CN107519540B - High-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film - Google Patents
High-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film Download PDFInfo
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Abstract
The invention provides a high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film, which comprises micro-nano coconut bacterial cellulose, fibroin, graphene and electrodes, and the preparation method comprises the following steps: crushing coconut bacterial cellulose to form a micro-nano bacterial cellulose solution, uniformly mixing the micro-nano bacterial cellulose solution with a fibroin aqueous solution to form a composite solution, dropwise adding a graphene aqueous solution, and performing vacuum filtration to remove a solvent to obtain a concentrated composite solution; and then sequentially placing the Ti/Au electrode, the concentrated composite solution and the polycarbonate film on a PE substrate, naturally drying by adopting a laminating method until the Ti/Au electrode, the concentrated composite solution and the polycarbonate film are solidified, and removing the PE substrate and the polycarbonate film to obtain the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film. The preparation method is simple, the raw materials are uniformly mixed, and the prepared film has high strength, good flexibility, good transparency, good biocompatibility and conductivity and meets the requirements of implantable medical materials.
Description
Technical Field
The invention belongs to the technical field of textile materials, and particularly relates to a high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
Background
The fibroin is a natural high molecular fibrin extracted from silk, consists of 18 α -amino acids, has biocompatibility, degradability, nontoxicity, certain brittleness and oxygen permeability in a wet state, can be used as a raw material independently or combined with other raw materials to form materials such as artificial fibers, films, non-woven fabrics, porous scaffolds, hydrogel, micro-nano particles and the like, is a porous reticular nano-scale biopolymer polymer synthesized by microbial fermentation and formed by linearly linking D-glucopyranose with β -1-4 glycosidic bonds, and compared with plant cellulose, the bacterial fiber has an ultrafine nano-scale reticular structure, high chemical purity, high crystallinity, high polymerization degree, high tensile strength and elastic modulus, excellent tearing resistance, shape maintenance capability and high water holding capability, and is widely applied in the field of food.
The fibroin/bacterial cellulose composite hydrogel disclosed by Chinese patent CN 106492286A and a preparation method and application thereof are characterized in that bacterial cellulose hydrogel subjected to surface modification by glycidyl trimethyl ammonium chloride, fibroin and bone morphogenetic protein-2 are used as raw materials, a composite hydrogel material is prepared by an electrocoagulation technology, and the fibroin forms a network structure in the bacterial cellulose hydrogel to form a double-network pore scaffold, so that the attachment growth of the bone morphogenetic protein-2 is facilitated. The composite material for preparing artificial small-caliber blood vessels and the preparation method thereof disclosed by Chinese patent CN 105031736A are characterized in that a bacterial cellulose membrane is placed in a fibroin solution after carboxylation treatment, and the composite material is formed by crosslinking and compounding. According to the prior art, researches on composite materials prepared by taking bacterial cellulose and fibroin as raw materials are rare at present, because the bacterial cellulose has the problems of low yield and high production cost, and the bacterial cellulose is added in a hydrogel or film mode and combined with a fibroin material, so that the mixing and crosslinking difficulty of the bacterial cellulose and the fibroin is increased, and the overall performance of the composite materials is influenced.
The coconut is a gelatinous hydrophilic polysaccharide substance, is a colloidal bacterial cellulose prepared by culturing and fermenting coconut juice serving as a main raw material by using bacillus aceticus, has wide raw material source and low cost, has the properties of high purity, high crystallinity, strong water absorption, good tensile strength and the like, is insoluble in water, is not easily polluted by other polysaccharide substances, has high water holding capacity, has binding and exchanging capacity on cations, and has adsorption effect on organic matters. The invention takes micro-nano coconut bacterial fiber, fibroin and graphene as main raw materials, and prepares the high-strength flexible light-transmitting implantable composite conductive film by vacuum filtration and lamination.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film, wherein micro-nano coconut bacterial fibers, fibroin and graphene are used as main raw materials and are uniformly mixed, and then the fibroin/bacterial cellulose/graphene composite film is prepared by a vacuum filtration and lamination method.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the utility model provides a high strong flexible printing opacity implantable fibroin/bacterial cellulose/graphite alkene composite conductive film, fibroin/bacterial cellulose/graphite alkene composite conductive film includes coconut palm bacterial cellulose, fibroin, graphite alkene and Ti/Au electrode, coconut palm bacterial cellulose is micro-nano coconut palm bacterial cellulose.
Preferably, the fibroin/bacterial cellulose/graphene composite conductive film is prepared by performing vacuum filtration and lamination on a fibroin/bacterial cellulose/graphene composite solution through a polycarbonate filter membrane.
Preferably, the preparation method comprises the following steps:
(1) adding coconut bacterial cellulose into deionized water, transferring to a juicer, crushing to form a micro-nano bacterial cellulose solution, degumming silkworm cocoons by using a sodium bicarbonate solution, dissolving a calcium chloride ternary solution, dialyzing for 3 days to prepare a fibroin aqueous solution, and uniformly mixing the micro-nano bacterial cellulose solution and the fibroin solution to form a fibroin/bacterial cellulose composite solution;
(2) dropwise adding a graphene aqueous solution into the fibroin/bacterial cellulose composite solution prepared in the step (1), stirring while dropwise adding to obtain a fibroin/bacterial cellulose/graphene composite solution, and filtering by a polycarbonate membrane under a vacuum condition to remove a solvent to obtain a concentrated composite solution;
(3) and (3) sequentially placing the Ti/Au electrode, the concentrated composite solution prepared in the step (2) and the polycarbonate film on a PE substrate, respectively applying opposite pressure to the PE substrate and the polycarbonate film by adopting a laminating method, naturally drying until the PE substrate and the polycarbonate film are solidified, and removing the PE substrate and the polycarbonate film to obtain the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
Preferably, in the step (1), the diameter of the bacterial cellulose in the micro-nano-scale bacterial cellulose solution is 60-100nm, and the length is 0.8-8 um.
Preferably, in the step (1), the mass fraction of the fibroin in the fibroin aqueous solution is 7-10%.
Preferably, in the step (1), the mass ratio of the fibroin to the bacterial cellulose in the fibroin/bacterial cellulose composite solution is 3-5.5: 1.
Preferably, in the step (2), the mass fraction of graphene in the fibroin/bacterial cellulose/graphene composite solution is not higher than 20%.
Preferably, in the step (2), the degree of vacuum under vacuum is 0.01 to 0.1 MPa.
Preferably, in the step (2), the solid content of the concentrated composite solution is 50-70%.
Preferably, in the step (3), the pressure for applying the opposite pressure is 5 to 7MPa, and the time for applying the opposite pressure is 5 to 15 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film prepared by the invention comprises micro-nano-scale coconut fruit bacterial cellulose, wherein the micro-nano-scale coconut fruit bacterial cellulose is formed by randomly orienting and combining 100 angstrom microfiber bundles, the micro-nano-scale coconut fruit bacterial cellulose and free water form a weak gel system, then the coconut fruit bacterial cellulose and the fibroin are derived from natural organisms, the compatibility of the bacterial cellulose and the fibroin is good, the uniform mixing of the bacterial cellulose and the fibroin can be realized, the uniform mixed gel system is realized, finally, a graphene water solution is slowly dripped while stirring, a graphene material is dispersed to the maximum extent, the bacterial cellulose microfiber bundles have adsorption performance, graphene can be adsorbed and fixed, the graphene is placed to have an agglomeration phenomenon, and the micro-nano-scale coconut fruit bacterial cellulose, The fibroin and the graphene are uniformly distributed in the system, so that the problem of uniform dispersion among raw materials is solved, and the uniformity of the performance of the film material is favorably realized.
(2) The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film prepared by the invention comprises micro-nano-scale nata de coco bacterial cellulose, fibroin and graphene, wherein the micro-nano-scale nata de coco bacterial cellulose and the fibroin are used as main raw materials and form a double-layer network hole structure in a film, so that the prepared film material has high tensile strength, Young modulus and elasticity and excellent mechanical properties, the light transmittance of the micro-nano-scale nata de coco bacterial cellulose and the fibroin is good, the light transmittance of the film material prepared by mixing the micro-nano-scale nata de coco bacterial cellulose and the fibroin can reach 90%, and then a small amount of graphene material is added, so that the film material is endowed with electric conductivity under the condition that the light transmittance of the film material is not. In addition, the coconut bacterial cellulose and the fibroin are derived from natural organisms, have strong affinity with cells, can provide extracellular matrix support conditions similar to in vivo growth and development for the cells, can enable the cells to aggregate into tissues, regulate and control the structure of the tissues, have good biocompatibility and provide possibility for implantable medical materials.
(3) The fibroin, the bacterial cellulose and the graphene prepared by the preparation method are uniformly mixed to form a mixed system, then the polycarbonate film is adopted for filtering and removing the solvent, and the natural drying is carried out by adopting a laminating method until the mixture is solidified, so that the fibroin/bacterial cellulose/graphene composite conductive film is simple in preparation method and good in controllability, has high strength, good flexibility, good light transparency and good biocompatibility, also has certain conductivity, and meets the requirements of implantable medical materials.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a drawing of a solution of coconut bacterial cellulose;
FIG. 2 is a schematic diagram of the preparation process of the fibroin solution;
FIG. 3 is a diagram of a fibroin/bacterial cellulose composite solution;
FIG. 4 is a diagram of a fibroin/bacterial cellulose/graphene composite solution;
FIG. 5 is a schematic diagram of the preparation of the fibroin/bacterial cellulose solution filtration;
FIG. 6 is a schematic diagram of a fibroin/bacterial cellulose/graphene solution lamination method;
FIG. 7 is a diagram of a fibroin/bacterial cellulose/graphene composite flexible conductive film;
FIG. 8 is a transmission electron microscope image of the fibroin/bacterial cellulose/graphene composite flexible conductive film;
FIG. 9 is a graph of light transmission of a thin film material;
FIG. 10 is a 3T3 cell culture of the film material.
Wherein, 1, 2 micro-nano coconut bacterial celluloses, 3 fibroin, 4 polycarbonate films, 5 Ti/Au electrodes and a PE substrate.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1:
(1) adding coconut bacterial cellulose into deionized water, transferring to a juicer, crushing to form a micro-nano bacterial cellulose solution with the diameter of 60-100nm and the length of 0.8-8um, degumming silkworm cocoons for 45min by using 0.5 wt% of sodium bicarbonate solution, washing and drying, dissolving in a calcium chloride ternary solution for 2h at 60 ℃, dialyzing for 3 days by using the deionized water to prepare a 7 wt% fibroin aqueous solution, and uniformly mixing the micro-nano bacterial cellulose solution and the fibroin solution to form the fibroin/bacterial cellulose composite solution.
(2) Dropwise adding a graphene aqueous solution into the fibroin/bacterial cellulose composite solution, stirring while dropwise adding to obtain the fibroin/bacterial cellulose/graphene composite solution, and filtering by a polycarbonate membrane under the vacuum condition of 0.01MPa of vacuum degree to remove the solvent to obtain a concentrated composite solution with the solid content of 50%.
(3) And sequentially placing the Ti/Au electrode, the concentrated composite solution and the polycarbonate film on a PE substrate, respectively applying opposite pressure with the pressure of 5MPa to the PE substrate and the polycarbonate film for 5min by adopting a laminating method, naturally drying to solidify, removing the PE substrate and the polycarbonate film, and obtaining the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
Example 2:
(1) adding coconut bacterial cellulose into deionized water, transferring to a juicer, crushing to form a micro-nano bacterial cellulose solution with the diameter of 60-100nm and the length of 0.8-8um, degumming silkworm cocoons for 45min by using 0.5 wt% of sodium bicarbonate solution, washing and drying, dissolving in a calcium chloride ternary solution for 3h at 70 ℃, dialyzing for 3 days by using the deionized water to prepare a 10 wt% fibroin aqueous solution, and uniformly mixing the micro-nano bacterial cellulose solution and the fibroin solution to form the fibroin/bacterial cellulose composite solution.
(2) Dropwise adding a graphene aqueous solution into the fibroin/bacterial cellulose composite solution, stirring while dropwise adding to obtain the fibroin/bacterial cellulose/graphene composite solution, and filtering by a polycarbonate membrane under the vacuum condition of 0.1MPa of vacuum degree to remove the solvent to obtain a concentrated composite solution with the solid content of 70%.
(3) And sequentially placing the Ti/Au electrode, the concentrated composite solution and the polycarbonate film on a PE substrate, respectively applying opposite pressure with the pressure of 7MPa to the PE substrate and the polycarbonate film for 15min by adopting a laminating method, naturally drying to solidify, removing the PE substrate and the polycarbonate film, and obtaining the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
Example 3:
(1) adding coconut bacterial cellulose into deionized water, transferring to a juicer, crushing to form a micro-nano bacterial cellulose solution with the diameter of 60-100nm and the length of 0.8-8um, degumming silkworm cocoons for 45min by using 0.5 wt% of sodium bicarbonate solution, washing and drying, dissolving in a calcium chloride ternary solution for 2.5h at 65 ℃, dialyzing for 3 days by using the deionized water to prepare an 8 wt% fibroin aqueous solution, and uniformly mixing the micro-nano bacterial cellulose solution and the fibroin solution to form the fibroin/bacterial cellulose composite solution.
(2) Dropwise adding a graphene aqueous solution into the fibroin/bacterial cellulose composite solution, stirring while dropwise adding to obtain the fibroin/bacterial cellulose/graphene composite solution, and filtering by a polycarbonate membrane under the vacuum condition of 0.05MPa of vacuum degree to remove the solvent to obtain a concentrated composite solution with the solid content of 60%.
(3) And sequentially placing the Ti/Au electrode, the concentrated composite solution and the polycarbonate film on a PE substrate, respectively applying opposite pressure with the pressure of 6MPa to the PE substrate and the polycarbonate film for 10min by adopting a laminating method, naturally drying to solidify, removing the PE substrate and the polycarbonate film, and obtaining the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
Example 4:
(1) adding coconut bacterial cellulose into deionized water, transferring to a juicer, crushing to form a micro-nano bacterial cellulose solution with the diameter of 60-100nm and the length of 0.8-8um, degumming silkworm cocoons for 45min by using 0.5 wt% of sodium bicarbonate solution, washing and drying, dissolving in a calcium chloride ternary solution for 2h at 70 ℃, dialyzing for 3 days by using the deionized water to prepare a 9 wt% fibroin aqueous solution, and uniformly mixing the micro-nano bacterial cellulose solution and the fibroin solution to form the fibroin/bacterial cellulose composite solution.
(2) Dropwise adding a graphene aqueous solution into the fibroin/bacterial cellulose composite solution, stirring while dropwise adding to obtain the fibroin/bacterial cellulose/graphene composite solution, and filtering by a polycarbonate membrane under the vacuum condition of the vacuum degree of 0.03MPa to remove the solvent to obtain a concentrated composite solution with the solid content of 55%.
(3) And sequentially placing the Ti/Au electrode, the concentrated composite solution and the polycarbonate film on a PE substrate, respectively applying opposite pressure with the pressure of 5.5MPa to the PE substrate and the polycarbonate film for 9min by adopting a laminating method, naturally drying to solidify, removing the PE substrate and the polycarbonate film, and obtaining the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
Example 5:
(1) adding coconut bacterial cellulose into deionized water, transferring to a juicer, crushing to form a micro-nano bacterial cellulose solution with the diameter of 60-100nm and the length of 0.8-8um, degumming silkworm cocoons for 45min by using 0.5 wt% of sodium bicarbonate solution, washing and drying, dissolving in a calcium chloride ternary solution for 3h at 60 ℃, dialyzing for 3 days by using the deionized water to prepare an 8 wt% fibroin aqueous solution, and uniformly mixing the micro-nano bacterial cellulose solution and the fibroin solution to form the fibroin/bacterial cellulose composite solution.
(2) Dropwise adding a graphene aqueous solution into the fibroin/bacterial cellulose composite solution, stirring while dropwise adding to obtain the fibroin/bacterial cellulose/graphene composite solution, and filtering by a polycarbonate membrane under the vacuum condition of 0.1MPa of vacuum degree to remove the solvent to obtain a concentrated composite solution with the solid content of 65%.
(3) And sequentially placing the Ti/Au electrode, the concentrated composite solution and the polycarbonate film on a PE substrate, respectively applying opposite pressures with the pressure of 7MPa to the PE substrate and the polycarbonate film for 10min by adopting a laminating method, naturally drying to solidify, and removing the PE substrate and the polycarbonate film to obtain the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
Through detection, the results of the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive films prepared in examples 1-5 and the fibroin/bacterial cellulose films and fibroin films of the prior art are as follows:
the table shows that the mechanical property of the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film prepared by the invention is far superior to that of a pure regenerated fibroin film, and the mechanical property is not greatly influenced and the conductivity is obviously improved under the condition of adding a small amount of graphene.
And the accompanying drawing results show that all components in the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film are uniformly mixed, a small amount of graphene is added, the influence on the light transmission performance is small, and the higher the graphene content is, the smaller the transmittance of the light film is. In addition, the left side of fig. 10 is a cell diagram of the fibroin/bacterial cellulose/graphene film and the right side is a cell diagram of the fibroin/bacterial cellulose/graphene film 3T3 cell culture for 3 days, which shows that the conductive film prepared by the invention has good biocompatibility.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (8)
1. The utility model provides a high strong flexible printing opacity implantable fibroin/bacterial cellulose/graphite alkene composite conducting film which characterized in that: the fibroin/bacterial cellulose/graphene composite conductive film comprises coconut fruit bacterial cellulose, fibroin, graphene and a Ti/Au electrode, the coconut fruit bacterial cellulose is micro-nano coconut fruit bacterial cellulose, the fibroin/bacterial cellulose/graphene composite conductive film is prepared by a fibroin/bacterial cellulose/graphene composite solution through polycarbonate filtering membrane vacuum filtration and a lamination method,
the preparation method of the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film comprises the following steps:
(1) adding coconut bacterial cellulose into deionized water, transferring to a juicer, crushing to form a micro-nano bacterial cellulose solution, degumming silkworm cocoons by using a sodium bicarbonate solution, dissolving a calcium chloride ternary solution, dialyzing for 3 days to prepare a fibroin aqueous solution, and uniformly mixing the micro-nano bacterial cellulose solution and the fibroin solution to form a fibroin/bacterial cellulose composite solution;
(2) dropwise adding a graphene aqueous solution into the fibroin/bacterial cellulose composite solution prepared in the step (1), stirring while dropwise adding to obtain a fibroin/bacterial cellulose/graphene composite solution, and filtering by a polycarbonate membrane under a vacuum condition to remove a solvent to obtain a concentrated composite solution;
(3) and (3) sequentially placing the Ti/Au electrode, the concentrated composite solution prepared in the step (2) and the polycarbonate film on a PE substrate, respectively applying opposite pressure to the PE substrate and the polycarbonate film by adopting a laminating method, naturally drying until the PE substrate and the polycarbonate film are solidified, and removing the PE substrate and the polycarbonate film to obtain the high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film.
2. The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film according to claim 1, is characterized in that: in the step (1), the diameter of the bacterial cellulose in the micro-nano bacterial cellulose solution is 60-100nm, and the length is 0.8-8 um.
3. The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film according to claim 1, is characterized in that: in the step (1), the mass fraction of the fibroin in the fibroin aqueous solution is 7-10%.
4. The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film according to claim 1, is characterized in that: in the step (1), the mass ratio of the fibroin to the bacterial cellulose in the fibroin/bacterial cellulose composite solution is 3-5.5: 1.
5. The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film according to claim 1, is characterized in that: in the step (2), the mass fraction of graphene in the fibroin/bacterial cellulose/graphene composite solution is not higher than 20%.
6. The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film according to claim 1, is characterized in that: in the step (2), the vacuum degree under the vacuum condition is 0.01-0.1 MPa.
7. The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film according to claim 1, is characterized in that: in the step (2), the solid content of the concentrated composite solution is 50-70%.
8. The high-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film according to claim 1, is characterized in that: in the step (3), the pressure for applying the opposite pressure is 5-7MPa, and the time for applying the opposite pressure is 5-15 min.
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