CN107412882B - Preparation method of attached flexible artificial skin receptor - Google Patents

Preparation method of attached flexible artificial skin receptor Download PDF

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CN107412882B
CN107412882B CN201710645263.1A CN201710645263A CN107412882B CN 107412882 B CN107412882 B CN 107412882B CN 201710645263 A CN201710645263 A CN 201710645263A CN 107412882 B CN107412882 B CN 107412882B
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polyvinyl alcohol
fibroin
artificial skin
graphene
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CN107412882A (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
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Zhejiang Sci Tech University ZSTU
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    • 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
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
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    • 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
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    • C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
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    • 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
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    • 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
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    • A—HUMAN NECESSITIES
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    • 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
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    • 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 invention relates to the field of artificial skin, and discloses a preparation method of an attached breathable artificial skin receptor, which comprises the following steps: (1) preparing a polyvinyl alcohol solution; (2) preparing a fibroin solution; (3) preparing a fibroin-polyvinyl alcohol solution; (4) anti-sticking treatment; (5) spin coating silk fibroin-polyvinyl alcohol solution to form a film; (6) uncovering the film and drying-absorbing moisture for repeated treatment; (7) carrying silver on graphene; (8) centrifuging and vacuum drying; (9) the graphene-silver nanocomposite is plated on a base film by a vapor deposition method. The artificial skin has good biocompatibility, can change resistance under the action of certain external force, and has good physical and mechanical properties. When the conductive material is used, the non-plated surface is attached to the skin, a small amount of water is used for dissolving polyvinyl alcohol and wetting silk fibroin, so that the conductive material is tightly attached to the surface of the skin, and due to the addition of the auxiliary agent and the transformation of a silk fibroin structure, the flexibility and toughness are ensured while the conductive material is tightly attached.

Description

Preparation method of attached flexible artificial skin receptor
Technical Field
The invention relates to the field of artificial skin, in particular to a preparation method of an attached flexible artificial skin receptor.
Technical Field
The artificial skin is a dressing for treating skin wound, and is mainly prepared from biological materials or synthetic materials with good biocompatibility. Artificial skin has a good effect on scalds, burns and skin damages in the medical field and can even be used as a substitute for natural skin in some cases. The artificial skin which is successfully developed and applied at present mainly plays a certain role in protecting subcutaneous tissues, provides a composite material bracket for promoting the growth of epidermal cells of a wound surface, or has some slow-release medicinal factors capable of promoting the growth of skin. Such artificial skin has good biocompatibility, physical and mechanical properties and medical properties, but is complicated to produce, high in cost and does not have the tactile sensation and signal transmission functions of natural skin.
The artificial skin receptor is a film-shaped composite material which is added with an external stimulation perception function and an electric signal transmission function on the basis of the original artificial skin. The sensors have certain sensing functions on the change and stimulation of the external environment, for example, the temperature sensors can sense the change of the skin temperature, and the touch sensors can sense the deformation of the skin under the action of external force. However, the common problems of the current artificial skin sensors are that the sensors are uncomfortable when contacting with human bodies and the physical and mechanical properties of the sensors do not meet the use requirements.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of an attached flexible artificial skin receptor. The invention uses silk fibroin with good biocompatibility and polyvinyl alcohol with good water solubility as a substrate, and a layer of conductive material is plated on a single surface by vapor deposition. The fibroin can promote the growth of epidermal cells of the wound surface, the graphene and the silver nano-particles have excellent conductivity and electrochemical sensitivity, the resistance can be changed under the action of external force, and the Ag particles have a good bacteriostatic effect. When the skin-care product is used, the polyvinyl alcohol is dissolved in water and the fibroin is moistened, so that the conductive material is tightly attached to the surface of the skin, due to the existence of the toughening material and the transformation of the crystal structure of the fibroin, the softness and toughness are ensured while the tight attachment is realized, and the common problem of the traditional artificial skin receptor is solved.
The specific technical scheme of the invention is as follows: a preparation method of an attached flexible artificial skin receptor comprises the following steps:
(1) heating polyvinyl alcohol to dissolve into aqueous solution, stirring to completely dissolve, and adding ethanol to obtain polyvinyl alcohol solution.
The surface tension of the solution can be changed by adding ethanol, and the film-forming property of the solution is improved.
(2) Extracting silk fibroin, and preparing silk fibroin solution.
(3) Stirring the fibroin solution and the polyvinyl alcohol solution, dropwise adding glycerol and glutaraldehyde, mixing and ultrasonically treating to form a uniform fibroin-polyvinyl alcohol mixed solution.
The glycerol is added as a toughening agent, so that the product has good toughness. Glutaraldehyde is added as a cross-linking agent, which can promote the cross-linking of the fibroin and improve the strength of the product.
(4) Carrying out anti-sticking treatment on the substrate silicon base: placing the monocrystalline silicon piece in an evaporating dish, adding trimethylchlorosilane liquid, sealing the evaporating dish, and evaporating for 8-12min in the evaporating dish to be used as an anti-sticking layer.
(5) And (3) forming a basement membrane by using the fibroin-polyvinyl alcohol mixed solution through a spin coating method, using the basement membrane as a conductive intermediate layer, and drying.
(6) And removing the formed base film under the condition of water vapor, drying at 40-80 ℃ and absorbing moisture at room temperature for 3-5 times.
Repeated moisture absorption and desorption can change the crystal structure of the silk fibroin membrane, and the strength and the stability of the silk fibroin membrane are effectively improved.
(7) Dispersing graphene in deionized water, and dropwise adding AgNO under ultrasonic condition3And (3) after the solution is reacted for a period of time, adjusting the pH value of the solution to 11-12 by adding NaOH solution, and then reacting the mixed solution under an oil bath.
(8) And after the reaction is finished, centrifuging the mixed solution to obtain a precipitate, respectively centrifuging and washing the precipitate by using absolute ethyl alcohol and deionized water, and drying the precipitate in vacuum to obtain the graphene-silver nano composite material.
The addition of Ag nano particles can improve the antibacterial performance and electrochemical sensitivity of the material.
(9) And plating the graphene-silver nano composite material on the treated basement membrane by using a vapor deposition method to obtain the attached flexible artificial skin receptor. The graphene-silver nanocomposite is plated on one surface of a fibroin nanofiber PVA fiber sample by a vapor deposition method to obtain an attached breathable artificial skin receptor, a non-plated surface is attached to the skin when the skin receptor is used, PVA is dissolved by a small amount of water and fibroin is wetted, so that the conductive material is tightly attached to the surface of the skin, and due to the existence of the toughening material and the transformation of the crystal structure of the fibroin, the softness and toughness are ensured while the skin receptor is tightly attached.
The artificial skin adopts the method of plating the conductive material on the porous membrane by single-side vapor deposition, when in use, the non-plated surface is attached to the skin, a small amount of water is used for dissolving PVA and wetting silk fibroin, so that the conductive material is tightly attached to the surface of the skin, and because of the existence of the toughening material and the transformation of the crystal structure of the silk fibroin, the softness and toughness are ensured while the tight attachment is realized,
the silk fibroin-polyvinyl alcohol nanofiber prepared by spin coating is used as a substrate framework, and graphene and nano silver are used as conductive materials. Ag and graphene have good electrochemical performance, silk fibroin has excellent biocompatibility, and the existence of a toughening material and the transformation of a crystal structure of the silk fibroin have excellent strength and tensile property within a certain range. Compared with the prior art, the method has the advantages of small environmental pollution and simple preparation method. The prepared artificial skin receptor has the advantages of wound healing promotion, external force response and good physical and mechanical properties.
Preferably, in the step (1), the alcoholysis degree of the polyvinyl alcohol is less than 88 percent of the mole fraction, the heating temperature is less than 40 ℃, the concentration of the polyvinyl alcohol solution is 6 to 10 weight percent, and the adding amount of the ethanol is 0.5 to 5 weight percent.
Preferably, in the step (2), the fibroin is prepared by degumming, enzymolysis in ionic liquid, dialysis and freeze drying. Specifically, it is preferable that:
A) weighing 4g of mulberry silk as a sample, washing with deionized water, removing surface pollutants, and drying.
B) Oven dried samples were dried in a 1: 100 bath containing 0.5% Na2PO4And 1% of C17H35Boiling the mixed solution of COONa for 30min, and degumming twice.
C) After degumming, rubbing the sample with deionized water for more than 4 times, and putting the sample into a 60 ℃ oven to obtain dry fibroin fibers.
D) Weighing 2g of dry silk fibroin fiber, immersing the silk fibroin fiber into ionic liquid according to a bath ratio of 1: 40, simultaneously adding 0.15g of PEG-alkaline protease powder, stirring the mixture in an oil bath at 40 ℃ for 6 hours to obtain a silk fibroin/ionic liquid solution, and then preserving the heat in the oil bath at the temperature of more than 80 ℃ for at least 30min for enzyme deactivation.
E) And (3) when the silk fibroin/ionic liquid solution is cooled to room temperature, adding absolute ethyl alcohol, and repeatedly soaking to separate out silk fibroin. And (3) carrying out vacuum filtration on the mixture, adding deionized water into the filtered silk fibroin, repeatedly soaking and filtering, and then putting the solution into a dialysis bag with the cut-off molecular weight of 7000-10000 for dialysis for 24 hours to obtain the pure silk fibroin solution.
F) And (3) freeze-drying the obtained silk fibroin solution to obtain silk fibroin powder.
Wherein, the preparation of PEG-alkaline protease: weighing alkaline protease 0.15g, PEG (1000MW polyethylene glycol) 0.17g, K2HPO40.16g of (dipotassium hydrogen phosphate) is dissolved in 10mL of deionized water, the temperature is kept for 2h at 40 ℃, then the mixture is frozen for 4h at the temperature of minus 20 ℃, and PEG-alkaline protease powder is obtained after freeze drying for 96h for standby.
Preparation of ionic liquid: adding 137mL of 2-methallyl chloride and 80mL of LN-methylimidazole into a 250mL three-neck flask, stirring and refluxing for 3h in an oil bath at 80 ℃, removing excessive 2-methallyl chloride by rotary evaporation after the reaction is finished to obtain light yellow transparent liquid, namely 1- (2-methyl) allyl-3-methylimidazole chloride ionic liquid, and unfreezing for later use after freeze drying for 24 h.
In the preparation process of silk fibroin, the invention modifies alkaline protease by using PEG 1000, and improves the stability and the reactivity of the enzyme by using the affinity action of the PEG to the ionic liquid, and simultaneously increases the dispersion uniformity of the enzyme in the ionic liquid, thereby being beneficial to the hydrolysis of the silk fibroin. In the degumming process of the invention, C is added17H35COONa as buffering agent for maintaining alkaline environment, improving degumming efficiency, and reducingDamage to silk cellulose fibers. The invention utilizes the double dissolving action of the biological enzyme and the ionic liquid to simultaneously treat the silk fibroin, thereby improving the solubility of the silk fibroin. In the invention, the biological enzyme is non-toxic and harmless, is environment-friendly, has small dosage and saves resources; high specificity, mild action condition and little damage to the fibroin. The ionic liquid is a green solvent, is environment-friendly and harmless, can be used for designing radicals, is easy to recover and can be recycled.
Preferably, in the step (3), the silk fibroin solution and the polyvinyl alcohol solution are stirred and mixed at the temperature of 20-40 ℃, the stirring speed is 500-1500 r/min, the stirring time is 60-120 min, the addition amount of glycerol is 0.2-1 wt%, and the addition amount of glutaraldehyde is 0.2-1 wt%.
Preferably, in the step (5), the fibroin-polyvinyl alcohol mixed solution is subjected to ultrasonic oscillation treatment for 20min, and a freeze drying method is used for film formation.
The ultrasonic oscillation can promote the dispersion of the silk fibroin, and the freezing, drying and compressing treatment can ensure that the formed silk fibroin film has good pore-forming property and improves the air permeability of the silk fibroin film.
Preferably, in the step (5), the base film is post-treated by treating the dried nanofiber sample at 1MPa for 10-30 min.
The compression treatment can improve the mechanical properties of the film, so that the film has good strength.
Preferably, in the step (7), the graphene is obtained by a vapor deposition method or a mechanical exfoliation method.
In order to obtain reduced graphene with better conductivity, the graphene is obtained by a vapor deposition method or a mechanical stripping method instead of graphene oxide prepared by an oxidation-reduction method.
Preferably, in the step (7), the concentration of the graphene dispersion liquid is 0.1-1mol/L, and AgNO3The concentration of the solution is 0.1-1mol/L, and the volume ratio of dropwise adding is 0.5-2; NaOH solution is 0.1mol/L, the oil bath temperature is 40-80 ℃, and the reaction time is 20-50 min.
Preferably, in step (8), the conditions for centrifugal washing are 3000-8000rpm for 2-5 times, each for 2-5 min.
Preferably, in the step (9), the vapor deposition conditions include that the graphene gas is diluted to 2% by argon, the flow rate is controlled to be 250mL/min at 100-.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the waste silk as the raw material, realizes the recycling of the waste materials and reduces the experiment cost.
(2) The invention adopts the method of compounding polyvinyl alcohol and fibroin and plating the conductive material, and the product has the performance of promoting wound healing, good external force response performance and air permeability adhesion performance.
(3) The invention utilizes the electrochemical sensitivity of the silver nano particles, and the product responds sensitively to external force.
(4) The method uses less chemicals, and the experimental process is green and environment-friendly.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of an attached flexible artificial skin receptor adopts the following steps:
(1) heating polyvinyl alcohol to dissolve into 6 wt% water solution, stirring for 30min to dissolve completely, adding 0.5 wt% ethanol to form mixed solution; wherein, the alcoholysis degree of the polyvinyl alcohol is less than 88 percent of the mole fraction, and the heating temperature is less than 40 ℃.
(2) Extracting fibroin:
A) weighing 4g of mulberry silk as a sample, washing with deionized water, removing surface pollutants, and drying.
B) Oven dried samples were dried in a 1: 100 bath containing 0.5% Na2PO4And 1% of C17H35Boiling the mixed solution of COONa for 30min, and degumming twice.
C) After degumming, rubbing the sample with deionized water for more than 4 times, and putting the sample into a 60 ℃ oven to obtain dry fibroin fibers.
D) Weighing 2g of dry silk fibroin fiber, immersing the silk fibroin fiber into ionic liquid according to a bath ratio of 1: 40, simultaneously adding 0.15g of PEG-alkaline protease powder, stirring the mixture in an oil bath at 40 ℃ for 6 hours to obtain a silk fibroin/ionic liquid solution, and then preserving the heat in the oil bath at the temperature of more than 80 ℃ for at least 30min for enzyme deactivation.
E) And (3) when the silk fibroin/ionic liquid solution is cooled to room temperature, adding absolute ethyl alcohol, and repeatedly soaking to separate out silk fibroin. And (3) carrying out vacuum filtration on the mixture, adding deionized water into the filtered silk fibroin, repeatedly soaking, filtering, and then putting the solution into a dialysis bag with the molecular weight cutoff of 8000 for dialysis for 24 hours to obtain a pure silk fibroin solution.
F) And (3) freeze-drying the obtained silk fibroin solution to obtain silk fibroin powder.
Wherein, the preparation of PEG-alkaline protease: weighing alkaline protease 0.15g, PEG (1000MW polyethylene glycol) 0.17g, K2HPO40.16g of (dipotassium hydrogen phosphate) is dissolved in 10mL of deionized water, the temperature is kept for 2h at 40 ℃, then the mixture is frozen for 4h at the temperature of minus 20 ℃, and PEG-alkaline protease powder is obtained after freeze drying for 96h for standby.
Preparation of ionic liquid: adding 137mL of 2-methallyl chloride and 80mL of N-methylimidazole into a 250mL three-neck flask, stirring and refluxing for 3h in an oil bath at 80 ℃, removing excessive 2-methallyl chloride by adopting rotary evaporation after the reaction is finished to obtain light yellow transparent liquid, namely 1- (2-methyl) allyl-3-methylimidazole chloride ionic liquid, and unfreezing for later use after freeze drying for 24 h.
Preparing silk fibroin into a silk fibroin solution with the weight percent of 10 percent.
(3) Stirring the fibroin solution and the polyvinyl alcohol solution for 60min at 20 ℃, wherein the stirring speed is 1000r/min, and dropwise adding 0.2 wt% of each of glycerol and glutaraldehyde for mixing and ultrasonic treatment to form a uniform fibroin-polyvinyl alcohol mixed solution;
(4) carrying out anti-sticking treatment on a substrate silicon base used for the multilayer composite artificial skin, placing a monocrystalline silicon piece in an evaporation vessel, adding a small amount of trimethylchlorosilane liquid, sealing the evaporation vessel, and evaporating for 10min in the evaporation vessel to be used as an anti-sticking layer; (ii) a
(5) Forming a basement membrane from the fibroin-polyvinyl alcohol mixed solution by using a spin coating method, taking the basement membrane as a conductive intermediate layer, and freeze-drying; wherein the fibroin-polyvinyl alcohol mixed solution needs to be subjected to ultrasonic oscillation treatment for 20min, and is subjected to film formation by a freeze drying method. The basement membrane needs to be subjected to post-treatment, and the treatment method is to treat the dried nanofiber sample for 20min under the air pressure of 1 MPa.
(6) Removing the formed base film under the condition of water vapor, drying at 60 ℃ and absorbing moisture at room temperature for 3-5 times;
(7) dispersing graphene in deionized water, and dropwise adding AgNO under the ultrasonic condition3After reacting for a period of time, adding NaOH solution to adjust the pH value of the solution to 11-12, and then reacting the mixed solution in an oil bath; wherein the graphene is obtained by a vapor deposition method or a mechanical exfoliation method. The concentration of the graphene dispersion liquid is 0.5mol/L, and AgNO3The concentration of the solution is 0.5mol/L, and the volume ratio of dropwise adding is 1; NaOH solution is 0.1mol/L, oil bath temperature is 60 ℃, and reaction time is 35 min.
(8) After the reaction is finished, centrifuging the mixed solution to obtain a precipitate, and then respectively centrifuging and washing by using absolute ethyl alcohol and deionized water, wherein the condition of centrifuging and washing is that centrifuging is carried out for 3 times at 5000rpm, and centrifuging for 3min each time. Vacuum drying to obtain the graphene-silver nano composite material;
(9) and plating the graphene-silver nano composite material on the treated basement membrane by using a vapor deposition method to obtain the attached flexible artificial skin receptor. The vapor deposition conditions are that graphene gas is diluted to 2% by argon, the flow is controlled to be 180mL/min, the growth temperature is 150 ℃, the reaction pressure is 75Pa, and the growth time is 3 min.
Example 2
A preparation method of an attached flexible artificial skin receptor adopts the following steps:
(1) heating polyvinyl alcohol to dissolve into 8 wt% water solution, stirring for 40min to dissolve completely, adding 0.2 wt% ethanol to form mixed solution; wherein, the alcoholysis degree of the polyvinyl alcohol is less than 88 percent of the mole fraction, and the heating temperature is less than 40 ℃.
(2) Extracting fibroin:
A) weighing 4g of mulberry silk as a sample, washing with deionized water, removing surface pollutants, and drying.
B) Oven dried samples were dried in a 1: 100 bath containing 0.5% Na2PO4And 1% of C17H35Boiling the mixed solution of COONa for 30min, and degumming twice.
C) After degumming, rubbing the sample with deionized water for more than 4 times, and putting the sample into a 60 ℃ oven to obtain dry fibroin fibers.
D) Weighing 2g of dry silk fibroin fiber, immersing the silk fibroin fiber into ionic liquid according to a bath ratio of 1: 40, simultaneously adding 0.15g of PEG-alkaline protease powder, stirring the mixture in an oil bath at 40 ℃ for 6 hours to obtain a silk fibroin/ionic liquid solution, and then preserving the heat in the oil bath at the temperature of more than 80 ℃ for at least 30min for enzyme deactivation.
E) And (3) when the silk fibroin/ionic liquid solution is cooled to room temperature, adding absolute ethyl alcohol, and repeatedly soaking to separate out silk fibroin. And (3) carrying out vacuum filtration on the mixture, adding deionized water into the filtered silk fibroin, repeatedly soaking, filtering, and then putting the solution into a dialysis bag with the molecular weight cutoff of 8000 for dialysis for 24 hours to obtain a pure silk fibroin solution.
F) And (3) freeze-drying the obtained silk fibroin solution to obtain silk fibroin powder.
Wherein, the preparation of PEG-alkaline protease: weighing alkaline protease 0.15g, PEG (1000MW polyethylene glycol) 0.17g, K2HPO40.16g of (dipotassium hydrogen phosphate) is dissolved in 10mL of deionized water, the temperature is kept for 2h at 40 ℃, then the mixture is frozen for 4h at the temperature of minus 20 ℃, and PEG-alkaline protease powder is obtained after freeze drying for 96h for standby.
Preparation of ionic liquid: adding 137mL of 2-methallyl chloride and 80 mLN-methylimidazole into a 250mL three-neck flask, stirring and refluxing for 3h in an oil bath at 80 ℃, removing excessive 2-methallyl chloride by adopting rotary evaporation after the reaction is finished to obtain light yellow transparent liquid, namely 1- (2-methyl) allyl-3-methylimidazole chloride ionic liquid, and unfreezing for later use after freeze drying for 24 h.
Preparing silk fibroin into a silk fibroin solution with the weight percent of 10 percent.
(3) Stirring the fibroin solution and the polyvinyl alcohol solution for 80min at 20 ℃, wherein the stirring speed is 500r/min, and dropwise adding 0.4 wt% of each of glycerol and glutaraldehyde for mixing and ultrasonic treatment to form a uniform fibroin-polyvinyl alcohol mixed solution;
(4) carrying out anti-sticking treatment on a substrate silicon base used for the multilayer composite artificial skin, placing a monocrystalline silicon piece in an evaporation vessel, adding a small amount of trimethylchlorosilane liquid, sealing the evaporation vessel, and evaporating for 10min in the evaporation vessel to be used as an anti-sticking layer; (ii) a
(5) Forming a basement membrane from the fibroin-polyvinyl alcohol mixed solution by using a spin coating method, taking the basement membrane as a conductive intermediate layer, and freeze-drying; wherein the fibroin-polyvinyl alcohol mixed solution needs to be subjected to ultrasonic oscillation treatment for 20min, and is subjected to film formation by a freeze drying method. The basement membrane needs to be subjected to post-treatment, and the treatment method is to treat the dried nanofiber sample for 10min under the air pressure of 1 MPa.
(6) Removing the formed base film under the condition of water vapor, drying at 40 ℃ and absorbing moisture at room temperature for 3 times;
(7) dispersing graphene in deionized water, and dropwise adding AgNO under the ultrasonic condition3After reacting for a period of time, adding NaOH solution to adjust the pH value of the solution to 11-12, and then reacting the mixed solution in an oil bath; wherein the graphene is obtained by a vapor deposition method or a mechanical exfoliation method. The concentration of the graphene dispersion liquid is 0.1mol/L, and AgNO3The concentration of the solution is 0.1mol/L, and the volume ratio of dropwise adding is 0.5; NaOH solution is 0.1mol/L, oil bath temperature is 40 ℃, and reaction time is 50 min.
(8) After the reaction is finished, the mixed solution is centrifuged to obtain a precipitate, and then the precipitate is respectively centrifuged and washed by absolute ethyl alcohol and deionized water, wherein the centrifugation and washing conditions are 3000rpm for 5 times, and each centrifugation is 2 min. Vacuum drying to obtain the graphene-silver nano composite material;
(9) and plating the graphene-silver nano composite material on the treated basement membrane by using a vapor deposition method to obtain the attached flexible artificial skin receptor. The vapor deposition conditions are that graphene gas is diluted to 2% by argon, the flow is controlled to be 100mL/min, the growth temperature is 100 ℃, the reaction pressure is 50Pa, and the growth time is 1 min.
Example 3
A preparation method of an attached flexible artificial skin receptor adopts the following steps:
(1) heating polyvinyl alcohol to dissolve into 10 wt% water solution, stirring for 60min to dissolve completely, and adding 1 wt% ethanol to form mixed solution; wherein, the alcoholysis degree of the polyvinyl alcohol is less than 88 percent of the mole fraction, and the heating temperature is less than 40 ℃.
(2) Extracting fibroin:
A) weighing 4g of mulberry silk as a sample, washing with deionized water, removing surface pollutants, and drying.
B) Oven dried samples were dried in a 1: 100 bath containing 0.5% Na2PO4And 1% of C17H35Boiling the mixed solution of COONa for 30min, and degumming twice.
C) After degumming, rubbing the sample with deionized water for more than 4 times, and putting the sample into a 60 ℃ oven to obtain dry fibroin fibers.
D) Weighing 2g of dry silk fibroin fiber, immersing the silk fibroin fiber into ionic liquid according to a bath ratio of 1: 40, simultaneously adding 0.15g of PEG-alkaline protease powder, stirring the mixture in an oil bath at 40 ℃ for 6 hours to obtain a silk fibroin/ionic liquid solution, and then preserving the heat in the oil bath at the temperature of more than 80 ℃ for at least 30min for enzyme deactivation.
E) And (3) when the silk fibroin/ionic liquid solution is cooled to room temperature, adding absolute ethyl alcohol, and repeatedly soaking to separate out silk fibroin. And (3) carrying out vacuum filtration on the mixture, adding deionized water into the filtered silk fibroin, repeatedly soaking, filtering, and then putting the solution into a dialysis bag with the molecular weight cutoff of 8000 for dialysis for 24 hours to obtain a pure silk fibroin solution.
F) And (3) freeze-drying the obtained silk fibroin solution to obtain silk fibroin powder.
Wherein, the preparation of PEG-alkaline protease: weighing alkaline protease 0.15g, PEG (1000MW polyethylene glycol) 0.17g, K2HPO4(dipotassium hydrogen phosphate) 0.16g of the PEG-alkaline protease powder is dissolved in 10mL of deionized water, the temperature is kept at 40 ℃ for 2h, then the mixture is frozen at-20 ℃ for 4h, and the PEG-alkaline protease powder is obtained after freeze drying for 96h for later use.
Preparation of ionic liquid: adding 137mL of 2-methallyl chloride and 80mL of LN-methylimidazole into a 250mL three-neck flask, stirring and refluxing for 3h in an oil bath at 80 ℃, removing excessive 2-methallyl chloride by rotary evaporation after the reaction is finished to obtain light yellow transparent liquid, namely 1- (2-methyl) allyl-3-methylimidazole chloride ionic liquid, and unfreezing for later use after freeze drying for 24 h.
Preparing silk fibroin into a silk fibroin solution with the weight percent of 10 percent.
(3) Stirring the fibroin solution and the polyvinyl alcohol solution for 90min at 30 ℃, wherein the stirring speed is 1500r/min, and dropwise adding 0.5 wt% of each of glycerol and glutaraldehyde for mixing and ultrasonic treatment to form a uniform fibroin-polyvinyl alcohol mixed solution;
(4) carrying out anti-sticking treatment on a substrate silicon base used for the multilayer composite artificial skin, placing a monocrystalline silicon piece in an evaporation vessel, adding a small amount of trimethylchlorosilane liquid, sealing the evaporation vessel, and evaporating for 10min in the evaporation vessel to be used as an anti-sticking layer; (ii) a
(5) Forming a basement membrane from the fibroin-polyvinyl alcohol mixed solution by using a spin coating method, taking the basement membrane as a conductive intermediate layer, and freeze-drying; wherein the fibroin-polyvinyl alcohol mixed solution needs to be subjected to ultrasonic oscillation treatment for 20min, and is subjected to film formation by a freeze drying method. The basement membrane needs to be subjected to post-treatment, and the treatment method is to treat the dried nanofiber sample for 30min under the air pressure of 1 MPa.
(6) Removing the formed base film under the condition of water vapor, drying at 40-80 ℃ and repeatedly treating for 3-5 times by absorbing moisture at room temperature;
(7) dispersing graphene in deionized water, and dropwise adding AgNO under the ultrasonic condition3After reacting for a period of time, adding NaOH solution to adjust the pH value of the solution to 11-12, and then reacting the mixed solution in an oil bath; wherein the graphene is obtained by a vapor deposition method or a mechanical exfoliation method. The concentration of the graphene dispersion liquid is 1mol/L, and AgNO3The concentration of the solution is 1mol/L, and the volume ratio of the solution to be added isIs 2; NaOH solution is 0.1mol/L, oil bath temperature is 80 ℃, and reaction time is 20 min.
(8) After the reaction is finished, the mixed solution is centrifuged to obtain a precipitate, and then the precipitate is respectively centrifuged and washed by absolute ethyl alcohol and deionized water, wherein the centrifugation and washing conditions are 8000rpm for 2 times, and each centrifugation is 5 min. Vacuum drying to obtain the graphene-silver nano composite material;
(9) and plating the graphene-silver nano composite material on the treated basement membrane by using a vapor deposition method to obtain the attached flexible artificial skin receptor. The vapor deposition conditions are that graphene gas is diluted to 2% by argon, the flow is controlled to be 250mL/min, the growth temperature is 200 ℃, the reaction pressure is 100Pa, and the growth time is 6 min.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. A preparation method of an attached flexible artificial skin receptor is characterized by comprising the following steps:
(1) heating polyvinyl alcohol to dissolve the polyvinyl alcohol into an aqueous solution, stirring the aqueous solution to completely dissolve the polyvinyl alcohol, and adding ethanol to obtain a polyvinyl alcohol solution;
(2) extracting silk fibroin and preparing a silk fibroin solution;
(3) stirring the fibroin solution and the polyvinyl alcohol solution, dropwise adding glycerol and glutaraldehyde, mixing and ultrasonically treating to form a uniform fibroin-polyvinyl alcohol mixed solution;
(4) carrying out anti-sticking treatment on the substrate silicon base: placing a monocrystalline silicon wafer in an evaporation pan, adding trimethylchlorosilane liquid, sealing the evaporation pan, and evaporating for 8-12min in the evaporation pan to serve as an anti-sticking layer;
(5) forming a basement membrane from the fibroin-polyvinyl alcohol mixed solution by using a spin coating method, taking the basement membrane as a conductive intermediate layer, and drying;
(6) removing the formed base film under the condition of water vapor, drying at 40-80 ℃ and repeatedly treating for 3-5 times by absorbing moisture at room temperature;
(7) dispersing graphene in deionized water, and dropwise adding AgNO under ultrasonic condition3After reacting for a period of time, adding NaOH solution to adjust the pH value of the solution to 11-12, and then reacting the mixed solution in an oil bath;
(8) after the reaction is finished, centrifuging the mixed solution to obtain a precipitate, respectively centrifuging and washing the precipitate by using absolute ethyl alcohol and deionized water, and drying the precipitate in vacuum to obtain the graphene-silver nano composite material;
(9) and plating the graphene-silver nano composite material on the treated basement membrane by using a vapor deposition method to obtain the attached flexible artificial skin receptor.
2. The method for preparing a flexible artificial skin receptor according to claim 1, wherein in the step (1), the alcoholysis degree of the polyvinyl alcohol is less than 88 mol%, the heating temperature is less than 40 ℃, the concentration of the polyvinyl alcohol solution is 6-10 wt%, and the amount of the ethanol added is 0.5-5 wt%.
3. The method for preparing an attached flexible artificial skin receptor according to claim 1, wherein in the step (2), the fibroin is obtained by degumming, enzymolysis in ionic liquid, dialysis and freeze drying.
4. The method for preparing an attached flexible artificial skin receptor according to claim 1, wherein in the step (3), the fibroin solution and the polyvinyl alcohol solution are stirred and mixed at 20-40 ℃, the stirring rate is 500-1500 r/min, the stirring time is 60-120 min, the addition amount of glycerol is 0.2-1 wt%, and the addition amount of glutaraldehyde is 0.2-1 wt%.
5. The method for preparing an attached flexible artificial skin receptor according to claim 1, wherein in the step (5), the fibroin-polyvinyl alcohol mixed solution is subjected to ultrasonic oscillation treatment for 20min, and a freeze-drying method is used for film formation.
6. The method for preparing an attached flexible artificial skin receptor according to claim 1 or 5, wherein in the step (5), the basement membrane is post-treated by treating the dried nanofiber sample at 1MPa for 10-30 min.
7. The method for preparing a flexible artificial skin receptor according to claim 1, wherein in the step (7), the graphene is obtained by vapor deposition or mechanical exfoliation.
8. The method for preparing the attached flexible artificial skin receptor according to claim 1 or 7, wherein in the step (7), the concentration of the graphene dispersion liquid is 0.1-1mol/L, AgNO3The concentration of the solution is 0.1-1mol/L, and the volume ratio of dropwise adding is 0.5-2; NaOH solution is 0.1mol/L, the oil bath temperature is 40-80 ℃, and the reaction time is 20-50 min.
9. The method as claimed in claim 1, wherein the step (8) is performed under centrifugation washing conditions of 3000-8000rpm for 2-5 times, each time for 2-5 min.
10. The method as claimed in claim 1, wherein in the step (9), the vapor deposition conditions include that the graphene gas is diluted to 2% with argon, the flow rate is controlled to be 250mL/min, the growth temperature is 100-.
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