CN107115561B - A kind of 3D printing timbering material and its preparation method and application - Google Patents
A kind of 3D printing timbering material and its preparation method and application Download PDFInfo
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- CN107115561B CN107115561B CN201710463999.7A CN201710463999A CN107115561B CN 107115561 B CN107115561 B CN 107115561B CN 201710463999 A CN201710463999 A CN 201710463999A CN 107115561 B CN107115561 B CN 107115561B
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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
- A61L27/14—Macromolecular materials
- A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
- A61L27/222—Gelatin
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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
- A61L27/12—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
- A61L27/14—Macromolecular materials
- A61L27/20—Polysaccharides
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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
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
- A61L2300/414—Growth factors
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/45—Mixtures of two or more drugs, e.g. synergistic mixtures
-
- 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
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Abstract
The present invention relates to a kind of 3D printing timbering materials and its preparation method and application, more particularly to a kind of 3D printing timbering material and preparation method thereof rebuild for periodontium, the material includes following component: stromal cell derived factor-1 (Stromal cell-derived factor-1,) and bone morphogenetic protein 2 (Bone Morphogenetic Proteins, BMPs) SDF-1.The present invention uses two kinds of functional moleculars of SDF-1 and BMP2, it raises endogenous retinal stem cells and to paradental defect region and promotes its Osteoblast Differentiation, promote paradenlal tissue regeneration, simultaneously, the bionical degradable macromolecule bracket of individuation is designed based on 3D printing, by computer to the carry out accuracy controlling of material outer form and internal microstructure.
Description
Technical field
The present invention relates to Material Fields, and in particular to a kind of 3D printing timbering material and its preparation method and application, especially
It is related to a kind of 3D printing timbering material and preparation method thereof for periodontal.
Background technique
Periodontosis is a kind of chronic infectious disease for destroying tooth supporting tissue, while being also that adult's tooth is caused to lack
The main reason for mistake, the adult in China 80%~97% suffer from different degrees of periodontosis.Its fall ill main mechanism be
Bacterium invades periodontium, by directly invading and the nonspecific immune reaction of body, causes the chronic inflammation of periodontium,
And then causes the destruction of periodontium especially alveolar bone, eventually lead to supporting tissue's forfeiture, tooth mobility and fall off.Periodontosis
The final goal for the treatment of is can to eliminate the inflammation of periodontal local organization, while making Periodontal Supporting Tissue (including the alveolus destroyed
The hard and soft tissues such as bone, periodontal ligament, gum, cementum) the biological sexual function such as reparative regeneration recovery.
Currently, clinical treatment periodontosis mainly mechanically carries out scaling on gum, subgingival curettage removal
The pathogenic factors such as dental calculus, plaque eliminate the chemical stimulation of microorganism and plaque, inhibit the further development of inflammation, however
Cellular oxidation stress reaction caused by these treatment methods and fully erased periodontal disease stimulate；For the alveolus lost
The Periodontal Supporting Tissues such as bone, gum, mainly again by autologous bone, the transplanting of allograph bone or biomaterial and inducting osseous tissue
The methods of raw bone amount for attempting to restore missing, but certain complication, allograph bone can occur for the area autologous bone limited source Qie Qugu
There are immunological rejections for transplanting, and have infection risk.
In recent years, the organizational engineering treatment method based on stem cells technology provides new thinking for paradenlal tissue regeneration
With method.Seed cell, timbering material, growth factor are the main contents of traditional organizational project research field.Currently, it is a variety of at
Somatic stem cell has been applied to paradenlal tissue regeneration.Wherein, mesenchymal stem cell (BMSCs) and periodontal ligament stem cell
It (PDLSCs) is considered as ideal seed cell.BMSCs is wherein most one group of cell of differentiation potential, but BMSCs is necessary
It is obtained from marrow, painful of drawing materials, cell characteristics are closely related with the age, and self-renewing and differentiation potential are limited.
PDLSCs is the adult stem cell separated from parodontium in recent years, and under inducing in vitro, periodontal ligament stem cell being capable of shape
The Various Tissues such as skeletonization, cartilage, nerve, fat, blood vessel, and cementum-parodontium-alveolar bone sample is formed after capable of transplanting in vivo
Works is considered having played important function in periodontal remodeling, regeneration, repair process, is more satisfactory in periodontal regenerative treatment
Seed cell.However, materials are difficult, cell origin is few, isolate and purify the above such as difficulty feature all seriously limit it is dry
Extensive development and application of the cell transplantation in the following periodontal treatment.Therefore, cell is gone back to the nest as research hotspot in recent years.It is dry
Cell, which must go back to the nest, could generate therapeutic effect to target area.A word of going back to the nest originates from the development of bone marrow transplantation therapy, meaning
Justice is specifically implanted in the bone marrow microenvironment for supporting its growth and development for the stem cell inputted through vein by blood circulation
Process.With the extension of research range, the meaning gone back to the nest at present has been extended to stem cell and migrates simultaneously under the induction of specified conditions
It is positioned at the process of body destination organization.
Chemotaxis refers to directed movement of the cell from low concentration to high concentration stimulant.And chemotactic factor (CF) can exactly make carefully
This type cytokines of born of the same parents' generation Chemotaxis.Stromal cell derived factor-1 (Stromal cell-derived factor-
1, SDF-1) it is a kind of chemotactic protein by marrow stromal cell and other relevant mesothelial cells and epithelial cells, belongs to
Macrophage endocrine type inflammatory protein superfamily member.The biological function of SDF-1 is complicated, mainly has: (1) participating in cell hair
Educate: for SDF-1 wide expression in the whole process of embryonic development, experiment confirms the mouse for lacking SDF-1 expression with multiple systems
Depauperation prompts important function of the SDF-1 in cell development；(2) migration of regulating cell: SDF-1 is controllable a variety of dry
Cell is migrated and is played a role along SDF-1 concentration gradient, and in the mouse for lacking SDF-1, candidate stem cell cannot be moved to
In marrow；(3) promote the growth and transfer of malignant tumour: many tumours can generate SDF-1, and stimulated and swollen in the form of autocrine
Tumor growth, while can also promote tumor vascular generation.Research finds that SDF-1/CXCR4 can promote the blood in cancer cell tissue
Pipe is formed and the migration of cancer cell.
SDF-1 is as important chemotactic factor (CF), and in rabbit hearts Ischemia-Reperfusion Injury Model, SDF-1 can be with chemotactic
The recruitment damaged tissue repair of MSCs.In the research of rat tibia bone defect model, discovery SDF-1 can not only promote
The recruitment of MSCs is gone back to the nest, and can also increase the expression of BMP2, to promote bone defect healing.In addition, SDF-1 can guide tooth
All film stem cell migrations promote the activation of PDLSCs to damage field, improve proliferative capacity and differentiation capability to reach tissue
The purpose of reparation.
It is bone morphogenetic protein (Bone Morphogenetic that new bone formation, which studies more deep biotic factor,
Proteins, BMPs) BMPs play a decisive role to the differentiation of osteogenic cell be promote skeletonization Main Factors.BMPs family at
More more than the 40 kinds of bmp proteins existing so far of member are had successfully been isolated.Wherein BMP2 is transforming growth factor β (TGF-β) superfamily
In multifunctional cytokine cell Proliferation can be promoted to improve its alkaline phosphatase activities in bone injury part and dystopy be also only
One signaling molecule that can be individually formed in dystopy induced osteogenesis this so that it is especially fractured in bone and joint diseases, bone defect faces
There is great potential using value in bed treatment.Research shows that BMP2 be in BMP family member bone inductive effect it is strongest because
Son, many experiments, which are also demonstrated, can promote bon e formation directly or by carrier topical application for BMP2.
Hydrogel is one of most common high molecular material of paradenlal tissue regeneration.Hydrogel is a kind of with high water content
Hydrophily or amphiphilic polymers three-dimensional network.Since hydrogel has good biocompatibility, and and human body soft tissue
Similar mechanical property is therefore widely used in the controlled release of tissue engineering bracket material and drug.Currently, traditional
Hydrogel preparation method is mainly chemical reaction or the Physical interaction passed through between macromolecular chain, it is difficult to be realized outside to hydrogel
The accuracy controlling in portion and internal structure.And 3D printing technique is then able to achieve the accurate tune to material outer form and internal microstructure
Control is conducive to the distribution of regulating cell and the matching of material and organism, therefore has unique advantage.Suitable for solid
The common raw material that printing technology prepares hydrogel includes the PEG of (methyl) acrylate ended, and can pass through introducing cell adhesion
The biomolecule such as peptide RGD, heparin, realize in microstructure regulating cell stick or the release of growth factor.In addition, passing through
Stereosopic printing technology, using methacrylic acid modification PLA-PEG-PLA triblock copolymer as raw material, can prepare it is porous or
Non-porous hydrogel, material have relatively narrow pore-size distribution, good connectivity and mechanical property.Resulting hydrogel can promote
Human mesenchymal stem cell sticks and grows.
Therefore, the response to oxidative stress inside and outside effective method elimination periodontal tissue is found, inducing endogenous is dry thin
The self-renewing and differentiation of born of the same parents realizes the regeneration of endogenous Periodontal Supporting Tissue, restores phatnoma bone height, reduce loss of tooth rate,
It is that periodontal disease treats problem urgently to be resolved.For saving denture, masticatory function is improved, quality of making the life better has great meaning
Justice.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of 3D printing timbering material and its preparation method and application,
The present invention uses two kinds of functional moleculars of SDF-1 and BMP2, raises endogenous retinal stem cells and to paradental defect region and promotes its skeletonization
Differentiation promotes paradenlal tissue regeneration, meanwhile, the bionical degradable macromolecule bracket of individuation is designed based on 3D printing, passes through calculating
Carry out accuracy controlling of the machine to material outer form and internal microstructure.
For this purpose, the invention adopts the following technical scheme:
In a first aspect, the material includes following component: stroma cell the present invention provides a kind of 3D printing timbering material
Derivative factor -1 (SDF-1) and bone morphogenetic protein 2 (BMP2).
In the present invention, the SDF-1 plays a significant role in Periodontium remodeling, to present in Periodontal Supporting Tissue
The recruitment of the stem cells such as BMSCs, PDLSCs and proliferation play a crucial role, the full mistake that SDF-1 is mobilized, migrates and raised in BMSCs
Cheng Zhong plays a significant role, and moreover, SDF-1 can increase the expression of BMP2, and two kinds of components of SDF-1 and BMP2 act synergistically,
Collectively promote paradenlal tissue regeneration.
According to the present invention, the mass concentration of the SDF-1 be 800-1200 μ g/L, preferably 800 μ g/L, 810 μ g/L,
820μg/L、830μg/L、850μg/L、860μg/L、880μg/L、900μg/L、910μg/L、930μg/L、950μg/L、980μ
g/L、990μg/L、1000μg/L、1010μg/L、1030μg/L、1050μg/L、1080μg/L、1100μg/L、1110μg/L、
1130 μ g/L, 1150 μ g/L, 1160 μ g/L, 1180 μ g/L or 1200 μ g/L, preferably 900-1050 μ g/L, further preferably
1000μg/L。
According to the present invention, the mass concentration of the BMP2 is 800-1200 μ g/L, preferably 800 μ g/L, 810 μ g/L, 820
μg/L、830μg/L、850μg/L、860μg/L、880μg/L、900μg/L、910μg/L、930μg/L、950μg/L、980μg/L、
990μg/L、1000μg/L、1010μg/L、1030μg/L、1050μg/L、1080μg/L、1100μg/L、1110μg/L、1130μ
G/L, 1150 μ g/L, 1160 μ g/L, 1180 μ g/L or 1200 μ g/L, preferably 900-1050 μ g/L, further preferably 1000 μ
g/L。
Inventors have found that SDF-1 and BMP2 can promote tooth when mass concentration range is 800-1200 μ g/L
The regeneration that week organizes, when the mass concentration of SDF-1 and BMP2 is 1000 μ g/L, SDF-1 and BMP-2 can each other utmostly
Ground plays synergistic effect, promotes the effect of periodontal regenerative best.
According to the present invention, the 3D printing timbering material further includes sodium alginate, gelatin and nano-hydroapatite particles.
According to the present invention, the mass concentration of the sodium alginate be 150-300mg/L, such as can be 150mg/L,
160mg/L、170mg/L、180mg/L、190mg/L、200mg/L、210mg/L、220mg/L、230mg/L、240mg/L、
250mg/L, 260mg/L, 270mg/L, 280mg/L, 290mg/L or 300mg/L, preferably 180-250mg/L, further preferably
For 220mg/L.
According to the present invention, the mass concentration of the gelatin be 150-250mg/L, such as can be 150mg/L, 160mg/L,
170mg/L, 180mg/L, 190mg/L, 200mg/L, 210mg/L, 220mg/L, 230mg/L, 240mg/L or 250mg/L, preferably
For 180-220mg/L, further preferably 200mg/L.
According to the present invention, the mass concentration of the nano-hydroapatite particles is 60-160mg/L, such as be can be
60mg/L, 70mg/L, 80mg/L, 90mg/L, 100mg/L, 110mg/L, 120mg/L, 130mg/L, 140mg/L, 150mg/L or
160mg/L, preferably 80-120mg/L, further preferably 100mg/L.
As optimal technical scheme, the 3D printing timbering material includes following component: SDF-1800- by mass concentration
1200 μ g/L, BMP2 800-1200 μ g/L, sodium alginate 150-300mg/L, gelatin 150-250mg/L and nano-hydroxy-apatite
Stone particle 60-160mg/L.
In the present invention, the preparation of each component of the 3D printing bracket material is prepared using distilled water.
Second aspect, the present invention provide a kind of preparation method of 3D printing timbering material as described in relation to the first aspect, including
Following steps:
(1) sodium alginate, gelatin and nano-hydroapatite particles are mixed by formula ratio, is stirred, until
It is formed uniformly without the clear solution of precipitating；
(2) SDF-1 and BMP2 is added by formula ratio to the clear solution of step (1), is placed in and stirs on ice, after 4 DEG C of pre-coolings
It is spare.
According to the present invention, step (1) the mixed temperature is 30-40 DEG C, such as can be 30 DEG C, 31 DEG C, 32 DEG C, 33
DEG C, 34 DEG C, 35 DEG C, 36 DEG C, 37 DEG C, 38 DEG C, 39 DEG C or 40 DEG C, preferably 35-38 DEG C, further preferably 37 DEG C.
According to the present invention, the time of step (1) described stirring be 2-5h, such as can be 2h, 2.5h, 3h, 3.5h, 4h,
4.5h or 5h, preferably 3h.
According to the present invention, the time of step (2) described stirring be 10-60min, such as can be 10min, 15min,
20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, preferably 20-50min, further
Preferably 30min.
As optimal technical scheme, the preparation method includes the following steps:
(1) sodium alginate, gelatin and nano-hydroapatite particles are mixed at 30-40 DEG C by formula ratio,
2-5h is stirred, until being formed uniformly without the clear solution of precipitating；
(2) SDF-1 and BMP2 is added by formula ratio to the clear solution of step (1), is placed in and stirs 10-60min on ice, 4
DEG C pre-cooling after it is spare.
The third aspect, the 3D printing timbering material that the present invention provides a kind of as described in first party are used for periodontal in-situ regeneration
The application of skeleton.
According to the present invention, described by the way that the 3D printing timbering material is carried out 3D printing, it is in situ again to generate the periodontal
Raw skeleton.
According to the present invention, the method for the 3D printing includes the following steps:
(A) setting printing coded program；
(B) 3D printing, cross moulding are carried out according to the program of step (A) with 3D printer.
According to the present invention, the printing coded program is the conventional coded program of 3D printing, and those skilled in the art can be with
Set as needed, do not do particular determination herein, the present invention is set with the following method: (a) threedimensional model constructs；(b)
The layered shaping of threedimensional model；(c) section processes；(d) section is superimposed.
According to the present invention, step (a) the threedimensional model building can use the Three-dimensional Design Software of this field routine, lead to
The CT image for crossing tooth carries out three-dimensional modeling, and the present invention carries out three-dimensional modeling using solid work software.
According to the present invention, the layered shaping of threedimensional model described in step (b) specifically includes: the size at selected interval, will
The threedimensional model of step (a) is separated into a series of orderly two-dimentional synusia.
In the present invention, the gap size is determined by the precision of the derived result of CT figure, and the application is preferably
0.01-0.05mm, such as can be 0.01mm, 0.02mm, 0.03mm, 0.04mm or 0.05mm, preferably 0.02mm.
According to the present invention, the processing of section described in step (c) specifically includes: the spray head of printer is controlled by digital control system,
Under the control of the computer, the scanning and extruding/injection that spray head is controlled according to the synusia information of input obtain a corresponding layer cross section.
According to the present invention, the superposition of section described in step (d) specifically includes: after step (c) layer cross section is formed, next layer
Material is sent in molded level, and bonding with preceding layer then in the molding for carrying out later layer, thus will from level to level
Section be gradually superimposed together, ultimately form 3D solid.
It according to the present invention, further include that the 3D printer is sterilized with ultraviolet lamp before step (B) described 3D printing, institute
State sterilization time be 20-40min, such as can be 20min, 21min, 22min, 23min, 24min, 25min, 26min,
27min, 28min, 29min or 30min, preferably 30min.
According to the present invention, the printing needle diameter of step (B) described 3D printing be 80-120 μm, such as can be 80 μm,
81μm、82μm、83μm、85μm、86μm、88μm、90μm、91μm、93μm、95μm、96μm、98μm、100μm、102μm、103μ
M, 105 μm, 108 μm, 110 μm, 112 μm, 115 μm, 118 μm or 120 μm, preferably 90-110 μm, further preferably 100 μ
m。
According to the present invention, the print speed of step (B) described 3D printing is 3-8mm/s, such as can be 3mm/s, 4mm/
S, 5mm/s, 6mm/s, 7mm/s or 8mm/s, preferably 4-7mm/s, preferably 5mm/s.
According to the present invention, the fiber spacing of step (B) described 3D printing is 250-380 μm, such as can be 250 μm, 260
μm, 270 μm, 280 μm, 290 μm, 300 μm, 310 μm, 320 μm, 330 μm, 340 μm, 350 μm, 360 μm, 370 μm or 380 μm,
Preferably 280-350 μm, further preferably 300 μm.
According to the present invention, the extrusion pressure of step (B) described 3D printing be 0.1-0.6MPa, such as can be 0.1MPa,
0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa or 0.6MPa, preferably 0.2-0.5MPa, further preferably 0.3MPa.
According to the present invention, cross moulding described in step (B) specifically includes: it is immersed in 10-30min in calcium chloride solution,
Preferably 20min, then at 1-6 DEG C of temperature, at preferably 4 DEG C, it is immersed in 1- (3- dimethylamino-propyl) -3 ethyl carbodiimides
It is crosslinked overnight in hydrochloride (EDC) solution.
Preferably, the mass concentration of the calcium chloride solution is 1-5%, for example, can be 1%, 1.5%, 2%, 2.5%,
3%, 3.5%, 4%, 4.5% or 5%, preferably 2%.
Preferably, the mass concentration of the EDC solution is 0.8-3%, for example, can be 0.8%, 0.9%, 1%,
1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8% or 3%, preferably 1%.
As optimal technical scheme, the method for the 3D printing includes the following steps:
(A) setting printing coded program；
(a) threedimensional model constructs: carrying out three-dimensional modeling according to the CT image of object using solid work software；
(b) layered shaping of threedimensional model: the threedimensional model of step (a) is separated by the interval of selected 0.01-0.05mm
A series of orderly two-dimentional synusia；
(c) section processes: the spray head of printer is controlled by digital control system, under the control of the computer, according to the synusia of input
Information controls the scanning and extruding/injection of spray head, obtains a corresponding layer cross section；
(d) section is superimposed: after step (c) layer cross section is formed, lower layer of material is sent in molded level, then
It is and bonding with preceding layer in the molding for carrying out later layer, so that section from level to level is gradually superimposed together, ultimately form
3D solid；
(B) 3D printer is subjected to sterilizing 20-40min with ultraviolet lamp, with 3D printer according to the program of step (A)
3D printing is carried out, the printing needle diameter of the 3D printing is 80-120 μm, and the print speed is 3-8mm/s, the fiber
Spacing is 250-380 μm, and the extrusion pressure of the 3D printing is 0.1-0.6MPa；
(C) crosslinking is stayed overnight: step (B) molding structure printed is immersed in the calcium chloride solution that mass concentration is 1-5%
Middle 10-30min, then at 1-6 DEG C of temperature, it is immersed in -3 ethyl carbon of 1- (3- dimethylamino-propyl) that mass concentration is 0.8-3%
It is crosslinked overnight in diimmonium salt hydrochlorate (EDC) solution.
Compared with prior art, the present invention at least has the advantages that
(1) present invention is bionical degradable based on 3D printing design individuation compared with traditional chemical synthesizes polymeric stent
Polymeric stent, by computer to the carry out accuracy controlling of material outer form and internal microstructure, according to periodontal support group
Defect different parts, form, size are knitted, such as the different horizontal type bone resorption in forward and backward tooth area, vertical-type bone resorption, angle-style absorb
And irregular absorption, the bionical gel stent of individuation that design matches with defect pass through and change porosity and internal junction
Structure optimizes the physicochemical property of bracket, and the adherency of cell is promoted to grow；
(2) present invention prints the raw material of bracket synthesis with nanoparticle altogether, and nanoparticle is made to be uniformly distributed in bracket, realizes medicine
Object constantly equably discharges；
(3) based on the present invention goes back to the nest theory by cell, simultaneously using chemotactic factor (CF) SDF-1 inducing endogenous stem cell recruitment
In-situ regeneration, meanwhile, select growth factor B MP2 to promote the Osteoblast Differentiation of endogenous retinal stem cells；
(4) the method for the present invention not only solves Method of Tissue Engineering and promotes in tissue regeneration processes, existing for cell transplantation
Materials are difficult, and cell origin is few, isolate and purify difficulty, and there are immunological rejection risk may etc. drawbacks, meanwhile, SDF-1 and
The combination of two kinds of functional moleculars of BMP2 also plays the effect that collaboration promotes osteanagenesis.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1 prepares 3D printing timbering material
The 3D printing timbering material includes following component by mass concentration: 1000 μ g/L of SDF-1, BMP21000 μ g/L,
Sodium alginate 220mg/L, gelatin 200mg/L and nano-hydroapatite particles 100mg/L；
The 3D printing timbering material the preparation method is as follows:
(1) sodium alginate, gelatin and nano-hydroapatite particles are dissolved in distilled water by formula ratio, 37
It DEG C is mixed, stirs 3h, until being formed uniformly without the clear solution of precipitating；
(2) SDF-1 and BMP2 is added by formula ratio to the clear solution of step (1), is placed in and stirs 30min on ice, 4 DEG C pre-
It is spare after cold.
The case where 3D printing timbering material cell adherence growth being prepared, is good.
Embodiment 2 prepares 3D printing timbering material
The 3D printing timbering material includes following component by mass concentration: 900 μ g/L of SDF-1, BMP2900 μ g/L, sea
Mosanom 180mg/L, gelatin 180mg/L and nano-hydroapatite particles 80mg/L；
The 3D printing timbering material the preparation method is as follows:
(1) sodium alginate, gelatin and nano-hydroapatite particles are dissolved in distilled water by formula ratio, 35
It DEG C is mixed, stirs 4h, until being formed uniformly without the clear solution of precipitating；
(2) SDF-1 and BMP2 is added by formula ratio to the clear solution of step (1), is placed in and stirs 20min on ice, 4 DEG C pre-
It is spare after cold.
The case where 3D printing timbering material cell adherence growth being prepared, is good.
Embodiment 3 prepares 3D printing timbering material
The 3D printing timbering material includes following component by mass concentration: 1050 μ g/L of SDF-1, BMP-21050 μ g/
L, sodium alginate 250mg/L, gelatin 220mg/L and nano-hydroapatite particles 120mg/L；
The 3D printing timbering material the preparation method is as follows:
(1) sodium alginate, gelatin and nano-hydroapatite particles are dissolved in distilled water by formula ratio, 38
It DEG C is mixed, stirs 2h, until being formed uniformly without the clear solution of precipitating；
(2) SDF-1 and BMP2 is added by formula ratio to the clear solution of step (1), is placed in and stirs 50min on ice, 4 DEG C pre-
It is spare after cold.
The case where 3D printing timbering material cell adherence growth being prepared, is good.
Embodiment 4 prepares 3D printing timbering material
The 3D printing timbering material includes following component by mass concentration: 800 μ g/L of SDF-1, BMP-2800 μ g/L,
Sodium alginate 150mg/L, gelatin 150mg/L and nano-hydroapatite particles 60mg/L；
The 3D printing timbering material the preparation method is as follows:
(1) sodium alginate, gelatin and nano-hydroapatite particles are dissolved in distilled water by formula ratio, 30
It DEG C is mixed, stirs 5h, until being formed uniformly without the clear solution of precipitating；
(2) SDF-1 and BMP-2 is added by formula ratio to the clear solution of step (1), is placed in and stirs 10min on ice, 4 DEG C
It is spare after pre-cooling.
The case where 3D printing timbering material cell adherence growth being prepared, is good.
Embodiment 5 prepares 3D printing timbering material
The 3D printing timbering material includes following component by mass concentration: 1200 μ g/L of SDF-1, BMP-21200 μ g/
L, sodium alginate 300mg/L, gelatin 250mg/L and nano-hydroapatite particles 160mg/L；
The 3D printing timbering material the preparation method is as follows:
(1) sodium alginate, gelatin and nano-hydroapatite particles are dissolved in distilled water by formula ratio, 40
It DEG C is mixed, stirs 2h, until being formed uniformly without the clear solution of precipitating；
(2) SDF-1 and BMP-2 is added by formula ratio to the clear solution of step (1), is placed in and stirs 60min on ice, 4 DEG C
It is spare after pre-cooling.
The case where 3D printing timbering material cell adherence growth being prepared, is good.
Comparative example 1
Compared with Example 1, other same as Example 1 in addition to there is no SDF-1.
Comparative example 2
Compared with Example 1, other same as Example 1 in addition to there is no BMP2.
Comparative example 3
Compared with Example 1, g/L parts of 1400 μ of SDF-1 is removed, it is other same as Example 1 except 600 μ g/L of BMP2.
Comparative example 4
Compared with Example 1, g/L parts of 600 μ of SDF-1 is removed, it is other same as Example 1 except 1400 μ g/L of BMP2.
In conclusion comparative example 1-4, compared to embodiment 1-5, cell adherence growth significantly reduces, comparative example 1-2 cell
Growth even can not be adhered to, the effect that can be seen that the growth of 1 cell adherence of embodiment from embodiment 1-5 is best, embodiment 2-3
Cell adherence growth effect take second place, embodiment 4-5 cell adherence growth effect be not so good as embodiment 1-3, it is seen then that SDF-1 and
Two kinds of component synergistic effects of BMP2, collectively promote paradenlal tissue regeneration, when the mass concentration of SDF-1 and BMP2 is 1000 μ g/L
When, SDF-1 and BMP2 can farthest play synergistic effect each other.
6 3D printing of embodiment
The 3D printing timbering material that embodiment 1-5 and comparative example 1-4 are prepared carries out 3D printing, the 3D printing
Method includes the following steps:
(A) setting printing coded program；
(a) threedimensional model constructs: carrying out three-dimensional modeling according to the CT image of tooth using solid work software；
(b) layered shaping of threedimensional model: the threedimensional model of step (a) is separated by the size 0.02mm at selected interval
A series of orderly two-dimentional synusia；
(c) section processes: the spray head of printer is controlled by digital control system, under the control of the computer, according to the synusia of input
Information controls the scanning and extruding/injection of spray head, obtains a corresponding layer cross section；
(d) section is superimposed: after step (c) layer cross section is formed, lower layer of material is sent in molded level, then
It is and bonding with preceding layer in the molding for carrying out later layer, so that section from level to level is gradually superimposed together, ultimately form
3D solid；
(B) 3D printer is subjected to sterilizing 30min with ultraviolet lamp, with 3D printer according to step (A) program into
Row 3D printing, the printing needle diameter of the 3D printing are 100 μm, and the print speed is 5mm/s, and the fiber spacing is
300 μm, the extrusion pressure of the 3D printing is 0.3MPa；
(C) crosslinking is stayed overnight: step (B) molding structure printed being immersed in the calcium chloride solution that mass concentration is 2%
20min, then at 4 DEG C of temperature, it is immersed in 1- (3- dimethylamino-propyl) -3 ethyl-carbodiimide hydrochlorides that mass concentration is 1%
(EDC) it is crosslinked in solution overnight, can print molding.
Embodiment 7
The 3D printing timbering material that embodiment 1 is prepared carries out 3D printing, and the method for the 3D printing includes as follows
Step:
(A) setting printing coded program；
(a) threedimensional model constructs: carrying out three-dimensional modeling according to the CT image of tooth using solid work software；
(b) layered shaping of threedimensional model: the threedimensional model of step (a) is separated by the size 0.01mm at selected interval
A series of orderly two-dimentional synusia；
(c) section processes: the spray head of printer is controlled by digital control system, under the control of the computer, according to the synusia of input
Information controls the scanning and extruding/injection of spray head, obtains a corresponding layer cross section；
(d) section is superimposed: after step (c) layer cross section is formed, lower layer of material is sent in molded level, then
It is and bonding with preceding layer in the molding for carrying out later layer, so that section from level to level is gradually superimposed together, ultimately form
3D solid；
(B) 3D printer is subjected to sterilizing 20min with ultraviolet lamp, with 3D printer according to step (A) program into
Row 3D printing, the printing needle diameter of the 3D printing are 80 μm, and the print speed is 3mm/s, and the fiber spacing is 250
μm, the extrusion pressure of the 3D printing is 0.1MPa；
(C) crosslinking is stayed overnight: step (B) molding structure printed being immersed in the calcium chloride solution that mass concentration is 5%
10min, then at 1 DEG C of temperature, it is immersed in 1- (3- dimethylamino-propyl) -3 ethyl carbodiimide hydrochlorides that mass concentration is 0.8%
It is crosslinked in salt (EDC) solution overnight, can print molding.
Embodiment 8
The 3D printing timbering material that embodiment 1 is prepared carries out 3D printing, and the method for the 3D printing includes as follows
Step:
(A) setting printing coded program；
(a) threedimensional model constructs: carrying out three-dimensional modeling according to the CT image of tooth using solid work software；
(b) layered shaping of threedimensional model: the threedimensional model of step (a) is separated by the size 0.05mm at selected interval
A series of orderly two-dimentional synusia；
(c) section processes: the spray head of printer is controlled by digital control system, under the control of the computer, according to the synusia of input
Information controls the scanning and extruding/injection of spray head, obtains a corresponding layer cross section；
(d) section is superimposed: after step (c) layer cross section is formed, lower layer of material is sent in molded level, then
It is and bonding with preceding layer in the molding for carrying out later layer, so that section from level to level is gradually superimposed together, ultimately form
3D solid；
(B) 3D printer is subjected to sterilizing 40min with ultraviolet lamp, with 3D printer according to step (A) program into
Row 3D printing, the printing needle diameter of the 3D printing are 120 μm, and the print speed is 8mm/s, and the fiber spacing is
380 μm, the extrusion pressure of the 3D printing is 0.6MPa；
(C) crosslinking is stayed overnight: step (B) molding structure printed being immersed in the calcium chloride solution that mass concentration is 1%
10min, then at 6 DEG C of temperature, it is immersed in 1- (3- dimethylamino-propyl) -3 ethyl-carbodiimide hydrochlorides that mass concentration is 3%
(EDC) it is crosslinked in solution overnight, can print molding.
In conclusion SDF-1 can increase the expression of BMP2, two kinds of component synergistic effects of SDF-1 and BMP2 collectively promote tooth
All regenerations, when the mass concentration of SDF-1 and BMP2 is 1000 μ g/L, SDF-1 and BMP2 can each other farthest
Synergistic effect is played, promotes the effect of periodontal regenerative best.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (49)
1. a kind of 3D printing timbering material, which is characterized in that the 3D printing timbering material includes following component by mass concentration:
Stromal cell derived factor-1 900-1050 μ g/L, bone morphogenesis protein-2 900-1050 μ g/L, sodium alginate 150-
300mg/L, gelatin 150-250mg/L and nano-hydroapatite particles 60-160mg/L.
2. 3D printing timbering material according to claim 1, which is characterized in that the matter of the stromal cell derived factor-1
Amount concentration is 1000 μ g/L.
3. 3D printing timbering material according to claim 1, which is characterized in that the quality of the bone morphogenesis protein-2
Concentration is 1000 μ g/L.
4. 3D printing timbering material according to claim 3, which is characterized in that the mass concentration of the sodium alginate is
180-250mg/L。
5. 3D printing timbering material according to claim 4, which is characterized in that the mass concentration of the sodium alginate is
220mg/L。
6. 3D printing timbering material according to claim 1, which is characterized in that the mass concentration of the gelatin is 180-
220mg/L。
7. 3D printing timbering material according to claim 6, which is characterized in that the mass concentration of the gelatin is 200mg/
L。
8. 3D printing timbering material according to claim 1, which is characterized in that the matter of the nano-hydroapatite particles
Amount concentration is 80-120mg/L.
9. 3D printing timbering material according to claim 8, which is characterized in that the matter of the nano-hydroapatite particles
Amount concentration is 100mg/L.
10. a kind of preparation method of the 3D printing timbering material as described in any one of claim 1-9, which is characterized in that including
Following steps:
(1) sodium alginate, gelatin and nano-hydroapatite particles are mixed by formula ratio, is stirred, until being formed
Uniformly without the clear solution of precipitating；
(2) stromal cell derived factor-1 and bone morphogenesis protein-2 is added by formula ratio to the clear solution of step (1), sets
It is stirred on ice, it is spare after 4 DEG C of pre-coolings.
11. preparation method as claimed in claim 10, which is characterized in that step (1) the mixed temperature is 30-40 DEG C.
12. preparation method according to claim 11, which is characterized in that step (1) the mixed temperature is 35-38
℃。
13. preparation method according to claim 12, which is characterized in that step (1) the mixed temperature is 37 DEG C.
14. preparation method according to claim 13, which is characterized in that the time of step (1) described stirring is 2-5h.
15. preparation method according to claim 14, which is characterized in that the time of step (1) described stirring is 3h.
16. preparation method according to claim 10, which is characterized in that the time of step (2) described stirring is 10-
60min。
17. preparation method according to claim 16, which is characterized in that the time of step (2) described stirring is 20-
50min。
18. preparation method according to claim 16, which is characterized in that the time of step (2) described stirring is 30min.
19. preparation method as claimed in claim 10, which comprises the steps of:
(1) sodium alginate, gelatin and nano-hydroapatite particles are mixed by formula ratio at 30-40 DEG C, is stirred
2-5h, until being formed uniformly without the clear solution of precipitating；
(2) stromal cell derived factor-1 and bone morphogenesis protein-2 is added by formula ratio to the clear solution of step (1), sets
It is spare after 4 DEG C of pre-coolings in stirring 10-60min on ice.
20. a kind of 3D printing timbering material as claimed in any one of claims 1-9 wherein is answered for periodontal in-situ regeneration skeleton
With.
21. application as claimed in claim 20, which is characterized in that by the way that the 3D printing timbering material is carried out 3D printing,
Generate the periodontal in-situ regeneration skeleton.
22. application according to claim 21, which is characterized in that the method for the 3D printing includes the following steps:
(A) setting printing coded program；
(B) 3D printing, cross moulding are carried out according to the program of step (A) with 3D printer.
23. application as claimed in claim 22, which is characterized in that the printing coded program includes the following steps: (a) three-dimensional
Model construction；(b) layered shaping of threedimensional model；(c) section processes；(d) section is superimposed.
24. application according to claim 23, which is characterized in that step (a) threedimensional model is configured to using three-dimensional
Design software carries out three-dimensional modeling to object.
25. application according to claim 23, which is characterized in that the layered shaping of threedimensional model described in step (b) has
Body includes: the size at selected interval, and the threedimensional model of step (a) is separated into a series of orderly two-dimentional synusia.
26. application according to claim 23, which is characterized in that the processing of section described in step (c) specifically includes: printing
The spray head of machine is controlled by digital control system, under the control of the computer, according to the synusia information of input control spray head scanning and extruding/
Injection obtains a corresponding layer cross section.
27. application according to claim 23, which is characterized in that the superposition of section described in step (d) specifically includes: step
(c) after a layer cross section is formed, lower layer of material is sent in molded level, then carries out the molding of later layer again, and with
Preceding layer is bonding, so that section from level to level is gradually superimposed together, ultimately forms 3D solid.
28. application according to claim 22, which is characterized in that further include by the 3D before step (B) described 3D printing
The step of printer is sterilized with ultraviolet lamp.
29. application according to claim 28, which is characterized in that the sterilization time is 20-40min.
30. application according to claim 29, which is characterized in that the sterilization time is 30min.
31. application according to claim 23, which is characterized in that the printing needle diameter of step (B) described 3D printing is
80-120μm。
32. application according to claim 31, which is characterized in that the printing needle diameter of step (B) described 3D printing is
90-110μm。
33. application according to claim 32, which is characterized in that the printing needle diameter of step (B) described 3D printing is
100μm。
34. application according to claim 22, which is characterized in that the print speed of step (B) described 3D printing is 3-
8mm/s。
35. application according to claim 34, which is characterized in that the print speed of step (B) described 3D printing is 4-
7mm/s。
36. application according to claim 35, which is characterized in that the print speed of step (B) described 3D printing is 5mm/
s。
37. application according to claim 22, which is characterized in that the fiber spacing of step (B) described 3D printing is 250-
380μm。
38. the application according to claim 37, which is characterized in that the fiber spacing of step (B) described 3D printing is 280-
350μm。
39. the application according to claim 38, which is characterized in that the fiber spacing of step (B) described 3D printing is 300 μ
m。
40. application according to claim 22, which is characterized in that the extrusion pressure of step (B) described 3D printing is 0.1-
0.6MPa。
41. application according to claim 40, which is characterized in that the extrusion pressure of step (B) described 3D printing is 0.2-
0.5MPa。
42. application according to claim 41, which is characterized in that the extrusion pressure of step (B) described 3D printing is
0.3MPa。
43. application according to claim 22, which is characterized in that cross moulding described in step (B) specifically includes: impregnating
The 10-30min in calcium chloride solution, then 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide salt is immersed at 1-6 DEG C of temperature
It is crosslinked overnight in acid salt solution.
44. application according to claim 43, which is characterized in that cross moulding described in step (B) specifically includes: impregnating
The 20min in calcium chloride solution, then 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide hydrochloride is immersed at 4 DEG C of temperature
It is crosslinked overnight in salting liquid.
45. application according to claim 44, which is characterized in that the mass concentration of the calcium chloride solution is 1-5%.
46. application according to claim 45, which is characterized in that the mass concentration of the calcium chloride solution is 2%.
47. application according to claim 44, which is characterized in that 1- (3- the dimethylamino-propyl) -3- ethyl carbon two
The mass concentration of imide hydrochloride salting liquid is 0.8-3%.
48. application according to claim 47, which is characterized in that 1- (3- the dimethylamino-propyl) -3- ethyl carbon two
The mass concentration of imide hydrochloride salting liquid is 1%.
49. application as claimed in claim 22, which is characterized in that the method for the 3D printing includes the following steps:
(A) setting printing coded program；
(a) threedimensional model constructs: carrying out three-dimensional modeling according to the CT image of object using solid work software；
(b) layered shaping of threedimensional model: the threedimensional model of step (a) is separated into a series of orderly by the size at selected interval
Two-dimentional synusia；
(c) section processes: the spray head of printer is controlled by digital control system, under the control of the computer, according to the synusia information of input
The scanning and extruding/injection for controlling spray head obtain a corresponding layer cross section；
(d) section be superimposed: after step (c) layer cross section is formed, lower layer of material is sent in molded level, then again into
The molding of row later layer, and it is bonding with preceding layer, so that section from level to level is gradually superimposed together, ultimately form three-dimensional
Entity；
(B) 3D printer is subjected to sterilizing 20-40min with ultraviolet lamp, is carried out with 3D printer according to the program of step (A)
3D printing, the printing needle diameter of the 3D printing are 80-120 μm, and the print speed of the 3D printing is 3-8mm/s, described
The fiber spacing of 3D printing is 250-380 μm, and the extrusion pressure of the 3D printing is 0.1-0.6MPa；
(C) crosslinking is stayed overnight: step (B) molding structure printed is immersed in 10- in the calcium chloride solution that mass concentration is 1-5%
30min, then at 1-6 DEG C of temperature, it is sub- to be immersed in 1- (3- the dimethylamino-propyl) -3- ethyl carbon two that mass concentration is 0.8-3%
It is crosslinked overnight in amide hydrochloride.
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| CN108030957A (en) * | 2017-12-29 | 2018-05-15 | 成都新柯力化工科技有限公司 | A kind of gel rubber material and preparation method and application for 3D printing artificial cartilage |
| CN108144114A (en) * | 2018-01-05 | 2018-06-12 | 浙江省医学科学院 | For the 3D printing material of organizational project and the preparation method of Biodegradable scaffold material |
| CN108355167A (en) * | 2018-04-27 | 2018-08-03 | 昆明医科大学第附属医院 | A kind of chitosan coating BCBB bone renovating bracket materials and preparation method thereof being sustained SDF-1 |
| CN109400917B (en) * | 2018-11-02 | 2021-06-01 | 郑州大学 | Preparation method of collagen/sodium alginate composite hydrogel for slowly releasing SDF-1 |
| CN110433331B (en) * | 2019-08-26 | 2021-08-24 | 四川大学 | Bioactive scaffold and preparation method thereof |
| CN111110922B (en) * | 2019-12-25 | 2020-10-27 | 四川大学 | Periodontal biological module for 3D biological printing and construction method and application thereof |
| CN112220967B (en) * | 2020-11-26 | 2021-08-03 | 山东大学 | Targeting antibacterial and in-situ bone-promoting dual-functional material and preparation method and application thereof |
| CN115300147B (en) * | 2022-08-24 | 2023-05-09 | 四川大学 | Construction method of 3D printing personalized biological tooth root bracket |
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