CN114470335A - Preparation method of safe, nontoxic and environment-friendly intelligent bionic skin - Google Patents

Abstract

The invention belongs to the field of medical and artificial intelligent skin materials, and particularly relates to intelligent bionic skin with an environmental response function and a preparation method thereof. According to the invention, a self-assembly structure is formed on the surface of a solid through hyaluronic acid and graphene oxide in a certain proportion, so that the safe, non-toxic and environment-friendly intelligent bionic skin with an environment response function is obtained. The intelligent bionic skin obtained by the invention can effectively respond to touch, environmental moisture and light intensity, and has high sensitivity, high repeatability and good biocompatibility. The preparation method of the safe, non-toxic and environment-friendly intelligent bionic skin has the advantages of short route and easy implementation, can be used for producing bionic skin products in batches, and ensures the safety and reliability to human bodies and environment by using safe and non-toxic hyaluronic acid and graphene oxide as raw materials. The intelligent skin obtained by the method can be used for repairing damaged parts of the skin, can also be used for preparing surface sensing layers of wearable equipment and robots, and has wide industrial application prospects.

Description

A kind of preparation method of safe, non-toxic and environmentally friendly intelligent bionic skin

technical field

The invention belongs to the field of medical and artificial intelligence skin materials, and in particular relates to an intelligent bionic skin with an environment response function and a preparation method thereof.

Background technique

Smart biomimetic skins have received extensive attention due to their unique response and feedback capabilities, such as electronic skins, artificial hydrophobic/hydrophilic surfaces, deformable actuators, etc. In order to meet different market demands and pursue more product functions, higher and higher requirements are placed on smart materials. Among them, some intelligent bionic skin materials can transmit light intensity, temperature, humidity and other stimuli through electrical signals to achieve the function of simulating human skin. Using graphene as a cross-linking agent to prepare intelligent bionic skin is an important direction worth exploring. The high electrical conductivity and photothermal conversion properties of graphene also contribute to the construction of intelligent biomimetic skins responsive to multiple stimuli environments.

In recent years, in the field of biomimetic smart skin, most of them are based on a single stimulus-response signal. Liang et al. (Phys.Chem, 2009, 113, 9921-9927) used sulfonated graphene and thermoplastic polyurethane materials to prepare highly sensitive graphene-based light-stimulus-responsive thin-film smart skin materials, realizing the response to infrared light . Wan et al. (ACS Appl Mater Interfaces, 2017, 9, 25559-25570) developed a pressure response by combining polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) polymers complexed with cellulose nanocrystals/Fe ³⁺ The type of hydrogel smart skin material can be used as a wearable sensor smart material to monitor human respiration and pulse. However, it is difficult for this hydrogel-type smart skin to respond to weak pressure, and the material has poor biocompatibility. These two types of smart skins have certain defects. They both contain refractory polymers, which will cause certain pollution to the environment. Zhao et al. (Advanced Materials, 2015, 27, 4351-4357) prepared a gradient graphene oxide thin film smart skin, which can generate current and voltage signal output under moisture stimulation, and used to detect human respiration. Although the related research on intelligent bionic skin is gradually increasing, the types of stimulus responses are still relatively single, and there is still a lack of biocompatibility and biodegradability. Therefore, it is urgent to construct a dual, multiple, and environment-friendly intelligent bionic skin to adapt to the rapid development of biomedicine and intelligent machine fields.

For the above problems, the present invention skillfully utilizes the van der Waals force, hydrogen bond and ionic interaction between natural macromolecules, namely hyaluronic acid and graphene oxide, to form a self-assembled structure on the solid surface, so as to obtain a safe, free and environmentally responsive structure. Toxic, environmentally friendly smart bionic skin. By testing the changes of the electrical signals caused by the changes of touch, environmental humidity and light intensity, the smart bionic skin can feedback the sensitivity of the smart skin.

In the present invention, graphene oxide is derived from the oxidation of natural graphite, and is combined with safe and non-toxic hyaluronic acid to ensure the safety, air permeability and comfort of the material, and the preparation process is simple, green, environmentally friendly and pollution-free, and the overall material is harmful to the human body. Safe and environmentally friendly, it is suitable for human skin repair, wearable devices and robotic surface bionic skin sensing, suitable for mass and large-scale production, and has broad commercial application prospects.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide an intelligent skin with bionic effect and environment response function and a preparation method thereof. The response layer material is graphene oxide doped with hyaluronic acid, and the two form a self-assembled structure on the surface of the solid substrate.

The method for preparing a safe, non-toxic and environmentally friendly intelligent bionic skin proposed by the present invention comprises the following specific steps:

(1) prepare a mixed solution containing graphene oxide and hyaluronic acid (or its sodium salt, potassium salt);

(2) adding auxiliary agent to the mixed solution prepared above, mixing and dissolving evenly;

(3) The above-prepared mixture is prepared on a solid substrate to form a film, that is, a biomimetic skin with an environment-responsive function, safe, non-toxic and environment-friendly is obtained.

The preparation method of the above-mentioned safe, non-toxic and environmentally friendly intelligent bionic skin, the step (1) of preparing a mixed solution containing graphene oxide and hyaluronic acid (or its sodium salt, potassium salt) is to prepare Graphene oxide and hyaluronic acid (or its sodium salt, potassium salt) are added to the water to prepare a mixed solution; the preparation method of the mixed solution can also use water as a solvent to prepare 0.05～10g L ^-1 of oxidized solution respectively. Graphene dispersion liquid and 0.01-15 g·L ^-1 hyaluronic acid (or its sodium salt, potassium salt) solution, and then mixed to obtain a mixed liquid. Based on the molecular weight of hyaluronic acid, the time it takes to dissolve in water is different. Professionals know that this macromolecule similar to hyaluronic acid, including some of the adjuvants mentioned later, needs a swelling process when it dissolves in water, so the time used is different. , some are completely dissolved in a few hours, and some need more than 12h, so there should be enough time to completely dissolve these substances when preparing the mixed solution.

In the above-mentioned preparation method of the safe, non-toxic and environmentally friendly intelligent bionic skin, the dosage (mass) ratio of the graphene oxide and hyaluronic acid (or its sodium salt and potassium salt) is 100:1-0.05:1.

In the above-mentioned preparation method of a safe, non-toxic and environmentally friendly intelligent bionic skin, the addition of an auxiliary agent in the step (2) is to selectively add an auxiliary agent to the mixed solution to improve the interfacial performance and production of the mixed solution. The fluidity of the film and improve the strength of the film. The above-mentioned auxiliary agent is a surfactant, which is selected from methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyanionic cellulose, hydroxypropyl cellulose, hydroxypropyl carboxymethyl cellulose , Water-soluble starch, starch ester ether, amylopectin, amylose, dextrin, carboxymethyl starch, hydroxypropyl starch, cross-linked starch, alkyl glycosides, sodium alginate, propylene glycol alginate, xanthan gum , Arabic gum, agar gum, gelatin, pectin, carrageenan, chitosan, tamarind gum, guar gum, polyvinyl alcohol, polyethylene glycol, povidone, fatty acid sodium soap, fatty acid potassium soap, fatty alcohol Sulfate, alkyl aryl sulfonate (such as sodium dodecyl p-toluenesulfonate, sodium lauryl sulfate), quaternary ammonium salt (such as benzalkonium chloride, benzalkonium bromide), phospholipids, N-carboxymethyl Base-N,N-dimethyldodecyl betaine, fatty acid glycerides, fatty acid sucrose esters, sorbitan fatty acid esters, oxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid esters One or more of oxyethylene-polyoxypropylene copolymers can be used to improve the uniformity, fluidity and film-forming properties of the mixed solution. The amount of the surfactant is 0-10% of the mass of the mixed solution.

In the above-mentioned preparation method of safe, non-toxic and environmentally friendly intelligent bionic skin, the substrate for preparing the film is glass, ceramics, paper, non-woven fabric, rubber, plastic, and the prepared film can be peeled off from the substrate as an artificial intelligence For skin use, it can also be used together with a base as a smart skin. For example, a composite structure prepared from a non-woven fabric can be directly used as a skin surface or a robot surface, which not only increases the strength and air permeability of the material, but also simplifies the preparation process. It can be used without peeling, forming a non-woven fabric reinforced Artificial skin.

In the above-mentioned preparation method of safe, non-toxic and environmentally friendly intelligent bionic skin, the method of preparing film is drop coating, spin coating, dip coating and spray coating on the surface of solid substrate, which can be a one-time preparation of thin film, or a After repeated drop coating, spin coating, dip coating or spray coating, a film with a certain thickness is obtained through layer-by-layer self-assembly.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The preparation method of the safe, non-toxic and environmentally friendly intelligent bionic skin of the present invention is obtained by self-assembly of safe and non-toxic hyaluronic acid and graphene oxide according to a certain proportion, and utilizes hyaluronic acid and graphite oxide. The van der Waals forces, hydrogen bonds and ionic interactions between olefins utilize the electrical conductivity of graphene oxide after self-assembly and the degradability of raw materials to ensure the environmental response function of the material and the safety of the human body and the environment. and reliability.

(2) The addition of hyaluronic acid or its salt improves the structure of the smart bionic skin, increases the gas permeability of the material, and makes the wearable device more comfortable.

(3) The method for preparing the safe, non-toxic and environmentally friendly intelligent bionic skin of the present invention has a short route and is easy to implement, and can produce bionic skin products in batches.

(4) The method for preparing a safe, non-toxic and environmentally friendly intelligent bionic skin according to the present invention has strong universality, which can be used for the repair of skin damaged parts and the preparation of the surface sensing layer of robots, and has broad industrialization application prospects.

Description of drawings

Figure 1 is a schematic diagram of the structure of the smart skin.

Fig. 2 Touch response performance of smart skin.

Figure 3 Humidity responsive performance of smart skin.

Figure 4. Photoresponsive-capacitive performance of smart skin.

Figure 5 Light response-current performance of smart skin.

Figure 6 Light response-voltage performance of smart skin.

Detailed ways

In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, typical but non-limiting examples of the present invention are as follows:

Example 1

The solid substrate used in Example 1 was natural rubber. First, clean the surface of natural rubber (cut into 5cm diameter discs, 1mm thick) with deionized water to remove impurities on the surface; then, use 0.5g·L ^-1 sodium hydroxide solution to clean the surface to remove grease on the surface; finally, Wash and wipe with 95% ethanol solution, rinse twice with deionized water, and dry at 40°C for later use.

Using water as a solvent, respectively, prepare 5mL of graphene oxide dispersion with a concentration of 2g·L ^-1 and 5mL of a sodium hyaluronate solution with a concentration of 0.5g·L ^-1 (the molecular weight of sodium hyaluronate is 1 million Daltons), After mixing the two (volume ratio 1:1) uniformly, add auxiliary 5mg carboxymethyl cellulose, and ultrasonically mix for 1 hour to obtain a dispersion, which is spin-coated on the pretreated rubber substrate to form a film ( 2000r/min, 20s), consuming 6.5mL of dispersion liquid. The membrane was slowly dried at 50°C for 8 hours, and a flexible biomimetic skin with a thickness of 5.1 μm, which was environmentally responsive, safe, non-toxic and environmentally friendly, was obtained.

The left picture in Figure 1 is a schematic diagram of the electrode structure, and the right picture is a SEM image of a cross-section of the smart skin material. As shown in the figure, the thickness of the smart skin tested by scanning electron microscopy is about 5.1 μm, and the smart bionic skin is a sandwich-type layer-by-layer structure.

The performance test area of the smart skin is 1 × 1 cm ² , and the electrical performance changes are recorded using a Keysight multimeter 34460A from the United States. During measurement, the smart skin obtained in Example 1 was placed on the surface of the glass sheet substrate and fixed, and silver sheets were used at both ends as measuring electrodes to test the capacitance or voltage changes of the smart skin to obtain the touch response, environmental humidity response, and ambient light response. Multifactor response performance.

Figure 2 is a graph of the touch response performance of the smart skin. The smart skin can sensitively perceive the touch response, and can effectively feedback the capacitance change caused by the touch in the figure.

Figure 3 is a graph of the humidity response of the smart skin, which exhibits typical humidity sensing properties. Between 30% and 80% relative humidity, the smart skin voltage increases positively with the increase of humidity. At 80% relative humidity, the maximum voltage that can be generated per unit area is 0.3V. The humidity switching response test of the membrane was tested by humidifying-dehumidifying cycles in different humidity environments between 30% and 80%, and the membrane voltage increased with the increase of relative humidity in a wide humidity range. During each humidification-dehumidification cycle, the highest voltage the membrane can generate can reach 0.3V. The smart skin exhibits excellent repeatability with low hysteresis.

FIG. 4 is a schematic diagram of the capacitance change of the smart skin caused by the change of the light intensity. During the test, by changing the distance between the light source and the smart skin, the test area is 1×1cm ² . The capacitance performance changes with the light intensity, and is recorded by using the Keysight Multimeter 34460A in the United States. During the measurement, the intelligent bionic skin was placed on the surface of the glass substrate to be fixed, silver sheets were used as measuring electrodes at both ends, and a 300W xenon lamp was used as the light source to change the distance between the light source and the membrane material, and observe the change of the capacitance signal. The relationship between light intensity and capacitance is shown in the following table:

Distance (cm) Light Intensity(μw·cm^-2) Capacitance change (μF) 5 34400 0.2454 10 22300 0.1044 15 12750 0.0615 20 7240 0.0477

It can be seen from the above table that the capacitance generated by the smart skin device increases as the distance decreases, and increases as the light intensity increases. The smart skin has obvious changes in light intensity and shows good light response performance.

Figure 5 is a schematic diagram of the voltage change of the smart skin caused by the change of the light intensity. Under the light intensity of 22300μW·cm ^-2 xenon lamp, the voltage-time test was performed on the smart skin, the voltage change could reach 0.0052V, and there was no attenuation after repeated repetitions, and the smart skin showed good repeatability, sensitivity, and low hysteresis. sex.

FIG. 6 is a schematic diagram of the current change of the smart skin caused by the change of the light intensity. Under the light intensity of 22300μW·cm ^-2 xenon lamp, the current-time test was carried out on the smart skin, and the current change amount could reach 0.1059μA, and the smart skin showed good sensitivity.

Example 2

The solid substrate used in Example 2 is nitrile rubber, and the surface pretreatment method is the same as that in Example 1.

Add 20 mg of graphene oxide to 10 mL of water, and ultrasonically disperse it uniformly for 40 minutes, then add 50 mg of sodium hyaluronate (molecular weight 1 million Daltons), stir and dissolve to obtain a uniform dispersion, and place the obtained dispersion in the pretreated rubber. A film is formed by blade coating on the substrate, and dried at 50 °C to obtain a safe, non-toxic and environmentally friendly flexible bionic skin with a film thickness of 0.2 mm and an environment-responsive function. The prepared film is well bonded to the substrate without peeling off, and can be used together with the substrate as a smart skin.

Example 3

The solid substrate used in Example 3 was a polystyrene disc. Firstly, the polystyrene discs (diameter 5cm, thickness 2mm) were cleaned with household detergent, rinsed with water, then washed in 0.5g·L ^-1 sodium hydroxide solution to further remove the grease on the surface, and then rinsed with water to remove Sodium hydroxide, put it into 95% ethanol solution for washing once, take it out, and dry it at 40°C for later use.

Prepare 5mL of graphene oxide dispersion with a concentration of 1g·L ^-1 and 1mL of a sodium hyaluronate solution with a concentration of 2g·L ^-1 respectively with water, mix the two (volume ratio 5:1) uniformly, and add 20mg of auxiliary agent. Gelatin and 5 mg of fatty alcohol polyoxyethylene ether (AEO) were stirred at room temperature for 1 hour, and the mixture was slowly heated to 50°C, and stirred and mixed at this temperature for 3 hours to obtain a uniform dispersion. 6 mL of liquid was drop-coated on the pretreated polystyrene substrate to form a film. After drying at 50°C, a flexible biomimetic skin with a thickness of 52 μm, which has an environment-responsive function, is safe, non-toxic and environmentally friendly, is obtained.

Example 4

The solid substrate used in Example 4 was a polytetrafluoroethylene sheet. The pretreatment method of the polytetrafluoroethylene surface (disk with a diameter of 4 cm and a thickness of 3 mm) is the same as that in Example 3.

Add 60 mg of graphene oxide to 10 mL of water, and after ultrasonication for 40 minutes to disperse uniformly, add 0.6 mg of sodium hyaluronate (molecular weight: 1.5 million Daltons), stir to dissolve, and obtain a uniform dispersion. Add auxiliary agent 5mg nonylphenol polyoxyethylene ether, and ultrasonically mix for 50 minutes to obtain a dispersion, which is sprayed on the polytetrafluoroethylene base for three times to form a film (after each sprayed film is dried at 50 ° C, the first Second spraying), the actual consumption of dispersion liquid 5.5mL. After peeling off from the PTFE-based substrate, a safe, non-toxic and environmentally friendly flexible biomimetic skin with a film thickness of 47 μm was obtained.

Example 5

The solid substrate used in Example 5 was polyethylene (5 cm in diameter, 0.1 mm in thickness), and the surface pretreatment method was the same as that in Example 3.

Add 5 mg of graphene oxide to 10 mL of water, and after 30 minutes of ultrasonic dispersion, add 100 mg of sodium hyaluronate (molecular weight 400,000 Daltons), stir and dissolve, and obtain a uniform dispersion. Add auxiliary agent 50mg sodium carboxymethyl cellulose, and ultrasonically mix for 1.5 hours to obtain a dispersion liquid, and the obtained dispersion liquid is drop-coated on the polyethylene base to form a film (drop-coating 2 times, each time 4mL dispersion liquid is consumed. The first drop After coating, it was slowly dried with an infrared lamp for 6 hours, then dripped again, and dried naturally for 12 hours) to obtain a safe, non-toxic and environmentally friendly flexible bionic skin with a film thickness of 120 μm and an environment-responsive function. The prepared film does not need to be peeled off and can be used as a smart skin together with a plastic substrate.

Example 6

The solid substrate used in Example 6 was a glass sheet (ordinary glass plate, 5 cm in diameter, 3 mm in thickness), and the surface pretreatment method was the same as that in Example 3.

Prepare 5mL of graphene oxide dispersion liquid with a concentration of 2g·L ^-1 and a 5mL concentration of 0.1g·L ^-1 sodium hyaluronate (molecular weight 1 million Daltons) solution with water respectively, and mix the two (volume ratio 1: 1) After homogeneous, add auxiliary 30mg chitosan and 2mg sodium dodecylbenzenesulfonate, stir and mix for 3 hours to obtain a homogeneous dispersion. Take 8 mL of the dispersion to form a film on a glass substrate, and slowly dry under an infrared lamp to make the molecules self-assemble. After peeling off from the glass substrate, a safe, non-toxic and environmentally friendly biomimetic skin with a film thickness of 0.1 mm and an environment-responsive function was obtained.

Example 7

The solid substrate used in Example 7 was a ceramic sheet (white, 3 cm in diameter, 4 mm in thickness), and its surface pretreatment method was the same as that in Example 3.

Prepare 2.5mL of graphene oxide dispersion with a concentration of 1g·L ^-1 and 2.5mL of a sodium hyaluronate solution with a concentration of 10g·L ^-1 (molecular weight 400,000 Daltons) with water, respectively, and mix the two (volume ratio 1 : 1) After homogenization. Add 0.5 g of povidone as an adjuvant, and stir and mix for 2.5 hours to obtain a dispersion. 2 mL of the obtained dispersion was spin-coated on a glass substrate (1000 r/min, 20 s), and dried under vacuum at 40°C. Then continue to use the same dispersion liquid 2mL spin coating (1000r/min, 20s) on this film to form a film, and slowly dry under a xenon lamp to form a second layer of self-assembled film. After peeling off from the glass substrate, a safe, non-toxic, and environmentally friendly bionic skin with a film thickness of 0.3 mm was obtained.

Example 8

The type of solid substrate used in Example 8 was nonwoven. First, use detergent to clean the non-woven fabric (non-woven fabric for napkins, cut into a 4×4cm ² square, about 0.3mm thick), rinse with water, rinse with 95% ethanol and acetone in turn, and rinse with deionized water , and then dried at 80°C for later use.

Add 60 mg of graphene oxide to 10 mL of water, and after ultrasonication for 40 minutes to disperse uniformly, add 15 mg of sodium hyaluronate (molecular weight: 1.2 million Daltons), stir and dissolve to obtain a uniform dispersion. Add 10 mg of sodium alginate as an auxiliary, and ultrasonically mix for 1 hour to obtain a dispersion. Dip the non-woven fabric in the obtained dispersion to form a film (the non-woven fabric is completely immersed in the material liquid, and slowly pulled out at a constant speed after 10 minutes), and dried at 40 ° C to obtain a safe, non-toxic and environmentally friendly product with environmental response function. flexible bionic skin. In this example, the non-woven fabric became part of the filler of the smart skin, increasing the strength of the film, and the prepared film was used as the smart skin together with the non-woven fabric substrate.

Example 9

The type of solid substrate used in Example 9 is non-woven fabric, and the pretreatment method of the non-woven fabric (polyester material, cut into a circle with a diameter of 5 cm, and a thickness of 0.2 mm) is the same as that in Example 8.

5 mL of graphene oxide solution with a concentration of 5 g·L ^-1 and 1 mL of a potassium hyaluronate solution with a concentration of 5 g·L ^-1 were prepared with water respectively, and the two were mixed (volume ratio 5:1) uniformly. Add auxiliary 15 mg hydroxypropyl starch and 5 mg lauryl dimethyl betaine, and ultrasonically mix for 1.5 hours to obtain a dispersion. The obtained dispersion droplets are coated on the non-woven fabric substrate (2 times of drop coating) to form a film. After each drop coating, it is dried at 50 ° C to obtain a safe, non-toxic and environmentally friendly film with a film thickness of 0.05mm and an environmental response function. flexible bionic skin. In this example, the non-woven fabric became part of the filler of the smart skin, increasing the strength of the film, and the prepared film was used as the smart skin together with the non-woven fabric substrate.

Example 10

The type of solid substrate used in Example 10 was mesoporous filter paper (cut into a 5 cm diameter circle) commonly used in laboratories.

Add 40 mg of graphene oxide to 10 mL of water, and after ultrasonication for 30 minutes to disperse uniformly, add 30 mg of sodium hyaluronate (molecular weight: 400,000 Daltons), stir to dissolve, and obtain a uniform dispersion. 15 mg of methyl cellulose and 5 mg of benzalkonium bromide as auxiliary agents were added, and the mixture was stirred and mixed for 2 hours to obtain a dispersion liquid. The obtained dispersion was sprayed on the filter paper for 3 times to form a film (drying with an infrared lamp after each drop coating, and then sprayed for the second time, the consumption of each spraying liquid was about 2mL), and the obtained film thickness was about 30 μm (higher than 30 μm). The thickness of the paper fiber layer) is an environmentally responsive, safe, non-toxic and environmentally friendly bionic skin. The paper enhances the mechanical strength of the smart film, which along with the paper base acts as a smart skin.

The intelligent biomimetic skins with environmental response functions prepared in Examples 2 to 10 have similar performance to the intelligent skin devices prepared in Example 1, as shown in Figures 2 to 6 .

Claims (8)

1. the preparation method of a kind of safe, nontoxic and environmentally friendly intelligent bionic skin, is characterized in that, it comprises the following steps: (1) prepare a mixed solution containing graphene oxide and hyaluronic acid (or its sodium salt, potassium salt); (2) adding an auxiliary agent to the mixed solution prepared in the above step (1), mixing and dissolving evenly; (3) The mixed solution obtained above is prepared into a film on a solid substrate, that is, a biomimetic skin with an environment-responsive function, safe, non-toxic and environment-friendly is obtained. 2. the preparation method of safe, non-toxic and environmentally friendly intelligent bionic skin according to claim 1, is characterized in that, the described preparation of step (1) contains graphene oxide and hyaluronic acid (or its sodium salt, potassium salt) The preparation method of the mixed solution is to add graphene oxide and hyaluronic acid (or its sodium salt, potassium salt) into the water to prepare a mixed solution; the preparation method of the mixed solution can also be water as a solvent, respectively 0.05-10 g·L ^-1 of graphene oxide dispersion liquid and 0.01-15 g·L ^-1 of hyaluronic acid (or its sodium salt, potassium salt) solution, and then mixed to obtain a mixed liquid. 3. the preparation method of the safe, nontoxic and environmentally friendly intelligent bionic skin according to claim 1 and 2, is characterized in that, the consumption (quality) of described graphene oxide and hyaluronic acid (or its sodium salt, potassium salt) ) ratio is 100:1 to 0.05:1. 4. the preparation method of the safe, non-toxic and environmentally friendly intelligent bionic skin according to claim 1, is characterized in that, adding auxiliary agent described in step (2) is to graphene oxide and hyaluronic acid (or its sodium) Add surfactant to the mixed solution of salt, potassium salt). 5. The surfactant according to claim 4, which is added in an amount of 0-10% of the mass of the mixed solution. 6. surfactant according to claim 4 is selected from methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyanionic cellulose, hydroxypropyl cellulose, hydroxypropyl carboxymethyl Cellulose, water-soluble starch, starch ester ether, amylopectin, amylose, dextrin, carboxymethyl starch, hydroxypropyl starch, cross-linked starch, alkyl glycosides, sodium alginate, propylene glycol alginate, yellow Original gum, gum arabic, agar gum, gelatin, pectin, carrageenan, chitosan, tamarind gum, guar gum, polyvinyl alcohol, polyethylene glycol, povidone, fatty acid sodium soap, fatty acid potassium soap, Fatty alcohol sulfates, alkylaryl sulfonates (such as sodium dodecyl p-toluenesulfonate, sodium lauryl sulfate), quaternary ammonium salts (such as benzalkonium chloride, benzalkonium bromide), phospholipids, N- Carboxymethyl-N,N-dimethyldodecyl betaine, fatty acid glycerides, fatty acid sucrose esters, sorbitan fatty acid esters, oxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters , one or more of polyoxyethylene-polyoxypropylene copolymers. 7. The method for preparing a safe, non-toxic and environmentally friendly intelligent bionic skin according to claim 1, wherein the solid substrate described in step (2) is glass, ceramics, paper, non-woven fabric, rubber, and plastic. 8. The preparation method of the safe, non-toxic and environmentally friendly intelligent bionic skin according to claim 1, wherein the film-making method described in the step (3) is to carry out drop coating, spin coating, dipping on the surface of the solid substrate Layer-by-layer self-assembly of coating, spraying, and repeating these coating methods.

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