CN104127916A - Absorbable orthopedic apparatus material having antibiosis and bone growth promotion functions, and preparation method thereof - Google Patents

Absorbable orthopedic apparatus material having antibiosis and bone growth promotion functions, and preparation method thereof Download PDF

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CN104127916A
CN104127916A CN201410337147.XA CN201410337147A CN104127916A CN 104127916 A CN104127916 A CN 104127916A CN 201410337147 A CN201410337147 A CN 201410337147A CN 104127916 A CN104127916 A CN 104127916A
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magnesium
solution
ceramic layer
magnesium alloy
pure magnesium
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CN104127916B (en
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储成林
李旋
刘珣
白晶
郭超
薛烽
林萍华
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Southeast University
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Southeast University
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Abstract

The invention relates to an absorbable orthopedic apparatus material having antibiosis and bone growth promotion functions, and a preparation method thereof. The orthopedic apparatus material is obtained by compounding medical pure magnesium or magnesium alloy with an absorbable high-molecular polymer, the surface of the pure magnesium or magnesium alloy has a porous ceramic layer, the surface of the porous ceramic layer is a functional load layer loaded with bone morphogenetic proteins and copper ions with B-type gelatin as a carrier by adopting an electrophoresis-electrodeposition process, the volume fraction of the pure magnesium or magnesium alloy is 1-99%, the micropore aperture and the thickness of the porous ceramic layer on the surface of the pure magnesium or magnesium alloy are 1-100[mu]m and 1-100[mu]m respectively, and the surface of the porous ceramic layer is the functional load layer loaded with bone morphogenetic proteins and copper ions with B-type gelatin as the carrier by adopting the electrophoresis-electrodeposition process. An orthopedic apparatus can slowly release copper ions having a sterilizing effect and bone morphogenetic proteins having a bone growth promotion effect in the use process, can be applied to restore and fix various bone injuries, and has a wide application prospect.

Description

There is antibacterial and promotion osteogenesis function adsorbable bone section's device material and preparation method
Technical field
The present invention relates to a kind of adsorbable bone section apparatus antibacterial and promotion osteogenesis function that has, this orthopedic instrument in vivo can degradable absorption under environment, and in degradation process, slowly release and can promote the bone morphogenetic protein of osteogenesis and the copper ion of bactericidal action, be applicable to the reparation of various bone injuries in human body and fix, belonging to orthopedic instrument technical field.
Background technology
In the last few years, degradable bone injury reparation and immobilization material are because more and more being paid close attention to without second operation taking-up and good biocompatibility, publication CN102764454A and publication CN102871715A mention that a kind of magnesium alloy strengthens the degradable absorption orthopedic fixer tool of high molecular polymer, and this class orthopedic fixer tool has good fixed effect and degradable characteristic.But for bone injury healing process, except fixed effect, wish that toward contact apparatus can promote bone growth, thereby reduce the time of curing.In addition it is also the problem that needs solution that the antibacterial in instrumentation process, infects.
Bone morphogenetic protein (BMP) can break up to bone and chondrocyte direction by the undifferentiated mesenchymal cell of induction of vascular around and in connective tissue, thereby forms osseous tissue.It has efficient osteogenic activity, can reduce the probability that bone does not connect occurs fracture, improve effect and the success rate of fracture healing, in addition BMP has good high-temperature resistance, 55～75 DEG C of high temperature of ability, but being greater than at pH value can inefficacy (UristMR, etal.Science, 220 (1983): 680-686) in 8.5 environment.BMP can not make separately the shape of bone, could use after must relying on other backing material molding.In addition,, because BMP is water insoluble and ethanol, often BMP is dissolved in to guanidine hydrochloride solution, adopt again dipping method to load on carrier material, because BMP in dipping process and carrier material are simple physical contact, cause BMP adsorption rate low, cannot give full play to the good effect of BMP.Therefore selecting suitable carrier material and carrying method is its key playing one's part to the full by replanting defective region to the marrow after BMP absorption.
In addition,, for orthopaedics implantation instrument, the antibacterial infection how reducing in use procedure is one of clinical subject matter that needs solution.Function (the CatherineGerard of the bactericidal action of copper ion and promotion collagen deposition and revascularization, etal.Biomaterials, 31 (2010): 824-831) be confirmed, if can be by copper ion payload to orthopedic instrument, orthopedic instrument in use can slowly release copper ion, thereby play sterilization and promote role of Vasculogenesis, improve fracture healing effect.
Gelatin is a kind of peptide molecule mixture with good biocompatibility and degradable characteristic, and it is insoluble to organic solvent and cold water, but is soluble in warm water, and in cooling procedure, forms colloid or gel.In addition gelatin is a kind of two property material; when PH values electronegative during higher than isoelectric point, IP; and be positively charged lower than isoelectric point, IP; the isoelectric point, IP of general A type gelatin is between 6～9.5; and the isoelectric point, IP of Type B gelatin is generally 4.7～5.0; according to electrophoresis theory, under electric field action, can there is directed movement and closely load on corresponding electrode in charged gelatin gels granule.In addition gelatin can form complex with copper ion, and pH value is higher, easier complexation (Tang Shihua, Huang Jianbin. Acta PhySico-Chimica Sinica, 2001,17 (10): 875-878).Illustrate that gelatin can be used as medium payload BMP and copper ion.
In sum, the orthopedic instrument of having reported is at present containing promoting osteogenesis function and bactericidal effect, load BMP and copper ion can make orthopedic instrument have above-mentioned functions, are the problems of needing solution badly but select suitable carrier material and suitable carrying method payload BMP and copper ion under the prerequisite of not destroying BMP activity.
Summary of the invention
Technical problem: the object of the invention is to provide a kind of adsorbable bone section device material antibacterial and promotion osteogenesis function that has, select suitable carrier material and load technology, can promote the BMP of bone growth and the copper ion of bactericidal action to load in degradable orthopedic instrument, do not reduce the activity of BMP, make apparatus in use can slowly release BMP and copper ion.Meanwhile, do not destroying the load effect that should improve as far as possible BMP and copper ion under the active prerequisite of BMP.Therefore the key technology that the present invention solves comprises the selection of load carriers material, the load technology of BMP and copper ion, and realize both release slowly for a long time.
Technical scheme: for achieving the above object, the present invention has adsorbable bone section device material antibacterial and that promote osteogenesis function by medical pure magnesium or magnesium alloy and can absorb high molecular polymer and is composited, pure magnesium or Mg alloy surface have porous ceramic layer, be taking Type B gelatin as carrier on the surface of this porous ceramic layer and adopt the load of electrophoresis-electro-deposition method to have the function load layer of bone morphogenetic protein and copper ion, wherein the volume fraction of pure magnesium or magnesium alloy is 1%～99%, the micropore size of its porous surface ceramic layer is 1～100 μ m, and bed thickness is 1～100 μ m.
The present invention has antibacterial and promotes that the preparation method of adsorbable bone section device material of osteogenesis function is as follows:
1) select suitable medical pure magnesium or magnesium alloy, make a material, sheet material or bar by methods such as drawing, rolling, extruding or die casting, and be processed into required form and structure;
2) select one or more methods in differential arc oxidation, anodic oxidation, bonderizing, electro-deposition, plasma spray, chemical conversion, ion implantation, sputter or vapour deposition in step 1) the pure magnesium or the Mg alloy surface that obtain prepare porous ceramic layer;
3) Type B gelatin is dissolved in 40～90 DEG C of distilled water and obtains gelatin solution, adding alkaline solution regulator solution pH value is 8.0～14.0, add subsequently copper ions solution to form the complex of copper, adding afterwards acid solution regulator solution pH value is 4.7～8.5, after reducing solution temperature to 10～75 DEG C, add again bone morphogenetic protein to stir, obtain the mixed solution of gelatin-bone morphogenetic protein-copper-bearing complex;
4) cooling step 3) mixed solution to 10～50 DEG C that obtain, insert the electrode of electrophoretic apparatus, wherein step 2) to have the pure magnesium of porous ceramic layer or magnesium alloy be anode for the surface that obtains, graphite or platinum are negative electrode, deenergization after energising certain hour, takes out pure magnesium after treatment or magnesium alloy and dries;
5) can absorb high molecular polymer with organic solvent dissolution and form slurry, the method of dip-coating, brushing or spraying of employing is by high molecular polymer and step 4) pure magnesium or the magnesium alloy processed be compound, at 10～75 DEG C, adopt mold pressing, extruding or Hubbing method molding, then the orthopedic instrument of machined one-tenth desired structure.
Described absorbed high molecular polymer is a kind of of polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol or polyamide or wherein two or more their copolymer or blend.
Beneficial effect: beneficial effect of the present invention is as follows:
1) this apparatus has simultaneously and can absorb, promote the function such as osteogenesis and sterilization.Promote the BMP of osteogenesis function and the copper ion of sterilizing function to load in orthopedic instrument by having, in instrumentation process, slowly release BMP and copper ion, thereby improve bone injury curative effect and reduce antibacterial and infect.
2) BMP activity is not destroyed.Conventional load BMP method is first dissolved in BMP the organic reagent such as guanidine hydrochloride or carbamide wiring solution-forming conventionally, then adopt dipping method load, new organic solvent is introduced in this load, tend to increase the toxicity of apparatus, the more important thing is that this method may change the conformation of BMP, thereby reduce the activity of BMP.And BMP powder is in the distribution and aqueous solution of disperse in the present invention, and dissolve without introducing other organic reagents, meanwhile, BMP is mainly coated and adsorption load by the physics of gelatine particle, can not destroy molecular conformation and the activity of BMP.In addition, because BMP is greater than in 8.5 environment and easily lost efficacy at pH value, for Type B gelatin, its isoelectric point, IP is generally 4.7～5.0, therefore can regulator solution pH higher than the isoelectric point, IP of Type B gelatin, the pH value simultaneously losing efficacy lower than BMP, thus give full play to the beneficial effect of BMP.
3) copper ion and BMP load effect are good.There is complex reaction and generate complex in copper ion and gelatin, obtain subsequently copper-loaded gelatin gels granule in cooling procedure under alkalescence effect.Simultaneously, in gelatin gels granule forming process, can be coated BMP, and colloidal solid further adsorbs the BMP that disperse distributes in electrophoresis motion subsequently, under the effect of accelerating field, charged colloidal solid can deposit on the pure magnesium or magnesium alloy carrier as anode closely, thus payload copper ion and BMP.In addition, the ceramic layer of pure magnesium or magnesium alloy surfaces of carrier materials porous again can be for load provides high specific surface area, thereby further improve load capacity.
4) copper ion and BMP can slowly discharge for a long time.Because gelatin degradation speed in human body environment is fast; make copper ion and the BMP rate of release of load very fast, but the absorbed high molecular polymer degradation speed in described orthopedic instrument is slower, can protect gelatin; make the release that copper ion and BMP can be slowly long-term, thereby continue to play a role.
5) cooperative effect between heterogeneity macromolecular material.Gelatin has that other can absorb the better hydrophilic of high molecular polymer than polylactic acid etc., there is better cell and histocompatibility, simultaneously, function load layer taking gelatin as carrier is under the effect of hydrone, can automatically form the very large gelatin gels of viscosity, this colloid volumetric expansion with and inner porous ceramic layer and outside degradable high polymer material effect of contraction under, can automatically penetrate in the pore structure of inner porous ceramic layer and outside degradable macromolecule layer, form a kind of special sealing of hole self-shield synergism, thereby effectively control BMP, the degradation rate of copper ion rate of release and orthopedic instrument, this cooperative effect is to use separately the not available control effect of degradable high polymer material.
Detailed description of the invention
The present invention is a kind of to be had antibacterial and promotes the adsorbable bone section apparatus of osteogenesis function to be achieved through the following technical solutions: described orthopedic instrument is by medical pure magnesium or magnesium alloy and can absorbs high molecular polymer and be composited, pure magnesium or Mg alloy surface have porous ceramic layer, be taking Type B gelatin as carrier on the surface of this porous ceramic layer and adopt the load of electrophoresis-electro-deposition method to have the function load layer of bone morphogenetic protein and copper ion, wherein the volume fraction of pure magnesium or magnesium alloy is 1%～99%, the micropore size of its porous surface ceramic layer is 1～100 μ m, bed thickness is 1～100 μ m, embodiment 1
There is absorbable bone peg antibacterial and that promote osteogenesis function by medical pure magnesium bar and can absorb high molecular polymer and be composited, pure magnesium surface has porous ceramic layer, be taking Type B gelatin as carrier on the surface of this porous ceramic layer and adopt the load of electrophoresis-electro-deposition method to have the function load layer of bone morphogenetic protein and copper ion, its preparation process is as follows:
1) the pure magnesium bar that is 5mm by diameter is processed into threaded and nail nut;
2) magnesium nail is carried out to differential arc oxidation processing.Selecting electrolyte main component is 10g/L sodium silicate, 2g/LNaOH and 8g/L hydroxyapatite nanoparticle, magnesium nail is dipped in wherein, apply 420V voltage, carry out the differential arc oxidation processing of 15 minutes, make its surface in situ generate one deck and be rich in magnesium oxide, magnesium silicate, hydroxyapatite porous ceramic layer, the average micropore size of ceramic layer is 8 μ m, and average bed thickness is 20 μ m;
3) get in 75 DEG C of distilled water that 1gB type gelatin is dissolved in 1L and obtain gelatin solution, in solution, add appropriate K 2cO 3solution regulator solution pH value is 11.0, then adds the Cu (NO of 10ml2g/L 3) 2solution, adds appropriate KH after stirring 30min 2pO 4solution, regulating pH value is 6.5, cooling solution to 40 DEG C, then add 0.01gBMP powder to stir, obtain the mixed solution of gelatin-BMP-copper-bearing complex;
4) by step 3) mixed solution that obtains is cooled to 30 DEG C of a period of times and obtains colloid solution, and the electrode of electrophoretic apparatus is put into solution, and wherein magnesium nail is anode, and platinum is negative electrode, applies 150V voltage 6min, and powered-down takes out magnesium nail and dries;
5) by the chloroformic solution dip-coating that is dissolved with polylactic acid in step 4) magnesium that obtains nail surface, dry and form required nail.
Embodiment 2
There is absorbable-bone plate antibacterial and that promote osteogenesis function by medical AZ31B magnesium alloy plate and can absorb high molecular polymer and be composited, AZ31B Mg alloy surface has porous ceramic layer, be taking Type B gelatin as carrier on the surface of this porous ceramic layer and adopt the load of electrophoresis-electro-deposition method to have the function load layer of bone morphogenetic protein and copper ion, its preparation process is as follows:
1) hot rolling of AZ31B magnesium alloy or machining are become to the sheet material that 1.0mm is thick, and machinery processes the hone lamella of required form and structure;
2) bonderizing is carried out in magnesium alloy hone lamella surface, solution is NH 4h 2pO 4120g/L, (NH 4) 2sO 3h 2o30g/L, ammonia (30%) 6mL/L, generates taking the phosphate of magnesium as main porous ceramic layer, and the average micropore size of ceramic layer is 10 μ m, and average bed thickness is 30 μ m;
3) get in 80 DEG C of distilled water that 2gB type gelatin is dissolved in 1L and obtain gelatin solution, in solution, add appropriate K 2cO 3solution regulator solution pH value is 11.5, then adds the Cu (NO of 10ml2g/L 3) 2solution, adds appropriate KH after stirring 30min 2pO 4solution, regulating pH value is 7.0, cooling solution to 45 DEG C, then add 0.01gBMP to stir, obtain the mixed liquor of gelatin-BMP-copper-bearing complex;
4) by step 3) mixed solution that obtains is cooled to 30 DEG C of a period of times and obtains colloid solution, and the electrode of electrophoretic apparatus is put into solution, and wherein magnesium alloy hone lamella is anode, graphite is negative electrode, apply 80V voltage 7min, powered-down, takes out hone lamella and dries;
5) by the chloroformic solution dip-coating that is dissolved with polylactic acid in step 4) the magnesium alloy hone lamella surface that obtains, dry and form required hone lamella.
Embodiment 3
Have antibacterial and promote the adsorbable bone section apparatus of osteogenesis function to be composited by medical AZ31B magnesium alloy silk material and the copolymer (PLGA) that can absorb polylactic acid and polyglycolic acid, there is porous ceramic layer on magnesium alloy silk material surface, be taking Type B gelatin as carrier on the surface of this porous ceramic layer and adopt the load of electrophoresis-electro-deposition method to have the function load layer of bone morphogenetic protein and copper ion, its preparation process is as follows:
1) AZ31B magnesium alloy is drawn into the silk material that diameter is 0.3mm;
2) magnesium silk material is carried out to differential arc oxidation processing.Selecting electrolyte main component is 10g/L sodium silicate, 2g/LNaOH, magnesium silk material is dipped in wherein, apply 380V voltage, carry out the differential arc oxidation processing of 10 minutes, make its surface in situ generate one deck and be rich in magnesium oxide, magnesium silicate porous ceramic layer, the average micropore size of ceramic layer is 5 μ m, and average bed thickness is 20 μ m;
3) get in 75 DEG C of distilled water that 3gB type gelatin is dissolved in 1L and obtain gelatin solution, in solution, add appropriate K 2cO 3solution regulator solution pH value is 11.0, then adds the Cu (NO of 10ml2g/L 3) 2solution, adds appropriate KH after stirring 15min 2pO 4solution, regulating pH value is 7.0, cooling solution to 40 DEG C afterwards, then add 0.02gBMP to stir, obtain the mixed liquor of gelatin-BMP-copper-bearing complex;
4) by step 3) mixed liquor that obtains is cooled to 30 DEG C of a period of times and obtains colloid solution, and the electrode of electrophoretic apparatus is put into solution, and wherein magnesium alloy silk material is anode, and platinum is negative electrode, applies 100V voltage 8min, and powered-down takes out silk material and dries;
5) will being dissolved with the chloroform slurry and step 4 of PLGA) the silk material that obtains mixes, and is drawn into bar, then the orthopedic instrument of machined one-tenth desired structure at 65 DEG C.
Above-mentioned embodiment is several example of the present invention, is not for limiting enforcement of the present invention and interest field, and all equivalences of making according to the content described in the present patent application scope of patent protection change and modify, and all should be included in the present patent application the scope of the claims.

Claims (3)

1. one kind has antibacterial and promotion osteogenesis function adsorbable bone section device material, it is characterized in that: described orthopedic instrument material is by medical pure magnesium or magnesium alloy and can absorbs high molecular polymer and be composited, pure magnesium or Mg alloy surface have porous ceramic layer, be taking Type B gelatin as carrier on the surface of this porous ceramic layer and adopt the load of electrophoresis-electro-deposition method to have the function load layer of bone morphogenetic protein and copper ion, wherein the volume fraction of pure magnesium or magnesium alloy is 1%～99%, the micropore size of its porous surface ceramic layer is 1～100 μ m, bed thickness is 1～100 μ m.
2. there is a preparation method antibacterial and promotion osteogenesis function adsorbable bone section device material, it is characterized in that concrete preparation method is as follows:
1) select suitable medical pure magnesium or magnesium alloy, make a material, sheet material or bar by methods such as drawing, rolling, extruding or die casting, and be processed into required form and structure;
2) select one or more methods in differential arc oxidation, anodic oxidation, bonderizing, electro-deposition, plasma spray, chemical conversion, ion implantation, sputter or vapour deposition in step 1) the pure magnesium or the Mg alloy surface that obtain prepare porous ceramic layer;
3) Type B gelatin is dissolved in 40～90 DEG C of distilled water and obtains gelatin solution, adding alkaline solution regulator solution pH value is 8.0～14.0, add subsequently copper ions solution to form the complex of copper, adding afterwards acid solution regulator solution pH value is 4.7～8.5, after reducing solution temperature to 10～75 DEG C, add again bone morphogenetic protein to stir, obtain the mixed solution of gelatin-bone morphogenetic protein-copper-bearing complex;
4) cooling step 3) mixed solution to 10～50 DEG C that obtain, insert the electrode of electrophoretic apparatus, wherein step 2) to have the pure magnesium of porous ceramic layer or magnesium alloy be anode for the surface that obtains, graphite or platinum are negative electrode, deenergization after energising certain hour, takes out pure magnesium after treatment or magnesium alloy and dries;
5) can absorb high molecular polymer with organic solvent dissolution and form slurry, the method of dip-coating, brushing or spraying of employing is by high molecular polymer and step 4) pure magnesium or the magnesium alloy processed be compound, at 10～75 DEG C, adopt mold pressing, extruding or Hubbing method molding, then the orthopedic instrument of machined one-tenth desired structure.
3. according to claim 2 have antibacterial and promote to it is characterized in that the preparation method of osteogenesis function adsorbable bone section device material: described absorbed high molecular polymer is a kind of of polylactic acid, polyglycolic acid, polycaprolactone, Polyethylene Glycol or polyamide or wherein two or more their copolymer or blend.
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CN108379658A (en) * 2018-02-06 2018-08-10 中国科学院金属研究所 With the orthopaedics implant devices and preparation method thereof containing copper coating
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CN108866616A (en) * 2018-07-10 2018-11-23 中南大学 Mix control method, system and the storage medium of additive in electroplate liquid
CN109432514A (en) * 2018-12-12 2019-03-08 西南大学 Have degradable magnesium alloy bone nail and preparation method that squamous imitates bone nano-structured coating
CN111068106A (en) * 2019-11-27 2020-04-28 东南大学 Medical degradable antibacterial composite material and preparation method and application thereof
CN113181438A (en) * 2021-04-26 2021-07-30 东南大学 Thermosensitive responsive absorbable orthopedic instrument material capable of self-healing and promoting bone growth and preparation method thereof
CN114917414A (en) * 2022-04-26 2022-08-19 东南大学 Multifunctional composite coating for preparing magnesium alloy cardiac stent material and preparation method thereof

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CN109432514A (en) * 2018-12-12 2019-03-08 西南大学 Have degradable magnesium alloy bone nail and preparation method that squamous imitates bone nano-structured coating
CN111068106A (en) * 2019-11-27 2020-04-28 东南大学 Medical degradable antibacterial composite material and preparation method and application thereof
CN113181438A (en) * 2021-04-26 2021-07-30 东南大学 Thermosensitive responsive absorbable orthopedic instrument material capable of self-healing and promoting bone growth and preparation method thereof
CN114917414A (en) * 2022-04-26 2022-08-19 东南大学 Multifunctional composite coating for preparing magnesium alloy cardiac stent material and preparation method thereof
CN114917414B (en) * 2022-04-26 2023-09-29 东南大学 Multifunctional composite coating for preparing magnesium alloy heart stent material and preparation method thereof

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