CN107412882A - A kind of preparation method for attaching flexible artificial skin receptor - Google Patents

A kind of preparation method for attaching flexible artificial skin receptor Download PDF

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Publication number
CN107412882A
CN107412882A CN201710645263.1A CN201710645263A CN107412882A CN 107412882 A CN107412882 A CN 107412882A CN 201710645263 A CN201710645263 A CN 201710645263A CN 107412882 A CN107412882 A CN 107412882A
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fibroin
solution
artificial skin
preparation
graphene
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CN107412882B (en
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万军民
汪坚
胡智文
王秉
彭志勤
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Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
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Zhejiang Sci Tech University ZSTU
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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
    • A61L27/60—Materials for use in artificial skin
    • 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
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/303—Carbon
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • 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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • C07K14/43504—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates
    • C07K14/43563—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects
    • C07K14/43586—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from invertebrates from insects from silkworms
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P21/00—Preparation of peptides or proteins
    • C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/06—Coatings containing a mixture of two or more compounds
    • 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
    • A61L2430/34—Materials or treatment for tissue regeneration for soft tissue reconstruction

Abstract

The present invention relates to artificial skin field, discloses a kind of preparation method for attaching ventilative artificial skin receptor, including：(1) poly-vinyl alcohol solution is prepared；(2) silk fibroin solution is prepared；(3) fibroin poly-vinyl alcohol solution is prepared；(4) release treatment；(5) by fibroin poly-vinyl alcohol solution spin-coating film；(6) take off film and dry moisture absorption reprocessing；(7) graphene carries silver；(8) centrifuge, be dried in vacuo；(9) graphene argentum nano composite material is plated on basilar memebrane using vapour deposition process.The artificial skin of the present invention has good bio-compatible sexual function, and resistance, which can occur, under the effect of certain external force changes, and has good physical and mechanical properties.Non- surfacing is attached into skin during use, with a small amount of water-soluble Polyvinyl alcohol and fibroin is soaked, conductive material is closely attached to skin surface, and addition and the transformation of fibroin structure due to auxiliary agent, flexibility and toughness are ensure that while close attach.

Description

A kind of preparation method for attaching flexible artificial skin receptor
Technical field
The present invention relates to artificial skin field, more particularly to a kind of preparation method for attaching flexible 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 to produce sense of discomfort and physical and mechanical properties with human contact not up to make at present With requiring.
The content of the invention
In order to solve the above-mentioned technical problem, the invention provides a kind of preparation side for attaching flexible artificial skin receptor Method.The present invention is used as substrate, one side gas phase by the use of the silk fibroin of good biocompatibility and the polyvinyl alcohol of good water solubility Deposition plates layer of conductive material.Fibroin can promote surface of a wound epidermal growth, and graphene and silver nanoparticle have excellent lead Electrical property and electrochemistry sensitiveness, in the lower size that can change resistance of external force, wherein Ag particles have good antibacterial effect Fruit.Water-soluble Polyvinyl alcohol and fibroin is soaked during use, conductive material is closely attached to skin surface, due to toughening material In the presence of and fibroin crystalline structure transformation, ensure that flexibility and toughness while close attach, overcome Traditional Man Skin receptor common problem.
The present invention concrete technical scheme be：A kind of preparation method for attaching flexible artificial skin receptor, including it is as follows Step：
(1) take polyvinyl alcohol to dissolve by heating to be allowed to be completely dissolved into the aqueous solution, stirring, add ethanol and obtain poly-vinyl alcohol solution.
Ethanol, which adds, can change solution surface tension, improve the filming performance of solution.
(2) fibroin is extracted, and prepares silk fibroin solution.
(3) stirred with silk fibroin solution and poly-vinyl alcohol solution, glycerine and glutaraldehyde mixing ultrasound is added dropwise, is formed uniform Fibroin-polyvinyl alcohol solution.
Glycerine adds as toughener, and can improve makes product have good toughness.Glutaraldehyde adds as crosslinking agent Enter, the crosslinking of fibroin can be promoted, improve product strength.
(4) release treatment is carried out to substrate silicon substrate：Monocrystalline silicon piece is positioned in evaporating dish, adds trim,ethylchlorosilane liquid Body, closed evaporating ware, 8-12min is evaporated wherein and is used for doing antistick layer.
(5) spin-coating method is utilized, as the intermediate layer of conduction, to be dried into basilar memebrane fibroin-polyvinyl alcohol solution.
(6) basilar memebrane of forming is taken off under the conditions of water vapour, and inhaled under 40 DEG C of -80 DEG C of dryings and room temperature condition It is wet to reprocess 3-5 times.
Moisture adsorption and releasing repeatedly can change the crystalline structure of fibroin membrane, effectively improve the strength and stability of fibroin membrane.
(7) take graphene dispersion that AgNO is added dropwise dropwise under ultrasound condition in deionized water3Solution, when reacting one section Between after, adjust the pH value of solution to 11-12 by adding NaOH solution, then react mixed liquor under oil bath.
(8) after reaction terminates, mixed liquor is centrifuged into taking precipitate, is then centrifuged washed respectively with absolute ethyl alcohol, deionized water Wash, vacuum drying obtains graphene-argentum nano composite material.
The addition of Ag nano-particles can improve the anti-microbial property and electrochemistry sensitiveness of material.
(9) graphene-argentum nano composite material is plated on treated basilar memebrane using vapour deposition process, attached Flexible artificial skin receptor.Graphene-argentum nano composite material is plated in a nanometer fibroin PVA fiber-likes using vapour deposition process On product one side, obtain attaching ventilative artificial skin receptor, non-surfacing is attached into skin during use, with a small amount of water dissolving PVA simultaneously Fibroin is soaked, conductive material is closely attached to skin surface, and the presence due to toughening material and the crystalline structure of fibroin Transformation, ensure that soft and toughness while close attach.
The artificial skin of the present invention is vapor-deposited the method that conductive material is plated on perforated membrane using one side, will be non-during use Surfacing attaches skin, with a small amount of water dissolving PVA and soaks fibroin, conductive material is closely attached to skin surface, and due to The presence of toughening material and the transformation of the crystalline structure of fibroin, soft and toughness is ensure that while close attach,
The present invention by fibroin-polyvinyl alcohol nano for being formed using spin coating as substrate skeleton, with graphene and Nano Silver As conductive material.Ag and graphene have a good chemical property, and fibroin has an excellent biocompatibility, and toughness reinforcing material The presence of material and the transformation of the crystalline structure of fibroin, within the specific limits with excellent intensity and tensile 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 alcoholysis degree of polyvinyl alcohol is less than molar fraction 88%, and heating-up temperature is less than 40 DEG C, For poly-vinyl alcohol solution concentration in 6wt%-10wt%, the amount that ethanol adds is 0.5wt%-5wt%.
Preferably, in step (2), 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.
Preferably, in step (3), silk fibroin solution need to be stirred at 20 DEG C -40 DEG C with poly-vinyl alcohol solution and mix, and stir It is 500r/min-1500r/min to mix speed, and mixing time 60min-120min, the addition of glycerine is 0.2wt%- 1wt%, the addition of glutaraldehyde is 0.2wt%-1wt%.
Preferably, in step (5), fibroin-polyvinyl alcohol solution need to pass through ultrasonic vibration processing 20min, and profit With freeze-drying film forming.
Ultrasonic vibration can promote the scattered of fibroin, coordinate freeze-drying compression processing to make the fibroin membrane pore-forming of shaping Property is good, improves the permeability of fibroin membrane.
Preferably, in step (5), the basilar memebrane need to pass through post processing, and processing method is, by dried Nanowire Dimension sample handles 10-30min under 1MPa air pressure.
Compression handles the mechanical performance that can improve film, with good intensity.
Preferably, in step (7), the graphene is obtained by vapour deposition process or mechanical stripping method.
For the present invention to obtain the more preferable reduced graphene of electric conductivity, the graphene is prepared using oxidation-reduction method Graphene oxide, but obtained by vapour deposition process or mechanical stripping method.
Preferably, in step (7), the concentration of the graphene dispersing solution is 0.1-1mol/L, AgNO3The concentration of solution For 0.1-1mol/L, the volume ratio of dropwise addition is 0.5-2；NaOH solution is 0.1mol/L, and oil bath temperature is 40 DEG C -80 DEG C, reaction Time is 20-50min.
Preferably, in step (8), the condition of centrifuge washing centrifuges 2-5 times for 3000-8000rmp, centrifuges 2- every time 5min。
Preferably, in step (9), vapor deposition conditions are graphene gas argon-dilution to 2%, and flow control exists 100-250mL/min, growth temperature are 100-200 DEG C, reaction pressure 50-100Pa, growth time 1-6min.
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) there is promotion to create simultaneously for method that is of the invention compound using polyvinyl alcohol and fibroin and plating conductive material, product Hinder healing properties, good external force response performance and ventilative attaching performance.
(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 for attaching flexible artificial skin receptor, using following steps：
(1) take polyvinyl alcohol to dissolve by heating to be allowed to be completely dissolved into the 6wt% aqueous solution, stirring 30min, add each 0.5wt% second Alcohol forms mixed solution；Wherein, the alcoholysis degree of polyvinyl alcohol is less than molar fraction 88%, and heating-up temperature is less than 40 DEG C.
(2) 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.
(3) with silk fibroin solution and poly-vinyl alcohol solution 20 DEG C of stirrings 60min, stir speed (S.S.) 1000r/min, it is added dropwise each 0.2wt% glycerine and glutaraldehyde mixing ultrasound, form uniform fibroin-polyvinyl alcohol solution；
(4) release treatment is carried out to the substrate silicon substrate used in MULTILAYER COMPOSITE artificial skin, monocrystalline silicon piece is positioned in evaporating dish, A small amount of trim,ethylchlorosilane liquid is added, closed evaporating ware, 10min is evaporated wherein and is used for doing antistick layer；；
(5) fibroin-polyvinyl alcohol solution is utilized into spin-coating method into basilar memebrane, as the intermediate layer of conduction, freeze-drying；Its In, fibroin-polyvinyl alcohol solution need to pass through ultrasonic vibration processing 20min, and utilize freeze-drying film forming.The substrate Film need to pass through post processing, and processing method is that dried nanofiber sample is handled into 20min under 1MPa air pressure.
(6) basilar memebrane of forming is taken off under the conditions of water vapour, and dried and moisture absorption weight under room temperature condition at 60 DEG C Handle 3-5 times again；
(7) graphene is disperseed in deionized water, AgNO is added dropwise dropwise under conditions of ultrasound3Solution, reaction a period of time Afterwards, the pH value of solution is adjusted to 11-12 by adding NaOH solution, then react mixed liquor under oil bath；Wherein, it is described Graphene is obtained by vapour deposition process or mechanical stripping method.The concentration of the graphene dispersing solution is 0.5mol/L, AgNO3It is molten The concentration of liquid is 0.5mol/L, and the volume ratio of dropwise addition is 1；NaOH solution is 0.1mol/L, and oil bath temperature is 60 DEG C, the reaction time For 35min.
(8) after reaction terminates, mixed liquor is centrifuged into taking precipitate, is then centrifuged washed respectively with absolute ethyl alcohol, deionized water Wash, the condition of centrifuge washing centrifuges 3 times for 5000rmp, centrifuges 3min every time.It is compound that vacuum drying obtains graphene-silver nanoparticle Material；
(9) graphene-argentum nano composite material is plated on treated basilar memebrane using vapour deposition process, obtains attaching flexibility Artificial skin receptor.Wherein, vapor deposition conditions are graphene gas argon-dilution to 2%, and flow is controlled in 180mL/ Min, growth temperature are 150 DEG C, reaction pressure 75Pa, growth time 3min.
Embodiment 2
A kind of preparation method for attaching flexible artificial skin receptor, using following steps：
(1) take polyvinyl alcohol to dissolve by heating to be allowed to be completely dissolved into the 8wt% aqueous solution, stirring 40min, add each 0.2wt% second Alcohol forms mixed solution；Wherein, the alcoholysis degree of polyvinyl alcohol is less than molar fraction 88%, and heating-up temperature is less than 40 DEG C.
(2) 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.
(3) with silk fibroin solution and poly-vinyl alcohol solution 20 DEG C of stirrings 80min, stir speed (S.S.) 500r/min, it is added dropwise each 0.4wt% glycerine and glutaraldehyde mixing ultrasound, form uniform fibroin-polyvinyl alcohol solution；
(4) release treatment is carried out to the substrate silicon substrate used in MULTILAYER COMPOSITE artificial skin, monocrystalline silicon piece is positioned in evaporating dish, A small amount of trim,ethylchlorosilane liquid is added, closed evaporating ware, 10min is evaporated wherein and is used for doing antistick layer；；
(5) fibroin-polyvinyl alcohol solution is utilized into spin-coating method into basilar memebrane, as the intermediate layer of conduction, freeze-drying；Its In, fibroin-polyvinyl alcohol solution need to pass through ultrasonic vibration processing 20min, and utilize freeze-drying film forming.The substrate Film need to pass through post processing, and processing method is that dried nanofiber sample is handled into 10min under 1MPa air pressure.
(6) basilar memebrane of forming is taken off under the conditions of water vapour, and dried and moisture absorption weight under room temperature condition at 40 DEG C Handle 3 times again；
(7) graphene is disperseed in deionized water, AgNO is added dropwise dropwise under conditions of ultrasound3Solution, reaction a period of time Afterwards, the pH value of solution is adjusted to 11-12 by adding NaOH solution, then react mixed liquor under oil bath；Wherein, it is described Graphene is obtained by vapour deposition process or mechanical stripping method.The concentration of the graphene dispersing solution is 0.1mol/L, AgNO3It is molten The concentration of liquid is 0.1mol/L, and the volume ratio of dropwise addition is 0.5；NaOH solution is 0.1mol/L, and oil bath temperature is 40 DEG C, during reaction Between be 50min.
(8) after reaction terminates, mixed liquor is centrifuged into taking precipitate, is then centrifuged washed respectively with absolute ethyl alcohol, deionized water Wash, the condition of centrifuge washing centrifuges 5 times for 3000rmp, centrifuges 2min every time.It is compound that vacuum drying obtains graphene-silver nanoparticle Material；
(9) graphene-argentum nano composite material is plated on treated basilar memebrane using vapour deposition process, obtains attaching flexibility Artificial skin receptor.Wherein, vapor deposition conditions are graphene gas argon-dilution to 2%, and flow is controlled in 100mL/ Min, growth temperature are 100 DEG C, reaction pressure 50Pa, growth time 1min.
Embodiment 3
A kind of preparation method for attaching flexible artificial skin receptor, using following steps：
(1) take polyvinyl alcohol to dissolve by heating to be allowed to be completely dissolved into the 10wt% aqueous solution, stirring 60min, add each 1wt% ethanol Form mixed solution；Wherein, the alcoholysis degree of polyvinyl alcohol is less than molar fraction 88%, and heating-up temperature is less than 40 DEG C.
(2) 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.
(3) with silk fibroin solution and poly-vinyl alcohol solution 30 DEG C of stirrings 90min, stir speed (S.S.) 1500r/min, it is added dropwise each 0.5wt% glycerine and glutaraldehyde mixing ultrasound, form uniform fibroin-polyvinyl alcohol solution；
(4) release treatment is carried out to the substrate silicon substrate used in MULTILAYER COMPOSITE artificial skin, monocrystalline silicon piece is positioned in evaporating dish, A small amount of trim,ethylchlorosilane liquid is added, closed evaporating ware, 10min is evaporated wherein and is used for doing antistick layer；；
(5) fibroin-polyvinyl alcohol solution is utilized into spin-coating method into basilar memebrane, as the intermediate layer of conduction, freeze-drying；Its In, fibroin-polyvinyl alcohol solution need to pass through ultrasonic vibration processing 20min, and utilize freeze-drying film forming.The substrate Film need to pass through post processing, and processing method is that dried nanofiber sample is handled into 30min under 1MPa air pressure.
(6) basilar memebrane of forming is taken off under the conditions of water vapour, and inhaled under 40 DEG C of -80 DEG C of dryings and room temperature condition It is wet to reprocess 3-5 times；
(7) graphene is disperseed in deionized water, AgNO is added dropwise dropwise under conditions of ultrasound3Solution, reaction a period of time Afterwards, the pH value of solution is adjusted to 11-12 by adding NaOH solution, then react mixed liquor under oil bath；Wherein, it is described Graphene is obtained by vapour deposition process or mechanical stripping method.The concentration of the graphene dispersing solution is 1mol/L, AgNO3Solution Concentration be 1mol/L, the volume ratio of dropwise addition is 2；NaOH solution is 0.1mol/L, and oil bath temperature is 80 DEG C, and the reaction time is 20min。
(8) after reaction terminates, mixed liquor is centrifuged into taking precipitate, is then centrifuged washed respectively with absolute ethyl alcohol, deionized water Wash, the condition of centrifuge washing centrifuges 2 times for 8000rmp, centrifuges 5min every time.It is compound that vacuum drying obtains graphene-silver nanoparticle Material；
(9) graphene-argentum nano composite material is plated on treated basilar memebrane using vapour deposition process, obtains attaching flexibility Artificial skin receptor.Wherein, vapor deposition conditions are graphene gas argon-dilution to 2%, and flow is controlled in 250mL/ Min, growth temperature are 200 DEG C, reaction pressure 100Pa, growth time 6min.
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 (10)

1. a kind of preparation method for attaching flexible artificial skin receptor, it is characterised in that comprise the following steps：
(1) take polyvinyl alcohol to dissolve by heating to be allowed to be completely dissolved into the aqueous solution, stirring, add ethanol and obtain poly-vinyl alcohol solution；
(2) fibroin is extracted, and prepares silk fibroin solution；
(3) stirred with silk fibroin solution and poly-vinyl alcohol solution, glycerine and glutaraldehyde mixing ultrasound is added dropwise, forms uniform silk Element-polyvinyl alcohol solution；
(4) release treatment is carried out to substrate silicon substrate：Monocrystalline silicon piece is positioned in evaporating dish, adds trim,ethylchlorosilane liquid, Closed evaporating ware, 8-12min is evaporated wherein and is used for doing antistick layer；
(5) spin-coating method is utilized, as the intermediate layer of conduction, to be dried into basilar memebrane fibroin-polyvinyl alcohol solution；
(6) basilar memebrane of forming is taken off under the conditions of water vapour, and the moisture absorption weight under 40 DEG C of -80 DEG C of dryings and room temperature condition Handle 3-5 times again；
(7) take graphene dispersion that AgNO is added dropwise dropwise under ultrasound condition in deionized water3Solution, after reacting a period of time, The pH value of solution is adjusted to 11-12 by adding NaOH solution, then reacts mixed liquor under oil bath；
(8) after reaction terminates, mixed liquor is centrifuged into taking precipitate, then distinguishes centrifuge washing with absolute ethyl alcohol, deionized water, very Sky is dried to obtain graphene-argentum nano composite material；
(9) graphene-argentum nano composite material is plated on treated basilar memebrane using vapour deposition process, obtains attaching flexibility Artificial skin receptor.
A kind of 2. preparation method for attaching flexible artificial skin receptor as claimed in claim 1, it is characterised in that step (1) in, the alcoholysis degree of polyvinyl alcohol is less than molar fraction 88%, and heating-up temperature is less than 40 DEG C, and poly-vinyl alcohol solution concentration exists 6wt%-10wt%, the amount that ethanol adds is 0.5wt%-5wt%.
A kind of 3. preparation method for attaching flexible artificial skin receptor as claimed in claim 1, it is characterised in that step (2) in, the fibroin is made by enzymolysis, dialysis, freeze-drying in degumming, ionic liquid.
A kind of 4. preparation method for attaching flexible artificial skin receptor as claimed in claim 1, it is characterised in that step (3) in, silk fibroin solution need to be stirred at 20 DEG C -40 DEG C with poly-vinyl alcohol solution and mix, stir speed (S.S.) 500r/min- 1500r/min, mixing time 60min-120min, the addition of glycerine is 0.2wt%-1wt%, and the addition of glutaraldehyde is 0.2wt%-1wt%。
A kind of 5. preparation method for attaching flexible artificial skin receptor as claimed in claim 1, it is characterised in that step (5) in, fibroin-polyvinyl alcohol solution need to pass through ultrasonic vibration processing 20min, and utilize freeze-drying film forming.
A kind of 6. preparation method of attaching flexibility artificial skin receptor as described in claim 1 or 5, it is characterised in that step Suddenly in (5), the basilar memebrane need to pass through post processing, and processing method is, by dried nanofiber sample under 1MPa air pressure Handle 10-30min.
A kind of 7. preparation method for attaching flexible artificial skin receptor as claimed in claim 1, it is characterised in that step (7) in, the graphene is obtained by vapour deposition process or mechanical stripping method.
A kind of 8. preparation method of attaching flexibility artificial skin receptor as described in claim 1 or 7, it is characterised in that step Suddenly in (7), the concentration of the graphene dispersing solution is 0.1-1mol/L, AgNO3The concentration of solution is 0.1-1mol/L, dropwise addition Volume ratio is 0.5-2；NaOH solution is 0.1mol/L, and oil bath temperature is 40 DEG C -80 DEG C, reaction time 20-50min.
A kind of 9. preparation method for attaching flexible artificial skin receptor as claimed in claim 1, it is characterised in that step (8) in, the condition of centrifuge washing centrifuges 2-5 times for 3000-8000rmp, centrifuges 2-5min every time.
A kind of 10. preparation method for attaching flexible artificial skin receptor as claimed in claim 1, it is characterised in that step (9) in, vapor deposition conditions are graphene gas argon-dilution to 2%, and flow is controlled in 100-250mL/min, growth temperature For 100-200 DEG C, reaction pressure 50-100Pa, growth time 1-6min.
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