CN106693050B - A kind of preparation method of the compound support frame material based on collagen and collagenous fibres - Google Patents
A kind of preparation method of the compound support frame material based on collagen and collagenous fibres Download PDFInfo
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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
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/24—Collagen
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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
- 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
- A61L27/14—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
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/108—Elemental carbon, e.g. charcoal
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/26—Cellulose ethers
- C08J2401/28—Alkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/02—Dextran; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention discloses a kind of preparation methods of compound support frame material based on collagen and collagenous fibres, its main feature is that aggregated structure body collagenous fibres are organic mixes with its by collagen, and compound modified synergic is carried out to collagen-collagen fiber composite solution using functional oxidation of polysaccharides and graphene oxide, then, by collagen-collagen fiber composite solution and a certain amount of chitosan, polyvinyl alcohol blending, then by techniques such as 3D printing, microwave drying film forming, electrospray, sterilizings, the preparation method of the compound support frame material based on collagen and collagenous fibres is finally obtained.The material uses the collagenous fibres of the stronger native collagen structures of bio-imitability, and biological design is carried out to bracket microstructure and pattern using 3D printing technique, chemically composition and bionical natural activity tissue abundant on natural structure, gained timbering material stable structure, physicochemical property are superior, with good cell compatibility and biological degradability, and can induce regeneration and restoration, it can be used as all types of tissue engineering brackets.
Description
Technical field
The present invention relates to a kind of compound support frame material based on collagen and collagenous fibres belongs to bio-medical material preparation
Field.
Background technique
Tissue engineering bracket is the most basic framework of engineered tissue, provides suitable ring for cell and tissue growth
Border, and gradually degrade and disappear with the building of tissue, so that new space is supplied to tissue and cell.The structure is thin
Born of the same parents obtain the place of nutrition, gas exchanges, waste discharge and growth metabolism, are to form the new group with certain form and function
It knits, the basis of organ.For decades, people are all the time by one " two-step method " manufacture active mass.The first step is to use certain
The bracket of biodegradable material design organization.In order to use the bracket of conventional method designing for manufacturing, researcher needs for it
It models, carve out, or go out a porous shape using chemicals etch.Second step is that a branch is cultivated using living cells
Frame.Numerous studies prove that there are many drawbacks for these technologies, for example largely use highly toxic organic solvent, and the manufacturing cycle is long,
Labour-intensive process can not completely remove the residue in polymeric matrix, and repeatability is poor, and irregular shape is presented in hole
Shape is unable to fully connect between hole, and structure is partially thin etc..In addition, these method majorities are unable to control shape.
Compared with this method, shape and structure that 3D printing is organized needed for can accurately printing.The bone of 3D printing is planted
Enter object, corona, contact lenses and hearing aid etc. and repair form without life to be already present on the internal of thousands of people all over the world.
Currently, 3D printing physical feeling uses single material, such as metal, ceramics or plastics.They have commercial significance, because they
Market value can be fitted closely with a special body of shape from them.However, these materials are also only capable of becoming
Abiotic alternative site, real 3D biometric print, which should be, creates active mass.Biometric print, the i.e. use of " ink living ", it is interior
Portion left floating the printable gel of living cells.By living cells and " gap fillers " (such as collagen, with temporarily fill space until with
Other cell fusions) many special and accurate shape of tissue is printed, living cells secrets out of substance and enters hydrogel, from
And ultimately form a support parent.With the growth of cell, parent development is active mass.
Collagen and collagenous fibres, have good biocompatibility and biodegradability, and promote cell growth with
The performance of adherency, and there is pH and temperature sensitivity, it is conducive to molding, has been applied to 3D printing active mass field.However, pure
The 3D printing active mass of collagen or collagenous fibres also is not enough to support the tissue of certain shapes in mechanical property, therefore adds
Other biomaterials or micro crosslinking agent are added to become necessary element during 3D printing.
Therefore a kind of this patent method of the compound support frame material based on collagen and collagenous fibres obtained is in 3D printing
Active mass field has broad application prospects.
Summary of the invention
It is provided the purpose of the present invention is the deficiency for existing the relevant technologies a kind of based on collagen and collagenous fibres
Compound support frame material.The timbering material cell compatibility is excellent, is very beneficial for growth, proliferation and the migration of cell, cell energy
It is enough preferably to grow into internal stent, and there is centainly anti-inflammatory, anti-oxidant, antibacterial and other effects, bioactivity is good, can be used as tissue
Engineering rack.
The purpose of the present invention can be realized that preparation methods steps are as follows by following technology of preparing:
(1) preparation of the collagen-collagen fiber composite swelling solution based on oxidation of polysaccharides and graphene oxide: will in mass ratio
It is mixed for the collagen and collagenous fibres of 1~9: 9~1 1~2 parts by weight, it is 4.0 that stirring, which is swollen in pH, at 4~10 DEG C
In Acetic acid-sodium acetate buffer system, the collagen-collagen fiber composite swelling solution that concentration is 1~2wt% is obtained；Then to above-mentioned multiple
The oxidation of polysaccharides that 0.05~0.4 parts by weight are added in swelling solution is closed, it is protected from light 10 at 4~10 DEG C~for 24 hours, it is completed wait react
Afterwards, then to compound swelling solution the graphene oxide of 0.01~0.2 parts by weight is added, the reaction was continued at 4~10 DEG C 24~48h is obtained
To the collagen-collagen fiber composite swelling solution based on oxidation of polysaccharides and graphene oxide；
(2) preparation of the stoste of the compound support frame material based on collagen and collagenous fibres: by the shell of 0.5~1.5 parts by weight
Glycan is added to above-mentioned collagen-collagen fiber composite swelling solution, and stirring obtains mixed liquor A to whole dissolutions at 4~10 DEG C；?
At 40~80 DEG C in deionized water by the polyvinyl alcohol dissolution of 6~12 parts by weight, the polyethylene that concentration is 6~12wt% is obtained
Alcohol solution；It will mix for 1~10: 0.01~2 mixing A liquid with polyvinyl alcohol water solution, be stirred at 4~10 DEG C by volume
It is molten to being sufficiently total to, obtain the stoste of the compound support frame material based on collagen and collagenous fibres；
(3) by the preparation of collagen and the compound support frame material of collagenous fibres: according to required bracket form, structure based on
Calculation machine Autocad compiles the mobile program of control platform, by the above-mentioned compound rest material based on collagen and collagenous fibres
The stoste of material injects 3D biometric print machine, and 3D printing forms to obtain collagen-collagen fibrous composite scaffold, and compound rest is shifted
It forms a film on to microwave dryer；It in the acetum of 0.05~0.5M, is prepared followed by by 1~2 parts by weight collagen solution
The collagen solution collagen for being 1~2wt% at concentration, is sprayed on collagen-collagen fiber for above-mentioned collagen solution using electrostatic sprayer
Compound rest tow sides, final freeze-dried, dosage are 6~30KGy/h60Gamma-rays sterilization caused by Co, at
Type packaging, obtains the final finished of the compound support frame material based on collagen and collagenous fibres.
It is by carboxymethyl cellulose, hyaluronic acid, shell that oxidation of polysaccharides is used in above-mentioned preparation method, in step (1)
Glycan, glucan etc. through obtained by sodium periodate oxidation, specific preparation method referring to this seminar publication early period [but Wei Hua,
Liu Xinhua, but time wait to have antibacterial/bacteriostasis efficacy collagen aggregate composite type medical fiber Chinese invention patent
201510127304.9；But time, but Wei Hua, Liu Xinhua wait oxidation chitosan oligosaccharide and preparation method thereof patent authorization number: CN
104004112 A；But Wei Hua, Liu Xinhua, but time, wait the modified pig dermis collagen micro-nano fiber film of oxidation chitosan graft and
Preparation method patent authorization number: 104013995 A of CN]；Graphene oxide as described in step (1), polyvinyl alcohol, shell are poly-
Sugar is medical grade；The 3D printing program of the compound support frame material of collagen and collagenous fibres need to be according to specific bracket in step (1)
Depending on purposes, form, fine structure.
The present invention has the following advantages:
(1) different from the existing collagen class timbering material reported mostly, present invention employs collagens and collagenous fibres, wherein
Collagenous fibres are the aggregation of collagen, and structure is increasingly complex, more can in bionical active mass's body collagen there are structural form,
Research shows that its physicochemical property, bioactivity, tissue regeneration induction repair ability are significant relatively strong；
(2) present invention uses oxidation of polysaccharides and graphene oxide for the modifying agent of collagen, one side oxidation of polysaccharides energy and glue
Primary raw schiff bases bond, which is closed, to be achieved the effect that effectively to be crosslinked, and polysaccharide is still able to maintain the functionality of its ontology after aoxidizing, non-
Often be conducive to the preparation of functionalization collagen；On the other hand be graphene oxide can while not influencing collagenous biological activity,
The physicochemical property of collagen can be significantly increased, and can assign collagen certain antibacterial/biocidal property；
(3) using 3D printing technique can form, microstructure to bracket etc. carry out bionical biology design, pass through regulation
The microstructure of bracket, pattern are to realize the control for growing into, growing to cell.
Specific embodiment
Below by implementing that the present invention is specifically described, it is necessary to which indicated herein is that the present embodiment is served only for pair
The present invention is described further, and should not be understood as limiting the scope of the invention, and the person skilled in the art in the field can
Nonessential modifications and adaptations are made with the content according to foregoing invention.
Embodiment 1
(1) preparation of the collagen-collagen fiber composite swelling solution based on oxidation of polysaccharides and graphene oxide: will in mass ratio
It is mixed for the collagen and collagenous fibres of 1: 91 parts by weight, stirring is swollen in the Acetic acid-sodium acetate that pH is 4.0 and delayed at 4 DEG C
It rushes in system, obtains the collagen-collagen fiber composite swelling solution that concentration is 1wt%；Then it is added into above-mentioned compound swelling solution
The oxidation of polysaccharides of 0.05 parts by weight is protected from light at 4 DEG C for 24 hours, to after the reaction was completed, then 0.2 weight is added into compound swelling solution
The graphene oxide for measuring part, the reaction was continued at 4 DEG C 48h obtain the collagen-collagen fiber based on oxidation of polysaccharides and graphene oxide
Compound swelling solution；
(2) preparation of the compound support frame material stoste based on collagen and collagenous fibres: the chitosan of 0.5 parts by weight is added
Into above-mentioned collagen-collagen fiber composite swelling solution, stirring obtains mixed liquor A to whole dissolutions at 4 DEG C；By 6 weights at 40 DEG C
The polyvinyl alcohol dissolution for measuring part in deionized water, obtains the polyvinyl alcohol water solution that concentration is 6wt%；It will by volume be 1: 2
Mixing A liquid mixed with polyvinyl alcohol water solution, stirring obtains answering based on collagen and collagenous fibres to sufficiently molten altogether at 4 DEG C
Close the stoste of timbering material；
(3) by the preparation of collagen and the compound support frame material of collagenous fibres: according to required bracket form, structure based on
Calculation machine Autocad compiles the mobile program of control platform, by the above-mentioned compound rest material based on collagen and collagenous fibres
The stoste of material injects 3D biometric print machine, and 3D printing forms to obtain collagen-collagen fibrous composite scaffold, and compound rest is shifted
Extremely form a film on microwave dryer；In the acetum of 0.05M, concentration is configured to followed by by 1 parts by weight collagen solution
For the collagen solution collagen of 1wt%, above-mentioned collagen solution is sprayed on collagen-collagen fibrous composite scaffold using electrostatic sprayer
Tow sides, final freeze-dried, dosage 6KGy/h60Gamma-rays sterilization caused by Co, shaping packaging obtain
The final finished of compound support frame material based on collagen and collagenous fibres.
Embodiment 2
(1) preparation of the collagen-collagen fiber composite swelling solution based on oxidation of polysaccharides and graphene oxide: will in mass ratio
It is mixed for the collagen and collagenous fibres of 3: 7 1.5 parts by weight, stirring is swollen in the Acetic acid-sodium acetate that pH is 4.0 at 5 DEG C
In buffer system, the collagen-collagen fiber composite swelling solution that concentration is 1.5wt% is obtained；Then add into above-mentioned compound swelling solution
Enter the oxidation of polysaccharides of 0.2 parts by weight, be protected from light 15h at 5 DEG C, 0.1 weight is added to after the reaction was completed, then to compound swelling solution
Part graphene oxide, the reaction was continued at 5 DEG C 24~48h obtains based on the collagen-collagen of oxidation of polysaccharides and graphene oxide fibre
Tie up compound swelling solution；
(2) preparation of the stoste of the compound support frame material based on collagen and collagenous fibres: the chitosan of 1 parts by weight is added
To above-mentioned collagen-collagen fiber composite swelling solution, stirring obtains mixed liquor A to whole dissolutions at 5 DEG C；By 8 weight at 60 DEG C
The polyvinyl alcohol dissolution of part in deionized water, obtains the polyvinyl alcohol water solution that concentration is 8wt%；It will be by volume 5: 1
Mixing A liquid mix with polyvinyl alcohol water solution, stirs molten to being sufficiently total at 5 DEG C, is obtained compound based on collagen and collagenous fibres
The stoste of timbering material；
(3) by the preparation of collagen and the compound support frame material of collagenous fibres: according to required bracket form, structure based on
Calculation machine Autocad compiles the mobile program of control platform, by the above-mentioned compound rest material based on collagen and collagenous fibres
The stoste of material injects 3D biometric print machine, and 3D printing forms to obtain collagen-collagen fibrous composite scaffold, and compound rest is shifted
Extremely form a film on microwave dryer；In the acetum of 0.1M, concentration is configured to followed by by 1.5 parts by weight collagen solutions
For the collagen solution collagen of 1.5wt%, above-mentioned collagen solution is sprayed on collagen-collagen fiber composite branch using electrostatic sprayer
Frame tow sides, final freeze-dried, dosage 15KGy/h60Gamma-rays sterilization caused by Co, shaping packaging obtain
To the final finished based on collagen and the compound support frame material of collagenous fibres.
Embodiment 3
(1) preparation of the collagen-collagen fiber composite swelling solution based on oxidation of polysaccharides and graphene oxide: will in mass ratio
It is mixed for the collagen and collagenous fibres of 9: 12 parts by weight, stirring is swollen in the Acetic acid-sodium acetate that pH is 4.0 at 10 DEG C
In buffer system, the collagen-collagen fiber composite swelling solution that concentration is 2wt% is obtained；Then it is added into above-mentioned compound swelling solution
The oxidation of polysaccharides of 0.4 parts by weight is protected from light 10h at 10 DEG C, and 0.01 weight is added to after the reaction was completed, then to compound swelling solution
The graphene oxide for measuring part, the reaction was continued at 4~10 DEG C for 24 hours, obtains the collagen-collagen based on oxidation of polysaccharides and graphene oxide
Fiber composite swelling solution；
(2) preparation of the stoste of the compound support frame material based on collagen and collagenous fibres: the chitosan of 1.5 parts by weight is added
Enter to above-mentioned collagen-collagen fiber composite swelling solution, stirring obtains mixed liquor A to whole dissolutions at 10 DEG C；By 6 at 80 DEG C
The polyvinyl alcohol dissolution of~12 parts by weight in deionized water, obtains the polyvinyl alcohol water solution that concentration is 12wt%；It will be by volume
Than being mixed for 10: 0.01 mixing A liquid with polyvinyl alcohol water solution, at 10 DEG C stirring to sufficiently molten altogether, obtain based on collagen and
The stoste of the compound support frame material of collagenous fibres；
(3) by the preparation of collagen and the compound support frame material of collagenous fibres: according to required bracket form, structure based on
Calculation machine Autocad compiles the mobile program of control platform, by the above-mentioned compound rest material based on collagen and collagenous fibres
The stoste of material injects 3D biometric print machine, and 3D printing forms to obtain collagen-collagen fibrous composite scaffold, and compound rest is shifted
Extremely form a film on microwave dryer；Followed by by 2 parts by weight collagen solutions, in the acetum of 0.5M, being configured to concentration is
Above-mentioned collagen solution is being sprayed on collagen-collagen fibrous composite scaffold just using electrostatic sprayer by the collagen solution collagen of 2wt%
Anti- two sides, final freeze-dried, dosage 30KGy/h60Gamma-rays sterilization caused by Co, shaping packaging obtain base
In the final finished of collagen and the compound support frame material of collagenous fibres.
Claims (3)
1. a kind of preparation method of the compound support frame material based on collagen and collagenous fibres, it is characterised in that this method includes following
Step:
(1) preparation of the collagen-collagen fiber composite swelling solution based on oxidation of polysaccharides and graphene oxide: will be 1 in mass ratio
The collagen and collagenous fibres of~9: 9~1 1~2 parts by weight mix, and stir at a temperature of 4~10 DEG C, being swollen in pH is
In 4.0 Acetic acid-sodium acetate buffer system, the collagen-collagen fiber composite swelling solution that concentration is 1~2wt% is obtained；Then to
The oxidation of polysaccharides of 0.05~0.4 parts by weight is added in above-mentioned compound swelling solution, it is protected from light 10 at 4~10 DEG C~for 24 hours, wait react
After the completion, then to compound swelling solution the graphene oxide of 0.01~0.2 parts by weight is added, the reaction was continued at 4~10 DEG C 24~
48h obtains the collagen-collagen fiber composite swelling solution based on oxidation of polysaccharides and graphene oxide；
(2) preparation of the stoste of the compound support frame material based on collagen and collagenous fibres: by the chitosan of 0.5~1.5 parts by weight
It is added to above-mentioned collagen-collagen fiber composite swelling solution, stirring obtains mixed liquor A to whole dissolutions at 4~10 DEG C；40~
At 80 DEG C in deionized water by the polyvinyl alcohol dissolution of 6~12 parts by weight, the polyvinyl alcohol water that concentration is 6~12wt% is obtained
Solution；It will mix, stir at 4~10 DEG C to filling with polyvinyl alcohol water solution for 1~10: 0.01~2 mixing A liquid by volume
Point altogether it is molten, obtain the stoste of the compound support frame material based on collagen and collagenous fibres；
(3) computer the preparation of the compound support frame material based on collagen and collagenous fibres: is used according to required bracket form, structure
Autocad compiles the mobile program of control platform, by the above-mentioned compound support frame material based on collagen and collagenous fibres
Stoste injects 3D biometric print machine, and 3D printing forms to obtain collagen-collagen fibrous composite scaffold, and compound rest is transferred to micro-
It forms a film on wave drying machine；It is dissolved in the acetum of 0.05~0.5M followed by by 1~2 parts by weight collagen, is configured to concentration
For the collagen solution of 1~2wt%, above-mentioned collagen solution is being sprayed on collagen-collagen fibrous composite scaffold just using electrostatic sprayer
Anti- two sides, final freeze-dried, dosage are 6~30KGy/h60Gamma-rays sterilization caused by Co, shaping packaging obtain
To the final finished based on collagen and the compound support frame material of collagenous fibres；Compound rest material based on collagen and collagenous fibres
Material, mainly includes four kinds of collagen, collagenous fibres, chitosan and polyvinyl alcohol base-materials, Key Performance Indicator is as follows:
Average pore size: >=20 μm；
Content of beary metal :≤10 μ g/g (m/m)；
Cytotoxicity: cell-cytotoxic reaction is not more than 1 grade；
Sterility test: sterile；
Sensitization test (STT): without delayed type hypersensitivity, DTH；
Intradermal reaction test: primary stimulus index PII < 0.4.
2. the preparation method of the compound support frame material described in claim 1 based on collagen and collagenous fibres, which is characterized in that institute
The collagen and collagenous fibres stated are to extract to obtain from any one of pigskin, pig tendon, ox-hide, beef tendon, donkey hide or rat-tail tendon
?.
3. the preparation method of the compound support frame material described in claim 1 based on collagen and collagenous fibres, which is characterized in that institute
The oxidation of polysaccharides stated be polysaccharide obtained by sodium periodate oxidation, selected oxidation chitosan, oxidized hyaluronic acid, oxidized dextran,
Any one in oxidated carboxymethyl cellulose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710109808.7A CN106693050B (en) | 2017-02-28 | 2017-02-28 | A kind of preparation method of the compound support frame material based on collagen and collagenous fibres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710109808.7A CN106693050B (en) | 2017-02-28 | 2017-02-28 | A kind of preparation method of the compound support frame material based on collagen and collagenous fibres |
Publications (2)
| Publication Number | Publication Date |
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| CN106693050A CN106693050A (en) | 2017-05-24 |
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| CN108340569B (en) * | 2018-01-04 | 2019-11-08 | 艾伯尔三氐打印技术（重庆）有限公司 | A kind of 3D printing method of three-dimensional cell hydrogel composite construction |
| CN109464697A (en) * | 2018-12-26 | 2019-03-15 | 重庆石墨烯研究院有限公司 | A kind of polyvinyl alcohol/chitosan/graphene combine dressing and preparation method thereof |
| CN111378149B (en) * | 2018-12-30 | 2021-08-31 | 中国科学院沈阳自动化研究所 | Factor slow-release neutral gel system for 3D printing or in-situ injection and preparation method thereof |
| CN111501121A (en) * | 2019-01-31 | 2020-08-07 | 华北水利水电大学 | Method for preparing collagen fiber by wet spinning |
| CN112354013B (en) * | 2020-10-26 | 2022-10-18 | 杜明春 | Bionic collagen aqueous solution and preparation method and use method thereof |
| CN114149610A (en) * | 2021-12-17 | 2022-03-08 | 四川大学 | Method for preparing hemostatic sponge by using oxidized bletilla striata modified collagen fibers |
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