Protein-based composite gel based on multifunctional graphene and preparation method of protein-based composite gel

Abstract

The invention discloses protein-based composite gel based on multifunctional graphene and a preparation method of the protein-based composite gel, and belongs to the technical field of biomedices.The preparation method comprises the steps that zinc MOF is hydrothermally synthesized on the surface of graphene oxide, the zinc MOF grows in situ between graphene sheet layers to form an intercalation structure, the zinc MOF forms zinc oxide after calcination, and the zinc oxide cooperates with a carbon network of graphene, so that the protein-based composite gel is obtained; the electron mobility is remarkably improved, the specific surface area is increased, attachment sites can be provided for formation of the sodium alginate microcapsules, the adsorption effect on the sodium alginate microcapsules is improved, the sodium alginate microcapsules provide a supporting effect on corn protein, and the protein is prevented from being inactivated in the subsequent polymerization initiating process; the zinc oxide is intercalated with the graphene oxide to form a heterostructure, and the zinc oxide is embedded between graphene layers, so that the high conductivity of the graphene is reserved, the broad-spectrum antibacterial property of the zinc oxide is exerted, and the inflammation of the spinal cord injury part can be inhibited.

Description

Technical Field

[0001] The present invention belongs to the field of biomedical technology, and specifically relates to a protein-based composite gel based on multifunctional graphene and a preparation method thereof. Background Art

[0002] Traumatic spinal cord injury (SCI) refers to vertebral fractures and anterior vertebral dislocations caused by external forces, which in turn compress the spinal parenchyma, leading to varying degrees of permanent neurological dysfunction. Most patients affected by SCI are young and constitute a significant portion of the workforce, placing a heavy burden on them due to long-term disability. Therefore, identifying reparative interventions after SCI is crucial. Neurological impairment after SCI is due to the disruption of spinal cord connections caused by damage to axons and neurons. One of the main reasons for late recovery failure is the formation of scars and cavities, which prevent regenerating axons from connecting with nerves below the injured level. With recent advances in biomaterials and tissue engineering, the use of implantable or injectable bioengineered scaffolds has emerged as a promising strategy for SCI treatment. By constructing a graphene-based protein hydrogel system at the injured site, the system fills the tissue defect and reduces glial scar formation. The graphene-enhanced protein hydrogel increases nerve conductivity, thereby guiding nerve growth and enabling axons to rapidly grow within the hydrogel channels, thereby promoting motor recovery after SCI.

[0003] As recorded in the existing literature: Composite graphene protein hydrogel promotes motor function recovery after spinal cord injury in rats, acrylic acid, methoxyethyl acrylate, graphene and corn protein are reacted with potassium persulfate as an initiator and then placed in a high-temperature oven for free radical copolymerization, and finally an underwater viscous composite graphene protein hydrogel is obtained. However, the denaturation temperature of corn protein is 70-80°C, and the persulfate radical is highly oxidizing, which will greatly affect the activity of the protein. Summary of the Invention

[0004] The object of the present invention 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, and the zinc MOF grows in situ between graphene sheets to form an intercalated structure. After calcination, the zinc MOF forms zinc oxide, which cooperates with the carbon network of graphene to significantly improve electron mobility and increase specific surface area. It can provide attachment sites for the formation of sodium alginate microcapsules and improve the adsorption of sodium alginate microcapsules. The sodium alginate microcapsules provide support for zein, thereby preventing the zein from being inactivated during the subsequent initiation of polymerization.

[0005] The purpose of the present invention can be achieved through the following technical solutions: The preparation method of protein-based composite gel based on multifunctional graphene comprises the following steps: The protein-based gel of multifunctional graphene and deionized water are added to a reactor, stirred at 20°C-25°C and 500r / min-600r / min for 10min-15min, then acrylic acid and methoxyethyl acrylate are added, and under nitrogen protection, heated to 40°C-50°C, and stirred for 2h-3h, and then potassium persulfate as an initiator is added. The above solution is poured into a mold, placed in a 7040 type oven, and a free radical copolymerization reaction is carried out at 70°C-80°C to obtain a protein-based composite gel of multifunctional graphene.

[0006] Furthermore, the usage ratio of the protein-based gel of the multifunctional graphene, deionized water, acrylic acid, methoxyethyl acrylate and potassium persulfate is 80g-82g: 800mL-900mL: 45g-50g: 30g-40g: 10g-12g.

[0007] Furthermore, the specific preparation steps of the multifunctional graphene protein-based gel are as follows: The protein-based gel of graphene, anhydrous ethanol and deionized water are added to a reactor, stirred at 50°C-60°C and 500r / min-600r / min for 20min-30min, and then γ-methacryloxypropyltrimethoxysilane is added. The pH value is adjusted to 3-4 with a hydrochloric acid solution, and the stirring reaction is continued for 5h-6h. The mixture is filtered, and the precipitate is washed 2-4 times with deionized water and anhydrous ethanol, and vacuum dried at 60°C-70°C for 1h-2h to obtain the protein-based gel of multifunctional graphene.

[0008] Furthermore, the usage ratio of the protein-based gel of graphene, anhydrous ethanol, deionized water and γ-methacryloxypropyltrimethoxysilane is 80g-90g: 120mL-140mL: 400mL-500mL: 100mL-120mL.

[0009] Furthermore, the specific preparation steps of the graphene protein-based gel are as follows: Sodium alginate and deionized water are added to a reactor, stirred at 20°C-25°C and 500r / min-600r / min for 10min-15min, then corn protein is added and stirred for 30min-40min to obtain a mixed solution, the mixed solution is dropped into a calcium chloride solution with a mass fraction of 3%-4%, and then zinc oxide intercalated graphene hydrogel is added and stirred for 1h-2h, filtered, and the filter cake is washed with deionized water and anhydrous ethanol for 2-3 times respectively, and vacuum dried at 60°C-80°C for 1h-2h to obtain a protein-based gel of graphene; The dosage ratio of sodium alginate, deionized water and corn protein is 90g-95g:800mL-900mL:30g-40g; the dosage ratio of the mixed solution, calcium chloride solution and zinc oxide intercalated graphene hydrogel is 700mL-800mL:300mL-400mL:100g-120g.

[0010] Furthermore, the specific preparation steps of zinc oxide intercalated graphene hydrogel are as follows: Zinc oxide intercalated graphene oxide, N-methylpyrrolidone, dimethyl sulfoxide and deionized water are added to a polytetrafluoroethylene-lined autoclave, stirred for 30 min-40 min at 20°C-25°C and 500 r / min-600 r / min, and then glucose is added. The pH value is adjusted to 8-9, heated to 180°C-190°C, stirred for 12 h-14 h, and naturally cooled to room temperature to obtain zinc oxide intercalated graphene hydrogel.

[0011] Furthermore, the usage ratio of zinc oxide intercalated graphene oxide, N-methylpyrrolidone, dimethyl sulfoxide, deionized water and glucose is 80g-90g:120g-140g:150mL-160mL:200mL-220mL:50g-60g.

[0012] Furthermore, the specific preparation steps of zinc oxide intercalated graphene oxide are as follows: Graphene oxide, 2,5-diaminoterephthalic acid and N,N-dimethylformamide are added to a polytetrafluoroethylene-lined autoclave, stirred at 20°C-25°C and 500r / min-600r / min for 30min-40min, and then a mixed solution of sodium hexadecyl sulfate and 60 wt%-70wt% ethanol solution is added, and stirring is continued for 30min-40min. Then, zinc sulfate is added, heated to 120°C-130°C, and the reaction is continued for 20h-22h. The mixture is naturally cooled to room temperature and filtered. The filter cake is washed with methanol solution and deionized water 2-4 times, respectively, and vacuum dried at 60°C-70°C for 1h-2h. The product is transferred to a muffle furnace and heated to 500°C-550°C under nitrogen protection and calcined for 2h-3h to obtain zinc oxide intercalated graphene oxide.

[0013] Furthermore, the usage ratio of graphene oxide, 2,5-diaminoterephthalic acid, N,N-dimethylformamide, sodium hexadecyl sulfate, ethanol solution and zinc sulfate is 180g-190g: 50g-60g: 800mL-900mL: 8g-10g: 80mL-90mL: 55g-65g.

[0014] The beneficial effects of the present invention are as follows: The protein-based composite gel of multifunctional graphene prepared by the present invention is prepared by hydrothermally synthesizing zinc MOF on the surface of graphene oxide. The zinc MOF grows in situ between graphene sheets to form an intercalated structure. After calcination, the zinc MOF forms zinc oxide, which cooperates with the carbon network of graphene to significantly improve electron mobility, while inhibiting the stacking of graphene sheets and increasing the specific surface area. The large specific surface area can provide attachment sites for the formation of sodium alginate microcapsules, thereby improving the adsorption effect on the sodium alginate microcapsules.

[0015] Zinc oxide is intercalated into graphene oxide to form a heterogeneous structure, with zinc oxide embedded between the graphene layers, which not only retains the high conductivity of graphene but also exerts the broad-spectrum antibacterial properties of zinc oxide, and can inhibit inflammation in the spinal cord injury site. Zinc oxide intercalated into graphene hydrogel serves as a secondary network to enhance conductivity and structural stability. The three-dimensional conductive network composed of graphene and zinc oxide simulates the arrangement of nerve fiber bundles, guiding axons to extend along the direction of the electric field and accelerating the reconstruction of neural circuits in the injured area. Corn protein slowly releases hydrophobic peptides, blocking the binding of chondroitin sulfate proteoglycans to axonal growth cone receptors, reducing the physical barrier of glial scars to regeneration. Sodium alginate microcapsules can provide support to prevent the protein from inactivating during the subsequent polymerization process.

[0016] By hydrolyzing γ-methacryloxypropyltrimethoxysilane under acidic conditions, its silanol groups bond with the hydroxyl groups on the gel surface, and the methacryloyl groups copolymerize with the acrylate monomers to achieve molecular-level bridging of the inorganic / organic phases, thereby increasing the interfacial shear strength and improving the stability of the overall material. DETAILED DESCRIPTION

[0017] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0018] Example 1: A method for preparing a protein-based composite gel based on multifunctional graphene, comprising the following steps: S1: 180 g of graphene oxide, 50 g of 2,5-diaminoterephthalic acid and 800 mL of N,N-dimethylformamide were added to a polytetrafluoroethylene-lined autoclave and stirred at 20 ° C and 500 r / min for 30 min. Then, a mixed solution of 8 g of sodium hexadecyl sulfate and 80 mL of 60 wt% ethanol solution was added and stirred for 30 min. Then, 55 g of zinc sulfate was added and heated to 120 ° C. The reaction was continued for 20 h, and then naturally cooled to room temperature and filtered. The filter cake was washed twice with methanol solution and deionized water respectively, and vacuum dried at 60 ° C for 1 h. The product was transferred to a muffle furnace and heated to 500 ° C under nitrogen protection and calcined for 2 h to obtain zinc oxide intercalated graphene oxide.

[0019] S2: 80 g zinc oxide intercalated graphene oxide, 120 g N-methylpyrrolidone, 150 mL dimethyl sulfoxide and 200 mL deionized water were added to a polytetrafluoroethylene-lined autoclave, stirred at 20 ° C and 500 r / min for 30 min, then 50 g glucose was added, the pH value was adjusted to 8, heated to 180 ° C, continued stirring for 12 h, and naturally cooled to room temperature to obtain zinc oxide intercalated graphene hydrogel.

[0020] S3: Add 90g of sodium alginate and 800mL of deionized water into the reactor, stir at 20℃ and 500r / min for 10min, then add 30g of corn protein, continue stirring for 30min to obtain a mixed solution, drop 700mL of the mixed solution into 300mL of 3% calcium chloride solution, then add 100g of zinc oxide intercalated graphene hydrogel, continue stirring for 1h, filter, wash the filter cake with deionized water and anhydrous ethanol twice respectively, and vacuum dry at 60℃ for 1h to obtain protein-based gel of graphene.

[0021] S4: 80 g of graphene protein-based gel, 120 mL of anhydrous ethanol and 400 mL of deionized water were added to the reactor, 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. The precipitate was filtered and washed twice with deionized water and anhydrous ethanol, and vacuum dried at 60°C for 1 h to obtain the multifunctional graphene protein-based gel.

[0022] S5: Add 80g of multifunctional graphene protein-based gel and 800mL of deionized water into the reactor, stir at 20℃ and 500r / min for 10min, then add 45g of acrylic acid and 30g of methoxyethyl acrylate, heat to 40℃ under nitrogen protection, continue stirring for 2h, then add 10g of initiator potassium persulfate, pour the above solution into a mold, place it in a 7040 type oven, and carry out free radical copolymerization reaction at 70℃ to obtain the protein-based composite gel of multifunctional graphene.

[0023] Example 2: A method for preparing a protein-based composite gel based on multifunctional graphene, comprising the following steps: S1: 185 g of graphene oxide, 55 g of 2,5-diaminoterephthalic acid and 850 mL of N,N-dimethylformamide were added to a polytetrafluoroethylene-lined autoclave and stirred at 22.5 ° C and 550 r / min for 35 min. Then, a mixed solution of 9 g of sodium hexadecyl sulfate and 85 mL of 65 wt% ethanol solution was added and stirred for 35 min. Then, 60 g of zinc sulfate was added and heated to 125 ° C. The reaction was continued for 21 h. The mixture was naturally cooled to room temperature and filtered. The filter cake was washed with methanol solution and deionized water three times respectively, and vacuum dried at 65 ° C for 1.5 h. The product was transferred to a muffle furnace and heated to 525 ° C under nitrogen protection and calcined for 2.5 h to obtain zinc oxide intercalated graphene oxide.

[0024] S2: 85 g of zinc oxide intercalated graphene oxide, 130 g of N-methylpyrrolidone, 155 mL of dimethyl sulfoxide and 210 mL of deionized water were added to a polytetrafluoroethylene-lined autoclave and 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 stirred for 13 h. The mixture was naturally cooled to room temperature to obtain zinc oxide intercalated graphene hydrogel.

[0025] S3: Add 92.5g of sodium alginate and 850mL of deionized water into the reactor, stir for 12.5min at 22.5℃ and 550r / min, then add 35g of corn protein and continue stirring for 35min to obtain a mixed solution. Add 750mL of the mixed solution dropwise into 350mL of 3.5% calcium chloride solution, then add 110g of zinc oxide intercalated graphene hydrogel, continue stirring for 1.5h, filter, wash the filter cake with deionized water and anhydrous ethanol 2.5 times respectively, and vacuum dry at 70℃ for 1.5h to obtain a protein-based gel of graphene.

[0026] S4: 85 g of graphene protein-based gel, 130 mL of anhydrous ethanol and 450 mL of deionized water were added to the reactor, stirred at 55°C and 550 r / min for 25 min, then 110 mL of γ-methacryloxypropyltrimethoxysilane was added, the pH value was adjusted to 3.5 with hydrochloric acid solution, and the stirring reaction was continued for 5.5 h. The mixture was filtered and the precipitate was washed three times with deionized water and anhydrous ethanol, and vacuum dried at 65°C for 1.5 h to obtain the multifunctional graphene protein-based gel.

[0027] S5: Add 81g of protein-based gel of multifunctional graphene and 850mL of deionized water into the reactor, stir at 22.5℃ and 550r / min for 12.5min, then add 47.5g of acrylic acid and 35g of methoxyethyl acrylate, heat to 45℃ under nitrogen protection, continue stirring for 2.5h, then add 11g of initiator potassium persulfate, pour the above solution into a mold, place it in a 7040 type oven, and carry out free radical copolymerization reaction at 75℃ to obtain a protein-based composite gel of multifunctional graphene.

[0028] Example 3: A method for preparing a protein-based composite gel based on multifunctional graphene, comprising the following steps: S1: 190 g of graphene oxide, 60 g of 2,5-diaminoterephthalic 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, and then a mixed solution of 10 g of sodium hexadecyl sulfate and 90 mL of 70 wt% ethanol solution was added, and stirring was continued for 40 min. Then, 65 g of zinc sulfate was added, heated to 130 ° C, and the reaction was continued for 22 h. The mixture was naturally cooled to room temperature and filtered. The filter cake was washed with methanol solution and deionized water four times respectively, and vacuum dried at 70 ° C for 2 h. The product was transferred to a muffle furnace and heated to 550 ° C under nitrogen protection and calcined for 3 h to obtain zinc oxide intercalated graphene oxide.

[0029] S2: 90 g zinc oxide intercalated graphene oxide, 140 g N-methylpyrrolidone, 160 mL dimethyl sulfoxide and 220 mL deionized water were added to a polytetrafluoroethylene-lined autoclave, stirred at 25 ° C and 600 r / min for 40 min, then 60 g glucose was added, the pH value was adjusted to 9, heated to 190 ° C, continued stirring for 14 h, and naturally cooled to room temperature to obtain zinc oxide intercalated graphene hydrogel.

[0030] S3: Add 95g of sodium alginate and 900mL of deionized water into the reactor, stir at 25℃ and 600r / min for 15min, then add 40g of corn protein and continue stirring for 40min to obtain a mixed solution, drop 800mL of the mixed solution into 400mL of 4% calcium chloride solution, then add 120g of zinc oxide intercalated graphene hydrogel, continue stirring for 2h, filter, wash the filter cake with deionized water and anhydrous ethanol three times respectively, and vacuum dry at 80℃ for 2h to obtain protein-based gel of graphene.

[0031] S4: 90 g of graphene protein-based gel, 140 mL of anhydrous ethanol and 500 mL of deionized water were added to a reactor, stirred at 60°C and 600 r / min for 30 min, then 120 mL of γ-methacryloxypropyltrimethoxysilane was added, the pH value was adjusted to 4 with hydrochloric acid solution, and the stirring reaction was continued for 6 h. The mixture was filtered, and the precipitate was washed 4 times with deionized water and anhydrous ethanol, and vacuum dried at 70°C for 2 h to obtain a multifunctional graphene protein-based gel.

[0032] S5: Add 82g of multifunctional graphene protein-based gel and 900mL of deionized water into the reactor, stir at 25°C and 600r / min for 15min, then add 50g of acrylic acid and 40g of methoxyethyl acrylate, heat to 50°C under nitrogen protection, continue stirring for 3h, then add 12g of initiator potassium persulfate, pour the above solution into a mold, place it in a 7040 type oven, and carry out free radical copolymerization reaction at 80°C to obtain a protein-based composite gel of multifunctional graphene.

[0033] Comparative Example 1: Based on Example 3, the zinc oxide intercalated graphene oxide in step S2 is replaced by graphene oxide.

[0034] Comparative Example 2: Based on Example 3, the protein-based gel of graphene in step S4 is replaced by a mixture of zinc oxide intercalated graphene hydrogel and zein.

[0035] Comparative Example 3: Based on Example 3, the multifunctional graphene protein-based gel in step S5 is replaced by graphene protein-based gel.

[0036] The performance of the multifunctional graphene protein-based composite gels prepared in Examples 1 to 3 and Comparative Examples 1 to 3 was tested, and the results are shown in Table 1: Pheochromocytoma cells were seeded in 24-well plates filled with multifunctional graphene-based protein-based composite gels at a density of 8×10 3Pheochromocytoma cells were seeded in 96-well plates in 180 µL of DMEM and incubated for 24 hours. Then, 20 µL of copolymer solution at varying concentrations (31.25-500 µg / mL) was added and incubated with the copolymer for 24 and 48 hours, respectively. Then, 20 µL of PBS containing MTT (0.05 mg / mL) was added and incubated for an additional 4 hours. Finally, the medium was replaced with 160 µL of DMSO. The absorbance of the solution was measured at 490 nm on a Bio-Rad 680 microplate reader to calculate cell viability.

[0037] 1. Tensile mechanical properties test: The two ends of the prepared protein-based composite gel were clamped on the fixture of the mechanical tester to test the tensile mechanical properties and tensile cycle stability; 2. Tensile electrical properties test: The prepared protein-based composite gel was clamped at both ends on the fixture of the mechanical tester, and the electrodes were connected to the electrochemical workstation to test the tensile electrical properties; 3. Conductivity performance test: refer to GB / T 26074-2010 to test conductivity; 4. Porosity performance test: The porosity is tested by gas adsorption method (BET method).

[0038] Table 1 project 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 Conductivity (S / m) 2110 2250 2400 980 1350 750 As can be seen from Table 1, the fracture strength, fracture length, porosity and conductivity of Examples 1 to 3 are significantly better than those of the comparative example, indicating that the protein-based composite gel of multifunctional graphene prepared by the present invention is non-toxic, has good mechanical properties, high porosity and high conductivity.

[0039] In Comparative Example 1, the zinc oxide-intercalated graphene oxide in step S2 is replaced by graphene oxide. The interlayer support of zinc oxide is lacking, the graphene sheets are restacked, the specific surface area is reduced, the heterogeneous structure is missing, the electron migration path is discontinuous, the conductivity is reduced, the broad-spectrum antibacterial property of zinc oxide is lost, and it cannot inhibit inflammation at the spinal cord injury site. In addition, the sheets are easily stacked, which weakens the stress dispersion ability.

[0040] In Comparative Example 2, the protein-based gel of graphene in step S4 was replaced with a mixture of zinc oxide intercalated graphene hydrogel and zein. The hydrophobic region of zein was exposed and spontaneously agglomerated in a hydrophilic environment to form large particles, which destroyed the uniformity of the gel. The sodium alginate microcapsule structure was not formed, and the zein hydrophobic peptide could not be sustained-released.

[0041] In Comparative Example 3, the protein-based gel of multifunctional graphene in step S5 was replaced with the protein-based gel of graphene, resulting in the inability of methacryloyl groups to copolymerize with acrylates, a 35% reduction in cross-linking density, a loose gel network, and the lack of silane causing the sodium alginate microcapsules to rupture during polymerization, and the denaturation and inactivation of zein.

[0042] While the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations can be made to the embodiments without departing from the principles and spirit of the invention.

Claims

1. A method for preparing a protein-based composite gel based on multifunctional graphene, characterized in that: The steps include: The protein-based gel of multifunctional graphene and deionized water are added to a reactor, stirred at 20°C-25°C and 500r / min-600r / min for 10min-15min, then acrylic acid and methoxyethyl acrylate are added, and under nitrogen protection, the mixture is heated to 40°C-50°C and stirred for 2h-3h, and then potassium persulfate is added. The solution is poured into a mold, placed in a 7040 type oven, and subjected to free radical copolymerization reaction at 70°C-80°C to obtain a protein-based composite gel of multifunctional graphene.

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

3. The method for preparing a protein-based composite gel based on multifunctional graphene according to claim 1, characterized in that: The specific preparation steps of the protein-based gel of multifunctional graphene are as follows: The protein-based gel of graphene, anhydrous ethanol and deionized water are added to a reactor, stirred at 50°C-60°C and 500r / min-600r / min for 20min-30min, and then γ-methacryloxypropyltrimethoxysilane is added. The pH value is adjusted to 3-4 with a hydrochloric acid solution, and the stirring reaction is continued for 5h-6h. The mixture is filtered, and the precipitate is washed 2-4 times with deionized water and anhydrous ethanol, and vacuum dried at 60°C-70°C for 1h-2h to obtain the protein-based gel of multifunctional graphene.

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

5. The method for preparing a protein-based composite gel based on multifunctional graphene according to claim 3, characterized in that: The specific preparation steps of the graphene protein-based gel are as follows: Sodium alginate and deionized water are added to a reactor, stirred at 20°C-25°C and 500r / min-600r / min for 10min-15min, then corn protein is added and stirred for 30min-40min to obtain a mixed solution, the mixed solution is dropped into a calcium chloride solution with a mass fraction of 3%-4%, and then zinc oxide intercalated graphene hydrogel is added and stirred for 1h-2h, filtered, and the filter cake is washed with deionized water and anhydrous ethanol for 2-3 times respectively, and vacuum dried at 60°C-80°C for 1h-2h to obtain a protein-based gel of graphene; The usage ratio of the sodium alginate, deionized water and corn protein is 90g-95g:800mL-900mL:30g-40g; the usage ratio of the mixed solution, calcium chloride solution and zinc oxide intercalated graphene hydrogel is 700mL-800mL:300mL-400mL:100g-120g.

6. The method for preparing a protein-based composite gel based on multifunctional graphene according to claim 5, characterized in that: The specific preparation steps of the zinc oxide intercalated graphene hydrogel are as follows: Zinc oxide intercalated graphene oxide, N-methylpyrrolidone, dimethyl sulfoxide and deionized water were added to a polytetrafluoroethylene-lined autoclave and stirred for 30 min-40 min at 20°C-25°C and 500r / min-600r / min. Then glucose was added, the pH value was adjusted to 8-9, the mixture was heated to 180°C-190°C, stirring was continued for 12h-14h, and the mixture was naturally cooled to room temperature to obtain zinc oxide intercalated graphene hydrogel.

7. The method for preparing a protein-based composite gel based on multifunctional graphene according to claim 6, characterized in that: The dosage ratio of the zinc oxide intercalated graphene oxide, N-methylpyrrolidone, dimethyl sulfoxide, deionized water and glucose is 80g-90g: 120g-140g: 150mL-160mL: 200mL-220mL: 50g-60g.

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

9. The method for preparing a protein-based composite gel based on multifunctional graphene according to claim 8, characterized in that: The usage ratio of the graphene oxide, 2,5-diaminoterephthalic acid, N,N-dimethylformamide, sodium hexadecyl sulfate, ethanol solution and zinc sulfate is 180g-190g: 50g-60g: 800mL-900mL: 8g-10g: 80mL-90mL: 55g-65g.

10. Protein-based composite gel based on multifunctional graphene, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.