CN104707183B - Absorbable orthopaedics internal fixation material based on silk-fibroin(s) and preparation method thereof - Google Patents
Absorbable orthopaedics internal fixation material based on silk-fibroin(s) and preparation method thereof Download PDFInfo
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- CN104707183B CN104707183B CN201510076427.4A CN201510076427A CN104707183B CN 104707183 B CN104707183 B CN 104707183B CN 201510076427 A CN201510076427 A CN 201510076427A CN 104707183 B CN104707183 B CN 104707183B
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- silk
- fibroin
- internal fixation
- material based
- fixation material
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Abstract
The invention discloses a kind of absorbable orthopaedics internal fixation material based on silk-fibroin(s) and preparation method thereof.The present invention is by changing environment temperature and changing the mass volume ratio of fibroin albumen, the absorbable orthopaedics internal fixation material based on silk-fibroin(s) for preparing has more superior mechanical strength, and good biocompatibility, inflammatory reaction is small, convenient implantation, can autoclaving and maintenance fix 48 weeks, can farthest reduce stress shielding, be with a wide range of applications.
Description
Technical field
The invention belongs to Material Field, and in particular to a kind of system of the absorbable orthopaedics internal fixation material based on fibroin albumen
Preparation Method.
Background technology
With developing rapidly for materialogy, various absorbable materials arise at the historic moment and are applied to Fracture internal fixaiion system rapidly
In, including the materials such as PLGA, PGA and the recent fibroin material for occurring, in these materials, due to PLA/PGA
A kind of acidic materials can be produced in degradation process, and then influences local woanded surface healing, tunnel, mechanical strength is not good enough, because
And non-weight bearing bone is currently only used for, and fibroin material has good biocompatibility, inflammatory reaction is small, can autoclaving, mesh
Before have been widely used for surgical operation, suture, fibroin membrane and timbering material such as in art, due to traditional extraction silk
The method of fibroin is than relatively time-consuming, and the mechanical strength of products therefrom has still been short of, therefore traditional fibroin albumen is still not
It is suitable to be widely used in orthopaedics internal fixation system.
The content of the invention
For the deficiency in the presence of prior art, prepared by new method it is an object of the invention to provide a kind of
Absorbable orthopaedics internal fixation material based on silk-fibroin(s).
The technical solution used in the present invention is：
A kind of absorbable orthopaedics internal fixation material based on fibroin albumen, its preparation method is as follows：
1) by Na2CO3Or NaHCO3In the water that addition is boiled, stir, add silk to boil degumming, obtain degumming
Silk；
2) boiled silk that will be obtained adds ternary solution CaCl2·CH3CH2OH·H2In O, 80-90 DEG C of water-bath makes silk
It is completely dissolved, obtains silk fibroin solution；
3) silk fibroin solution loading bag filter is placed in water dialysis and removes CaCl2And CH3CH2OH, obtains fibroin albumen molten
Liquid；
4) 15000~20000rpm of silk fibroin protein solution is centrifuged 15-25min, takes supernatant, the supernatant freezing for obtaining is dry
It is dry；
5) fibroin albumen of freeze-drying is dissolved in HFIP, obtains H liquid；
6) H liquid is poured into mould, is subsequently placed in methyl alcohol, induce β-pleated sheet conversion, replace HFIP；
7) HFIP and methyl alcohol in fibroin albumen are replaced out step by step with pure water；
8) by step 7) product that obtains dries, sterilizing, obtains the absorbable orthopaedics internal fixation material based on silk-fibroin(s).
As preferred, step 1) by bath raio 1:50~100 (w:V) silk is added in boiling water.
As preferred, step 2) in, boiled silk presses 1:5~15 bath raioes add ternary solution CaCl2·CH3CH2OH·
H2In O.CaCl in ternary solution2、CH3CH2OH、H2The mol ratio of O is 1:2:8.
As preferred, step 3) operation be：Bag filter is placed in deionized water 4 DEG C and dialyses 2~4 days, and every 1~3 is small
Deionized water of Shi Genghuan.
As preferred, step 5) in, 3~10mL HFIP dissolvings are added per 1g fibroin albumens.
The beneficial effects of the invention are as follows：The absorbable orthopaedics internal fixation material based on fibroin albumen that the present invention is prepared
With more superior mechanical strength, and good biocompatibility, inflammatory reaction is small, convenient implantation, can autoclaving and maintenance fixation
4-8 weeks, stress shielding can be farthest reduced, be with a wide range of applications.
Brief description of the drawings
The outline drawing of the absorbable orthopaedics internal fixation material based on fibroin albumen that Fig. 1 is prepared for the inventive method；
Fig. 2 is the fibroin albumen orthopaedics bioabsorbable interference screw for processing；
Fig. 3 is absorbable orthopaedics internal fixation material of the invention and MC3T3 co-culture of cells result figures.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but is not limited thereto.
Embodiment 1
A kind of preparation method of the absorbable orthopaedics internal fixation material based on fibroin albumen of the present invention, comprises the following steps：
1st, 5000mL deionized waters are measured, Na is added after boiling2CO33g stirs, by bath raio 1:50(w:V) life is added
Silk 100g boils degumming 30min.
2nd, cleaned up with deionized water after degumming, be repeated 3 times, the silk of degumming is placed in 60 DEG C of baking ovens dry it is standby
With.
3rd, boiled silk that step 2 obtains is weighed with 1:10 bath raioes add ternary solution CaCl2·CH3CH2OH·H2O (rubs
You compare 1:2:8) in, it is completely dissolved to silk under 80-90 DEG C of water-bath effect, obtains silk fibroin solution.
Concrete operations are：200g CaCl are added in 260ml ultra-pure waters2Thoroughly after dissolving, 208ml ethanol and 50g are added
Boiled silk, in 80-90 DEG C of water-soluble pot heating.Silk only needs to can dissolve for 1 hour in this operation, and extraction egg is greatly reduced
The white time.
4th, silk fibroin solution is fitted into bag filter, is subsequently placed in deionized water 4 DEG C and dialyses 3 days, changed once within every 2 hours
Deionized water, obtains final product silk fibroin protein solution.Concentration is needed after this step, can be concentrated using ordinary room temperature concentration method and thickener.
5th, it is centrifuged：With 18000 turns of speed from 20 minutes on supercentrifuge, it is centrifuged 2 times, takes supernatant, inserts square
Container, freezes 2-5 days, vacuum drying, and -20~0 DEG C until purifying.
6th, put into after the fibroin albumen of vacuum freeze drying is crushed in needle tubing, add HFIP (hexafluoroisopropanol) to make its molten
Solution, obtains H liquid, and fibroin albumen is 1g with the ratio of HFIP：4mL.
7th, adjusting screw mould is made with paraffin, is made that 3.3cm is high, 6 through holes of a diameter of 0.76cm are made a call to above；0.25cm
Thick thin slice, melting paraffin mass two ends makes thin slice adhere to mold bottom, filament plate Mold Making rectangle paraffin, inside dimensions：
4.45×4.45×3.30cm。
8th, H liquid is poured into adjusting screw mould, is placed in 3-4 days in methyl alcohol, induce β-pleated sheet conversion, replace HFIP.
9th, methanol-water gradient effect：1/4,2/4,3/4,4/4 pure water is sequentially added, 1h is stood every time, repeat to grasp
Make, the HFIP and methyl alcohol in fibroin albumen are replaced out step by step；
10th, the purified product that step 9 is obtained is placed in and is dried in fume hood at least one week, then at least baked in 60 DEG C of baking boxs
5 days, then high pressure steam sterilization treatment.Obtain the aseptic absorbable orthopaedics internal fixation material based on silk-fibroin(s).According to orthopaedics
Operation is different to be needed to produce orthopedic fixation device tool of different shapes.
The mechanical property of the present embodiment absorbable orthopaedics internal fixation material of the gained based on silk-fibroin(s) is as shown in table 1-3：
1 three points of performance parameters of curved product of table
The performance parameter of the Compressive Mechanical of table 2 experiment
Biocompatibility experiment：The material that the present embodiment is prepared is good with MC3T3 co-culture of cells display cell growth
Good, form is normal, as shown in Figure 3.Diagram：Yl moiety is edge of materials.White portion is MC3T3 cell growths area.
Embodiment 2
In except step 1, by bath:1：100(w:V) add outside raw silk, remaining operation is same as Example 1.The present embodiment
The mechanical property of resulting materials is as shown in Table 4-6.
4 three points of performance parameters of curved product of table
The performance parameter of the Compressive Mechanical of table 5 experiment
The performance parameter of the stretching mechanical of table 6 experiment
The material that the present embodiment is prepared is good with MC3T3 co-culture of cells display cell growth, and form is normal, says
Bright material just has preferable biocompatibility.
Embodiment 3
Except in step 3, fibroin fiber is with 1:50 bath raioes add ternary solution CaCl2·CH3CH2OH·H2O, remaining behaviour
Make same as Example 1.The mechanical property of the present embodiment resulting materials is as shown in table 7-9.
7 three points of performance parameters of curved product of table
The performance parameter of the Compressive Mechanical of table 8 experiment
The material that the present embodiment is prepared is good with MC3T3 co-culture of cells display cell growth, and form is normal, says
Bright material just has preferable biocompatibility.
Embodiment 4
Except in step 6, fibroin fiber is with 1:15 bath raioes add ternary solution CaCl2·CH3CH2OH·H2O, remaining behaviour
Make same as Example 1.The mechanical property of the present embodiment resulting materials is as shown in table 10-12.
10 3 points of performance parameters of curved product of table
The performance parameter of the Compressive Mechanical of table 11 experiment
The performance parameter of the stretching mechanical of table 12 experiment
The material that the present embodiment is prepared is good with MC3T3 co-culture of cells display cell growth, and form is normal, says
Bright material just has preferable biocompatibility.
Embodiment 5
Except the ratio of fibroin albumen and HFIP in step 6 is 1g：Outside 3mL, remaining operation is same as Example 1.This reality
The mechanical property of a resulting materials is applied as shown in table 13-15.
13 3 points of performance parameters of curved product of table
The performance parameter of the Compressive Mechanical of table 14 experiment
The performance parameter of the stretching mechanical of table 15 experiment
The material that the present embodiment is prepared is good with MC3T3 co-culture of cells display cell growth, and form is normal, says
Bright material just has preferable biocompatibility.
Embodiment 6
Except the ratio of fibroin albumen and HFIP in step 6 is 1g：Outside 8mL, remaining operation is same as Example 1.This reality
The mechanical property of a resulting materials is applied as shown in table 16-18.
16 3 points of performance parameters of curved product of table
The performance parameter of the Compressive Mechanical of table 17 experiment
The performance parameter of the stretching mechanical of table 18 experiment
The material that the present embodiment is prepared is good with MC3T3 co-culture of cells display cell growth, and form is normal, says
Bright material just has preferable biocompatibility.
Above example shows that the absorbable orthopaedics internal fixation material based on fibroin albumen that the present invention is prepared has
More superior mechanical strength, and good biocompatibility, inflammatory reaction are small, convenient implantation, can autoclaving and the fixed 4-8 of maintenance
In week, stress shielding can be farthest reduced, be with a wide range of applications.
Above example is only to introduce preferred case of the invention, to those skilled in the art, without departing substantially from this
Any obvious changes and improvements carried out in the range of spirit, are regarded as a part of the invention.
Claims (7)
1. a kind of absorbable orthopaedics internal fixation material based on fibroin albumen, its preparation method is as follows：
1）By Na2CO3Or NaHCO3In the water that addition is boiled, stir, add silk to boil degumming, obtain the silk of degumming；
2）The boiled silk that will be obtained is by 1:5~15（w:v）Bath raio adds ternary solution CaCl2•CH3CH2OH•H2In O, water-bath makes
Silk is completely dissolved, and obtains silk fibroin solution；
3）Silk fibroin solution loading bag filter is placed in water dialysis and removes CaCl2And CH3CH2OH, obtains silk fibroin protein solution；
4）Supernatant is taken after silk fibroin protein solution is centrifuged, the supernatant freeze-drying for obtaining；
5）The fibroin albumen of freeze-drying is dissolved in HFIP, H liquid is obtained；
6）H liquid is poured into mould, is subsequently placed in methyl alcohol, induce β-pleated sheet conversion, replace HFIP；
7）Replace out the HFIP and methyl alcohol in fibroin albumen step by step with pure water；
8）By step 7）The product for obtaining is dried, sterilizing, obtains the absorbable orthopaedics internal fixation material based on silk-fibroin(s).
2. the absorbable orthopaedics internal fixation material based on fibroin albumen according to claim 1, it is characterised in that step 1）
By bath raio 1:50~100（w:v）Silk is added in boiling water.
3. the absorbable orthopaedics internal fixation material based on fibroin albumen according to claim 1, it is characterised in that step 2）
CaCl in ternary solution2、CH3CH2OH、H2The mol ratio of O is 1:2:8.
4. the absorbable orthopaedics internal fixation material based on fibroin albumen according to claim 1, it is characterised in that step 3）
Operation be：Bag filter is placed in deionized water 4 DEG C and dialyses 2~4 days, changes a deionized water within every 1~3 hour.
5. the absorbable orthopaedics internal fixation material based on fibroin albumen according to claim 1, it is characterised in that step 2）
The water-bath refers to the water-bath at 80-90 DEG C.
6. the absorbable orthopaedics internal fixation material based on fibroin albumen according to claim 1, it is characterised in that step 4）
The centrifugation refers in 15000~20000 rpm centrifugation 15-25 min.
7. the absorbable orthopaedics internal fixation material based on fibroin albumen according to claim 1, it is characterised in that step 5）
In, 3~10mL HFIP dissolvings are added per 1g fibroin albumens.
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| CN201510076427.4A CN104707183B (en) | 2015-01-29 | 2015-02-11 | Absorbable orthopaedics internal fixation material based on silk-fibroin(s) and preparation method thereof |
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| CN201510046794 | 2015-01-29 | ||
| CN201510046794X | 2015-01-29 | ||
| CN201510076427.4A CN104707183B (en) | 2015-01-29 | 2015-02-11 | Absorbable orthopaedics internal fixation material based on silk-fibroin(s) and preparation method thereof |
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| CN104707183B true CN104707183B (en) | 2017-06-13 |
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| CN108409992B (en) * | 2017-02-09 | 2020-07-31 | 江西丝科生物科技有限公司 | Silk fibroin block and preparation method thereof |
| CN106822992A (en) * | 2017-03-14 | 2017-06-13 | 张帆 | The preparation method of the implantation human body degradable biomaterial based on silk fibroin |
| CN108159501A (en) * | 2018-01-23 | 2018-06-15 | 武汉大学 | A kind of preparation method of fibroin material of composite Nano grade hydroxyapatite and its application in repair of fractures position |
| CN108126247B (en) * | 2018-01-29 | 2020-08-14 | 广州科越生物科技有限公司 | Fibroin orthopedic internal fixation assembly and preparation method thereof |
| CN108273143A (en) * | 2018-03-09 | 2018-07-13 | 中科国思生物科技研究（广州）有限公司 | A kind of preparation method of silk nail |
| CN108498877A (en) * | 2018-06-27 | 2018-09-07 | 蒲小兵 | The preparation method of fibroin albumen antibacterial orthopaedics internal fixation material |
| CN113332498B (en) * | 2021-05-20 | 2022-05-13 | 湖北赛罗生物材料有限公司 | Silk fibroin/hydroxyapatite composite material and preparation method and application thereof |
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| CN1262579C (en) * | 2004-05-27 | 2006-07-05 | 复旦大学 | Preparation of porous sericin sponge material |
| GB0807868D0 (en) * | 2008-04-30 | 2008-06-04 | Knight David P | Cartilage repair material and a method for the preparation thereof |
| CN101905035B (en) * | 2010-07-22 | 2013-04-10 | 苏州大学 | Method for preparing silk fibroin three-dimensional porous material |
| CN102430155B (en) * | 2011-12-08 | 2014-04-23 | 西安交通大学 | Cellular silk fibroin porous scaffold, and preparation method thereof |
| 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 |
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