CN106048765A - Preparation method of artificial ligament material - Google Patents
Preparation method of artificial ligament material Download PDFInfo
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- CN106048765A CN106048765A CN201610552268.5A CN201610552268A CN106048765A CN 106048765 A CN106048765 A CN 106048765A CN 201610552268 A CN201610552268 A CN 201610552268A CN 106048765 A CN106048765 A CN 106048765A
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- graphene oxide
- artificial ligament
- silk fibroin
- regenerated silk
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/443—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with carbon fillers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dermatology (AREA)
- Composite Materials (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Materials Engineering (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides a preparation method of an artificial ligament material. Degummed silk is dissolved by salt and a formic acid dissolution system, silk fibroin can be dissolved in a nano fibril level through the dissolution method, and the silk growing condition is provided for the high-performance regenerated silk fibroin; water is used as a coagulating bath, the regenerated silk fibroin is formed by adopting a gellike spinning method, and an artificial ligament is constructed in the mode of bundling collecting by winding of a winding roll. The preparation method is easy to operate. In addition, graphene oxide is added into the regenerated silk fibroin, graphene is a high-strength nanomaterial, and the elasticity modulus and the tensile strength of the material can be improved by adding the graphene into the regenerated silk fibroin, so that application of the material in the artificial ligament is met.
Description
Technical field
The present invention relates to a kind of new textile material applied technical field, be specifically related to the preparation side of a kind of artificial ligament material
Method.
Background technology
Healing ability extreme difference after cruciate ligament, the most clinical material rebuilding ligamentaum cruciatum use includes autotransplantation
Thing, allotransplant and synthetic material.Artificial ligament have without for district complication, easy to use, early rehabilitation, without disease
Propagate many clear superiorities such as dangerous.Preferably artificial ligament material, it should possess lasting high intensity, wear-resistant, inorganization is anti-
Should wait fundamental characteristics, and there is the function of normal ligament, allow physiology arrangement simultaneously, regenerate the tissue of new ligament tendency gradually
Grow into, but the artificial ligament complying fully with above-mentioned condition not yet emerges.The most currently used more for carbon fiber ligament,
The fabric that terylene and polypropylene etc. are with holes.
Fibroin albumen, as a kind of natural macromolecular material, has good breathability, biocompatibility and biodegradation
Property, have broad application prospects at aspects such as bio-medical material, drug controlled release, textile finishings.Due to fibroin albumen
Material has the mechanical property unique than other natural fiber and high-performance synthetic fibers；Fiber surface is prone to chemical covalent and repaiies
Decorations stick site and cytokine, can be processed by distinct methods and obtain variform and change surface property, the most permissible
Slowly be degraded to aminoacid, and catabolite to organism without danger, therefore using fibroin albumen as the structure of artificial ligament
One of material focus object becoming Recent study.But the method that existing use fibroin albumen builds artificial ligament is the most multiple
Miscellaneous, and the mechanical property of the artificial ligament prepared is poor, it is therefore necessary to invent a kind of preparation method simple to operation, with
Improve the mechanical property of artificial ligament.
Summary of the invention
In order to achieve the above object, the invention provides the preparation method of a kind of artificial ligament material, be used for solving above-mentioned
Problem.
The preparation method of a kind of artificial ligament material that the present invention provides, comprises the following steps:
Step one: provide boiled silk, is dissolved in salt and forms regenerated silk egg in the dissolution system of formic acid formation
White solution, salt concentration range described in described dissolution system is 1.0～10.0wt.%, described formic acid concn be 10～
98wt.%；
Step 2: the described regenerated silk fibroin solution formed is mixed with graphene oxide dispersion and is sufficiently stirred for 3
～10min, it is thus achieved that graphene oxide/fibroin albumen spinning liquid；
Step 3: with water as coagulating bath, is shaped to above-mentioned graphene oxide/fibroin albumen spinning liquid in water aoxidize stone
Being wound roller after ink alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning liquid enters the speed in water
Degree is 2～10mL/h, described take-up roll be involved in the speed of described graphene oxide/regenerated silk fibroin filament yarn be 50～
120cm/min；
Step 4: the graphene oxide above-mentioned take-up roll being involved in/regenerated silk fibroin filament yarn is tested in strength and elongation
Constant speed stretching on instrument, is stretched to the 0.5 of graphene oxide/regenerated silk fibroin filament yarn length that a length of step 3 is formed
～shape after 4 times, then soak and desalt in deionized water, drying at room temperature, form tow；
Step 5: select at described tow two ends salt to dissolve molding again with the dissolution system that formic acid is formed, make described silk
Same one end of each bar silk thread in bundle is consolidated into one, it is thus achieved that artificial ligament.
As preferably, described salt is the one in lithium bromide, calcium chloride, magnesium chloride, lithium rhodanate, sodium rhodanate or several
Kind, when described salt is lithium bromide, calcium chloride, magnesium chloride, lithium rhodanate, sodium rhodanate, corresponding described regenerated silk fibroin
The mass ratio that solution mixes with graphene oxide dispersion is respectively 9.5:0.5 or 9:1 or 8.5:1.5 or 8:2.
As preferably, the concentration of the described regenerated silk fibroin solution formed in step one is 10.0～30.0wt.%.
As preferably, in step 2, pH value is regulated to 10～11 by graphene oxide dispersion in advance.
As preferably, step 3 is involved in described graphene oxide/regenerated silk fibroin filament yarn by described take-up roll
Time, adjust every 0.5～2h and be involved in position.
As preferably, step 4 is stretched to graphene oxide/regenerated silk fibroin long filament that a length of step 3 is formed
Shape after 0.5～4 times of length of yarn 48h, and desalt 24h.
As preferably, step 5 adds in described tow boiled silk and forms described artificial ligament.
As preferably, graphene oxide described in described artificial ligament/regenerated silk fibroin filament yarn and described degumming
The ratio of silkworm silk is 1:1～1:5.
Compared with prior art, the invention has the beneficial effects as follows: the preparation of a kind of artificial ligament material that the present invention provides
Method, dissolves boiled silk with salt and formic acid dissolution system, and this dissolving method can dissolve fibroin in nanometer fibril level, it is provided that
The condition of high-performance regenerated silk long filament, uses water as coagulating bath, uses gellike spinning process by regenerated silk fibroin
Molding, and the boundling collection mode structure artificial ligament wound by take-up roll, this preparation method easily operates.This external regenerated silk
Adding graphene oxide in fibroin, owing to Graphene is high-strength nano material, being added in regenerated silk fibroin can
Improve the elastic modelling quantity of material self, hot strength, so that it meets the application of artificial ligament.
Accompanying drawing explanation
The graphene oxide that Fig. 1 provides for the present invention/regenerated silk fibroin filament yarn shaping schematic view；
The graphene oxide that Fig. 2 provides for the present invention/regenerated silk fibroin filament yarn and boiled silk are mixed to form people
Work ligament flow chart.
In figure: 1～graphene oxide/fibroin albumen spinning liquid 1,2～water, 3～take-up roll.
Detailed description of the invention
Understandable, below in conjunction with the accompanying drawings to the present invention for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from
Detailed description of the invention be described in detail.
Embodiment one
Refer to Fig. 1 and Fig. 2, the preparation method of a kind of artificial ligament material that the present invention provides, comprise the following steps:
Step one: provide boiled silk, is dissolved in the dissolution system of lithium bromide and formic acid formation, forms regenerated silk
Fibroin solution, lithium bromide concentration scope described in described dissolution system is 1.0wt.%, and described formic acid concn is 90wt.%；
Step 2: graphene oxide dispersion in advance by pH value regulation between 10～11, the described regenerated silk that will be formed
Fibroin solution and graphene oxide dispersion are mixed in the ratio of 9.5:0.5 and are sufficiently stirred for 3～10min, it is thus achieved that oxidation stone
Ink alkene/fibroin albumen spinning liquid 1, wherein the concentration range of graphene oxide dispersion is 0.05～1wt.%；
Step 3: with water 2 as coagulating bath, is shaped to oxygen by above-mentioned graphene oxide/fibroin albumen spinning liquid 1 in water 2
Being wound roller 3 after functionalized graphene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning liquid 1 enters water
Speed in 2 is 2mL/h, and described take-up roll 3 is involved in the speed of described graphene oxide/regenerated silk fibroin filament yarn and is
50cm/min, usually, 3 weeks a length of 10cm of take-up roll, adjust every 0.5～2h and be involved in position, boundling forms a branch of filament yarn
Line；
Step 4: by the constant speed stretching on strength and elongation tester of a branch of filament yarn of above-mentioned formation, be stretched to a length of
Shape after 0.5 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed 48h, is then immersed in
Desalt in deionized water 2 24h, drying at room temperature, forms tow；
Step 5: adding boiled silk in tow, described graphene oxide/regenerated silk fibroin filament yarn is with described
The ratio of boiled silk is 1:1, and the dissolution system then selecting salt and formic acid to be formed at described tow two ends is dissolved, in making tow
Same one end of each bar silk thread be consolidated into one when molding again, it is thus achieved that artificial ligament.
Embodiment two
The preparation method of the another kind of artificial ligament material that the present invention provides, comprises the following steps:
Step one: provide boiled silk, is dissolved in calcium chloride and forms regenerated silk in the dissolution system of formic acid formation
Fibroin solution, calcium chloride concentration scope described in described dissolution system is 4.0wt.%, and described formic acid concn is 90wt.%；
Step 2: graphene oxide dispersion in advance by pH value regulation between 10～11, the described regenerated silk that will be formed
Fibroin solution and graphene oxide dispersion are mixed in the ratio of 9:1 and are sufficiently stirred for 3～10min, it is thus achieved that and graphene oxide/
Fibroin albumen spinning liquid 1, wherein the concentration range of graphene oxide dispersion is 0.05～1wt.%；
Step 3: with water 2 as coagulating bath, is shaped to oxygen by above-mentioned graphene oxide/fibroin albumen spinning liquid 1 in water 2
Being wound roller 3 after functionalized graphene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning liquid 1 enters water
Speed in 2 is 4mL/h, and described take-up roll 3 is involved in the speed of described graphene oxide/regenerated silk fibroin filament yarn and is
70cm/min, usually, 3 weeks a length of 10cm of take-up roll, adjust every 0.5～2h and be involved in position, boundling forms a branch of filament yarn
Line；
Step 4: by the constant speed stretching on strength and elongation tester of a branch of filament yarn of above-mentioned formation, be stretched to a length of
Shape after 1.5 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed 48h, is then immersed in
Desalt in deionized water 2 24h, drying at room temperature, forms tow；
Step 5: adding boiled silk in tow, described graphene oxide/regenerated silk fibroin filament yarn is with described
The ratio of boiled silk is 1:2, and the dissolution system then selecting salt and formic acid to be formed at described tow two ends is dissolved, in making tow
Same one end of each bar silk thread be consolidated into one when molding again, it is thus achieved that artificial ligament.
Embodiment three
The preparation method of the another kind of artificial ligament material that the present invention provides, comprises the following steps:
Step one: provide boiled silk, is dissolved in magnesium chloride and forms regenerated silk in the dissolution system of formic acid formation
Fibroin solution, density of magnesium chloride scope described in described dissolution system is 5.0wt.%, and described formic acid concn is 90wt.%；
Step 2: graphene oxide dispersion in advance by pH value regulation between 10～11, the described regenerated silk that will be formed
Fibroin solution and graphene oxide dispersion are mixed in the ratio of 8.5:1.5 and are sufficiently stirred for 3～10min, it is thus achieved that oxidation stone
Ink alkene/fibroin albumen spinning liquid 1, wherein the concentration range of graphene oxide dispersion is 0.05～1wt.%；
Step 3: with water 2 as coagulating bath, is shaped to oxygen by above-mentioned graphene oxide/fibroin albumen spinning liquid 1 in water 2
Being wound roller 3 after functionalized graphene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning liquid 1 enters water
Speed in 2 is 8mL/h, and described take-up roll 3 is involved in the speed of described graphene oxide/regenerated silk fibroin filament yarn and is
100cm/min, usually, 3 weeks a length of 10cm of take-up roll, adjust every 0.5～2h and be involved in position, boundling forms a branch of filament yarn
Line；
Step 4: by the constant speed stretching on strength and elongation tester of a branch of filament yarn of above-mentioned formation, be stretched to a length of
Shape after 1.5 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed 48h, is then immersed in
Desalt in deionized water 2 24h, drying at room temperature, forms tow；
Step 5: adding boiled silk in tow, described graphene oxide/regenerated silk fibroin filament yarn is with described
The ratio of boiled silk is 1:3, and the dissolution system then selecting salt and formic acid to be formed at described tow two ends is dissolved, in making tow
Same one end of each bar silk thread be consolidated into one when molding again, it is thus achieved that artificial ligament.
Embodiment four
The preparation method of the another kind of artificial ligament material that the present invention provides, comprises the following steps:
Step one: provide boiled silk, is dissolved in lithium rhodanate and forms regeneration in the dissolution system of formic acid formation
Silk fibroin protein solution, lithium rhodanate concentration range described in described dissolution system is 10.0wt.%, and described formic acid concn is
98wt.%；
Step 2: graphene oxide dispersion in advance by pH value regulation between 10～11, the described regenerated silk that will be formed
Fibroin solution and graphene oxide dispersion are mixed in 8:2 ratio and are sufficiently stirred for 3～10min, it is thus achieved that graphene oxide/silk
Fibroin spinning liquid 1, wherein the concentration range of graphene oxide dispersion is 0.05～1wt.%；
Step 3: with water 2 as coagulating bath, is shaped to oxygen by above-mentioned graphene oxide/fibroin albumen spinning liquid 1 in water 2
Being wound roller 3 after functionalized graphene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning liquid 1 enters water
Speed in 2 is 10mL/h, and described take-up roll 3 is involved in the speed of described graphene oxide/regenerated silk fibroin filament yarn and is
120cm/min, usually, 3 weeks a length of 10cm of take-up roll, adjust every 0.5～2h and be involved in position, boundling forms a branch of filament yarn
Line；
Step 4: by the constant speed stretching on strength and elongation tester of a branch of filament yarn of above-mentioned formation, be stretched to a length of
Shape after 4 times of former graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed 48h, is then immersed in
Desalt in ionized water 2 24h, drying at room temperature, forms tow；
Step 5: adding boiled silk in tow, described graphene oxide/regenerated silk fibroin filament yarn is with described
The ratio of boiled silk is 1:5, and the dissolution system then selecting salt and formic acid to be formed at described tow two ends is dissolved, in making tow
Same one end of each bar silk thread be consolidated into one when molding again, it is thus achieved that artificial ligament.
Artificial ligament prepared by the preparation method of the artificial ligament material present invention provided is prepared with traditional method
The traditional fibroin albumen artificial ligament gone out carries out Mechanics Performance Testing, specifically:
Instron3365 type universal testing machine (Instron, USA) is used to measure the mechanical property of artificial ligament.Power
Before learning performance test, balance under the conditions of first sample is placed in constant temperature and humidity (temperature is 20 ± 2 DEG C, and relative humidity is 65 ± 2%)
24h, a length of 40mm of sample clamping during test, rate of extension is 20mm/min, pretension 0.2N.
The result then recorded is:
The mechanical property of epoxy functionalized graphene/fibroin albumen artificial ligament material
The mechanical property phase of the artificial ligament prepared by method building artificial ligament that the present invention provides as can be known from the above table
The mechanical property of the fibroin albumen artificial ligament prepared for traditional method is greatly improved.
Obviously, those skilled in the art can carry out various change and the modification spirit without deviating from the present invention to invention
And scope.If these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then
The present invention is also intended to change and including modification include these.
Claims (8)
1. the preparation method of an artificial ligament material, it is characterised in that comprise the following steps:
Step one: provide boiled silk, is dissolved in formation regenerated silk fibroin in the dissolution system that salt and formic acid are formed molten
Liquid, salinity described in described dissolution system is 1.0～10.0wt.%, and described formic acid concn is 10～98wt.%；
Step 2: the described regenerated silk fibroin solution formed is mixed with graphene oxide dispersion and be sufficiently stirred for 3～
10min, it is thus achieved that graphene oxide/fibroin albumen spinning liquid；
Step 3: with water as coagulating bath, is shaped to graphite oxide by above-mentioned graphene oxide/fibroin albumen spinning liquid in water
Being wound roller after alkene/regenerated silk fibroin filament yarn to be involved in, graphene oxide/fibroin albumen spinning liquid enters the speed in water
Be 2～10mL/h, described take-up roll be involved in the speed of described graphene oxide/regenerated silk fibroin filament yarn be 50～
120cm/min；
Step 4: the graphene oxide above-mentioned take-up roll being 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 a length of step 3 is formed
After times, sizing, then soaks and desalts in deionized water, drying at room temperature, forms tow；
Step 5: select at described tow two ends salt to dissolve molding again with the dissolution system that formic acid is formed, make in described tow
Same one end of each bar silk thread be consolidated into one, it is thus achieved that artificial ligament.
2. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that described salt is lithium bromide, chlorination
One or more in calcium, magnesium chloride, lithium rhodanate, sodium rhodanate, when described salt is lithium bromide, calcium chloride, magnesium chloride, sulfur cyanogen
During acid lithium, sodium rhodanate, the mass ratio that corresponding described regenerated silk fibroin solution mixes with graphene oxide dispersion is respectively
For 9.5:0.5 or 9:1 or 8.5:1.5 or 8:2.
3. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that step one is formed described again
The concentration of fibroin protein solution is 10.0～30.0wt.%.
4. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that in step 2, graphene oxide divides
PH value is regulated to 10～11 by scattered liquid in advance, and the concentration range of described graphene oxide dispersion is 0.05～1wt.%.
5. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that use described take-up roll in step 3
When being involved in described graphene oxide/regenerated silk fibroin filament yarn, adjust every 0.5～2h and be involved in position.
6. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that be stretched to a length of in step 4
Shape after 0.5～4 times of graphene oxide/regenerated silk fibroin filament yarn length that step 3 is formed 48h, and desalt 24h.
7. the preparation method of artificial ligament material as claimed in claim 1, it is characterised in that in step 5 in described tow
Add boiled silk and form described artificial ligament.
8. the preparation method of artificial ligament material as claimed in claim 7, it is characterised in that oxygen described in described artificial ligament
Functionalized graphene/regenerated silk fibroin filament yarn is 1:1～1:5 with the ratio of described boiled silk.
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Cited By (7)
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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 |
| CN112752872A (en) * | 2018-09-28 | 2021-05-04 | 丝芭博株式会社 | Method for preparing protein fiber |
| 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112752872A (en) * | 2018-09-28 | 2021-05-04 | 丝芭博株式会社 | Method for preparing protein fiber |
| EP3859056A4 (en) * | 2018-09-28 | 2022-08-03 | Spiber Inc. | Protein fiber production method |
| KR20220043524A (en) * | 2020-09-29 | 2022-04-05 | 연세대학교 산학협력단 | Silk fibroin composite material comprising polysaccharide-derived two-dimensional carbon body and method for manufacturing the same |
| 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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