Multifunctional graphene-based protein-based composite hydrogel and method of making the same

Abstract

The application discloses a protein-based composite gel based on multifunctional graphene and a preparation method thereof, and belongs to the technical field of biomedicine. Zinc MOF is hydrothermally synthesized on the surface of graphene oxide, the zinc MOF is in-situ grown between graphene layers to form an intercalation structure, and after calcination, the zinc MOF forms zinc oxide, which is coordinated with the carbon network of graphene, significantly improves the electron mobility, increases the specific surface area, can provide an attachment site for the formation of sodium alginate microcapsules, improves the adsorption of the sodium alginate microcapsules, the sodium alginate microcapsules provide support for corn protein, and the protein is prevented from being inactivated in the subsequent initiation polymerization process; the zinc oxide intercalated graphene forms a heterostructure, the zinc oxide is embedded between the graphene layers, the high conductivity of the graphene is retained, the broad-spectrum antibacterial property of the zinc oxide is exerted, and the inflammation at a spinal cord injury site can be inhibited.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of biomedicine, and particularly relates to a protein-based composite gel based on multifunctional graphene and a preparation method thereof. BACKGROUND

[0002] Traumatic spinal cord injury refers to that due to external force, a vertebral body is fractured, a vertebral body is dislocated in front, and then a spinal column is compressed, thereby causing permanent nerve dysfunction in different degrees. Most patients affected by SCI (spinal cord injury) are young and are main parts of social labor force. Long-term disability brings heavy burden to them. Therefore, it is very important to determine the repair intervention measures after SCI. The nerve dysfunction after SCI is caused by the interruption of spinal cord connection due to axon and nerve cell damage. One of the main reasons for the failure of later recovery is that the regenerated nerve axon cannot form connection with nerves below the damaged segment due to the formation of scars and cavities. With the latest progress of biological materials and tissue engineering disciplines, the application of implantable or injectable bioengineering scaffolds gradually becomes a promising strategy for SCI treatment. The composite graphene protein hydrogel system is constructed in the damaged area to fill the tissue defect, reduce the formation of glial scars, and increase the nerve conductivity through graphene, so as to guide the nerve growth direction, make the axon grow rapidly in the channel formed by the hydrogel, and thus promote the recovery of motor function after SCI.

[0003] As recorded in the existing document: Composite graphene protein hydrogel promotes the recovery of motor function after spinal cord injury in rats, acrylic acid, methoxyethyl acrylate, graphene and corn protein are placed in a high-temperature oven for free radical copolymerization reaction after an initiator potassium persulfate, and finally underwater viscous composite graphene protein hydrogel is obtained. However, the denaturation temperature of corn protein is 70-80 DEG C, and the persulfate free radical has strong oxidizing property, which greatly affects the activity of the protein. SUMMARY

[0004] The purpose of the present application is to provide a protein-based composite gel based on multifunctional graphene and a preparation method thereof. Zinc MOF is hydrothermally synthesized on the surface of graphene oxide, the zinc MOF grows in situ between the graphene layers to form an intercalation structure, and after calcination, the zinc MOF forms zinc oxide, which cooperates with the carbon network of graphene, significantly improves the electron mobility, increases the specific surface area, can provide attachment sites for the formation of sodium alginate microcapsules, improves the adsorption of sodium alginate microcapsules, and sodium alginate microcapsules provide support for corn protein to avoid inactivation of corn protein in the subsequent initiation polymerization process.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] The preparation method of the multifunctional graphene-based protein-based composite gel comprises the following steps:

[0007] The multifunctional graphene-based protein-based gel and deionized water are added into a reaction kettle, stirred at 20-25°C and 500-600 r / min for 10-15 min, then acrylic acid and methoxy ethyl acrylate are added, heated to 40-50°C under nitrogen protection, and continue to stir for 2-3 h, then the initiator potassium persulfate is added, and the above solution is poured into a mold, placed in a 7040 oven, and subjected to free radical copolymerization at 70-80°C to obtain the multifunctional graphene-based protein-based composite gel.

[0008] Further, the use amount ratio of the multifunctional graphene-based protein-based gel, deionized water, acrylic acid, methoxy ethyl acrylate and potassium persulfate is 80-82 g:800-900 mL:45-50 g:30-40 g:10-12 g.

[0009] Further, the specific preparation steps of the multifunctional graphene-based protein-based gel are as follows:

[0010] The graphene-based protein-based gel, anhydrous ethanol and deionized water are added into a reaction kettle, stirred at 50-60°C and 500-600 r / min for 20-30 min, then γ-methacryloxypropyl trimethoxysilane is added, the pH value is adjusted to 3-4 with hydrochloric acid solution, and the reaction is continued to stir for 5-6 h, then filtration is performed, the precipitate is washed with deionized water and anhydrous ethanol for 2-4 times, vacuum dried at 60-70°C for 1-2 h, and the multifunctional graphene-based protein-based gel is obtained.

[0011] Further, the use amount ratio of the graphene-based protein-based gel, anhydrous ethanol, deionized water and γ-methacryloxypropyl trimethoxysilane is 80-90 g:120-140 mL:400-500 mL:100-120 mL.

[0012] Further, the specific preparation steps of the graphene-based protein-based gel are as follows:

[0013] Sodium alginate and deionized water are added into a reaction kettle, stirred at 20-25℃ and 500-600r / min for 10-15min, then corn protein is added, continue to stir for 30-40min, to obtain a mixed solution, the mixed solution is dropped into a calcium chloride solution with a mass fraction of 3-4%, then zinc oxide intercalated graphene hydrogel is added, continue to stir for 1-2h, filter, the filter cake is washed with deionized water and anhydrous ethanol for 2-3 times respectively, vacuum dried at 60-80℃ for 1-2h, to obtain a protein-based gel of graphene;

[0014] The amount ratio of sodium alginate, deionized water and corn protein is 90-95g:800-900mL:30-40g; the amount ratio of the mixed solution, calcium chloride solution and zinc oxide intercalated graphene hydrogel is 700-800mL:300-400mL:100-120g.

[0015] Further, the specific preparation steps of zinc oxide intercalated graphene hydrogel are as follows:

[0016] Zinc oxide intercalated graphene oxide, N-methyl pyrrolidone, dimethyl sulfoxide and deionized water are added into a polytetrafluoroethylene lined autoclave, stirred at 20-25℃ and 500-600r / min for 30-40min, then glucose is added, the pH value is adjusted to 8-9, heated to 180-190℃, continue to stir for 12-14h, naturally cooled to room temperature, to obtain zinc oxide intercalated graphene hydrogel.

[0017] Further, the amount ratio of zinc oxide intercalated graphene oxide, N-methyl pyrrolidone, dimethyl sulfoxide, deionized water and glucose is 80-90g:120-140g:150-160mL:200-220mL:50-60g.

[0018] Further, the specific preparation steps of zinc oxide intercalated graphene oxide are as follows:

[0019] The graphene oxide, 2, 5-diamino terephthalic acid and N, N-dimethylformamide are added into a polytetrafluoroethylene lining autoclave, stirred at 20-25 DEG C and 500-600 r / min for 30-40 min, then a mixed solution of sodium dodecyl sulfate and 60-70 wt% ethanol solution is added, and the stirring is continued for 30-40 min, then zinc sulfate is added, heated to 120-130 DEG C, and the reaction is continued for 20-22 h, and then the mixture is naturally cooled to room temperature, filtered, and the filter cake is washed with methanol solution and deionized water for 2-4 times, and vacuum dried at 60-70 DEG C for 1-2 h, and then the product is transferred to a muffle furnace, calcined at 500-550 DEG C under nitrogen protection for 2-3 h to obtain zinc oxide intercalated graphene oxide.

[0020] Further, the amount ratio of the graphene oxide, 2, 5-diamino terephthalic acid, N, N-dimethylformamide, sodium dodecyl sulfate, ethanol solution and zinc sulfate is 180-190 g: 50-60 g: 800-900 mL: 8-10 g: 80-90 mL: 55-65 g.

[0021] The beneficial effects of the present application are as follows:

[0022] The multifunctional graphene protein-based composite gel prepared by the present application can form an intercalation structure by hydrothermally synthesizing zinc MOF on the surface of graphene oxide, and the zinc MOF grows in situ between the graphene layers to form an intercalation structure, and after calcination, the zinc MOF forms zinc oxide, which cooperates with the carbon network of graphene to significantly improve the electron mobility and inhibit the stacking of graphene layers, thereby increasing the specific surface area, providing attachment sites for the formation of sodium alginate microcapsules, and improving the adsorption of sodium alginate microcapsules.

[0023] The zinc oxide intercalated graphene oxide forms a heterostructure, and the zinc oxide is embedded between the graphene layers, which not only retains the high conductivity of graphene, but also plays a broad-spectrum antibacterial role, and can inhibit inflammation at the site of spinal cord injury. The zinc oxide intercalated graphene hydrogel serves as a secondary network to enhance the conductivity and structural stability. The three-dimensional conductive network composed of graphene and zinc oxide simulates the arrangement of nerve fiber bundles, guides the extension of axons along the direction of the electric field, accelerates the reconstruction of the neural circuit in the injury area, and the zein releases the hydrophobic polypeptide, which blocks the binding of chondroitin sulfate proteoglycan and axon growth cone receptors, reduces the physical barrier of glial scar to regeneration, and the sodium alginate microcapsule can provide support to avoid the inactivation of the protein in the subsequent polymerization process.

[0024] By hydrolysis of gamma-methacryloxypropyl trimethoxysilane under acidic conditions, its silicon hydroxyl bonds with the gel surface hydroxyl, and the methacryl group copolymerizes with the acrylate monomer, realizing inorganic / organic phase molecular level bridging, improving the interface shear strength, and improving the stability of the overall material. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0026] Embodiment 1: A preparation method of a protein-based composite gel based on multifunctional graphene, comprising the following steps:

[0027] S1: 180 g of graphene oxide, 50 g of 2,5-diamino terephthalic acid, and 800 mL of N,N-dimethylformamide were added into a polytetrafluoroethylene-lined autoclave, stirred at 20℃ and 500 r / min for 30 min, then a mixed solution of 8 g of sodium dodecyl sulfate and 80 mL of 60wt% ethanol solution was added, and stirring was continued for 30 min, then 55 g of zinc sulfate was added, heated to 120℃, and the reaction was continued for 20 h, and then naturally cooled to room temperature, filtered, and the filter cake was washed with a methanol solution and deionized water for 2 times respectively, and vacuum dried at 60℃ for 1 h, and then the product was transferred to a muffle furnace, heated to 500℃ under nitrogen protection, and calcined for 2 h to obtain zinc oxide intercalated graphene oxide.

[0028] S2: 80 g of zinc oxide intercalated graphene oxide, 120 g of N-methyl pyrrolidone, 150 mL of dimethyl sulfoxide, and 200 mL of deionized water were added into a polytetrafluoroethylene-lined autoclave, stirred at 20℃ and 500 r / min for 30 min, then 50 g of glucose was added, the pH value was adjusted to 8, heated to 180℃, and stirring was continued for 12 h, and then naturally cooled to room temperature to obtain zinc oxide intercalated graphene hydrogel.

[0029] S3: 90 g of sodium alginate and 800 mL of deionized water were added into a reaction kettle, stirred at 20℃ and 500 r / min for 10 min, then 30 g of corn protein was added, and stirring was continued for 30 min to obtain a mixed solution, 700 mL of the mixed solution was added dropwise into 300 mL of a 3% calcium chloride solution, then 100 g of zinc oxide intercalated graphene hydrogel was added, and stirring was continued for 1 h, and then filtered, and the filter cake was washed with deionized water and anhydrous ethanol for 2 times respectively, and vacuum dried at 60℃ for 1 h to obtain a protein-based gel of graphene.

[0030] S4: 80 g of the protein-based gel of graphene, 120 mL of anhydrous ethanol and 400 mL of deionized water were added into the reaction kettle, stirred at 50 °C and 500 r / min for 20 min, then 100 mL of γ-methacryloxypropyltrimethoxysilane was added, the pH value was adjusted to 3 with hydrochloric acid solution, and the stirring reaction was continued for 5 h. After filtration, the precipitate was washed with deionized water and anhydrous ethanol for 2 times, and vacuum dried at 60 °C for 1 h to obtain the multifunctional protein-based gel of graphene.

[0031] S5: 80 g of the multifunctional protein-based gel of graphene and 800 mL of deionized water were added into the reaction kettle, stirred at 20 °C and 500 r / min for 10 min, then 45 g of acrylic acid and 30 g of methoxyethyl acrylate were added, heated to 40 °C under nitrogen protection, and the stirring was continued for 2 h. Then 10 g of initiator potassium persulfate was added, and the above solution was poured into a mold and placed in a 7040 type oven for free radical copolymerization reaction at 70 °C to obtain the multifunctional protein-based composite gel of graphene.

[0032] Example 2: A preparation method of the multifunctional protein-based composite gel of graphene, comprising the following steps:

[0033] S1: 185 g of graphene oxide, 55 g of 2,5-diamino terephthalic acid and 850 mL of N,N-dimethylformamide were added into a polytetrafluoroethylene-lined autoclave, stirred at 22.5 °C and 550 r / min for 35 min, then a mixed solution of 9 g of sodium dodecyl sulfate and 85 mL of 65 wt% ethanol solution was added, and the stirring was continued for 35 min. Then 60 g of zinc sulfate was added, heated to 125 °C, and the reaction was continued for 21 h. After natural cooling to room temperature, the filter cake was washed with methanol solution and deionized water for 3 times respectively, and vacuum dried at 65 °C for 1.5 h. The product was transferred to a muffle furnace, heated to 525 °C under nitrogen protection, and calcined for 2.5 h to obtain zinc oxide intercalated graphene oxide.

[0034] S2: 85 g of zinc oxide intercalated graphene oxide, 130 g of N-methyl pyrrolidone, 155 mL of dimethyl sulfoxide and 210 mL of deionized water were added into a polytetrafluoroethylene-lined autoclave, stirred at 22.5 °C and 550 r / min for 35 min, then 55 g of glucose was added, the pH value was adjusted to 8.5, heated to 185 °C, and the stirring was continued for 13 h. After natural cooling to room temperature, zinc oxide intercalated graphene hydrogel was obtained.

[0035] S3: 92.5 g of sodium alginate and 850 mL of deionized water were added to a reaction kettle, stirred at 22.5 °C and 550 r / min for 12.5 min, then 35 g of corn protein was added, and stirring was continued for 35 min to obtain a mixed solution, 750 mL of the mixed solution was added dropwise into 350 mL of a 3.5% by mass calcium chloride solution, then 110 g of zinc oxide intercalated graphene hydrogel was added, and stirring was continued for 1.5 h, then filtration was performed, the filter cake was washed with deionized water and anhydrous ethanol for 2.5 times respectively, and vacuum drying was performed at 70 °C for 1.5 h to obtain a protein-based gel of graphene.

[0036] S4: 85 g of the protein-based gel of graphene, 130 mL of anhydrous ethanol and 450 mL of deionized water were added to a reaction kettle, stirred at 55 °C and 550 r / min for 25 min, then 110 mL of γ-methacryloxypropyl trimethoxysilane was added, the pH value was adjusted to 3.5 with a hydrochloric acid solution, and stirring was continued for 5.5 h, then filtration was performed, the precipitate was washed with deionized water and anhydrous ethanol for 3 times, and vacuum drying was performed at 65 °C for 1.5 h to obtain a multifunctional protein-based gel of graphene.

[0037] S5: 81 g of the multifunctional protein-based gel of graphene and 850 mL of deionized water were added to a reaction kettle, stirred at 22.5 °C and 550 r / min for 12.5 min, then 47.5 g of acrylic acid and 35 g of methoxy ethyl acrylate were added, heated to 45 °C under nitrogen protection, and stirring was continued for 2.5 h, then 11 g of initiator potassium persulfate was added, and the above solution was poured into a mold, which was placed in a 7040 type oven for free radical copolymerization at 75 °C to obtain a multifunctional protein-based composite gel of graphene.

[0038] Example 3: A preparation method of a multifunctional protein-based composite gel of graphene, comprising the following steps:

[0039] S1: 190 g of graphene oxide, 60 g of 2,5-diamino terephthalic acid and 900 mL of N,N-dimethylformamide were added to a polytetrafluoroethylene-lined autoclave, stirred at 25 °C and 600 r / min for 40 min, then a mixed solution of 10 g of sodium dodecyl sulfate and 90 mL of a 70 wt% ethanol solution was added, stirring was continued for 40 min, then 65 g of zinc sulfate was added, heated to 130 °C, and reaction was continued for 22 h, then natural cooling was performed to room temperature, filtration was performed, the filter cake was washed with a methanol solution and deionized water for 4 times respectively, vacuum drying was performed at 70 °C for 2 h, the product was transferred to a muffle furnace, heated to 550 °C under nitrogen protection, and calcination was performed for 3 h to obtain zinc oxide intercalated graphene oxide.

[0040] S2: 90 g of zinc oxide intercalated graphene oxide, 140 g of N-methyl pyrrolidone, 160 mL of dimethyl sulfoxide and 220 mL of deionized water were added into a polytetrafluoroethylene lined autoclave, stirred at 25 °C and 600 r / min for 40 min, then 60 g of glucose was added, the pH value was adjusted to 9, heated to 190 °C, and stirring was continued for 14 h, and then naturally cooled to room temperature to obtain a zinc oxide intercalated graphene hydrogel.

[0041] S3: 95 g of sodium alginate and 900 mL of deionized water were added into a reaction kettle, stirred at 25 °C and 600 r / min for 15 min, then 40 g of corn protein was added, and stirring was continued for 40 min to obtain a mixed solution, 800 mL of the mixed solution was added dropwise into 400 mL of a calcium chloride solution with a mass fraction of 4%, then 120 g of zinc oxide intercalated graphene hydrogel was added, and stirring was continued for 2 h, then filtration was performed, the filter cake was washed with deionized water and anhydrous ethanol for 3 times respectively, and vacuum drying was performed at 80 °C for 2 h to obtain a protein-based gel of graphene.

[0042] S4: 90 g of the protein-based gel of graphene, 140 mL of anhydrous ethanol and 500 mL of deionized water were added into a reaction kettle, stirred at 60 °C and 600 r / min for 30 min, then 120 mL of γ-methacryloxypropyl trimethoxysilane was added, the pH value was adjusted to 4 with a hydrochloric acid solution, and stirring was continued for 6 h, then filtration was performed, the precipitate was washed with deionized water and anhydrous ethanol for 4 times, and vacuum drying was performed at 70 °C for 2 h to obtain a multifunctional protein-based gel of graphene.

[0043] S5: 82 g of the multifunctional protein-based gel of graphene and 900 mL of deionized water were added into a reaction kettle, stirred at 25 °C and 600 r / min for 15 min, then 50 g of acrylic acid and 40 g of methoxy ethyl acrylate were added, heated to 50 °C under nitrogen protection, and stirring was continued for 3 h, then 12 g of an initiator potassium persulfate was added, and the above solution was poured into a mold, and then placed in a 7040 type oven to perform a free radical copolymerization reaction at 80 °C to obtain a multifunctional protein-based composite gel of graphene.

[0044] Comparative Example 1: on the basis of Example 3, the zinc oxide intercalated graphene oxide in step S2 was replaced by graphene oxide.

[0045] Comparative Example 2: on the basis of Example 3, the protein-based gel of graphene in step S4 was replaced by a mixture of zinc oxide intercalated graphene hydrogel and corn protein.

[0046] Comparative Example 3: on the basis of Example 3, the multifunctional protein-based gel of graphene in step S5 was replaced by a protein-based gel of graphene.

[0047] The protein-based composite gel of multifunctional graphene prepared in Example 1 to Example 3 and Comparative Example 1 to Comparative Example 3 was subjected to performance testing, and the results are shown in Table 1:

[0048] Chromaffin cell tumor cells were inoculated in the multifunctional graphene protein-based composite gel filled 24-well plate, respectively, and the density was 8 x 10 3 Chromaffin cell tumor cells were inoculated in the multifunctional graphene protein-based composite gel filled 24-well plate, respectively, and the density was 8 x 10

[0049] 1. Tensile mechanical property test: The prepared protein-based composite gel was clamped at both ends of the mechanical tester, and the tensile mechanical property and tensile cycle stability were tested;

[0050] 2. Tensile electrical property test: The prepared protein-based composite gel was clamped at both ends of the mechanical tester, and the electrodes were connected to the electrochemical workstation at the same time, and the tensile electrical property was tested;

[0051] 3. Electrical conductivity performance test: The electrical conductivity was tested according to GB / T 26074-2010;

[0052] 4. Porosity performance test: The porosity was tested by gas adsorption method (BET method).

[0053] Table 1

[0054] Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Cell survival rate (%) 95.6 96.2 97.3 94.8 95.6 97.4 Breaking strength (KPa) 120 125 130 75 85 70 Breaking length (%) 2400 2500 2600 1500 1800 1400 Porosity (%) 95.6 96.2 96.8 88.3 92.5 86.7 Electrical conductivity (S / m) 2110 2250 2400 980 1350 750

[0055] As can be seen from Table 1, the breaking strength, breaking length, porosity and electrical conductivity of Example 1 to Example 3 are significantly better than those of Comparative Example, which shows that the multifunctional graphene protein-based composite gel prepared by the present application is non-toxic, has good mechanical properties, high porosity and high electrical conductivity.

[0056] Comparative Example 1 replaces the zinc oxide intercalated graphene oxide in step S2 with graphene oxide, which lacks the interlayer support of zinc oxide, the graphene sheet layer is restacked, the specific surface area decreases, the heterostructure is missing, the electronic migration path is discontinuous, the electrical conductivity decreases, the broad-spectrum antibacterial property of zinc oxide is lost, and the inflammation at the spinal cord injury site cannot be inhibited, and the sheet layer is easily stacked, which weakens the stress dispersion ability.

[0057] Comparative Example 2 replaces the protein-based gel of graphene in Step S4 with a mixture of zinc oxide intercalated graphene hydrogel and corn protein, the hydrophobic region of corn protein is exposed, spontaneously agglomerates in a hydrophilic environment, forms large particles, destroys the uniformity of the gel, the sodium alginate microcapsule structure is not formed, and the corn protein hydrophobic peptide cannot be released slowly.

[0058] Comparative Example 3 replaces the protein-based gel of multifunctional graphene in Step S5 with a protein-based gel of graphene, resulting in the inability of the methacryl group to copolymerize with the acrylate, a 35% reduction in crosslinking density, a loose gel network, and the absence of silane causes the sodium alginate microcapsule to break during polymerization, and the corn protein is denatured and inactivated.

[0059] Although embodiments of the present application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the present application.

Claims

1. A method for the preparation of a protein-based composite gel based on multifunctional graphene, characterized by, Comprising the following steps: The multifunctional graphene protein-based gel and deionized water are added into a reaction kettle, stirred at 20-25 DEG C and 500-600 r / min for 10-15 min, then acrylic acid and methoxy ethyl acrylate are added, heated to 40-50 DEG C under nitrogen protection, continue to stir for 2-3 h, then add potassium persulfate, pour the solution into a mold, and place it in a 7040 oven to carry out free radical copolymerization at 70-80 DEG C, to obtain a multifunctional graphene protein-based composite gel; The graphene protein-based gel, anhydrous ethanol and deionized water are added into a reaction kettle, stirred at 50-60 DEG C and 500-600 r / min for 20-30 min, then gamma-methacryloxypropyl trimethoxysilane is added, the pH value is adjusted to 3-4 with hydrochloric acid solution, continue to stir for 5-6 h, filter, the precipitate is washed with deionized water and anhydrous ethanol for 2-4 times, vacuum dried at 60-70 DEG C for 1-2 h, to obtain a multifunctional graphene protein-based gel; The graphene protein-based gel is prepared according to the following steps: Sodium alginate and deionized water are added into a reaction kettle, stirred at 20-25 DEG C and 500-600 r / min for 10-15 min, then corn protein is added, continue to stir for 30-40 min to obtain a mixed solution, the mixed solution is dropped into a calcium chloride solution with a mass fraction of 3-4%, then zinc oxide intercalated graphene hydrogel is added, continue to stir for 1-2 h, filter, the filter cake is washed with deionized water and anhydrous ethanol for 2-3 times, vacuum dried at 60-80 DEG C for 1-2 h, to obtain a graphene protein-based gel; The zinc oxide intercalated graphene hydrogel is prepared according to the following steps: Zinc oxide intercalated graphene oxide, N-methyl pyrrolidone, dimethyl sulfoxide and deionized water are added into a polytetrafluoroethylene lined autoclave, stirred at 20-25 DEG C and 500-600 r / min for 30-40 min, then glucose is added, the pH value is adjusted to 8-9, heated to 180-190 DEG C, continue to stir for 12-14 h, naturally cooled to room temperature, to obtain zinc oxide intercalated graphene hydrogel.

2. The method for preparing a multifunctional graphene-based protein-based composite gel according to claim 1, characterized in that, The amount ratio of the multifunctional graphene protein-based gel, deionized water, acrylic acid, methoxy ethyl acrylate and potassium persulfate is 80-82 g:800-900 mL:45-50 g:30-40 g:10-12 g.

3. The method for preparing a multifunctional graphene-based protein-based composite hydrogel according to claim 1, characterized in that, The amount ratio of the graphene protein-based gel, anhydrous ethanol, deionized water and gamma-methacryloxypropyl trimethoxysilane is 80-90 g:120-140 mL:400-500 mL:100-120 mL.

4. The method for preparing a multifunctional graphene-based protein-based composite hydrogel according to claim 1, characterized in that, The use amount ratio of the sodium alginate, deionized water and corn protein is 90g-95g:800mL-900mL:30g-40g; the use amount ratio of the mixed solution, calcium chloride solution and zinc oxide intercalated graphene hydrogel is 700mL-800mL:300mL-400mL:100g-120g.

5. The method for preparing the protein-based composite gel based on multifunctional graphene according to claim 1, characterized in that, The use amount ratio of the zinc oxide intercalated graphene oxide, N-methyl pyrrolidone, dimethyl sulfoxide, deionized water and glucose is 80g-90g:120g-140g:150mL-160mL:200mL-220mL:50g-60g.

6. The method for preparing the protein-based composite gel based on multifunctional graphene according to claim 1, characterized in that, The zinc oxide intercalated graphene oxide is prepared according to the following steps: The graphene oxide, 2,5-diamino terephthalic acid and N,N-dimethylformamide are added into a polytetrafluoroethylene lined autoclave, stirred at 20℃-25℃ and 500r / min-600r / min for 30min-40min, then a mixed solution of sodium dodecyl sulfate and 60wt%-70wt% ethanol solution is added, and the stirring is continued for 30min-40min, then zinc sulfate is added, heated to 120℃-130℃, and the reaction is continued for 20h-22h, and then the mixture is naturally cooled to room temperature, filtered, and the filter cake is washed with methanol solution and deionized water for 2-4 times, respectively, and vacuum dried at 60℃-70℃ for 1h-2h, and then the product is transferred to a muffle furnace, heated to 500℃-550℃ under nitrogen protection, and calcined for 2h-3h to obtain the zinc oxide intercalated graphene oxide.

7. The method of claim 6, wherein the multifunctional graphene-based protein-based composite gel is prepared by the steps of: The use amount ratio of the graphene oxide, 2,5-diamino terephthalic acid, N,N-dimethylformamide, sodium dodecyl sulfate, ethanol solution and zinc sulfate is 180g-190g:50g-60g:800mL-900mL:8g-10g:80mL-90mL:55g-65g.

8. A protein-based composite gel based on multifunctional graphene, characterized in that, The zinc oxide intercalated graphene oxide is prepared by the preparation method of any one of claims 1-7. The zinc oxide intercalated graphene oxide is prepared by the preparation method of any one of claims 1-7.