CN208243822U - A kind of 3D printing composite magnetic metallic support - Google Patents

A kind of 3D printing composite magnetic metallic support Download PDF

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Publication number
CN208243822U
CN208243822U CN201721385983.0U CN201721385983U CN208243822U CN 208243822 U CN208243822 U CN 208243822U CN 201721385983 U CN201721385983 U CN 201721385983U CN 208243822 U CN208243822 U CN 208243822U
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metallic support
composite magnetic
poly
dimensional porous
dopamine
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黄振飞
于凌佳
贺宇
王海
吴志宏
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Peking Union Medical College Hospital Chinese Academy of Medical Sciences
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Peking Union Medical College Hospital Chinese Academy of Medical Sciences
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Abstract

The utility model discloses a kind of 3D printing composite magnetic metallic supports, including three-dimensional porous metallic support, poly-dopamine shell and composite magnetic nanoparticle, the three-dimensional porous metallic support is in the three-dimensional porous network structure penetrated through, the poly-dopamine shell is coated on the surface of the three-dimensional porous metallic support, and the composite magnetic nanoparticle uniform adhesion is on the surface of the three-dimensional porous metallic support for being coated with poly-dopamine shell.The 3D printing composite magnetic metallic support of the utility model can be applied in preparing bone impairment renovation material, bone renovating material is not only met for the needs of mechanical strength, and there is better biocompatibility and hydrophily, be conducive to the adherency of cell, and the material after coating has weak magnetic, be conducive to osteoblast differentiation, can promote skeletonization.

Description

A kind of 3D printing composite magnetic metallic support
Technical field
The utility model relates to technical field of biomedical materials, and in particular to a kind of 3D printing composite magnetic metal branch Frame.
Background technique
Bone defect healing is always to perplex clinical problem.Experiment in vivo shows 6 × 6 × 10mm3Bone defect i.e. need It is repaired by bone collection.It has been reported that there is a situation where delayed union or disunion up to 13% after fracture of tibia, in addition, whole Large segmental bone defect caused by shape surgery, Oral and Maxillofacial Surgery and serious wound, infection, bone tumour and skeleton deformity Deng requiring to repair by bone collection.
Clinically the graft materials of bone defect include autologous bone and allograph bone.Autologous bone transplanting is always bone defect healing " goldstandard ", but autologous bone is generally derived from the ilium and fibula of patient, not only takes bone amount limited, and will also result in wound even It takes and is infected at bone;Then there is immunological rejection, pathophorous risk in allograph bone.
Currently, the biomaterial for being applied to bone tissue engineer mainly includes 4 classes: bioceramic, high molecular material, metal material Material, composite material.Every kind of material has the advantages that its is peculiar, but also in the prevalence of respective deficiency.The first kind: biology pottery Porcelain, including calcium sulfate, calcium phosphate, hydroxyapatite (hydroxyapatite), β-TCP (β-Tricalciumphosphate), Bio-vitric etc..All there are many similarities for the inorganic constituents and crystal structure of ceramic material and natural people's bone, have splendid Biocompatibility is a kind of good bone alternate material.Hydroxyapatite and tricalcium phosphate are for filling and rebuilding bone defect, It is widely applied through having in orthopaedics and gear division.The researchs such as Ambrosio also found that ceramic material has and promote stem cell to skeletonization The effect of cell Proliferation and differentiation.Although bioceramic has including high elastic modulus, high mechanical strength and its excellent wear-resisting spy Property etc. many merits, but also there is brittleness height, poor plasticity, the shortcomings such as be difficult to, and its is caused to answer in clinical With much being constrained.In addition to this, how to regulate and control the difficult point place that the rate of ceramics bracket degradation is also research.Second class: High molecular material is divided into natural macromolecular material, including collagen, chitosan, alginate etc.;And artificial synthesized macromolecule material Material, including polylactic acid (PLA), poly lactide-glycolide acid (PLGA), polycaprolactone (PCL) etc..Collagen, chitosan, sea The natural macromolecular materials such as alginates have good bioactivity, can promote the adherency and proliferation of cell, have at the same time There is a good degradability, but the problem is that processing plastotype performance is poor, and its prepared product mechanical strength is often not Foot is limited in clinical use.Artificial synthesized high molecular material is to develop faster field in recent years, and ingredient is single, property Shape is controllable, and prepared product has certain mechanical strength, can also make various satisfactory complexity by rapid shaping technique Porous structure, has become the research main force of technical field of biological material, but it is general lack of bioactivity the problem is that lack The site of cell recognition, and its catabolite often has a negative impact to local cells.There is scholar to study discovery poly- Acidic materials can be generated after the material degradations such as D-lactic acid and polyglycolic acid, the pH value of local environment is reduced, leads to cell and group Knit necrosis.Third class: metal material, including stainless steel, titanium alloy, vitallium, tantalum metal, magnesium alloy etc., they excellent Gesture is that for enough mechanical strengths and good biocompatibility can be possessed, but the disadvantage is that without bioactivity and past Toward the absorption that cannot degrade.4th class: composite material, as the term suggests it is exactly to combine constructed by two or more above-mentioned material Composite tissue engineering bracket.Homogenous material more or less has such or such deficiency, and multiple material is used in combination can be real Now learn from other's strong points to offset one's weaknesses, have complementary advantages, is the new hot spot of current biomaterial research.For example bioceramic and high molecular material are answered It closes, can not only obtain enough mechanical strengths, good biocompatibility and bioactivity can also be obtained.
Titanium or titanium alloy in metal material has many advantages, such as good biocompatibility and corrosion-resistant in clinic because of it Using many years, while its excellent mechanical property is also fully confirmed, however the elasticity modulus of titanium alloy is about 103-110GPa, And the elasticity modulus of normal cancellous bone is about 0.5-3.5GPa, it is seen that the normal bone tissues elasticity modulus of titanium alloy and human body is serious It mismatches, differs greatly between titanium alloy and bone tissue when by stress, be easy to appear stress-shielding effect, seriously affect titanium conjunction The stability of golden implantation material and bone tissue.The appearance of 3D printing technique allows people to recognize titanium alloy again, utilizes 3D printing Titanium alloy can be prepared into porous structure by technology, these porous structures can not only simulate the porous knot of normal natural bone tissue Structure has supplied space for growing into for area of new bone, the elasticity modulus of material is reduced also by the change of porous structure, makes its springform Amount reduces implantation material to the stress shielding of bone close to bone tissue, hence it is evident that improves stability of the implantation material in conjunction with bone tissue.So And titanium alloy belongs to inert metal, itself does not have bioactivity, the site that can also identify without cell, therefore how to use Promoting the modification technique of skeletonization to carry out modification to titanium alloy implant is the key content studied at present.But due to titanium alloy The porous structure of bracket is to traditional handicraft, such as the various modification skills such as plasma spraying, surface active coating, growth factor-loaded The application of art brings difficulty, therefore how to carry out comprehensive bone modification of facilitating to cellular structure metals bracket is research heat Point.
In recent years, with the continuous development of organizational engineering, have some scholars begin trying using magnetic nanoparticle as One kind of organizational project facilitates bone factor to be used to prepare bone biologic material bracket.It is well known that magnetic nanoparticle is being studied Middle application for many years, is previously concentrated mainly on molecular biology field, comprising Magnetic resonance imaging, pharmaceutical carrier, targeted therapy, thin The fields such as born of the same parents' screening.By the inspiration of electromagnetic stimulation effect, some research teams of recent domestic are prepared for containing magnetic Nano A variety of composite material brackets of particle (MNPs) explore magnetic nano-particle to the effect of osteoblast and its in bone defect healing With the application in terms of improvement implant/bone interface associativity.RajendraK.Singh has studied poly- containing magnetic nano-particle The physics, chemistry, mechanics and biological property of caprolactone (PCL) bracket and its influence to osteanagenesis.Nano-magnetic grain is added The apatite Forming ability that submounts are soaked in simulated body fluid greatly improves, and the adherency of osteoblast and proliferative capacity are substantially better than Simple PCL bracket, biocompatibility aspect, they have found the bad of PCL-MNPs fibrous framework implantation subcutaneous rat performance tissue Reaction is minimum, and can induce a large amount of new vessels.It is better that PCL-MNPs fibrous framework is also demonstrated in animal experiments Bone regeneration capability.
In recent years a large number of studies show that, poly-dopamine (PDA) is at any material (even polytetrafluoroethylene (PTFE) (PTFE)) Wet structure can adhere to well.These materials had both included the organic materials such as macromolecule, also included metal and nonmetallic oxygen The inorganic material such as compound, ceramics.Moreover, poly-dopamine has very excellent biocompatibility, in 2007 at " Science " Cause numerous concerns after report, and the surface for being widely used in bio-medical material therewith is modified.Poly-dopamine can adhere to In the wet structure of almost all of organic and inorganic materials, also, the phenolic hydroxyl group of poly-dopamine itself and group containing N can trigger Secondary response obtains function by electrochemistry or graft reaction in poly-dopamine forming metal layer on surface or other macromoleculars The composite material of change.Si etc. has registered a kind of method for preparing monodisperse magnetic nanoparticle, i.e., in Fe3O4Wet structure deposition Poly-dopamine has prepared the Fe of one shell structure of core3O4@PDA composite nanoparticle, it is compound after nanoparticle significantly reduce Exposed Fe3O4Cytotoxicity.In addition, a large amount of phenolic hydroxyl group and amino all have hydrophily on poly-dopamine strand, therefore, The hydrophilicity and dispersibility of material after deposition poly-dopamine can be greatly improved.Zhu et al. is using dopamine to charcoal Black to have carried out surface modification, research is successfully realized carbon black from hydrophobic to hydrophilic conversion.
Utility model content
For overcome the deficiencies in the prior art, the purpose of this utility model is to provide a kind of large aperture, high porosity, holes The 3D printing composite magnetic metallic support of hole connection and appropriate elasticity modulus.
The second of the utility model is designed to provide the composite magnetic metallic support and is preparing bone impairment renovation material In application.
To achieve the above object, the utility model provides a kind of 3D printing composite magnetic metallic support, the composite magnetic Metallic support includes three-dimensional porous metallic support, poly-dopamine shell and composite magnetic nanoparticle, the three-dimensional porous metal Bracket is coated on the table of the three-dimensional porous metallic support in the three-dimensional porous network structure penetrated through, the poly-dopamine shell Face, table of the composite magnetic nanoparticle uniform adhesion in the three-dimensional porous metallic support for being coated with poly-dopamine shell Face.
Preferably, the three-dimensional porous metallic support is basic unit by regular dodecahedron or granatohedron, according to The three-dimensional porous perforation bracket being connected to hole hole that certain pore size is printed with the 3D mathematical model of hole post.
Preferably, the aperture of the three-dimensional porous metallic support is 300-800 μm, and hole post is 200-300 μm.
Preferably, the material of the three-dimensional porous metallic support is titanium alloy, pure titanium, cobalt alloy or stainless steel.
It is furthermore preferred that the material of the three-dimensional porous metallic support is titanium alloy.
Preferably, the poly-dopamine shell with a thickness of 50-200nm.
Preferably, the composite magnetic nanoparticle is the Fe of poly-dopamine modification3O4, i.e. Fe3O4@PDA;It is described compound Magnetic nano-particle is core-shell structure, wherein Fe3O4For kernel, poly-dopamine is shell.
Preferably, the poly-dopamine with a thickness of 50-200nm.
Beneficial effect
1, the 3D printing composite magnetic metallic support of the utility model is three-dimensional porous perforation bracket, has large aperture, height Porosity and appropriate elasticity modulus can meet the requirement of bone renovating material mechanical strength while reducing metal consumption, realize The optimization of metal consumption.
2, the 3D printing composite magnetic metal support surface of the utility model coats poly-dopamine coating, not only increases branch The hydrophily of frame is conducive to sticking for cell, while can also reduce the cytotoxicity of metallic support, hence it is evident that increases the compound rest Biocompatibility.
3, the composite magnetic nanoparticle of the utility model by method that poly-dopamine is modified can uniform adhesion in gold Belong to rack surface, increases the magnetism of material, promote the adherency and proliferation of osteoblast, greatly strengthen the osteogenic ability of bracket.
4, the 3D printing composite magnetic metal standoff structure of the utility model design is simple, is readily produced, while biofacies Capacitive is more preferable, promotes the ability of skeletonization stronger, is very excellent bone renovating material.
Detailed description of the invention
The three-dimensional porous titanium alloy bracket of Fig. 1 3D printing technique preparation;
Fig. 2 is coated with the schematic diagram of the three-dimensional porous titanium alloy bracket of poly-dopamine shell;
Fig. 3 sticks the schematic diagram for having the three-dimensional porous titanium alloy bracket of composite magnetic nanoparticle;
The cross section structure schematic diagram of Fig. 4 composite magnetic nanoparticle;
Appended drawing reference is as follows in figure:
Three-dimensional porous metallic support 1, poly-dopamine shell 2, composite magnetic nanoparticle 3, Fe3O431, poly-dopamine 32.
Specific embodiment
The following examples illustrate the utility model, but is not intended to limit the scope of the present invention.
Term " Fe used in the utility model3O4@PDA " is composite magnetic nanoparticle, is a kind of core-shell structure, i.e., In Fe3O4Surface deposits poly-dopamine.
As Figure 1-Figure 4, the utility model provides a kind of 3D printing composite magnetic metallic support, including three-dimensional porous Metallic support 1, poly-dopamine shell 2 and composite magnetic nanoparticle 3, the three-dimensional porous metallic support 1 is in three-dimensional perforation Porous network structure, as shown in Figure 1;The poly-dopamine shell 2 is coated on the surface of the three-dimensional porous metallic support 1, such as Shown in Fig. 2;3 uniform adhesion of composite magnetic nanoparticle is in the three-dimensional porous metal for being coated with poly-dopamine shell 2 The surface of bracket 1, as shown in Figure 3.
The three-dimensional porous metallic support 1 is basic unit by regular dodecahedron or granatohedron, according to certain hole The three-dimensional porous perforation bracket being connected to hole hole that diameter is printed with the 3D mathematical model of hole post, as shown in Figure 1, the three-dimensional is more Mesoporous metal bracket is the 1 three-dimensional porous perforation bracket by granatohedron for basic unit.
The aperture of the three-dimensional porous metallic support 1 is 300-800 μm, and hole post is 200-300 μm.
The aperture of three-dimensional porous metallic support is 300 μm in a preferred embodiment, and hole post is 200 μm.
The aperture of three-dimensional porous metallic support is 600 μm in another preferred embodiment, and hole post is 300 μm.
The aperture of three-dimensional porous metallic support is 800 μm in another preferred embodiment again, and hole post is 300 μm.
The material of the three-dimensional porous metallic support 1 is titanium alloy, pure titanium, cobalt alloy bracket or stainless steel.
The material of the three-dimensional porous metallic support 1 described in a preferred embodiment is titanium alloy.
The poly-dopamine shell with a thickness of 50-200nm.
The composite magnetic nanoparticle 3 is the Fe of poly-dopamine modification3O4, i.e. Fe3O4@PDA;The composite magnetic is received Rice corpuscles is core-shell structure, wherein Fe3O431 be kernel, and poly-dopamine 32 is shell, as shown in Figure 4.The thickness of the poly-dopamine Degree is 50-200nm.
Although above having made detailed description to the utility model with a general description of the specific embodiments, But on the basis of the utility model, it can be made some modifications or improvements, this is aobvious and easy to those skilled in the art See.Therefore, these modifications or improvements on the basis of without departing from the spirit of the present invention, belong to the utility model Claimed range.

Claims (8)

1. a kind of 3D printing composite magnetic metallic support, which is characterized in that the composite magnetic metallic support includes three-dimensional porous Metallic support, poly-dopamine shell and composite magnetic nanoparticle, the three-dimensional porous metallic support are porous in three-dimensional perforation Reticular structure, the poly-dopamine shell are coated on the surface of the three-dimensional porous metallic support, the composite magnetic nanoparticle Sub- uniform adhesion is on the surface of the three-dimensional porous metallic support for being coated with poly-dopamine shell.
2. 3D printing composite magnetic metallic support as described in claim 1, which is characterized in that the three-dimensional porous metallic support It is basic unit by regular dodecahedron or granatohedron, according to having for the 3D mathematical model of certain pore size and hole post printing The three-dimensional porous perforation bracket of hole hole connection.
3. 3D printing composite magnetic metallic support as claimed in claim 2, which is characterized in that the three-dimensional porous metallic support Aperture be 300-800 μm, hole post is 200-300 μm.
4. 3D printing composite magnetic metallic support as claimed in any one of claims 1-3, which is characterized in that the three-dimensional is more The material of mesoporous metal bracket is titanium alloy, pure titanium, cobalt alloy or stainless steel.
5. 3D printing composite magnetic metallic support as claimed in claim 4, which is characterized in that the three-dimensional porous metallic support Material be titanium alloy.
6. 3D printing composite magnetic metallic support as described in claim 1, which is characterized in that the thickness of the poly-dopamine shell Degree is 50-200nm.
7. 3D printing composite magnetic metallic support as described in claim 1, which is characterized in that the composite magnetic nanoparticle For the Fe of poly-dopamine modification3O4, i.e. Fe3O4@PDA;The composite magnetic nanoparticle is core-shell structure, wherein Fe3O4It is interior Core, poly-dopamine are shell.
8. 3D printing composite magnetic metallic support as claimed in claim 7, which is characterized in that the poly-dopamine with a thickness of 50-200nm。
CN201721385983.0U 2017-10-25 2017-10-25 A kind of 3D printing composite magnetic metallic support Active CN208243822U (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109717971A (en) * 2019-03-11 2019-05-07 四川大学 A kind of bone grafting guide plate and preparation method thereof
CN114504677A (en) * 2022-01-11 2022-05-17 武汉亚洲生物材料有限公司 3D printing skull repairing titanium mesh and preparation method thereof
CN114939187A (en) * 2022-03-24 2022-08-26 上海大学 3D prints MnPSe 3 Nano-sheet composite support and preparation method and application thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109717971A (en) * 2019-03-11 2019-05-07 四川大学 A kind of bone grafting guide plate and preparation method thereof
CN109717971B (en) * 2019-03-11 2020-11-27 四川大学 Bone-grafting guide plate and manufacturing method thereof
CN114504677A (en) * 2022-01-11 2022-05-17 武汉亚洲生物材料有限公司 3D printing skull repairing titanium mesh and preparation method thereof
CN114504677B (en) * 2022-01-11 2023-03-10 武汉亚洲生物材料有限公司 3D printing skull repairing titanium mesh and preparation method thereof
CN114939187A (en) * 2022-03-24 2022-08-26 上海大学 3D prints MnPSe 3 Nano-sheet composite support and preparation method and application thereof

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