CN106822992A - The preparation method of the implantation human body degradable biomaterial based on silk fibroin - Google Patents
The preparation method of the implantation human body degradable biomaterial based on silk fibroin Download PDFInfo
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- CN106822992A CN106822992A CN201710149780.XA CN201710149780A CN106822992A CN 106822992 A CN106822992 A CN 106822992A CN 201710149780 A CN201710149780 A CN 201710149780A CN 106822992 A CN106822992 A CN 106822992A
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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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
- A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
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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
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Abstract
The invention discloses a kind of preparation method of the implantation human body degradable biomaterial based on silk fibroin, methods described step is：By Na2CO3Add in boiling water, add silk to boil degumming, obtain boiled silk；Boiled silk is added to CaCl2·CH3CH2OH·H2In O or lithium-bromide solution, silk mixed solution is obtained；Silk mixed solution is crossed into resin ion exchange column, silk fibroin water solution is obtained；By silk fibroin water solution freeze-drying, cotton-shaped dry state fibroin albumen is obtained；Cotton-shaped dry state fibroin albumen is dissolved in hexafluoroisopropanol, fibroin albumen alcoholic solution is obtained；By fibroin albumen alcoholic solution by electrostatic spinning machine, membranaceous or block biomaterial is made.The present invention can obtain the biomaterial of different medical purposes and controllable degradation speed by being dissolved in the difference of organic solvent fibroin albumen manufacturing conditions, and the biomaterial possesses splendid biocompatibility, without obvious inflammatory reaction, with extensive medical prospect.
Description
Technical field
The invention belongs to field of material technology, it is related to a kind of preparation method of degradable biomaterial, more particularly to it is a kind of
The preparation method of the implantation human body degradable biomaterial based on silk fibroin.
Background technology
With developing rapidly for materialogy, various absorbable materials arise at the historic moment and be applied to rapidly tissue it is various lack
The reparation of damage, including the materials such as PLGA, PGA and the recent fibroin material for occurring.In these materials, due to
PLA/PGA can produce a kind of stronger acidic materials in degradation process, have obvious local irritant effect, and then influence the surface of a wound
Healing, can form sinus, and fragility is big, and mechanical strength is not good enough, and fibroin material good biocompatibility, and inflammatory reaction is small,
Can high steam or irradiation sterilization, in having been widely used for surgical operation at present, suture, fibroin membrane and support such as in art
Material etc..
The content of the invention
The deficiency that the present invention exists for current material, there is provided a kind of implantation human body based on silk fibroin can drop
Solve the preparation method of biomaterial.The present invention can be obtained not by being dissolved in the difference of organic solvent fibroin albumen manufacturing conditions
With medical application and the biomaterial of controllable degradation speed, the biomaterial possesses splendid biocompatibility, without substantially scorching
Property reaction, can high pressure steam sterilization or irradiation sterilization, with extensive medical prospect.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the implantation human body degradable biomaterial based on silk fibroin, comprises the following steps：
First, by Na2CO3In the water that addition is boiled, add silk to boil degumming, obtain boiled silk；
The 2nd, boiled silk is added to 80 ~ 100 DEG C of ternary solution CaCl2·CH3CH2OH·H2In O or 45 ~ 55 DEG C of bromine
Change in lithium solution, be completely dissolved silk, obtain silk mixed solution；
3rd, silk mixed solution, except deionization and other small-molecule substances, is obtained into fibroin albumen by resin ion exchange column
The aqueous solution；
4th, by silk fibroin water solution freeze-drying, cotton-shaped dry state fibroin albumen is obtained；
5th, cotton-shaped dry state fibroin albumen is dissolved in hexafluoroisopropanol, obtains fibroin albumen alcoholic solution；
6th, fibroin albumen alcoholic solution is injected into electrostatic spinning machine, is made membranaceous biomaterial, be subsequently placed in 7 ~ 10 in fume hood
My god, obtain the biomaterial to repair membrane, cartilage and ligament defect.
In above-mentioned preparation method, silk presses bath raio 1 in the step one:50~100（w:v）It is added in boiling water.
In above-mentioned preparation method, Na in the step one2CO3It is 1 with silk ratio:10~15（w:w）.
In above-mentioned preparation method, in the step 2, boiled silk presses bath raio 1:5~15（w:v）It is added to ternary solution
CaCl2·CH3CH2OH·H2In O, CaCl in ternary solution2、CH3CH2OH、H2The mol ratio of O is 1:2:8.
In above-mentioned preparation method, in the step 2, boiled silk presses bath raio 1:10~15（w:v）It is added to 9.3mol/L
Lithium-bromide solution in.
In above-mentioned preparation method, the dissolving of 6 ~ 12mL hexafluoroisopropanols is added in the step 5 per 1g fibroin albumens.
In above-mentioned preparation method, in the step 6 by fibroin albumen alcoholic solution masking after, in fume hood air drying or
To increase mechanical strength, the extension degradation time in vivo of film, the steps such as methyl alcohol immersion, high temperature drying can be increased.
In above-mentioned preparation method, the step 6 can be replaced：By fibroin albumen alcoholic solution through electrostatic spinning machine mole
Concentration is made thicker block biomaterial to be molded in 25 ~ 45% methanol gas environment, is subsequently placed in 7 in high temperature drying case
~ 10 days, then be placed in 7 ~ 10 days in fume hood, obtain quality hard and have the orthopaedics internal fixation material of certain toughness.
The present invention has the advantages that：
1st, the absorbable biological material based on fibroin albumen that the present invention is prepared can change system according to different medical applications
Make step and condition, obtain different mechanical strengths, pliability and in organism degradation speed biomaterial.
2nd, the absorbable biological material based on fibroin albumen that the present invention is prepared has more superior bio-compatible
Property, without obvious inflammatory reaction, convenient implantation, can vapor injection or irradiation sterilization, with extensive medical applications prospect.
Brief description of the drawings
Fig. 1 is membranaceous sample 72 hours cultivation results of external l cell（A left side is culture dish, and bottom right is material list
Face）.
Fig. 2 is bulk sample 48 hours cultivation results of external l cell（Upper left is culture dish, and bottom right is material
Surface）.
Specific embodiment
Technical scheme is further described with reference to embodiment, but is not limited thereto, it is every right
Technical solution of the present invention is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should be contained
Cover in protection scope of the present invention.
Embodiment 1
In the present embodiment, the implantation human body degradable biomaterial based on silk fibroin is prepared according to following steps：
First, 5000mL deionized waters are measured, 10g Na is added after boiling2CO3Stirring, by bath raio 1:50（w:v）Add raw silk
100g boils degumming 15min, is washed with deionized 3 times.
2nd, boiling soda ash water degumming 1 time is repeated, boiled silk is placed in dry for standby in 37 DEG C of baking ovens.
3rd, 200g CaCl are added in 300ml ultra-pure waters2Thoroughly after dissolving, 200ml ethanol and 50g degummings are added
Silk, is heated to silk and is completely dissolved in 90 ~ 100 DEG C of water-baths, obtains fibroin mixed solution.
4th, fibroin mixed solution is obtained into silk fibroin water solution by resin ion exchange column.
5th, silk fibroin water solution is inserted into vacuum drier, sets -60 DEG C of pre-freezes, -50~30 DEG C of temperature increment vacuum
Dry, 35 DEG C of constant-temperature vacuums are dried, and 60 hours or so altogether, obtain cotton-shaped dry state fibroin albumen.
6th, cotton-shaped dry state fibroin albumen is put into conical flask, adds hexafluoroisopropanol concussion dissolving, obtain fibroin albumen alcohol
Liquid, wherein：The ratio of fibroin albumen and hexafluoroisopropanol is 1g：8mL.
7th, fibroin albumen alcohol liquid is injected into electrostatic spinning machine, is made relatively thin membranaceous biomaterial, be placed in fume hood and do
Dry one week, obtain membranaceous biomaterial finished product, steam high-temperature sterilization when using.
As shown in Figure 1, the external l cell of membranaceous sample is cultivated for 72 hours, and cell growth is good.
The performance parameter of different-thickness film material stretching mechanical test is shown in Table 1, and the performance parameter of suture strength test is shown in
Table 2.
Table 1
Table 2
Embodiment 2
In the present embodiment, the implantation human body degradable biomaterial based on silk fibroin is prepared according to following steps：
First, 5000mL deionized waters are measured, 10g Na is added after boiling2CO3Stirring, by bath raio 1:50（w:v）Add raw silk
100g boils degumming 15min, is washed with deionized 3 times.
2nd, boiling soda ash water degumming 1 time is repeated, boiled silk is placed in dry for standby in 37 DEG C of baking ovens.
3rd, 200g CaCl are added in 300ml ultra-pure waters2Thoroughly after dissolving, 200ml ethanol and 50g degummings are added
Silk, is heated to silk and is completely dissolved in 90 ~ 100 DEG C of water-baths, obtains fibroin mixed solution.
4th, fibroin mixed solution is obtained into silk fibroin water solution by resin ion exchange column.
5th, silk fibroin water solution is inserted into vacuum drier, sets -60 DEG C of pre-freezes, -50 ~ 30 DEG C of temperature increment vacuum
Dry, 35 DEG C of constant-temperature vacuums are dried, and 60 hours or so altogether, obtain cotton-shaped dry state fibroin albumen.
6th, dry state fibroin albumen is put into conical flask, adds hexafluoroisopropanol concussion dissolving, obtain fibroin albumen alcohol liquid,
Wherein：The ratio of fibroin albumen and hexafluoroisopropanol is 1g：8mL.
7th, fibroin albumen alcohol liquid is molded by electrostatic spinning machine in the methanol gas that molar concentration is 30%, be made compared with
Thick biomaterial, is subsequently placed in 7 days in high temperature drying case, then is placed in dried for a week in fume hood, obtains block biomaterial
Finished product, steam high-temperature sterilization when using.
As shown in Figure 2, the external l cell of bulk sample is cultivated for 48 hours, and cell growth is good.
The performance parameter of different-thickness bulk material stretching mechanical test is shown in Table 3, wherein：It is 10% to determine elongation, experiment speed
It is 200.00mm/min to spend, and determines stress for 2MPa, and sample 1,2 is without hyperthermia treatment.
Table 3
The performance parameter of different-thickness bulk material Compressive Mechanical test is shown in Table 4, wherein：Sample 2,5 is without hyperthermia treatment.
Table 4
The performance parameter of different-thickness bulk material three-point bend test is shown in Table 5, wherein：Amount of deflection is determined for 0.01mm, test speed
It is 2mm/min.
Table 5
Claims (9)
1. it is a kind of based on silk fibroin implantation human body degradable biomaterial preparation method, it is characterised in that the system
Preparation Method step is as follows：
First, by Na2CO3In the water that addition is boiled, add silk to boil degumming, obtain boiled silk；
2nd, boiled silk is added to ternary solution CaCl2·CH3CH2OH·H2In O or lithium-bromide solution, make silk completely molten
Solution, obtains silk mixed solution；
3rd, silk mixed solution is crossed into resin ion exchange column, obtains silk fibroin water solution；
4th, by silk fibroin water solution freeze-drying, cotton-shaped dry state fibroin albumen is obtained；
5th, cotton-shaped dry state fibroin albumen is dissolved in hexafluoroisopropanol, obtains fibroin albumen alcoholic solution；
6th, fibroin albumen alcoholic solution is injected into electrostatic spinning machine, is made membranaceous biomaterial, be subsequently placed in 7 ~ 10 in fume hood
My god, obtain the biomaterial to repair membrane, cartilage and ligament defect.
2. it is according to claim 1 based on silk fibroin implantation human body degradable biomaterial preparation method,
It is characterized in that in the step one, silk presses bath raio 1:50~100（w:v）It is added in boiling water.
3. it is according to claim 1 based on silk fibroin implantation human body degradable biomaterial preparation method,
It is characterized in that in the step one, Na2CO3It is 1 with silk ratio:10~15（w:w）.
4. it is according to claim 1 based on silk fibroin implantation human body degradable biomaterial preparation method,
It is characterized in that in the step 2, boiled silk presses bath raio 1:5~15（w:v）It is added to ternary solution CaCl2·
CH3CH2OH·H2In O.
5. according to claim 1 or 4 based on silk fibroin implantation human body degradable biomaterial preparation side
Method, it is characterised in that the ternary solution CaCl2·CH3CH2OH·H2The temperature of O is 80 ~ 100 DEG C, CaCl2、CH3CH2OH、H2O
Mol ratio be 1:2:8.
6. it is according to claim 1 based on silk fibroin implantation human body degradable biomaterial preparation method,
It is characterized in that in the step 2, boiled silk presses bath raio 1:10~15（w:v）It is added in lithium-bromide solution.
7. it is according to claim 1 based on silk fibroin implantation human body degradable biomaterial preparation method,
It is characterized in that the temperature of the lithium-bromide solution is 45 ~ 55 DEG C, concentration is 9.3mol/L.
8. it is according to claim 1 based on silk fibroin implantation human body degradable biomaterial preparation method,
It is characterized in that in the step 5, the dissolving of 6 ~ 12mL hexafluoroisopropanols is added per 1g fibroin albumens.
9. it is according to claim 1 based on silk fibroin implantation human body degradable biomaterial preparation method,
It is characterized in that the step 6 is replaced with：Fibroin albumen alcoholic solution is molded through electrostatic spinning machine in methanol gas environment,
Block biomaterial is made, is subsequently placed in 7 ~ 10 days in high temperature drying case, then be placed in 7 ~ 10 days in fume hood, obtain solid in orthopaedics
Determine material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558093A (en) * | 2020-05-19 | 2020-08-21 | 温州医科大学附属眼视光医院 | Lacrimal passage suppository capable of being degraded in medium and long periods and preparation method thereof |
| CN115721768A (en) * | 2022-12-01 | 2023-03-03 | 国纳之星(上海)纳米科技发展有限公司 | Preparation method of anti-inflammatory silk fibroin film, product and application thereof |
| CN116574283A (en) * | 2023-07-12 | 2023-08-11 | 江西丝科生物科技有限公司 | Preparation method of fibroin block material and fibroin block material |
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| CN116574283A (en) * | 2023-07-12 | 2023-08-11 | 江西丝科生物科技有限公司 | Preparation method of fibroin block material and fibroin block material |
| CN116574283B (en) * | 2023-07-12 | 2023-10-10 | 江西丝科生物科技有限公司 | Preparation method of fibroin block material and fibroin block material |
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