CN107737370A - It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel - Google Patents
It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel Download PDFInfo
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/08—Carbon ; Graphite
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- A—HUMAN NECESSITIES
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- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/427—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/06—Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus
Abstract
It is used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel the invention discloses a kind of, belongs to technical field of biological materials.The imitative organization of human body of the present invention, which constructs, has excellent mechanical performances, " bone muscle " hydrogel of electric conductivity concurrently；First, natural polymer/Nano filling complex stephanoporate bracket with good adsorption properties is prepared using freeze-drying；Secondly go absorption to be dispersed with the hydrogel pre-polymerization liquid for the conductive material that poly-dopamine is modified using the support, finally polymerize and form " bone muscle " hydrogel；The mechanical property for significantly improving hydrogel of natural polymer/Nano filling support in the present invention, enough mechanical strengths and extracellular matrix microenvironment can be provided for the reparation of cartilaginous tissue；In addition the hydrogel has good electric conductivity, it may be possible to responds reparation and regeneration that extraneous electro photoluminescence promotes cartilaginous tissue；This method is improving the mechanical property of hydrogel and is expanding its clinical practice etc. and have important researching value.
Description
Technical field
The present invention relates to technical field of biological materials, and in particular to a kind of to be used for the high-strength of repair of cartilage, superlastic, conductivity water
The preparation method of gel.
Background technology
Hydrogel is widely used in because having the characteristics that good biocompatibility, biological degradability and easy processing to be molded
Cartilaginous tissue reparation；Cartilage is a kind of fine and close connective organ of specialization, and cytoplasm is firm and elastic, therefore cartilaginous tissue is to repairing
The mechanical property requirements of multiple material are higher；However, the usual mechanical performance of conventional hydrogels it is poor can not be cartilaginous tissue reparation with
Regeneration provides enough mechanical strengths；Thus build the hydrogel with excellent mechanical performance and referred to as hydrogel preparation field
Focus, and the high intensity hydrogel prepared at this stage has double-network hydrogel, Nanometer composite hydrogel, slides hydrogel etc.；
But the poor mechanical property of conventional hydrogels, poor flexibility, electric conductivity are also inadequate；The external worlds such as existing research report light, electricity, magnetic
The adhesion of cartilage cell can be promoted by stimulating, and bred and broken up and can induce regenerative agent of cartilaginous tissue；The present invention is by traditional water-setting
The flexible back bone for the natural polymer subbase that glue internal build one can be used for energy dissipation, the mechanicalness of hydrogel can be significantly improved
Energy；Hydrogel is set to provide enough mechanical strengths and extracellular matrix microenvironment for the reparation of cartilaginous tissue；The present invention passes through
Conductive material is added in hydrogel pre-polymerization liquid and imparts the good electric conductivity of hydrogel and responds extraneous electric signal and cooperate with and is promoted
The reparation and regeneration of cartilaginous tissue；And there is good electric conductivity can be used for perceiving and conduct myoelectricity letter for subject hydrogel
Number reflection cartilaginous tissue reparation situation.
The content of the invention
The present invention, which provides one kind, has excellent conductive performance, can experience and conduct the height for repair of cartilage of electric signal
By force, superlastic, the preparation method of conductive hydrogel.
The technical solution adopted by the present invention is：It is a kind of to be used for the high-strength of repair of cartilage, superlastic, the preparation side of conductive hydrogel
Method, comprise the following steps：
Step 1：Natural macromolecular material and Nano filling are dispersed in acid solution, it is dense to obtain natural macromolecular material
Spend the mixed liquor for being 1~20mg/mL for 5~100mg/mL, Nano filling concentration；
Step 2：Formed into step 1 in mixed liquor and add crosslinking agent, form pre-polymerization liquid A；Low-temperature frozen is freeze-dried after build-uping ice
The compound rest of natural polymer and Nano filling is formed afterwards；
Step 3：It is 0.5~5mg/ that conductive material uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
ML, the mixed liquor that conductive material concentration is 1~26mg/mL；Dopamine oxidation auto polymerization carries out polymerization dopamine to conductive material
Modification；
Step 4：Add hydrogel monomer in the solution formed into step 3, the concentration of hydrogel monomer is 100 in final solution
~400mg/mL；Initiator, crosslinking agent and auxiliary agent are added, forms hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Compound rest fully adsorbs pre-
Poly- liquid B, pre-polymerization liquid B polymerize in compound rest, form target product.
Further, natural macromolecular material is polysaccharide or albumen in the step 1.
Further, the concentration of crosslinking agent is 0.005%~0.1%v/v in the step 2.
Further, natural macromolecular material is chitosan, chitin, n-trimethyl chitosan chloride, quaternary phosphonium in the step 1
One kind in chitosan, gelatin and cellulose.
Further, Nano filling is clay, graphene, poly-dopamine particle, ferroso-ferric oxide in the step 1
One kind in grain, gold nanorods, silver nano-grain, hydroxyapatite and calcium phosphate.
Further, the conductive material in the step 3 is polypyrrole, redox graphene, CNT, poly- 3,4-
One kind in ethene dioxythiophene.
Further, the hydrogel monomer in the step 4 is acrylamide, NIPA, acrylic acid, first
One kind in base dimethylaminoethyl acrylate, gelatin, polyethyleneglycol diacrylate, 2- acrylamide-2-methyl propane sulfonics.
Further, the crosslinking agent in the step 2 is in glutaraldehyde, poly- glutaraldehyde, oxidized sodium alginate, Geniposide
It is a kind of.
Further, the initiator in the step 4 is ammonium persulfate.
Further, the crosslinking agent in the step 4 is BIS, and the auxiliary agent in the step 4 is TMEDA.
The beneficial effects of the invention are as follows：
（1）The present invention constructs the support with good adsorption ability, the addition of support using natural polymer and Nano filling
Be advantageous to hydrogel dissipation energy, significantly improve the mechanical strength of hydrogel；
（2）Hydrogel prepared by the present invention is not only with high intensity but also with excellent elasticity, close to the mechanical strength of cartilaginous tissue,
Enough mechanical strengths can be provided for cartilaginous tissue reparation and regeneration；
（3）Hydrogel prepared by the present invention has good electric conductivity, and the corresponding extraneous electro photoluminescence of energy promotes the increasing of cartilage cell
Grow and break up, accelerate the reparation and regeneration of cartilage defects；The electromyographic signal that hydrogel can be used to detect human body simultaneously is for feeding back
With the reparation situation of monitoring cartilaginous tissue；
（4）Conductive material in the present invention is modified by Dopamineization, and poly-dopamine is because with well dispersed and super
Strong adhesive capacity, can allow conductive material being dispersed in hydrogel pre-polymerization liquid and significantly increasing the conduction of hydrogel evenly
Property；And can allows hydrogel to have more close combination with natural polymer submounts, so as to be not easy between hydrogel and natural polymer
Ftractureed under additional effect.
Brief description of the drawings
Fig. 1 is the SEM figures of the chitosan that the step 2 in embodiment 1 is formed and clay compound rest.
Fig. 2 is the SEM figures of product after acrylamide polymerize in chitosan and clay compound rest.
Fig. 3 is the SEM figures of the conductive hydrogel formed in embodiment 1.
Fig. 4 is the compression stress strain curve figure of embodiment 1.
Embodiment
The present invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of high-strength, superpower, conductive hydrogel preparation method for repair of cartilage, comprise the following steps：
Step 1：Chitosan and nano clay are dispersed in acid solution, obtain chitosan concentration as 20mg/mL, nanometer
Clay concentration is 20mg/mL mixed liquor；
Step 2：Formed into step 1 in mixed liquor and add glutaraldehyde and be uniformly dispersed to form chitosan and nanometer sticks as crosslinking agent
Native pre-polymerization liquid；The concentration for making glutaraldehyde in chitosan and nano clay mixed liquor is 0.02%v/v；By chitosan and nano clay
Pre-polymerization liquid is placed in -20 DEG C of glaciations；Finally chitosan and nano clay shaft ice frozen are dried and to form chitosan and nano clay
Compound rest；
Step 3：It is 1mg/mL, carbon that CNT uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
Concentrations of nanotubes is 13mg/mL mixed liquor；It is amine-modified that dopamine oxidation auto polymerization carries out polymerization DOPA to CNT；
Step 4：Acrylamide gel monomer is added in the solution formed into step 3, hydrogel monomer in final solution
Concentration is 260mg/mL；Then ammonium persulfate initiator, BIS crosslinking agents are added to it, TMEDA auxiliary agents form acrylamide and carbon
Nanotube mixing hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Chitosan and nano clay are answered
Close support and fully adsorb pre-polymerization liquid B, the CNT of acrylamide and poly-dopamine functional modification mixes at ambient temperature
Pre-polymerization liquid polymerize in compound rest, forms target product.
Polymerization in step 5 spontaneous can be carried out, and liquid can use the modes such as photopolymerization；Initiator, crosslinking agent in step 4
Needed with the composition and content of auxiliary agent depending on the composition of the polymer monomer used in step 4 and concentration；It is specific in step 5
Polymerizing condition also specifically adjusts with the component content of initiator, crosslinking agent and auxiliary agent.
Comparative example
Effect to illustrate the invention, setting comparative example, comparative example preparation method are as follows：
Step 1：Chitosan and nano clay are dispersed in acid solution, obtain chitosan concentration as 20mg/mL, nanometer
Clay concentration is 20mg/mL mixed liquor；
Step 2：Formed into step 1 in mixed liquor and add glutaraldehyde and be uniformly dispersed to form chitosan and nanometer sticks as crosslinking agent
Native pre-polymerization liquid；The concentration for making glutaraldehyde in chitosan and nano clay mixed liquor is 0.02%v/v；By chitosan and nano clay
Pre-polymerization liquid is placed in -20 DEG C of glaciations；Finally chitosan and nano clay shaft ice frozen are dried and to form chitosan and nano clay
Compound rest；
Step 3：Using acrylamide as hydrogel monomer, the concentration for forming hydrogel monomer in solution is 260mg/mL；Then
Ammonium persulfate initiator, BIS crosslinking agents are added to it, TMEDA auxiliary agents form acrylamide gel pre-polymerization liquid；
Step 4：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid that step 3 is formed；Chitosan and nano clay are compound
Support fully adsorbs acrylamide gel pre-polymerization liquid, and acrylamide pre-polymerization liquid polymerize in compound rest at ambient temperature,
Form target product.
Fig. 1 is the SEM figures of the chitosan that the step 2 in embodiment 1 is formed and clay compound rest, as can be seen from the figure
(CS/Clay) compound rest prepared by freeze-gel process, has three-dimensional porous structure, has good adsorption capacity and height
Porosity, be advantageous to the absorption of follow-up pre-polymerization liquid.
Fig. 2 is the SEM figures of the product in comparative example；Fig. 3 is the SEM figures of the conductive hydrogel formed in embodiment 1；From figure
In it can be seen that with the chitosan that is formed in Fig. 1 and the microcosmic hole wall of clay compound rest, answering after adsorbing pre-polymerization liquid and polymerizeing
Support is closed, hole wall is thicker；Just cause the material finally prepared that there is excellent mechanical property just because of this structure；Because having
The CNT of poly-dopamine PDA modifications is so also have certain conductive capability.
Fig. 4 is the compression stress strain curve figure of embodiment 1；A is that the compression of virgin pp acid amides PAM hydrogels should in figure
Stress-strain curve；B is the compression stress strain curve of product in comparative example；C is the compression stress for the target product that step 5 is formed
Strain curve figure；As can be seen from the figure the stress that pure PAM hydrogels are compressed to 80% is 0.3MPa, and works as and constructed in PAM
Its compression stress is 1.8MPa after CS/Clay compound rests；As can be seen from the figure CS/Clay compound rests significantly enhance
The compression performance of PAM hydrogels；If importing the CNT of PDA modifications again in PAM, the compression stress of hydrogel is 1.25MPa；
Because PDA importing reduces the mechanical property of hydrogel.
Embodiment 2
A kind of high-strength, superpower, conductive hydrogel preparation method for repair of cartilage, comprise the following steps：
Step 1：Chitin and nano clay are dispersed in acid solution, obtain chitin concentration as 20mg/mL, nanometer
Clay concentration is 20mg/mL mixed liquor；
Step 2：Formed into step 1 in mixed liquor and add glutaraldehyde and be uniformly dispersed to form chitin and nanometer sticks as crosslinking agent
Native pre-polymerization liquid；The concentration for making glutaraldehyde in chitin and nano clay mixed liquor is 0.02%v/v；By chitin and nano clay
Pre-polymerization liquid is placed in -20 DEG C of glaciations；Finally chitin and nano clay shaft ice frozen are dried and to form chitin and nano clay
Compound rest；
Step 3：It is 1mg/mL, carbon that CNT uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
Concentrations of nanotubes is 13mg/mL mixed liquor；It is amine-modified that dopamine oxidation auto polymerization carries out polymerization DOPA to CNT；
Step 4：Acrylamide gel monomer is added in the solution formed into step 3, hydrogel monomer in final solution
Concentration is 260mg/mL；Then ammonium persulfate initiator, BIS crosslinking agents are added to it, TMEDA auxiliary agents form acrylamide and carbon
Nanotube mixing hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Chitin and nano clay are answered
Close support and fully adsorb pre-polymerization liquid B, the CNT of acrylamide and poly-dopamine functional modification mixes at ambient temperature
Pre-polymerization liquid polymerize in compound rest, forms target product.
Embodiment 3
A kind of high-strength, superpower, conductive hydrogel preparation method for repair of cartilage, comprise the following steps：
Step 1：Chitosan and graphene uniform are scattered in acid solution, obtain chitosan concentration as 20mg/mL, graphene
Concentration is 10mg/mL mixed liquor；
Step 2：Formed into step 1 in mixed liquor and add glutaraldehyde and be uniformly dispersed to form chitosan and nanometer sticks as crosslinking agent
Native pre-polymerization liquid；The concentration for making glutaraldehyde in chitosan and graphene mixed liquor is 0.02%v/v；By chitosan and graphene pre-polymerization
Liquid is placed in -20 DEG C of glaciations；Finally chitosan and graphene shaft ice frozen are dried to form chitosan and graphene compound rest；
Step 3：It is 1mg/mL, carbon that CNT uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
Concentrations of nanotubes is 13mg/mL mixed liquor；It is amine-modified that dopamine oxidation auto polymerization carries out polymerization DOPA to CNT；
Step 4：Acrylamide gel monomer is added in the solution formed into step 3, hydrogel monomer in final solution
Concentration is 260mg/mL；Then ammonium persulfate initiator, BIS crosslinking agents are added to it, TMEDA auxiliary agents form acrylamide and carbon
Nanotube mixing hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Chitosan and graphene are compound
Support fully adsorbs pre-polymerization liquid B, and the mixing of the CNT of acrylamide and poly-dopamine functional modification is pre- at ambient temperature
Poly- liquid polymerize in compound rest, forms target product.
Embodiment 4
A kind of high-strength, superpower, conductive hydrogel preparation method for repair of cartilage, comprise the following steps：
Step 1：By chitosan and poly-dopamine even particulate dispersion in acid solution, obtain chitosan concentration for 20mg/mL,
Poly-dopamine granule density is 20mg/mL mixed liquor；
Step 2：Addition glutaraldehyde in mixed liquor is formed into step 1 to be uniformly dispersed to form chitosan and poly- DOPA as crosslinking agent
Amine particle pre-polymerization liquid；The concentration for making glutaraldehyde in chitosan and poly-dopamine particle mixed liquor is 0.02%v/v；By chitosan and
Poly-dopamine particle pre-polymerization liquid is placed in -20 DEG C of glaciations；Finally chitosan and poly-dopamine granular ice are freeze-dried and formed
Chitosan and poly-dopamine Particles dispersed support；
Step 3：It is 1mg/mL, carbon that CNT uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
Concentrations of nanotubes is 13mg/mL mixed liquor；It is amine-modified that dopamine oxidation auto polymerization carries out polymerization DOPA to CNT；
Step 4：Acrylamide gel monomer is added in the solution formed into step 3, hydrogel monomer in final solution
Concentration is 260mg/mL；Then ammonium persulfate initiator, BIS crosslinking agents are added to it, TMEDA auxiliary agents form acrylamide and carbon
Nanotube mixing hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Chitosan and poly-dopamine
Grain compound rest fully adsorbs pre-polymerization liquid B, at ambient temperature the CNT of acrylamide and poly-dopamine functional modification
Mixing pre-polymerization liquid polymerize in compound rest, forms target product.
Embodiment 5
A kind of high-strength, superpower, conductive hydrogel preparation method for repair of cartilage, comprise the following steps：
Step 1：Chitosan and nano clay are dispersed in acid solution, obtain chitosan concentration as 20mg/mL, nanometer
Clay concentration is 20mg/mL mixed liquor；
Step 2：Into step 1 formed mixed liquor in add oxidized sodium alginate be uniformly dispersed as crosslinking agent to be formed chitosan with
Nano clay pre-polymerization liquid；The concentration for making oxidized sodium alginate in chitosan and nano clay mixed liquor is 20mg/mL；By chitosan
- 20 DEG C of glaciations are placed in nano clay pre-polymerization liquid；Finally chitosan and nano clay shaft ice frozen are dried and to form chitosan
With nano clay compound rest；
Step 3：It is 1mg/mL, carbon that CNT uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
Concentrations of nanotubes is 13mg/mL mixed liquor；It is amine-modified that dopamine oxidation auto polymerization carries out polymerization DOPA to CNT；
Step 4：Acrylamide gel monomer is added in the solution formed into step 3, hydrogel monomer in final solution
Concentration is 260mg/mL；Then ammonium persulfate initiator, BIS crosslinking agents are added to it, TMEDA auxiliary agents form acrylamide and carbon
Nanotube mixing hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Chitosan and nano clay are answered
Close support and fully adsorb pre-polymerization liquid B, the CNT of acrylamide and poly-dopamine functional modification mixes at ambient temperature
Pre-polymerization liquid polymerize in compound rest, forms target product.
Embodiment 6
A kind of high-strength, superpower, conductive hydrogel preparation method for repair of cartilage, comprise the following steps：
Step 1：Chitosan and graphene uniform are scattered in acid solution, obtain chitosan concentration as 20mg/mL, graphene
Concentration is 20mg/mL mixed liquor；
Step 2：Addition glutaraldehyde in mixed liquor is formed into step 1 to be uniformly dispersed to form chitosan and graphene as crosslinking agent
Pre-polymerization liquid；The concentration for making glutaraldehyde in chitosan and graphene mixed liquor is 0.02%v/v；By chitosan and graphene pre-polymerization liquid
It is placed in -20 DEG C of glaciations；Finally chitosan and graphene shaft ice frozen are dried to form chitosan and graphene compound rest；
Step 3：It is 1mg/mL, carbon that CNT uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
Concentrations of nanotubes is 13mg/mL mixed liquor；It is amine-modified that dopamine oxidation auto polymerization carries out polymerization DOPA to CNT；
Step 4：The different acrylic acid-acrylamide hydrogel monomers of N- are added in the solution formed into step 3, water-setting in final solution
The concentration of glue monomer is 260mg/mL；Then ammonium persulfate initiator is added to it, BIS crosslinking agents, it is different that TMEDA auxiliary agents form N-
Acrylic acid-acrylamide and CNT mixing hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Chitosan and graphene are compound
Support fully adsorbs pre-polymerization liquid B, at ambient temperature the carbon nanometer of the different acrylic acid-acrylamides of N- and poly-dopamine functional modification
Pipe mixing pre-polymerization liquid polymerize in compound rest, forms target product.
Embodiment 7
A kind of high-strength, superpower, conductive hydrogel preparation method for repair of cartilage, comprise the following steps：
Step 1：Chitosan and graphene uniform are scattered in acid solution, obtain chitosan concentration as 20mg/mL, graphene
Concentration is 10mg/mL mixed liquor；
Step 2：Formed into step 1 in mixed liquor and add glutaraldehyde and be uniformly dispersed to form chitosan and nanometer sticks as crosslinking agent
Native pre-polymerization liquid；The concentration for making glutaraldehyde in chitosan and graphene mixed liquor is 0.02%v/v；By chitosan and graphene pre-polymerization
Liquid is placed in -20 DEG C of glaciations；Finally chitosan and graphene shaft ice frozen are dried to form chitosan and graphene compound rest；
Step 3：Polypyrrole uniform dissolution/be distributed to forms to dopamine concentration is 1mg/mL, carbon receives in dopamine alkaline solution
Mitron concentration is 13mg/mL mixed liquor；It is amine-modified that dopamine oxidation auto polymerization carries out polymerization DOPA to polypyrrole；
Step 4：Acrylamide gel monomer is added in the solution formed into step 3, hydrogel monomer in final solution
Concentration is 260mg/mL；Then ammonium persulfate initiator, BIS crosslinking agents are added to it, TMEDA auxiliary agents form acrylamide and gathered
Pyrroles mixes hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Chitosan and graphene are compound
Support fully adsorbs pre-polymerization liquid B, at ambient temperature the polypyrrole mixing pre-polymerization of acrylamide and poly-dopamine functional modification
Liquid polymerize in compound rest, forms target product.
Flexible back bone of the invention in one natural polymer subbase that can be used for energy dissipation of hydrogel internal build, significantly
Improve the mechanical performance of hydrogel；The present invention can provide enough mechanical strengths for the reparation of cartilaginous tissue and extracellular matrix is micro-
Environment；The environmental stimulis such as light, electricity, magnetic can promote adhesion, increment and the differentiation of cartilage cell and can induce regenerative agent of cartilaginous tissue；It is logical
Cross to add conductive material in hydrogel pre-polymerization liquid and impart the good electric conductivity of hydrogel and respond extraneous electric signal and cooperate with and promote
Enter the reparation and regeneration of tissue；In addition, the hydrogel of the present invention perceives and passed to myoelectricity because can be used for good electric conductivity
Signal reflects the reparation situation of cartilaginous tissue；The superpower adsorption capacity that natural polymer submounts are prepared using freeze-drying is adsorbed
Hydrogel monomer pre-polymerization liquid builds skeleton-muscularity hydrogel；The problem of significantly improving conventional hydrogels poor mechanical property, and
And impart its good elasticity；Hydrogel prepared by the present invention has good electric conductivity, can experience and pass to electric model,
New approach has been started for the clinical practice of hydrogel.
Claims (8)
1. a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, it is characterised in that including following step
Suddenly：
Step 1：Natural macromolecular material and Nano filling are dispersed in acid solution, it is dense to obtain natural macromolecular material
Spend the mixed liquor for being 1~20mg/mL for 5~100mg/mL, Nano filling concentration；
Step 2：Formed into step 1 in mixed liquor and add crosslinking agent, form pre-polymerization liquid A；Low-temperature frozen is freeze-dried after build-uping ice
The compound rest of natural polymer and Nano filling is formed afterwards；
Step 3：It is 0.5~5mg/ that conductive material uniform dissolution/be distributed to is formed to dopamine concentration in dopamine alkaline solution
ML, the mixed liquor that conductive material concentration is 1~26mg/mL；Dopamine oxidation auto polymerization carries out polymerization dopamine to conductive material
Modification；
Step 4：Add hydrogel monomer in the solution formed into step 3, the concentration of hydrogel monomer is 100 in final solution
~400mg/mL；Initiator, crosslinking agent and auxiliary agent are added, forms hydrogel pre-polymerization liquid B；
Step 5：The compound rest that step 2 is formed is dipped into the pre-polymerization liquid B that step 4 is formed；Compound rest fully adsorbs pre-
Poly- liquid B, pre-polymerization liquid B polymerize in compound rest, form target product.
2. it is according to claim 1 it is a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, its
It is characterised by, natural macromolecular material is polysaccharide or albumen in the step 1.
3. it is according to claim 1 it is a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, its
It is characterised by, the concentration of crosslinking agent is 0.005%~0.1%v/v in the step 2.
4. it is according to claim 2 it is a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, its
Be characterised by, in the step 1 natural macromolecular material be chitosan, chitin, n-trimethyl chitosan chloride, quaternary phosphonium chitosan,
One kind in gelatin and cellulose.
5. it is according to claim 1 it is a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, its
It is characterised by, Nano filling is clay, graphene, poly-dopamine particle, ferriferrous oxide particles, gold nano in the step 1
One kind in rod, silver nano-grain, hydroxyapatite and calcium phosphate.
6. it is according to claim 1 it is a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, its
It is characterised by, the conductive material in the step 3 is polypyrrole, redox graphene, CNT, poly- 3,4- ethylene dioxies
One kind in thiophene.
7. it is according to claim 1 it is a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, its
It is characterised by, the hydrogel monomer in the step 4 is acrylamide, NIPA, acrylic acid, methacrylic acid
One kind in dimethylaminoethyl, gelatin, polyethyleneglycol diacrylate, 2- acrylamide-2-methyl propane sulfonics.
8. it is according to claim 1 it is a kind of be used for the high-strength of repair of cartilage, superlastic, the preparation method of conductive hydrogel, its
It is characterised by, the crosslinking agent in the step 2 is one kind in glutaraldehyde, poly- glutaraldehyde, oxidized sodium alginate, Geniposide.
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