CN106048765B - A kind of preparation method of artificial ligament material - Google Patents
A kind of preparation method of artificial ligament material Download PDFInfo
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- CN106048765B CN106048765B CN201610552268.5A CN201610552268A CN106048765B CN 106048765 B CN106048765 B CN 106048765B CN 201610552268 A CN201610552268 A CN 201610552268A CN 106048765 B CN106048765 B CN 106048765B
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- graphene oxide
- artificial ligament
- regenerated silk
- silk fibroin
- preparation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/10—Materials or treatment for tissue regeneration for reconstruction of tendons or ligaments
Abstract
A kind of preparation method of artificial ligament material provided by the invention, with salt and formic acid dissolution system dissolving boiled silk, the dissolving method can be in the horizontal dissolving fibroin of nanometer fibril, provide the condition of high-performance regenerated silk long filament, it is molded using water as coagulating bath, using gellike spinning process by regenerated silk fibroin, and the boundling collection mode wound by take-up roll builds artificial ligament, the preparation method is easy to operate.In addition graphene oxide is added in regenerated silk fibroin, since graphene is high-strength nano material, elasticity modulus, the tensile strength that material itself can be improved in regenerated silk fibroin are added into, so that it meets the application of artificial ligament.
Description
Technical field
The present invention relates to a kind of new textile material applied technical field, and in particular to a kind of preparation side of artificial ligament material
Method.
Background technology
Healing ability is very poor after cruciate ligament, and the material that clinical reconstruction ligamentaum cruciatum uses at present includes autotransplantation
Thing, allogeneic and synthetic material.Artificial ligament with no district complication, easy to use, early rehabilitation, without disease
Propagate many clear superiorities such as danger.Preferable artificial ligament material, it should possess lasting high intensity, wear-resistant, inorganization is anti-
Fundamental characteristics should be waited, and there is normal ligament, at the same allow to have physiology arrangement, the tissue that regenerates new ligament tendency it is gradual
Grow into, but the artificial ligament for complying fully with above-mentioned condition not yet emerges.Therefore use at present it is more for carbon fiber ligament,
The fabric with holes such as terylene and polypropylene.
Fibroin albumen has good gas permeability, biocompatibility and biodegradation as a kind of natural macromolecular material
Property, have broad application prospects in bio-medical material, drug controlled release, textile finishing etc..Due to fibroin albumen
Material has the mechanical property unique than other natural fibers and high-performance synthetic fibers；Fiber surface is easy to chemical covalent and repaiies
Decorations stick site and cell factor, can be handled by distinct methods and obtain variform and change surface property, in vivo can be with
Slowly be degraded to amino acid, and catabolite to organism without danger, therefore the structure using fibroin albumen as artificial ligament
Material becomes one of hot spot object of Recent study.But the existing method using fibroin albumen structure artificial ligament is more multiple
It is miscellaneous, and the mechanical property for the artificial ligament prepared is poor, it is therefore necessary to a kind of preparation method simple to operation is invented, with
Improve the mechanical property of artificial ligament.
The content of the invention
In order to achieve the above object, it is above-mentioned for solving the present invention provides a kind of preparation method of artificial ligament material
Problem.
A kind of preparation method of artificial ligament material provided by the invention, comprises the following steps：
Step 1：Boiled silk is provided, is dissolved in forming regenerated silk egg in the dissolution system that salt is formed with formic acid
White solution, salt concentration range described in the dissolution system are 1.0~10.0wt.%, the formic acid concn for 10~
98wt.%；
Step 2：The regenerated silk fibroin solution of formation is mixed with graphene oxide dispersion and is sufficiently stirred 3
~10min, obtains graphene oxide/fibroin albumen spinning solution；
Step 3：Using water as coagulating bath, above-mentioned graphene oxide/fibroin albumen spinning solution is shaped to oxidation stone in water
Roller is wound after black alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning solution enters the speed in water
Spend for 2~10mL/h, the take-up roll be involved in the speed of the graphene oxide/regenerated silk fibroin filament yarn for 50~
120cm/min；
Step 4：The graphene oxide that above-mentioned take-up roll is involved in/regenerated silk fibroin filament yarn is tested in strength and elongation
Constant speed stretches on instrument, is stretched to the 0.5 of graphene oxide/regenerated silk fibroin filament yarn length that length is formed for step 3
Shape after~4 times, then soak and desalt in deionized water, drying at room temperature, forms tow；
Step 5：Select the dissolution system dissolving that salt is formed with formic acid to be molded again at the tow both ends, make the silk
The same end consolidation of each bar silk thread in beam is integral, obtains artificial ligament.
Preferably, the salt is lithium bromide, calcium chloride, magnesium chloride, lithium rhodanate, one kind in sodium sulfocyanate or several
Kind, when the salt is lithium bromide, calcium chloride, magnesium chloride, lithium rhodanate, sodium sulfocyanate, the corresponding regenerated silk fibroin
The mass ratio that solution is mixed with graphene oxide dispersion is respectively 9.5：0.5 or 9：1 or 8.5：1.5 or 8：2.
Preferably, the concentration of the regenerated silk fibroin solution formed in step 1 is 10.0~30.0wt.%.
Preferably, graphene oxide dispersion is in advance adjusted pH value to 10~11 in step 2.
Preferably, the graphene oxide/regenerated silk fibroin filament yarn is involved in the take-up roll in step 3
When, it is involved in position every 0.5~2h adjustment.
Preferably, it is graphene oxide/regenerated silk fibroin long filament that step 3 is formed that length is stretched in step 4
Shape 48h after 0.5~4 times of length of yarn, and desalt 24h.
Preferably, adding boiled silk in the tow in step 5 forms the artificial ligament.
Preferably, graphene oxide described in the artificial ligament/regenerated silk fibroin filament yarn and the degumming
The ratio of silk is 1:1~1:5.
Compared with prior art, the beneficial effects of the invention are as follows：A kind of preparation of artificial ligament material provided by the invention
Method, with salt and formic acid dissolution system dissolving boiled silk, which can be in the horizontal dissolving fibroin of nanometer fibril, there is provided
The condition of high-performance regenerated silk long filament, using water as coagulating bath, using gellike spinning process by regenerated silk fibroin
Shaping, and the boundling collection mode wound by take-up roll builds artificial ligament, the preparation method is easy to operate.In addition in regenerated silk
Graphene oxide is added in fibroin, since graphene is high-strength nano material, being added into regenerated silk fibroin can
Elasticity modulus, the tensile strength of material itself are improved, so that it meets the application of artificial ligament.
Brief description of the drawings
Fig. 1 is graphene oxide provided by the invention/regenerated silk fibroin filament yarn shaping schematic view；
Fig. 2 is mixed to form people for graphene oxide provided by the invention/regenerated silk fibroin filament yarn with boiled silk
Work ligament flow chart.
In figure：1~graphene oxide/fibroin albumen spinning solution 1,2~water, 3~take-up roll.
Embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings to the present invention
Embodiment be described in detail.
Embodiment one
Referring to Fig.1 and 2, a kind of preparation method of artificial ligament material provided by the invention, comprises the following steps：
Step 1：Boiled silk is provided, is dissolved in the dissolution system that lithium bromide is formed with formic acid, forms regenerated silk
Fibroin solution, lithium bromide concentration scope described in the dissolution system are 1.0wt.%, and the formic acid concn is 90wt.%；
Step 2：Graphene oxide dispersion is in advance adjusted pH value between 10~11, by the regenerated silk of formation
Fibroin solution presses 9.5 with graphene oxide dispersion：0.5 ratio mixes and is sufficiently stirred 3~10min, obtains oxidation stone
Black alkene/fibroin albumen spinning solution 1, wherein the concentration range of graphene oxide dispersion is in 0.05~1wt.%；
Step 3：It is coagulating bath with water 2, above-mentioned graphene oxide/fibroin albumen spinning solution 1 is shaped to oxygen in water 2
Roller 3 is wound after graphite alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning solution 1 enters water
Speed in 2 is 2mL/h, and the speed that the take-up roll 3 is involved in the graphene oxide/regenerated silk fibroin filament yarn is
50cm/min, usually, 3 weeks a length of 10cm of take-up roll, are involved in position, boundling forms a branch of filament yarn every 0.5~2h adjustment
Line；
Step 4：By a branch of filament yarn of above-mentioned formation, constant speed stretches on strength and elongation tester, and being stretched to length is
Shape 48h after 0.5 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed, is then immersed in
Desalt 24h in deionized water 2, drying at room temperature, forms tow；
Step 5：Add boiled silk in tow, the graphene oxide/regenerated silk fibroin filament yarn with it is described
The ratio of boiled silk is 1:1, then select salt to be dissolved with the dissolution system that formic acid is formed at the tow both ends, make in tow
Each bar silk thread the same end when being molded again consolidation it is integral, obtain artificial ligament.
Embodiment two
The preparation method of another kind artificial ligament material provided by the invention, comprises the following steps：
Step 1：Boiled silk is provided, is dissolved in forming regenerated silk in the dissolution system that calcium chloride is formed with formic acid
Fibroin solution, calcium chloride concentration scope described in the dissolution system are 4.0wt.%, and the formic acid concn is 90wt.%；
Step 2：Graphene oxide dispersion is in advance adjusted pH value between 10~11, by the regenerated silk of formation
Fibroin solution presses 9 with graphene oxide dispersion：1 ratio mixes and is sufficiently stirred 3~10min, and acquisition graphene oxide/
The concentration range of fibroin albumen spinning solution 1, wherein graphene oxide dispersion is in 0.05~1wt.%；
Step 3：It is coagulating bath with water 2, above-mentioned graphene oxide/fibroin albumen spinning solution 1 is shaped to oxygen in water 2
Roller 3 is wound after graphite alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning solution 1 enters water
Speed in 2 is 4mL/h, and the speed that the take-up roll 3 is involved in the graphene oxide/regenerated silk fibroin filament yarn is
70cm/min, usually, 3 weeks a length of 10cm of take-up roll, are involved in position, boundling forms a branch of filament yarn every 0.5~2h adjustment
Line；
Step 4：By a branch of filament yarn of above-mentioned formation, constant speed stretches on strength and elongation tester, and being stretched to length is
Shape 48h after 1.5 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed, is then immersed in
Desalt 24h in deionized water 2, drying at room temperature, forms tow；
Step 5：Add boiled silk in tow, the graphene oxide/regenerated silk fibroin filament yarn with it is described
The ratio of boiled silk is 1:2, then select salt to be dissolved with the dissolution system that formic acid is formed at the tow both ends, make in tow
Each bar silk thread the same end when being molded again consolidation it is integral, obtain artificial ligament.
Embodiment three
The preparation method of another kind artificial ligament material provided by the invention, comprises the following steps：
Step 1：Boiled silk is provided, is dissolved in forming regenerated silk in the dissolution system that magnesium chloride is formed with formic acid
Fibroin solution, density of magnesium chloride scope described in the dissolution system are 5.0wt.%, and the formic acid concn is 90wt.%；
Step 2：Graphene oxide dispersion is in advance adjusted pH value between 10~11, by the regenerated silk of formation
Fibroin solution presses 8.5 with graphene oxide dispersion：1.5 ratio mixes and is sufficiently stirred 3~10min, obtains oxidation stone
Black alkene/fibroin albumen spinning solution 1, wherein the concentration range of graphene oxide dispersion is in 0.05~1wt.%；
Step 3：It is coagulating bath with water 2, above-mentioned graphene oxide/fibroin albumen spinning solution 1 is shaped to oxygen in water 2
Roller 3 is wound after graphite alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning solution 1 enters water
Speed in 2 is 8mL/h, and the speed that the take-up roll 3 is involved in the graphene oxide/regenerated silk fibroin filament yarn is
100cm/min, usually, 3 weeks a length of 10cm of take-up roll, are involved in position, boundling forms a branch of filament yarn every 0.5~2h adjustment
Line；
Step 4：By a branch of filament yarn of above-mentioned formation, constant speed stretches on strength and elongation tester, and being stretched to length is
Shape 48h after 1.5 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed, is then immersed in
Desalt 24h in deionized water 2, drying at room temperature, forms tow；
Step 5：Add boiled silk in tow, the graphene oxide/regenerated silk fibroin filament yarn with it is described
The ratio of boiled silk is 1:3, then select salt to be dissolved with the dissolution system that formic acid is formed at the tow both ends, make in tow
Each bar silk thread the same end when being molded again consolidation it is integral, obtain artificial ligament.
Example IV
The preparation method of another kind artificial ligament material provided by the invention, comprises the following steps：
Step 1：Boiled silk is provided, is dissolved in forming regeneration in the dissolution system that lithium rhodanate is formed with formic acid
Silk fibroin protein solution, lithium rhodanate concentration range described in the dissolution system are 10.0wt.%, and the formic acid concn is
98wt.%；
Step 2：Graphene oxide dispersion is in advance adjusted pH value between 10~11, by the regenerated silk of formation
Fibroin solution presses 8 with graphene oxide dispersion：2 ratios mix and are sufficiently stirred 3~10min, obtain graphene oxide/silk
The concentration range of fibroin spinning solution 1, wherein graphene oxide dispersion is in 0.05~1wt.%；
Step 3：It is coagulating bath with water 2, above-mentioned graphene oxide/fibroin albumen spinning solution 1 is shaped to oxygen in water 2
Roller 3 is wound after graphite alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning solution 1 enters water
Speed in 2 is 10mL/h, and the speed that the take-up roll 3 is involved in the graphene oxide/regenerated silk fibroin filament yarn is
120cm/min, usually, 3 weeks a length of 10cm of take-up roll, are involved in position, boundling forms a branch of filament yarn every 0.5~2h adjustment
Line；
Step 4：By a branch of filament yarn of above-mentioned formation, constant speed stretches on strength and elongation tester, and being stretched to length is
Shape 48h after 4 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed, is then immersed in
Desalt 24h in ionized water 2, drying at room temperature, forms tow；
Step 5：Add boiled silk in tow, the graphene oxide/regenerated silk fibroin filament yarn with it is described
The ratio of boiled silk is 1:5, then select salt to be dissolved with the dissolution system that formic acid is formed at the tow both ends, make in tow
Each bar silk thread the same end when being molded again consolidation it is integral, obtain artificial ligament.
It is prepared by the artificial ligament prepared by the preparation method of artificial ligament material provided by the invention and conventional method
The traditional fibroin albumen artificial ligament gone out carries out Mechanics Performance Testing, specifically：
Using the mechanical property of Instron3365 types universal testing machine (Instron, USA) measure artificial ligament.Power
Before learning performance test, first sample is placed under the conditions of constant temperature and humidity (temperature is 20 ± 2 DEG C, and relative humidity is 65 ± 2%) and is balanced
24h, sample clamping length during test is 40mm, rate of extension 20mm/min, pretension 0.2N.
The result then measured is：
The mechanical property of table graphene oxide/fibroin albumen artificial ligament material
The mechanical property phase of artificial ligament prepared by the method for structure artificial ligament provided by the invention as can be known from the above table
The mechanical property of the fibroin albumen artificial ligament prepared for conventional method greatly improves.
Obviously, those skilled in the art can carry out invention spirit of the various modification and variations without departing from the present invention
And scope.If these modifications and changes of the present invention belongs within the scope of the claims in the present invention and its equivalent technologies, then
The present invention is also intended to including these modification and variations.
Claims (7)
1. a kind of preparation method of artificial ligament material, it is characterised in that comprise the following steps：
Step 1：Boiled silk is provided, it is molten to be dissolved in formation regenerated silk fibroin in the dissolution system that salt is formed with formic acid
Liquid, salinity described in the dissolution system are 1.0~10.0wt.%, and the formic acid concn is 10~98wt.%, the salt
For the one or more in lithium bromide, calcium chloride, magnesium chloride, lithium rhodanate, sodium sulfocyanate, when the salt is lithium bromide, chlorination
When calcium, magnesium chloride, lithium rhodanate, sodium sulfocyanate, the corresponding regenerated silk fibroin solution is mixed with graphene oxide dispersion
The mass ratio of conjunction is respectively 9.5：0.5 or 9：1 or 8.5：1.5 or 8：2；
Step 2：The regenerated silk fibroin solution of formation mix and is sufficiently stirred 3 with graphene oxide dispersion~
10min, obtains graphene oxide/fibroin albumen spinning solution；
Step 3：Using water as coagulating bath, above-mentioned graphene oxide/fibroin albumen spinning solution is shaped to graphite oxide in water
Roller is wound after alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning solution enters the speed in water
For 2~10mL/h, the take-up roll be involved in the speed of the graphene oxide/regenerated silk fibroin filament yarn for 50~
120cm/min；
Step 4：The graphene oxide that above-mentioned take-up roll is involved in/regenerated silk fibroin filament yarn is on strength and elongation tester
Constant speed stretches, and is stretched to the 0.5~4 of graphene oxide/regenerated silk fibroin filament yarn length that length is formed for step 3
Sizing, then soaks and desalts in deionized water after times, drying at room temperature, forms tow；
Step 5：Select the dissolution system dissolving that salt is formed with formic acid to be molded again at the tow both ends, make in the tow
Each bar silk thread the same end consolidation it is integral, obtain artificial ligament.
2. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that formed in step 1 it is described again
The concentration of fibroin protein solution is 10.0~30.0wt.%.
3. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that graphene oxide point in step 2
Dispersion liquid is in advance adjusted pH value to 10~11, and the concentration range of the graphene oxide dispersion is 0.05~1wt.%.
4. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that with the take-up roll in step 3
When being involved in the graphene oxide/regenerated silk fibroin filament yarn, position is involved in every 0.5~2h adjustment.
5. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that length is stretched in step 4 is
Shape 48h after 0.5~4 times of graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed, and desalt 24h.
6. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that in step 5 in the tow
Add boiled silk and form the artificial ligament.
7. the preparation method of artificial ligament material as claimed in claim 6, it is characterised in that oxygen described in the artificial ligament
The ratio of graphite alkene/regenerated silk fibroin filament yarn and the boiled silk is 1:1~1:5.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106906531A (en) * | 2017-02-21 | 2017-06-30 | 南通强生石墨烯科技有限公司 | The preparation method of Graphene fibroin protein functional fiber |
| CN107189080A (en) * | 2017-05-23 | 2017-09-22 | 苏州市晨煊纺织科技有限公司 | A kind of preparation method of the regenerated silk fibroin hydrogel with graphene oxide |
| CN108144116A (en) * | 2018-02-26 | 2018-06-12 | 丁文铃 | A kind of novel antibacterial artificial ligament |
| CN108261563A (en) * | 2018-02-26 | 2018-07-10 | 丁文铃 | A kind of bionical ligament of activeness and quietness |
| EP3859056A4 (en) * | 2018-09-28 | 2022-08-03 | Spiber Inc. | Protein fiber production method |
| KR102447857B1 (en) * | 2020-09-29 | 2022-09-28 | 연세대학교 산학협력단 | Silk fibroin composite material comprising polysaccharide-derived two-dimensional carbon body and method for manufacturing the same |
| CN113652760A (en) * | 2021-06-17 | 2021-11-16 | 苏州市晨煊纺织科技有限公司 | Graphene oxide and regenerated silk fibroin blending spinning process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107021A (en) * | 2010-08-10 | 2011-06-29 | 贾庆卫 | Silk ligament and preparation method thereof |
| CN103173882A (en) * | 2013-04-11 | 2013-06-26 | 大连海事大学 | Method for preparing graphene/ silk composite fiber |
| CN103357067A (en) * | 2013-07-08 | 2013-10-23 | 苏州大学 | Fibroin-base artificial ligament repair material and preparation method thereof |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107021A (en) * | 2010-08-10 | 2011-06-29 | 贾庆卫 | Silk ligament and preparation method thereof |
| CN103173882A (en) * | 2013-04-11 | 2013-06-26 | 大连海事大学 | Method for preparing graphene/ silk composite fiber |
| CN103357067A (en) * | 2013-07-08 | 2013-10-23 | 苏州大学 | Fibroin-base artificial ligament repair material and preparation method thereof |
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