CN1301137C - Silk fibrin and hydroxyapatite compound material and preparation process thereof - Google Patents
Silk fibrin and hydroxyapatite compound material and preparation process thereof Download PDFInfo
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- CN1301137C CN1301137C CNB200510040925XA CN200510040925A CN1301137C CN 1301137 C CN1301137 C CN 1301137C CN B200510040925X A CNB200510040925X A CN B200510040925XA CN 200510040925 A CN200510040925 A CN 200510040925A CN 1301137 C CN1301137 C CN 1301137C
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- hydroxyapatite
- fibroin
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- silk fibroin
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Abstract
The present invention discloses a silk fibroin hydroxyapatite compound material and a preparation method thereof. The silk fibroin hydroxyapatite compound material uses hydroxyapatite and silk fibroin as basal bodies, and degummed cultivated silk or fabric as a reinforcement body, and adopts a solution blending-freezing gel method to make HA powder realize rapid solidification in even solution. After an even refrigeration body is formed, the temperature of the even refrigeration body is raised higher than a glass-transition temperature of the silk fibroin solution, a volatile organic reagent with a low molecular weight is added to realign silk fibroin molecules in the refrigeration body, and the refrigeration body is jellified to fix the HA powder; after the refrigeration body is heated and dried, and the water and the organic reagent are removed, a pore with a certain structure is formed, and the silk fibroin hydroxyapatite porous compound material is formed. The silk fibroin hydroxyapatite porous compound material has the advantages of good mechanical property, good cellular compatibility and proper degradation rate, meets the requirement of a cell culture support frame, can be used as a bone defect repair material, a drug controlled release material and a bone tissue engineering material, and has wide application prospects.
Description
Technical field
The present invention relates to a kind of biomedical material, be specifically related to a kind of with hydroxyapatite, fibroin albumen be matrix, domestic silkworm silk or fabric after coming unstuck be the composite porous and preparation technology who strengthens body.
Background technology
Bone is damaged, bone does not connect is clinical common bone wound, infect sequela, and how repairing bone defect, bone does not connect are the thorny problems of orthopedics circle always.Therefore the biologically active artificial bone material that in surgical operations such as orthopaedics, dentistry, face-lifting, the reparation of jaw face, often needs advantageous property.Hydroxyapatite (Hydoxyapatite is called for short HA), its chemical formula is Ca
10(PO
4)
6(OH)
2, be the main inanimate matter that constitutes bone and tooth, its chemical constituent, crystal structure, physical and chemical performance are all similar to the inorganic matter of people's normal bone, have excellent biological compatibility and biological activity, but the pure ha material is more crisp, and bending strength is low, does not almost have toughness, can not adapt to bone and transplant [Pompea W, Worch H, Schulte K, Materials Science andEngineering, 2003,362 (1): 40-60].For pliability and the machinability that improves calcium phosphate material, the composition construction features of imitation nature bone, inorganic/organic composite biological the material of preparation biologically active and good mechanical properties is subjected to extensive attention day by day as the main body of bone reparation, substitution material and the organizational project bone repair material of sclerous tissues.
At present, many methods oneself be used for the toughened and reinforced of hydroxylapatite ceramic.For example, layer structure, nano-particle, intermetallic compound particle, metallic particles, whisker, carbon fiber etc.[preparation of carbon fibre reinforced hydroxylapatite/epoxy resin composite material and mechanical property such as Zhao Junliang, the Materials Science and Engineering journal, 2003,21 (5): 640-643] adopt epoxy resin, carbon fiber and hydroxyapatite compound, the toughness and the intensity of hydroxylapatite ceramic are improved, but, owing in compound process, introduced second phase, tend to cause the decline of biocompatibility, in general, the biological activity with the enhanced hydroxyapatite material of bio-inert material can be lower than the pure ha.Therefore must adopt the material of good biocompatibility to increase the toughness of hydroxyapatite material.
Studies show that nontoxic, the nonirritant of fibroin, have excellent biological compatibility, can promote the growth of human body cell, have biodegradability (David L.Kaplan, Silk-basedbiomaterials; Biomaterials, 2003,24:401-416), owing to contain many polar groups on the fibroin strand, this group and the compatibility of polarity inorganic material are good, can be used for improving the toughness of hydroxyapatite.With hydroxyapatite and fibroin compound after, can make the abundant combination of premium properties of the two, thereby can obtain biocompatibility and bioactive bone repair and reconstruction bone repair material.Silk fiber and fabric have high toughness and intensity, can improve the intensity and the toughness of material after adding as reinforcing material.
Before the present invention makes, Chinese patent " cranial bone implant of hydroxyapatite " (publication number CN1370507A) discloses a kind of at the silkworm silk net, layering adds the technology that hydroxylapatite powder is made cranial bone implant between the hollow nylon wire, its adopt layer with layer between be connected by binding agent, heat the then scheme of 100 ℃ of left and right sides molding, because manual coating or mechanical compression-moulding methods make the artificial material for repairing skull of lamination layer structure, the space that does not have mutual perforation in the material, therefore, this hydroxyapatite composite material is not suitable for the cell culturing bracket in the organizational project.Equally, [Materials Science and Engineering .2001 such as Hu Jiashan, 19 (3): 79-83] carbon fiber and former silkworm silk being made length after organic reagent carries out surface treatment is fiber and hydroxyapatite mix about 2mm, and with the compression moulding of 10MPa pressure, the composite bone cement that adopts above-mentioned technology to obtain can not form the space of a certain size mutual perforation, can't realize the cultivation of cell, therefore, its application surface is restricted.
At present, in field of biomedical materials, very need a kind ofly not only have excellent biological compatibility and mechanical property, and can be applicable to the tissue engineering material of cell culture.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, and provides a kind of and possesses excellent mechanical performances, cell compatibility and suitably the fibroin hydroxyapatite of degradation rate is composite porous and preparation method thereof, for organizational project provides a kind of new material.
For achieving the above object, the technical solution used in the present invention is: a kind of fibroin hydroxyapatite composite material, it is made up of hydroxyapatite, silk fibroin protein, silkworm silk reinforcing material, its mass ratio is 1: 0.1～5: 0.001～0.1, have the hole that the aperture is 1～100 micron mutual perforation in the composite, pore volume accounts for 50～90%.Its bending strength is 0.1～20MPa, and composite bending modulus is 50～2000MPa.
The method for preparing above-mentioned fibroin hydroxyapatite composite material, its preparation process is as follows:
1, is 1～20% silk fibroin protein solution and hydroxyapatite powder mix homogeneously to concentration, adds the silkworm silk reinforcing material again, mixture is placed metal die;
2,, make the mixture in the mould form Frozen Body with above-mentioned metal die cryogenic quick freezing 10min～24h;
3, the metal die that will contain Frozen Body is behind freezing 10～24h under-10～-30 ℃ the temperature conditions, molecular weight is lower than 100 alcohols, ketone, aldehydes organic reagent and infiltrates in the Frozen Body, and is predrying under 20～40 ℃ temperature conditions again;
4, dryness finalization under 110～130 ℃ temperature conditions, it is composite porous to obtain the fibroin hydroxyapatite.
In the technique scheme, described hydroxyapatite is a nanoscale; Described silkworm silk reinforcing material is cocoon shell monofilament, doubling, the real silk fabric that took off glue; It is one or more of methanol, ethanol, propanol, isopropyl alcohol, butanols, isobutanol, the tert-butyl alcohol, acetone, butanone, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde that described molecular weight is lower than 100 alcohols, ketone, aldehydes organic reagent; Described cryogenic quick freezing is freezing in the liquid below-70 ℃.
Fibroin hydroxyapatite provided by the present invention is composite porous, in preparation process, owing to adopted solution blending-freezing gel method, just pass through solution blending, quick freezing in the liquid below-70 ℃, make HA powder fast setting in uniform solution, form uniform Frozen Body, elevated temperature is to more than the glass transition temperature (34～-20 ℃) of silk fibroin solution then, add the volatile organic reagent of low-molecular-weight, silk fibroin molecular in the Frozen Body is rearranged, gelation by heat drying, is removed the volatile organic reagent of moisture content and low-molecular-weight again with fixing HA powder, owing to the volatilization of these materials stays the hole of a fixed structure, thereby obtain composite porous.Do not need to add chemical cross-linking agent in the preparation process, the molecular weight of adding is lower than 100 alcohols, ketone, aldehydes organic reagent ratio and is easier to volatilization and removes, can, can keep the material excellent biological compatibility.In the preparation, can also be by changing the proportion of composing of hydroxyapatite and fibroin constituents, reach and improve the porous bone repair, the purpose of comprehensively adjusting to satisfy different clinical needs at many-sided impacts of performance such as biological activity, mechanical characteristics.Simultaneously, the fibroin hydroxyapatite composite material after preparation is shaped no longer needs to carry out calcination technology, therefore, can keep the activity of fibroin in the material, provides good matrix for adding various medicines or somatomedin.
Because accounting for the hydroxyapatite composition of natural bone weight about 65% mainly is nanometer hydroxyapatite, therefore, for the fine powder that makes above-mentioned hydroxyl base apatite composition of the present invention and fibroin constituents can have better uniform mixing degree, a preferred measure, be in above-mentioned preparation process, as hydroxyl phosphorus apatite composition the best of important source material is to be adopted as nano level hydroxyapatite.
Compared with prior art, the present invention has the following advantages:
1, fibroin albumen (SF), hydroxyapatite (HA), silk fiber all have better biocompatibility, SF is biodegradable and can guide promotion cell regeneration, HA has bone conduction effect, can be used as extracellular matrix material and be converted into osseous tissue, finally being substituted by autologous tissue, is ideal tissue engineering material.
2, adopt solution blending-freezing gel method, can SF, HA, silk fiber is disposable compound when freezing curing, can make three's osmotic even, and add the volatile organic reagent of low-molecular-weight, by heat drying, the volatilization of moisture content and the easy organic reagent of low-molecular-weight forms the hole of a fixed structure, thereby obtain composite porously, satisfied the needs of the cell culturing bracket that is used for organizational project.
3, metal die easy-formation, shape are easy to control, and therefore, the composite of molding also can easily obtain required size and shape in metal die, can satisfy the needs that difformity requires easily.
4, adopt the silk fiber reinforcing material, thereby do not need to solve the mechanical property of material by agglomerating method, make the composite porous intensity preferably that has, and because the active existence of fibroin, for compound bone morphogenetic protein(BMP) (BMP) or other medicines, protein factor etc. in material provide a kind of new materials and methods.
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
It is in 3% fibroin albumen (SF) solution that 0.6g hydroxyapatite (HA) is joined 20ml concentration, stirs to be placed in the ultrasound wave homogenization behind the 10min and to handle, and adds to come unstuck in advance and be cut into the long silk fiber 0.04g of 5mm again, stirs 30min.
In the in type metal die of said mixture impouring, it is placed-80 ℃ ethanol bath cryogenic quick freezing 1 hour, make the mixture in the mould form Frozen Body.
Taking-up contains the metal die of Frozen Body, and the refrigerator and cooled that it is placed on-10 ℃ was frozen 20 hours, entire die is immersed in the adequate amount of ethanol solution again, allows ethanol penetrate at leisure in the fibroin hydroxyapatite Frozen Body, makes silk extract gelization, behind the 2h with its taking-up.
Metal die is placed baking oven, under 30 ℃ condition predrying 20 hours, then, again it was placed under 110 ℃ the temperature dry 5 hours, it is composite porous to make the fibroin hydroxyapatite after the demoulding, is numbered 1
#, its performance is referring to table one.
Embodiment two:
It is in 6% the silk fibroin solution that 4.8gHA is joined 20ml concentration, stirs 10min, then with its with ultrasonic Treatment 10min after, add 0.36g silk fiber (come unstuck in advance, be cut into 10mm long), continue to stir 10min, form in the emulsion form mixture.
In this mixture impouring metal die, at once mould is placed-85 ℃ acetaldehyde to bathe cryogenic quick freezing 5 hours, form Frozen Body, after the taking-up under-30 ℃ temperature conditions freezing 24 hours again, then, entire die is immersed in an amount of acetaldehyde solution, acetaldehyde slowly is penetrated in the Frozen Body, make silk extract gelization, with its taking-up, placed 30 ℃ of dryings of baking oven 20 hours behind the 24h, again in 120 ℃ of dryings 5 hours, it is composite porous to obtain the fibroin hydroxyapatite after the demoulding, is numbered 2
#, its performance is referring to table one.
Embodiment three:
HA content is 3.6g, and silk fibroin solution concentration is 9%, and it is long that the silk fiber after coming unstuck in advance is cut into 2mm, adds 0.5g, adopts liquid nitrogen cryogenics quick freezing 10min, and other preparation process is with embodiment 2, and it is composite porous to make the fibroin hydroxyapatite, is numbered 3
#, its performance is referring to table one.
Embodiment four:
It is in 9% the silk fibroin solution that 10.8gHA is joined 30ml concentration, stirs 10min, then it use ultrasonic Treatment 5min, continues stirring 10min and obtains HA fibroin pastel; Get 1.1g silkworm silk plain cloth, come unstuck, airing is cut into 5, is respectively 10 * 1cm size.
In metal die, add one deck HA fibroin pastel earlier, spread one deck silk fabric then, spread layer repeatedly successively, reach thickness and be about 2mm, be coated with one deck HA fibroin pastel at last on its surface, obtain complex layered materials; At once metal die is placed-75 ℃ the freezing 8h of ethanol bath, under-10 ℃, freeze 10 then, soak 12h in the acetone under-20 ℃ again.
Predrying in 30 ℃ air blast, after the demoulding, in 130 ℃ of dryings 5 hours, it was composite porous to make the fibroin hydroxyapatite, is numbered 4 again
#, its performance is referring to table one.
Table one is the performance table that adopts the fibroin hydroxyapatite composite material of embodiment of the invention technical scheme preparation.Referring to table one, the resulting composite products of the present invention, apparent density lower (being lower than 0.5g/cm3), porosity is higher, and the cumulative volume of hole accounts for 50～90% of total composite volume; The bending strength of composite is at 0.1～20MPa, and composite bending modulus has the hole that the aperture is 1～100 micron mutual perforation at 50～2000MPa.The raw material of forming composite has excellent biological compatibility, this specific character that has fully kept material in the preparation process, add behind the composite material forming and have mechanical property, porosity and bigger aperture preferably, therefore, provided by the present inventionly composite porously can be used as the damaged reparation of bone, medicine sustained release and engineering material of bone tissue, application prospect is very wide.
Table one:
| Numbering | Bending strength (MPa) | Composite bending modulus (MPa) | Hot strength (MPa) | Stretch modulus (MPa) | Apparent density (g/cm 3) | Porosity (%) | Average pore size (μ m) |
| 1 # | 4.93 | 175 | 3.86 | 249 | 0.25 | 88 | 50.39 |
| 2 # | 0.50 | 52.6 | 1.40 | 208 | 0.38 | 82 | 2.76 |
| 3 # | 6.12 | 1255 | 20 | 1396 | 0.49 | 89 | 15.5 |
| 4 # | 14.3 | 261 | 15.3 | 708 | 0.46 | 75 | 15 |
Claims (7)
1. fibroin hydroxyapatite composite material, it is characterized in that: it is made up of hydroxyapatite, silk fibroin protein, silkworm silk reinforcing material, and its mass ratio is 1: 0.1～5: 0.001～0.1; Have the hole that the aperture is 1～100 micron mutual perforation in the described composite, pore volume accounts for 50～90%.
2. a kind of fibroin hydroxyapatite composite material according to claim 1 is characterized in that: its bending strength is 0.1～20MPa, and composite bending modulus is 50～2000MPa.
3. a kind of fibroin hydroxyapatite composite material according to claim 1 is characterized in that: described hydroxyapatite is a nanoscale.
4. a kind of fibroin hydroxyapatite composite material according to claim 1 is characterized in that: described silkworm silk reinforcing material is cocoon shell monofilament, doubling, the real silk fabric that took off glue.
5. the preparation method of a fibroin hydroxyapatite composite material as claimed in claim 1 is characterized in that preparation process is as follows:
A. be concentration 1～20% silk fibroin protein solution and hydroxyapatite powder mix homogeneously, add the silkworm silk reinforcing material again, mixture is placed metal die;
B. with above-mentioned metal die cryogenic quick freezing 10min～24h, make the mixture in the mould form Frozen Body;
The metal die that c. will contain Frozen Body is lower than 100 alcohols, ketone, aldehydes organic reagent to molecular weight and infiltrates in the Frozen Body behind freezing 10～24h under-10～-30 ℃ the temperature conditions, and is predrying under 20～40 ℃ temperature conditions again;
D. dryness finalization under 110～130 ℃ temperature conditions, it is composite porous to obtain the fibroin hydroxyapatite.
6. the preparation method of a kind of fibroin hydroxyapatite composite material according to claim 5 is characterized in that: it is in methanol, ethanol, propanol, isopropyl alcohol, butanols, isobutanol, the tert-butyl alcohol, acetone, butanone, formaldehyde, acetaldehyde, propionic aldehyde, the butyraldehyde one or more that described molecular weight is lower than 100 alcohols, ketone, aldehydes organic reagent.
7. the preparation method of a kind of fibroin hydroxyapatite composite material according to claim 5 is characterized in that: the cryogenic quick freezing described in the step b is freezing in the liquid below-70 ℃.
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| CNB200510040925XA CN1301137C (en) | 2005-07-05 | 2005-07-05 | Silk fibrin and hydroxyapatite compound material and preparation process thereof |
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| CNB200510040925XA CN1301137C (en) | 2005-07-05 | 2005-07-05 | Silk fibrin and hydroxyapatite compound material and preparation process thereof |
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| CN1301137C true CN1301137C (en) | 2007-02-21 |
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Families Citing this family (17)
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|---|---|---|---|---|
| CN101293114B (en) * | 2007-04-23 | 2013-06-05 | 佳木斯大学 | Method for preparing nano-multiple phase calcium phosphate/fibroin protein composite bracket |
| WO2009100280A2 (en) * | 2008-02-07 | 2009-08-13 | Trustees Of Tufts College | 3-dimensional silk hydroxyapatite compositions |
| 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 |
| CN101502672B (en) * | 2009-03-19 | 2012-08-08 | 浙江大学 | Method for preparing hydroxyapatite/silk fibroin compound porous stand material |
| CN101703798B (en) * | 2009-11-05 | 2013-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano hydroxyapatite coating and preparation method thereof and electrostatic atomization device |
| CN101905037B (en) * | 2010-07-23 | 2013-04-10 | 山东大学 | Biological composite scaffold and tissue engineering bone used for repairing bone defects |
| CN102423272B (en) * | 2011-09-20 | 2016-03-30 | 复旦大学 | A kind of porous support with network channel and preparation method thereof |
| CN104250926B (en) * | 2014-09-25 | 2016-11-30 | 海门市彼维知识产权服务有限公司 | A kind of production method of the silk fabric of hydroxyapatite functionalization |
| CN108498877A (en) * | 2018-06-27 | 2018-09-07 | 蒲小兵 | The preparation method of fibroin albumen antibacterial orthopaedics internal fixation material |
| CN109678488B (en) * | 2019-01-18 | 2022-01-18 | 华南理工大学 | Ion-doped and protein-impregnated dual-modified porous calcium phosphate ceramic and preparation method thereof |
| 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 |
| CN110591143A (en) * | 2019-09-26 | 2019-12-20 | 北京大学第三医院（北京大学第三临床医学院） | Preparation and application method of silk fibroin freezing sponge |
| CN110624135B (en) * | 2019-09-26 | 2022-02-08 | 北京大学第三医院（北京大学第三临床医学院） | Preparation method of silk fibroin scaffold material capable of realizing long-acting drug sustained release |
| CN110917400B (en) * | 2019-12-05 | 2022-03-29 | 中山大学 | Nano-hybrid silk fibroin hydrogel 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 |
| CN116262147A (en) * | 2021-12-15 | 2023-06-16 | 西湖大学 | Silk protein/biological ceramic composite material and preparation method and application thereof |
| CN115501396B (en) * | 2022-09-13 | 2024-03-22 | 长春达康园医疗器械有限公司 | Degradable tissue scaffold and preparation method and application thereof |
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| JPH06220288A (en) * | 1993-01-28 | 1994-08-09 | Dainippon Ink & Chem Inc | Synthetic resin composition and fiber coated with the same |
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| CN1370507A (en) * | 2001-02-15 | 2002-09-25 | 李雅娟 | Cranial bone implant of hydroxyapatite |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06220288A (en) * | 1993-01-28 | 1994-08-09 | Dainippon Ink & Chem Inc | Synthetic resin composition and fiber coated with the same |
| JPH10127752A (en) * | 1996-11-06 | 1998-05-19 | Norin Suisansyo Sanshi Konchu Nogyo Gijutsu Kenkyusho | Bone binding material and its manufacture |
| CN1370507A (en) * | 2001-02-15 | 2002-09-25 | 李雅娟 | Cranial bone implant of hydroxyapatite |
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