CN104645413B - A kind of dentistry implant and preparation method thereof - Google Patents

A kind of dentistry implant and preparation method thereof Download PDF

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CN104645413B
CN104645413B CN201510016985.1A CN201510016985A CN104645413B CN 104645413 B CN104645413 B CN 104645413B CN 201510016985 A CN201510016985 A CN 201510016985A CN 104645413 B CN104645413 B CN 104645413B
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cobalt
dentistry implant
loaded
implant
cobalt element
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CN104645413A (en
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赵领洲
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Fourth Military Medical University FMMU
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Abstract

The present invention relates to a kind of dentistry implant and preparation method thereof, involved dentistry implant is the anodized coating with nanotopography, nanotube coatings is loaded with efficiently facilitates blood vessel differentiation material cobalt element, involved method includes that the dentistry implant matrix by outer surface is Nano tube array of titanium dioxide coating is immersed in containing in cobalt acetate solution, under suitable reaction condition, cobalt element is loaded on nanotube coatings, it is thus achieved that be loaded with the dentistry implant of cobalt element.The present invention uses hydrothermal crystallization technique that load cobalt mixture is loaded into anodized coating, carry outside in cobalt mixture hydrothermal crystallization thing may be uniformly distributed in the hole of anodized coating and hole, will not come off easily because of External Force Acting, and the nanotopography of anodized coating will not be changed egregiously.

Description

A kind of dentistry implant and preparation method thereof
Technical field
The present invention relates to dentistry implant material, particularly to a kind of dentistry implant being loaded with cobalt element and Preparation method.
Background technology
Along with planting technology develops, dentistry implant is widely used to defect of dentition and the disappearance patient of clinic Reparation.But titanium or titanium alloy is after implanting in bone, it is possible that the bad bone of bone regeneration around implant In conjunction with, ultimately result in the failure that implantation body implants.Implant necessarily also results in during implanting osseous tissue The destruction of osseous tissue, this destruction includes the successional destruction of bone, hemorrhage, can approximate and be interpreted as a kind of people For the fracture manufactured, the osseous tissue that " fracture " is occurred together afterwards heals, the formation of defect area area of new bone will be straight Connecing and affect implantation body and osseointegration intensity, this process is affected by various factors, including osteoblastic work Property, the pattern of implantation body, blood supply etc..Wherein blood supply for bone regeneration around implant sclerotin healing, Bone remodeling has critically important impact, and the good blood supply of bone regeneration around implant both can be to damage field supply Oxygen, various nutrient substance, can also get rid of the metabolic waste of tissue simultaneously in time.So it is contemplated that carrying High implantation body is implanted to power from promoting that skeletonization is started with in terms of promoting into blood vessel two.Now, in order to promote office Portion's skeletonization, existing multiple implant surface pattern occurs and is applied to clinic, mainly use anodic oxidation, The technology such as the slurry spraying of differential arc oxidation, titanium or sandblasting acid etching are to improve implant surface pattern.Anodic oxidation conduct The implant surface treatment technology of one of which comparative maturity is in wide clinical application, and its implant surface has There is nano tubular structure, synosteosis speed can be improved.
In order to improve into vessel patency, have been reported now and mainly facilitate the blood vessel differentiation factor to be loaded into plantation The scientific research report of surface, mainly has the vascular endothelial cell factor (VEGF), oxygen deficient induction factor 1 (HIF-1 α) etc..But when there is activity reduction, release of cytokines after cytokine is transformed in various degree in said method Between shorter, can not more persistently promote into the problems such as blood vessel.Its a kind of loading method is by VEGF (blood Endothelial cell somatomedin) load in poly-dopamine coating, and it is wrapped in pure titanium surface.Another kind side Method, it is simply that implantation body's matrix is immersed in biotic factor VEGF.VEGF activity warp in said method Cannot ensure after crossing transformation;Additionally above-mentioned steps is loaded down with trivial details, it is necessary first to use multi-step preparation more unstable Coatings etc., then could load after mixing with the albumen such as VEGF;The most above-mentioned loading method can not be simultaneously Promote titanium surface osteogenetic process, do not consider simultaneously other somatomedin for Osseointegrated implants with become blood vessel Facilitation.Cobalt element has been widely studied the generation of induction ischaemia environment, then promotes HIF-1 α, produces the change of a series of adaptation anaerobic environment then, including promoting local environment new vessels Generate.
Summary of the invention
It is an object of the present invention to provide a kind of dentistry implant, this dentistry implant is for having nanometer shape The anodized coating of looks, nanotube coatings is loaded with efficiently facilitates blood vessel differentiation material cobalt element, cobalt unit Element has been proved to induce local cells to secrete HIF-1 α, thus inducing cell is to anoxia ring further The adaptation in border, including the generation promoting local new vessels.The present invention can improve bone more rapidly Promote while association rate that local becomes vascular process, thus improve synestotic quality.
Further object is that the preparation method that above-mentioned dentistry implant is provided.
The method provided includes: by the dentistry implant base that outer surface is Nano tube array of titanium dioxide coating Body is immersed in containing in cobalt acetate solution, under suitable reaction condition, cobalt element is loaded into nanotube and is coated with On layer, it is thus achieved that be loaded with the dentistry implant of cobalt element.
Further, the preparation method of the present invention includes:
Step 1, is immersed in dress by the dentistry implant matrix that outer surface is Nano tube array of titanium dioxide coating It is loaded with in the politef High Temperature High Pressure hydro-thermal still of cobalt acetate solution;
Step 2, is placed in the politef High Temperature High Pressure hydro-thermal still of step 1 in low-temperature sintering stove, uses Cobalt element is loaded on nanotube coatings by hydrothermal crystallisation methods, it is thus achieved that be loaded with the dentistry implant of cobalt element.
Optionally, in described cobalt acetate solution, cobaltous acetate concentration is 0.01-0.1M.
Optionally, described hydrothermal crystallisation methods temperature is 200 DEG C, and heating rate is 5-10 DEG C/min, packing density Being 40%, the hydrothermal crystallization time is 1-3h.
The dentistry implant of the present invention, uses anode oxidation process to have in implantation body's outer surface of matrix preparation and receives The anodized coating of mitron pattern, nanotopography is tubular structure, and aperture is nanoscale;Employing hydro-thermal is tied Load cobalt mixture is loaded into anodized coating by brilliant technique, and carrying cobalt mixture hydrothermal crystallization thing can uniformly divide In being distributed in the hole of anodized coating and outside hole, will not come off easily because of External Force Acting, and will not be excessive Ground changes the nanotopography of anodized coating.
Accompanying drawing explanation
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is scanning electron microscope (SEM) the photo figure of dentistry implant anodizing morphology, wherein (a) For not carrying the anodizing morphology figure of cobalt element;B () is the anodizing morphology figure after loading cobalt element 3h.
Fig. 2 is the Energy Dispersive X-ray detector that dentistry implant anodizing morphology carries cobalt element (EDX) figure, wherein (a) is the EDX energy spectrogram not carrying cobalt element;B () is for loading cobalt element 3h After EDX can spectrogram;
Fig. 3 is to cultivate cell scanning electron microscope after 7 days after dentistry implant anodizing morphology carries cobalt element (SEM) photo figure;
Fig. 4 is that reverse transcription was passed through after 14 days in different disposal surface cultivation Rat Mesenchymal Stem Cells (MSCs) The block diagram of blood vessel gene expression is correlated with in quantitative PCR (qRT-PCR) detection, and wherein CP is cell training Supporting plate surface, PT is polishing pure titanium pure titanium surface, and NT is the titanium plantation not loading cobalt element after anodic oxidation Surface, NT-Co is the titanium implant surface loading cobalt element after anodic oxidation;Wherein (a) is HIF-1 The expression of α gene;B () is the expression of VEGF gene;## represents poor compared to CP group Opposite sex p < 0.01.
Detailed description of the invention
Although the healing after the implantation of implantation body depend heavilys on the foundation of blood vessel network, but conventional literary composition Chapter more attention is implantation body's different-shape and the load impact on the osteogenetic process of surrounding, good Vascularization itself can play the healing accelerating bone regeneration around implant to realize the best bone union process Effect because bone itself is the tissue of a kind of very vascular, it is highly dependent on the supply of blood, blood Liquid can bring nutrient substance, takes away the refuse that metabolism produces simultaneously, this process with angiopoietic how much, The distance etc. of blood vessel and tissue distance has direct relation.If the nearest blood vessel distance of tissue distance exceedes 150 μm-200 μm (oxygen and the limit of diffusion of nutrient substance) will be unable to ensure to obtain enough nutrition, So being necessary for freshman bone tissue's new vessels.
The critically important mechanism of the promotion vascularization function of cobalt is exactly that the anaerobic environment of cobalt induction makes HIF-1 alpha molecule Raising, the existence of cobalt can cause cell peripheral to form the environment of hypoxia inducible.Hypoxia inducible factor passes through target The expression of gene enhances the cell toleration to oxygen deprivation stress, and the HIF-1 α that histology's aspect raises causes Increasing and the reinforcement of local one-tenth blood vessel of erythrocyte yield, and then the supply of local blood is added By force.The HIF-1 α raised in the aspect of individual cells embodies the cell adaptation for anaerobic environment.Cobalt Toxicity mechanism realizes possibly by HIF-1 α.Cobalt ion can directly suppress proline hydroxylase (PHD), oxygen dependence hydroxylase, HIF-α aspartyl hydroxylase (FIH), above-mentioned three kinds of materials The degraded or the activity that all have adjusted HIFs reduce, and the existence of cobalt ion makes HIF degraded reduce, transcriptional activity Strengthen.Therefore, by the suppression to PHD and the FIH-1 hydroxylase activity effect relying on oxygen, hypoxia, cobalt Ion blocks the HIFa degraded of PHD-HIFa-VHL and is combined two paths with p300 with CAD, makes respectively There is quickly reversion in HIF protein content and transcriptional activity.The regulation and control of HIF proteins downstream promote into blood vessel in a large number Gene, cobalt element greatly have stimulated local environment by the path of HIF albumen and produces new vessels.
Titanium surface carry out the formed nano tube structure of anodic oxidation perhaps can preferable simulated in vivo environment, sun The TiO2 nanotube caliber that pole oxidation is formed can be tens by different voltage, different electrolyte quota Change in hundreds of nanometer range, can screen, with this, the size that applicable different tissues combines, owing to cell exists The interface contacted in body is nano level structure, if the basement membrane of various tissues is by 50~200nm Recessed, prominent, the hole of size and fiber composition, the average mineral granularity of woven bone is 10~50nm, lamellar bone by Diameter 2~5nm and the inorganic mineral particles composition of long 20~50nm, organic principle I type main in bone Collagen is the triple helix structure of a width of 0.5nm, a length of 300nm.TiO2Nanotube can analog bone group Knit the size and arrangement of middle collagen fibril, and close with the elastic modelling quantity of osseous tissue, may obtain more preferably Biological activity, so titanium implant surface carry out anodic oxidation formed nano tube structure for implant after bone In conjunction with serving optimum facilitation.
The dentistry implant matrix of the present invention be in prior art use implantation body's matrix, as: use Pure titanium titanium sheet represents the most most commonly seen pure titanium implant system.
The following is the specific embodiment that inventor provides, so that technical scheme to be further explained Bright.
Embodiment 1:
1) select pure titanium to be processed into dentistry implant matrix, after the polishing of dentistry implant matrix surface, use successively Each 5 minutes of acetone, dehydrated alcohol and deionized water ultrasonic cleaning, dry up stand-by;
2) configuration anode oxidation process electrolyte: ethylene glycol is solvent, and solute is 0.5% mass fraction NH4F, the CH of 5% volume fraction3OH, and 5% volume fraction deionized water;
3) anode oxidation process is used to prepare Nano tube array of titanium dioxide coating at implantation body's outer surface of matrix: Graphite carbon rod is negative electrode, and dentistry implant matrix, as anode, puts into the electrolyte of previous step configuration, Concrete technology parameter is: supply frequency 50Hz ± 2Hz, and voltage is 40V, processes time 1h, reaction temperature For room temperature;
4) after prepared by implantation body's matrix surface Nano tube array of titanium dioxide coating, by acetone, anhydrous second Alcohol and deionized water clean each 5min successively;
5) configuration hydrothermal crystallization mother solution: 1g cobaltous acetate powder joins 40ml deionized water, forms 0.1M Cobalt acetate solution, be sufficiently stirred for Glass rod, obtain the hydrothermal crystallization mother solution containing cobalt element;
6) the dentistry implant matrix of anodic oxidation is immersed in the hydrothermal crystallization mother solution containing cobalt element, It is placed in high pressure water heating kettle, tightens lid mouth, water heating kettle is positioned in low-temperature sintering stove heating;Use hydro-thermal Cobalt element is loaded into anodized coating by the method for crystallization, and wherein, temperature is 200 DEG C, and heating rate is 10 DEG C/min, the hydro-thermal time is 1h;Finally lower the temperature at room temperature, stand after taking out dentistry implant, to obtain final product It is loaded with the dentistry implant of cobalt element.
Embodiment 2:
1) select pure titanium to be processed into dentistry implant matrix, after the polishing of dentistry implant matrix surface, use successively Each 5 minutes of acetone, dehydrated alcohol and deionized water ultrasonic cleaning, dry up stand-by;
2) configuration anode oxidation process electrolyte: ethylene glycol is solvent, and solute is 0.5% mass fraction NH4F, the CH of 5% volume fraction3OH, and 5% volume fraction deionized water;
3) anode oxidation process is used to prepare Nano tube array of titanium dioxide coating at implantation body's outer surface of matrix: Graphite carbon rod is negative electrode, and dentistry implant matrix, as anode, puts into the electrolyte of previous step configuration, Concrete technology parameter is: supply frequency 50Hz ± 2Hz, and voltage is 40V, processes time 1h, reaction temperature For room temperature;
4) after prepared by implantation body's matrix surface Nano tube array of titanium dioxide coating, by acetone, anhydrous second Alcohol and deionized water clean each 5min successively;
5) configuration hydrothermal crystallization mother solution: 1g cobaltous acetate powder joins 40ml deionized water, forms 0.1M Cobalt acetate solution, be sufficiently stirred for Glass rod, obtain the hydrothermal crystallization mother solution containing cobalt element;
6) the dentistry implant matrix of anodic oxidation is immersed in the hydrothermal crystallization mother solution containing cobalt element, It is placed in high pressure water heating kettle, tightens and withdraw the previous remark, water heating kettle is positioned in low-temperature sintering stove heating;Use hydro-thermal Cobalt element is loaded into anodized coating by the method for crystallization, and wherein, temperature is 200 DEG C, and heating rate is 10 DEG C/min, the hydro-thermal time is 2h;Finally lower the temperature at room temperature, stand, i.e. after taking out dentistry implant The dentistry implant of cobalt element must be loaded with.
Embodiment 3:
1) select pure titanium to be processed into dentistry implant matrix, after the polishing of dentistry implant matrix surface, use successively Each 5 minutes of acetone, dehydrated alcohol and deionized water ultrasonic cleaning, dry up stand-by;
2) configuration anode oxidation process electrolyte: ethylene glycol is solvent, and solute is 0.5% mass fraction NH4F, the CH of 5% volume fraction3OH, and 5% volume fraction deionized water;
3) anode oxidation process is used to prepare Nano tube array of titanium dioxide coating at implantation body's outer surface of matrix: Graphite carbon rod is negative electrode, and dentistry implant matrix, as anode, puts into the electrolyte of previous step configuration, Concrete technology parameter is: supply frequency 50Hz ± 2Hz, and voltage is 40V, processes time 1h, reaction temperature For room temperature;
4) after prepared by implantation body's matrix surface Nano tube array of titanium dioxide coating, by acetone, anhydrous second Alcohol and deionized water clean each 5min successively;
5) configuration hydrothermal crystallization mother solution: 1g cobaltous acetate powder joins 40ml deionized water, forms 0.1M Cobalt acetate solution, be sufficiently stirred for Glass rod, obtain the hydrothermal crystallization mother solution containing cobalt element;
6) the dentistry implant matrix of anodic oxidation is immersed in the hydrothermal crystallization mother solution containing cobalt element, It is placed in high pressure water heating kettle, tightens lid mouth, water heating kettle is positioned in low-temperature sintering stove heating;Use hydro-thermal Cobalt element is loaded into anodized coating by the method for crystallization, and wherein, temperature is 200 DEG C, and heating rate is 10 DEG C/min, the hydro-thermal time is 3h;Finally lower the temperature at room temperature, stand, i.e. after taking out dentistry implant The dentistry implant of cobalt element must be loaded with.
With the dentistry implant being loaded with cobalt element of embodiment 3 preparation, and combine relevant drawings to the present invention It is further described.With reference to Fig. 1, for pattern before and after implantation body's matrix anode oxidized surface loading cobalt element Surface sweeping Electronic Speculum (SEM) photo, comparison diagram 1 (a) does not carries the microscopic appearance before cobalt element, it is seen that figure 1 (b), after hydro-thermal loads, nanostructured surface covers one layer of cobalt granule.Fig. 2 is implantation body's matrix sun Energy Dispersive X-ray (EDX) the energy spectrogram of pattern before and after the oxidized surface loading cobalt element of pole, from figure Can be seen that anodised implant surface goes out for cobalt element peak value really after cobalt element hydro-thermal loads Existing, it was demonstrated that cobalt element is deposited on implant surface.Fig. 3 loads the implant surface after cobalt element cultivate Mescenchymal stem cell scanning electron microscopic picture after 7 days, it is seen that load unobvious to cellularity shadow after cobalt element Ring, cell can normally in material surface field planting, sprawl.Fig. 4 contrasts the thin of different disposal front and rear surfaces Born of the same parents HIF-1 α and the expression of VEGF gene.Tissue Culture Plate surface (CP), pure titanium surface (PT), receive HIF-1 α with VEGF of rice array topographical surface cell is correlated with into the expression of blood vessel gene does not has notable difference Property, and after loading cobalt element, the HIF-1 α of titanium implant and the expression of VEGF related gene are substantially raised. Illustrate loading titanium implant after cobalt element for the HIF-1 α of superficial cell and VEGF related gene Expression has obvious facilitation.This heals for rear osseous tissue during implant implantation osseous tissue, lacks The formation damaging region area of new bone has directly impact.It is first herein and is loaded by implant surface inorganic Metallic element and realize facilitating the titanium implant of blood vessel purpose.
Other embodiments prepare dentistry implant, have similar results.After i.e. cobalt element hydro-thermal loads, anodic oxygen The nanostructured surface changed has one layer of cobalt granule still to remain with complete nano tube structure while of covering, and truly has The deposition of cobalt element.After loading cobalt element, titanium implant is relevant for HIF-1 α with VEGF of superficial cell The expression becoming blood vessel gene has obvious facilitation.

Claims (3)

1. the preparation method of a dentistry implant, it is characterised in that method includes:
Step 1, is immersed in dress by the dentistry implant matrix that outer surface is Nano tube array of titanium dioxide coating It is loaded with in the politef High Temperature High Pressure hydro-thermal still of cobalt acetate solution;
Step 2, is placed in the politef High Temperature High Pressure hydro-thermal still of step 1 in low-temperature sintering stove, uses Cobalt element is loaded on nanotube coatings by hydrothermal crystallisation methods, it is thus achieved that be loaded with the dentistry implant of cobalt element.
2. the preparation method of dentistry implant as claimed in claim 1, it is characterised in that described acetic acid In cobalt liquor, cobaltous acetate concentration is 0.01-0.1M.
3. the preparation method of dentistry implant as claimed in claim 1, it is characterised in that described hydro-thermal Crystallization process temperature is 200 DEG C, and heating rate is 5-10 DEG C/min, and packing density is 40%, the hydrothermal crystallization time For 1-3h.
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CN105597157B (en) * 2015-12-28 2018-07-27 周建宏 One kind can promote vascularization and anti-infection bio active coating and its preparation method and application
CN107019571A (en) * 2017-06-02 2017-08-08 南方医科大学 A kind of method that selective laser melting prepares dentistry implant
CN109692051A (en) * 2018-12-12 2019-04-30 佛山市安齿生物科技有限公司 A kind of cobalt carried titanium dioxide film layer and preparation method thereof
CN113186579B (en) * 2021-04-20 2024-02-27 北京科技大学 Titanium alloy oral cavity restoration surface whitening self-cleaning coating and preparation method thereof

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