CN104127916B - Have antibacterial and promote osteogenesis function absorbable orthopedic instrument material and preparation method - Google Patents

Have antibacterial and promote osteogenesis function absorbable orthopedic instrument material and preparation method Download PDF

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CN104127916B
CN104127916B CN201410337147.XA CN201410337147A CN104127916B CN 104127916 B CN104127916 B CN 104127916B CN 201410337147 A CN201410337147 A CN 201410337147A CN 104127916 B CN104127916 B CN 104127916B
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magnesium
ceramic layer
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gelatin
orthopedic instrument
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CN104127916A (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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Abstract

The present invention is that one has antibacterial and promotes osteogenesis function absorbable orthopedic instrument material and preparation method, described orthopedic instrument material is composited by medical pure magnesium or magnesium alloy and Absorbable rod high molecular polymer, pure magnesium or Mg alloy surface have porous ceramic layer, adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion with Type B gelatin for carrier on the surface of this porous ceramic layer, 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 μm, thickness is 1 ~ 100 μm, be carrier with gelatin and adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion on the surface of this porous ceramic layer.In use procedure, this orthopedic instrument can slowly release the copper ion with bactericidal action and the bone morphogenetic protein promoting osteogenesis, and this orthopedic instrument can be applied to the reparation of various bone injury and fix, and has a extensive future.

Description

Have antibacterial and promote osteogenesis function absorbable orthopedic instrument material and preparation method
Technical field
The present invention relates to and a kind ofly have antibacterial and promote the Absorbable rod orthopedic instrument of osteogenesis function, this orthopedic instrument in vivo can degradable absorption under environment, and slowly release in degradation process and can promote the bone morphogenetic protein of osteogenesis and the copper ion of bactericidal action, be applicable to the reparation of various bone injury 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 the need to second operation taking-up and excellent biocompatibility, publication CN102764454A and publication CN102871715A mentions that a kind of magnesium alloy strengthens the degradable absorption orthopedic fixer tool of high molecular polymer, and this kind of orthopedic fixer tool has excellent fixed effect and degradable characteristic.But for bone injury healing process, except fixed effect, wish that apparatus can promote bone growth toward contact, thus reduce the time of curing.In addition, the bacteriological infection in instrumentation process is also the problem that need solve.
Bone morphogenetic protein (BMP) can undifferentiated mesenchymal cell around induction of vascular and in connective tissue to bone and the differentiation of chondrocyte direction, thus form osseous tissue.It has efficient osteogenic activity, the probability that bone does not connect occurs fracture can be reduced, improve effect and the success rate of fracture healing, in addition BMP has good high-temperature resistance, ability 55 ~ 75 DEG C of high temperature, but be greater than in 8.5 environment at pH value can lose efficacy (UristMR, etal.Science, 220 (1983): 680-686).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 guanidine hydrochloride solution, dipping method is adopted to load on carrier material again, because BMP in dipping process and carrier material are simple physical contact, cause BMP adsorption rate low, the good effect of BMP cannot be given full play to.Therefore replanting defective region to the marrow after selecting suitable carrier material and carrying method to be adsorbed by BMP is the key that it plays one's part to the full.
In addition, for orthopaedics implantation instrument, the bacteriological infection how reduced in use procedure is one of clinical subject matter that need solve.The bactericidal action of copper ion and the function (CatherineGerard of promotion collagen deposition and revascularization, etal.Biomaterials, 31 (2010): 824-831) be confirmed, if can by copper ion payload on orthopedic instrument, then orthopedic instrument in use can slowly release copper ion, thus 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, form colloid or gel.In addition gelatin is a kind of two property material; when PH values is higher than electronegative during isoelectric point, IP; and lower than positively charged during 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; theoretical according to electrophoresis, 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 media payload BMP and copper ion.
In sum, the orthopedic instrument reported at present is containing promoting osteogenesis function and bactericidal effect, load BMP and copper ion can make orthopedic instrument have above-mentioned functions, but select suitable carrier material and suitable carrying method payload BMP and copper ion under the prerequisite not destroying BMP activity to be the problems needing solution badly.
Summary of the invention
Technical problem: the object of the invention is to provide a kind ofly to be had antibacterial and promotes the absorbable orthopedic instrument material of osteogenesis function, namely suitable carrier material and load technology is selected, can promote that the BMP of bone growth and the copper ion of bactericidal action load in degradable orthopedic instrument, do not reduce the activity of BMP, make apparatus in use can slowly release BMP and copper ion.Meanwhile, the load effect that should improve BMP and copper ion under the active prerequisite of BMP is not as far as possible being destroyed.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 discharges slowly for a long time both realizing.
Technical scheme: for achieving the above object, the present invention has antibacterial and promotes that the absorbable orthopedic instrument material of osteogenesis function is composited by medical pure magnesium or magnesium alloy and Absorbable rod high molecular polymer, pure magnesium or Mg alloy surface have porous ceramic layer, adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion with Type B gelatin for carrier on the surface of this porous ceramic layer, 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 μm, and thickness is 1 ~ 100 μm.
The present invention has antibacterial and promotes that the preparation method of the absorbable orthopedic instrument 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) one or more methods in differential arc oxidation, anodic oxidation, bonderizing, electro-deposition, plasma spray, chemical conversion, ion implantation, sputtering or vapour deposition are selected in step 1) the pure magnesium that obtains or Mg alloy surface prepare porous ceramic layer;
3) Type B gelatin is dissolved in 40 ~ 90 DEG C of distilled water obtains gelatin solution, adding alkaline solution regulates solution ph to be 8.0 ~ 14.0, add the complex that copper ions solution forms copper subsequently, adding acid solution afterwards regulates solution ph to be 4.7 ~ 8.5, add bone morphogenetic protein again after reducing solution temperature to 10 ~ 75 DEG C 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) surface that obtains has the pure magnesium of porous ceramic layer or magnesium alloy to be anode, graphite or platinum are negative electrode, deenergization after energising certain hour, takes out the pure magnesium after process or magnesium alloy is dried;
5) slurry is formed with organic solvent dissolution Absorbable rod high molecular polymer, adopt dip-coating, brushing or spraying method by high molecular polymer and step 4) the pure magnesium that processed or magnesium alloy compound, mold pressing, extruding or Hubbing method molding is adopted at 10 ~ 75 DEG C, then the orthopedic instrument of machined one-tenth desired structure.
Described Absorbable rod 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 Absorbable rod simultaneously, promotes the function such as osteogenesis and sterilization.Promoting that the BMP of osteogenesis function and the copper ion of sterilizing function load in orthopedic instrument by having, in instrumentation process, slowly releasing BMP and copper ion, thus improve bone injury curative effect and reduce bacteriological infection.
2) BMP activity is not destroyed.BMP is first dissolved in the organic reagent such as guanidine hydrochloride or carbamide wiring solution-forming by conventional load BMP method usually, then dipping method load is adopted, new organic solvent is introduced in this load, often increase the toxicity of apparatus, the more important thing is that this method may change the conformation of BMP, thus reduce the activity of BMP.And BMP powder is in the distribution of disperse and aqueous solution in the present invention, and dissolve without the need to introducing other organic reagents, meanwhile, BMP is coated and adsorption load mainly through the physics of gelatine particle, can not destroy molecular conformation and the activity of BMP.In addition, easily lost efficacy, for Type B gelatin because BMP is greater than in 8.5 environment at pH value, its isoelectric point, IP is generally 4.7 ~ 5.0, therefore pH value of solution can be regulated higher than the isoelectric point, IP of Type B gelatin, simultaneously lower than the pH value that BMP lost efficacy, thus give full play to the beneficial effect of BMP.
3) copper ion and BMP load effect excellent.There is complex reaction and generate complex in copper ion and gelatin, obtain copper-loaded gelatin gels granule subsequently in cooling procedure under alkalescence effect.Simultaneously, the coated BMP of meeting in gelatin gels granule forming process, and colloidal solid adsorbs the BMP of Dispersed precipitate further in electrophoresis motion subsequently, under the effect of accelerating field, charged colloidal solid can deposit to closely as on the pure magnesium of anode or magnesium alloy carrier, thus payload copper ion and BMP.In addition, the ceramic layer of pure magnesium or magnesium alloy surfaces of carrier materials porous can provide high specific surface area for load again, thus improves load capacity further.
4) copper ion and BMP can long-term slow releasing.Because gelatin degradation speed in human body environment is fast; make the copper ion of load and BMP rate of release very fast, but the Absorbable rod high molecular polymer degradation speed in described orthopedic instrument is comparatively slow, can protect gelatin; make the release that copper ion and BMP can be slowly long-term, thus continue to play a role.
5) cooperative effect between heterogeneity macromolecular material.Gelatin has hydrophilic more better than other Absorbable rod high molecular polymers such as polylactic acid, there is the better biological cells and tissues compatibility, simultaneously, be that the function load layer of carrier is under the effect of hydrone with gelatin, can automatically form the very large gelatin gels of viscosity, this colloid is under volumetric expansion and its internal porous ceramic layer and outside degradable high polymer material effect of contraction, can automatically penetrate in the pore structure of internal porous ceramic layer and outside degradable macromolecule layer, form a kind of special sealing of hole self-shield synergism, thus effective control BMP, the degradation rate of copper ion rate of release and orthopedic instrument, this cooperative effect is the control effects be used alone not available for degradable high polymer material.
Detailed description of the invention
Of the present invention a kind ofly have antibacterial and promote that the Absorbable rod orthopedic instrument of osteogenesis function is achieved through the following technical solutions: described orthopedic instrument is composited by medical pure magnesium or magnesium alloy and Absorbable rod high molecular polymer, pure magnesium or Mg alloy surface have porous ceramic layer, adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion with Type B gelatin for carrier on the surface of this porous ceramic layer, 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 μm, thickness is 1 ~ 100 μm.
Embodiment 1
Have antibacterial and promote that the absorbable bone peg of osteogenesis function is composited by medical pure magnesium bar and Absorbable rod high molecular polymer, pure magnesium surface has porous ceramic layer, be adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion with Type B gelatin for carrier on the surface of this porous ceramic layer, its preparation process is as follows:
1) be that the pure magnesium bar of 5mm is processed into threaded and nail that is nut by diameter;
2) differential arc oxidation process is carried out to magnesium nail.Electrolyte main component is selected to be 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 process of 15 minutes, make its surface in situ generate one deck and be rich in magnesium oxide, magnesium silicate, hydroxyapatite porous ceramic layer, the mean pore size of ceramic layer is 8 μm, and average thickness is 20 μm;
3) get 1gB type gelatin to be dissolved in 75 DEG C of distilled water of 1L and to obtain gelatin solution, in solution, add appropriate K 2cO 3solution regulates solution ph to be 11.0, then adds the Cu (NO of 10ml2g/L 3) 2solution, adds appropriate KH after stirring 30min 2pO 4solution, adjust ph is 6.5, cooling solution to 40 DEG C, then adds 0.01gBMP powder and stir, and obtains 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, powered-down, takes out magnesium nail and dries;
5) the chloroformic solution dip-coating of polylactic acid will be dissolved with in step 4) magnesium that obtains nail surface, dry and form required nail.
Embodiment 2
Have antibacterial and promote that the absorbable-bone plate of osteogenesis function is composited by medical AZ31B magnesium alloy plate and Absorbable rod high molecular polymer, AZ31B Mg alloy surface has porous ceramic layer, be adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion with Type B gelatin for carrier on the surface of this porous ceramic layer, its preparation process is as follows:
1) by the sheet material that the hot rolling of AZ31B magnesium alloy or machining become 1.0mm thick, and machinery processes the hone lamella of required form and structure;
2) carry out bonderizing to magnesium alloy plate surface, solution is NH 4h 2pO 4120g/L, (NH 4) 2sO 3h 2o30g/L, ammonia (30%) 6mL/L, generate based on the porous ceramic layer of the phosphate of magnesium, and the mean pore size of ceramic layer is 10 μm, and average thickness is 30 μm;
3) get 2gB type gelatin to be dissolved in 80 DEG C of distilled water of 1L and to obtain gelatin solution, in solution, add appropriate K 2cO 3solution regulates solution ph to be 11.5, then adds the Cu (NO of 10ml2g/L 3) 2solution, adds appropriate KH after stirring 30min 2pO 4solution, adjust ph is 7.0, cooling solution to 45 DEG C, then adds 0.01gBMP and stir, and obtains 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, take out hone lamella and dry;
5) the chloroformic solution dip-coating of polylactic acid will be dissolved with in step 4) the magnesium alloy plate surface that obtains, dry and form required hone lamella.
Embodiment 3
Have antibacterial and promote that the Absorbable rod orthopedic instrument of osteogenesis function is composited by the copolymer (PLGA) of medical AZ31B magnesium alloy silk material and Absorbable rod polylactic acid and polyglycolic acid, there is porous ceramic layer on magnesium alloy silk material surface, be adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion with Type B gelatin for carrier on the surface of this porous ceramic layer, its preparation process is as follows:
1) AZ31B magnesium alloy is drawn into the silk material that diameter is 0.3mm;
2) differential arc oxidation process is carried out to magnesium silk material.Electrolyte main component is selected to be 10g/L sodium silicate, 2g/LNaOH, magnesium silk material is dipped in wherein, apply 380V voltage, carry out the differential arc oxidation process of 10 minutes, make its surface in situ generate one deck and be rich in magnesium oxide, magnesium silicate porous ceramic layer, the mean pore size of ceramic layer is 5 μm, and average thickness is 20 μm;
3) get 3gB type gelatin to be dissolved in 75 DEG C of distilled water of 1L and to obtain gelatin solution, in solution, add appropriate K 2cO 3solution regulates solution ph to be 11.0, then adds the Cu (NO of 10ml2g/L 3) 2solution, adds appropriate KH after stirring 15min 2pO 4solution, adjust ph is 7.0, cooling solution to 40 DEG C afterwards, then adds 0.02gBMP and stir, and obtains 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, powered-down, takes out silk material and dries;
5) chloroform slurry and the step 4 of PLGA will be dissolved with) the silk material that obtains mixes, and is drawn into bar at 65 DEG C, then the orthopedic instrument of machined one-tenth desired structure.
Above-mentioned embodiment is several example of the present invention, is not used to limit enforcement of the present invention and interest field, and all equivalences made 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 (2)

1. one kind has antibacterial and promotes osteogenesis function absorbable orthopedic instrument material, it is characterized in that: described orthopedic instrument material is composited by medical pure magnesium or magnesium alloy and Absorbable rod high molecular polymer, pure magnesium or Mg alloy surface have porous ceramic layer, adopt electrophoresis-electro-deposition method load to have the function load layer of bone morphogenetic protein and copper ion with Type B gelatin for carrier on the surface of this porous ceramic layer, wherein the volume fraction of pure magnesium or magnesium alloy is 1% ~ 99%, its porous surface ceramic layer is that one deck contains magnesium oxide, magnesium silicate and/or hydroxyapatite porous ceramic layer, its micropore size is 1 ~ 100mm, thickness is 1 ~ 100mm,
Described Absorbable rod 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.
2. there is antibacterial and promotion osteogenesis function absorbable orthopedic instrument material a preparation method as claimed in claim 1, 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 the method for drawing, rolling, extruding or die casting, and be processed into required form and structure;
2) one or more methods in differential arc oxidation, anodic oxidation, bonderizing, electro-deposition, plasma spray, chemical conversion, ion implantation, sputtering or vapour deposition are selected in step 1) the pure magnesium that obtains or Mg alloy surface prepare porous ceramic layer;
3) Type B gelatin is dissolved in 40 ~ 90 DEG C of distilled water obtains gelatin solution, adding alkaline solution regulates solution ph to be 8.0 ~ 14.0, add the complex that copper ions solution forms copper subsequently, adding acid solution afterwards regulates solution ph to be 4.7 ~ 8.5, add bone morphogenetic protein again after reducing solution temperature to 10 ~ 75 DEG C 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) surface that obtains has the pure magnesium of porous ceramic layer or magnesium alloy to be anode, graphite or platinum are negative electrode, deenergization after applying 150V voltage 6min or 100V voltage 8min or 80V voltage 7min, takes out the pure magnesium after process or magnesium alloy is dried;
5) form slurry with organic solvent dissolution Absorbable rod high molecular polymer, adopt dip-coating, brushing or spraying method by high molecular polymer and step 4) the pure magnesium that process or magnesium alloy compound, sheet material or bar needed for oven dry formation; Or by polymer pulp and step 4) the silk material that obtains mixes, 65 DEG C are drawn into bar, then the orthopedic instrument of machined one-tenth desired structure.
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CN108866537B (en) * 2017-12-06 2023-04-25 济南大学 Preparation process of magnesium-polylactic acid porous magnesium coating
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