CN114713150A - Novel crosslinking method and application of sodium alginate hydrogel containing graphene oxide - Google Patents
Novel crosslinking method and application of sodium alginate hydrogel containing graphene oxide Download PDFInfo
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Abstract
The invention discloses a novel crosslinking method of graphene oxide-containing sodium alginate hydrogel and application thereof. The invention provides a novel three-component crosslinking method capable of improving the crosslinking speed and the mechanical property of hydrogel.
Description
Technical Field
The invention belongs to the field of medical materials, relates to a core crosslinking link in a hydrogel preparation process, and particularly relates to a novel crosslinking method of a sodium alginate hydrogel containing graphene oxide, wherein the crosslinking application of three components is realized, the crosslinking efficiency in the hydrogel preparation process is high, the crosslinking time is short, and the prepared hydrogel has high mechanical property, good antibacterial activity and good air permeability.
Background
Tissue engineering achieves the therapeutic goal by combining biological materials with specific biologically active cells to construct tissues/organs with functional activity. Among a plurality of effective biomaterials applied to tissue engineering, alginate hydrogel is used as a natural hydrophilic polymer network capable of highly loading water, and because the alginate hydrogel has a similar macromolecular structure with components of a natural extracellular matrix, the alginate hydrogel can provide a bionic porous microenvironment of the extracellular matrix for various tissue cells so as to promote cell activity, and is a popular research for the tissue engineering biomaterials. The alginate is derived from byproducts of iodine extraction from brown algae kelp, has rich source and low cost, can perform ion exchange reaction with divalent calcium ions under extremely mild conditions to form an ion bridge between units, and leads alpha-L-guluronic acid units in the structure to be stacked and crosslinked to form hydrogel. The sodium alginate hydrogel is easy to prepare, has an extracellular matrix which can be sufficient in vivo, promotes high expression of type II collagen, is widely applied to research of phenotype, tissue and turnover of chondrocytes or intervertebral disc cells, differentiation of adipose-derived adult stem cells and bone marrow-derived mesenchymal stem cells and other related problems, and can provide a bionic natural biomaterial which is low in cost, easy to prepare and high in biocompatibility by solving the existing tissue engineering.
However, two key problems of the sodium alginate hydrogel are not solved at present: 1. alginate hydrogels generally exhibit poor mechanical strength (about 100kPa) due to a single cross-linked network structure and are susceptible to cracking after implantation causing implant failure; 2. because alginate has negative charge balance, the alginate generates electrostatic repulsion with most of proteins with negative charge on the surface, and the cell adhesion on the surface of the material is poor. In addition, in the application and preparation process of the existing sodium alginate hydrogel, an organic solvent or a crosslinking agent containing toxicity is introduced, so that the green environmental protection concept is not met, the cytotoxicity is increased, the crosslinking time is long, and the crosslinking efficiency is low.
Graphene has a very large specific surface area and a large number of surface functional groups, such as hydroxyl, carboxyl, epoxide and carbon groups, has a very strong adsorption capacity on protein, can enhance the adhesion of a material interface and cells, and can be subjected to various functional modifications. However, graphene has strong hydrophobicity and poor hydrophilicity, so that graphene is difficult to disperse, is easy to agglomerate and delaminate and has a short storage period in a system with water as a dispersion medium.
Meanwhile, as the electronegativity of the graphene is the same as that of sodium alginate, the graphene can only be used as a reinforcing phase to form a single network structure with a polymer, and the reinforcing effect on the hydrogel is very limited, so that natural high-molecular chitosan is introduced, the chitosan is used for functionalizing and neutralizing the electronegativity of the graphene, and meanwhile, the high biocompatibility of the chitosan is used for improving the cell adhesiveness of the sodium alginate hydrogel.
Disclosure of Invention
In order to overcome the defects of poor mechanical strength, poor cell adhesion, longer crosslinking time, lower crosslinking efficiency and environmental pollution of the existing sodium alginate-chitosan hydrogel, the invention provides the crosslinking method of the environment-friendly hydrogel containing the graphene oxide, which has the advantages of simple preparation, high crosslinking efficiency, short crosslinking time, no biotoxicity and green and environment-friendly raw materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of crosslinking an environmentally friendly graphene oxide-containing hydrogel, comprising the steps of:
1) preparing graphene oxide;
2) adding the graphene oxide prepared in the step 1) into deionized water, and performing ultrasonic dispersion to obtain a solution A;
3) dissolving sodium chloride, potassium chloride, disodium hydrogen phosphate and dipotassium hydrogen phosphate in deionized water, and regulating the pH value of the solution by using hydrochloric acid to obtain a solution B;
4) weighing sodium alginate powder and chitosan powder, and fully and uniformly mixing to obtain mixed powder a;
5) adding the mixed powder a in the step 4) into the solution B in the step 3), then adding the solution A in the step 2), and heating and stirring the whole system to obtain a solution C;
6) injecting the solution C obtained in the step 5) into a container to enable the solution C to uniformly cover the surface of the container;
7) weighing calcium carbonate powder, calcium sulfate powder and calcium chloride powder, and fully mixing uniformly to obtain mixed powder b;
8) adding the mixed powder b obtained in the step 7) into deionized water to obtain a solution D;
9) and (3) immersing the container covered with the solution C into the solution D, taking out, standing for crosslinking, and thus obtaining the graphene oxide-containing environment-friendly hydrogel.
According to the invention, a biochemical graphene/chitosan single-network structure is prepared by functionalizing natural high-molecular chitosan and neutralizing the electronegativity of graphene, the mechanical strength and porosity are optimized by controlling a microstructure, and then self-assembly crosslinking is realized on the basis of an original network through an ion crosslinking reaction and alginate to construct the double-network chitosan/graphene/alginate hydrogel. The good protein adsorption function and mechanical enhancement function of the graphene are utilized, the functional defects of the alginate hydrogel are overcome, and only natural high polymer materials with low cost and wide sources, such as chitosan, are adopted in the preparation process, so that the toxicity and environmental protection problems are solved, the graphene is promoted to be dispersed in the hydrogel and forms a double-network enhanced structure with sodium alginate, and the mechanical property and the anti-cracking property of the hydrogel are improved. Meanwhile, due to the antibacterial function of the graphene, the hydrogel has long-term bacteriostatic ability, and the effect of controlling germ infection for a long time is achieved. The hydrogel biological composite material has high mechanical property, inhibits the growth of microorganisms, promotes cell attachment, proliferation and differentiation, has a simple preparation method and has no biological toxicity.
According to the invention, a mixed system of calcium carbonate powder, calcium sulfate powder and calcium chloride powder is used as a crosslinking agent, so that the crosslinking efficiency is high and the crosslinking time is short in the hydrogel preparation process.
As a preferable scheme of the present invention, in step 1), the specific preparation method is:
a) graphite powder is dispersed in concentrated sulfuric acid and heated to 80 ℃ for reaction under the stirring of magnetons;
b) transferring the mixture obtained in the step a) to an ice bath, adding potassium permanganate, stirring and uniformly mixing to react for 12 hours;
c) heating and diluting the mixture obtained in the step b), and continuing the reaction;
d) adding hydrogen peroxide into the mixture obtained in the step c), and quickly mixing;
e) centrifuging the mixture obtained in the step d), removing the supernatant, and washing for several times by using dilute hydrochloric acid and deionized water;
f) peeling the mixture obtained in the step e) by using an ultrasonic probe, and centrifuging to obtain a supernatant;
g) and f), further carrying out ultrasonic treatment on the supernatant obtained in the step f) by using an ultrasonic probe, filtering and drying to obtain a graphene oxide solid.
In the technical scheme, in the step a), the mass-to-volume ratio of the graphite powder to the concentrated sulfuric acid is 1: 20-1: 25 g/mL; and/or the mass fraction of the concentrated sulfuric acid is 97-99%; the reaction temperature is 15-35 ℃ at room temperature; the reaction time is 10-14 h;
in the step b), the mass of the potassium permanganate is 3.5-4.5 g; the stirring time is 0.5-1.5 h; the reaction temperature is 30-50 ℃; the reaction time is 20-40 min;
in the step c), the heating temperature is 80-120 ℃; the final dilution volume is 90-110 mL; the reaction time is 20-40 min;
in the step d), the volume fraction of the added hydrogen peroxide is 20-40%; the volume of the added hydrogen peroxide is 5-15 mL; the solution mixed by adding the hydrogen peroxide is characterized by quickly becoming bright yellow;
in the step e), the volume fraction of the added dilute hydrochloric acid is 2-8%; the solution after being washed for a plurality of times is characterized by being neutral; the power of the ultrasonic stripping is 200-600W; and/or the ultrasonic stripping time is 10-50 min; the rotating speed of the centrifugation is 8000-12000 rpm; and/or the centrifugation time is 20-40 min;
in the step f), the power of ultrasonic stripping is 400-600W; and/or the ultrasonic time is 1-3 h; the drying time was 12 h.
As a preferable scheme of the invention, in the step 2), the number of times of ultrasonic dispersion is 2-5, the time of each ultrasonic dispersion is 15-25min, the gap time is 25-35min, the ultrasonic power is 250-300W, and the concentration of the graphene oxide in the solution A is 8-12 mg/mL.
As a preferable scheme of the present invention, in step 3), the mass ratio of sodium chloride, potassium chloride, disodium hydrogen phosphate, dipotassium hydrogen phosphate to deionized water is 8: 0.2: 1.44: 0.24: 1000, and the pH value is 7-8.
As a preferable scheme of the invention, in the step 4), the mass ratio of sodium alginate to chitosan is 1: 0.1-1: 10.
as a preferable scheme of the invention, in the step 5), the mixed powder a is 2 to 20 parts, the solution B is 94 parts, and the solution A is 0 to 20 parts by weight; the reaction temperature is 40-60 ℃, and the stirring time is 2-12 h.
As a preferable scheme of the present invention, in the step 7), the mass ratio of calcium carbonate, calcium sulfate and calcium chloride is 1: 0.1: 0.1-1: 10: 10.
as a preferable scheme of the present invention, in the step 8), the mass ratio of the mixed powder b to the deionized water is 1: 13-1: 53.
as a preferable scheme of the invention, in the step 9), the immersion time of the container covered with the solution C is 0-60 min; the crosslinking time is 2-12 h.
As a preferable scheme of the invention, the method further comprises the step 10), and the hydrogel after crosslinking is placed under an ultraviolet lamp for irradiating for 1-3 h.
Compared with the prior art, the invention has the following beneficial effects:
1) the chitosan in the raw materials is low in cost and wide in source, solves the problems of toxicity and environmental protection, and accords with the concept of environmental protection;
2) according to the invention, the antibacterial function of the graphene oxide is utilized, so that the hydrogel has long-term antibacterial capability, and the effect of controlling bacterial infection for a long time is achieved;
3) according to the invention, abundant hydroxyl, carboxyl, epoxy group and other groups on the surface of graphene oxide are utilized, and a good interface effect is formed with a hydrophilic matrix through hydrogen bonds and chemical bonds, so that the swelling performance of the hydrogel can be improved; in addition, the mechanical strength of the hydrogel is also improved due to the mechanical properties of graphene oxide;
4) according to the crosslinking application of the three components, the crosslinking efficiency is high and the crosslinking time is short in the hydrogel preparation process;
5) the hydrogel biological composite material prepared by the invention can be applied to the field of 1) medical cosmetology, and has great potential value in developing wound dressings and artificial skin; 2) the field of biological tissue engineering, which can be used for developing artificial implanted cartilage tissues; 3) the drug-carrying and targeted transportation field can provide reference value for drug-carrying materials; 4) the medicine packaging field can be further developed as an oral medicine capsule material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a crosslinking method of an environment-friendly graphene oxide-containing hydrogel, which comprises the following steps:
(1) preparing graphite powder into graphene oxide, wherein the graphene oxide comprises the following components:
a) graphite powder and concentrated sulfuric acid are dispersed in the concentrated sulfuric acid with the mass fraction of 98% according to the mass-volume ratio of 1:23g/mL, and the graphite powder and the concentrated sulfuric acid react for 12 hours at 25 ℃ under the stirring of magnetons;
b) transferring the mixture obtained in the step a) to an ice bath, adding 4g of potassium permanganate, stirring for 1h, uniformly mixing, and heating at 40 ℃ for reaction for 30 min;
c) heating the mixture obtained in the step b) at 100 ℃, diluting the mixture to be 100mL, and continuing to react for 30 min;
d) and c) adding 10mL of 30% hydrogen peroxide into the mixture obtained in the step c), quickly mixing, and quickly changing the mixed solution into bright yellow.
e) Centrifuging the mixture obtained in the step d), removing supernatant, and washing for several times by using dilute hydrochloric acid with the volume fraction of 5% and deionized water, wherein the finally obtained solution is neutral;
f) peeling the mixture obtained in the step e) for 30min by using an ultrasonic probe with the power of 400W, and centrifuging for 30min at the rotating speed of 10000rpm to obtain supernatant;
g) further carrying out ultrasonic treatment on the supernatant obtained in the step f) for 2h by using an ultrasonic probe with the power of 520W, filtering, and drying for 12h to obtain a graphene oxide solid;
(2) weighing a proper amount of graphene oxide, and ultrasonically dispersing in deionized water, wherein the ultrasonic power is 285W, the ultrasonic dispersion time is 20 minutes each time and 3 times in total, and the intermittent time is 30 minutes, so that a uniform solution A of 10mg/mL is finally obtained;
(3) dissolving 8g of sodium chloride, 0.2g of potassium chloride, 1.44g of disodium hydrogen phosphate and 0.24g of dipotassium hydrogen phosphate in 1000g of deionized water, and adjusting the pH value of the solution to 7.4 by using hydrochloric acid to prepare a solution B;
(4) according to the weight percentage of sodium alginate: chitosan ═ 1: 1, weighing sodium alginate powder and chitosan powder, and fully and uniformly mixing to obtain mixed powder a;
(5) adding 0.6g of the mixed powder a into 9.4g of the solution B, then adding 0.4g of the solution A, and heating and stirring the whole system at 50 ℃ for 8 hours to obtain a solution C;
(6) pouring the solution C into a culture dish, and uniformly covering the surface of the culture dish;
(7) according to the calcium carbonate powder: calcium sulfate powder: calcium chloride powder 1: 1.721: 2.219, mixing calcium carbonate powder, calcium sulfate powder and calcium chloride powder to obtain mixed powder b;
(8) according to the weight percentage of mixed powder b: deionized water 1: 53, adding the mixed powder b into deionized water to prepare a solution D;
(9) the petri dish covered with the solution C was immersed in the solution D for 5min, then taken out, and left to stand for crosslinking for 4 h.
Example 2
The embodiment provides a crosslinking method of an environment-friendly hydrogel containing graphene oxide, which comprises the following steps:
(1) preparing graphite powder into graphene oxide, wherein the graphene oxide comprises the following components:
a) graphite powder and concentrated sulfuric acid are dispersed in the concentrated sulfuric acid with the mass fraction of 98% according to the mass volume ratio of 1:25g/mL, and the reaction is carried out for 14h at 35 ℃ under the stirring of magnetons;
b) transferring the mixture obtained in the step a) to an ice bath, adding 4.5g of potassium permanganate, stirring for 1.5h, uniformly mixing, and heating at 50 ℃ for reaction for 40 min;
c) heating the mixture obtained in the step b) at 120 ℃, diluting the mixture to 110mL, and continuing to react for 40 min;
d) adding 15mL of 40% hydrogen peroxide by volume fraction into the mixture obtained in the step c), quickly mixing, and quickly changing the mixed solution into bright yellow.
e) Centrifuging the mixture obtained in the step d), removing supernatant, and washing for several times by using dilute hydrochloric acid with the volume fraction of 8% and deionized water, wherein the finally obtained solution is neutral;
f) peeling the mixture obtained in the step e) for 50min by using an ultrasonic probe with the power of 600W, and centrifuging for 40min at the rotating speed of 12000rpm to obtain a supernatant;
g) further carrying out ultrasonic treatment on the supernatant obtained in the step f) for 3h by using an ultrasonic probe with the power of 600W, filtering, and drying for 12h to obtain a graphene oxide solid;
(2) weighing a proper amount of graphene oxide, and ultrasonically dispersing in deionized water, wherein the ultrasonic power is 285W, the ultrasonic dispersion time is 20 minutes each time and 3 times in total, and the intermittent time is 30 minutes, so that a uniform solution A of 10mg/mL is finally obtained;
(3) dissolving 8g of sodium chloride, 0.2g of potassium chloride, 1.44g of disodium hydrogen phosphate and 0.24g of dipotassium hydrogen phosphate in 1000g of deionized water, and adjusting the pH value of the solution to 7.4 by using hydrochloric acid to prepare a solution B;
(4) according to the weight percentage of sodium alginate: chitosan ═ 1: 1, weighing sodium alginate powder and chitosan powder, and fully and uniformly mixing to obtain mixed powder a;
(5) adding 0.6g of the mixed powder a into 9.4g of the solution B, then adding 1g of the solution A, and heating and stirring the whole system at 50 ℃ for 8 hours to obtain a solution C;
(6) pouring the solution C into a culture dish, and uniformly covering the surface of the culture dish;
(7) according to the calcium carbonate powder: calcium sulfate powder: calcium chloride powder 1: 1.721: 2.219, mixing calcium carbonate powder, calcium sulfate powder and calcium chloride powder to obtain mixed powder b;
(8) according to the weight percentage of mixed powder b: deionized water 1: 53, adding the mixed powder b into deionized water to prepare a solution D;
(9) the petri dish covered with the solution C was immersed in the solution D for 5min, then taken out, and left to stand for cross-linking for 4 h.
Example 3
The embodiment provides a crosslinking method of an environment-friendly graphene oxide-containing hydrogel, which comprises the following steps:
(1) preparing graphite powder into graphene oxide, wherein the graphene oxide comprises the following components:
a) graphite powder and concentrated sulfuric acid are dispersed in the concentrated sulfuric acid with the mass fraction of 98% according to the mass volume ratio of 1:20g/mL, and the reaction is carried out for 10h at 15 ℃ under the stirring of magnetons;
b) transferring the mixture obtained in the step a) to an ice bath, adding 3.5g of potassium permanganate, stirring for 0.5h, uniformly mixing, and heating at 30 ℃ for reaction for 20 min;
c) heating the mixture obtained in the step b) at 80 ℃, diluting to 90mL, and continuing to react for 20 min;
d) and d) adding 5mL of hydrogen peroxide with the volume fraction of 20% into the mixture obtained in the step c), quickly mixing, and quickly changing the mixed solution into bright yellow.
e) Centrifuging the mixture obtained in the step d), removing supernatant, and washing for several times by using dilute hydrochloric acid with the volume fraction of 2% and deionized water, wherein the finally obtained solution is neutral;
f) peeling the mixture obtained in the step e) for 10min by using an ultrasonic probe with the power of 200W, and centrifuging for 20min at the rotating speed of 8000rpm to obtain a supernatant;
g) further carrying out ultrasonic treatment on the supernatant obtained in the step f) for 1h by using an ultrasonic probe with the power of 400W, filtering, and drying for 12h to obtain a graphene oxide solid;
(2) weighing a proper amount of graphene oxide, and ultrasonically dispersing in deionized water, wherein the ultrasonic power is 285W, the ultrasonic dispersion time is 20 minutes each time and 3 times in total, and the intermittent time is 30 minutes, so that a uniform solution A of 10mg/mL is finally obtained;
(3) dissolving 8g of sodium chloride, 0.2g of potassium chloride, 1.44g of disodium hydrogen phosphate and 0.24g of dipotassium hydrogen phosphate in 1000g of deionized water, and adjusting the pH value of the solution to 7.4 by using hydrochloric acid to prepare a solution B;
(4) according to the weight percentage of sodium alginate: chitosan ═ 1: 1, weighing sodium alginate powder and chitosan powder, and fully and uniformly mixing to obtain mixed powder a;
(5) adding 0.6g of the mixed powder a into 9.4g of the solution B, then adding 1.2g of the solution A, and heating and stirring the whole system at 50 ℃ for 8 hours to obtain a solution C;
(6) pouring the solution C into a culture dish, and uniformly covering the surface of the culture dish;
(7) according to the calcium carbonate powder: calcium sulfate powder: calcium chloride powder 1: 1.721: 2.219, mixing calcium carbonate powder, calcium sulfate powder and calcium chloride powder to obtain mixed powder b;
(8) according to the weight percentage of mixed powder b: deionized water 1: 53, adding the mixed powder b into deionized water to prepare a solution D;
(9) the petri dish covered with the solution C was immersed in the solution D for 5min, then taken out, and left to stand for crosslinking for 4 h.
(10) The crosslinked hydrogel was placed under an ultraviolet lamp for 2 hours.
Comparative example 1, the same as example 1, except that the crosslinker component was not added with calcium chloride powder.
Comparative example 2, same as example 1, except that only calcium chloride powder was added to the crosslinker component.
The environmental protection hydrogel containing graphene oxide prepared in example 1 and the hydrogels prepared in comparative examples 1 and 2 were subjected to a cross-linking rate test, and the results are shown in table 1.
TABLE 1 Cross-linking time measurement
As can be seen from Table 1, the crosslinking time of the hydrogel is significantly reduced after the addition of calcium chloride as a crosslinker component.
The hydrogel is crosslinked by three components of calcium chloride, calcium sulfate and calcium carbonate, wherein chitosan promotes graphene to disperse and form a double-network reinforced structure with sodium alginate, and due to the existence of graphene oxide, the hydrogel has a self-assembly multilayer porous structure, and macromolecules with various forms, such as various crystals and metal particles, can be modified on the surface to load different functional factors.
For example, the hydrogel of the present invention can be loaded with a combination of ingredients based on mussel extract and onion extract for scar removal and itching relief; can be loaded with growth factors for promoting cell repair and proliferation.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalents to the disclosed technology without departing from the spirit and scope of the present invention, and all such changes, modifications and equivalents are intended to be included therein as equivalents of the present invention; meanwhile, any equivalent changes, modifications and evolutions of the above embodiments according to the essential technology of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A method for crosslinking an environmentally friendly hydrogel containing graphene oxide, comprising the steps of:
1) preparing graphene oxide;
2) adding the graphene oxide prepared in the step 1) into deionized water, and performing ultrasonic dispersion to obtain a solution A;
3) dissolving sodium chloride, potassium chloride, disodium hydrogen phosphate and dipotassium hydrogen phosphate in deionized water, and regulating the pH value of the solution by using hydrochloric acid to obtain a solution B;
4) weighing sodium alginate powder and chitosan powder, and fully and uniformly mixing to obtain mixed powder a;
5) adding the mixed powder a in the step 4) into the solution B in the step 3), then adding the solution A in the step 2), and heating and stirring the whole system to obtain a solution C;
6) injecting the solution C obtained in the step 5) into a container to enable the solution C to uniformly cover the surface of the container;
7) weighing calcium carbonate powder, calcium sulfate powder and calcium chloride powder, and fully and uniformly mixing to obtain mixed powder b;
8) adding the mixed powder b obtained in the step 7) into deionized water to obtain a solution D;
9) and (3) immersing the container covered with the solution C into the solution D, then taking out, standing for crosslinking, and thus obtaining the environment-friendly hydrogel containing graphene oxide.
2. The method for crosslinking the environmentally-friendly hydrogel containing graphene oxide according to claim 1, wherein the specific preparation method in the step 1) comprises the following steps:
a) graphite powder is dispersed in concentrated sulfuric acid and heated to 80 ℃ for reaction under the stirring of magnetons;
b) transferring the mixture obtained in the step a) to an ice bath, adding potassium permanganate, stirring and uniformly mixing to react for 12 hours;
c) heating and diluting the mixture obtained in the step b), and continuing the reaction;
d) adding hydrogen peroxide into the mixture obtained in the step c), and quickly mixing;
e) centrifuging the mixture obtained in the step d), removing the supernatant, and washing for several times by using dilute hydrochloric acid and deionized water;
f) peeling the mixture obtained in the step e) by using an ultrasonic probe, and centrifuging to obtain a supernatant;
g) and f), further carrying out ultrasonic treatment on the supernatant obtained in the step f) by using an ultrasonic probe, filtering and drying to obtain a graphene oxide solid.
3. The crosslinking method of the environment-friendly hydrogel containing graphene oxide as claimed in claim 1, wherein in the step 2), the number of ultrasonic dispersions is 2-5, the time of each ultrasonic dispersion is 15-25min, the gap time is 25-35min, the ultrasonic power is 250-300W, and the concentration of graphene oxide in the solution A is 8-12 mg/mL.
4. The method for crosslinking the environmentally-friendly graphene oxide-containing hydrogel according to claim 1, wherein in the step 3), the mass ratio of the sodium chloride, the potassium chloride, the disodium hydrogen phosphate, the dipotassium hydrogen phosphate and the deionized water is 8: 0.2: 1.44: 0.24: 1000, and the pH value is 7-8.
5. The method for crosslinking the graphene oxide-containing environment-friendly hydrogel according to claim 1, wherein in the step 4), the mass ratio of sodium alginate to chitosan is 1: 0.1-1: 10.
6. the method for crosslinking the environmentally friendly hydrogel containing graphene oxide according to claim 1, wherein in the step 5), the mixed powder a is 2 to 20 parts, the solution B is 94 parts, and the solution A is 0 to 20 parts by weight; the reaction temperature is 40-60 ℃, and the stirring time is 2-12 h.
7. The method for crosslinking the graphene oxide-containing environment-friendly hydrogel according to claim 1, wherein in the step 7), the mass ratio of calcium carbonate, calcium sulfate and calcium chloride is 1: 0.1: 0.1-1: 10: 10; in the step 8), the mass ratio of the mixed powder b to the deionized water is 1: 10-1: 100.
8. the method for crosslinking the environmentally friendly hydrogel containing graphene oxide according to claim 1, wherein in the step 9), the immersion time of the container covered with the solution C is 0-60 min; the crosslinking time is 2-12 h.
9. The method for crosslinking the environmentally friendly hydrogel containing graphene oxide according to claim 1, further comprising a step 10) of irradiating the crosslinked hydrogel under an ultraviolet lamp for 1-3 hours.
10. Use of an environmentally friendly graphene oxide-containing hydrogel, characterized in that the environmentally friendly graphene oxide-containing hydrogel obtained by the crosslinking method according to any one of claims 1 to 9 is used in the medical and cosmetic fields or in dressings.
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