CN107376027A - A kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation and preparation method thereof - Google Patents
A kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation and preparation method thereof Download PDFInfo
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- CN107376027A CN107376027A CN201710450039.7A CN201710450039A CN107376027A CN 107376027 A CN107376027 A CN 107376027A CN 201710450039 A CN201710450039 A CN 201710450039A CN 107376027 A CN107376027 A CN 107376027A
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- China
- Prior art keywords
- crystal whisker
- hydroxyapatite crystal
- electrostatic spinning
- macromolecule
- complex stephanoporate
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 89
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 89
- 239000013078 crystal Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920002521 macromolecule Polymers 0.000 title claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 47
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000002861 polymer material Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 229920001610 polycaprolactone Polymers 0.000 claims description 48
- 239000004632 polycaprolactone Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 19
- 239000004626 polylactic acid Substances 0.000 claims description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 238000009987 spinning Methods 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 210000000481 breast Anatomy 0.000 claims description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 230000000975 bioactive effect Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 238000002513 implantation Methods 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 239000000463 material Substances 0.000 description 22
- 210000001519 tissue Anatomy 0.000 description 17
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000002574 poison Substances 0.000 description 6
- 231100000614 poison Toxicity 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 5
- 230000012010 growth Effects 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 210000000845 cartilage Anatomy 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 4
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 3
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 3
- 210000002744 extracellular matrix Anatomy 0.000 description 3
- 229960004275 glycolic acid Drugs 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229940123373 Adenovirus E1A gene Drugs 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 108010087230 Sincalide Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010609 cell counting kit-8 assay Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 231100000263 cytotoxicity test Toxicity 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 210000002919 epithelial cell Anatomy 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000037353 metabolic pathway Effects 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
-
- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention discloses a kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation and preparation method thereof, using high polymer material and hydroxyapatite crystal whisker as raw material, using organic solvent as solvent, hydroxyapatite crystal whisker is added in proportion, and electrostatic spinning solution is made, the technique such as cleaned, sterilized, being dried after electrostatic spinning, preparing macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket；Present invention process is simple and convenient, easy to operation, stable yield, and the compound rest prepared not only has good biocompatibility, nontoxicity and the aperture characteristic such as suitably；Due to the addition of hydroxyapatite crystal whisker, improve the intensity of support, make it have good bioactivity, the bioactive ions such as calcium, phosphorus can be produced in degradation process, the elongation at break that compound rest is prepared by hydroxyapatite crystal whisker can reach 157.32%, hydroxy apatite powder is substantially better than, is had a good application prospect in terms of cartilaginous tissue implantation.
Description
Technical field
The present invention relates to a kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation and its
Preparation method, belong to bio-medical artificial bone graft material technology and use field.
Background technology
With cartilage tissue engineered fast development, important composition of the timbering material as repair of cartilage, its mechanical strength,
Biocompatibility, the design of bioactivity are particularly important, and support should imitate the environment of extracellular matrix on bionics
With structure, good 3-D solid structure is provided for the growth of cell, adhesion, propagation, differentiation.And with the development of science and technology, quiet
Electrospinning has a wide range of applications in bio-medical material Technology application field.Nanometer prepared by electrostatic spinning technique
Level high-biocompatibility material, its morphosis is similar to the morphosis of natural extracellular matrix, has 3-D solid structure,
The advantages that porosity is high, and specific surface area is big；So as to be advantageous to the adhesion of cell, propagation and differentiation and nutrient and metabolic waste
Exchange.
Polycaprolactone（PCL）It is a kind of acyclic straight polyester of fully biodegradable, fusing point is 60-63 DEG C, low temperature
It is plastic, it is easy to make, and there is good biocompatibility, its catabolite is not easy to cause inflammatory reaction；It is a kind of appearance
Easily crystallization, has the advantages that thermoplastic semi-crystalline's polymer of bioactivity, biocompatibility, biological degradability, permeability.Together
When, PCL has good pliability, processability and preferable heat endurance at room temperature, can be as a kind of good cartilage
Organizational project alternative materials.The polycaprolactone tissue engineering bracket and extra-cellular matrix structure phase prepared by electrostatic spinning technique
Seemingly, the adhesion and growth of cell are advantageous to, but its mechanical property is poor, it is difficult to the load-bearing material as organizational project.
PLA（PLA）It is at present in a kind of relatively more extensive biological absorbable macromolecule material of biomedical sector application
Material, be it is a kind of have excellent biocompatibility, chemical inertness, workability, nontoxic, high tensile, can completely biology drop
The thermoplastic polymer of solution property, is one of most promising biodegradable polymer, is widely used to organizational project
The fields such as support, bone material.Early in the 1950s, people to PLA synthesize and application furtherd investigate,
The seventies, the tight security of degradability and catabolite of the PLA in human body are confirmed, and it enjoys pass as one kind
The novel biodegradable of note applies high polymer material.
Poly(D,L-lactide-co-glycolide（PLGA）It is a kind of nontoxic, nothing being polymerized by PLA and hydroxyacetic acid
Harmful biomaterial, there is good biocompatibility and biodegradability and its degradation speed can control, catabolite
It is lactic acid and hydroxyacetic acid, while is also the accessory substance of people's metabolic pathway, institute is applied when medicine is with biomaterial not when it
Meeting toxic side effect, therefore, is widely used in bioengineering field.But Poly(D,L-lactide-co-glycolide fragility it is too big and
The shortcomings of toughness deficiency.At present, the research that electrostatic spinning prepares the membranaceous supports of PLGA has at home and abroad had very big progress,
PLGA nano-scale fibers prepared by electrostatic spinning are because having what higher specific surface area and porosity was advantageous to cell to be adhered to increasing
Grow, therefore PLGA turns into a kind of relatively good Medical rack material.
Hydroxyapatite（HAw）It is a kind of current most widely used bioactive materials, its chemical formula is Ca10(PO4)6
(OH)2, it is similar with the chemical composition and structure of human skeleton and tooth inorganic constituents, there is good bioactivity, biology
The good characteristics such as compatibility, degradability, nontoxicity, osteoconductive, three dimensional pore structures can be processed into, it is thin to be advantageous to skeletonization
Born of the same parents' sticks, grows, and induces the growth of bone, can be gradually degraded as calcium phosphorus in vivo, produces free Ca2+、PO4 3-, it is body
Bring a certain amount of active component into, promote the growth of bone.But its shortcomings that is that mechanical strength is inadequate, and matter is crisp, and toughness is inadequate.Whisker
The hydroxyapatite of shape, for the hydroxyapatite of powder shaped, hydroxyapatite crystal whisker has higher fracture tough
Property and bending resistance anti-pressure ability, it is not easy to break in preparation process.This can rely on bridge joint, the crackle of whisker inclined mainly due to material
Turn and extract effect to absorb energy, eliminate the stress that crack tip is concentrated, strengthen matrix strength；On the other hand, material by
During power, stress can be made by load transmission in whisker, so as to reduce the stress that the base material of surrounding is born, so as to
Reach the purpose for improving material mechanical performance.
The content of the invention
The present invention provides a kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation, institute
The complex stephanoporate bracket stated is made up of high polymer material and hydroxyapatite crystal whisker, high polymer material be polycaprolactone, PLA,
One kind in Poly(D,L-lactide-co-glycolide.
It is multiple another object of the present invention is to provide the macromolecule/hydroxyapatite crystal whisker for cartilaginous tissue reparation
The preparation method of porous support is closed, is comprised the following steps that：
（1）According to the ratio that mass volume ratio g/mL is 5-12 ︰ 100, high polymer material is added in organic solvent, normal temperature ring
With 2 hours of magnetic stirrer to being mixed thoroughly under border, mixing speed is 400 revs/min, obtains solution A；
（2）High polymer material quality 1%-20% ratio is accounted for according to hydroxyapatite crystal whisker, by hydroxyapatite crystal whisker and is disperseed
Agent is added to step together（1）In obtained solution A, 1 hour is stirred under normal temperature environment, ultrasonic vibration 10min, makes its mixing
Uniformly, solution B is obtained；
（3）Step is taken with 5mL syringe（2）Obtained solution B carries out electrostatic spinning, electrostatic spinning as electrostatic spinning solution
It is 18KV that syringe needle, which connects positive voltage, and power cathode connects the steel plate for posting 10 × 10cm tinfoil paper, to receive spinning fibre, adjusts electrostatic
The distance of the fltting speed of spinning solution, tinfoil paper and electrostatic spinning syringe needle, open high voltage power supply carry out electrostatic spinning obtain it is compound
Support C；
（4）By step（3）The support C of gained is rinsed 4-6 times in water, and 2h is then soaked in 75% medicinal alcohol and is carried out disinfection,
Normal temperature dries afterwards, finally gives macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket D.
Step（1）It is mixture that 1 ︰ 3 is mixed that the organic solvent, which is methanol with dichloromethane according to volume ratio,.
Step（2）The dispersant is one kind in polyethylene glycol, polypropylene, polystyrene, vinyl bis-stearamides,
The addition of dispersant is the 0.1%-5% of hydroxyapatite crystal whisker quality.
Step（3）The electrostatic spinning injection needle is No. 19 syringe needles.
Step（3）Fltting speed of the electrostatic spinning solution in syringe is 0.1 ~ 0.4mm/min；Tinfoil paper and electrostatic
The distance of spinning syringe needle is 15cm.
Step（3）Every 20min is needed to carry out 2min ultrasonic vibration to electrostatic spinning solution during the electrostatic spinning,
Continue electrostatic spinning afterwards.
Beneficial effects of the present invention：
（1）Complex stephanoporate bracket is made using method of electrostatic spinning in the present invention, and its preparation method is simple to operation, experimental raw source
Extensively, macromolecule while will not also be destroyed（Polycaprolactone, PLA, Poly(D,L-lactide-co-glycolide）, hydroxyapatite whisker
The advantages of palpus itself, had great application prospect in cartilage tissue engineered field.
（2）The obtained complex stephanoporate bracket of the present invention can effectively improve support due to the addition of hydroxyapatite crystal whisker
Intensity, while stenter to implant body in after, due to the presence of hydroxyapatite crystal whisker, be gradually degraded as calcium phosphorus in vivo, produce
Free Ca2+、PO4 3-, a certain amount of active component is brought into for body, so as to promote the growth of bone.
（3）Complex stephanoporate bracket prepared by the present invention has higher porosity, and sizeable aperture, is advantageous to
Cell sticks and bred.
（4）Complex stephanoporate bracket produced by the present invention, there is higher elongation at break, can reach 157.32%.
Brief description of the drawings
Fig. 1 is the XRD of the embodiment of the present invention 1 and 2 polycaprolactones of embodiment/hydroxyapatite crystal whisker complex stephanoporate bracket
Figure；
Fig. 2 is that the embodiment of the present invention 1 and the FTIR of 2 polycaprolactones of embodiment/hydroxyapatite crystal whisker complex stephanoporate bracket scheme；
Fig. 3 is that the embodiment of the present invention 1 and the SEM of 2 polycaprolactones of embodiment/hydroxyapatite crystal whisker complex stephanoporate bracket scheme,（a）
12%PCL/1%HAw amplifies 20000 times of SEM figures,（b）12%PCL/5%HAw amplifies 10000 times of SEM figures；
Fig. 4 is complex stephanoporate bracket obtained by Example 1 and Example 2 of the present invention and is not added with high molecular hydroxyapatite crystal whisker
Individually carry out the elongation at break comparison diagram for the product that electrostatic spinning obtains.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
The present embodiment is used for polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation, by polycaprolactone
Formed with hydroxyapatite crystal whisker, preparing chemical substance material used is：Polycaprolactone, dichloromethane, hydroxyapatite whisker
Palpus, deionized water, methanol, 75% medicinal alcohol, polyethylene glycol, it is as follows that it prepares dosage：
Dichloromethane 15mL
Methanol 5mL
Hydroxyapatite crystal whisker：Ca10(PO4)6(OH)2 0.024g
Polycaprolactone 2.4g
Deionized water 300mL
Polyethylene glycol 0.00024g
75% medicinal alcohol 20mL
The present embodiment is used for the preparation method of the polylactic acid/hydroxy apatite whisker complex stephanoporate bracket of cartilaginous tissue reparation, tool
Body comprises the following steps：
（1）2.4g PLA is added in the organic solvent that 15mL dichloromethane and 5mL methanol mix, normal temperature environment
It is lower that 2 hours are stirred to being mixed thoroughly with 400 revs/min of speed with magnetic stirring apparatus, obtain solution A；
（2）0.024g hydroxyapatite crystal whisker and 0.00024g polyethylene glycol are added to step together（1）Obtained solution A
In, stirred under normal temperature environment 1 hour, ultrasonic vibration 10min, make it well mixed, obtain solution B；
（3）Step is taken with 5mL syringe（2）Obtained solution B, injection needle are No. 19 syringe needles, and injection needle is connected to 18KV
Positive voltage, power cathode connects the steel plate for posting 10 × 10cm tinfoil paper, to receive spinning fibre；Adjust the fltting speed of syringe
For 0.2mm/min and the distance 15cm of tinfoil paper and syringe needle；Unlatching high voltage power supply progress 1h electrostatic spinning obtains compound
Support C, need during electrostatic spinning every 20min to carry out 2min ultrasonic vibration to electrostatic spinning solution, continue afterwards
Electrostatic spinning；
（4）By step（3）The support C of gained is rinsed 6 times in ultra-pure water, and 2h is then soaked in 75% medicinal alcohol and is disappeared
Poison, rear normal temperature dry, and finally give polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket D.
Embodiment 2
The present embodiment is used for the polylactic acid/hydroxy apatite whisker complex stephanoporate bracket of cartilaginous tissue reparation, by polycaprolactone and
Hydroxyapatite crystal whisker forms, and prepares chemical substance material used and is：Polycaprolactone, dichloromethane, hydroxyapatite crystal whisker,
Deionized water, methanol, 75% medicinal alcohol, polypropylene, it is as follows that it prepares dosage：
Dichloromethane 15mL
Methanol 5mL
Hydroxyapatite crystal whisker：Ca10(PO4)6(OH)2 0.12g
Polycaprolactone 2.4g
Deionized water 300mL
75% medicinal alcohol 20mL
Polypropylene 0.0024g
The present embodiment is used for the preparation method of the polylactic acid/hydroxy apatite whisker complex stephanoporate bracket of cartilaginous tissue reparation, tool
Body comprises the following steps：
（1）2.4g PLA is added in the organic solvent that 15mL dichloromethane and 5mL methanol mix, normal temperature environment
It is lower that 2 hours are stirred to being mixed thoroughly with 400 revs/min of speed with magnetic stirring apparatus, obtain solution A；
（2）0.12g hydroxyapatite crystal whisker and 0.0024g polypropylene are added to step together（1）In obtained solution A,
Stirred under normal temperature environment 1 hour, ultrasonic vibration 10min, make it well mixed, obtain solution B；
（3）Step is taken with 5mL syringe（2）Obtained solution B, injection needle are No. 19 syringe needles, and injection needle is connected to 18KV
Positive voltage, power cathode connects the steel plate for posting 10 × 10cm tinfoil paper, to receive spinning fibre；Adjust the fltting speed of syringe
0.4mm/min and tinfoil paper and syringe needle distance 15cm；The electrostatic spinning for opening high voltage power supply progress 1h obtains composite support
Frame C, need during electrostatic spinning every 20min to carry out 2min ultrasonic vibration to electrostatic spinning solution, continue afterwards quiet
Electrospun；
（4）By step（3）The support C of gained is rinsed 5 times in ultra-pure water, and 2h is then soaked in 75% medicinal alcohol and is disappeared
Poison, rear normal temperature dry, and finally give polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket D.
The XRD analysis of polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket prepared by embodiment 1 and embodiment 2 are such as
Shown in Fig. 1, as can be seen from the figure 2 θ are 21.4 ° and 23.8 ° two obvious diffraction maximums of appearance nearby, illustrate to gather oneself in support
The presence of lactone, while PCL is crystallization；Furthermore it is possible to the as can be seen clearly from figure 1 presence at HA peaks, such as：Each diffraction maximum（2
θ=25.9 °, 2 θ=31.7 °, 2 θ=45.6 °）Position and standard card（JCPDS）It is consistent, but due to the less characteristic peak of HAw contents
It is less obvious；But from FTIR points of the polycaprolactone of embodiment 1 and embodiment 2/hydroxyapatite crystal whisker complex stephanoporate bracket
As can be seen that the infrared signature peak in Fig. 2 fits like a glove with PCL and HAw in analysis Fig. 2, such as 2942 cm-1It is nearby CH2It is not right
Claim flexible, 2865cm-1CH2It is symmetrical flexible, 1738 cm-1Neighbouring carbonyl absorption peak, 1637 cm-1Neighbouring absworption peak is C
The characteristic peak of=O keys, it is PCL characteristic peaks；Such as 3439cm-1Neighbouring peak is-OH, 1170 cm-1With 585 cm-1It is nearby P-O
cm-1The absworption peak of key, it is HAw characteristic peak, it was demonstrated that HAw presence.
SEM such as Fig. 3 institutes of polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket prepared by embodiment 1 and embodiment 2
Show, as seen from the figure, support prepared by embodiment 1 and embodiment 2 is respectively provided with tridimensional network, and the surface and its inside of support have
Higher porosity, and good pore communication.
The elongation at break of polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket prepared by embodiment 1 and embodiment 2
As shown in figure 4, as seen from the figure, the elongation at break of pure PCL supports is 112.78%, and 1% HAw/PCL fracture is stretched
Long rate is maximum, and up to 150.49%, 5%HAw elongation at break is also up to 133.76%, therefore the addition of hydroxyapatite crystal whisker
Improve the elongation at break of HAw/PCL complex stephanoporate brackets.
According to standard GB/T/T14233.3-2005, using from 293T cells（Transfect people's kidney of Adenovirus E1A gene
Epithelial cell）, polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket for being prepared to embodiment 1 and embodiment 2 of CCK-8 methods
Material carries out cytotoxicity test, and experimental result is as shown in table 1, with reference to standard GB/T/T14233.3-2005 relevant regulations,
Cytotoxicity result shows that for support concentration in 0.5-2mg/mL, relative growth rate is between 95-120, cytotoxicity 0
Level or 1 grade, thus illustrate polycaprolactone/hydroxyapatite crystal whisker composite porous support material prepared by embodiment 1 and embodiment 2
No cytotoxicity.
The relative growth rate of the embodiment 1 of table 1 and 2 polycaprolactones of embodiment/hydroxyapatite crystal whisker complex stephanoporate bracket
。
Embodiment 3
The present embodiment is used for the polylactic acid/hydroxy apatite whisker complex stephanoporate bracket of cartilaginous tissue reparation, by PLA and hydroxyl
Base apatite whiskers form, and prepare chemical substance material used and are：PLA, dichloromethane, hydroxyapatite crystal whisker, go from
Sub- water, methanol, 75% medicinal alcohol, polystyrene, it is as follows that it prepares dosage：
Dichloromethane 15mL
Methanol 5mL
Hydroxyapatite crystal whisker：Ca10(PO4)6(OH)2 0.01g
PLA 1g
Deionized water 300mL
75% medicinal alcohol 20mL
Polystyrene 0.0003g
The present embodiment is used for the preparation method of the polylactic acid/hydroxy apatite whisker complex stephanoporate bracket of cartilaginous tissue reparation, tool
Body comprises the following steps：
（1）1g PLA is added in the organic solvent that 15mL dichloromethane and 5mL methanol mix, under normal temperature environment
2 hours are stirred to being mixed thoroughly with 400 revs/min of speed with magnetic stirring apparatus, obtain solution A；
（2）0.01g hydroxyapatite crystal whisker and 0.0003g polystyrene are added to step together（1）Obtained solution A
In, stirred under normal temperature environment 1 hour, ultrasonic vibration 10min, make it well mixed, obtain solution B；
（3）Step is taken with 5mL syringe（2）Obtained solution B, injection needle are No. 19 syringe needles, and injection needle is connected to 18KV
Positive voltage, power cathode connects the steel plate for posting 10 × 10cm tinfoil paper, to receive spinning fibre；Adjust the fltting speed of syringe
0.1mm/min and tinfoil paper and syringe needle distance 15cm；The electrostatic spinning for opening high voltage power supply progress 1h obtains composite support
Frame C, need during electrostatic spinning every 20min to carry out 2min ultrasonic vibration to electrostatic spinning solution, continue afterwards quiet
Electrospun；
（4）By step（3）The support C of gained is rinsed 5 times in ultra-pure water, and 2h is then soaked in 75% medicinal alcohol and is disappeared
Poison, rear normal temperature dry, and finally give polylactic acid/hydroxy apatite whisker complex stephanoporate bracket D.
The tear type variability of polylactic acid/hydroxy apatite whisker complex stephanoporate bracket manufactured in the present embodiment is up to
157.32%。
Embodiment 4
The present embodiment is used for polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation, by polycaprolactone
Formed with hydroxyapatite crystal whisker, preparing chemical substance material used is：Polycaprolactone, dichloromethane, hydroxyapatite whisker
Palpus, deionized water, methanol, 75% medicinal alcohol, polyethylene glycol, it is as follows that it prepares dosage：
Dichloromethane 15mL
Methanol 5mL
Hydroxyapatite crystal whisker：Ca10(PO4)6(OH)2 0.24g
Polycaprolactone 2.4g
Deionized water 300mL
75% medicinal alcohol 20mL
Polyethylene glycol 0.0096g
The present embodiment is used for the preparation method of polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation,
Specifically include following steps：
（1）2.4g polycaprolactone is added in the organic solvent that 15mL dichloromethane and 5mL methanol mix, normal temperature ring
2 hours are stirred to being mixed thoroughly with 400 revs/min of speed with magnetic stirring apparatus under border, obtain solution A；
（2）0.24g hydroxyapatite crystal whisker and 0.0096g polyethylene glycol are added to step together（1）Obtained solution A
In, stirred under normal temperature environment 1 hour, ultrasonic vibration 10min, make it well mixed, obtain solution B；
（3）Step is taken with 5mL syringe（2）Obtained solution B, injection needle are No. 19 syringe needles, and injection needle is connected to 18KV
Positive voltage, power cathode connects the steel plate for posting 10 × 10cm tinfoil paper, to receive spinning fibre；Adjust the fltting speed of syringe
0.1mm/min and tinfoil paper and syringe needle distance 15cm；The electrostatic spinning for opening high voltage power supply progress 1h obtains composite support
Frame C, need during electrostatic spinning every 20min to carry out 2min ultrasonic vibration to electrostatic spinning solution, continue afterwards quiet
Electrospun；
（4）By step（3）The support C of gained is rinsed 4 times in ultra-pure water, and 2h is then soaked in 75% medicinal alcohol and is disappeared
Poison, rear normal temperature dry, and finally give polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket D.
Embodiment 5
The present embodiment is used for the compound porous branch of Poly(D,L-lactide-co-glycolide/hydroxyapatite crystal whisker of cartilaginous tissue reparation
Frame, it is made up of Poly(D,L-lactide-co-glycolide and hydroxyapatite crystal whisker, preparing chemical substance material used is：Poly- breast
Acid-co-glycolic acid, dichloromethane, hydroxyapatite crystal whisker, deionized water, methanol, 75% medicinal alcohol, polystyrene,
It is as follows that it prepares dosage：
Dichloromethane 15mL
Methanol 5mL
Hydroxyapatite crystal whisker：Ca10(PO4)6(OH)2 0.2g
Poly(D,L-lactide-co-glycolide 2g
Deionized water 300mL
75% medicinal alcohol 20mL
Polystyrene 0.002g
The present embodiment is used for the compound porous branch of Poly(D,L-lactide-co-glycolide/hydroxyapatite crystal whisker of cartilaginous tissue reparation
The preparation method of frame, specifically includes following steps：
（1）By 2g Poly(D,L-lactide-co-glycolide be added to 15mL dichloromethane and 5mL methanol mix it is organic molten
In agent, 2 hours are stirred to being mixed thoroughly with 400 revs/min of speed with magnetic stirring apparatus under normal temperature environment, obtained molten
Liquid A；
（2）0.2g hydroxyapatite crystal whisker and 0.002g polystyrene are added to step together（1）In obtained solution A,
Stirred under normal temperature environment 1 hour, ultrasonic vibration 10min, make it well mixed, obtain solution B；
（3）Step is taken with 5mL syringe（2）Obtained solution B, injection needle are No. 19 syringe needles, and injection needle is connected to 18KV
Positive voltage, power cathode connects the steel plate for posting 10 × 10cm tinfoil paper, to receive spinning fibre；Adjust the fltting speed of syringe
0.3mm/min and tinfoil paper and syringe needle distance 15cm；The electrostatic spinning for opening high voltage power supply progress 1h obtains composite support
Frame C, need during electrostatic spinning every 20min to carry out 2min ultrasonic vibration to electrostatic spinning solution, continue afterwards quiet
Electrospun；
（4）By step（3）The support C of gained is rinsed 4 times in ultra-pure water, and 2h is then soaked in 75% medicinal alcohol and is disappeared
Poison, rear normal temperature dry, and finally give Poly(D,L-lactide-co-glycolide/hydroxyapatite crystal whisker complex stephanoporate bracket D.
Embodiment 6
The present embodiment is used for polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation, by polycaprolactone
Formed with hydroxyapatite crystal whisker, preparing chemical substance material used is：Polycaprolactone, dichloromethane, hydroxyapatite whisker
Palpus, deionized water, methanol, 75% medicinal alcohol, vinyl bis-stearamides, it is as follows that it prepares dosage：
Dichloromethane 15mL
Methanol 5mL
Hydroxyapatite crystal whisker：Ca10(PO4)6(OH)2 0.48g
Polycaprolactone 2.4g
Deionized water 300mL
75% medicinal alcohol 20mL
Vinyl bis-stearamides 0.024g
The present embodiment is used for the preparation method of polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation,
Specifically include following steps：
（1）2.4g polycaprolactone is added in the organic solvent that 15mL dichloromethane and 5mL methanol mix, normal temperature ring
2 hours are stirred to being mixed thoroughly with 400 revs/min of speed with magnetic stirring apparatus under border, obtain solution A；
（2）0.48g hydroxyapatite crystal whisker and 0.024g vinyl bis-stearamides are added to step together（1）It is obtained
In solution A, stirred under normal temperature environment 1 hour, ultrasonic vibration 10min, make it well mixed, obtain solution B；
（3）Step is taken with 5mL syringe（2）Obtained solution B, injection needle are No. 19 syringe needles, and injection needle is connected to 18KV
Positive voltage, power cathode connects the steel plate for posting 10 × 10cm tinfoil paper, to receive spinning fibre；Adjust the fltting speed of syringe
0.4mm/min and tinfoil paper and syringe needle distance 15cm；The electrostatic spinning for opening high voltage power supply progress 1h obtains composite support
Frame C, need during electrostatic spinning every 20min to carry out 2min ultrasonic vibration to electrostatic spinning solution, continue afterwards quiet
Electrospun；
（6）By step（5）The support C of gained is rinsed 6 times in ultra-pure water, and 2h is then soaked in 75% medicinal alcohol and is disappeared
Poison, rear normal temperature dry, and finally give polycaprolactone/hydroxyapatite crystal whisker complex stephanoporate bracket D.
Claims (7)
1. a kind of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket for cartilaginous tissue reparation, it is characterised in that described
Complex stephanoporate bracket is made up of high polymer material and hydroxyapatite crystal whisker, and high polymer material is PLA, polycaprolactone, poly- breast
One kind in acid-co-glycolic acid.
2. it is used for the preparation of macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation described in claim 1
Method, it is characterised in that comprise the following steps that：
（1）According to the ratio that mass volume ratio g/mL is 5-12 ︰ 100, high polymer material is added in organic solvent, under normal temperature
Magnetic agitation mixes for 2 hours to complete, and mixing speed is 400 revs/min, obtains solution A；
（2）High polymer material quality 1%-20% ratio is accounted for according to hydroxyapatite crystal whisker, by hydroxyapatite crystal whisker and is disperseed
Agent is added to step together（1）In obtained solution A, stirred 1 hour, ultrasonic vibration 10min under normal temperature, mix, obtain solution
B；
（3）Take step（2）Obtained solution B carries out electrostatic spinning as electrostatic spinning solution, and electrostatic spinning syringe needle connects positive voltage
For 18KV, power cathode, which connects, posts the steel plate of tinfoil paper to receive spinning fibre, adjusts fltting speed, the tinfoil paper of electrostatic spinning solution
With the distance of electrostatic spinning syringe needle, open high voltage power supply progress electrostatic spinning and obtain compound rest C；
（4）By step（3）The support C of gained is rinsed 4-6 times in water, then soaks 2h in 75% medicinal alcohol, normal temperature dries in the air
It is dry, finally give macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket D.
3. it is used for macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation according to claim 2
Preparation method, it is characterised in that step（1）The organic solvent is that methanol with dichloromethane is that 1 ︰ 3 is mixed according to volume ratio
Mixture.
4. it is used for macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation according to claim 2
Preparation method, it is characterised in that step（2）The dispersant is polyethylene glycol, polypropylene, polystyrene, the double tristearin of vinyl
One kind in acid amides, the addition of dispersant are the 1%-5% of hydroxyapatite crystal whisker quality.
5. it is used for macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation according to claim 2
Preparation method, it is characterised in that step（3）The electrostatic spinning syringe needle is No. 19 syringe needles.
6. it is used for macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation according to claim 2
Preparation method, it is characterised in that step（3）The fltting speed of the electrostatic spinning solution is 0.1 ~ 0.4mm/min；Tinfoil paper with it is quiet
The distance of Electrospun syringe needle is 15cm.
7. it is used for macromolecule/hydroxyapatite crystal whisker complex stephanoporate bracket of cartilaginous tissue reparation according to claim 2
Preparation method, it is characterised in that step（3）2min is carried out to electrostatic spinning solution every 20min during the electrostatic spinning
Ultrasonic vibration.
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