CN107412872B - Preparation method of multilayer composite artificial skin sensor - Google Patents
Preparation method of multilayer composite artificial skin sensor Download PDFInfo
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- CN107412872B CN107412872B CN201710626806.5A CN201710626806A CN107412872B CN 107412872 B CN107412872 B CN 107412872B CN 201710626806 A CN201710626806 A CN 201710626806A CN 107412872 B CN107412872 B CN 107412872B
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Abstract
The invention relates to the field of sensors, and discloses a preparation method of a multilayer composite artificial skin sensor, which comprises the following steps: (1) treating graphene with HI/HAC solution, and then freeze-drying; (2) putting the mixture into toluene for ultrasonic crushing and centrifugal cleaning; (3) carrying silver on the graphene sponge solution; (4) centrifuging and washing the precipitate to obtain a graphene-silver nano composite material; (5) carrying out anti-sticking treatment on the substrate silicon base to form a non-stick layer; (6) extracting silk fibroin; (7) forming a film on a silicon wafer substrate by using an ethanol solution of silk fibroin and a medicament by using a spin coating method, and freeze-drying; (8) taking the graphene-silver nano composite material as an intermediate layer, spin-coating to form a film, and drying; (9) PDMS was formed into a film and dried to form an insulating layer. The artificial skin obtained by the method has a good function of promoting wound healing, can change resistance under the action of a certain external force, and has good physical and mechanical properties.
Description
Technical Field
The invention relates to the field of sensors, in particular to a preparation method of a multilayer composite artificial skin sensor.
Background
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 sensor is a film-shaped composite material which is added with an external stimulation sensing function and an electric signal transmission function on the basis of the original artificial skin. The sensor has certain sensing function for the change and stimulation of the external environment, for example, the temperature sensor can sense the change of the skin temperature, and the touch sensor can sense the deformation of the skin under the action of external force. However, the general problem of the current artificial skin sensor is that the physical and mechanical properties do not meet the use requirements.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a multilayer composite artificial skin sensor. The silk fibroin and PDMS with good biocompatibility are respectively used for preparing a bottom layer membrane and a surface layer membrane, and the graphene-silver nano composite material is used for preparing an intermediate membrane. The silk fibroin film is used as a skeleton to promote the growth of epidermal cells of the wound surface, and the added medicine and the sulfonated silk fibroin have good effects of stopping bleeding, sterilizing and promoting the growth of skin. The middle layer is made of micron-sized sheet graphene-silver nano composite materials, has excellent conductivity and electrochemical sensitivity, can change the resistance under the action of external force, and has good antibacterial effect. And because the sensor is formed by stacking micron-sized sheets, the sensor has excellent strength and tensile property in a certain range, and overcomes the common problems of the traditional artificial skin sensor.
The specific technical scheme of the invention is as follows: a preparation method of a multilayer composite artificial skin sensor comprises the following steps:
(1) grinding and crushing graphene, and adding the graphene into HI/HAC solution for freeze drying.
(2) And (3) putting the freeze-dried sample into toluene for ultrasonic crushing to obtain crushed graphene sponge, and centrifugally washing with deionized water.
(3) Dispersing graphene sponge in deionized water, and dropwise adding AgNO under the ultrasonic condition3After the solution is reacted, the pH value of the solution is adjusted to 11-12 by adding NaOH solution, and then the mixed solution is reacted under oil bath.
(4) And after the reaction is finished, centrifuging the mixed solution to obtain a precipitate, and then respectively centrifuging and washing with absolute ethyl alcohol and deionized water to obtain the graphene-silver nano composite material.
(5) And (2) carrying out anti-sticking treatment on the substrate silicon base used for the multilayer composite artificial skin, placing the monocrystalline silicon piece in an evaporation vessel, adding trimethylchlorosilane liquid, sealing the evaporation vessel, and evaporating for 8-12min in the evaporation vessel to be used as an anti-sticking layer.
(6) And (3) preparing silk fibroin.
(7) Mixing silk fibroin, antibacterial hemostatic wound healing promoting medicine and ethanol solution to obtain silk fibroin gel solution, performing ultrasonic oscillation treatment, forming silk fibroin film on silicon wafer substrate by spin coating method, and drying.
(8) Preparing the graphene-silver nano composite material into aqueous dispersion, performing ultrasonic dispersion, forming a film by using a spin coating method on the basis of a silk fibroin film to serve as a conductive intermediate layer, and drying the conductive intermediate layer in an oven at the temperature of 40-80 ℃.
(9) And (3) forming a PDMS film on the film by using a spin coating method, drying the PDMS film to form an insulating layer, and obtaining the multilayer composite artificial skin sensor.
According to the invention, graphene and Ag ions are prepared into a micron-scale sheet-shaped composite material to be used as an intermediate layer of the artificial skin, silk fibroin and a medicament are compounded to be used as a basement membrane of the artificial skin, and PDMS is dried to form a membrane to be used as an insulating outer layer of the artificial skin. Compared with the prior art, the method has the advantages of small environmental pollution and simple preparation method. The prepared artificial skin sensor has the advantages of wound healing promotion, external force response and good physical and mechanical properties.
Preferably, in the step (1), after the graphene is added to the HI/HAC solution for dispersion, the concentration of the graphene is 0.1g/mL-0.5g/mL, and the concentrations of HI and HAC in the HI/HAC solution are both 0.1-1 mol/L.
Preferably, in the step (2), the time of the ultrasonic treatment is 1h-4h, and the centrifugation and washing conditions are 3000-8000rpm for 2-5 times, and each time for 2-5 min.
Preferably, in the step (3), the concentration of the graphene sponge in the deionized water is 0.1-1mol/L, and AgNO3The concentration of the solution is 0.1-1mol/L, the graphene sponge solution and AgNO3The volume dosage ratio of the solution is 0.5-2: 1; the concentration of NaOH solution is 0.1mol/L, the oil bath temperature is 40-80 ℃, and the reaction time is 20-50 min.
The addition of the Ag nano particles can improve the antibacterial performance and the electrochemical sensitivity of the material, thereby achieving two purposes.
Preferably, in step (4), the centrifugal washing conditions are 3000-8000rpm for 2-5 times, and each time for 2-5 min.
Preferably, in the step (6), the silk 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 sample was dried at a 1:100 bath ratio in the presence of 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 (1000 MW 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.
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 is used as a buffering agent, so that an alkaline environment is maintained, the degumming efficiency is improved, and the damage to the silk cellulose is reduced. 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 (7), the ultrasonic oscillation treatment time is 15-25min, and the film is formed by a freeze drying method.
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 (7), the silk membrane is subjected to post-treatment, and the silk membrane is subjected to SO treatment2The surface is sulfonated by working gas, the treatment pressure is 15-25Pa, the discharge power is 25-35W, and the treatment time is 3-8 min.
The sulfonic acid group has excellent hemostatic effect, and the medical performance of the artificial skin can be improved by the sulfonation treatment of the silk film.
Preferably, in the steps (7), (8) and (9), the spin coating is performed at a rotation speed of 300-800rpm for 30-90s and at a drying temperature of 40-80 ℃.
Preferably, in the step (8), the graphene-silver nanocomposite is a micron-sized sheet material.
The micron-sized sheet material plays a role in simulating the buffering action of the crustacean biological shell under the stretching and shearing action of external force, and can have rebound resilience and conductivity in a wider stretching range.
Compared with the prior art, the invention has the beneficial effects that:
the silk fibroin and PDMS with good biocompatibility are respectively used for preparing a bottom layer membrane and a surface layer membrane, and the graphene-silver nano composite material is used for preparing an intermediate membrane. The silk fibroin film is used as a skeleton to promote the growth of epidermal cells of the wound surface, and the added medicine and the sulfonated silk fibroin have good effects of stopping bleeding, sterilizing and promoting the growth of skin. The middle layer is made of micron-sized sheet graphene-silver nano composite materials, has excellent conductivity and electrochemical sensitivity, can change the resistance under the action of external force, and has good antibacterial effect. And because the sensor is formed by stacking micron-sized sheets, the sensor has excellent strength and tensile property in a certain range, and overcomes the common problems of the traditional artificial skin sensor.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a multilayer composite artificial skin sensor comprises the following steps:
(1) 5g of graphene is ground and crushed, and then added into 100mL of 1mol/L HI/HAC (1: 1) solution, and the mixture is stirred, mixed uniformly and then freeze-dried.
(2) And putting the freeze-dried sample into 300mL of toluene, performing ultrasonic treatment for 3h to obtain a crushed graphene sponge, and performing centrifugal washing by using deionized water. Wherein the ultrasonic time is 2.5h, and the condition of centrifugal washing is that the centrifugation is carried out for 4 times at 5000rpm, and each centrifugation is carried out for 3 min.
(3) Dispersing graphene sponge in deionized water to prepare 0.5mol/L solution, and dropwise adding 50mL of 0.5mol/LAgNO under the ultrasonic condition3After the solution is reacted for a period of time, the pH value of the solution is adjusted to 10 by adding 0.1mol/L NaOH solution, and then the mixed solution is reacted for 30min under the condition that the oil bath temperature is 60 ℃.
(4) And after the reaction is finished, centrifuging the mixed solution to obtain a precipitate, and then respectively centrifuging and washing with absolute ethyl alcohol and deionized water to obtain the micron-grade flaky graphene-silver nano composite material. Wherein the ultrasonic time is 2.5h, and the condition of centrifugal washing is that the centrifugation is carried out for 4 times at 5000rpm, and each centrifugation is carried out for 3 min.
(5) And carrying out anti-sticking treatment on a substrate silicon base used by the flexible composite film, placing the 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.
(6) The preparation method of the silk fibroin comprises the following steps:
A) weighing 4g of mulberry silk as a sample, washing with deionized water, removing surface pollutants, and drying.
B) Oven-dried sample was dried at a 1:100 bath ratio in the presence of 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 (1000 MW 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.
(7) Preparing ethanol solution from silk fibroin and antibacterial hemostatic wound healing promoting medicine, treating with ultrasonic oscillation for 20min, forming film on silicon wafer substrate by spin coating method, freeze drying, treating at 1MPa for 10min, and treating with SO2The surface was sulfonated with a treatment pressure of 20Pa, a discharge power of 30W, and a treatment time of 5 min.
(8) Preparing the graphene-silver nano composite material into aqueous dispersion, performing ultrasonic dispersion, forming a film on the basis of a silk fibroin film by using a spin coating method, taking the film as a conductive intermediate layer, and drying the conductive intermediate layer in an oven at 80 ℃.
(9) And forming a PDMS film on the basis of the former film by using a spin coating method, and drying the PDMS film to be used as an insulating layer to obtain the multilayer composite artificial skin sensor. In steps (7) to (9), the spin coating was performed at 500rpm for 60 seconds at a drying temperature of 60 ℃.
Example 2
(1) 5g of graphene is ground and crushed, and then is added into 50mL of 1mol/L HI/HAC (1: 1) solution, and the mixture is stirred, mixed uniformly and then is frozen and dried.
(2) The frozen and dried sample is placed into 500mL toluene for 5h of ultrasonic treatment, and the precipitated product is added into deionized water for washing for 3 times. Wherein the ultrasonic time is 1h, and the centrifugal washing condition is 8000rpm for 5 times, each time for 2 min.
(3) Preparing 0.5mol/L aqueous solution from graphene sponge, and dropwise adding 100mL of 0.5mol/LAgNO into 50mL of dispersion liquid under the ultrasonic condition3After the solution is reacted for a period of time, the pH value of the solution is adjusted to 10 by adding 0.1mol/L alkaline solution, and then the mixed solution is reacted for 20min under the condition that the temperature of an oil bath is 80 ℃.
(4) And after the reaction is finished, centrifuging the mixed solution to obtain a precipitate, and then respectively centrifuging and washing the precipitate for 3 times by using absolute ethyl alcohol and deionized water to obtain the micron-grade flaky graphene-silver nanocomposite. Wherein the ultrasonic time is 1h, and the centrifugal washing condition is 8000rpm for 5 times, each time for 2 min.
(5) And carrying out anti-sticking treatment on a substrate silicon base used by the flexible composite film, placing the 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.
(6) The preparation method of the silk fibroin comprises the following steps:
A) weighing 4g of mulberry silk as a sample, washing with deionized water, removing surface pollutants, and drying.
B) Oven-dried sample was dried at a 1:100 bath ratio in the presence of 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, filling the solution into a dialysis bag with the cut-off molecular weight of 7000, and dialyzing 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 (1000 MW 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.
(7) Preparing the silk fibroin and the antibacterial hemostatic wound healing promotion medicine into an ethanol solution, carrying out ultrasonic oscillation treatment for 15min, forming a film on a silicon wafer substrate by using a spin coating method, and carrying out freeze drying and treatment for 30min under the air pressure of 1 MPa. Coating the silk fibroin film on SO2The surface was sulfonated with a treatment pressure of 20Pa, a discharge power of 25W, and a treatment time of 6 min.
(8) Preparing the graphene-silver nano composite material into aqueous dispersion, performing ultrasonic dispersion, forming a film on the basis of a silk fibroin film by using a spin coating method, taking the film as a conductive intermediate layer, and drying the conductive intermediate layer in an oven at 60 ℃.
(9) And forming a PDMS film on the basis of the former film by using a spin coating method, and drying the PDMS film to be used as an insulating layer to obtain the multilayer composite artificial skin sensor. In steps (7) to (9), the spin coating was performed at 300rpm for 90 seconds and at a drying temperature of 40 ℃.
Example 3
(1) 5g of graphene is ground and crushed, and then is added into 75mL of 1mol/L HI/HAC (1: 1) solution, and the mixture is stirred, mixed uniformly and then is frozen and dried.
(2) And putting the freeze-dried sample into 300mL of toluene, performing ultrasonic treatment for 5h, centrifuging, taking the precipitate, and centrifugally washing with deionized water. Wherein the ultrasonic time is 4h, and the centrifugation and washing conditions are 3000rpm for 2 times, and each centrifugation time is 5 min.
(3) Dispersing graphene sponge in deionized water to prepare 0.5mol/L solution, and dropwise adding 50mL of 0.5mol/LAgNO into 100mL of dispersion liquid under the ultrasonic condition3After the solution is reacted for a period of time, the pH value of the solution is adjusted to 10.7 by adding 0.1mol/L NaOH solution, and then the mixed solution is reacted for 30min under the condition that the oil bath temperature is 60 ℃.
(4) And after the reaction is finished, centrifuging the mixed solution to obtain a precipitate, and then respectively centrifuging and washing with absolute ethyl alcohol and deionized water to obtain the micron-grade flaky graphene-silver nano composite material. Wherein the ultrasonic time is 4h, and the centrifugation and washing conditions are 3000rpm for 2 times, and each centrifugation time is 5 min.
(5) And carrying out anti-sticking treatment on a substrate silicon base used by the flexible composite film, placing the 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.
(6) The preparation method of the silk fibroin comprises the following steps:
A) weighing 4g of mulberry silk as a sample, washing with deionized water, removing surface pollutants, and drying.
B) Oven-dried sample was dried at a 1:100 bath ratio in the presence of 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 cut-off molecular weight of 10000 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 (1000 MW 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.
(7) Preparing ethanol solution from silk fibroin and antibacterial hemostatic wound healing promoting medicine, treating with ultrasonic oscillation for 25min, forming film on silicon wafer substrate by spin coating method, freeze drying, treating at 1MPa for 20min, and treating with SO2The working gas of (2) sulfonating the surfaceAnd (4) treating at a treatment pressure of 20Pa, a discharge power of 35W and a treatment time of 5 min.
(8) Preparing the graphene-silver nano composite material into aqueous dispersion, performing ultrasonic dispersion, forming a film on the basis of a silk fibroin film by using a spin coating method, taking the film as a conductive intermediate layer, and drying the conductive intermediate layer in an oven at 70 ℃.
(9) And forming a PDMS film on the basis of the former film by using a spin coating method, and drying the PDMS film to be used as an insulating layer to obtain the multilayer composite artificial skin sensor. In steps (7) to (9), the spin coating was carried out at 800rpm for 30 seconds and at a drying temperature of 80 ℃.
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 (7)
1. A preparation method of a multilayer composite artificial skin sensor is characterized by comprising the following steps:
(1) grinding and crushing graphene, and adding the graphene into HI/HAC solution for freeze drying; after graphene is added into the HI/HAC solution for dispersion, the concentration of the graphene is 0.1g/mL-0.5g/mL, and the concentrations of HI and HAC in the HI/HAC solution are both 0.1-1 mol/L;
(2) putting the freeze-dried sample into toluene for ultrasonic crushing to obtain crushed graphene sponge, and centrifugally washing with deionized water;
(3) dispersing graphene sponge in deionized water, and dropwise adding AgNO under the ultrasonic condition3After the solution reacts, the pH value of the solution is adjusted to 11-12 by adding NaOH solution, and then the mixed solution reacts for 20-50min under the condition of oil bath at the temperature of 40-80 ℃; the concentration of the graphene sponge in deionized water is 0.1-1mol/L, and AgNO3The concentration of the solution is 0.1-1mol/L, the graphene sponge solution and AgNO3The volume dosage ratio of the solution is 0.5-2: 1; the concentration of the NaOH solution is 0.1 mol/L;
(4) after the reaction is finished, centrifuging the mixed solution to obtain a precipitate, and then respectively centrifuging and washing with absolute ethyl alcohol and deionized water to obtain the graphene-silver nano composite material;
(5) 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 trimethylchlorosilane liquid, sealing the evaporation vessel, and evaporating for 8-12min in the evaporation vessel to be used as an anti-sticking layer;
(6) preparing silk fibroin;
(7) mixing silk fibroin, antibacterial hemostatic wound healing promoting medicine and ethanol solution to prepare silk fibroin gel solution, performing ultrasonic oscillation treatment, forming a silk fibroin film on a silicon wafer substrate by using a spin coating method, and drying; the silk fibroin film is subjected to post-treatment in SO2The surface is sulfonated by working gas, the treatment pressure is 15-25Pa, the discharge power is 25-35W, and the treatment time is 3-8 min;
(8) preparing a graphene-silver nano composite material into aqueous dispersion, performing ultrasonic dispersion, forming a film by using a spin coating method on the basis of a silk fibroin film to serve as a conductive intermediate layer, and drying the conductive intermediate layer in an oven at the temperature of 40-80 ℃;
(9) and (3) forming a PDMS film on the film by using a spin coating method, drying the PDMS film to form an insulating layer, and obtaining the multilayer composite artificial skin sensor.
2. The method for preparing the multilayer composite artificial skin sensor as claimed in claim 1, wherein in the step (2), the ultrasound time is 1h-4h, and the centrifugation and washing conditions are 3000-.
3. The method as claimed in claim 1, wherein in step (4), the centrifugation and washing conditions are 3000-8000rpm for 2-5 times, and each centrifugation time is 2-5 min.
4. The method for preparing the multilayer composite artificial skin sensor according to claim 1, wherein in the step (6), the silk fibroin is prepared by degumming, enzymolysis in ionic liquid, dialysis and freeze drying.
5. The method for preparing the multilayer composite artificial skin sensor according to claim 1, wherein in the step (7), the ultrasonic vibration treatment time is 15-25min, and the film is formed by a freeze drying method.
6. The method for preparing the multi-layer composite artificial skin sensor as claimed in claim 1, wherein the spin coating is performed at a rotation speed of 300-800rpm for 30-90s and at a drying temperature of 40-80 ℃ in steps (7), (8) and (9).
7. The method for preparing a multi-layered composite artificial skin sensor according to claim 1, wherein in the step (8), the graphene-silver nanocomposite material is a micron-sized sheet material.
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