CN109938896A - A kind of bone tissue engineering scaffold - Google Patents
A kind of bone tissue engineering scaffold Download PDFInfo
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- CN109938896A CN109938896A CN201910316934.9A CN201910316934A CN109938896A CN 109938896 A CN109938896 A CN 109938896A CN 201910316934 A CN201910316934 A CN 201910316934A CN 109938896 A CN109938896 A CN 109938896A
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- zinc
- bone tissue
- tissue engineering
- base metal
- engineering scaffold
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 104
- 239000010953 base metal Substances 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 31
- 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 claims abstract description 30
- 239000003814 drug Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 6
- 230000007547 defect Effects 0.000 abstract description 48
- 238000006731 degradation reaction Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 15
- 210000002901 mesenchymal stem cell Anatomy 0.000 abstract description 6
- 230000001599 osteoclastic effect Effects 0.000 abstract description 6
- 230000004069 differentiation Effects 0.000 abstract description 4
- 230000004072 osteoblast differentiation Effects 0.000 abstract description 4
- 230000017423 tissue regeneration Effects 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 22
- 239000000956 alloy Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- 238000013461 design Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- -1 alginic acid Salt Chemical class 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
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- 239000000945 filler Substances 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
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- 229910000831 Steel Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 210000000130 stem cell Anatomy 0.000 description 4
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- 239000012620 biological material Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
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- 239000010931 gold Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
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- 239000011787 zinc oxide Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
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- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000012981 Hank's balanced salt solution Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
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- 230000014509 gene expression Effects 0.000 description 2
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- 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 description 2
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- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 241001061264 Astragalus Species 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
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- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- BKUKLPQANLPGEV-UHFFFAOYSA-N [Li].[Mg].[Zn] Chemical compound [Li].[Mg].[Zn] BKUKLPQANLPGEV-UHFFFAOYSA-N 0.000 description 1
- WCULPSIYAQDUJW-UHFFFAOYSA-N [Li].[Sr] Chemical compound [Li].[Sr] WCULPSIYAQDUJW-UHFFFAOYSA-N 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- VVZJQVZLLAFNFB-UHFFFAOYSA-N [Sr].[Zn].[Li] Chemical compound [Sr].[Zn].[Li] VVZJQVZLLAFNFB-UHFFFAOYSA-N 0.000 description 1
- ISZIYIIDGMIKEV-UHFFFAOYSA-N [Zn].[Li].[Ca] Chemical compound [Zn].[Li].[Ca] ISZIYIIDGMIKEV-UHFFFAOYSA-N 0.000 description 1
- VCQAIUIHXQEIHD-UHFFFAOYSA-N [Zn].[Sr] Chemical compound [Zn].[Sr] VCQAIUIHXQEIHD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229960001126 alginic acid Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000006533 astragalus Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 210000004271 bone marrow stromal cell Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- USOPFYZPGZGBEB-UHFFFAOYSA-N calcium lithium Chemical compound [Li].[Ca] USOPFYZPGZGBEB-UHFFFAOYSA-N 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
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- 229960004275 glycolic acid Drugs 0.000 description 1
- 210000002758 humerus Anatomy 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
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- 230000002980 postoperative effect Effects 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
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- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
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- Prostheses (AREA)
Abstract
The invention discloses a kind of bone tissue engineering scaffold, including hollow latticed bracket and be filled in porous zinc-base metal ball therein, porous zinc-base metal ball can have for surface hole slot medicine ball may be by coil of wire at fluffy ball；Also settable interior support posts in bracket, to provide more mechanical property；Fillable β-TCP particle, to be enriched with mesenchymal stem cell.Present invention combination titanium or the standby net grid support and its interior support posts of zinc-base made of metal, a kind of bone tissue engineering scaffold that mechanical property is splendid is prepared, porous zinc-base metal ball therein can promote Osteoblast Differentiation and inhibit osteoclastic differentiation, while support is provided, promote the new life of bone tissue and grows into, then it is gradually substituted by bone tissue in degradation process, and β-TCP particle enriching mesenchymal stem cells and can promote Bone Defect Repari.Present invention can apply to the large segmental bone defects of weight bearing area, promote bone tissue regeneration on the basis of playing mechanical support, reach the curative effect for repairing large segmental bone defect.
Description
Technical field
The invention belongs to biomaterial for medical purpose field, being related to a kind of bone tissue engineering scaffold more particularly to one kind be can promote
The degradable bone tissue engineering scaffold of Bone Defect Repari.
Background technique
It is most using stainless steel, titanium alloy, cobalt-base alloys, niti-shaped memorial alloy as the medical inert metal material of representative
The medical material in human body is early applied, since it has high intensity, endurance, easy processing molding, interior state stabilization, biofacies
The features such as capacitive is good has become quantity maximum, most popular one kind medical bio material at present.However pass through several generation
The use of discipline, people and the conventional attribute for being not content with medical inert metal material.Traditional medical inert material there is also
Some inherent shortcomings, such as the stress-shielding effect caused by medical inert metal material high elastic modulus in orthopaedics application,
And angiocarpy bracket is at a specified future date and freeze such as stent thrombosis, bracket are broken, and furthermore often has in inert metal material
Evil metallic element such as aluminium, cobalt, chromium etc., retains in the risk that also will increase allergic reaction and inflammatory reaction in vivo for a long time.
With the change for the treatment of concept, people more wish that medical embedded material temporary execution repair function and can be deposited
It stays in reparation process that is internal, while matching tissue, being gradually degraded into after completing its mechanics and biological function can be by people
Body absorbs or the catabolite of excretion, final degradable absorption.Therefore, the appearance of degradable medical material, which has just started, grinds
The upsurge studied carefully.
In bone tissue engineer field, common osseous tissue renovating material includes artificial synthesized inorganic material and macromolecule material
Material and natural macromolecular material.Common artificial synthesized inorganic material includes hydroxyapatite (HAP), bata-tricalcium phosphate (β-
TCP), bioactivity glass (BG), calcium carbonate bone cement (CPC) etc.；And some high molecular materials, such as polylactic acid (PLA) are gathered
Hydroxyacetic acid (PGA) and poly lactide-glycolide acid (PLGA) etc.；Natural macromolecular material mainly has collagen, alginic acid
Salt, chitosan (CTS) etc..These materials have been widely used in clinic, and suffer from good biocompatibility and biology work
Property, but due to the defect of its intrinsic mechanical strength, tend not to meet the needs of large segmental bone defect reparation.
Bata-tricalcium phosphate (β-TCP) has good biocompatibility and certain osteoinductive, can be enriched between marrow
Mesenchymal stem cells simultaneously promote osteogenetic process, and repairing bone defect has been used as bone renovating material to be widely used in clinic.And simple
β-TCP mechanical property is intersected, and compression strength is only 2MPa or so, so being difficult to use in the large segmental bone defect for repairing weight bearing area.
The Chinese patent document of Publication No. CN102764888A provides titanium alloy people's astragalus support of compound porous β-TCP a kind of
Stick is the paste for injecting β-TCP and hydrogen peroxide, polyvinyl alcohol in the cellular support stick made of toward titanium alloy and being modulated into
Slurry obtains after high temperature sintering.But since the intensity of β-TCP is lower, the mechanics of support stick is still reduced on the whole
Performance is unable to satisfy large segmental bone defect to the intensity requirement of tissue scaffold design.
Degradable metal material is widely studied due to its intrinsic mechanical strength superiority.Degradable metal material is main
Including degradable magnesium Base Metal, degradable zinc-base metal and degradable ferrous metals.Wherein, magnesium-base metal and ferrous metals have been
It is widely studied.However two class materials are there is clearly disadvantageous place, as magnesium-base metal in human body environment degradation speed
Too fast and degradation inhomogeneities, often results in mechanical property and declines rapidly and be not enough to provide enough fixations and support function, this
Outer magnesium-base metal degradation can generate bulk gas and local PH is caused to increase；And ferrous metals are then since the protection of catabolite is made
With keeping its degradation rate very slow, so as to cause the problem similar with non-degradable metal.Therefore researchers have attempted greatly
Amount method attempts to improve the degradation rate problem of magnesium-base metal and ferrous metals, not yet obtains perfect result at present.
Compared with magnesium-base metal and ferrous metals, zinc-base metal mainly has following advantage: 1. due to the normal electrode electricity of Zn
Position (- 0.763V) is between Mg (- 2.372V) and Fe (- 0.447V), and therefore, zinc and kirsite have degradation speed preferably
Rate.It is protein synthesis 2. Zn-ef ficiency category micro elements needed by human, the Zn-ef ficiency of human body 90% are stored in muscle and bone
One of with element most important in energy metabolism, the growth of participant's somatocyte development, gene expression, immune system and nerve
A large amount of physiological reaction processes such as system, this provides the foundation that zinc-base metal has good biocompatibility.3. zinc-base metal drops
It is relatively stable compared with magnesium to solve product；After Zn-ef ficiency degradation, dead end product may be zinc oxide and zinc hydroxide, and the latter can be
It is further formed soluble villaumite under homadamon border, therefore does not generate strong basicity microenvironment and gas release theoretically；4. zinc-base
Intermetallic composite coating performance is good, and zinc-base melting point metal is lower, and chemical activity and machining property are moderate, is easy to cast and process.
Zinc is stored in muscle and bone as a kind of human essential elements, the Zn-ef ficiency of human body 90%, is that protein closes
At one of with element most important in energy metabolism, the growth of participant's somatocyte development, gene expression, immune system and mind
Through a large amount of physiological reaction processes such as system, there is good promotion osteogenic action, and mesenchymal stem cell can be enriched with.Zinc-base
Metal can gradually degrade in human body and release zinc ion, therefore mechanical strength is excellent, and the excellent zinc-base of bone formation performance can be with
As ideal bone renovating material.The Chinese patent document of Publication No. CN103845762A disclose a kind of laser prepare it is porous
Bone bracket simultaneously adds zinc oxide and proposes high performance method, but it only adds a small amount of ZnO powder in the raw material of β-TCP to make
Make porous support, it is limited to the raising effect of bracket mechanical property；And the Chinese patent text of Publication No. CN104258458A
Part discloses a kind of biodegradable porous openings zinc and zinc alloy biomaterials, although it is mentioned that the material can be used as a new generation can
Degradation bone tissue engineering scaffold, but the mechanical property of the Zinc material of aperture will receive very big influence；Both the above contains zinc-base
The tissue engineering bracket of metal is still difficult to the mechanical property requirements for meeting large segmental bone defect to tissue scaffold design.
In addition, the Biofunctional of zinc-base metal also merits attention, Zn, which has been reported, can promote Osteoblast Differentiation and inhibit
Osteoclastic differentiation can advanced optimize it and facilitate after assigning its different alloying element (such as Mg, Li, Cu, Ag, Ca, Sr, Mn)
Bone presses down osteoclastic biological function, can prepare bone impairment renovation material based on this.
Summary of the invention
In view of the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of both strong with high support
Degree, and can promote the degradable tissue scaffold design of newborn bon e formation.
To achieve the above object, the present invention provides a kind of bone tissue engineering scaffold, including hollow latticed bracket and
It is filled in porous zinc-base metal ball therein.
Further, the hollow latticed bracket can be made of the pure titanium or titanium alloy of good mechanical performance；But according to need
It wants, in other embodiments of the present invention, the bracket can also be by degradable zinc-base metal material or other degradable gold
Belong to material to be made, it can finally be fully absorbed by human body in this way.
It include but is not limited to class cylinder, class to be suitable for the global shape of different application scenarios, the bracket
Spherical shape and many irregular shapes etc..In the preferred embodiment of the present invention, the global shape of the bracket is circle
Cylindricality, diameter are preferably 1-5cm, in fact it is highly preferred that are 2-10cm.
Further, the shape of the grid can be rectangular, diamond shape or circle, ellipse or it is other all can be real
The shape applied, the aperture of grid are preferably 0.5-2mm, and size is not fallen out with the filler in bracket to be advisable.
Preferably, the hollow latticed bracket has interior support posts.The quantity of the interior support posts is preferably 3-5
Root, the material of support column and the material of contoured cradle can be the same or different, but should be the metal of good mechanical performance, such as
Titanium, titanium alloy, zinc or kirsite.In cylindrical stent, the top and bottom of interior support posts connecting bracket；It is propped up in spherical shape
In frame, interior support posts at least one can connect any of spherical surface by the centre of sphere, other support columns parallel or not parallelly
Two o'clock.In the preferred embodiment of the present invention, the interior support posts are cylinder, and diameter 0.3-0.8mm is more excellent
It is selected as 0.4-0.6mm.
Further, the porous zinc-base metal ball can may be porous fluffy ball for porous medicine ball.
In a kind of better embodiment of the invention, the porous zinc-base metal ball is on surface with several hole slots
Medicine ball；Preferably, the present invention burns tap hole trough on zinc-base metal medicine ball using laser burn method, and the purpose of hole slot is arranged
It is to promote growing into for osteocyte, also increases the surface area of metal ball, and can promote the release of zinc ion, accelerates its degradation speed
Degree.
Further, the partial size of the medicine ball on the surface with several hole slots is preferably 0.5-5mm, and the hole slot is circle
Shape, diameter are preferably 0.1-0.3mm, and porosity is preferably 60%-90%.
In another better embodiment of the invention, the porous zinc-base metal ball is by degradable zinc-base coil of wire
At porous fluffy ball, the diameter of the wire is 0.1-0.3mm；Preferably, preparation method are as follows: first draw zinc-base metal
At the filament of diameter 0.1-0.3mm, it is then curled into different size of silk thread ball.The purpose for being rolled into silk thread ball is also to promote
Osteocyte is grown into, and is increased metal surface area, is promoted the release of zinc ion, accelerate its degradation speed.After completing, by silk thread
Ball is placed in the hollow latticed bracket.
Further, the partial size of the porous fluffy ball is preferably 2-8mm.
The size of heretofore described porous zinc-base metal ball is without consistent, it is however preferred to have following accounting:
Big partial size accounts for 30%-50%；
Middle partial size accounts for 20%-40%；
Small particle accounts for 20%-40%.
For example, big partial size is greater than 3.5mm, and middle partial size is when the porous zinc-base metal ball is porous medicine ball
1.0-3.5mm small particle is less than 1.0mm；Or big partial size is greater than 4mm, middle partial size is 2-4mm, small particle be less than
2mm.When the porous zinc-base metal ball is porous fluffy ball, big partial size is greater than 5mm, and middle partial size is 3-5mm, and small particle is
Less than 3mm.
The porous zinc-base metal ball mixed according to the above ratio can preferably play its biological function, double regulation control skeletonization and broken
Bone behavior promotes the reparation of bone defect.
Preferably, β-TCP particle is also filled in the hollow latticed bracket.β-TCP the particle can be commercially available
Product can also be prepared voluntarily, and the partial size of β-TCP particle is preferably 0.5-5mm, and porosity is preferably 60%-90%, and aperture is
500 μm hereinafter, preferably 200 μm or so.
Preferably, the particle diameter distribution of the β-TCP particle is also in compliance with following ratio:
Big partial size accounts for 30%-50%；
Middle partial size accounts for 20%-40%；
Small particle accounts for 20%-40%；
Wherein, big partial size is greater than 3.5mm, and middle partial size is 1.0-3.5mm, and small particle is less than 1.0mm.
In the preferred embodiment of the present invention, the size of the β-TCP particle and the porous zinc-base metal ball
And its distribution proportion follows above-mentioned distribution principle jointly.
In the preferred embodiment of the present invention, the β-TCP particle and the porous zinc-base metal ball quantity
Ratio is 6:4-4:6.The porous beta-TCP particle mixed according to the above ratio and porous zinc-base metal ball are maintaining to be enriched with marrow
On the basis of mescenchymal stem cell promotes Bone Defect Repari, the mechanical property of the bone repairing support can be significantly improved.
Preferably, zinc-base metal of the present invention refers to the zinc conjunction that pure zinc or the mass fraction containing zinc reach 90% or more
Gold.
Further, single or Determination of multiple metal elements can be added in above-mentioned kirsite, addible element includes but is not limited to:
Magnesium Mg, copper Cu, silver Ag, lithium Li, manganese Mn, strontium Sr, calcium Ca, yttrium Y, gadolinium G, dysprosium Dy；Wherein the quality of every kind of element in the alloy accounts for
Than being no more than 5%, and the total mass fraction of each element is no more than 10%；Further, wherein silver, lithium, manganese, strontium, yttrium, gadolinium, dysprosium
The respective mass fraction of element is no more than 1%, more preferably less than 0.6%.
We add alloying element in pure zinc, prepare different zinc-containing alloys, and the degradable zinc-base for establishing multiplicity closes
Golden system further enhances the rush osteogenic action and medulla mesenchyma of zinc-base metal while improving pure zinc mechanical property
The enrichment function of stem cell, such as magnesium Mg, copper Cu, strontium Sr element are added in pure zinc, prepare the zinc-magnesium, zinc-copper, zinc of binary
Strontium, manganese alloy system, show excellent bone formation performance.
In better embodiment of the invention, the kirsite is bianry alloy, for example, zinc strontium bianry alloy, wherein
Mass fraction containing strontium is 0.5%-2%, further preferably 1%-1.5%；Alternatively, zinc-manganese bianry alloy, the wherein matter of manganese
Amount score is 0.1-1.5%, further preferably 0.3-1.2%；Alternatively, zinc-copper bianry alloy, the wherein mass fraction of cupric
For 1-3%, further preferably 1.5-2.5%.
In another better embodiment of the invention, the kirsite is ternary alloy three-partalloy containing lithium, such as zinc lithium magnesium, zinc lithium
Calcium or zinc lithium strontium ternary alloy three-partalloy, wherein the sum of mass fraction of lithium magnesium, lithium calcium or lithium strontium is not more than 2%.
Bone tissue engineering scaffold of the present invention can be used for repairing large segmental bone defect.
The present invention has following advantageous effects:
1. it can promote Osteoblast Differentiation using porous zinc-base metal ball as core and inhibit osteoclastic differentiation, porous zinc-base metal ball
While support is provided, osteogenic activity can be also activated, promote the new life of bone tissue and is grown into, then in degradation process gradually
Substituted by bone tissue, play bone balance effect, adjust skeletonization and osteoclastic differentiation process, promote local new bone formation, gradually by
Bone tissue is substituted, and is completed its biological function, is then repaired large segmental bone defect；
2. providing mechanical support using mesh structural porous bracket prepared by titanium or titanium alloy, the interior of bracket is further additionally provided
Portion's support column significantly improves the mechanical property of the bone repairing support, even if using zinc-base metal as bracket can also early stage
Good mechanical support is provided, can be applied to the large segmental bone defect of weight bearing area；
3. porous beta-TCP particle and porous zinc-base metal ball are mixed in a certain ratio, on the basis of playing mechanical support
Promote bone tissue regeneration, mesenchymal stem cell can be enriched with and promote Bone Defect Repari.
To sum up, the present invention provides a kind of mechanical property is splendid, enriching mesenchymal stem cells and the bone of Bone Defect Repari can be promoted
Tissue engineering bracket, and then reach the curative effect for repairing large segmental bone defect.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific structure and generation, with
It is fully understood from the purpose of the present invention, feature and effect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram (non-filler) of a preferred embodiment of bone tissue engineering scaffold of the present invention；
Fig. 2 is the structural schematic diagram (non-filler) of the another preferred embodiment of bone tissue engineering scaffold of the present invention；
Fig. 3 is the structural schematic diagram (non-filler) of the another embodiment of bone tissue engineering scaffold of the present invention；
Fig. 4 is the structural schematic diagram of porous zinc-base metal medicine ball in bone tissue engineering scaffold of the present invention；
Fig. 5 is the structural schematic diagram of the porous fluffy ball of zinc-base metal in bone tissue engineering scaffold of the present invention；
Fig. 6 is the β-TCP particle schematic diagram of bone tissue engineering scaffold of the present invention, and a is large-size particles, and b is middle partial size
Grain, c is small size particle.
Specific embodiment
Embodiment 1
A kind of preferred construction of bone tissue engineering scaffold of the invention as shown in Figure 1, its latticed bracket 11 is cylinder,
Diameter is 1-5cm, is highly 2-10cm, and it is equally cylindrical support column 12, diameter 0.3- that internal stent, which has four,
0.8mm, more preferably 0.4-0.6mm, the position of support column can symmetry arrangement or any arrangement, 13 shape of grid of cylindrical stent
Shape be it is rectangular, the diagonal line length of grid is 0.5-2mm, size with porous zinc-base metal ball and β-TCP particle do not fall out for
Preferably.According to actual needs, the interior support posts 12 in the present embodiment can also not have, further, the hollow latticed bracket
11 and its interior support posts 12 can be made of the pure titanium or titanium alloy of good mechanical performance, but as needed can also be by degradable
Zinc-base metal material or other degradable metal materials are made.
Grid can also be diamond shape or circle other than rectangular, and Fig. 2 shows another preferred embodiments of the invention
Structure, bracket 21 also for cylinder, but the shape of grid 23 thereon be circle, the circular diameter be 0.5-2mm.
Fig. 3 shows the embodiment that bone tissue engineering scaffold shape of the present invention is spherical shape 31, and three supports are arranged inside
Column 32 has the center by sphere, and other two are arranged in both sides not parallelly, and the shape of grid 33 is also rectangular.
Porous zinc-base metal ball is filled in the bracket of embodiment, if a kind of form of the metal ball is to have on surface
The medicine ball (as shown in Figure 4) of dry hole slot, preparation method are the solid metal balls 4 that zinc-base metal is first made to different-diameter,
Then tap hole trough 41 is burnt in zinc-base metal ball 4 using laser burn method, the diameter of hole slot is preferably 0.1-0.3mm, hole
Rate is preferably 60%-90%, and the partial size of porous zinc-base solid metal ball is preferably 0.5-5mm；Another form of the metal ball
For by zinc-base coil of wire at porous fluffy ball (as shown in Figure 5), the diameter of wire is 0.1-0.3mm, preparation method
Are as follows: zinc-base metal is first pulled into the filament of diameter 0.1-0.3mm, is then curled into different size of silk thread ball, porous zinc-base is fluffy
The partial size of loose metal ball is preferably 2-8mm.It is to promote growing into for osteocyte that zinc-base metal ball, which is prepared into porous purpose, is also increased
The surface area of metal ball, and can promote the release of zinc ion, accelerate its degradation speed.In addition, can also be wrapped in bracket filler
β-TCP particle is included, can be commercial product (as shown in Figure 6), can also voluntarily prepare, skilled person will appreciate that, β-TCP
Particle inherently contains aperture, and porosity is preferably 60%-90%, and aperture is 500 μm hereinafter, preferably 200 μm or so, β-
The ratio of TCP particle and porous zinc-base metal ball quantity is preferably 6:4-4:6.
The zinc-base metal refers to the kirsite that pure zinc or the mass fraction containing zinc reach 90% or more, and preferably scheme is
Granular size in bracket is inhomogenous, but is in certain gradient distribution；Wherein big partial size accounts for 30%-50%, and middle partial size accounts for 20%-
40%, small particle accounts for 20%-40%.The filler mixed according to the above ratio can preferably play its biological function, double regulation control
Skeletonization and osteoclastic behavior can significantly improve the bone and repair on the basis of maintaining enrichment mesenchymal stem cell to promote Bone Defect Repari
The mechanical property of multiple bracket.
Embodiment 2
The femoral shaft large segmental bone defect for being about 5cm for one, first according to bone defect form Design class cylinder network,
Outer stent and interior support posts are prepared using TC4 titanium alloy as raw material, support Design is the class of diameter 3.5cm, height 5cm
Cylinder, bracket grid hole are designed as rectangular or diamond shape, and major diameter 0.5mm or grid hole are designed as circle, diameter 0.5mm,
The support column of 4 diameter 0.5mm is arranged inside.Then Zn-1Sr alloy (Sr1wt.%, ultimate tensile strength UTS=are selected
160MPa, yield strength YS=120MPa, elongation percentage > 30%) porous zinc-base solid metal ball is prepared, metal bulb diameter exists
0.5-5mm etc., with laser burn method in punching slot in Zn-1Sr metal ball, diameter 0.2mm, porosity 60%-90%,
Select commercially available β-TCP particle (200 μm of granular size 0.5-5mm, porosity 60%-90% or so, aperture).By β-TCP particle
It is mixed with degradable zinc-base metal ball in 5:5 ratio, then by different size of grain diameter in following ratios filling bracket:
Big partial size 3.5-5mm accounts for 50%；
Middle partial size 1.0-3.5mm accounts for 30%；
Small particle is less than 1.0mm and accounts for 20%.
After filling is complete, bracket is placed in bone defect position, is fixedly secured with steel plate screw, excellent in mechanical performance titanium alloy
Supporting support provides mechanical support, and the interior β-TCP particle filled and Zn-1Sr metal ball are gradually degraded, played stem cell enriched
Function promotes its Osteoblast Differentiation, accelerates Bone Defect Repari process, to accelerate the reparation of bone defect.
Embodiment 3
Patient, the spherical bone defect of Postoperative Residual diameter about 3cm are cut off for a tumor of proximal humerus.It is lacked first according to bone
The spherical network of form Design is damaged, with Zn-0.8Li-0.1Mg alloy (Li0.8wt.%, Mg0.1wt.%, UTS=
680MPa, YS=540MPa, elongation percentage 10%) it is used as raw material to prepare outer stent and interior support posts, bracket size is set
Meter by paste on the basis of bone defect form.Support Design be diameter 3cm spherical bracket, bracket grid hole be designed as it is rectangular or
Diamond shape, major diameter 0.5mm or grid hole are designed as circle, and diameter 0.5mm inside sets the support column of 3 diameter 0.5mm.So
Zn-0.8Mg alloy (Mg0.8wt.%, UTS=370MPa, YS=300MPa, elongation percentage 10%) is selected to prepare zinc-base metal afterwards
Ball (diameter 0.5-5mm is differed).With laser burn method in punching slot in Zn-0.8Mg metal ball, diameter 0.2mm, porosity I
60%-90% selects commercially available β-TCP particle (granular size 0.5-5mm, porosity 60%-90% or so, 200 μm of aperture).It will
β-TCP particle and degradable zinc-base metal ball are mixed in 6:4 ratio, then fill out different size of grain diameter in following ratios
Enter in bracket:
Big partial size 3.5-5mm accounts for 50%；
Middle partial size 1.0-3.5mm accounts for 30%；
Small particle is less than 1.0mm and accounts for 20%.
After β-TCP particle and zinc-base metal ball are filled up bracket, be put at bone defect, with excellent in mechanical performance can
Degradation zinc-containing alloy prepares bracket and provides mechanical support, the excellent β-TCP particle of interior bone formation performance and Zn-0.8Mg metal ball
It gradually degrades after merging in vivo, plays stem cell enriched function, promote skeletonization, accelerate Bone Defect Repari process, and then repair bone and lack
Damage.
Embodiment 4
The femoral shaft large segmental bone defect for being about 5cm for one, first according to bone defect form Design class cylinder network,
Outer stent is prepared using TC4 titanium alloy as raw material, support Design is diameter 3.5cm, the class of height 5cm is cylindrical, bracket
Grid hole is designed as rectangular or diamond shape, and major diameter 2mm or grid hole are designed as circle, diameter 2mm.Then Zn-1Sr is selected
Alloy (Sr1wt.%, UTS=160MPa, YS=120MPa, elongation percentage > 30%) prepares porous zinc-base solid metal ball, metal
Spherolite diameter is in punching slot, diameter 0.2mm, porosity in Zn-1Sr metal ball in 2-5mm etc., with laser burn method
60%-90%.In in following ratios filling bracket:
Big partial size 4-5mm accounts for 50%；
Middle partial size 3-4mm accounts for 30%；
Small particle 2-3mm accounts for 20%.
After filling is complete, bracket is placed in bone defect position, is fixedly secured with steel plate screw, it is made to provide mechanical support
While play bone balance effect, promote skeletonization process, inhibit osteoclast activity, and then promote bone defect reparation.
Embodiment 5
For the long 4cm large segmental bone defect of a distal radius.First according to the spherical network of bone defect form Design, with
Zn-0.8Li-0.1Mg alloy (Li0.8wt.%, Mg0.1wt.%, UTS=680MPa, YS=540MPa, elongation percentage 10%) is made
Prepare outer stent for raw material, the design of bracket size by paste on the basis of bone defect form.Support Design be diameter 2cm,
The class cylindrical stent of height 4cm.Then Zn-1Mn alloy (Mn1wt.%, UTS=200MPa, YS=160MPa, extension are selected
Rate > 80%) porous zinc-base solid metal ball is prepared, metal ball partial size is that 2-5mm is differed.With laser burn method in Zn-1Mn gold
Belong to and punch slot on ball, different size of metal ball is inserted branch in following ratios by diameter 0.2mm, porosity 60%-90%
In frame:
Big partial size 4-5mm accounts for 50%；
Middle partial size 3-4mm accounts for 30%；
Small particle 2-3mm accounts for 20%.
After filling is complete, bracket is placed in bone defect position, is fixedly secured with steel plate screw, it is made to provide mechanical support
While play bone balance effect, promote skeletonization process, inhibit osteoclast activity, and then promote bone defect reparation.
Embodiment 6
The femoral shaft large segmental bone defect for being about 5cm for one, first according to bone defect form Design class cylinder network,
With Zn-0.8Li-0.1Ca alloy (Li0.8wt.%, Ca0.1wt.%, UTS=560MPa, YS=300MPa, elongation percentage >
30%) outer stent is prepared as raw material, support Design is diameter 3.5cm, the class of height 5cm is cylindrical, bracket grid hole
It is designed as rectangular or diamond shape, major diameter 2mm or grid hole are designed as circle, diameter 2mm.Then Zn-1Mn alloy is selected
(Mn1wt.%, UTS=160MPa, YS=120MPa, elongation percentage > 80%) prepares the porous fluffy ball of zinc-base metal, first by Zn-
1Mn alloy pulls into the filament of diameter 0.2mm, is then curled into different size of silk thread ball (as shown in Figure 5).It is filled out in following ratios
Enter in bracket:
Big partial size > 5mm accounts for 50%；
Middle partial size 3-5mm accounts for 30%；
Small particle < 3mm accounts for 20%.
After the completion of bracket filling, bracket is placed in bone defect position, is fixedly secured with steel plate screw, early stage, the bracket could
Mechanical support is provided, then gradually degrades, releases Zn2+、Li+、Ca2+、Mn2+, play and promote osteogenic action, with delaying for bracket
Slow degradation, newborn bone tissue gradually fill up at bone defect, are finally reached the effect for repairing large segmental bone defect.
Embodiment 7
For the long 3cm large segmental bone defect of a distal radius.First according to the class ball-type of bone defect form Design diameter about 3cm
Porous support (Li0.8wt.%, Mg0.8wt.%, UTS=503MPa, YS=380MPa, is prolonged with Zn-0.8Li-0.8Mg alloy
Stretch rate > 30%) prepare outer stent as raw material, the design of bracket size by paste on the basis of bone defect form.Then it selects
Porous zinc-base metal is prepared with Zn-2Cu alloy (Cu2.0wt.%, UTS=270MPa, YS=240MPa, elongation percentage > 40%)
Zn-2Cu alloy, is first pulled into the filament of diameter 0.2mm by fluffy ball, is then curled into different size of silk thread ball (such as Fig. 4 institute
Show).Wire thread ball is pressed and is stated in ratio Stent Implantation:
Big partial size > 5mm accounts for 50%；
Middle partial size 3-4mm accounts for 30%；
Small particle 2-3mm accounts for 20%.
After the completion of spherical bracket preparation filling, place it at bone defect.In slowly degradation in vivo after merging, release
Release Zn2+、Li+、Mg2+、Cu2+, play and promote osteogenic action, with the slow degradation of bracket, newborn bone tissue is gradually filled up
At bone defect, it is finally reached the effect of repairing bone defect.
Embodiment 8
Its chemical property and corrosive nature are tested according to following normal process to zinc-containing alloy selected by the present invention:
(1) electro-chemical test
At room temperature using electrochemical workstation (Autolab, Metrohm, Switzerland), Hank ' s solution
In tested.Electro-chemical test is used for using the three-electrode system of platinum electrode-saturated calomel electrode (SCE).To each sample
Carry out open circuit potential (Open-circuit potential, OCP) monitoring in 5400 seconds.Electrochemical impedance spectroscopy
(Electrochemical impedance spectroscopy, EIS) test is in 10mV, measurement frequency 105To 10-2Hz
Under conditions of carry out.Potentiodynamic polarization test (Potentiodynamic polarization is then carried out with the rate of 1mV/s
), test test area 0.2826cm2(φ6mm).Each sample group at least carries out five measurements.By Linearfit and
Tafel extrapolation method analyzes the cathode of polarization curve and the corrosion parameter of anode portion, including open circuit potential
(OCP), corrosion potential (Ecorr) and corrosion electric current density (icorr)。
1.2 immersion test
Immersion test carries out in 37 DEG C of Hank ' s solution.Pass through pH meter (Mettler during immersion in different time points
FiveEasy pH FE20K) recording solution pH value.After removing corrosion product, in electronic balance (XS105, METTLER
TOLERDO the weight that sample is measured on) is lost, and measurement sensitivity 0.1mg, every group averagely carries out five measurements.According to following
Formula calculates external corrosion rate: C=Δ m/ ρ At, wherein C is the corrosion rate as unit of mm/, and Δ m is weight loss,
ρ is the density of material, and A is the surface area initially impregnated, and t is Implantation Time.
The results are shown in Table 1 for partial test.
The electrochemical parameter (37 ± 0.2 DEG C) of pure zinc and kirsite in 1 SBF solution of table
Note: the number in bracket is standard deviation
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (13)
1. a kind of bone tissue engineering scaffold, which is characterized in that including hollow latticed bracket and be filled in porous zinc therein
Base Metal ball.
2. bone tissue engineering scaffold as described in claim 1, which is characterized in that the hollow latticed bracket is by pure titanium or titanium
Alloy, or be made of degradable zinc-base metal.
3. bone tissue engineering scaffold as described in claim 1, which is characterized in that the hollow latticed bracket has internal branch
Dagger.
4. bone tissue engineering scaffold as described in claim 1, which is characterized in that the porous zinc-base metal ball is to have on surface
There is the medicine ball of several hole slots.
5. bone tissue engineering scaffold as claimed in claim 4, which is characterized in that solid with several hole slots on the surface
The partial size of ball is 0.5-5mm, and the hole slot is circle, a diameter of 0.1-0.3mm, porosity 60%-90%.
6. bone tissue engineering scaffold as described in claim 1, which is characterized in that the porous zinc-base metal ball is by degradable
Zinc-base coil of wire at porous fluffy ball.
7. bone tissue engineering scaffold as claimed in claim 6, which is characterized in that the partial size of the porous fluffy ball is 2-8mm.
8. bone tissue engineering scaffold as described in claim 1, which is characterized in that the size accounting of the porous zinc-base metal ball
Are as follows:
Big partial size accounts for 30%-50%；
Middle partial size accounts for 20%-40%；
Small particle accounts for 20%-40%.
9. bone tissue engineering scaffold as described in claim 1, which is characterized in that be also filled in the hollow latticed bracket
β-TCP particle.
10. bone tissue engineering scaffold as claimed in claim 9, which is characterized in that the partial size of the β-TCP particle is 0.5-
5mm, porosity 60%-90%, aperture are 500 μm or less.
11. bone tissue engineering scaffold as claimed in claim 9, which is characterized in that the β-TCP particle and the porous zinc-base
The ratio of metal ball quantity is 6:4-4:6.
12. bone tissue engineering scaffold as claimed in claim 9, which is characterized in that the porous zinc-base metal ball and the β-
The size accounting of TCP particle are as follows:
Big partial size accounts for 30%-50%；
Middle partial size accounts for 20%-40%；
Small particle accounts for 20%-40%.
13. a kind of bone tissue engineering scaffold, which is characterized in that the porous zinc-base metal ball is by pure zinc or or quality containing zinc point
The kirsite that number reaches 90% or more is made.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110478089A (en) * | 2019-07-25 | 2019-11-22 | 中国人民解放军总医院 | A kind of vascularization neuralization osteogenic activity bracket suitable for large segmental bone defect reparation |
| CN110670095A (en) * | 2019-11-08 | 2020-01-10 | 南方科技大学 | Porous zinc material and preparation method thereof |
| CN114850469A (en) * | 2022-04-18 | 2022-08-05 | 北京科技大学 | Metal bone cement, porous metal microspheres and preparation method thereof |
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| CN101032632A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | Material for bone tissue engineering scaffold and making method thereof |
| US20150306282A1 (en) * | 2014-04-28 | 2015-10-29 | John James Scanlon | Bioresorbable Stent |
| CN205252143U (en) * | 2015-10-29 | 2016-05-25 | 张智勇 | Bionical bone repair materials structure that mechanical properties and biological activity are good |
| US20190083685A1 (en) * | 2016-03-10 | 2019-03-21 | Shandong Rientech Medical Tech Co., Ltd. | Degradable zinc base alloy implant material and preparation method and use thereof |
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| CN101032632A (en) * | 2006-03-08 | 2007-09-12 | 中国科学院金属研究所 | Material for bone tissue engineering scaffold and making method thereof |
| US20150306282A1 (en) * | 2014-04-28 | 2015-10-29 | John James Scanlon | Bioresorbable Stent |
| CN205252143U (en) * | 2015-10-29 | 2016-05-25 | 张智勇 | Bionical bone repair materials structure that mechanical properties and biological activity are good |
| US20190083685A1 (en) * | 2016-03-10 | 2019-03-21 | Shandong Rientech Medical Tech Co., Ltd. | Degradable zinc base alloy implant material and preparation method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110478089A (en) * | 2019-07-25 | 2019-11-22 | 中国人民解放军总医院 | A kind of vascularization neuralization osteogenic activity bracket suitable for large segmental bone defect reparation |
| CN110670095A (en) * | 2019-11-08 | 2020-01-10 | 南方科技大学 | Porous zinc material and preparation method thereof |
| CN114850469A (en) * | 2022-04-18 | 2022-08-05 | 北京科技大学 | Metal bone cement, porous metal microspheres and preparation method thereof |
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