CN108144116A - A kind of novel antibacterial artificial ligament - Google Patents
A kind of novel antibacterial artificial ligament Download PDFInfo
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- CN108144116A CN108144116A CN201810160063.1A CN201810160063A CN108144116A CN 108144116 A CN108144116 A CN 108144116A CN 201810160063 A CN201810160063 A CN 201810160063A CN 108144116 A CN108144116 A CN 108144116A
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- artificial ligament
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- fibroin
- novel antibacterial
- pcl
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- 210000003041 ligament Anatomy 0.000 title claims abstract description 46
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 33
- 108010022355 Fibroins Proteins 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000835 fiber Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 241000255789 Bombyx mori Species 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 230000003115 biocidal effect Effects 0.000 claims description 3
- 238000009954 braiding Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000000578 dry spinning Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 15
- 230000004069 differentiation Effects 0.000 abstract description 4
- 230000012010 growth Effects 0.000 abstract description 4
- 230000005847 immunogenicity Effects 0.000 abstract description 4
- 238000005452 bending Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002421 anti-septic effect Effects 0.000 abstract description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- 210000000988 bone and bone Anatomy 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 235000013601 eggs Nutrition 0.000 description 3
- -1 compound quaternary ammonium salt Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000021197 fiber intake Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 208000003322 Coinfection Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 208000034874 Product colour issue Diseases 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000000130 stem cell Anatomy 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Classifications
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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
- A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
-
- 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
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
-
- 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
-
- 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
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- 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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- 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
- A61L27/58—Materials at least partially resorbable by the body
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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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
- A61L2300/208—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
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- 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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- A61L2400/00—Materials characterised by their function or physical properties
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/10—Materials or treatment for tissue regeneration for reconstruction of tendons or ligaments
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Abstract
The present invention provides a kind of novel antibacterial artificial ligament, novel antibacterial artificial ligament of the present invention is made by modified silk albumen, the raw materials used in the present invention is PCL materials and modified silk albumen, and fibroin also has excellent biocompatibility, nontoxic, conducive to cell adherence, growth and differentiation；Thus the artificial ligament prepared has good biocompatibility and degradability, modified silk azelon is utilized quaternary ammonium salt antiseptic and fibroin is handled, make its with high mechanical strength general formula also with antibacterial effect, can meet the needs of patient is to tough band strength, PCL materials have well-known biocompatibility, ligament has high tractive resistance made of PCL, bending force and torsion, artificial ligament transplanting provided by the present invention is simple and convenient, securely and reliably, patient tolerability is good, the advantages that immunogenicity is small, it has broad application prospects.
Description
Technical field
The present invention relates to medical instruments field more particularly to a kind of novel antibacterial artificial ligaments.
Background technology
Due to being on the increase for the high energy wound such as traffic accident, bone defect caused by wound or secondary infection becomes orthopedist
The a major challenge faced, autologous bone transplanting art is to treat the effective means of bone defect, however itself bone amount is limited, and increases trouble
The risk and pain of person many places operation.Bone renovating material made of organizational engineering material combination multipotential stem cell, can promote to plant
Enter position new bone formation, be expected to reduce the needs to autologous bone, partially or completely substitute self bone tissue.
Material based on metal is initially applied in bone tissue reparation, however the implantation material of metal needs second operation
It takes out, larger pain is brought to patient.A variety of absorbable materials (hand over by such as polylactide (PLA), pla-pcl (PCL) and poly- second
Compound lactide of ester (PLGA) etc.) succeed is substituted by cambium in an experiment, obtain extensive concern.Wherein, gather in oneself
Ester material (PCL) ductility is good, can degrade in vivo, Various Tissues functional material has been made.Using fibroin as representative
Natural degradable material then has relatively low immunogenicity, and fibroin mechanical strength is preferable, and has good biofacies
Capacitive.The process of fibroin degradation in vivo and has certain experiment basis to the supporting function of bone remoulding.It is however, single
Pure fibroin ductility in the application of electrostatic spinning is poor, it is impossible to provide the tension of initial stage ligament needs after operation, easily
Lead to operative failure.
Natural protein structure makes silk become the material for having fine affinity to human body, but is also that bacteria breed is numerous
The suitable place spread out and propagated.The breeding of bacterium not only makes silk product discoloration, mouldy and degradation, and also the health of the mankind is generated
Harm, therefore, research and development anti bacteria natural silk product are extremely important, and it is artificial that the present invention provides a kind of novel antibacterial
Ligament, have excellent biocompatibility, it is nontoxic, conducive to cell adherence, growth and differentiation, antibacterial, resist fungi, bacterium, disease
The invasion of the microorganisms such as poison, the artificial ligament thus prepared have good biocompatibility and degradability.
Invention content
In order to solve the above technical problem, the present invention provides a kind of novel antibacterial artificial ligaments.
The present invention is realized with following technical solution：
A kind of novel antibacterial artificial ligament, the artificial ligament are compiled by anti bacteria natural silk azelon and Biodegradable fibers PCL
It knits, fibroin fiber dosage described in artificial ligament accounts for the 55~85% of total amount, and the PCL fiber consumptions account for total amount
15~45%.
Further, the preparation method of the artificial ligament is：
Step 1: use Na2CO3Then aqueous solution dissolves, and by centrifugation, dialysis degumming silkworm cocoons with LiBr aqueous solutions
Afterwards, regenerated silk fibroin water solution is obtained, and then the mass percent for being concentrated into fibroin albumen is 10%~20%；
Step 2: the regenerated silk fibroin water solution obtained after graphene oxide water solution previous step is concentrated is 1 in mass ratio:
100~10000 are blended, and obtain graphene oxide/fibroin albumen mixed solution；
Step 3: addition calcium carbonate aqueous solution, it is 0.2~0.5mol/L to adjust calcium ion molar concentration in solution, continues to concentrate,
Until the percentage that fibroin albumen obtains quality is 50%~70%, the spinning solution of fibroin albumen/graphene oxide has been obtained at this time；
Step 4: carrying out dry spinning at room temperature using the solution after concentration as spinning solution, the silk egg of activeness and quietness is obtained
White fiber；
Step 5: antibiotic finish, bath raio 1 are carried out to fibroin fiber with 11-20 g/L HBP-HTC solution:70, temperature
It is 100 DEG C, impregnates 5 minutes, two leachings two is rolled, and control pick-up is 100%, is dried after washing and obtains anti bacteria natural silk azelon；
Step 6: by the anti bacteria natural silk azelon obtained in step 5 and Biodegradable fibers PCL windings braiding, suture
It immerses in ethanol solution afterwards, after drawn, fixed length are soaked for a period of time, take out and obtain novel antibacterial artificial ligament.
Further, the ethanol solution, the volume fraction of ethyl alcohol is 50%~75%；The multiple of the stretching is 3~5
Times, the time that the fixed length is impregnated is 5~10 hours.
Further, the artificial ligament length be 25~50cm, it is a diameter of to be repaired the 0.9 of ligament diameter~
1.2 again；A diameter of 80~200 μm of the fibroin fiber.
Further, the metal oxide hydrosol, the metal can also be added in the preparation process of the artificial ligament
Metal oxide in the oxide hydrosol can be TiO2、ZnO、Al2O3Or ZrO2One or more of mixing, and the gold
It is 10~100nm to belong to the nano particle diameter in the oxide hydrosol.
The beneficial effects of the invention are as follows：
The raw materials used in the present invention is PCL materials and modified silk albumen, and fibroin also has excellent biocompatibility, nothing
Poison, conducive to cell adherence, growth and differentiation；Thus the artificial ligament prepared has good biocompatibility and degradability.
Modified silk azelon is utilized quaternary ammonium salt antiseptic and fibroin is handled.Make it with high mechanical strength
General formula also has antibacterial effect, can meet the needs of patient is to tough band strength.PCL materials have well-known bio-compatible
Property, ligament has high tractive resistance, bending force and torsion made of PCL.Artificial ligament transplanting provided by the present invention
It is simple and convenient, securely and reliably, the advantages that patient tolerability is good, and immunogenicity is small, have broad application prospects.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention will be made below further detailed
Description.
Embodiment 1：
A kind of novel antibacterial artificial ligament, the artificial ligament are compiled by anti bacteria natural silk azelon and Biodegradable fibers PCL
It knits.Fibroin fiber dosage described in artificial ligament accounts for the 55~85% of total amount, and the PCL fiber consumptions account for total amount
15~45%.The fibroin fiber amine-terminated hyperbranced compound quaternary ammonium salt（HBP-HTC）It arranges.
The preparation method of the novel antibacterial artificial ligament is：
Step 1: use Na2CO3Then aqueous solution dissolves, and by centrifugation, dialysis degumming silkworm cocoons with LiBr aqueous solutions
Afterwards, regenerated silk fibroin water solution is obtained, and then the mass percent for being concentrated into fibroin albumen is 10%~20%；
Step 2: the regenerated silk fibroin water solution obtained after graphene oxide water solution previous step is concentrated is 1 in mass ratio:
100~10000 are blended, and obtain graphene oxide/fibroin albumen mixed solution；
Step 3: addition calcium carbonate aqueous solution, it is 0.2~0.5mol/L to adjust calcium ion molar concentration in solution, continues to concentrate,
Until the percentage that fibroin albumen obtains quality is 50%~70%, the spinning solution of fibroin albumen/graphene oxide has been obtained at this time；
Step 4: carrying out dry spinning at room temperature using the solution after concentration as spinning solution, the silk egg of activeness and quietness is obtained
White fiber；
Step 5: antibiotic finish, bath raio 1 are carried out to fibroin fiber with 11-20 g/L HBP-HTC solution:70, temperature
It is 100 DEG C, impregnates 5 minutes, two leachings two is rolled, and control pick-up is 100%, is dried after washing and obtains anti bacteria natural silk azelon；
Step 6: by the anti bacteria natural silk azelon obtained in step 5 and Biodegradable fibers PCL windings braiding, suture
It immerses in ethanol solution afterwards, after drawn, fixed length are soaked for a period of time, take out and obtain novel antibacterial artificial ligament.
The artificial ligament length be 25~50cm, a diameter of to be repaired the 0.9~1.2 of ligament diameter times；It is described
A diameter of 80~200 μm of fibroin fiber.
Further, the metal oxide hydrosol, the metal can also be added in the preparation process of the artificial ligament
Metal oxide in the oxide hydrosol can be TiO2、ZnO、Al2O3Or ZrO2One or more of mixing, and the gold
It is 10~100nm to belong to the nano particle diameter in the oxide hydrosol.
Further, the ethanol solution, the volume fraction of ethyl alcohol is 75%~99%；The multiple of the stretching is 5~8
Times, the time that the fixed length is impregnated is 5~10 hours.
Embodiment 2：
The raw materials used in the present invention is PCL materials and modified silk albumen, and PCL materials have well-known biocompatibility, by
Ligament made of PCL has high tractive resistance, bending force and torsion.Fibroin also has excellent biocompatibility,
It is nontoxic, conducive to cell adherence, growth and differentiation；Thus the artificial ligament prepared have good biocompatibility with it is degradable
Property.
Graphene oxide and metal oxide nanoparticles are utilized in the fibroin fiber of activeness and quietness intensity is big,
The performances such as modulus height carry out activeness and quietness to fibroin fiber.Then amine-terminated hyperbranced compound quaternary ammonium salt is used（HBP-HTC）
Arrange and enhance the anti-microbial property of fibroin fiber, all silk eggs before the remote superorder of fracture strength, antibacterial efficacy
White fiber has high mechanical strength and preferable antibacterial effect, can meet the needs of patient is to tough band strength.
Artificial ligament transplanting provided by the present invention is simple and convenient, securely and reliably, patient tolerability is good, and immunogenicity is small etc.
Advantage has broad application prospects.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent variations made according to the claims of the present invention, is still within the scope of the present invention.
Claims (5)
1. a kind of novel antibacterial artificial ligament, it is characterised in that：The artificial ligament by anti bacteria natural silk azelon and can biology
Degradation of fibers PCL weaves, and fibroin fiber dosage described in artificial ligament accounts for the 55~85% of total amount, the PCL fibers
Dosage accounts for the 15~45% of total amount.
2. novel antibacterial artificial ligament according to claim 1, it is characterised in that：The preparation method of the artificial ligament
For：
Step 1: use Na2CO3Then aqueous solution dissolves, and by centrifugation, dialysis degumming silkworm cocoons with LiBr aqueous solutions
Afterwards, regenerated silk fibroin water solution is obtained, and then the mass percent for being concentrated into fibroin albumen is 10%~20%；
Step 2: the regenerated silk fibroin water solution obtained after graphene oxide water solution previous step is concentrated is 1 in mass ratio:
100~10000 are blended, and obtain graphene oxide/fibroin albumen mixed solution；
Step 3: addition calcium carbonate aqueous solution, it is 0.2~0.5mol/L to adjust calcium ion molar concentration in solution, continues to concentrate,
Until the percentage that fibroin albumen obtains quality is 50%~70%, the spinning solution of fibroin albumen/graphene oxide has been obtained at this time；
Step 4: carrying out dry spinning at room temperature using the solution after concentration as spinning solution, the silk egg of activeness and quietness is obtained
White fiber；
Step 5: antibiotic finish, bath raio 1 are carried out to fibroin fiber with 11-20 g/L HBP-HTC solution:70, temperature
It is 100 DEG C, impregnates 5 minutes, two leachings two is rolled, and control pick-up is 100%, is dried after washing and obtains anti bacteria natural silk azelon；
Step 6: by the anti bacteria natural silk azelon obtained in step 5 and Biodegradable fibers PCL windings braiding, suture
It immerses in ethanol solution afterwards, after drawn, fixed length are soaked for a period of time, take out and obtain novel antibacterial artificial ligament.
3. novel antibacterial artificial ligament according to claim 1, it is characterised in that：The ethanol solution, the volume of ethyl alcohol
Score is 50%~75%；The multiple of the stretching is 3~5 times, and the time that the fixed length is impregnated is 5~10 hours.
4. novel antibacterial artificial ligament according to claim 1, it is characterised in that：The artificial ligament length for 25~
50cm, a diameter of to be repaired the 0.9~1.2 of ligament diameter times；A diameter of 80~200 μm of the fibroin fiber.
5. novel antibacterial artificial ligament according to claim 1, it is characterised in that：In the preparation process of the artificial ligament
The metal oxide hydrosol can also be added, the metal oxide in the metal oxide hydrosol can be selected from TiO2、
ZnO、Al2O3Or ZrO2One or more, and the nano particle diameter in the metal oxide hydrosol be 10~100nm.
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