BIODEGRADABLE GRAPHENE OXIDE BIOCOMPOSITE FIBROUS MEMBRANE, PREPARATION METHOD AND USES THEREOF

Abstract

The invention relates to a biodegradable graphene oxide biocomposite fibrous membrane and a preparation method and uses thereof. The composite fibrous membrane comprises biodegradable graphene oxide biocomposite fibers, each fiber has an outer layer consisting of graphene oxide-biodegradable polymer nanofibers and an inner layer consisting of sodium alginate/polyvinyl alcohol nanocomposite fibers. The biodegradable graphene oxide biocomposite fibrous membrane of the invention has the advantages of good biocompatibility, biodegradability, swellability, bacteriostasis and good mechanical properties and chemical stability.

Claims

1. A biodegradable graphene oxide biocomposite fibrous membrane, characterized by comprising biodegradable graphene oxide biocomposite fibers, each fiber has an outer layer consisting of graphene oxide-biodegradable polymer nanofibers and an inner layer consisting of sodium alginate/polyvinyl alcohol nanocomposite fibers.

2. The biodegradable graphene biocomposite fibrous membrane according to claim 1, wherein the weight ratio of graphene oxide and the biodegradable polymer in the outer layer of the graphene oxide-biodegradable polymer nanofibers is about 1: (25-100).

3. The biodegradable graphene oxide biocomposite fibrous membrane according to claim 1, wherein the biodegradable polymer is polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polydioxanone (PDO) or a copolymer thereof.

4. The biodegradable graphene oxide biocomposite fibrous membrane according to claim 1, wherein the sodium alginate in the inner layer of the sodium alginate/polyvinyl alcohol nanocomposite fibers accounts for about 10%-40% by weight based on the total weight of sodium alginate and polyvinyl alcohol.

5. The method for preparing the biodegradable graphene oxide biocomposite fibrous membrane according to claim 1, comprising the steps of: (1) ultrasonically dispersing the graphene oxide in solvent A to form a uniform graphene oxide solution; dissolving the biodegradable polymer in solvent B to form a biodegradable polymer solution; (2) mixing the graphene oxide solution and the biodegradable polymer solution prepared in the step (1) and stirring uniformly to form an electrospinning solution C for the outer layer, wherein the weight ratio of the graphene oxide to the biodegradable polymer is about 1:(25-100); (3) separately dissolving sodium alginate and polyvinyl alcohol in deionized water to form an aqueous solution of sodium alginate and an aqueous solution of polyvinyl alcohol, then mixing the two aqueous solutions in proportion to form an electrospinning solution D for the inner layer, wherein the sodium alginate accounts for 10%-40% by weight based on the total weight of sodium alginate and polyvinyl alcohol; (4) adding the outer layer electrospinning solution C and the inner layer electrospinning solution D into an electrospinning machine, carrying out coaxial electrospinning and extruding the fibers from the inner tube and the outer tube into the coagulating bath of calcium chloride-ethanol solution for crosslinking for 30-60 mins, subsequently washing with absolute ethyl alcohol and vacuum drying to obtain a biodegradable graphene oxide biocomposite fibrous membrane.

6. The method for preparing a biodegradable graphene oxide biocomposite fibrous membrane according to claim 5, wherein the biodegradable polymer is polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polydioxanone (PDO) or a copolymer thereof.

7. The method for preparing a biodegradable graphene oxide biocomposite fibrous membrane according to claim 5, wherein the solvent A in the step (1) is N,N-dimethylformamide or absolute ethyl alcohol.

8. The method for preparing a biodegradable graphene oxide biocomposite fibrous membrane according to claim 5, wherein the solvent B in the step (1) is dichloromethane or trichloromcthane.

9. The method for preparing a biodegradable graphene oxide biocomposite fibrous membrane according to claim 5, wherein the weight percentage of calcium chloride in the coagulation bath of calcium chloride-ethanol solution is about 1 wt %-3 wt %.

10. Use of the biodegradable graphene oxide biocomposite fibrous membrane as medical dressing, surgical sutures, or drug carrier.

11. A method of preparing a medical dressing, surgical sutures, or drug carrier, the method comprising using the biodegradable graphene oxide biocomposite fibrous membrane of claim 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0026] The invention is further illustrated by the following specific examples, but the protection scope of the invention is not limited by the examples.

Example 1

[0027] The graphene oxide is ultrasonically dispersed in absolute ethyl alcohol to form a uniform graphene oxide solution; the polylactic acid is dissolved in trichloromethane to form a biodegradable polymer solution; the prepared graphene oxide solution and the biodegradable polymer solution are mixed and uniformly stirred to form an outer electrospinning solution C, wherein the weight ratio of the graphene oxide to the biodegradable polymer in the outer electrospinning solution C is 1:50; the sodium alginate and polyvinyl alcohol are seperately dissolved in deionized water to form an aqueous sodium alginate solution and an aqueous polyvinyl alcohol solution, the two aqueous solutions are mixed and stirred uniformly to form an inner layer electrospinning solution D, wherein the sodium alginate accounts for 10 wt % based on the total weight of sodium alginate and polyvinyl alcohol. Then the outer electrospinning solution C and the inner electrospinning solution D are added into an electrospinning machine for coaxial electrospinning with the process parameters are: voltage: 10 kV-20 kV, extrusion speed: 0.1-1 ml/h, the horizontal distance from the needle to the receiving device: 10-20 cm, temperature: 25-30 C., humidity 50-80%. The fibers from the inner and outer tube are extruded to the coagulating bath of calcium chloride-ethanol solution for crosslinking for 30-60 mins. The weight percentage of calcium chloride in the coagulation bath of calcium chloride-ethanol solution is 1 wt %. The resultant is washed with absolute ethanol and vacuum dried to obtain a biodegradable graphene oxide biocomposite fibrous membrane.

Example 2

[0028] The graphene oxide is ultrasonically dispersed in anhydrous ethanol to form a uniform graphene oxide solution; the polylactic acid is dissolved in dichloromethane to form a biodegradable polymer solution; the prepared graphene oxide solution and the biodegradable polymer solution are mixed and uniformly stirred to form an outer electrospinning solution C, wherein the weight ratio of the graphene oxide to the biodegradable polymer in the outer electrospinning solution C is 1:100; the sodium alginate and polyvinyl alcohol are separately dissolved in deionized water to form an aqueous sodium alginate solution and an aqueous polyvinyl alcohol solution, the two aqueous solutions are mixed and stirred uniformly to form an inner layer electrospinning solution D, wherein the sodium alginate accounts for 30 wt % based on the total weight of sodium alginate and polyvinyl alcohol. Then the outer electrospinning solution C and the inner electrospinning solution D are added into an electrospinning machine for coaxial electrospinning with the process parameters are: voltage: 10 kV-20 kV, extrusion speed: 0.1-1 ml/h, the horizontal distance from the needle to the receiving device: 10-20 cm, temperature: 25-30 C., humidity 100-80%. The fibers from the inner and outer tube are extruded to the coagulating bath of calcium chloride-ethanol solution for crosslinking for 30-60 mins. The weight percentage of calcium chloride in the coagulation bath of calcium chloride-ethanol solution is 1 wt %. The resultant is washed with absolute ethanol and vacuum dried to obtain a biodegradable graphene oxide biocomposite fibrous membrane.

Example 3

[0029] The graphene oxide is ultrasonically dispersed in N,N-dimethylformamide to form a uniform graphene oxide solution; the polylactic acid is dissolved in polycaprolactone to form a biodegradable polymer solution; the prepared graphene oxide solution and the biodegradable polymer solution are mixed and uniformly stirred to form an outer electrospinning solution C, wherein the weight ratio of the graphene oxide to the biodegradable polymer in the outer electrospinning solution C is 1:75; the sodium alginate and polyvinyl alcohol are separately dissolved in deionized water to form an aqueous sodium alginate solution and an aqueous polyvinyl alcohol solution, the two aqueous solutions are mixed and stirred uniformly to form an inner layer electrospinning solution D, wherein the sodium alginate accounts for 20 wt % based on the total weight of sodium alginate and polyvinyl alcohol. Then the outer electrospinning solution C and the inner electrospinning solution D are added into an electrospinning machine for coaxial electrospinning with the process parameters are: voltage: 10 kV-20 kV, extrusion speed: 0.1-1 ml/h, the horizontal distance from the needle to the receiving device: 10-20 cm, temperature: 25-30 C., humidity 100-80%. The fibers from the inner and outer tube are extruded to the coagulating bath of calcium chloride-ethanol solution for crosslinking for 30-60 mins. The weight percentage of calcium chloride in the coagulation bath of calcium chloride-ethanol solution is 1 wt %. The resultant is washed with absolute ethanol and vacuum dried to obtain a biodegradable graphene oxide biocomposite fibrous membrane.

Example 4

[0030] The graphene oxide is ultrasonically dispersed in absolute ethyl alcohol to form a uniform graphene oxide solution; the polyglycolic acid is dissolved in dichloromethane to form a biodegradable polymer solution; the prepared graphene oxide solution and the biodegradable polymer solution are mixed and uniformly stirred to form an outer electrospinning solution C, wherein the weight ratio of the graphene oxide to the biodegradable polymer in the outer electrospinning solution C is 1:25; the sodium alginate and polyvinyl alcohol are separately dissolved in deionized water to form an aqueous sodium alginate solution and an aqueous polyvinyl alcohol solution, the two aqueous solutions are mixed and stirred uniformly to form an inner layer electrospinning solution D, wherein the sodium alginate accounts for 40 wt % based on the total weight of sodium alginate and polyvinyl alcohol. Then the outer electrospinning solution C and the inner electrospinning solution D are added into an electrospinning machine for coaxial electrospinning with the process parameters are: voltage: 10 kV-20 kV, extrusion speed: 0.1-1 ml/h, the horizontal distance from the needle to the receiving device: 10-20 cm, temperature: 25-30 C., humidity 100-80%. The fibers from the inner and outer tube are extruded to the coagulating bath of calcium chloride-ethanol solution for crosslinking for 30-60 mins. The weight percentage of calcium chloride in the coagulation bath of calcium chloride-ethanol solution is 3 wt %. The resultant is washed with absolute ethanol and vacuum dried to obtain a biodegradable graphene oxide biocomposite fibrous membrane.

[0031] The biodegradable graphene oxide biocomposite fibrous membrane of the invention has the advantages of good biocompatibility, biodegradability and bacteriostasis, which is a good medical material. It can be used as a medical dressing or a surgical suture and also has a good prospect applied as drug carrier.