CN105968387A - Method for fast preparing silk fibroin hydrogel - Google Patents
Method for fast preparing silk fibroin hydrogel Download PDFInfo
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- CN105968387A CN105968387A CN201610292475.1A CN201610292475A CN105968387A CN 105968387 A CN105968387 A CN 105968387A CN 201610292475 A CN201610292475 A CN 201610292475A CN 105968387 A CN105968387 A CN 105968387A
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- silk fibroin
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- fibroin hydrogel
- silk
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
Abstract
The invention discloses a method for fast preparing silk fibroin hydrogel and belongs to the technical field of hydrogel preparation. The method comprises degumming silk, dissolving the silk in ethanol, orderly adding amino acids, sodium silicate, hydrochloric acid and acetic acid into the solution, carrying out a reaction process and carrying out centrifugation to obtain the silk fibroin hydrogel. An embodiment proves that the method can be simply and conveniently operated, is free of any chemical cross-linking agent, can form silk fibroin hydrogel in short time, shortens work time and improves work efficiency. The silk fibroin hydrogel has good biocompatibility, is green and safe and can be widely used for industries such as foods and medicine materials.
Description
Technical field
The invention discloses a kind of method quickly preparing silk fibroin hydrogel, belong to hydrogel preparing technical field.
Background technology
Fibroin albumen is nontoxic, nonirritant, there is good biocompatibility, the growth of human body cell can be promoted, there is certain biodegradability, by the comparative study of multiple biomaterial is shown, fibroin albumen has internal, the biocompatibility in vitro equal with collagen protein, and therefore, fibroin albumen is the more satisfactory raw material manufacturing biomedical material.
Gel is a kind of physical state between solid and liquid, there is the character of uniqueness, especially hydrogel, character is soft, certain shape can be kept, maintain substantial amounts of moisture content wherein, be currently widely used for the aspects such as artificial skin, tissue engineering material, drug release, artificial muscle, biosensor, segregation apparatus, heavy metal removal and Signa Gel.
Silk fibroin protein solution is understood gradually to gelation transition under standing, but this time changed is long, generally will be more than 1 month.The process of gelation can be accelerated by changing the pH value of silk fibroin protein solution.When pH value is close to isoelectric point, IP (about the pH=4) of fibroin albumen, fibroin albumen is susceptible to gelation, it also requires the time of 8 days just can complete gelation.Additionally, the concentration of fibroin albumen also has an impact for gel time, silk fibroin protein solution is easier to be formed gel when mass concentration is more than 10%, but needs long time could form gel when mass concentration is less than 10%.And the gel water content of high concentration silk fibroin protein solution formation is relatively low, porosity is relatively low, is subject to certain restrictions when application.Therefore the oversize use constraining silk fibroin hydrogel of the silk fibroin solution gelation time under low quality concentration.
At present, shortening the main method of silk fibroin hydrogel time is: add chemical cross-linking agent in silk fibroin water solution, the method can greatly shorten the time of silk fibroin water solution gelation, but gained gel can remain a certain amount of chemical cross-linking agent, thus bring certain toxicity, and this method reduce the biocompatibility of silk fibroin hydrogel.
Summary of the invention
The technical problem that present invention mainly solves: for current traditional method when shortening the silk fibroin hydrogel time, often add chemical cross-linking agent, but the gel of gained has a large amount of residue, not only bring certain toxicity, and reduce the biocompatibility of silk fibroin hydrogel, make the present situation that work efficiency reduces, provide one to dissolve with ethanol after natural silk degumming, it is sequentially added into aminoacid, sodium silicate, hydrochloric acid and acetic acid the most wherein, after reaction, centrifugation, thus the method quickly being prepared silk fibroin hydrogel.The method is easy and simple to handle, need not add any chemical cross-linking agent, silk fibroin hydrogel can be formed at short notice, shorten the working time, improve work efficiency, and the silk fibroin hydrogel good biocompatibility prepared, green safety, can be widely applied to the industry such as food, medical material.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) weigh 100～200g silkworm silks to be placed in reactor, and it is added thereto to silk quality 10～15 times of mass concentrations are 85% sodium carbonate liquor, promote temperature of reaction kettle to 75～80 DEG C, after insulation 1～2h, move in sonic oscillation instrument, it is 25～30KHz in supersonic frequency, ultrasonic power is sonic oscillation reaction 70～90min under 120～150W, question response terminates, reactant is filtered removing glue, and carry out cyclic washing with deionized water, remove sericin, move in baking oven and dry at 60 DEG C, subsequently drying object is placed in container, and it is added thereto to drying object quality 5～8 times of mass concentrations are 65% ethanol solution, at 35～38 DEG C continuously stirred, until being completely dissolved；
(2) treat that above-mentioned dissolving terminates, solute is poured in the there-necked flask with agitator, Dropping funnel and thermometer, drip solute quality 10～15% tryptophan and solute quality 8～12% aspartic acid wherein, completion of dropwise addition in controlling 30～35min, move into water-bath, be heated to 35～40 DEG C, start agitator, rotating speed with 200～250r/min stirs, stirring reaction 1～2h；
(3) question response terminates, reactant quality 20～25% sodium silicate is added again in reactant, temperature is promoted to 45～55 DEG C with the speed of 2～3 DEG C/min, continuously stirred make it be completely dissolved, stand overnight afterwards, after generating precipitation, dripping mass concentration with the speed of 3～5mL/min the most wherein is 35% hydrochloric acid solution, completion of dropwise addition in controlling 20～25min, keeps temperature-resistant, standing and reacting 1～2h；
(4) above-mentioned reactant is placed in beaker, under the conditions of 28～32 DEG C, it is added thereto to reactant quality 70～80% mass concentration is 36% acetic acid solution, mix homogeneously, it is placed on shaking table, shaking table oscillating reactions 45～55min, treats that vibration terminates, mixed liquor is poured in centrifuge, with 1000～1200r/min rotating speed centrifugal treating, remove supernatant, i.e. available a kind of silk fibroin hydrogel.
The principle of the present invention is: the present invention, by natural silk degumming, is dissolved with ethanol, and added aminoacid, forming it into ethyl amino acid ester, fibroin separates out, and generates aqueous phase and oil phase, add sodium silicate afterwards, react, form orthosilicic acid precipitation, drip hydrochloric acid subsequently, fibroin albumen is made to be attracted to orthosilicic acid surface, add acetic acid the most wherein so that orthosilicic acid separates with fibroin albumen, i.e. can get oil phase after centrifugal treating, be silk fibroin hydrogel.
The silk fibroin hydrogel color that the present invention prepares is milky, and aperture is 2～8 μm, and hot strength is 57～62MPa, and swelling ratio is 88～95%.
The invention has the beneficial effects as follows:
(1) the inventive method is novel, simple process, without adding any chemical cross-linking agent, green safety during preparation；
(2) present invention can form silk fibroin hydrogel at short notice, shortened for 50% working time, improves work efficiency, and the silk fibroin hydrogel good biocompatibility prepared；
(3) silk fibroin hydrogel that the present invention prepares is widely used in the industry such as food, medical material, and can be mass-produced application.
Detailed description of the invention
First weigh 100～200g silkworm silks to be placed in reactor, and it is added thereto to silk quality 10～15 times of mass concentrations are 85% sodium carbonate liquor, promote temperature of reaction kettle to 75～80 DEG C, after insulation 1～2h, move in sonic oscillation instrument, it is 25～30KHz in supersonic frequency, ultrasonic power is sonic oscillation reaction 70～90min under 120～150W, question response terminates, reactant is filtered removing glue, and carry out cyclic washing with deionized water, remove sericin, move in baking oven and dry at 60 DEG C, subsequently drying object is placed in container, and it is added thereto to drying object quality 5～8 times of mass concentrations are 65% ethanol solution, at 35～38 DEG C continuously stirred, until being completely dissolved；End to be dissolved, solute is poured in the there-necked flask with agitator, Dropping funnel and thermometer, drip solute quality 10～15% tryptophan and solute quality 8～12% aspartic acid wherein, completion of dropwise addition in controlling 30～35min, move into water-bath, be heated to 35～40 DEG C, start agitator, rotating speed with 200～250r/min stirs, stirring reaction 1～2h；Reaction afterwards terminates, reactant quality 20～25% sodium silicate is added again in reactant, temperature is promoted to 45～55 DEG C with the speed of 2～3 DEG C/min, continuously stirred make it be completely dissolved, stand overnight afterwards, after generating precipitation, dripping mass concentration with the speed of 3～5mL/min the most wherein is 35% hydrochloric acid solution, completion of dropwise addition in controlling 20～25min, keeps temperature-resistant, standing and reacting 1～2h；Finally above-mentioned reactant is placed in beaker, under the conditions of 28～32 DEG C, it is added thereto to reactant quality 70～80% mass concentration is 36% acetic acid solution, mix homogeneously, it is placed on shaking table, shaking table oscillating reactions 45～55min, treats that vibration terminates, mixed liquor is poured in centrifuge, with 1000～1200r/min rotating speed centrifugal treating, remove supernatant, i.e. available a kind of silk fibroin hydrogel.
Example 1
First weigh 100g silkworm silk to be placed in reactor, and to be added thereto to 10 times of mass concentrations of silk quality be 85% sodium carbonate liquor, promote temperature of reaction kettle to 75 DEG C, after insulation 1h, move in sonic oscillation instrument, it is 25KHz in supersonic frequency, ultrasonic power is sonic oscillation reaction 70min under 120W, question response terminates, reactant is filtered removing glue, and carry out cyclic washing with deionized water, remove sericin, move in baking oven and dry at 60 DEG C, subsequently drying object is placed in container, and to be added thereto to 5 times of mass concentrations of drying object quality be 65% ethanol solution, at 35 DEG C continuously stirred, until being completely dissolved；End to be dissolved, solute is poured in the there-necked flask with agitator, Dropping funnel and thermometer, dropping solute quality 10% tryptophan and solute quality 8% aspartic acid wherein, control completion of dropwise addition in 30min, move into water-bath, be heated to 35 DEG C, start agitator, stir with the rotating speed of 200r/min, stirring reaction 1h；Reaction afterwards terminates, reactant quality 20% sodium silicate is added again in reactant, temperature is promoted to 45 DEG C with the speed of 2 DEG C/min, continuously stirred make it be completely dissolved, stand overnight afterwards, after generating precipitation, dripping mass concentration with the speed of 3mL/min the most wherein is 35% hydrochloric acid solution, control completion of dropwise addition in 20min, keep temperature-resistant, standing and reacting 1h；Finally above-mentioned reactant is placed in beaker, being added thereto to reactant quality 70% mass concentration under the conditions of 28 DEG C is 36% acetic acid solution, mix homogeneously, it is placed on shaking table, shaking table oscillating reactions 45min, treats that vibration terminates, mixed liquor is poured in centrifuge, with 1000r/min rotating speed centrifugal treating, remove supernatant, i.e. available a kind of silk fibroin hydrogel.
This example operation is simple, without adding any chemical cross-linking agent during preparation, the silk fibroin hydrogel green safety prepared, good biocompatibility, after testing, aperture is 2 μm, hot strength is 57MPa, swelling ratio is 88%, is widely used in the industry such as food, medical material, and can be mass-produced application.
Example 2
First weigh 150g silkworm silk to be placed in reactor, and to be added thereto to 13 times of mass concentrations of silk quality be 85% sodium carbonate liquor, promote temperature of reaction kettle to 78 DEG C, after insulation 1.5h, move in sonic oscillation instrument, it is 28KHz in supersonic frequency, ultrasonic power is sonic oscillation reaction 80min under 130W, question response terminates, reactant is filtered removing glue, and carry out cyclic washing with deionized water, remove sericin, move in baking oven and dry at 60 DEG C, subsequently drying object is placed in container, and to be added thereto to 7 times of mass concentrations of drying object quality be 65% ethanol solution, at 37 DEG C continuously stirred, until being completely dissolved；End to be dissolved, solute is poured in the there-necked flask with agitator, Dropping funnel and thermometer, dropping solute quality 13% tryptophan and solute quality 10% aspartic acid wherein, control completion of dropwise addition in 33min, move into water-bath, be heated to 38 DEG C, start agitator, stir with the rotating speed of 260r/min, stirring reaction 1.5h；Reaction afterwards terminates, reactant quality 23% sodium silicate is added again in reactant, temperature is promoted to 50 DEG C with the speed of 2.5 DEG C/min, continuously stirred make it be completely dissolved, stand overnight afterwards, after generating precipitation, dripping mass concentration with the speed of 4mL/min the most wherein is 35% hydrochloric acid solution, control completion of dropwise addition in 23min, keep temperature-resistant, standing and reacting 1.5h；Finally above-mentioned reactant is placed in beaker, being added thereto to reactant quality 75% mass concentration under the conditions of 30 DEG C is 36% acetic acid solution, mix homogeneously, it is placed on shaking table, shaking table oscillating reactions 50min, treats that vibration terminates, mixed liquor is poured in centrifuge, with 1100r/min rotating speed centrifugal treating, remove supernatant, i.e. available a kind of silk fibroin hydrogel.
This example operation is simple, without adding any chemical cross-linking agent during preparation, the silk fibroin hydrogel green safety prepared, good biocompatibility, after testing, aperture is 6 μm, hot strength is 60MPa, swelling ratio 90%, is widely used in the industry such as food, medical material, and can be mass-produced application.
Example 3
First weigh 200g silkworm silk to be placed in reactor, and to be added thereto to 15 times of mass concentrations of silk quality be 85% sodium carbonate liquor, promote temperature of reaction kettle to 80 DEG C, after insulation 2h, move in sonic oscillation instrument, it is 30KHz in supersonic frequency, ultrasonic power is sonic oscillation reaction 90min under 150W, question response terminates, reactant is filtered removing glue, and carry out cyclic washing with deionized water, remove sericin, move in baking oven and dry at 60 DEG C, subsequently drying object is placed in container, and to be added thereto to 8 times of mass concentrations of drying object quality be 65% ethanol solution, at 38 DEG C continuously stirred, until being completely dissolved；End to be dissolved, solute is poured in the there-necked flask with agitator, Dropping funnel and thermometer, dropping solute quality 15% tryptophan and solute quality 12% aspartic acid wherein, control completion of dropwise addition in 35min, move into water-bath, be heated to 40 DEG C, start agitator, stir with the rotating speed of 250r/min, stirring reaction 2h；Reaction afterwards terminates, reactant quality 25% sodium silicate is added again in reactant, temperature is promoted to 55 DEG C with the speed of 3 DEG C/min, continuously stirred make it be completely dissolved, stand overnight afterwards, after generating precipitation, dripping mass concentration with the speed of 5mL/min the most wherein is 35% hydrochloric acid solution, control completion of dropwise addition in 25min, keep temperature-resistant, standing and reacting 2h；Finally above-mentioned reactant is placed in beaker, being added thereto to reactant quality 80% mass concentration under the conditions of 32 DEG C is 36% acetic acid solution, mix homogeneously, it is placed on shaking table, shaking table oscillating reactions 55min, treats that vibration terminates, mixed liquor is poured in centrifuge, with 1200r/min rotating speed centrifugal treating, remove supernatant, i.e. available a kind of silk fibroin hydrogel.
This example operation is simple, without adding any chemical cross-linking agent during preparation, the silk fibroin hydrogel green safety prepared, good biocompatibility, after testing, aperture is 8 μm, hot strength is 62MPa, swelling ratio is 95%, is widely used in the industry such as food, medical material, and can be mass-produced application.
Claims (1)
1. the method quickly preparing silk fibroin hydrogel, it is characterised in that concrete operation step is:
(1) weigh 100～200g silkworm silks to be placed in reactor, and it is added thereto to silk quality 10～15 times of mass concentrations are 85% sodium carbonate liquor, promote temperature of reaction kettle to 75～80 DEG C, after insulation 1～2h, move in sonic oscillation instrument, it is 25～30KHz in supersonic frequency, ultrasonic power is sonic oscillation reaction 70～90min under 120～150W, question response terminates, reactant is filtered removing glue, and carry out cyclic washing with deionized water, remove sericin, move in baking oven and dry at 60 DEG C, subsequently drying object is placed in container, and it is added thereto to drying object quality 5～8 times of mass concentrations are 65% ethanol solution, at 35～38 DEG C continuously stirred, until being completely dissolved；
(2) treat that above-mentioned dissolving terminates, solute is poured in the there-necked flask with agitator, Dropping funnel and thermometer, drip solute quality 10～15% tryptophan and solute quality 8～12% aspartic acid wherein, completion of dropwise addition in controlling 30～35min, move into water-bath, be heated to 35～40 DEG C, start agitator, rotating speed with 200～250r/min stirs, stirring reaction 1～2h；
(3) question response terminates, reactant quality 20～25% sodium silicate is added again in reactant, temperature is promoted to 45～55 DEG C with the speed of 2～3 DEG C/min, continuously stirred make it be completely dissolved, stand overnight afterwards, after generating precipitation, dripping mass concentration with the speed of 3～5mL/min the most wherein is 35% hydrochloric acid solution, completion of dropwise addition in controlling 20～25min, keeps temperature-resistant, standing and reacting 1～2h；
(4) above-mentioned reactant is placed in beaker, under the conditions of 28～32 DEG C, it is added thereto to reactant quality 70～80% mass concentration is 36% acetic acid solution, mix homogeneously, it is placed on shaking table, shaking table oscillating reactions 45～55min, treats that vibration terminates, mixed liquor is poured in centrifuge, with 1000～1200r/min rotating speed centrifugal treating, remove supernatant, i.e. available a kind of silk fibroin hydrogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610292475.1A CN105968387A (en) | 2016-05-05 | 2016-05-05 | Method for fast preparing silk fibroin hydrogel |
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| CN201610292475.1A CN105968387A (en) | 2016-05-05 | 2016-05-05 | Method for fast preparing silk fibroin hydrogel |
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| CN105968387A true CN105968387A (en) | 2016-09-28 |
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| CN201610292475.1A Withdrawn CN105968387A (en) | 2016-05-05 | 2016-05-05 | Method for fast preparing silk fibroin hydrogel |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109431971A (en) * | 2018-10-19 | 2019-03-08 | 广州医科大学 | A kind of injectable carries liquid medicine gel and preparation method thereof |
| CN110041536A (en) * | 2019-03-14 | 2019-07-23 | 江苏科技大学 | Functional sericin hydrogel and its preparation method and application |
-
2016
- 2016-05-05 CN CN201610292475.1A patent/CN105968387A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109431971A (en) * | 2018-10-19 | 2019-03-08 | 广州医科大学 | A kind of injectable carries liquid medicine gel and preparation method thereof |
| CN110041536A (en) * | 2019-03-14 | 2019-07-23 | 江苏科技大学 | Functional sericin hydrogel and its preparation method and application |
| CN110041536B (en) * | 2019-03-14 | 2022-04-15 | 江苏科技大学 | Functional sericin hydrogel and preparation method and application thereof |
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Application publication date: 20160928 |
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