layer periosteum-imitation material |
| CN105521525A (en) * | 2015-12-16 | 2016-04-27 | 广州创赛生物医用材料有限公司 | Porous composite scaffold for bone tissue engineering and preparation method therefor |
| CN105816919A (en) * | 2016-05-23 | 2016-08-03 | 烟台正海生物科技股份有限公司 | Composite material containing natural nano-hydroxyapatite and preparation method of composite material |
| CN106729947A (en) * | 2016-11-25 | 2017-05-31 | 江苏爱西施科技服务咨询股份有限公司 | A kind of antianaphylactic suture of pro-skin stretch-proof and preparation method thereof |
| CN107837425A (en) * | 2016-09-18 | 2018-03-27 | 浙江蓝怡医药有限公司 | Novel porous bioceramic bone material and preparation method thereof |
| CN108498861A (en) * | 2018-06-28 | 2018-09-07 | 河南省肿瘤医院 | A kind of preparation method of hydroxyapatite-fibroin-titanium dioxide biomaterial |
| CN110180024A (en) * | 2019-06-04 | 2019-08-30 | 苏州大学 | A kind of compound rest and preparation method thereof |
| CN110787324A (en) * | 2019-11-03 | 2020-02-14 | 太原理工大学 | Preparation method of drug controlled release polylactic acid-based bone repair scaffold material |
| CN111569149A (en) * | 2020-06-05 | 2020-08-25 | 武汉亚洲生物材料有限公司 | Co-assembled artificial periosteum and preparation method thereof |
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| WO2008096334A2 (en) * | 2007-02-09 | 2008-08-14 | Royal College Of Surgeons In Ireland | A collagen/hydroxyapatite composite scaffold, and process for the production thereof |
| CN101293114A (en) * | 2007-04-23 | 2008-10-29 | 佳木斯大学 | Method for preparing nano-multiple phase calcium phosphate/fibroin protein composite bracket |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008096334A2 (en) * | 2007-02-09 | 2008-08-14 | Royal College Of Surgeons In Ireland | A collagen/hydroxyapatite composite scaffold, and process for the production thereof |
| CN101293114A (en) * | 2007-04-23 | 2008-10-29 | 佳木斯大学 | Method for preparing nano-multiple phase calcium phosphate/fibroin protein composite bracket |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102028972A (en) * | 2010-12-23 | 2011-04-27 | 西安交通大学 | Honeycomb polymer-based bionic porous scaffold 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 |
| CN102058907B (en) * | 2010-12-31 | 2013-07-10 | 苏州大学 | Hydroxyapatite/silk fibroin composite material and preparation method thereof |
| CN102188753A (en) * | 2011-05-10 | 2011-09-21 | 中原工学院 | Nano bone biomimetic material containing tussah silk fibroin, and preparation method thereof |
| CN102188753B (en) * | 2011-05-10 | 2013-10-09 | 中原工学院 | Nano bone biomimetic material containing tussah silk fibroin, and preparation method thereof |
| CN102321270A (en) * | 2011-08-22 | 2012-01-18 | 陕西师范大学 | Preparation method of silk fibroin/hydroxyapatite/collagen composite porous stent |
| CN102321270B (en) * | 2011-08-22 | 2012-12-12 | 陕西师范大学 | Preparation method of silk fibroin/hydroxyapatite/collagen composite porous stent |
| CN102302804A (en) * | 2011-09-05 | 2012-01-04 | 济宁学院 | Hydroxyapatite-based biological composite scaffold and tissue engineered bone |
| CN102430155A (en) * | 2011-12-08 | 2012-05-02 | 西安交通大学 | Cellular silk fibroin porous scaffold, and preparation method thereof |
| CN105327401B (en) * | 2015-11-17 | 2018-07-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Fibroin albumen bilayer imitates the preparation method of periosteum material |
| CN105327401A (en) * | 2015-11-17 | 2016-02-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of silk fibroin two-layer periosteum-imitation material |
| CN105521525A (en) * | 2015-12-16 | 2016-04-27 | 广州创赛生物医用材料有限公司 | Porous composite scaffold for bone tissue engineering and preparation method therefor |
| CN105816919A (en) * | 2016-05-23 | 2016-08-03 | 烟台正海生物科技股份有限公司 | Composite material containing natural nano-hydroxyapatite and preparation method of composite material |
| CN105816919B (en) * | 2016-05-23 | 2019-06-11 | 烟台正海生物科技股份有限公司 | A kind of composite material and preparation method containing natural nano hydroxyapatite |
| CN107837425A (en) * | 2016-09-18 | 2018-03-27 | 浙江蓝怡医药有限公司 | Novel porous bioceramic bone material and preparation method thereof |
| CN106729947A (en) * | 2016-11-25 | 2017-05-31 | 江苏爱西施科技服务咨询股份有限公司 | A kind of antianaphylactic suture of pro-skin stretch-proof and preparation method thereof |
| CN108498861A (en) * | 2018-06-28 | 2018-09-07 | 河南省肿瘤医院 | A kind of preparation method of hydroxyapatite-fibroin-titanium dioxide biomaterial |
| CN110180024A (en) * | 2019-06-04 | 2019-08-30 | 苏州大学 | A kind of compound rest and preparation method thereof |
| CN110787324A (en) * | 2019-11-03 | 2020-02-14 | 太原理工大学 | Preparation method of drug controlled release polylactic acid-based bone repair scaffold material |
| CN111569149A (en) * | 2020-06-05 | 2020-08-25 | 武汉亚洲生物材料有限公司 | Co-assembled artificial periosteum and preparation method thereof |
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