CN102940907A - Graphene oxide and silk fibroin composite membrane and preparation method thereof - Google Patents
Graphene oxide and silk fibroin composite membrane and preparation method thereof Download PDFInfo
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- CN102940907A CN102940907A CN2012104444271A CN201210444427A CN102940907A CN 102940907 A CN102940907 A CN 102940907A CN 2012104444271 A CN2012104444271 A CN 2012104444271A CN 201210444427 A CN201210444427 A CN 201210444427A CN 102940907 A CN102940907 A CN 102940907A
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Abstract
The invention discloses a graphene oxide and silk fibroin composite membrane and a preparation method thereof, and is characterized in that the composite membrane consists of graphene oxide and silk fibroin; wherein the mass ratio of the graphene oxide to the silk fibroin is 1-50: 100; the composite membrane is prepared by adopting a layer-by-layer assembly, suction filtration or casting method. Graphene has excellent physicochemical and biological properties, but has certain cytotoxicity, and the toxicity can be greatly reduced by compounding with protein, so that the biocompatibility is improved, and the graphene can be more safely applied to the biological field. SF is used as natural high molecular protein and has special structural performance and excellent biological performance, the GO/SF composite material is prepared by compounding SF and GO by adopting a layer-by-layer assembling, suction filtering and casting method, good dispersion of GO and SF is realized, the biological toxicity of GO is reduced by SF, hydroxyapatite can be effectively deposited on the surface of the material, and the material has good in vitro biological activity and is expected to become a novel bone repair and bone substitute material.
Description
Technical field
The present invention relates to technical field of biomedical materials, relate in particular to a kind of graphene oxide with external activity and fibroin albumen composite membrane and preparation method thereof.
Background technology
The damaged of body bone tissue small size can obtain regeneration by self-reparing capability, but this self-repair function is subject to the impact of age, disease and other factor, so bone reparation, bone alternate material got more and more people's extensive concerning since the sixties in last century.Promote reproducibility material three phases from bio-inert material, biological reactivity material to tissue, people have proposed to activate the gene expression of repair tissue cell, improve propagation and the differentiation of cell, initiatively excite tissue neomorph, the concept of realization regeneration and restoration.Human body has strict requirement to bone impairment renovation material: good biocompatibility must be arranged, do not cause immunological rejection, to the receptor avirulence, to defective region similar profile and component be arranged, and good osteoinductive and conductivity are arranged.Hydroxyapatite is the main inorganic composition in the osseous tissue, has good biocompatibility, biological activity and bone conductibility.Therefore, can cause the bioactive materials of hydroxyapatite deposition, be expected to for bone tissue restoration and alternative.In recent years, people propose bionical concept, by to the constituent structure characteristic of natural bone itself and mineralization process imitation, particularly along with the deepening continuously of organizational project and regenerative medicine and stem-cell research, bionics becomes an important development trend of artificial bone repair materials research.This class height imitation natural bone constituent structure and the imitative material of the Novel imitation greenwood of function comprise the nano-calcium-phosphor ceramic material that imitates the natural bone ore deposit and bionic-type composite etc.
Carbon is one of basic element that all life body consists of on the earth, is the skeleton of life.Graphene is the Two-dimensional Carbon atomic crystal of monatomic thickness, it is the thinnest high-strength nano material that it is found that up to now, have specific surface area and excellent electricity, mechanics, optics and the thermal property of super large, make it all have great application prospect in fields such as electronic information, the energy, composite and biological medicines.Simultaneously, the application of Graphene derivant at aspects such as bio-sensing, microorganism detection and pharmaceutical carriers makes it become the focus of nano biological medical domain research.Graphene oxide (GO) is to be obtained by ultrasonic peeling off behind the graphite oxidation, its sheet surfaces and edge access the oxygen-content active groups such as a large amount of epoxy radicals, hydroxyl, carbonyl and carboxyl, so graphene oxide has good biocompatibility and aqueous stability.The aspects such as the modulus of elasticity of graphene oxide based composites, hot strength, electrical conductivity and heat stability all have excellent performance.But Graphene and GO have certain bio-toxicity, with unicellular interaction energy cell membrane injury.Protein is as the biomaterial of high-quality, and the energy adsorbed close is in the GO surface, and the defective on GO surface also can become the adsorption site of protein in addition, and the bio-toxicity of GO reduces after protein adsorption greatly.The people such as Hu (Hu W., et al.Protein Corona-Mediated Mitigation on Cytotoxicity of Graphene Oxide.2011) GO is coated with 10% hyclone after, can use safely in most of medium cells, the GO cytotoxicity reduces greatly.
Fibroin albumen (SF) is the natural polymer fibrin, has good biocompatibility and biodegradable.The good beta sheet structure of its orientation is given its excellent mechanical performance, comprise good pliability, tensile strength and moisture absorption poisture-penetrability etc., but large through the regeneration SF film water dissolubility that obtains after the sericin removal dissolving, intensity is low, process through soak with ethanol, the random coil structure can change beta sheet into, can improve the degree of crystallinity of SF, reduces the dissolve-loss ratio of fibroin membrane.The SF membrane material has been widely used in the fields such as bone induction and regeneration, biological support, biosensor and medicine controlled releasing, being fit to cell attaches, breeds, grows, the good compatibility is arranged in vivo, can be used as candidate's tissue engineering bracket of Growth of Cells, be used for repairing nerve damage.
Summary of the invention
The objective of the invention is to provide in order to improve the deficiencies in the prior art a kind of graphene oxide and fibroin albumen composite membrane; Another object of the present invention also provides the preparation method of above-mentioned graphene oxide and fibroin albumen composite membrane, will have the fibroin albumen of good biological performance and the graphene oxide of physicochemical property excellence to prepare composite membrane by layer assembly, sucking filtration and casting method.Graphite oxide is fully peeled off and is obtained the nanoscale graphene oxide, can Uniform Dispersion in material with fibroin albumen, by the effective sedimentary phosphor lime stone of material surface energy that soaked the simulated body fluid experimental verification, illustrate that composite membrane has good Bioactivity.
Technical scheme of the present invention is: graphene oxide and fibroin albumen composite membrane is characterized in that the composite membrane that is comprised of graphene oxide (GO) and fibroin albumen (SF); Wherein graphene oxide (GO) is 1-50:100 with the mass ratio of fibroin albumen (SF); Composite membrane adopts the method for layer assembly, sucking filtration or casting to prepare.
The present invention also provides the preparation method of above-mentioned graphene oxide and fibroin albumen composite membrane, and its concrete steps are as follows:
Method one: slide is soaked the activation of introducing hydroxyl in piranha solution, do substrate with the activation slide, alternating impregnating deposition graphene oxide (GO) solution and fibroin albumen (SF) solution, form graphene oxide (GO) and fibroin albumen (SF) composite membrane, the mass ratio of graphene oxide and fibroin albumen is 1-50:100 in the control composite membrane; Each soak SF after, immerse and soak again graphene oxide after making the fibroin albumen crystallization in the ethanol, so alternate cycles obtains layer assembly graphene oxide and fibroin albumen composite membrane;
Method two: be that 1-50:100 mixes by graphene oxide (GO) with the mass ratio of fibroin albumen (SF) with graphene oxide (GO) solution and fibroin albumen (SF) solution, obtain mixed solution, adopt the method for sucking filtration, in funnel, pour mixed solution into, by filter membrane, make graphene oxide and fibroin albumen composite membrane;
Method three: be that 1-50:100 mixes by graphene oxide (GO) with the mass ratio of fibroin albumen (SF) with graphene oxide (GO) solution and fibroin albumen (SF) solution, obtain mixed solution, adopt the method for casting, mixed solution is poured in the mould, normal temperature drying obtains graphene oxide and fibroin albumen composite membrane.
Slide each soak time in fibroin albumen (SF) solution and graphene oxide (GO) solution is 10-20min in the method for optimizing one; Behind each immersion SF, each soak time is 5-10min in ethanol; The concentration of the graphene oxide that adopts in the method one, two, three (GO) solution is 1-10mg/ml, and fibroin albumen (SF) solution concentration is 5-100mg/ml.
Mould is polystyrene or politef mould in the method for optimizing three.
The multi-form GO/SF composite membrane of three kinds of method preparations is soaked simulated body fluid (SBF solution), according to GO/SF composite membrane surface area (cm
2) and SBF liquor capacity (ml) than for 0.1-0.3cm
-1Ratio soak, place in 37 ℃ the water bath with thermostatic control shaking table, frequency of vibration is 60-80rpm, in the whole immersion process, changes a SBF solution every 12 hours, after the week composite membrane is taken out, and cleans with deionized water, characterizes after the drying at room temperature.
Beneficial effect:
Compare with composite is arranged now, the composite membrane of the present invention's preparation has adopted the GO of very good mechanical properties and the SF of good biological performance, makes composite guarantee the active energy of its good biological when having certain mechanical strength.The method of layer assembly, sucking filtration and casting has realized the fine dispersion of organic and inorganic in material, and the SBF immersion test shows that material has good Bioactivity.
Description of drawings
Fig. 1 is prepared graphene oxide and the photo of fibroin albumen composite membrane; Wherein (a) is the from level to level photo of assembled compound film of embodiment, (b) is the layer by layer photo of sucking filtration composite membrane of embodiment four, (c) is the photo of embodiment seven casting preparation composite membranes;
Fig. 2 is embodiment one GO/SF layer assembly composite membrane section SEM photo;
Fig. 3 is the SEM photo on (a) before the embodiment one GO/SF layer assembly composite membrane immersion SBF, rear (b) surface;
Fig. 4 is (a), rear (b) layer assembly GO/SF composite membrane XRD spectra before the embodiment one immersion SBF.
The specific embodiment
Below utilize embodiment to further describe the present invention, but can not think the restriction scope of invention.
Embodiment one
Slide soaked in piranha solution make surface hydroxylation.Compound concentration is the SF solution of 100mg/ml and the GO solution of 1mg/ml, the activation slide soaks 10min in GO solution, wash down with distilled water after taking out, in SF solution, soak 10min after the drying at room temperature, wash down with distilled water after taking out, in ethanol, soak 5min after the drying at room temperature, wash down drying at room temperature with distilled water after taking out.Above step is the primary depositing process, repeats above step, has prepared 50 layers composite film material, and GO and SF mass ratio are 1:100.Photo Fig. 1 (a) can find out layer assembly composite membrane color even, and section structure SEM photo Fig. 2 can see that material section has more uniform nacreous layer structure.
Embodiment two
Slide soaked in piranha solution make surface hydroxylation.Compound concentration is the GO solution of 5mg/ml and the SF solution of 20mg/ml, to activate slide and in GO solution, soak 20min, wash down with distilled water after taking out, in SF solution, soak 20min after the drying at room temperature, wash down with distilled water after taking out, in ethanol, soak 5min after the drying at room temperature, wash down drying at room temperature with distilled water after taking out.Above step is the primary depositing process, repeats above step, prepares 50 layers composite film material, and GO and SF mass ratio are 25:100.
Embodiment three
Slide soaked in piranha solution make surface hydroxylation.Compound concentration is the SF solution of 20mg/ml and the GO solution of 10mg/ml, to activate slide and in GO solution, soak 20min, wash down with distilled water after taking out, in SF solution, soak 20min after the drying at room temperature, wash down with distilled water after taking out, in ethanol, soak 10min after the drying at room temperature, wash down drying at room temperature with distilled water after taking out.Above step is the primary depositing process, repeats above step, prepares 50 layers composite film material, and GO and SF mass ratio are 50:100.
Embodiment four
Compound concentration is the GO solution of 1mg/ml and the SF solution of 50mg/ml, gets 10mlGO solution and the ultrasonic mixing of 20mlSF solution, is 50mm with diameter, and the aperture is that the PTFE film of 0.22 μ m is made filter paper, and sucking filtration makes the GO/SF composite membrane, and GO and SF mass ratio are 1:100.Photo Fig. 1 (b) is the sucking filtration composite membrane of color even.
Embodiment five
Compound concentration is the GO solution of 5mg/ml and the SF solution of 100mg/ml, getting 50mlGO solution and the ultrasonic mixing of 10mlSF solution, is 50mm with diameter, and the aperture is that the PTFE film of 0.22 μ m is made filter paper, sucking filtration makes the GO/SF composite film material, and GO and SF mass ratio are 25:100.
Embodiment six
Compound concentration is the GO solution of 10mg/ml and the SF solution of 20mg/ml, getting 50mlGO solution and the ultrasonic mixing of 50mlSF solution, is 50mm with diameter, and the aperture is that the PTFE film of 0.22 μ m is made filter paper, sucking filtration makes the GO/SF composite film material, and GO and SF mass ratio are 50:100.
Embodiment seven
Compound concentration is the GO solution of 2mg/ml and the SF solution of 50mg/ml, pour in the PS polystyrene mould that diameter is 90mm after getting 10mlGO solution and the ultrasonic mixing of 40mlSF solution, drying and forming-film under the room temperature, GO and SF mass ratio are 1:100, and photo Fig. 1 (c) can find out the cast membrane color even.
Embodiment eight
Compound concentration is the GO solution of 5mg/ml and the SF solution of 100mg/ml, pours in the PS politef mould that diameter is 90mm after getting 100mlGO solution and the ultrasonic mixing of 20mlSF solution, and drying and forming-film under the room temperature, GO and SF mass ratio are 25:100.
Embodiment nine
Compound concentration is the SF solution of the GO solution 5mg/ml of 10mg/ml, pours in the PS polystyrene mould that diameter is 90mm after getting 50mlGO solution and the ultrasonic mixing of 200mlSF solution, and drying and forming-film under the room temperature, GO and SF mass ratio are 50:100.
The various forms GO/SF composite membrane that above embodiment is prepared soaks SBF solution, the test Bioactivity.According to composite membrane area (cm
2) and SBF volume (ml) than for 0.3cm
-1Ratio soak, place in 37 ℃ the water bath with thermostatic control shaking table, frequency of vibration is 60rpm, in the process of whole immersion, changes a SBF every 12 hours.With the composite membrane taking-up, clean with deionized water after one week, use SEM and XRD to characterize the sample that soaks SBF solution front and back, the result shows all energy sedimentary phosphor lime stones of material surface, shows that material has good Bioactivity.Wherein the sample that obtains of the embodiment one surface texture SEM photo that soaks (a) before the SBF solution, rear (b) is seen Fig. 3, and after contrast can be found to soak SBF solution, material surface had the novel substance deposition; 25.9 ° (002), 31.9 ° (211) are the main diffraction maximum of hydroxyapatite in the XRD spectra (Fig. 4), and the equal display material of result surface has hydroxyapatite to form, and shows that material has good Bioactivity.
Claims (4)
1. graphene oxide and fibroin albumen composite membrane is characterized in that the composite membrane that is comprised of graphene oxide and fibroin albumen; Wherein the mass ratio of graphene oxide and fibroin albumen is 1-50:100; Composite membrane adopts the method for layer assembly, sucking filtration or casting to prepare.
2. one kind prepares the as claimed in claim 1 method of graphene oxide and fibroin albumen composite membrane, and its concrete steps are as follows:
Method one: slide is soaked the activation of introducing hydroxyl in piranha solution, do substrate with the activation slide, alternating impregnating deposition graphene oxide solution and silk fibroin protein solution, form graphene oxide and fibroin albumen composite membrane, the mass ratio of graphene oxide and fibroin albumen is 1-50:100 in the control composite membrane; Each soak SF after, immerse and soak again graphene oxide after making the fibroin albumen crystallization in the ethanol, so alternate cycles obtains layer assembly graphene oxide and fibroin albumen composite membrane;
Method two: be that 1-50:100 mixes by graphene oxide and the mass ratio of fibroin albumen with graphene oxide solution and silk fibroin protein solution, obtain mixed solution, adopt the method for sucking filtration, in funnel, pour mixed solution into, by filter membrane, make graphene oxide and fibroin albumen composite membrane;
Method three: be that 1-50:100 mixes by graphene oxide and the mass ratio of fibroin albumen with graphene oxide solution and silk fibroin protein solution, obtain mixed solution, adopt the method for casting, mixed solution is poured in the mould, drying obtains graphene oxide and fibroin albumen composite membrane.
3. method according to claim 2 is characterized in that slide each soak time in silk fibroin protein solution and graphene oxide solution is 10-20min in the method one; Behind each immersion fibroin albumen, each soak time is 5-10min in ethanol; The concentration of the graphene oxide solution that adopts in the method one, two, three is 1-10mg/ml, and silk fibroin protein solution concentration is 5-100mg/ml.
4. method according to claim 2 is characterized in that mould is polystyrene or politef mould in the method three.
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