CN107412881A - A kind of preparation method of composite strengthening artificial skin receptor - Google Patents
A kind of preparation method of composite strengthening artificial skin receptor Download PDFInfo
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- CN107412881A CN107412881A CN201710645262.7A CN201710645262A CN107412881A CN 107412881 A CN107412881 A CN 107412881A CN 201710645262 A CN201710645262 A CN 201710645262A CN 107412881 A CN107412881 A CN 107412881A
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Abstract
The present invention relates to artificial skin field, discloses a kind of preparation method of composite strengthening artificial skin receptor, including：(1) cellulose solution is prepared；(2) silver processing is carried；(3) electrostatic spinning, the nano-cellulose framework film of loaded Ag is obtained；(4) nano-cellulose framework film is handled under pneumatic pressure；(5) silk fibroin solution is prepared；(6) graphene oxide is taken to be configured to after the aqueous solution mixes with silk fibroin solution ultrasonic；(7) the nano-cellulose framework film of loaded Ag is transferred in the acetone soln of 3 aminopropyl triethoxysilanes, stood, take out dry solidification；(8) fibroin graphene mixed solution is totally submerged cellulose skeleton film, drying at room temperature solidification, obtains composite strengthening artificial skin receptor.The artificial skin that the inventive method obtains has good bio-compatible sexual function, the change of resistance can occur in the presence of certain external force, and have good physical and mechanical properties.
Description
Technical field
The present invention relates to artificial skin field, more particularly to a kind of preparation method of composite strengthening artificial skin receptor.
Technical background
Artificial skin is a kind of dressing for being used to treat skin trauma, mainly uses biomaterial or good biocompatibility
Synthetic material be prepared.Artificial skin medical field to scald, burn and skin injury missing play the role of it is good,
Even can be as the substitute of natural skin under certain situation.The artificial skin succeeded in developing and applied at present primarily serves
The covering effect of certain protection hypodermis, there is provided promote the composite material bracket of surface of a wound epidermal growth, or have
Some can promote the slow releasing pharmaceutical factor of skin growth.This kind of artificial skin has good biocompatibility, physical mechanical
Performance and medical performance, but its production is complicated, cost is high and the sense of touch impression without natural skin and signal transmit work(
Energy.
Artificial skin receptor is that environmental stimuli perceptional function and electric signal are added on the basis of original artificial skin
Transmit the membranaceous composite of function.This kind of receptor has certain perceptional function with the change to external environment and stimulation,
As thermoreceptor can perceive the change of skin temperature, thigmoreceptor can perceive the deformation that external force acts on lower skin.But
Artificial skin receptor common problem is that physical and mechanical properties is not up to requirement at present.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of preparation side of composite strengthening artificial skin receptor
Method.The present invention is born by the use of the silk fibroin of good biocompatibility and the graphene oxide of conductive energy as substrate
Ag cellulose is carried as enhancing skeleton.Fibroin can promote surface of a wound epidermal growth, and graphene and silver nanoparticle have excellent
Electric conductivity and electrochemistry sensitiveness, in the lower size that can change resistance of external force, wherein Ag particles have good suppression
Bacterium effect.The cellulose fibre film that electrostatic spinning forms is as enhancing skeleton, within the specific limits with excellent intensity and drawing
Performance is stretched, overcomes Traditional Man skin receptor common problem.
The present invention concrete technical scheme be：A kind of preparation method of composite strengthening artificial skin receptor, including it is as follows
Step：
(1) cellulose powder and dimethyl sulfoxide (DMSO) are dissolved in the N-methylmorpholine aqueous solution and are configured to cellulose solution.
Cellulose powder needs to be added in the mixed solution of N-methylmorpholine and dimethyl sulfoxide (DMSO) and dissolved, dimethyl
Sulfoxide can improve processing characteristics of the solution in electrostatic spinning as the auxiliary agent for reducing viscosity.
(2) cellulose solution is added into AgNO under condition of ice bath stirring3Solution, reductant solution is then added dropwise, stirs
It is allowed to fully react, heating concentration.
Need to add AgNO under ice bath and stirring condition in step (2)3Solution, and silver nitrate is reduced using reducing agent,
Elemental silver absorption in situ is generated on nano-cellulose surface.The method can prevent the reunion for the Ag particles being initially formed, so as to make
The standby Nano silver grain for having obtained scattered excellent absorption on nano-cellulose surface.
The addition of Ag nano-particles can improve the anti-microbial property and electrochemistry sensitiveness of material.
(3) cellulose solution of loaded Ag in step (2) is subjected to electrostatic spinning, with deionized water, methanol and ethanol
Mixed solution obtains the nano-cellulose framework film of loaded Ag as coagulating bath.
Using above-mentioned mixed liquor as coagulating bath, the separation of cellulose and solvent can be promoted.
(4) the nano-cellulose framework film after drying at room temperature is handled into 10-30min under 0.8-1.2MPa air pressure, as
The skeleton of composite strengthening film.
Cellulose membrane handles a period of time under 1MPa or so air pressure, and compression processing can be improved as composite membrane skeleton
Cellulose membrane mechanical performance, with good intensity.
(5) fibroin is extracted, and prepares silk fibroin solution.
(6) take the graphene oxide of surface carboxyl modification to be configured to the aqueous solution, and 1 is pressed with silk fibroin solution:8-10 quality
Than mixing, ultrasound, fibroin graphene mixed solution is made.
Graphene oxide have passed through surface carboxyl modification, and processing method is to add in graphene oxide to surpass in NaOH solution
Sound is separated into graphene oxide solution, and the hydroxyl on graphene oxide and epoxy radicals are converted into carboxylic using the monoxone of excess
Base.
(7) the nano-cellulose framework film of loaded Ag is transferred in the acetone soln of 3- aminopropyl triethoxysilanes,
Stand, take out dry solidification.
Cellulose skeleton film need to pass through 3- aminopropyl triethoxysilanes and handle, and 3- aminopropyl triethoxysilanes can incite somebody to action
The carboxyl on hydroxyl and fibroin, graphene on cellulose is combined together, and serves the effect of crosslinking curing.
(8) fibroin graphene mixed solution is added in polystyrene, adds cellulose skeleton film, be allowed to soak completely
Not yet, drying at room temperature solidifies, and obtains composite strengthening artificial skin receptor.
The present invention by using the cellulose of loaded Ag as strengthen skeleton, using graphene and fibroin as base material, and
Crosslinking agent is used as using 3- aminopropyl triethoxysilanes.Ag and graphene have good chemical property, and fibroin has excellent
Different biocompatibility, and cellulose conduct strengthens the defects of skeleton improves traditional fibroin membrane bad mechanical property.With existing skill
Art is compared, and this method environmental pollution is small, and preparation method is simple.Manufactured artificial skin receptor, which has, promotes wound healing,
Outer force-responsive and good physical and mechanical properties.
Preferably, in step (1), the concentration of cellulose is 10wt% in the cellulose solution, N-methylmorpholine it is dense
Spend for 96wt%, the concentration of dimethyl sulfoxide (DMSO) is 0.4wt%.
Preferably, in step (2), stir speed (S.S.) 500r/min-3000r/min, AgNO3The concentration of solution is
0.1mol/L-1mol/L, the volume ratio of addition is 0.1-0.5:1, the concentration of reductant solution is 0.1mol/L-1mol/L, drop
Rate of acceleration is 0.5 drop/s-2 drops/s, is added dropwise to after solution substantially changes colour and stops, and the stirring reaction time is 1-3h, heating concentration temperature
Spend for 40-45 DEG C.
Preferably, the reductant solution is NaBH4Solution or LiAlH4Solution.
Preferably, in step (3), spinning voltage 10-20kv, spinning flow rate is 0.5-1mL/h, needle point and collecting board
Between spinning away from for 9-15cm.The volume ratio of the deionized water, methanol and ethanol is 2:5:3.
Preferably, in step (5), the concentration of the silk fibroin solution is 10wt%.
Preferably, in step (6), the concentration of graphene oxide solution is 0.1-1wt%, ultrasonic time 0.5h-2h.
Preferably, in step (7), the volume ratio of 3- aminopropyl triethoxysilanes and acetone soln is 1:9, during standing
Between be 4-5 h, solidification temperature is 100-110 DEG C, and hardening time is 30-40 min.
Preferably, in step (5), the fibroin is made by enzymolysis, dialysis, freeze-drying in degumming, ionic liquid.
It is particularly preferred as：
A）4g mulberry silks are weighed as sample, is cleaned with deionized water, removes surface contaminant, drying.
B）By the sample of drying with 1:100 bath raio is containing 0.5% Na2PO4And 1%C17H35In COONa mixed solution
30min is boiled, carries out degumming process, common degumming is twice.
C）After degumming, sample is washed by rubbing with the hands more than 4 times with deionized water, is put into 60 DEG C of baking ovens, it is fine to obtain dry fibroin
Dimension.
D）The fibroin fiber of 2g dryings is weighed, with 1:40 bath raio is immersed in ionic liquid, while adds PEG- alkalescence eggs
White enzyme powder 0.15g, stirs 6h, after obtaining fibroin/ionic liquid solution, in the oil bath more than 80 DEG C in 40 DEG C of oil bath
At least 30min is incubated, carries out enzyme deactivation.
E）Treat that fibroin/ionic liquid solution is cooled to room temperature, add absolute ethyl alcohol, soak repeatedly, have fibroin albumen analysis
Go out.Mixture is filtered by vacuum, deionized water is added into the fibroin albumen filtered out, is filtered after soaking repeatedly, then will be molten
Liquid is fitted into molecular cut off 7000-10000 bag filter the 24h that dialyses, and obtains pure silk fibroin protein solution.
F）Obtained silk fibroin protein solution is freeze-dried, you can obtain silk fibroin powder.
Wherein, the preparation of PEG- alkali proteases：Weigh alkali protease 0.15g, PEG（1000MW polyethylene glycol）
0.17g, K2HPO4(dipotassium hydrogen phosphate) 0.16g, is dissolved in 10mL deionized waters, 40 DEG C of insulation 2h, then in -20 DEG C of conditions
After lower freezing 4h, freeze-dried 96h, PEG- basic protein enzyme powders are obtained, it is stand-by.
The preparation of ionic liquid：In 250mL three-necked flasks, 137mL 2- methallyl chlorides and 80mL N- first are added
Base imidazoles, 3h is stirred at reflux in 80 DEG C of oil baths, after completion of the reaction, excessive 2- methacrylics is removed using rotary evaporation
Chlorine, light yellow transparent liquid is obtained, be i.e. 1- (2- methyl) pi-allyl -3- methylimidazolium chloride ionic liquids, is freeze-dried 24h
Afterwards, thaw stand-by.
In fibroin albumen preparation process, the present invention is modified alkali protease using PEG 1000, utilizes PEG pairs
The affinity interaction of ionic liquid, not only increases the stability and reactivity of enzyme, while adds enzyme in ionic liquid
Dispersing uniformity, be advantageous to its hydrolysis to fibroin albumen.The present invention adds C in scouring processes17H35COONa is as buffering
Agent, alkaline environment is maintained, improve degumming efficiency, while reduce the injury to fibroin fiber.The present invention utilizes biology enzyme and ion
The dual dissolution effect of liquid, while fibroin albumen is handled, improve the solubility of fibroin albumen.It is raw in the present invention
Thing enzyme is nontoxic, with environment-friendly, while dosage is few, economizes on resources；Specific high, action condition is gentle, to fibroin albumen
Destruction it is small.Environmentally friendly and ionic liquid is " green solvent ", group can design, and be easily recycled, and can be recycled.
It is compared with the prior art, the beneficial effects of the invention are as follows：
(1) present invention realizes the recycling of waste material, reduces experimental cost using useless silk as raw material.
(2) present invention is compound using reinforcing material, and product has simultaneously promotes wound healing performance, good outer force-responsive
Performance and physical and mechanical properties.
(3) the electrochemistry sensitiveness of the invention for utilizing Nano silver grain, the external power action response of product are sensitive.
(4) present invention is less using chemicals, and experimentation is green.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
A kind of preparation method of composite strengthening artificial skin receptor, using following steps：
(1) take 10g cellulose powders to be dissolved in the 100mL96%NMMO aqueous solution, add 0.4g dimethyl sulfoxide (DMSO)s, be configured to fibre
Tie up element/N-methylmorpholine/dimethyl sulfoxide (DMSO) mixed solution；
(2) cellulose solution is added under condition of ice bath 500r/min stirrings, 100mL 0.1mol/LAgNO3Solution, then
0.1mol/L reducing agents KBH is added dropwise in 0.5 drop/s4Solution is to changing colour, and stirring 1h is allowed to fully react, and 42 DEG C of heating are concentrated into fiber
Plain concentration is 10wt%；
(3) cellulose solution of loaded Ag in step (2) is subjected to electrostatic spinning, spinning voltage 15kv, spinning flow rate is
1mL/h, spinning is away from for 12cm between needle point and collecting board.With deionized water, methanol and ethanol（Volume ratio is 2:5:3）Mixing it is molten
Liquid obtains the nano-cellulose framework film of loaded Ag as coagulating bath；
(4) the nano-cellulose framework film after drying at room temperature is handled into 10-30min under 1MPa air pressure, as composite strengthening film
Skeleton；
(5) extraction of fibroin：
A）4g mulberry silks are weighed as sample, is cleaned with deionized water, removes surface contaminant, drying.
B）By the sample of drying with 1:100 bath raio is containing 0.5% Na2PO4And 1%C17H35In COONa mixed solution
30min is boiled, carries out degumming process, common degumming is twice.
C）After degumming, sample is washed by rubbing with the hands more than 4 times with deionized water, is put into 60 DEG C of baking ovens, it is fine to obtain dry fibroin
Dimension.
D）The fibroin fiber of 2g dryings is weighed, with 1:40 bath raio is immersed in ionic liquid, while adds PEG- alkalescence eggs
White enzyme powder 0.15g, stirs 6h, after obtaining fibroin/ionic liquid solution, in the oil bath more than 80 DEG C in 40 DEG C of oil bath
At least 30min is incubated, carries out enzyme deactivation.
E）Treat that fibroin/ionic liquid solution is cooled to room temperature, add absolute ethyl alcohol, soak repeatedly, have fibroin albumen analysis
Go out.Mixture is filtered by vacuum, deionized water is added into the fibroin albumen filtered out, is filtered after soaking repeatedly, then will be molten
Liquid is fitted into the bag filter of molecular cut off 8000 24h that dialyses, and obtains pure silk fibroin protein solution.
F）Obtained silk fibroin protein solution is freeze-dried, you can obtain silk fibroin powder.
Wherein, the preparation of PEG- alkali proteases：Weigh alkali protease 0.15g, PEG（1000MW polyethylene glycol）
0.17g, K2HPO4(dipotassium hydrogen phosphate) 0.16g, is dissolved in 10mL deionized waters, 40 DEG C of insulation 2h, then in -20 DEG C of conditions
After lower freezing 4h, freeze-dried 96h, PEG- basic protein enzyme powders are obtained, it is stand-by.
The preparation of ionic liquid：In 250mL three-necked flasks, 137mL 2- methallyl chlorides and 80mL N- first are added
Base imidazoles, 3h is stirred at reflux in 80 DEG C of oil baths, after completion of the reaction, excessive 2- methacrylics is removed using rotary evaporation
Chlorine, light yellow transparent liquid is obtained, be i.e. 1- (2- methyl) pi-allyl -3- methylimidazolium chloride ionic liquids, is freeze-dried 24h
Afterwards, thaw stand-by.
Fibroin is formulated as to 10wt% silk fibroin solution.
(6) take the graphene oxide of surface carboxyl modification to be configured to the 0.1wt% aqueous solution, and 1 is pressed with silk fibroin solution:9 matter
Amount is than mixing, ultrasonic 1h；
(7) the nano-cellulose framework film of loaded Ag is transferred in the acetone soln of 3- aminopropyl triethoxysilanes, stood
1h, 100 DEG C of solidification 2h in drying box；
(8) fibroin graphene mixed solution is added in polystyrene culture dish, adds cellulose skeleton film, be allowed to soak completely
Not yet, drying at room temperature solidifies, and obtains composite strengthening artificial skin receptor.
Embodiment 2
A kind of preparation method of composite strengthening artificial skin receptor, using following steps：
(1) take 8g cellulose powders to be dissolved in the 100mL96%NMMO aqueous solution, add 0.5g dimethyl sulfoxide (DMSO)s, be configured to fiber
Element/N-methylmorpholine/dimethyl sulfoxide (DMSO) mixed solution；
(2) cellulose solution is added under condition of ice bath 800r/min stirrings, 80mL 0.5mol/LAgNO3Solution, then 0.5
1mol/L reducing agents KBH is added dropwise in drop/s4Solution is to changing colour, and stirring 1.5h is allowed to fully react, and 40 DEG C of heating are concentrated into cellulose
Concentration is 10wt%；
(3) cellulose solution of loaded Ag in step (2) is subjected to electrostatic spinning, spinning voltage 10kv, spinning flow rate is
0.5mL/h, spinning is away from for 9cm between needle point and collecting board.With deionized water, methanol and ethanol（Volume ratio is 2:5:3）Mixing
Solution obtains the nano-cellulose framework film of loaded Ag as coagulating bath；
(4) the nano-cellulose framework film after drying at room temperature is handled into 10-30min under 1MPa air pressure, as composite strengthening film
Skeleton；
(5) extraction of fibroin：
A）4g mulberry silks are weighed as sample, is cleaned with deionized water, removes surface contaminant, drying.
B）By the sample of drying with 1:100 bath raio is containing 0.5% Na2PO4And 1%C17H35In COONa mixed solution
30min is boiled, carries out degumming process, common degumming is twice.
C）After degumming, sample is washed by rubbing with the hands more than 4 times with deionized water, is put into 60 DEG C of baking ovens, it is fine to obtain dry fibroin
Dimension.
D）The fibroin fiber of 2g dryings is weighed, with 1:40 bath raio is immersed in ionic liquid, while adds PEG- alkalescence eggs
White enzyme powder 0.15g, stirs 6h, after obtaining fibroin/ionic liquid solution, in the oil bath more than 80 DEG C in 40 DEG C of oil bath
At least 30min is incubated, carries out enzyme deactivation.
E）Treat that fibroin/ionic liquid solution is cooled to room temperature, add absolute ethyl alcohol, soak repeatedly, have fibroin albumen analysis
Go out.Mixture is filtered by vacuum, deionized water is added into the fibroin albumen filtered out, is filtered after soaking repeatedly, then will be molten
Liquid is fitted into the bag filter of molecular cut off 8000 24h that dialyses, and obtains pure silk fibroin protein solution.
F）Obtained silk fibroin protein solution is freeze-dried, you can obtain silk fibroin powder.
Wherein, the preparation of PEG- alkali proteases：Weigh alkali protease 0.15g, PEG（1000MW polyethylene glycol）
0.17g, K2HPO4(dipotassium hydrogen phosphate) 0.16g, is dissolved in 10mL deionized waters, 40 DEG C of insulation 2h, then in -20 DEG C of conditions
After lower freezing 4h, freeze-dried 96h, PEG- basic protein enzyme powders are obtained, it is stand-by.
The preparation of ionic liquid：In 250mL three-necked flasks, 137mL 2- methallyl chlorides and 80mL N- first are added
Base imidazoles, 3h is stirred at reflux in 80 DEG C of oil baths, after completion of the reaction, excessive 2- methacrylics is removed using rotary evaporation
Chlorine, light yellow transparent liquid is obtained, be i.e. 1- (2- methyl) pi-allyl -3- methylimidazolium chloride ionic liquids, is freeze-dried 24h
Afterwards, thaw stand-by.
Fibroin is formulated as to 10wt% silk fibroin solution.
(6) take the graphene oxide of surface carboxyl modification to be configured to the 0.5wt% aqueous solution, and 1 is pressed with silk fibroin solution:9 matter
Amount is than mixing, ultrasonic 1.5h；
(7) the nano-cellulose framework film of loaded Ag is transferred in the acetone soln of 3- aminopropyl triethoxysilanes, stood
1h, 110 DEG C of solidification 1h in drying box；
(8) fibroin graphene mixed solution is added in polystyrene culture dish, adds cellulose skeleton film, be allowed to soak completely
Not yet, drying at room temperature solidifies, and obtains composite strengthening artificial skin receptor.
Embodiment 3
A kind of preparation method of composite strengthening artificial skin receptor, using following steps：
(1) take 12g cellulose powders to be dissolved in the 100mL96%NMMO aqueous solution, add 0.3g dimethyl sulfoxide (DMSO)s, be configured to fibre
Tie up element/N-methylmorpholine/dimethyl sulfoxide (DMSO) mixed solution；
(2) cellulose solution is added under condition of ice bath 1000r/min stirrings, 50mL 1mol/LAgNO3Solution, then 1 drop/
0.5mol/L reducing agents KBH is added dropwise in s4Solution is to changing colour, and stirring 2h is allowed to fully react, and 45 DEG C of heating are concentrated into cellulose concentration
For 10wt%；
(3) cellulose solution of loaded Ag in step (2) is subjected to electrostatic spinning, spinning voltage 20kv, spinning flow rate is
1mL/h, spinning is away from for 15cm between needle point and collecting board.With deionized water, methanol and ethanol（Volume ratio is 2:5:3）Mixing it is molten
Liquid obtains the nano-cellulose framework film of loaded Ag as coagulating bath；
(4) the nano-cellulose framework film after drying at room temperature is handled into 10-30min under 1MPa air pressure, as composite strengthening film
Skeleton；
(5) extraction of fibroin：
A）4g mulberry silks are weighed as sample, is cleaned with deionized water, removes surface contaminant, drying.
B）By the sample of drying with 1:100 bath raio is containing 0.5% Na2PO4And 1%C17H35In COONa mixed solution
30min is boiled, carries out degumming process, common degumming is twice.
C）After degumming, sample is washed by rubbing with the hands more than 4 times with deionized water, is put into 60 DEG C of baking ovens, it is fine to obtain dry fibroin
Dimension.
D）The fibroin fiber of 2g dryings is weighed, with 1:40 bath raio is immersed in ionic liquid, while adds PEG- alkalescence eggs
White enzyme powder 0.15g, stirs 6h, after obtaining fibroin/ionic liquid solution, in the oil bath more than 80 DEG C in 40 DEG C of oil bath
At least 30min is incubated, carries out enzyme deactivation.
E）Treat that fibroin/ionic liquid solution is cooled to room temperature, add absolute ethyl alcohol, soak repeatedly, have fibroin albumen analysis
Go out.Mixture is filtered by vacuum, deionized water is added into the fibroin albumen filtered out, is filtered after soaking repeatedly, then will be molten
Liquid is fitted into the bag filter of molecular cut off 8000 24h that dialyses, and obtains pure silk fibroin protein solution.
F）Obtained silk fibroin protein solution is freeze-dried, you can obtain silk fibroin powder.
Wherein, the preparation of PEG- alkali proteases：Weigh alkali protease 0.15g, PEG（1000MW polyethylene glycol）
0.17g, K2HPO4(dipotassium hydrogen phosphate) 0.16g, is dissolved in 10mL deionized waters, 40 DEG C of insulation 2h, then in -20 DEG C of conditions
After lower freezing 4h, freeze-dried 96h, PEG- basic protein enzyme powders are obtained, it is stand-by.
The preparation of ionic liquid：In 250mL three-necked flasks, 137mL 2- methallyl chlorides and 80mL N- first are added
Base imidazoles, 3h is stirred at reflux in 80 DEG C of oil baths, after completion of the reaction, excessive 2- methacrylics is removed using rotary evaporation
Chlorine, light yellow transparent liquid is obtained, be i.e. 1- (2- methyl) pi-allyl -3- methylimidazolium chloride ionic liquids, is freeze-dried 24h
Afterwards, thaw stand-by.
Fibroin is formulated as to 10wt% silk fibroin solution.
(6) take the graphene oxide of surface carboxyl modification to be configured to the 1wt% aqueous solution, and 1 is pressed with silk fibroin solution:9 quality
Than mixing, ultrasonic 2h；
(7) the nano-cellulose framework film of loaded Ag is transferred in the acetone soln of 3- aminopropyl triethoxysilanes, stood
1h, 120 DEG C of solidification 2h in drying box；
(8) fibroin graphene mixed solution is added in polystyrene culture dish, adds cellulose skeleton film, be allowed to soak completely
Not yet, drying at room temperature solidifies, and obtains composite strengthening artificial skin receptor.
Raw materials used in the present invention, equipment, it is the conventional raw material, equipment of this area unless otherwise noted；In the present invention
Method therefor, it is the conventional method of this area unless otherwise noted.
It is described above, only it is presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, it is every according to the present invention
Any simple modification, change and the equivalent transformation that technical spirit is made to above example, still fall within the technology of the present invention side
The protection domain of case.
Claims (9)
1. a kind of preparation method of composite strengthening artificial skin receptor, it is characterised in that comprise the following steps：
(1) cellulose powder and dimethyl sulfoxide (DMSO) are dissolved in the N-methylmorpholine aqueous solution and are configured to cellulose solution；
(2) cellulose solution is added into AgNO under condition of ice bath stirring3Solution, is then added dropwise reductant solution, and stirring is allowed to fill
Divide reaction, heating concentration；
(3) cellulose solution of loaded Ag in step (2) is subjected to electrostatic spinning, with the mixing of deionized water, methanol and ethanol
Solution obtains the nano-cellulose framework film of loaded Ag as coagulating bath；
(4) the nano-cellulose framework film after drying at room temperature is handled into 10-30min under 0.8-1.2MPa air pressure, as compound
Strengthen the skeleton of film；
(5) fibroin is extracted, and prepares silk fibroin solution；
(6) take the graphene oxide of surface carboxyl modification to be configured to the aqueous solution, and 1 is pressed with silk fibroin solution:8-10 mass ratio mixes
Close, ultrasound, fibroin graphene mixed solution is made；
(7) the nano-cellulose framework film of loaded Ag is transferred in the acetone soln of 3- aminopropyl triethoxysilanes, it is quiet
Put, take out dry solidification；
(8) fibroin graphene mixed solution is added in polystyrene, adds cellulose skeleton film, be allowed to be totally submerged, room
Warm dry solidification, obtain composite strengthening artificial skin receptor.
A kind of 2. preparation method of composite strengthening artificial skin receptor as claimed in claim 1, it is characterised in that step
(1) in, the concentration of cellulose is 10wt% in the cellulose solution, and the concentration of N-methylmorpholine is 96wt%, dimethyl sulfoxide (DMSO)
Concentration be 0.4wt%.
A kind of 3. preparation method of composite strengthening artificial skin receptor as claimed in claim 1, it is characterised in that step
(2) in, stir speed (S.S.) 500r/min-3000r/min, AgNO3The concentration of solution is 0.1mol/L-1mol/L, the body of addition
Product ratio is 0.1-0.5:1, the concentration of reductant solution is 0.1mol/L-1mol/L, and drop rate is 0.5 drop/s-2 drops/s, drop
Add to after solution substantially changes colour and stop, the stirring reaction time is 1-3h, and heating thickening temperature is 40-45 DEG C.
4. a kind of preparation method of composite strengthening artificial skin receptor as claimed in claim 3, it is characterised in that described to go back
Former agent solution is NaBH4Solution or LiAlH4Solution.
A kind of 5. preparation method of composite strengthening artificial skin receptor as claimed in claim 1, it is characterised in that step
(3) in, spinning voltage 10-20kv, spinning flow rate is 0.5-1mL/h, and spinning is away from for 9-15cm between needle point and collecting board；It is described
The volume ratio of deionized water, methanol and ethanol is 2:5:3.
A kind of 6. preparation method of composite strengthening artificial skin receptor as claimed in claim 1, it is characterised in that step
(5) in, the concentration of the silk fibroin solution is 10wt%.
A kind of 7. preparation method of composite strengthening artificial skin receptor as claimed in claim 1, it is characterised in that step
(6) in, the concentration of graphene oxide solution is 0.1-1wt%, ultrasonic time 0.5h-2h.
A kind of 8. preparation method of composite strengthening artificial skin receptor as claimed in claim 1, it is characterised in that step
(7) in, the volume ratio of 3- aminopropyl triethoxysilanes and acetone soln is 1:9, time of repose is 4-5 h, and solidification temperature is
100-110 DEG C, hardening time is 30-40 min.
A kind of 9. preparation method of composite strengthening artificial skin receptor as described in claim 1 or 6, it is characterised in that step
Suddenly in (5), the fibroin is made by enzymolysis, dialysis, freeze-drying in degumming, ionic liquid.
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