CN107118361A - A kind of fibroin albumen/carboxymethyl chitosan plural gel and preparation method thereof - Google Patents
A kind of fibroin albumen/carboxymethyl chitosan plural gel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of fibroin albumen/carboxymethyl chitosan plural gel and preparation method thereof.The plural gel is mainly made up of the composition of fibroin albumen and carboxymethyl chitosan, and mass ratio is (0.05~2)：1；Method is first to be handled to obtain fibroin fiber with cocoon layer, then prepares silk fibroin solution, carboxymethyl chitosan solution is made, and silk fibroin solution and carboxymethyl chitosan solution are well mixed and obtain mixed solution；Add a certain amount of crosslinking agent, then solution is stirred to pour into immediately after the short time in mould on magnetic stirring apparatus stood；Immerse again in ethanol water, finally give fibroin/carboxymethyl chitosan plural gel.The present invention prepares the gel with stronger mechanical property and better stability with better simply technique, shorter time, and the preparation method for improvement fibroin albumen plural gel provides new thinking, has also further expanded the application approach of fibroin albumen.
Description
Technical field
It is a kind of fibroin albumen/carboxymethyl shell specifically the invention belongs to a kind of processing technology of regenerated silk solution
Glycan plural gel and preparation method thereof.
Background technology
Recently, gel rubber material biomedical sector be a dark horse, be used for tissue engineering bracket, drug conveying carrier and
The fields such as wound dressing, obtain the favor of scientific research personnel, it is this honest and clean that gel material is locked regenerated silk fibroin by many researchers
The natural polymer biomaterial that valency is easy to get, bio-compatible is good, security performance is high.Regenerated silk fibroin solution is a kind of thermodynamics
Unstable increasing lyosol, in the case of not any external action, can be changed from random coil structure to beta sheet structure,
Spontaneously it is changed into gel state.Generally, the time that this transformation needs was up to 1~2 month, and obtained gel mechanics
Performance extreme difference, greatly limit Silk fibroin gel as a kind of application of excellent biomaterial.Silk fibroin gel material
It is modified to turn into study hotspot, primarily to improving the mechanical property and stability of gel.But there is presently no a kind of method system
The silk extract gel obtained can show higher mechanical property with better simply technique, shorter gel time.Carboxymethyl chitosan
It is a kind of water-soluble chitosan derivative, carboxymethyl chitosan carbohydrate composite has guiding nerve regneration, prevents tissue from sticking
Even, the advantages of promoting wound healing, reduce cicatrization, but the gel rubber material water absorbing capacity made with it is too strong, and matter is crisp frangible,
It is difficult in clinical medicine domain large-scale application.
1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL) has the spy of activated carboxyl
Property, because it has reaction condition gentle, yield is high, and selectivity is good, the features such as environmentally friendly, exists as condensing agent and crosslinking agent
([J] Desalination, 2008,234 are widely used in macromolecule modified：134-143).
The content of the invention
In order to solve problem present in background technology, the present invention is intended to provide a kind of fibroin albumen/carboxymethyl chitosan
Sugared plural gel and preparation method thereof, technique is simple, time-consuming short, and plural gel has excellent mechanical property.
The technical solution adopted in the present invention comprises the following steps：
First, a kind of fibroin albumen/carboxymethyl chitosan plural gel：
The plural gel is mainly made up of the composition of fibroin albumen and carboxymethyl chitosan.
In the plural gel, the mass ratio of fibroin albumen and carboxymethyl chitosan is (0.05~2)：1, preferably
(0.5~2)：1.
2nd, a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel：
The fibroin fiber that degumming is obtained carries out dissolution process in LiBr solution, and molten by the obtained regenerated silk of dialysis
Liquid, then it is mixed with carboxymethyl chitosan solution, then add crosslinking agent 1- ethyls-(3- dimethylaminopropyls) carbon two sub-
Amine hydrochlorate, is finally prepared into fibroin/carboxymethyl chitosan composite aquogel in the presence of ethanol.
Methods described detailed process is as follows：
(1) handled with cocoon layer and obtain fibroin fiber, then prepare silk fibroin solution；
(2) it is carboxymethyl chitosan is soluble in water, carboxymethyl chitosan solution is made；
(3) it is the carboxymethyl chitosan solution obtained in the silk fibroin solution obtained in step (1) and step (2) is well mixed
Obtain mixed solution；
(4) a certain amount of crosslinking agent is added in the mixed solution obtained in step (3), then by solution in magnetic stirring apparatus
Poured into mould and stand immediately after the upper stirring short time；
(5) immerse again in ethanol water, finally give fibroin/carboxymethyl chitosan plural gel.
The step (1) is specially：
(1) cocoon layer is placed in the Na that mass fraction is 0.5%2CO3Twice, each 30min is obtained for degumming in boiling water
Fibroin fiber with being wrung out after deionized water rinsing, and dry in an oven；
(2) fibroin fiber obtained in step (1) is placed in 9M LiBr solution, the dissolution process 4h under the conditions of 60 DEG C,
Obtained liquid is fitted into bag filter and dialysed in deionized water 4d after filtering, during which constantly changes water, the fibroin finally obtained is molten
Liquid.
The silk fibroin solution concentration of the step (1) is 0.5~10%w/v, the carboxymethyl chitosan solution of the step (2)
Concentration is 1~5%w/v, and silk fibroin solution and the mixed volume of carboxymethyl chitosan solution ratio are 1 in the step (3):1.
The final mass ratio for enabling to solute fibroin and carboxymethyl chitosan after mixing will be in (0.05~2)：1 scope
It is interior.It is preferred that the silk fibroin solution and carboxymethyl chitosan solution concentration ratio be (0.1~2)：1.
The deacetylation of the carboxymethyl chitosan is 55%~99%, and substitution value is 60%~99%.
Preferably, the concentration of silk fibroin solution is carboxymethyl chitosan in 0.5~8%w/v, step (2) in the step (1)
The concentration of solution is 1~4%w/v, and the deacetylation of carboxymethyl chitosan is 90%, and substitution value is 90%.
It is highly preferred that the concentration of silk fibroin solution is respectively carboxylic in 0.5~4%w/v and step (2) in the step (1)
The concentration of methyl chitosan solution is 4%w/v.
As most preferred, the concentration of silk fibroin solution of the present invention is 4%w/v and the concentration of carboxymethyl chitosan solution is
4%w/v, mixed volume ratio is 1:1, so that fibroin and carboxymethyl chitosan solution preparation are more simple in the present invention, and
It is easily controlled, mixes more uniform, obtained plural gel shaping is more preferable, and mechanical property is stronger, and plural gel water absorbent is stable
Property is excellent.
The molecular weight 8000~14000 of bag filter in the step (1).
In the step (4), crosslinking agent uses 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
(EDCHCL) solid powder, the addition of crosslinking agent is 0.3~0.75%w/v of system.
System refers to the mixed solution that step (4) is obtained.
Preferably, the addition of 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL) is
0.45%~0.6%w/v of fibroin albumen/carboxymethyl chitosan solution system.
It is highly preferred that the addition of 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL)
For the 0.6%w/v of fibroin albumen/carboxymethyl chitosan solution system.So that the cross-linking effect of the plural gel arrived is excellent,
Also it is unlikely to cause the excess of crosslinking agent.
The feed postition of the crosslinking agent is divided to two kinds：One kind is directly added into system for solid powder, and one kind is by solid powder
End it is soluble in water adds system, as long as ensure crosslinking agent powder can dissolve and add water volume must as far as possible it is small just
Can be with.
Preferably, 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate in step (5) of the present invention
(EDCHCL) feed postition adds system for first solid powder is dissolved in a small amount of water, so that crosslinking agent is in mixing
Being more evenly distributed in solution, reaction can be rapider efficient, and obtained plural gel structure is even closer, and performance is more excellent.
In the step (4), mixing time is 20s, and time of repose is 6-12h；In the step (5), ethanol water
In concentration of alcohol be 60~90%v/v, immersion ethanol water time be 12h.
Preferably, the time of repose that solution system pours into mould in the step (4) is 12h.
Preferably, the concentration of alcohol of ethanol water is 75%v/v.
The product of the present invention is tested by embodiment and obtains higher mechanical property and stable water retention property, springform
Amount reaches (363.94 ± 45.57) kPa, and compressive recovery rate reaches 100%, the volume phase in pH=7.4 phosphate buffer
To stabilization, swelling ratio is (9.32 ± 0.09) × 100%.
Crosslinked action and ethanol of the present invention by EDCHCL promote the characteristics of βization transformation occurs for fibroin albumen, promote
Make fibroin/carboxymethyl chitosan formation plural gel.Prepared with better simply technique, shorter time with stronger mechanical property
The gel of energy and better stability, the preparation method for improvement fibroin albumen plural gel provides new thinking, also further opens up
The application approach of fibroin albumen is opened up.
The present invention compared with prior art, with advantages below and effect：
1st, technique is simple：Prior art prepares fibroin albumen plural gel and generally requires organic solvent, ultrasonically treated, optics
The methods such as crosslinking, and the present invention can be completed in room temperature environment；
2nd, gel time is short：It is longer that prior art prepares the fibroin albumen plural gel commonly required time, and the present invention is only
Need 1~2 day or so, substantially increase efficiency；
3rd, crosslinking agent needed for the present invention can easily be removed as activating agent by WATER-WASHING METHOD, and biological safety is high；
4th, the plural gel prepared of the present invention has stronger mechanical property and well water suction stability, moisture retention, excellent
The fibroin albumen plural gel prepared in other method.Plural gel prepared by the present invention can be used for medical and health, tissue work
The fields such as journey, environmental protection, have expanded the application approach of fibroin albumen, also provide new think of to prepare the plural gel of high intensity
Road and new method.
Embodiment
Below by embodiment, the present invention is described in further detail, following examples be explanation of the invention and
The invention is not limited in following examples.
Embodiment 1
The preparation method of fibroin/carboxymethyl chitosan plural gel in turn includes the following steps in the present embodiment.
(1) cocoon layer that 10g shreds is weighed in the Na that mass fraction is 0.5%2CO3In boiling water degumming twice, every time
30min, obtained fibroin fiber is dried with being wrung out after deionized water rinsing in an oven；
(2) fibroin fiber obtained in step (1) is placed in 9M LiBr solution, the dissolution process 4h under the conditions of 60 DEG C,
Obtained liquid loads bag filter (molecular weight 8000~14000) in deionized water (3) by appropriate carboxymethyl chitosan after filtering
Sugared (deacetylation 90%, substitution value 90%) is soluble in water, and the carboxymethyl chitosan solution that concentration is 4%w/v is made.
(4) concentration obtained in the silk fibroin solution for being 0.5%w/v by the concentration obtained in step (2) and step (3) is
4%w/v carboxymethyl chitosan solution by volume 1：1 is well mixed, and obtains mixed solution.
(5) a certain amount of crosslinking agent 1- ethyls-(3- dimethylaminos are added in the mixed solution obtained in step (4)
Propyl group) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL), feed postition is divided to two kinds：One kind is directly added into system, one for solid powder
Plant and add system for first solid powder is dissolved in a small amount of water.Crosslinking agent addition is 0.3~0.75%w/v of system, excellent
Elect 0.45~0.6%w/v, most preferably 0.6%w/v as.The optimal feed postition of crosslinking agent is second.
(6) in the case where magnetic stirring apparatus is stirred continuously, EDCHCL is added into fibroin/carboxymethyl chitosan composite solution, 20s
Afterwards, solution is poured into mould, stands 6~12h, most preferably 12h.
(7) 12h in 60~90%v/v ethanol water is dipped in, ethanol optium concentration is 75%v/v, final
To fibroin/carboxymethyl chitosan plural gel.
(8) the present embodiment carries out uniaxial compression (compression speed using mechanics universal testing machine (Shimadzu, AGS-J series)：
1mm/min) determine the mechanical property of gel.The swelling behavior of gel is tested using quality weight method：First by plural gel
Material soaks 24h in deionized water or phosphate buffer and reaches swelling equilibrium, then sucks surface moisture with filter paper,
Its quality is called M1(g), then plural gel is placed in 60 DEG C of baking ovens and dried, its quality is surveyed for M2(g).Calculation formula is as follows：
Swelling ratio=(M1-M2)/M2× 100%.
The modulus of elasticity of the plural gel reaches (29.46 ± 16.70) kPa, and compressive recovery rate reaches 100%.Gel exists
Water absorption and swelling rate reaches (103.63 ± 4.91) × 100% in deionized water, the volume phase in pH=7.4 phosphate buffer
To stabilization, swelling ratio is (20.79 ± 2.64) × 100%.
Embodiment 2
The preparation method of fibroin/carboxymethyl chitosan plural gel in turn includes the following steps in the present embodiment.
(1) cocoon layer that 10g shreds is weighed in the Na that mass fraction is 0.5%2CO3In boiling water degumming twice, every time
30min, obtained fibroin fiber is dried with being wrung out after deionized water rinsing in an oven；
(2) fibroin fiber obtained in step (1) is placed in 9M LiBr solution, the dissolution process 4h under the conditions of 60 DEG C,
Obtained liquid is fitted into bag filter (molecular weight 8000~14000) after filtering, and dialyse 4d in deionized water, during which constantly changes
Water, the silk fibroin solution concentration finally obtained is 1.0%w/v.
(3) appropriate carboxymethyl chitosan (deacetylation 90%, substitution value 90%) is soluble in water, it is 4% that concentration, which is made,
W/v carboxymethyl chitosan solution.
(4) concentration obtained in the silk fibroin solution for being 1.0%w/v by the concentration obtained in step (2) and step (3) is
4%w/v carboxymethyl chitosan solution by volume 1：1 is well mixed, and obtains mixed solution.
(5) a certain amount of crosslinking agent 1- ethyls-(3- dimethylaminos are added in the mixed solution obtained in step (4)
Propyl group) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL), feed postition is that first solid powder is dissolved in a small amount of water to add system.
Crosslinking agent addition is the 0.6%w/v of system.
(6) in the case where magnetic stirring apparatus is stirred continuously, EDCHCL is added into fibroin/carboxymethyl chitosan composite solution, 20s
Afterwards, solution is poured into mould, stands 12h.
(7) 12h in 75%v/v ethanol water is dipped in, fibroin/carboxymethyl chitosan is finally given compound solidifying
Glue.
(8) tested by mode same as Example 1, the modulus of elasticity for obtaining the plural gel reach (78.89 ±
5.67) kPa, compressive recovery rate reaches 100%, gel in deionized water water absorption and swelling rate reach (56.95 ± 6.34) ×
100%, volume is stablized relatively in pH=7.4 phosphate buffer, and swelling ratio is (19.17 ± 4.30) × 100%.
Embodiment 3
The preparation method of fibroin/carboxymethyl chitosan plural gel in turn includes the following steps in the present embodiment.
(1) cocoon layer that 10g shreds is weighed in the Na that mass fraction is 0.5%2CO3In boiling water degumming twice, every time
30min, obtained fibroin fiber is dried with being wrung out after deionized water rinsing in an oven；
(2) fibroin fiber obtained in step (1) is placed in 9M LiBr solution, the dissolution process 4h under the conditions of 60 DEG C,
Obtained liquid is fitted into bag filter (molecular weight 8000~14000) after filtering, and dialyse 4d in deionized water, during which constantly changes
Water, the silk fibroin solution concentration finally obtained is 1.5%w/v.
(3) appropriate carboxymethyl chitosan (deacetylation 90%, substitution value 90%) is soluble in water, it is 4% that concentration, which is made,
W/v carboxymethyl chitosan solution.
(4) concentration obtained in the silk fibroin solution for being 1.5%w/v by the concentration obtained in step (2) and step (3) is
4%w/v carboxymethyl chitosan solution by volume 1：1 is well mixed, and obtains mixed solution.
(5) a certain amount of crosslinking agent 1- ethyls-(3- dimethylaminos are added in the mixed solution obtained in step (4)
Propyl group) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL), feed postition is that first solid powder is dissolved in a small amount of water to add system.
Crosslinking agent addition is the 0.6%w/v of system.
(6) in the case where magnetic stirring apparatus is stirred continuously, EDCHCL is added into fibroin/carboxymethyl chitosan composite solution, 20s
Afterwards, solution is poured into mould, stands 12h.
(7) 12h in 75%v/v ethanol water is dipped in, fibroin/carboxymethyl chitosan is finally given compound solidifying
Glue.
(8) tested by mode same as Example 1, the modulus of elasticity for obtaining the plural gel reach (99.03 ±
9.72) KPa, compressive recovery rate reaches 100%, gel in deionized water water absorption and swelling rate reach (51.74 ± 10.03) ×
100%, volume is stablized relatively in pH=7.4 phosphate buffer, and swelling ratio is (16.60 ± 2.11) × 100%.
Embodiment 4
The preparation method of fibroin/carboxymethyl chitosan plural gel in turn includes the following steps in the present embodiment.
(1) cocoon layer that 10g shreds is weighed in the Na that mass fraction is 0.5%2CO3In boiling water degumming twice, every time
30min, obtained fibroin fiber is dried with being wrung out after deionized water rinsing in an oven；
(2) fibroin fiber obtained in step (1) is placed in 9M LiBr solution, the dissolution process 4h under the conditions of 60 DEG C,
Obtained liquid is fitted into bag filter (molecular weight 8000~14000) after filtering, and dialyse 4d in deionized water, during which constantly changes
Water, the silk fibroin solution concentration finally obtained is 2.0%w/v.
(3) appropriate carboxymethyl chitosan (deacetylation 90%, substitution value 90%) is soluble in water, it is 4% that concentration, which is made,
W/v carboxymethyl chitosan solution.
(4) concentration obtained in the silk fibroin solution for being 2.0%w/v by the concentration obtained in step (2) and step (3) is
4%w/v carboxymethyl chitosan solution by volume 1：1 is well mixed, and obtains mixed solution.
(5) a certain amount of crosslinking agent 1- ethyls-(3- dimethylaminos are added in the mixed solution obtained in step (4)
Propyl group) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL), solid powder is first dissolved in a small amount of water by feed postition adds system.Hand over
Join the 0.6%w/v that agent addition is system.
(6) in the case where magnetic stirring apparatus is stirred continuously, EDCHCL is added into fibroin/carboxymethyl chitosan composite solution, 20s
Afterwards, solution is poured into mould, stands 12h.
(7) 12h in 75%v/v ethanol water is dipped in, fibroin/carboxymethyl chitosan is finally given compound solidifying
Glue.
(8) tested by mode same as Example 1, the modulus of elasticity for obtaining the plural gel reaches (248.60
± 34.47) kPa, compressive recovery rate reaches 100%, and water absorption and swelling rate reaches (35.78 ± 10.75) gel in deionized water
× 100%, volume is stablized relatively in pH=7.4 phosphate buffer, and swelling ratio is (13.18 ± 0.53) × 100%.
Embodiment 5
The preparation method of fibroin/carboxymethyl chitosan plural gel in turn includes the following steps in the present embodiment.
(1) cocoon layer that 10g shreds is weighed in the Na that mass fraction is 4.0%2CO3In boiling water degumming twice, every time
30min, obtained fibroin fiber is dried with being wrung out after deionized water rinsing in an oven；
(2) fibroin fiber obtained in step (1) is placed in 9M LiBr solution, the dissolution process 4h under the conditions of 60 DEG C,
Obtained liquid is fitted into bag filter (molecular weight 8000~14000) after filtering, and dialyse 4d in deionized water, during which constantly changes
Water, the silk fibroin solution concentration finally obtained is 0.5%w/v.
(3) appropriate carboxymethyl chitosan (deacetylation 90%, substitution value 90%) is soluble in water, it is 4% that concentration, which is made,
W/v carboxymethyl chitosan solution.
(4) concentration obtained in the silk fibroin solution for being 4.0%w/v by the concentration obtained in step (2) and step (3) is
4%w/v carboxymethyl chitosan solution by volume 1：1 is well mixed, and obtains mixed solution.
(5) a certain amount of crosslinking agent 1- ethyls-(3- dimethylaminos are added in the mixed solution obtained in step (4)
Propyl group) phosphinylidyne diimmonium salt hydrochlorate (EDCHCL), feed postition is that first solid powder is dissolved in a small amount of water to add system.
Crosslinking agent addition is the 0.6%w/v of system.
(6) in the case where magnetic stirring apparatus is stirred continuously, EDCHCL is added into fibroin/carboxymethyl chitosan composite solution, 20s
Afterwards, solution is poured into mould, stands 12h.
(7) 12h in 75%v/v ethanol water is dipped in, fibroin/carboxymethyl chitosan is finally given compound solidifying
Glue.
(8) tested by mode same as Example 1, the modulus of elasticity for obtaining the plural gel reaches (363.99
± 45.57) kPa, compressive recovery rate reaches 100%, gel in deionized water water absorption and swelling rate reach (20.79 ± 3.14) ×
100%, volume is stablized relatively in pH=7.4 phosphate buffer, and swelling ratio is (9.32 ± 0.09) × 100%.
As can be seen here, a kind of new method for preparing fibroin plural gel that the present invention is provided, preparation technology is simple, condition
Gently, gel time is short, and obtained plural gel has preferable mechanical property and water suction stability：Modulus of elasticity reaches
(363.94 ± 45.57) kPa, compressive recovery rate reaches 100%, i.e., when applying certain pressure thereon, plural gel is held
By very capable, it is not crushed, and when pressure is eliminated, gel restores to the original state again；In pH=7.4 phosphate buffer
Volume is stablized relatively, and swelling ratio is (9.32 ± 0.09) × 100%, and the sample of drying is placed in water and can quickly absorb a large amount of water
And expand, but still preferable form is kept, not loose crushing.
Listed above is only some embodiments of the present invention, it is clear that the invention is not restricted to above example, may be used also
To have many deformations, all changes that one of ordinary skill in the art directly can export or associate from present disclosure
Shape, is considered as protection scope of the present invention.
Claims (10)
1. a kind of fibroin albumen/carboxymethyl chitosan plural gel, it is characterised in that：
The plural gel is mainly made up of the composition of fibroin albumen and carboxymethyl chitosan.
2. a kind of fibroin albumen/carboxymethyl chitosan plural gel according to claim 1, it is characterised in that：It is described multiple
Close in gel, the mass ratio of fibroin albumen and carboxymethyl chitosan is (0.05~2)：1.
3. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel, it is characterised in that：
The fibroin fiber that degumming is obtained carries out dissolution process in LiBr solution, and regenerated silk solution is made by dialysis,
It is mixed with carboxymethyl chitosan solution again, crosslinking agent 1- ethyls-(3- dimethylaminopropyls) carbodiimide is then added
Hydrochloride, is finally prepared into fibroin/carboxymethyl chitosan composite aquogel in the presence of ethanol.
4. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel according to claim 3, its feature exists
In：Methods described detailed process is as follows：
(1) handled with cocoon layer and obtain fibroin fiber, then prepare silk fibroin solution；
(2) it is carboxymethyl chitosan is soluble in water, carboxymethyl chitosan solution is made；
(3) carboxymethyl chitosan solution obtained in the silk fibroin solution obtained in step (1) and step (2) is well mixed and obtained
Mixed solution；
(4) a certain amount of crosslinking agent is added in the mixed solution obtained in step (3), then solution is stirred on magnetic stirring apparatus
Mix to pour into immediately after the short time in mould and stand；
(5) immerse again in ethanol water, finally give fibroin/carboxymethyl chitosan plural gel.
5. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel according to claim 3, its feature exists
In：The step (1) is specially：
(1) cocoon layer is placed in the Na that mass fraction is 0.5%2CO3In boiling water degumming twice, each 30min, obtained silk
Cellulose fiber is dried with being wrung out after deionized water rinsing in an oven；
(2) fibroin fiber obtained in step (1) is placed in 9M LiBr solution, dissolution process 4h, is obtained under the conditions of 60 DEG C
Liquid be fitted into bag filter after filtering and dialysed in deionized water 4d, during which constantly change water, the silk fibroin solution finally obtained.
6. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel according to claim 3, its feature exists
In：The silk fibroin solution concentration of the step (1) is 0.5~10%w/v, the carboxymethyl chitosan solution concentration of the step (2)
For 1~5%w/v, silk fibroin solution and the mixed volume of carboxymethyl chitosan solution ratio are 1 in the step (3):1.
7. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel according to claim 3, its feature exists
In：The deacetylation of the carboxymethyl chitosan is 55%~99%, and substitution value is 60%~99%.
8. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel according to claim 3, its feature exists
In：In the step (4), crosslinking agent uses 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDC
HCL solid powder), the addition of crosslinking agent is 0.3~0.75%w/v of system.
9. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel according to claim 3, its feature exists
In：The feed postition of the crosslinking agent is divided to two kinds：One kind is directly added into system for solid powder, and one kind is to be dissolved in solid powder
System is added in water.
10. a kind of preparation method of fibroin albumen/carboxymethyl chitosan plural gel according to claim 3, its feature
It is：In the step (4), mixing time is 20s, and time of repose is 6-12h；In the step (5), in ethanol water
Concentration of alcohol is 60~90%v/v, and the time of immersion ethanol water is 12h.
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