CN101829357A - Implant surface biomimetic coating material for promoting sacralization and preparation method thereof - Google Patents
Implant surface biomimetic coating material for promoting sacralization and preparation method thereof Download PDFInfo
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- CN101829357A CN101829357A CN201010136805A CN201010136805A CN101829357A CN 101829357 A CN101829357 A CN 101829357A CN 201010136805 A CN201010136805 A CN 201010136805A CN 201010136805 A CN201010136805 A CN 201010136805A CN 101829357 A CN101829357 A CN 101829357A
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Abstract
The invention discloses an implant surface biomimetic coating material for promoting the sacralization and a preparation method thereof. The coating material is a compound of calcium phosphate cooperatively doped with various trace elements and organic macromolecules. The preparation method comprises the following steps of: immersing an artificial implant pretreated by acid or alkali in simulated body fluid containing various trace element ions and organic macromolecules; carrying out chemical precipitation treatment between 35 DEG C and 150 DEG C to ensure that the surface of the implant is subjected to calcium phosphate salt core forming and growth; and forming a continuous coating of calcium phosphate salt cooperatively doped with various trace elements and the organic macromolecules. The surface of the coating has a nanoscale fine structure, and the effects of slowly degrading and releasing active ions of calcium, phosphorus and various trace elements and promoting the sacralization of implants for diseased intraosseous injuries, bone fracture internal fixation and tooth root internal fixation in the oral cavity. The coating material has the characteristics of simple preparation process, controllable coating thickness, trace element content, crystallinity and degradation rate, and the like.
Description
Technical field
The present invention relates to a kind of metal or alloy base bio-medical implantation body material surface bioactivity coatings modification technology, be specifically related to implant surface biomimetic coating material that short bone merges and preparation method thereof, belong to the bio-medical material technical field.
Background technology
Osteoporotic fracture, tooth are damaged, cranium disease of brain etc. are the major reason of bone injury or bone lacks in each age groups, because hindering, the demand of biomechanics, this class bone tooth disease loss on transmission generally need metal or alloy class implantation body to carry out purposes such as internal fixation or sealing wound.The biologically active biological coating is the precondition that implantation body and implant site host bone realize merging fast and reaching satisfied biomechanics.In orthopaedics, orthopedics, plastic surgery, neurocranial surgery and the department of stomatology etc., titanium (or alloy), aluminium oxide, magnesium alloy etc. are because of its excellent biological compatibility, and mechanical property and corrosion resistance are used widely in bone tooth internal fixation field.But these can alloys itself are bio-inert material, can not form good synostosis with osseous tissue, thereby cause the plantation failure.Therefore, generally all need carry out the bioactivity coatings modification, in the hope of reaching quick fusion and satisfying biomechanics demand (Narayanan R, J Biomed Mater Res BAppl Biomater.2008,85,279) in implant surface.
From bibliographical information, common technology is to prepare hydroxyapatite coating layer and bio-vitric coating at implantation body's material surface.Hydroxyapatite (HA) is similar to the inorganic constituents of body bone tissue, contains necessary calcium of tissue and P elements.Under the environment of body fluid, can form chemical bond with the skeleton tissue and combine, induce the new bone tissue growth.The implant surface of clinical practice at present all is to adopt the HA coating of plasma spraying technology preparation, the HA coating of this technology preparation has highly crystalline, but pyroprocess causes that other separates out mutually, be difficult to ancient regular surfaces is implemented the uniform coating preparation, coating and substrate combinating strength and coating biology activity are undesirable simultaneously, and bone merges the effect that speed still can't reach the clinical treatment expectation.In addition, utilization gel colloidal sol, electrochemical deposition, layer-layer assembling, wet-chemical deposition technique etc. can be prepared the HA coating, but therefore problems such as these technical matters are loaded down with trivial details, long processing time, anchoring strength of coating difference still can not be used for clinical practice.
Bio-vitric (BG) is that a class contains CaO-SiO
2-P
2O
5-MO (M=B, Na etc.) non-crystalline material of metal-oxide, compare with the HA of plasma spraying, become the candidate of coating material with its good biological activity, but the coating that is used for implantation body's material surface produces problem (Hench LL such as dissolving, poor bonding strength faster, An introduction to biocermics.Singapore:World Scienctific, 1993,239).Nearest research is carried out pretreatment with the BG coating with simulated body fluid (SBF), can form bionical hydroxyapatite (CHA) at BG coating surface crystallization nucleation, can make coating adhere to stromal surface preferably, and mixed coating shows function (the Bloyer DR of good promotion osteoblastic proliferation and differentiation, Biomaterials.2007,28,4901; Foppiano S, Acta Biomater.2006,2,133).
Inorganic component in the tissue is not pure hydroxyapatite, but contains CO
3, Na, Mg and trace element ions such as Si, Sr, Zn, therefore in order to satisfy requirements for clinical application, the doping more trace elements improves its biological activity in pure HA, degradability is to improve the effective way of biomaterial combination property.Trace element at many bioprocesss, comprises that processes such as cellular signal transduction, nucleic acid synthesize, bone reconstruction play an important role as a kind of regulon of cellular process.Can regulate calcium concentration and bone metabolism (Marie PJ. in the skeleton as plain strontium, Calcif.Tissue Int.2001,69,121), and reducing the fracture effect of incidence rate of osteoporosis patient, experiment in vitro confirms that also strontium has the effect that promotes osteoblastic proliferation and suppress osteoclast activity; Silicon can activate osteoblast gene expression (Xynos I.D., Biochem.Biophys.Res.Commun.2000,276,461), synthetic to promotion collagen, as to activate osteoblast, promotion area of new bone mineralising, and the propagation of inhibition osteoclast has remarkable effect.In removing the test of ovary rat model, being used of the strontium of low dosage and element silicon can be brought into play the synergism of the two, suppresses the absorption again of bone and promotes skeletonization.In addition, a large amount of researchs show that also element zinc is the composition of many metalloenzyme, are promoting osteoblastic increment and differentiation to suppress aspect the osteoclast activity requisite important function is arranged.There are some researches show that zinc can increase alkaline phosphatase activities, and can improve dna content, improve bone strength (Ovesen J., Bone, 2001,29,565; Yamaguchi M., Biochem.Pharmacol.1986,35,773).On the other hand, the shortage of zinc causes rat bone density to descend, and also is to cause human body osteoporosis equivalent risk.In addition, in the damaged Regeneration and Repair research of bone, also demonstrate, silicon, strontium, zinc etc. mix biological activity, biological degradability and the bone defect repair effect that can improve material behind the synthos material (Pietal A.M., Biomaterials 2007,28,4023; Wong C.T., J Biomed.Mater Res.2004,513; Ishikawa K., Biomaterials 2002,23, and 423; SerreC.M., J Biomed.Mater.Res.1998,42,626).
Experiment and clinical application research all show in the body of above trace element, trace element is being regulated bone metabolism, is being promoted bone strength, and promote osteoporotic tissue regeneration aspect to have important function, still the multicomponent reactive trace element is used for collaborative doping of implant surface calcium phosphate coating material and performance and promotes the bone fusion that report is not arranged as yet.According to existing clinical practice product coating technology of preparing and research report, press for and explore utilization more trace elements and collaborative doping biomimetic calcium phosphate coating material of organic polymer and technology of preparing.Reach quick promotion implantation body the optimum efficiency that bone merges and improve biomechanical property takes place.
Summary of the invention
The purpose of this invention is to provide implant surface biomimetic coating material of a kind of short bone fusion and preparation method thereof,, promote the quick fusion of implant surface and diseaseization osseous tissue to improve medical implantation body coating material surface composition, micro structure and biological activity.
The artificial growth surface biomimetic coating material that short bone of the present invention merges is formed by containing in silicon, strontium, zinc and the magnesium two kinds of trace element and the collaborative adulterated synthos of organic macromolecule at least, and the mass percent content that its component is represented with oxide form is:
CaO 42～52.5％；
P
2O
5 38～45.5％；
Organic macromolecule 0.001～8.0%
The said components sum is 100%, and SiO
2, ZnO, MgO and at least two kinds of materials of SrO are not 0 simultaneously.
The preparation method of artificial growth of the present invention surface biomimetic coating material may further comprise the steps:
1) use acetone, ethanol and washed with de-ionized water clean successively the artificial growth body, soak pretreatment with the acid of 0.001～1.5mmol/L or the alkali of 1～8mmol/L then, reuse ethanol and washed with de-ionized water are clean, dry, and be standby;
2) manually prepare simulated body fluid by inorganic ions concentration dose in the human plasma, the concentration of each inorganic ions is respectively Na in the solution
+, 142mmol/L; K
+, 5mmol/L; Ca
2+, 2.5mmol/L; Mg
2+, 1.5mmol/L; SO
4 2-, 1mmol/L; HPO
4 2-, 1mmol/L; Cl
-, 163mmol/L and HCO
3 -, 4mmol/L; The pH value of solution is 7.25～7.40.In above-mentioned solution, add under the stirring condition and contain SiO
3 2-, Zn
2+And Sr
2+Inorganic salt solution, and Si in the control solution: the P mol ratio is 0～10: 100, Zn: the Ca mol ratio is 0～1.2: 100 and Sr: the Ca mol ratio is 0～10: 100, and SiO
3 2-, Zn
2+And Sr
2+At least two kinds of ions are not 0 simultaneously, add carboxylic organic macromolecule again in above-mentioned solution, or add the organic macromolecule that contains carboxyl and amino, and the concentration of control organic macromolecule is 0～50mmol/L, stirs;
3) the pretreated artificial growth body of step 1) is soaked the end in set by step 2) in the mixed solution of preparation, be warmed up to 35～150 ℃ and be incubated ageing 30～1200 minutes, take out the artificial growth body and use deionized water wash, drying obtains containing the biological activity bionic coating material that strontium, zinc, magnesium, silicon and organic macromolecule are worked in coordination with doping phosphoric acid calcium.
Among the present invention, all there is not strict kind restriction in the employed inorganic salt of the active trace element of doping Sr, Si, Zn or Mg, generally contains SiO
3 2-Inorganic salt adopt Na
2SiO
3Contain Sr
2+Inorganic salt adopts SrCl
2, Sr (NO
3)
2And Sr (CH
3COO)
2In one or more mixture.Contain Zn
2+Inorganic salt adopts ZnCl
2, Zn (NO
3)
2, Zn (CH
3COO)
2And ZnSO
4In one or more mixture.
Among the present invention, said carboxylic organic macromolecule is a kind of or both mixture in polypropylene acid, the polyglycolic acid; The organic macromolecule that contains carboxyl and amino is one or more mixture in poly-aspartate, polyacrylamide and the polylysine.
In the preparation process of the present invention, by changing SiO in the simulated body fluid
3 2-, Zn
2+And/or Sr
2+Concentration, can regulate the percentage composition of trace element in the bionical coating.
In the preparation process of the present invention,, can regulate features such as coating surface pattern and fine structure by changing organic molecule concentration.
In the preparation process of the present invention,, can regulate coating layer thickness by changing digestion time.
The application of artificial growth surface biomimetic coating material in treatment bone injury or bone lacks that short bone of the present invention merges.
Beneficial effect of the present invention is:
Its collaborative doping more trace elements and the bionical coating of organic macromolecule calcium phosphate, preparation process is implemented under 35～150 ℃ of biomimetic mineralization conditions, does not relate to the high heat treatment of high temperature, and it is low to consume energy, and preparation is simple.Secondly, whole technology is carried out in aqueous solution, and is irregular easy to implement with the modification of porous implant surface to configuration of surface, and form the bionical coating of uniform thickness.Such coating material has not only kept conventional calcium phosphate coating material excellent biological compatibility, and mix by multicomponent reactive ion and organic polymer and to enter calcium phosphate lattice or crystal grain boundary, with suitable biological degradability, and on forming, this main matter added the bioactive various trace elements of an amount of promotion.The cooperative effect of these trace element, can promote the biological activity of skeletonization relevant cell, especially in the repair process of bone injury, can promote skeletonization relevant cell propagation, inhibition osteoclast activity remarkable and fast, greatly improve the biological activity of embedded material and promote bone to merge.
Coating of the present invention is not subjected to the influence of host material shape, and have excellent biological safety, good biology describes property and suitable biological degradability, the production of coatings that can be used for the metal or alloy base implantation body material of variform and function is with a wide range of applications in fields such as orthopaedics, dentistry, plastic surgery, the reparations of cranium brain bone.
Description of drawings
Fig. 1 is the small angle X-ray diffraction collection of illustrative plates of the collaborative doping biomimetic calcium phosphate coating of quaternary trace element, (a) curve is not for containing the diffraction roc collection of illustrative plates after organic macromolecule and the bionical electrolyte solution chemical deposition of trace element among the figure, and (b) curve is the diffraction roc collection of illustrative plates that contains after organic macromolecule and the bionical electrolyte solution chemical deposition of trace element.
Fig. 2 is a biomimetic calcium phosphate coating stereoscan photograph, (a) is the surface of metal titanium after the alkali treatment among the figure, (b) for not containing the photo after organic macromolecule and the bionical electrolyte solution chemical deposition of trace element, (c) for containing the photo after organic macromolecule and the bionical electrolyte solution chemical deposition of trace element.
Fig. 3 is the collaborative doping biomimetic calcium phosphate coating x X-ray photoelectron spectroscopy X photo of quaternary trace element.
Fig. 4 is the stereoscan photograph of sour pretreatment and biomimetic calcium phosphate coating.(a) is the surface of metal titanium after the acid treatment among the figure, (b) for not containing the photo after organic macromolecule and the bionical electrolyte solution chemical deposition of trace element, (c) for containing the photo after organic macromolecule and the bionical electrolyte solution chemical deposition of trace element.
Fig. 5 is the collaborative doping biomimetic calcium phosphate coating stereoscan photograph of quaternary trace element.(a) is 37 ℃ of treatment surface among the figure, (b) is 60 ℃ of treatment surface, (c) is 90 ℃ of treatment surface.
Fig. 6 is the collaborative doping biomimetic calcium phosphate coating surface stereoscan photograph (scale is represented 500nm among the figure) of ternary trace element.
The specific embodiment
Further illustrate the present invention below in conjunction with example, but these examples do not limit the scope of the invention, all technology that realizes based on foregoing of the present invention and the material of preparation all belong to protection scope of the present invention.Reagent purity that embodiment uses all is not less than its analytical reagent purity index.
Embodiment 1
1) with the multi-disc metal titanium sheet (long * as widely to be: 10mm * 10mm) be dipped in the NaOH solution of 6mmol/L, and keeping 24 hours 60 ℃ of water-baths, take out the titanium sheet then, with deionized water and washing with alcohol number time, dry under the room temperature, standby.
2) preparation contains Na
+, 142mmol/L; K
+, 5mmol/L; Ca
2+, 2.5mmol/L; Mg
2+, 1.5mmol/L; SO
4 2-, 1mmol/L; HPO
4 2-, 1mmol/L; Cl
-, 163mmol/L and HCO
3 -, the simulated body fluid pH of the 1.0L of 4mmol/L is 7.4, five equilibrium is labeled as A and B respectively in the clean seed bottle of two 500ml.Under stirring condition, in above-mentioned A bottle solution, add Na
2SiO
3, Zn (NO
3)
2And Sr (NO
3)
2Solution.The mol ratio of control Sr: Ca, Si: Ca and Zn: Ca was respectively 3: 100,6: 100 and 0.8: 100, added poly-aspartate again in above-mentioned solution, and the concentration of control organic macromolecule is 20 μ M, and regulated pH value to 7.4; B bottle solution does not add any other ion, and is standby.
3) will be set by step 1) titanium sheet after handling is dipped in step 2 respectively) A and B bottle solution in, put into the saturated steam system, be warmed up to 120 ℃, heat treatment 200 minutes, natural cooling takes out the titanium sheet then, with deionized water and washing with alcohol number time, dries.As shown in Figure 1, the Titanium surface is difficult to detect synthos through not containing after the bionical solution chemistry deposition processes of organic macromolecule on the XRD figure spectrum, but the XRD figure spectrum turns out to be synthos after containing the bionical solution chemistry deposition processes of organic macromolecule; As shown in Figure 2, the Titanium surface forms sedimentary deposit after containing the bionical solution chemistry deposition processes of organic macromolecule; Do not contain organic high molecular bionical electrolyte solution chemical deposition and handle the back and form the almost spherical granule, and skewness, show that organic high score can regulate the uniformity that sedimentary deposit distributes.As shown in Figure 3, coating surface is made up of inorganic bioactivity ions such as calcium, phosphorus, zinc, strontium, silicon, magnesium.
Embodiment 2
Preparation method is with embodiment 1, and the metal titanium sheet that different is in the step 1) is carried out the hydrochloric acid pretreatment of 1.5mmol/L, to investigate the influence of different titanium sheet processing methods to coating.The acid treatment method is: metal titanium sheet is dipped in the 1.5mmol/L HCl solution soaked 4 minutes, and reuse deionized water and washing with alcohol, all the other are handled with embodiment 1.As shown in Figure 4, the Titanium surface forms sedimentary deposit after bionical solution chemistry deposition processes.
Embodiment 3
Preparation method is with embodiment 1, different is controlled step 2) in the mol ratio of Sr: Ca, Si: Ca and Zn: Ca be respectively 10: 100,8: 100 and 1.2: 100, with the solution five equilibrium in the clean clean seed bottle of 4 250ml, be labeled as A, B, C and D, the titanium sheet is immersed in the solution, the A bottle places 37,60 and 90 ℃ of water-baths 4 hours respectively, takes out then, washs and dries.As shown in Figure 5, the Titanium surface forms sedimentary deposit uniformity and thickness and raises along with treatment temperature and increase after bionical solution chemistry deposition processes.
Embodiment 4
Preparation method is with embodiment 1, and different is controlled step 2) the middle Na that adds
2SiO
3And Zn (NO
3)
2, the mol ratio of Si: Ca and Zn: Ca was respectively 6: 100 and 0.8: 100.The titanium sheet is immersed in the A solution, puts into the wet method disinfection system, be warmed up to 90 ℃, reaction aging is natural cooling after 6 hours, takes out the titanium sheet, cleans several times with distilled water, and is with after the ethanol flushing, dry under the room temperature then.As shown in Figure 6, Titanium surface chemistry formation of deposits uniform coating shows that calcium phosphate coating forms.
Claims (7)
1. artificial growth surface biomimetic coating material that short bone merges, it is characterized in that it forms by containing in silicon, strontium, zinc and the magnesium the collaborative adulterated synthos of two kinds of trace element and organic macromolecule at least, the mass percent content that its component is represented with oxide form is:
CaO 42～52.5％；
P
2O
5 38～45.5％；
SiO
2 0～3.0％；
SrO 0～3.0％；
ZnO 0～3.0％；
MgO 0～4.5％；
Organic macromolecule 0.001～8.0%
The said components sum is 100%, and SiO
2, ZnO, MgO and at least two kinds of materials of SrO are not 0 simultaneously.
2. prepare the method for the artificial growth surface biomimetic coating material of the described short bone fusion of claim 1, may further comprise the steps:
1) use acetone, ethanol and washed with de-ionized water clean successively the artificial growth body, soak pretreatment with the acid of 0.001～1.5mmol/L or the alkali of 1～8mmol/L then, reuse ethanol and washed with de-ionized water are clean, dry, and be standby;
2) manually prepare simulated body fluid by inorganic ions concentration dose in the human plasma, the concentration of each inorganic ions is respectively Na in the solution
+, 142mmol/L; K
+, 5mmol/L; Ca
2+, 2.5mmol/L; Mg
2+, 1.5mmol/L; SO
4 2-, 1mmol/L; HPO
4 2-, 1mmol/L; Cl
-, 163mmol/L and HCO
3 -, 4mmol/L; The pH value of solution is 7.25～7.40.In above-mentioned solution, add under the stirring condition and contain SiO
3 2-, Zn
2+And Sr
2+Inorganic salt solution, and Si in the control solution: the P mol ratio is 0～10: 100, Zn: the Ca mol ratio is 0～1.2: 100 and Sr: the Ca mol ratio is 0～10: 100, and SiO
3 2-, Zn
2+And Sr
2+At least two kinds of ions are not 0 simultaneously, add carboxylic organic macromolecule again in above-mentioned solution, or add the organic macromolecule that contains carboxyl and amino, and the concentration of control organic macromolecule is 0～50mmol/L, stirs;
3) the pretreated artificial growth body of step 1) is soaked the end in set by step 2) in the mixed solution of preparation, be warmed up to 35～150 ℃ and be incubated ageing 30～1200 minutes, take out the artificial growth body and use deionized water wash, drying obtains containing the biological activity bionic coating material that strontium, zinc, magnesium, silicon and organic macromolecule are worked in coordination with doping phosphoric acid calcium.
3. the preparation method of the artificial growth surface biomimetic coating material that short bone according to claim 2 merges is characterized in that the said SiO that contains
3 2-Inorganic salt be Na
2SiO
3
4. the preparation method of the artificial growth surface biomimetic coating material that short bone according to claim 2 merges is characterized in that the said Sr of containing
2+Inorganic salt is SrCl
2, Sr (NO
3)
2And Sr (CH
3COO)
2In one or more mixture.
5. the preparation method of the artificial growth surface biomimetic coating material that short bone according to claim 2 merges is characterized in that the said Zn of containing
2+Inorganic salt is ZnCl
2, Zn (NO
3)
2, Zn (CH
3COO)
2And ZnSO
4In one or more mixture.
6. the preparation method of the artificial growth surface biomimetic coating material that short bone according to claim 2 merges is characterized in that said carboxylic organic macromolecule is a kind of or both mixture in polypropylene acid, the polyglycolic acid; The organic macromolecule that contains carboxyl and amino is one or more mixture in poly-aspartate, polyacrylamide and the polylysine.
7. the application of artificial growth surface biomimetic coating material in treatment bone injury or disappearance of the described short bone fusion of claim 1.
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| CN103550825A (en) * | 2013-11-01 | 2014-02-05 | 南昌航空大学 | Method for preparing hydroxyapatite film on surface of medical titanium alloy |
| CN103933607A (en) * | 2014-04-17 | 2014-07-23 | 天津大学 | Preparation method of organic strontium coating on surface of TC4 titanium alloy |
| CN103933607B (en) * | 2014-04-17 | 2015-08-05 | 天津大学 | The preparation method of the organic strontium coating of TC4 titanium alloy surface |
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| CN111012949B (en) * | 2019-12-31 | 2022-05-31 | 山东第一医科大学(山东省医学科学院) | Preparation method of zinc ion-containing tissue engineering scaffold with anti-inflammatory function |
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| CN112076348B (en) * | 2020-07-22 | 2021-09-24 | 浙江大学 | Medical metal surface anti-infection and osseointegration promotion coating, preparation method and application |
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