CN109432493A - Porous titanium framework of nano hydroxyapatite coating and its preparation method and application - Google Patents
Porous titanium framework of nano hydroxyapatite coating and its preparation method and application Download PDFInfo
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- CN109432493A CN109432493A CN201811118085.8A CN201811118085A CN109432493A CN 109432493 A CN109432493 A CN 109432493A CN 201811118085 A CN201811118085 A CN 201811118085A CN 109432493 A CN109432493 A CN 109432493A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The present invention relates to technical field of biomedical materials, and in particular to a kind of porous titanium framework of nano hydroxyapatite coating and its preparation method and application.The porous titanium framework of nano hydroxyapatite coating provided by the invention, including 3D printing POROUS TITANIUM base material and nano hydroxyapatite coating；The 3D printing POROUS TITANIUM substrate material surface forms microporous network TiO2Layer；The nano hydroxyapatite coating is evenly distributed on the microporous network TiO2Layer surface.The invention also discloses a kind of preparation method of the porous titanium framework of nano hydroxyapatite coating and its applications in the preparation of bone tumour surgical defect repair materials.The porous titanium framework of nano hydroxyapatite coating provided by the invention not only has good skeletonization effect, but also can inhibit local residual tumor cells growth, reduces recurrence, shows good potential applicability in clinical practice.
Description
Technical field
The present invention relates to technical field of biomedical materials, and in particular to a kind of nano hydroxyapatite coating POROUS TITANIUM branch
Frame and its preparation method and application.
Background technique
Bone tumour is to betide the tumour of bone and its affiliated group, there is benign and malignant, the easy root of benign bone tumour
It controls, prognosis bona, malignant bone tumor is quickly grown, and prognosis is bad, and the death rate is high.Malignant bone tumor is divided into primary and secondary
Property, the reconstruction and inhibition Local neoplasm recurrence of the secondary postoperative segmental defect of malignant bone tumor are clinical one faced
Big important problem.
Operation excision at present is the main means for treating bone tumour, due to the progress of embolic chemotherapy, some scholars in recent years
Take to the work in terms of tumor resection or full distal femoral resection, manually prosthetic replacement, take limb preservation " part is extensively
Excision plus reconstruction " is aided with the measure of chemotherapy, eradicates to bone tumour disease.The reparation of the postoperative segmental defect of bone tumour
Local neoplasm recurrence is rebuild and inhibited, is the clinical a great problem faced.Titanium-based implant obtains in clinical load Bone Defect Repari
It is widely applied, the adjustable mechanical property of POROUS TITANIUM not only makes it that can effectively prevent bone tissue caused by implant stress shielding
It absorbs, and its surface modification appropriate can assign its excellent osteoinductive, promote the repair and reconstruction of bone defect.Nano HA
Particle can promote osteoblastic proliferation, while having good apoptosis or inhibiting tumor cell proliferation effect.Research and development can provide i.e.
The Structural bone graft repair materials of effect support are carved with, its antitumor and promoting bone regeneration function is assigned, to raising Patients with Bone Tumor
Long-term survival rate, the postoperative limb function of improvement patient and quality of life, mitigation society and family burden have highly important meaning
Justice.
Chinese patent CN101401976B discloses a kind of preparation method of anti-bone tumor composite bone reconstruction bracket, this method
Chemotherapeutics nanocapsule composite microsphere and nano zircite or calcium phosphate artificial bone frame is compound, Composite Bone reconstruction bracket is made.
The Composite Bone reconstruction bracket shows good resisting bone tumor effect by sustained-release chemotherapy drug.But the change that the bracket uses
Drug methotrexate is treated, is mainly shown as the inhibiting effect to cancer cell, and curative effect is slower.
Medical bio metal surface sedimentary organism active coating can give full play to metal material and bioactive materials
Advantage and one of the hot spot of bone tissue engineer research.The one kind of hydroxyapatite (HA) as calcium phosphate ceramic, its change
It is close with natural bone mineral to learn structure, therefore there is good osteoinductive and osteoconductive, in addition, being uniformly distributed in bone branch
The nano HA particle of frame substrate material surface also has good apoptosis or inhibits tumor cell proliferation effect.Chinese patent
CN103751840B discloses a kind of bone defect repair support with porous controllable low modulus, and the bone defect repair support is by having
There is the titanium alloy bracket of porous controllable low modulus and is applied in the hydroxyapatite coating layer or strontium-doped hydroxyapatite of its surface deposition
Layer composition, although the titanium alloy bracket of the porous controllable low modulus has and has with elasticity modulus similar in natural bone, porous structure
Conducive to growing into for growth factor, blood vessel and freshman bone tissue, bone-material interface stress problem is efficiently solved, is had than causing
The better mechanical compatibility of close material and Bone Ingrowth ability.But the bracket does not solve office caused by cells of tumorous bone residual
Portion's tumor recurrence problem.
Currently, bone tumour disease is relatively conventional, the prior art is in tumor post-operation defect repair speed and residual tumor cells
Application in terms of apoptosis is also less, becomes a direction of bone tumour repair materials research and development.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of porous titanium framework of nano hydroxyapatite coating and its systems
Preparation Method and application.The nano hydroxyapatite coating of the porous titanium framework of nano hydroxyapatite coating provided by the invention uses
Nanometer hydroxyapatite particle can not only promote osteoblastic proliferation, also have apoptotic tumor cell or inhibit tumour cell
The effect of proliferation achievees the effect that good apoptosis cancer cell, inhibits tumour growth and promoting bone regeneration, therefore, shows good
Application prospect.
The technical scheme is that
The present invention provides a kind of porous titanium frameworks of nano hydroxyapatite coating, including 3D printing POROUS TITANIUM base material
And nano hydroxyapatite coating；The 3D printing POROUS TITANIUM base material is by the certainly outer macropore group that aperture reduces step by step inwards
At；The microporous network TiO that the 3D printing POROUS TITANIUM substrate material surface is formed with a thickness of 0.5-2.0 μm2Layer；The nanometer hydroxyl
Base apatite coating is uniformly distributed in the microporous network TiO2Layer surface.
Further, the certainly outer macroporous structure that aperture reduces step by step inwards of the 3D printing POROUS TITANIUM base material is cube
One or more of body porous element, octahedra porous element, diamond point array element, spiral tetrahexahedron unit；Institute
The average pore size for stating 3D printing POROUS TITANIUM base material from the outer macropore that aperture reduces step by step inwards is 300-800 μm.
Further, the porosity of the 3D printing POROUS TITANIUM base material is 60-90%, compression strength 60-
120MPa, elasticity modulus 0.5-5.0GPa.
Further, the nano hydroxyapatite coating is made of nanometer hydroxyapatite particle；The nano-hydroxy
Apatite coating with a thickness of 20-100 μm.
Further, the crystallite pattern of the nanometer hydroxyapatite particle is one of subsphaeroidal, needle-shaped or rodlike
Or it is several.
Further, crystallinity successively reduces the nano hydroxyapatite coating from inside to outside, and binding force gradually weakens.
The present invention also provides a kind of preparation methods of the porous titanium framework of nano hydroxyapatite coating, including following step
It is rapid:
S1, POROUS TITANIUM base material is made using metal 3D printing technique；
S2, soda acid or thermokalite heat treatment are carried out to POROUS TITANIUM base material made from step S1, in its hole wall and Skeleton Table
The nanometer level microporous network TiO that face is formed with a thickness of 0.5-2.0 μm2Layer, is made nanometer level microporous network TiO2The porous titanium substrate of layer
Material；
S3, nanometer hydroxyapatite particle slurry is prepared using wet chemistry method, polyethylene glycol or polyvinyl alcohol high score is added
Subtemplate, and combine hydro-thermal process regulation nano-complex particle crystallite pattern be it is subsphaeroidal, needle-shaped or rodlike, obtain a nanometer hydroxyl
Base apatite coating slurry；
S4, H is added into nano hydroxyapatite coating slurry made from step S32O2And methylcellulose, it is placed in microwave
Foamable is assisted in furnace, and intumescent coating slurry is made；
S5, by nanometer level microporous network TiO made from step S22Layer POROUS TITANIUM base material is soaked by Fruit storage
It submerges in intumescent coating slurry made from step S4, is ultrasonically treated, coating paste foaming to be foamed is abundant and is packed into nanoscale
Microporous network TiO2It is taken out after layer POROUS TITANIUM base material internal void, 80 DEG C of drying in baking oven, in setting temperature in Muffle furnace
Degree lower heat treatment 1-2 hours；
S6, operation 3-5 times for repeating step S5, heat treatment temperature is successively from 600 DEG C, 500 DEG C, 400 DEG C, 300 DEG C, 150
It DEG C gradually decreases, obtaining coating layer thickness is 20-100 μm, the nanometer that crystallinity successively reduces, binding force gradually weakens from inside to outside
Hydroxyapatite coating layer POROUS TITANIUM timbering material；
S7, by nano hydroxyapatite coating POROUS TITANIUM timbering material made from step S6 be packaged sterilizing to get.
Further, the porous titanium framework of the nano hydroxyapatite coating answering in preparation bone tumour repair materials
With.
Further, the step S1 POROUS TITANIUM base material the preparation method comprises the following steps:
(1) CT image is imported into reverse engineering softwares, the three-dimensional reconstructions such as Mimics, simpleware and obtains targeted bony tissue
3-D image, average hole post is 100-1000 μm, average pore size is 300-800 μm, with cube porous element, octahedra more
Hole unit, the filling of spiral tetrahexahedron unit, extends the image at diamond point array element, obtains personalized porous connection
Three-dimensional digital model.
(2) 3D printer is used, the porous connection 3-dimensional digital using pure titanium or Titanium Powder as raw material, according to (1) design
Model prints porous titanium framework.
Further, it is found through antitumor test, compared with the control group, nano hydroxyapatite coating prepared by the present invention
Porous titanium framework can significantly inhibit growth of tumour cell, have preferable apoptosis of tumor cells effect, illustrate offer of the present invention
Nanometer hydroxyapatite particle play the role of apoptotic tumor cell.
It is found through cytotoxicity experiment, compared with the control group, nano hydroxyapatite coating POROUS TITANIUM prepared by the present invention
Bracket, without apparent inhibited proliferation, shows that nano hydroxyapatite coating provided by the invention can be to normal to normal cell
Cytotoxic side effect.
Compared with prior art, present invention has the advantage that
(1) nanometer hydroxyapatite particle provided by the invention has good apoptosis cancer cell, tumour is inhibited to increase
With the function of promoting bone regeneration；
(2) nano hydroxyapatite coating provided by the invention, crystallinity successively reduces from inside to outside, binding force gradually subtracts
It is weak, it has no toxic side effect to normal cell；
(3) it is porous to carry out appropriate modified nano hydroxyapatite coating obtained to POROUS TITANIUM substrate material surface by the present invention
Titanium framework has excellent promoting bone regeneration performance, can promote the repair and reconstruction of bone defect.
Detailed description of the invention
Fig. 1 is nanometer hydroxyapatite SR test figure；
Fig. 2 is bone tumour volume change figure.
Specific embodiment
The specific embodiment of form by the following examples makees further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiment.
The porous titanium framework of embodiment 1, nano hydroxyapatite coating
The preparation of S1, POROUS TITANIUM base material
(1) CT image is imported into simpleware three-dimensional imaging software, obtains the 3-D image of targeted bony tissue, average hole
Column is 500 μm, average pore size is 300 μm, with the filling of cube porous element, extends the image, obtains personalized porous company
Logical three-dimensional digital model；
(2) 3D printer is used, the porous connection three-dimensional digital model using titanium alloy as raw material, according to step (1) design
Print porous titanium alloy bracket；
S2, soda acid processing is carried out to POROUS TITANIUM base material made from step S1, it is standby thick in its hole wall and Skeleton Table wheat flour
The nanometer level microporous network TiO that degree is 0.5 μm2Layer, is made nanometer level microporous network TiO2Layer POROUS TITANIUM base material；
S3, nanometer hydroxyapatite particle slurry is prepared using wet chemistry method, high-molecular polyvinyl alcohol template is added, and tie
Heshui heat treatment regulation nano-complex particle crystallite pattern be it is needle-shaped, obtain nano hydroxyapatite coating slurry；
S4, H is added into nano hydroxyapatite coating slurry made from step S32O2And methylcellulose, it is placed in microwave
Foamable is assisted in furnace, and intumescent coating slurry is made；
S5, by nanometer level microporous network TiO made from step S22Layer POROUS TITANIUM base material is soaked by Fruit storage
It submerges in intumescent coating slurry made from step S4, is ultrasonically treated, coating paste foaming to be foamed is abundant and is packed into nanoscale
Microporous network TiO2It is taken out after layer POROUS TITANIUM base material internal void, 80 DEG C of drying in baking oven, in setting temperature in Muffle furnace
Degree lower heat treatment 1 hour；
S6, operation 3 times for repeating step S5, heat treatment temperature is successively gradually decreased from 600 DEG C, 400 DEG C, 150 DEG C, is obtained
The nano hydroxyapatite coating that coating layer thickness is 20 μm, crystallinity successively reduces, binding force gradually weakens from inside to outside is porous
Titanium framework material；
S7, by nano hydroxyapatite coating POROUS TITANIUM timbering material made from step S6 be packaged sterilizing to get.
The porous titanium framework of embodiment 2, nano hydroxyapatite coating
The preparation of S1, POROUS TITANIUM base material
(1) CT image is imported into simpleware three-dimensional imaging software, obtains the 3-D image of targeted bony tissue, average hole
Column is 600 μm, average pore size is 800 μm, with octahedra porous unit filling, extends the image, obtains personalized porous company
Logical three-dimensional digital model；
(2) 3D printer is used, using titanium alloy as raw material, prints porous titanium alloy bracket according to designing a model；
S2, alkali heat-treatment is carried out to POROUS TITANIUM base material made from step S1, forms thickness in its hole wall and skeleton surface
The nanometer level microporous network TiO that degree is 2.0 μm2Layer, is made nanometer level microporous network TiO2Layer POROUS TITANIUM base material；
S3, nanometer hydroxyapatite particle slurry is prepared using wet chemistry method, polyethylene glycol polymer template is added, and tie
Heshui heat treatment regulation nano-complex particle crystallite pattern be it is subsphaeroidal, obtain nano hydroxyapatite coating slurry；
S4, H is added into nano hydroxyapatite coating slurry made from step S32O2And methylcellulose, it is placed in microwave
Foamable is assisted in furnace, and intumescent coating slurry is made；
S5, by nanometer level microporous network TiO made from step S22Layer POROUS TITANIUM base material is soaked by Fruit storage
It submerges in intumescent coating slurry made from step S4, is ultrasonically treated, coating paste foaming to be foamed is abundant and is packed into nanoscale
Microporous network TiO2It is taken out after layer POROUS TITANIUM base material internal void, 80 DEG C of drying in baking oven, in setting temperature in Muffle furnace
Degree lower heat treatment 2 hours；
S6, operation 5 times for repeating step S5, heat treatment temperature is successively from 600 DEG C, 500 DEG C, 400 DEG C, 300 DEG C, 150 DEG C
It gradually decreases, obtaining coating layer thickness is 100 μm, the nano-hydroxy that crystallinity successively reduces, binding force gradually weakens from inside to outside
Apatite coating POROUS TITANIUM timbering material；
S7, by nano hydroxyapatite coating POROUS TITANIUM timbering material made from step S6 be packaged sterilizing to get.
The porous titanium framework of embodiment 3, nano hydroxyapatite coating
The preparation of S1, POROUS TITANIUM base material
(1) CT image is imported into simpleware three-dimensional imaging software, obtains the 3-D image of targeted bony tissue, average hole
Column is 400 μm, average pore size is 600 μm, with the porous unit filling of spiral dodecahedron, extends the image, obtains personalization
Porous connection three-dimensional digital model；
(2) 3D printer is used, using titanium alloy as raw material, prints porous titanium alloy bracket according to designing a model；
S2, soda acid processing is carried out to POROUS TITANIUM base material made from step S1, forms thickness in its hole wall and skeleton surface
The nanometer level microporous network TiO that degree is 1.2 μm2Layer, is made nanometer level microporous network TiO2Layer POROUS TITANIUM base material；
S3, nanometer hydroxyapatite particle slurry is prepared using wet chemistry method, polyethylene glycol polymer template is added, and tie
Heshui heat treatment regulation nano-complex particle crystallite pattern be it is rodlike, obtain nano hydroxyapatite coating slurry；
S4, H is added into nano hydroxyapatite coating slurry made from step S32O2And methylcellulose, it is placed in microwave
Foamable is assisted in furnace, and intumescent coating slurry is made；
S5, by nanometer level microporous network TiO made from step S22Layer POROUS TITANIUM base material is soaked by Fruit storage
It submerges in intumescent coating slurry made from step S4, is ultrasonically treated, coating paste foaming to be foamed is abundant and is packed into nanoscale
Microporous network TiO2It is taken out after layer POROUS TITANIUM base material internal void, 80 DEG C of drying in baking oven, in setting temperature in Muffle furnace
Degree lower heat treatment 1.5 hours；
S6, operation 4 times for repeating step S5, heat treatment temperature is successively gradually dropped from 600 DEG C, 400 DEG C, 300 DEG C, 150 DEG C
It is low, it obtains the nanometer hydroxyapatite that coating layer thickness is 60 μm, crystallinity successively reduces, binding force gradually weakens from inside to outside and applies
Layer POROUS TITANIUM timbering material；
S7, by nano hydroxyapatite coating POROUS TITANIUM timbering material made from step S6 be packaged sterilizing to get.
Comparative example 1, porous titanium alloy bracket
S1, CT image is imported into simpleware three-dimensional imaging software, obtains the 3-D image of targeted bony tissue, average hole
Column is 400 μm, average pore size is 600 μm, with the porous unit filling of spiral dodecahedron, extends the image, obtains personalization
Porous connection three-dimensional digital model；
S2, personalized three dimension of porous connection using 3D printer, using titanium alloy as raw material, according to step S1 design
Word model printing, obtains titanium alloy timbering material；
S3, soda acid processing is carried out to titanium alloy timbering material made from step S1, forms thickness in its hole wall and skeleton surface
The nanometer level microporous network TiO that degree is 1.2 μm2Layer, is made nanometer level microporous network TiO2The porous titanium alloy timbering material of layer；
S4, by porous titanium alloy timbering material made from step S3 be packaged sterilizing to get.
Comparative example 1 and the difference of embodiment 3 are that nano hydroxyapatite coating is not added for comparative example 1.
Test example one, nanometer hydroxyapatite SR test
1, test material: the porous titanium framework of nano hydroxyapatite coating prepared by embodiment 3.
2, test method: precision weighs the weight of the frame of nano hydroxyapatite coating POROUS TITANIUM, is respectively placed in 37 DEG C,
In the buffer solution of pH=6.5 and pH=7.4, the weight of nanometer hydroxyapatite is tested within the set time.
3, test result: test result is as shown in Figure 1.
As shown in Figure 1, the extension of the weight of the porous titanium framework of nano hydroxyapatite coating at any time is gradually reduced, and again
It measures reduced rate to gradually decrease, slow release effect is more preferable when pH=7.4, shows the porous titanium framework of nano hydroxyapatite coating
Nano hydroxyapatite coating has good slow releasing function within the scope of the pH of human normal, and extends at any time, and release is got over
Slowly.
Test example two, antitumor test
1, subjects: choosing 32 kind tumor New Zealand White Rabbit, is provided by Sichuan University's West China Experimental Animal Center.
2, test material: porous titanium framework prepared by embodiment 3 and comparative example 1.
3, test method:
32 New Zealand White Rabbit are randomly divided into 2 groups, every group 16, implantation embodiment 3 and comparative example 1 are prepared more respectively
Hole titanium framework, and it is denoted as 3 groups of embodiment and 1 group of comparative example.Observe two groups of New Zealand White Rabbit bone tumour tissue volume situations of change.
4, test result:
After 3 groups of embodiment, postoperative 2.5 weeks, New Zealand White Rabbit bone tumour tissue volume starts to reduce；It is 1 group of comparative example, postoperative
4 weeks, New Zealand White Rabbit bone tumour tissue volume not only increased without reducing instead.Test result shows produced by the present invention receive
The rice porous titanium framework of hydroxyapatite coating layer, has apoptosis cells of tumorous bone, inhibits the effect of tumour growth.
Fig. 2 is the bone tumour volume change figure of 3 groups of embodiment with 1 group of comparative example, as seen from the figure, nanometer provided by the invention
The porous titanium framework of hydroxyapatite coating layer has the function of apoptotic tumor cell and inhibits tumour growth.
Test example three, cell toxicity test
1, subjects: mesenchymal stem cell (BMSCs) and tumour cell (VX2) are chosen, by Sichuan University West China
Experimental Animal Center provides.
2, test material: porous titanium framework prepared by embodiment 3 and comparative example 1.
3, test method:
Porous titanium framework prepared by embodiment 3 and comparative example 1 is co-cultured respectively with BMSCs and VX2, two groups of observation is porous
The cell growth condition of titanium framework.
4, test result:
CCK-8 testing result shows the BMSCs proliferation activity no difference of science of statistics of embodiment 3 and comparative example 1, without obvious
Inhibiting effect；Embodiment 3 had apparent inhibition to VX2 cell Proliferation at cell culture 1,3 and 5 day, had system with comparative example 1
Meter learns difference.Test result shows in the porous titanium framework of nano hydroxyapatite coating provided by the invention, to normal cell without
Toxic side effect, alternative inhibit tumor cell proliferation.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (8)
1. a kind of porous titanium framework of nano hydroxyapatite coating, which is characterized in that including 3D printing POROUS TITANIUM base material and
Nano hydroxyapatite coating；The 3D printing POROUS TITANIUM base material from the outer macropore that aperture reduces step by step inwards by forming；
The microporous network TiO that the 3D printing POROUS TITANIUM substrate material surface is formed with a thickness of 0.5-2.0 μm2Layer；The nano-hydroxy
Apatite coating is uniformly distributed in the microporous network TiO2Layer surface.
2. the porous titanium framework of nano hydroxyapatite coating as described in claim 1, which is characterized in that the 3D printing is porous
The certainly outer macroporous structure that aperture reduces step by step inwards of titanium-based bottom material is cube porous element, octahedra porous element, Buddha's warrior attendant
One or more of stone point array element, spiral tetrahexahedron unit；The 3D printing POROUS TITANIUM base material is certainly outer inwards
The average pore size for the macropore that aperture reduces step by step is 300-800 μm.
3. the porous titanium framework of nano hydroxyapatite coating as claimed in claim 2, which is characterized in that the 3D printing is porous
The porosity of titanium-based bottom material is 60-90%, compression strength 60-120MPa, elasticity modulus 0.5-5.0GPa.
4. the porous titanium framework of nano hydroxyapatite coating as described in claim 1, which is characterized in that the nano hydroxyapatite
Lime stone coating is made of nanometer hydroxyapatite particle；The nano hydroxyapatite coating with a thickness of 20-100 μm.
5. the porous titanium framework of nano hydroxyapatite coating as claimed in claim 4, which is characterized in that the nano hydroxyapatite
The crystallite pattern of lime stone particle is one or more of subsphaeroidal, needle-shaped or rodlike.
6. the porous titanium framework of nano hydroxyapatite coating as described in claim 1, which is characterized in that the nano hydroxyapatite
Crystallinity successively reduces lime stone coating from inside to outside, and binding force gradually weakens.
7. a kind of preparation method of the porous titanium framework of nano hydroxyapatite coating as claimed in any one of claims 1 to 6,
It is characterized in that, comprising the following steps:
S1, POROUS TITANIUM base material is made using metal 3D printing technique；
S2, soda acid or thermokalite heat treatment are carried out to POROUS TITANIUM base material made from step S1, in its hole wall and skeleton surface shape
At the nanometer level microporous network TiO with a thickness of 0.5-2.0 μm2Layer, is made nanometer level microporous network TiO2The porous titanium substrate material of layer
Material；
S3, nanometer hydroxyapatite particle slurry is prepared using wet chemistry method, polyethylene glycol or high-molecular polyvinyl alcohol mould is added
Plate, and combine hydro-thermal process regulation nano-complex particle crystallite pattern be it is subsphaeroidal, needle-shaped or rodlike, obtain nano hydroxyapatite
Lime stone coating paste；
S4, H is added into nano hydroxyapatite coating slurry made from step S32O2And methylcellulose, it is placed in micro-wave oven
Foamable is assisted, intumescent coating slurry is made；
S5, by nanometer level microporous network TiO made from step S22Layer POROUS TITANIUM base material is submerged by Fruit storage
In intumescent coating slurry made from step S4, ultrasonic treatment, coating paste foaming to be foamed is abundant and is packed into nanometer level microporous
Network TiO2It is taken out after layer POROUS TITANIUM base material internal void, 80 DEG C of drying in baking oven, in Muffle furnace under set temperature
Heat treatment 1-2 hours；
S6, repeat operation 3-5 time of step S5, heat treatment temperature successively from 600 DEG C, 500 DEG C, 400 DEG C, 300 DEG C, 150 DEG C by
It gradually reduces, obtaining coating layer thickness is 20-100 μm, the nano-hydroxy that crystallinity successively reduces, binding force gradually weakens from inside to outside
Apatite coating POROUS TITANIUM timbering material；
S7, by nano hydroxyapatite coating POROUS TITANIUM timbering material made from step S6 be packaged sterilizing to get.
8. nano hydroxyapatite made from the preparation method of the porous titanium framework of nano hydroxyapatite coating as claimed in claim 7
Application of the lime stone coated porous titanium framework in preparation bone tumour repair materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811118085.8A CN109432493B (en) | 2018-09-26 | 2018-09-26 | Nano-hydroxyapatite coating porous titanium scaffold and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811118085.8A CN109432493B (en) | 2018-09-26 | 2018-09-26 | Nano-hydroxyapatite coating porous titanium scaffold and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181423A (en) * | 2021-05-26 | 2021-07-30 | 四川大学 | Titanium material with nano hydroxyapatite growing on surface in situ and preparation method and application thereof |
| CN114949355A (en) * | 2022-04-12 | 2022-08-30 | 宁波大学 | Auditory ossicle cartilage integrated auditory ossicle implant and manufacturing method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002041844A2 (en) * | 2000-10-20 | 2002-05-30 | Etex Corporation | Chemotherapeutic composition using nanocrystalline calcium phosphate paste |
| EP2061525A1 (en) * | 2006-08-30 | 2009-05-27 | The University of British Columbia | Bioceramic composite coatings and process for making same |
| CN103638557A (en) * | 2013-10-24 | 2014-03-19 | 陕西佰傲再生医学有限公司 | Antigen-removing biological bone and preparation method thereof |
| CN103751840A (en) * | 2014-02-12 | 2014-04-30 | 吴志宏 | Porous, controllable and low-modulus bone defect repair bracket and preparation method thereof |
| CN103845761A (en) * | 2014-02-24 | 2014-06-11 | 钟春燕 | Preparation of nano-carbon fiber composite nano-biphasic biological ceramic with three-dimensional network structure |
| CN103896234A (en) * | 2014-04-18 | 2014-07-02 | 四川大学 | Nanometer spherical hollow hydroxyapatite powder and preparation method thereof |
| CN104689370A (en) * | 2013-12-04 | 2015-06-10 | 江苏创英医疗器械有限公司 | Surface porous bioactive implant and preparation method thereof |
| CN105877874A (en) * | 2016-04-06 | 2016-08-24 | 四川大学 | Bionics design bone-line porous bone product and preparation method and purpose thereof |
| CN107007552A (en) * | 2017-04-26 | 2017-08-04 | 温州医科大学附属口腔医院 | A kind of preparation method for carrying anti-bone information medicament nano particle lipopolymer |
-
2018
- 2018-09-26 CN CN201811118085.8A patent/CN109432493B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002041844A2 (en) * | 2000-10-20 | 2002-05-30 | Etex Corporation | Chemotherapeutic composition using nanocrystalline calcium phosphate paste |
| EP2061525A1 (en) * | 2006-08-30 | 2009-05-27 | The University of British Columbia | Bioceramic composite coatings and process for making same |
| CN103638557A (en) * | 2013-10-24 | 2014-03-19 | 陕西佰傲再生医学有限公司 | Antigen-removing biological bone and preparation method thereof |
| CN104689370A (en) * | 2013-12-04 | 2015-06-10 | 江苏创英医疗器械有限公司 | Surface porous bioactive implant and preparation method thereof |
| CN103751840A (en) * | 2014-02-12 | 2014-04-30 | 吴志宏 | Porous, controllable and low-modulus bone defect repair bracket and preparation method thereof |
| CN103845761A (en) * | 2014-02-24 | 2014-06-11 | 钟春燕 | Preparation of nano-carbon fiber composite nano-biphasic biological ceramic with three-dimensional network structure |
| CN103896234A (en) * | 2014-04-18 | 2014-07-02 | 四川大学 | Nanometer spherical hollow hydroxyapatite powder and preparation method thereof |
| CN105877874A (en) * | 2016-04-06 | 2016-08-24 | 四川大学 | Bionics design bone-line porous bone product and preparation method and purpose thereof |
| CN107007552A (en) * | 2017-04-26 | 2017-08-04 | 温州医科大学附属口腔医院 | A kind of preparation method for carrying anti-bone information medicament nano particle lipopolymer |
Non-Patent Citations (6)
| Title |
|---|
| ELENA LANDI ET AL.: "Influence of synthesis and sintering parameters on the characteristics of carbonate apatite", 《BIOMATERIALS》 * |
| ELENA MAVROPOULOS ET AL.: "Biocompatibility of Carbonated Hydroxyapatite Nanoparticles with Different Crystallinities", 《KEY ENGINEERING MATERIALS》 * |
| JING WANG ET AL.: "Fabrication and preliminary biological evaluation of a highly porous biphasic calcium phosphate scaffold with nano-hydroxyapatite surface coating", 《CERAMICS INTERNATIONAL》 * |
| RUI ZHAO ET AL.: "Healing of osteoporotic bone defects by micro-/nano-structured calcium phosphate bioceramics", 《NANOSCALE》 * |
| SANGEETA DEY ET AL.: "Effect of hydroxyapatite particle size, morphology and crystallinity on proliferation of colon cancer HCT116 cells", 《MATERIALS SCIENCE AND ENGINEERING C》 * |
| 邓珍波等: "多孔钛骨组织工程支架设计及孔结构表征", 《稀有金属材料与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181423A (en) * | 2021-05-26 | 2021-07-30 | 四川大学 | Titanium material with nano hydroxyapatite growing on surface in situ and preparation method and application thereof |
| CN114949355A (en) * | 2022-04-12 | 2022-08-30 | 宁波大学 | Auditory ossicle cartilage integrated auditory ossicle implant and manufacturing method thereof |
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