CN106592007B - Graphene micrometer fibers, preparation method, nerve fiber bracket and repair system - Google Patents

Graphene micrometer fibers, preparation method, nerve fiber bracket and repair system Download PDF

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CN106592007B
CN106592007B CN201610282724.9A CN201610282724A CN106592007B CN 106592007 B CN106592007 B CN 106592007B CN 201610282724 A CN201610282724 A CN 201610282724A CN 106592007 B CN106592007 B CN 106592007B
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graphene oxide
micrometer fibers
reductive modification
polyglycolic acid
neural
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CN106592007A (en
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郭伟博
刘宏
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Beijing Institute of Nanoenergy and Nanosystems
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Beijing Institute of Nanoenergy and Nanosystems
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/08Carbon ; Graphite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/18Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/09Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/32Materials or treatment for tissue regeneration for nerve reconstruction

Abstract

The present invention provides reductive modification graphene oxide micrometer fibers and preparation method, nerve fiber bracket and drives neural restoration system certainly.The micrometer fibers include redox graphene and conducting high polymers object Polyglycolic acid fibre, and the micrometer fibers are continuous, and have regular porous surface nanostructure.The preparation method of the reductive modification graphene oxide micrometer fibers includes: the graphene oxide mixed solution of configuration doping Polyglycolic acid fibre, prepares reductive modification graphene oxide micrometer fibers with the solution.The nerve fiber bracket is made of reductive modification graphene oxide micrometer fibers.The separate type friction nanometer power generator for including the nerve fiber bracket from driving neural restoration system and driving certainly.Micrometer fibers proposed by the present invention have the characteristics that shape and surface topography is good, conductivity is good, have good attaching and proliferative capacity to mesenchymal stem cell, can promote the Neural Differentiation of mesenchymal stem cell.

Description

Graphene micrometer fibers, preparation method, nerve fiber bracket and repair system
Technical field
The present invention relates to nerve fiber field of stents, in particular to the artificial redox graphene as nerve fibre is micro- Rice fiber, the nerve fiber bracket comprising above-mentioned redox graphene micrometer fibers and includes the nerve at preparation method The neural restoration system of organization bracket.
Background technique
Neurotrosis is clinical common and multiple one of type of impairment, and only in China, neurotrosis case is new every year Promote million.With the continuous development of science and technology, repairing of neural injury material is constantly improve and is improved.It is so far Only, the main mode that repairing of neural injury is taken has: (1) performing the operation to short neurologic defect, stitch to injured nerve It closes, then self-heal;(2) longer injured nerve is replaced using substitute transplanting;(3) neurotrophic factor or outer is injected Add physiotherapy.
Implantable stent is to provide the available strategy of cell support.Clinically most common graft materials are autologous nerves, But donor diameter is thin, desirable quantity is extremely limited, it is difficult to meet clinical demand;Known artificial synthesized timbering material includes glue The materials such as former albumen, fibronectin, polylactic acid, polyglycolic acid, but the degradation speed of these materials is fast and uncontrollable, degradation Deleterious acidic substance, non-conductive is generated, Nerve Scaffold basic demand is also unable to satisfy.The therapeutic effect of these methods is not very Ideal cannot restore the function of injured nerve completely, and treatment cycle is long, and treatment cost is high.Therefore, develop a kind of more excellent Material and method become as medical research field urgent problem to be solved.
The purpose of nerve fiber bracket is to solve contradiction between histoorgan transplanting unevenness between supply and demand and more effective Solution injury repair problem.The tissue that completely new bracket replaces damage or defect is constructed, to successfully solve because of nerve Damage graft lack and substitute caused by the adverse consequences such as sequelae, be a kind of effective method and fundamental way.It is ideal Nerve fiber timbering material should have the three-dimensional structure of analog neuron tissue profile, and it is required to meet biocompatibility Good, high conductivity, no antigen are easy to get and the primary conditions such as low in cost.This is also exactly that the scientific research personnel of this field is long One of most popular since phase, most important research direction.
In recent years, many scientific research institutions and enterprise put into a large amount of human and material resources and financial resources to nerve repair material into Row research.But lack a kind of ideal nerve repair material in the neural restoration strategy having been reported, it can be mentioned for nerve regneration For optimal biology and physical and chemical microenvironment, the purpose for accelerating to promote neural restoration is realized.
That is, it needs to a kind of similar nerve fibre structure of modification, good, the high conductivity of cell compatibility production nerve branch The material of frame, and it is a kind of from driving neural restoration system that the material should be able to be allowed to constitute, and provides better solution for neural restoration Scheme.
Summary of the invention
In view of the aforementioned technical background the problem of, the present invention is specifically proposed.
In the present invention:
The meaning of " redox graphene " are as follows: surface of graphene oxide has a large amount of functional group, such as carboxyl, hydroxyl, ring Oxygroup, becomes redox graphene after carrying out reduction, the property of the redox graphene and property of original graphite is similar and oxygen The difference of graphite alkene is without or eliminates big well-behaved functional group.
The meaning of " nerve fiber bracket " are as follows: nerve fiber bracket refers to can simultaneously be implanted into life in conjunction with living body nerve cell In object, the material of the function of alternative nerve fiber.
It is an object of the present invention to provide a kind of methods for preparing reductive modification graphene oxide micrometer fibers, have It is easy to operate, at low cost, the advantages that modified effect is good.
The second purpose of the present invention is to provide neural group of a kind of reductive modification graphene oxide micrometer fibers and its composition Bracket is knitted, cell compatibility is good, surface large specific surface area, high conductivity, can simulate natural nerve fibre well, and can have Effect promotes stem cell differentiation, can be applied to inducing bone mesenchymal stem cell directional and is divided into nerve cell, in organizational project side Mask has broad application prospects.
The three of the object of the invention are to provide a kind of from driving neural restoration system comprising reductive modification oxygen of the invention The nerve fiber bracket and separate type self-powered dynamic friction nano generator that graphite alkene micrometer fibers are constituted,.It is neural to promote Injury repair provides a kind of new approaches and new method.Because the fiber of the invention has high conductivity, friction can be transmitted and received The pulse signal of rice generator, further can promote stem cell to Neural Differentiation.In addition, provided by the invention neural from driving Repair system has a good application prospect in terms of neural tissue engineering.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of reductive modification graphene oxide micrometer fibers, including redox graphene and conducting high polymers are provided Object Polyglycolic acid fibre, the micrometer fibers are that continuously, the micrometer fibers have regular porous surface nanostructure.
Further, the reductive modification graphene oxide micrometer fibers include the poly- ethylene of 0.1%~2%:1 of mass ratio Dioxy thiophene and redox graphene.
Further, the diameter of the reductive modification graphene oxide micrometer fibers is between 40 μm and 100 μm.
Further, the reductive modification graphene oxide micrometer fibers are by containing graphene oxide and poly- enedioxy thiophene The mixed solution of pheno is made after High-temperature water heat treatment.
The present invention also provides a kind of nerve fiber brackets, and it includes above-mentioned reductive modification graphene oxide micrometer fibers, institutes Nerve fiber bracket is stated for mesenchymal stem cell directional induction Neural Differentiation.
The present invention further provides a kind of to drive neural restoration system, the system packet comprising above-mentioned nerve fiber bracket certainly It includes: the nerve fiber bracket and the separate type friction nanometer power generator from driving;The separate type friction nanometer from driving Electrical power generators stimulation promotes mesenchymal stem cell to Neural Differentiation.
Further, above-mentioned from driving neural restoration system, the electric current of the self-powered dynamic friction nano generator exports For 20 μ of μ A~70 A.
The present invention also provides a kind of methods for preparing the reductive modification graphene oxide micrometer fibers, including following step It is rapid:
1) the graphene oxide mixed solution of configuration doping Polyglycolic acid fibre:
Graphene oxide powder is weighed, is dissolved in water, graphene oxide solution is configured;
Polyglycolic acid fibre powder is added in configured good graphene oxide solution, oscillation mixing;
Concentration of the graphene oxide in the graphene oxide solution is 5mg/ml~10mg/ml;It is added to institute The quality for stating the Polyglycolic acid fibre in oxidation graphene oxide solution is the 0.1wt% of the graphene oxide quality ~2wt%;
2) reductive modification graphene oxide micrometer fibers are prepared:
The mixed solution injection capillary of the configured mixing Polyglycolic acid fibre of above-mentioned steps and graphene oxide is long In glass tube;
It will be put into baking oven after the hair slender glass tube sealing two ends, carry out hydro-thermal reaction, temperature is 160 DEG C~260 Between DEG C, the time is between 2 hours~12 hours;
The micrometer fibers obtained after hydro-thermal reaction are blown out from the hair slender glass tube with nitrogen;
Fiber placement after blowout is spontaneously dried at room temperature, it is fine just to obtain reductive modification graphene oxide micron later Dimension.
Further, the water that the above method uses can be ultrapure water.
Further, in the above method, the internal diameter of the hair slender glass tube is between 0.4mm~1.0mm.
Compared with prior art, the beneficial effect comprise that
Functionalization has been made using the poly- two sample thiophene of ethylene of conducting high polymers object and redox graphene in the present invention Compound micrometer fibers, i.e. highly conductive graphene micrometer fibers (once referred to as " micrometer fibers ").Its cell compatibility is good, can give birth to Object degradation, diameter are distributed in 40 μm and 100 μm.Conductivity possessed by the micrometer fibers is high, and with the nerve in nerve fiber Fiber is similar, therefore is conducive to attaching, proliferation, the differentiation of cell, can especially stem cell be promoted to break up, such as medulla mesenchyma Stem cell directional is induced to differentiate into nerve cell.As it can be seen that it can be widely used in terms of neural tissue engineering.
The method for preparing micrometer fibers of the invention can be carried out by simple hydro-thermal reaction, easy to operate, at low cost It is honest and clean, mass production may be implemented.
Functionalization has been made using the poly- two sample thiophene of ethylene of conducting high polymers object and redox graphene in the present invention Compound micrometer fibers, i.e., highly conductive graphene micrometer fibers (hereinafter referred to as " micrometer fibers "), which has high electricity Conductance can be used in combination with a kind of separate type self-powered dynamic friction nano generator, constitute from driving neural restoration system, realize Promote mesenchymal stem cell on micrometer fibers to Neural Differentiation.
Detailed description of the invention
Fig. 1 a-1h is the redox graphene micron fibre being prepared in one embodiment of the invention using hydro-thermal method respectively Dimension (being hereinafter also referred to as " with reference to micrometer fibers ") and reductive modification graphene oxide micrometer fibers (are hereinafter also referred to as " Modified Micron Fiber ") SEM (scanning electron microscope) photo.
Fig. 2 is the reference micrometer fibers and Modified Micron fiber being prepared in one embodiment of the invention using hydro-thermal method Raman (Raman) spectrogram.
Fig. 3 is the reference micrometer fibers and Modified Micron fiber being prepared in one embodiment of the invention using hydro-thermal method Conductivity tests (I-V) figure.
Fig. 4 is the reference micrometer fibers and Modified Micron fiber being prepared in one embodiment of the invention using hydro-thermal method The CCK-8 figure of measurement cytotoxicity when the attaching experiment of mesenchymal stem cell.
Fig. 5 is the reference micrometer fibers and Modified Micron fiber being prepared in one embodiment of the invention using hydro-thermal method The qPCR figure of mesenchymal stem cell expressed neural marker gene Tuj1 and GFAP after differentiation culture 21 days.
Fig. 6 is in one embodiment of the invention from the schematic diagram for driving neural restoration system.
Fig. 7 is the reference micrometer fibers and Modified Micron fiber being prepared in one embodiment of the invention using hydro-thermal method Mesenchymal stem cell is in the institute after a kind of separate type self-powered dynamic friction nano generator electro photoluminescence induces differentiation culture 21 days Express the qPCR figure of neural marker gene Tuj1 and GFAP.
Specific embodiment
Specifically embodiments of the present invention with reference to the accompanying drawing.
The needs of this kind of knotty problems are repaired for solving the tissue damage of nerve or other organs in view of this field, and The deficiencies of replacing material in view of existing nerve, inventor is studied for a long period of time and is realized, technical side of the invention is proposed Case.
Generally, the present invention provides a kind of modifications for mesenchymal stem cell directional induction Neural Differentiation also Former graphene oxide micrometer fibers and preparation method thereof, the nerve fiber bracket based on the micrometer fibers and from driving neural restoration System.
Concretely, one aspect of the present invention provides a kind of reductive modification graphene oxide micrometer fibers, main Continuous micrometer fibers are made of redox graphene and Polyglycolic acid fibre instrument, and the micrometer fibers have rule Porous surface nanostructure.
Further, the diameter of the redox graphene Modified Micron fiber is between tens to one hundred micron, with The shape of nerve fibre is close, therefore can preferably be used as nerve-grafting substitute.
Further, in the present invention, used conducting high polymers object Polyglycolic acid fibre has excellent Electric conductivity, obtained reductive modification graphene oxide micrometer fibers have than not modified redox graphene micrometer fibers Higher conductivity can preferably transmit a kind of electro photoluminescence output of separate type self-powered dynamic friction nano generator, promote bone Efficiency of the bone marrow-drived mesenchymal stem to Neural Differentiation.
It is one of more preferred another aspect provides a kind of method for preparing aforementioned modified micrometer fibers Mode include: to take the mixed solution hydrothermal treatment containing Polyglycolic acid fibre and graphene oxide, it is micro- to obtain the modification Rice fiber.
Further, among a preferred embodiment, the graphene oxide of various concentration can be configured first Solution;Then Polyglycolic acid fibre is added in the graphene oxide solution after above-mentioned optimization and is shaken, be uniformly mixed it; Most the Modified Micron fiber is obtained through hydro-thermal reaction afterwards.It can obtain that pattern is good, fiber table by optimizing hydrothermal reaction condition The regular nano-porous structure of mask and the uniform micrometer fibers of fibre diameter.
Aforementioned oxidation graphene solution can be used under type such as and obtain: graphene oxide powder being taken to be dissolved in ultrapure water.
Preferably, the mixed solution may include the Polyglycolic acid fibre and oxygen reduction that mass ratio is 0.1%~2%:1 Graphite alkene.
Another aspect of the present invention provides the preparation method of aforementioned modified micrometer fibers comprising: it takes containing poly- ethylene two The mixed solution hydrothermal treatment of oxygen thiophene and graphene oxide obtains the Modified Micron fiber.
Among a preferred embodiment, the solution includes the graphene oxide that concentration is 5mg/ml~10mg/ml, and content is The Polyglycolic acid fibre of 0.1wt%~2wt% of the content of the graphene oxide and have to graphene oxide good The ultrapure water of solvability.
Further, the reductive modification graphene oxide micrometer fibers make by containing graphene oxide and poly- enedioxy The mixed aqueous solution of thiophene is made after the processing of high temperature hydro-thermal reaction in hair slender glass tube.
Inventor has found that for hair slender glass tube internal diameter between 0.4mm~1.0mm, hydro-thermal is anti-by many experiments It answers temperature control between 160 DEG C~260 DEG C, when reaction time control is between 2h~12h, can be obtained of good performance aforementioned Modified Micron fiber.
In addition, the present invention also provides the reductive modification graphene oxide micrometer fibers in preparation nerve fiber bracket Using the nerve fiber bracket includes the i.e. described Modified Micron fiber of repairing of neural injury material, is constituted for filling between marrow The tissue engineering material of matter stem cell directional inducing cell Neural Differentiation.
Invention further provides for combining the separate type friction nanometer power generator electro photoluminescence from driving to promote bone Bone marrow-drived mesenchymal stem is to Neural Differentiation from driving neural restoration system, and it includes reductive modification graphene oxides of the invention Micrometer fibers.
In the present invention, recommending the electric current output of self-powered dynamic friction nano generator is 20 μ of μ A~70 A.
Generally, the present invention electric conductivity and cell compatibility certain using redox graphene itself, and The excellent electric conductivity of conducting high polymers object Polyglycolic acid fibre, is prepared electric conductivity by simple hydro-thermal method and mentions The reductive modification graphene oxide micrometer fibers risen.The micrometer fibers being prepared by hydrothermal method, with nerve fibre structure It is similar, good support platform is provided for cell, and remarkably promote the Proliferation, Differentiation of cell.A kind of separate type is being combined to drive certainly From driving neural restoration system, Modified Micron fiber of the invention more effectively transmits friction to be received composition after friction nanometer power generator The electro photoluminescence output of rice generator, further promotes the Neural Differentiation of cell.
Technical solution of the present invention is described in more detail below in conjunction with attached drawing and case study on implementation.
Embodiment
Firstly, it is 5mg/ml's that the graphene oxide mixed solution of configuration doping Polyglycolic acid fibre, which configures two parts of concentration, Graphene oxide solution: weighing two parts of 500mg graphene oxide powders with electronic analytical balance, and it is super to be dissolved in two parts of 10ml respectively It is spare in pure water.
It configures the graphene oxide solution that two parts of concentration are 8mg/ml: weighing 800mg graphite oxide with electronic analytical balance Alkene powder is dissolved in respectively in two parts of 10ml ultrapure waters, spare.
It takes 5mg and 8mg Polyglycolic acid fibre powder respectively with electronic balance, is added separately to configured good portion In the graphene oxide solution of 5mg/ml and 8mg/ml, oscillation mixing.
As above, prepare come out four parts of solution, two parts be no addition polymerization ethylenedioxy thiophene powder graphene oxide solution, Two parts are the mixed solutions for having added 5mg and 8mg Polyglycolic acid fibre powder respectively.
Then, it is modified with the preparation of above-mentioned solution with reference to redox graphene micrometer fibers and with Polyglycolic acid fibre Redox graphene micrometer fibers.
Four kinds of graphene oxide mixed solutions of the above-mentioned mixing Polyglycolic acid fibre of fresh configuration are injected separately into interior Diameter is, then by the sealing two ends of hair slender glass tube, to be put into baking oven later in the hair slender glass tube of 0.8mm, 200 DEG C of guarantors Warm 4h carries out hydro-thermal reaction.The fiber obtained after reaction is blown out from glass capillary with nitrogen from oven, at this point, micro- Contain moisture in rice fiber, spontaneously dry at room temperature, obtains two kinds of pure redox graphene micrometer fibers (of the invention attached It is shown with " 5-rGO " and " 8-rGO " respectively in figure) and two kinds of Modified Micron fibers (respectively with " 5- in attached drawing of the invention RGO-PEDOT " and " 8-rGO-PEDOT " show it).
Later, it is produced with above-mentioned micrometer fibers from driving neural restoration system: selecting a kind of separate type self-powered dynamic friction Nano generator is connected with redox graphene micrometer fibers are improved.Schematic diagram is as shown in Figure 6.As it can be seen that being repaired from driving nerve Complex system specifically includes that micrometer fibers or Modified Micron fiber 1, and micrometer fibers or Modified Micron fiber and separate type rub nanometer The copper wire 2 that generator is connected, Tissue Culture Dish 3 and separate type friction nanometer power generator 4.
Finally, testing performance of the invention, to verify reductive modification graphene oxide micrometer fibers of the invention The performance (characterization) of (referred to as " Modified Micron fiber ")
1, scanning electron microscope characterizes
The characterization result of 5-rGO micrometer fibers is as shown in Fig. 1 a- Fig. 1 b, the characterization result of 8-rGO micrometer fibers such as Fig. 1 c- Shown in Fig. 1 d, the characterization result of 5-rGO-PEDOT micrometer fibers is as shown in Fig. 1 e- Fig. 1 f, the table of 8-rGO-PEDOT micrometer fibers Result is levied as shown in Fig. 1 g- Fig. 1 h.
Aforementioned SEM characterization result shows: can obtain continuous micrometer fibers by capillary water thermal response, and fiber is straight Diameter is unified, and fiber surface shows the consistent nano-porous structure of rule.
2, Raman Characterization
Curve a-d in Fig. 2 respectively corresponds 5-rGO, 8-rGO, 5-rGO-PEDOT, 8-rGO-PEDOT micrometer fibers.It draws Graceful spectrum shows chemical structure of the intervention without destruction redox graphene of Polyglycolic acid fibre, merely by physics Mixed mode is doped in micrometer fibers.
3, conductive test
Micrometer fibers are made into the electrode to be measured of 2cm long, test its I-V curve.Curve a-d in Fig. 3 respectively corresponds 5- RGO, 8-rGO, 5-rGO-PEDOT, 8-rGO-PEDOT micrometer fibers.
By experimental result as it can be seen that the electricity of redox graphene micrometer fibers can be improved in the intervention of two sample thiophene of poly- ethylene Conductance.
4, cytotoxicity test
Every group weighs 10mg micrometer fibers, is put into 24 orifice plates, and the inoculation number of cell is 300000/hole, when culture Between gradient be 1,3,5 day.According to the proliferative conditions of CCK-8 kit specification measurement cell.Fig. 4 is shown to be trained by 1,3,5 day After supporting, the ability of cell proliferation on four groups of fibers is suitable, illustrates that redox graphene micrometer fibers have good cell phase Capacitive, and the intervention of Polyglycolic acid fibre does not have an impact its cell compatibility.
5, cell differentiation qPCR is detected
Choosing most representative neuron Tuj1 and neuroglia GFAP is detection neural marker gene, the inoculation of cell Number is identical with cytotoxicity test step, and cell differential medium is normal cell culture medium, and test medulla mesenchyma is dry thin Spontaneous differentiation situation to nerve cell of the born of the same parents on micrometer fibers.As a result as shown in the figure: 5-rGO and 8-rGO micrometer fibers Tuj1 and GFAP gene expression amount is roughly the same, Tuj1 the and GFAP gene of 5-rGO-PEDOT and 8-rGO-PEDOT micrometer fibers Expression quantity is also roughly the same, but is above unmodified micrometer fibers.Illustrate redox graphene micrometer fibers inducing bone marrow The ability of mesenchymal stem cells into nerve differentiation is inadequate, but after mixing Polyglycolic acid fibre, Modified Micron fiber is to marrow Mesenchymal stem cells into nerve differentiation has apparent facilitation.
6, promote the qPCR detection of cell differentiation from driving neural restoration system
Selected friction nanometer power generator is a kind of separate type self-powered dynamic friction nano generator, and electric current output is 20 A~70 μ μA.It is daily 3000 times/day to the stimulation of cell, culture medium is normal cell culture medium, continued stimulus 21 days.Choose most generation The neuron Tuj1 and neuroglia GFAP of table are detection neural marker gene, and testing friction nano generator electro photoluminescence is to bone Differentiation situation to nerve cell of the bone marrow-drived mesenchymal stem on micrometer fibers.As a result as shown in Figure 7: being sent out in rubbed nanometer After motor electro photoluminescence, Tuj1 the and GFAP gene expression amount of 5-rGO and 8-rGO micrometer fibers is roughly the same, rubs compared to not adding The experimental group of nano generator electro photoluminescence is wiped, Tuj1 and GFAP gene expression amount significantly improves;5-rGO-PEDOT and 8-rGO- Tuj1 the and GFAP gene expression amount of PEDOT micrometer fibers is also roughly the same, compared to not plus friction nanometer power generator electro photoluminescence Experimental group, Tuj1 and GFAP gene expression amount also significantly improves, while compared to the 5- for adding friction nanometer power generator electro photoluminescence RGO and 8-rGO experimental group also improves.This illustrates that friction nanometer power generator electro photoluminescence can effectively facilitate oxygen reduction fossil To the ability of Neural Differentiation, Modified Micron fiber can more effectively conduct to rub mesenchymal stem cell on black alkene micrometer fibers The electric signal for wiping nano generator, has more obvious facilitation to Neural Differentiation to mesenchymal stem cell.
By the visible reductive modification graphene oxide micrometer fibers of the invention of previous embodiment and its constitute refreshing from driving Repaired system has the advantages that protrusion:
Polyglycolic acid fibre addition there is no change micrometer fibers chemical structure, while make fiber shape and Surface topography keeps good.On the other hand, the addition of Polyglycolic acid fibre enhances redox graphene micrometer fibers Conductivity.
Reductive modification graphene oxide micrometer fibers have good attaching and proliferative capacity to mesenchymal stem cell.
Reductive modification graphene oxide micrometer fibers can equally promote mesenchymal stem cell under normal culture conditions Neural Differentiation.
The intervention of friction nanometer power generator electro photoluminescence can on significantly more efficient promotion micrometer fibers medulla mesenchyma it is dry thin The neurophilic differentiation of born of the same parents, and Modified Micron fiber can preferably transmit the electrical stimulation signal of friction nanometer power generator, into one Step promotes on Modified Micron fiber mesenchymal stem cell to Neural Differentiation.
In addition, in preparation method of the invention, using glass capillary hydro-thermal method, and by poly- second by way of doping Support dioxy thiophene is added to micrometer fibers kind and obtains composite material, and the tissue engineering bracket material applied to repairing of neural injury is led Domain.Since the above technology is low for equipment requirements, raw material sources are cheap extensively, Yi Shixian industrialization.
It should be appreciated that in the present specification, the terms "include", "comprise" or its any other variant are intended to non-row His property includes, so that the process, method, article or equipment for including a series of elements not only includes those elements, and And further include other elements that are not explicitly listed, or further include for this process, method, article or equipment institute it is intrinsic Element.Postscript technical solution and technical concept can be made according to the present invention for those of ordinary skill in the art Other various corresponding changes and modifications, and these change and modification all should belong to the protection scope of the claims in the present invention.

Claims (9)

1. a kind of reductive modification graphene oxide micrometer fibers, including redox graphene and the poly- second of conducting high polymers object Dioxy thiophene is supportted, the micrometer fibers are that continuously, the micrometer fibers have regular porous surface nanostructure;It is described to change Property redox graphene micrometer fibers are by the mixed solution containing graphene oxide and Polyglycolic acid fibre through high temperature hydro-thermal It is made after processing.
2. reductive modification graphene oxide micrometer fibers according to claim 1, which is characterized in that the reductive modification oxygen Graphite alkene micrometer fibers include the Polyglycolic acid fibre and redox graphene of 0.1%~2%:1 of mass ratio.
3. reductive modification graphene oxide micrometer fibers according to claim 2, which is characterized in that the reductive modification oxygen The diameter of graphite alkene micrometer fibers is between 40 μm and 100 μm.
4. a kind of nerve fiber bracket, it includes according to claim 1 to reductive modification graphene oxide micron described in one of 3 Fiber, the nerve fiber bracket can be used in the directional induction Neural Differentiation of mesenchymal stem cell.
5. a kind of driving neural restoration system certainly comprising nerve fiber bracket as claimed in claim 4, comprising: the nerve group Knit bracket and the separate type friction nanometer power generator from driving;The separate type friction nanometer power generator from driving generates electricity and stimulates Promote mesenchymal stem cell to Neural Differentiation.
6. according to claim 5 from driving neural restoration system, which is characterized in that the self-powered dynamic friction nanometer generating The electric current output of machine is 20 μ of μ A~70 A.
7. a kind of method of the reductive modification graphene oxide micrometer fibers prepared as described in one of claims 1 to 3, including with Lower step:
1) the graphene oxide mixed solution of configuration doping Polyglycolic acid fibre:
Graphene oxide powder is weighed, is dissolved in water, graphene oxide solution is configured;
Polyglycolic acid fibre powder is added in configured good graphene oxide solution, oscillation mixing;
Concentration of the graphene oxide in the graphene oxide solution is 5mg/ml~10mg/ml;It is added to the oxygen Change graphene oxide solution in the Polyglycolic acid fibre quality be the graphene oxide quality 0.1wt%~ 2wt%;
2) reductive modification graphene oxide micrometer fibers are prepared:
By above-mentioned steps 1) it is configured mixing Polyglycolic acid fibre and graphene oxide mixed solution inject the long glass of capillary In glass pipe;
To be put into baking oven after the hair slender glass tube sealing two ends, carry out hydro-thermal reaction, temperature be 160 DEG C~260 DEG C it Between, the time is between 2 hours~12 hours;
The micrometer fibers obtained after hydro-thermal reaction are blown out from the hair slender glass tube with nitrogen;
Fiber placement after blowout is spontaneously dried at room temperature, just obtains reductive modification graphene oxide micrometer fibers later.
8. the method according to claim 7 for preparing reductive modification graphene oxide micrometer fibers, which is characterized in that described Water is ultrapure water.
9. the method according to claim 7 for preparing reductive modification graphene oxide micrometer fibers, which is characterized in that described The internal diameter of hair slender glass tube is between 0.4mm~1.0mm.
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