CN107320784A - Tissue engineering bracket of micron ball containing natural polymer/nanosphere and preparation method thereof - Google Patents

Tissue engineering bracket of micron ball containing natural polymer/nanosphere and preparation method thereof Download PDF

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Publication number
CN107320784A
CN107320784A CN201610977564.XA CN201610977564A CN107320784A CN 107320784 A CN107320784 A CN 107320784A CN 201610977564 A CN201610977564 A CN 201610977564A CN 107320784 A CN107320784 A CN 107320784A
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natural polymer
tissue engineering
synthetic material
engineering bracket
nanosphere
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Chinese (zh)
Inventor
王大平
刘威
何勇
王大明
黄江鸿
陈洁琳
段莉
李文翠
朱伟民
熊建义
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Shenzhen Second Peoples Hospital
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Shenzhen Second Peoples Hospital
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Priority to CN201610977564.XA priority Critical patent/CN107320784A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/06Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Prostheses (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The present invention discloses tissue engineering bracket of a kind of micron ball containing natural polymer/nanosphere and preparation method thereof.The tissue engineering bracket includes degradable synthetic material and natural polymer micron ball and/or natural polymer nanosphere.The preparation method of the tissue engineering bracket comprises the following steps:Degradable synthetic material is dissolved in solvent, synthetic material solution is obtained;Natural polymer micron ball and/or natural polymer nanosphere are added in synthetic material solution, homogenate must be mixed by stirring;Freeze-drying process after homogenate machine-shaping will be mixed, tissue engineering bracket is obtained.Because natural polymer micron ball and/or natural polymer nanosphere are dispersed in synthetic material, the homogeneity of the timbering material component and the biocompatibility of support are significantly improved.

Description

Tissue engineering bracket of micron ball containing natural polymer/nanosphere and preparation method thereof
Technical field
The invention belongs to technical field of biological materials, and in particular to a kind of group of micron ball containing natural polymer/nanosphere Weaver's engineering support and preparation method thereof.
Background technology
The equal Shortcomings of cartilage repair techniques clinically applied at present, tissue engineering technique develops into cartilage damage Repair and provide a new direction, played a significant role as the timbering material of one of organizational project three elements.Therefore, prepare Preferable tissue engineering bracket is one of current research focus.
Preferable cartilage support material should have beneficial to cell adherence growth, good biocompatibility, degradable and suitable Degradation rate, highly porous 3-D solid structure, good mechanical performance and plasticity in terms of characteristic.According to biological material Material, can be divided into natural, artificial synthesized high polymer material and composite by the difference of material.Natural macromolecular material can be from biology Extract and obtain in tissue, including collagen, fibrin, gelatin, agar etc., with good biocompatibility, small toxicity and can It is degradable in vivo and be easily absorbed by the body without producing the advantage such as inflammatory reaction, but its mechanical strength is weaker and degraded speed Rate is uncontrollable.Artificial synthesized high polymer material includes organic synthetic material and Inorganic synthese material.Wherein, organic synthesis material bag Include PLA (polylactic, PLA), polycaprolactone (polycarolactone, PCL), polyglycolic acid (polyglycolic, PGA) and their copolymer etc., Inorganic synthese material include tricalcium phosphate, nanometer hydroxyapatite Etc. ceramic-like materials.There is good mechanical property and plasticity, controllable degradation rate, but its parent artificial high polymer material more It is aqueous it is poor, poor to cell adhesion, can cause inflammatory reaction with certain immunogenicity and acid degradation products.Composite It is to be composited by two or more different materials, by compound with different performance material, can reach and " take long benefit It is short " effect, the problems such as effectively solving biocompatibility, intensity, toughness and the intensity of timbering material;Bionical natural cartilage Component, the composite material bracket of 26S Proteasome Structure and Function are cartilage tissue engineered developing direction.
Existing numerous rack forming technology respectively has advantage and disadvantage, is used as the low temperature rapid shaping skill of one of three-dimensional printing technology Art (LDM), because it has the advantage of accurate control support aperture size and porosity, it is adaptable to the system of cartilage tissue engineering rack It is standby.LDM is based on rapid shaping technique principle, have the advantages that personalized printing, it is simple to operate, waste less, pollution it is few, belong to green The category of color manufacture.At present, LDM successfully realizes part file printing, but still fail to realize natural macromolecular material with The homogeneous of synthetic material is combined.Because LDM is to dissolving the solvent requirement more harshness of printed material, it is necessary to which solvent is at normal temperatures The solution of printed material can be dissolved, and can be frozen quickly after solution extrudes the low temperature touched in forming cavity from nozzle, To ensure rack forming.Therefore, the solvent of the homogeneity of shaped article and dissolved material turns into the homogeneous composite wood of restriction LDM printings The problem of material.
The content of the invention
Present invention aims to overcome that there is provided a kind of micron ball containing natural polymer/nanometer for the above-mentioned deficiency of prior art Tissue engineering bracket of ball and preparation method thereof, when preparing tissue engineering bracket to solve prior art LDM, forming composite Homogeneity and the technical problem such as preparation process solvent restriction.
In order to realize foregoing invention purpose, there is provided a kind of tissue engineering bracket for an aspect of of the present present invention.The support bag Include degradable synthetic material and the natural polymer micron ball and/or natural polymer that are dispersed in the degradable synthetic material Nanosphere, the degradable synthetic material is with the natural polymer micron ball and/or natural polymer mass of the nanosphere ratio (1:1)-(99:1)。
The tissue engineering bracket that the present invention is provided, because natural polymer micron ball and/or natural polymer nanosphere are equal It is even to be dispersed in synthetic material, with the technique effect for significantly improving tissue engineering bracket homogeneity and biocompatibility.
Another aspect of the present invention comprises the following steps there is provided a kind of preparation method of above-mentioned tissue engineering bracket:
The degradable synthetic material is dissolved in solvent, stirs 24-48 hours, obtains synthetic material solution;
The natural polymer micron ball and/or natural polymer nanosphere are added in the synthetic material solution, stir Mix 24-48 hours, obtain mixing homogenate;
By freeze-drying process after the mixing homogenate machine-shaping, the tissue engineering bracket is obtained;
Wherein, the degradable synthetic material and the natural polymer micron ball and/or natural polymer nanosphere Mass ratio is (1:1)-(99:1).
The tissue engineering bracket preparation method that the present invention is provided, because preparing in solution processes, is incorporated as quantitative natural height Molecule micron ball and/or natural polymer nanosphere, can accurately control natural material and synthetic material in the support of final molding Ratio;And natural polymer micron ball and/or natural polymer nanosphere are easy to be mixed into synthetic material solution, and at it In it is dispersed, in moulding process, particularly in LDM technologies, the scope of institute's rapidoprint is not limited by solvent, expand LDM application field.Meanwhile, this method cost is low, and condition is easily controllable, and the support finally prepared has good 3 D stereo knot Structure, porous, component homogeneity and biocompatibility.
Brief description of the drawings
Fig. 1 is the tissue engineering bracket preparation method schematic diagram provided in the embodiment of the present invention;
Fig. 2 is the tissue engineering bracket structural representation provided in the embodiment of the present invention:Wherein a is the micron ball in support Or nanosphere;B is support vertical sectional drawing;C is rack forming figure.
Embodiment
In order that technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with Drawings and Examples, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used To explain the present invention, it is not intended to limit the present invention.
The embodiment of the present invention provides a kind of tissue engineering bracket, and the support includes degradable synthetic material and is dispersed in and can drop Solve the natural polymer micron ball and/or natural polymer nanosphere in synthetic material.Wherein degradable synthetic material with it is natural Macromolecule micron ball and/or natural polymer mass of the nanosphere ratio are (1:1)-(99:1).
The tissue engineering bracket that the present embodiment is provided, due to natural polymer micron ball and/or natural polymer nanosphere It is dispersed in synthetic material, with the technique effect for significantly improving support homogeneity and biocompatibility.
Specifically, in an embodiment of the present invention, the degradable synthetic material in the tissue engineering bracket material is PLGA (Poly(D,L-lactide-co-glycolide), PLCL (PLLA-caprolactone), PLLA (PLLA), PLA (PLA), One or more in PCL (polycaprolactone) and PVA (polyvinyl alcohol).Preferably, in the present embodiment, degradable synthetic material For PLCL or PLGA.
Specifically, in an embodiment of the present invention, natural polymer micron ball in the tissue engineering bracket and/or natural High molecular nanometer sphere is one kind in collagen, hyaluronic acid, chondroitin sulfate, chitosan, gelatin, fibroin and sodium alginate Or it is a variety of.Preferably, in the present embodiment, natural polymer micron ball and/or natural polymer nanosphere are I-type collagen (COL I) or chitosan.
The present embodiment provide degradable synthetic material both have good mechanical property and controllable degradation rate, and with The natural polymer micron ball and/or natural polymer nanosphere of the present embodiment are combined the composite of composition, overcome again Synthetic material itself hydrophily is poor, cell adhesion is poor, acid degradation products can cause the defects such as inflammatory reaction, while natural high Molecule micron ball and/or natural polymer nanosphere are dispersed in synthetic material, and two components make this reality by synergistic effect Apply the tissue engineering bracket of example offer has other timbering materials can not in terms of homogeneity, biological safety and biocompatibility The advantage of analogy.It is (1 particularly in both mass ratioes:1)-(99:1), preferably 5:1, a diameter of 1- of natural polymer micron ball 1000 μm, preferably 400 μm;And/or natural nano bulb diameter be 1-999nm, preferably 300nm or 400nm when, the organizational project branch Frame homogeneity, biocompatibility reach optimal.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned organizational project, as shown in figure 1, comprising the following steps:
S01:Degradable synthetic material is dissolved in solvent, stirs 24-48 hours, obtains synthetic material solution;
S02:Natural polymer micron ball and/or natural polymer nanosphere are added in synthetic material solution, 24- is stirred Homogenate must be mixed within 72 hours;
S03:Freeze-drying process after homogenate machine-shaping will be mixed, tissue engineering bracket is obtained;
Wherein, in the degradable synthetic material and step S02 in the step S01 natural polymer micron ball and/or The mass ratio of natural polymer nanosphere is (1:1)-(99:1).
The tissue engineering bracket preparation method that the present embodiment is provided, because preparing in solution processes, is incorporated as quantitative natural Macromolecule micron ball and/or natural polymer nanosphere, can accurately control natural material and synthesis material in the support of final molding The ratio of material;And natural polymer micron ball and/or natural polymer nanosphere are easy to dissolving, in moulding process, especially It is that in LDM technologies, the scope of institute's rapidoprint is not limited by solvent, expands LDM application field.Meanwhile, this method cost Low, condition is easily controllable, and the support finally prepared has good 3-D solid structure, porous, component homogeneity and biofacies Capacitive.
Specifically, in above-mentioned steps S01, solvent of the embodiment of the present invention is the alkane of Isosorbide-5-Nitrae-dioxy six (DIO).
Specifically, in above-mentioned steps S03, the processing molding method that the embodiment of the present invention is used is LDM printing shaping.Tool Body LDM printing process be:
Pretreatment is modeled with CAD software, Aurora softwares carry out hierarchy slicing, Cark Software for Design print parameters;
When room temperature to be formed is down to -25~-35 DEG C, the solvent in shaped platform smearing step S01;
Mixing homogenate is poured into batch can and printed.
The print procedure accurately controls the ratio of synthetic material and natural material, has both significantly improved synthetic material bioactivity And biocompatibility, while improving the homogeneous of natural polymer micron ball and/or natural polymer nanosphere and synthetic material again Property, the support of final molding is applied to clinical demand.
Specifically, in above-mentioned steps S03, the mixing homogenate of the embodiment of the present invention is joined by the printing of LDM print procedures Number is:1000 μm -400 μm of jet diameters, 300 μm -1000 μm of spinneret spacing, 15~30mm/s of sweep speed, spray head speed 1.0 ~2.0mm/s.Under the conditions of the print parameters, the homogeneity and biocompatibility of the tissue engineering bracket of the printing reach most It is excellent.
Specifically, in above-mentioned steps S03, the freezing dry process of the embodiment of the present invention is:In freezing chamber, -50 DEG C Under the conditions of freeze 72 hours.Under the conditions of the freeze drying process, the present embodiment printing tissue engineering bracket homogeneity and Biocompatibility is optimal.
It is of the invention successively to carry out test of many times, now lift A partial experiment result further detailed as reference pair invention progress Thin description, is described in detail with reference to specific embodiment.
Embodiment 1
The present embodiment provides a kind of tissue engineering bracket, and the support is specifically included:(1) degradable synthetic material:1.3g PLCL;(2) natural polymer micron ball:0.0133g COLI micron balls (400 μm of diameter);COLI micron balls are dispersed in In PLCL.The support concrete structure is as shown in Figure 2:Wherein a is the COLI micron balls in the support;B is the support vertical tangent plane Figure, rectangle is PLCL, and circle is COLI micron balls;C is the scaffold three-dimensional printing shaping figure.From figure 2 it can be seen that COLI Micron ball is dispersed in synthetic material PLCL.
The above-mentioned tissue engineering bracket material preparation method of the present embodiment is as shown in figure 1, concretely comprise the following steps:
S11:1.3g PLCL materials are weighed, and are added in 10mL DIO solvents, magnetic stirrer 48h are placed in extremely PLCL is completely dissolved, and forms PLCL solution;
S12:A diameter of 400 μm of 0.0133g COLI micron balls are weighed, is added in PLCL solution, uses magnetic stirring apparatus 72h is stirred, the mixed solution for being dispersed with COL I micron balls is formed;
S13:Pretreatment, Aurora softwares are modeled by CAD software to carry out hierarchy slicing, and set using Cark softwares Count the print parameters (jet diameters of three-dimensional composite material support:600μm;500 μm of spinneret spacing;Sweep speed:20mm/s, spray Head speed:1.5mm/s);When room temperature to be formed is down to -25~-35 DEG C, solvent is smeared in shaped platform, mixed solution is fallen Enter the prefabricated component that printing in batch can obtains three-dimensional rack material;It is freeze-dried after taking-up:Freezed 72 hours under the conditions of -50 DEG C, Obtain the present embodiment and contain COLI micron balls and PLCL tissue engineering bracket.
Embodiment 2
The present embodiment provides a kind of tissue engineering bracket, and the support is specifically included:(1) degradable synthetic material:1g's PLGA;(2) natural polymer nanosphere:1g COLI nanospheres (diameter 600nm);COLI nanospheres are dispersed in PLGA In.The support concrete structure is as shown in Figure 2:Wherein a is the COLI nanospheres in the support;B is the support vertical sectional drawing, long Square is PLGA, and circle is COLI nanospheres;C is the scaffold three-dimensional printing shaping figure.From figure 2 it can be seen that COLI nanometers Ball is dispersed in synthetic material PLGA.
The above-mentioned tissue engineering bracket material preparation method of the present embodiment is as shown in figure 1, concretely comprise the following steps:
S21:1g PLGA materials are weighed, and are added in 10mL DIO solvents, magnetic stirrer 48h to PLGA is placed in It is completely dissolved, forms PLGA solution;
S22:The a diameter of 600nm of 1g COLI nanospheres are weighed, is added in PLGA solution, uses magnetic stirrer 48h, forms the mixed solution for being dispersed with COLI nanospheres;
S23:Pretreatment, Aurora softwares are modeled by CAD software to carry out hierarchy slicing, and set using Cark softwares Count the print parameters (jet diameters of three-dimensional composite material support:400μm;450 μm of spinneret spacing;Sweep speed:20mm/s, spray Head speed:2mm/s);When room temperature to be formed is down to -25~-35 DEG C, solvent is smeared in shaped platform, mixed solution is poured into Printing obtains the prefabricated component of three-dimensional rack in batch can;It is freeze-dried after taking-up:Freeze 72 hours, obtain under the conditions of -50 DEG C The present embodiment contains COLI nanospheres and PLGA tissue engineering bracket material.
Embodiment 3
The present embodiment provides a kind of tissue engineering bracket, and the support is specifically included:(1) degradable synthetic material:1g PLGA;(2) natural polymer nanosphere:0.2g chitosan nano balls (diameter 300nm);Chitosan nano ball is dispersed in In PLGA.The concrete structure of the support is as shown in Figure 2:Wherein a is the chitosan nano ball in the support;B is the support vertical Sectional drawing, rectangle is PLGA, and circle is glycan nanosphere;C is the scaffold three-dimensional printing shaping figure.From figure 2 it can be seen that Chitosan nano ball is dispersed in synthetic material PLGA.
The above-mentioned tissue engineering bracket preparation method of the present embodiment is as shown in figure 1, specific steps include:
S31:1g PLGA materials are weighed, and are added in 10mL DIO solvents, magnetic stirrer 48h are placed in extremely PLGA is completely dissolved, and forms PLGA solution;
S32:The a diameter of 300nm of 0.2g chitosan nano ball is weighed, is added in PLGA solution, is stirred with magnetic stirring apparatus 72h is mixed, the mixed solution for being dispersed with chitosan nano ball is formed;
S33:Pretreatment, Aurora softwares are modeled by CAD software to carry out hierarchy slicing, and set using Cark softwares Count the print parameters (jet diameters of three-dimensional composite material support:400μm;500 μm of spinneret spacing;Sweep speed:20mm/s, spray Head speed:1.5mm/s);When room temperature to be formed is down to -25~-35 DEG C, solvent is smeared in shaped platform, mixed solution is fallen Enter the prefabricated component that printing in batch can obtains three-dimensional rack;It is freeze-dried after taking-up:Freeze 72 hours, obtain under the conditions of -50 DEG C Contain chitosan nano ball and PLGA tissue engineering bracket to the present embodiment.
Physicochemical property test is carried out to the support of above three embodiment, and carried out with prior art similar stents material Comparative example is analyzed, as a result such as table 1 below.
Table 1
Parameter index Embodiment 1 Embodiment 2 Embodiment 3 Comparative example
Porosity 83% 82% 85% 81%
Extensibility 90% 55% 60% 80%
Compression modulus 0.33MPa 32MPa 30MPa 0.3MPa
Degraded percentage 100% 100% 100% 100%
Shrinkage rates 15% 1% 1.5% 20%
As can be seen from the above table, the performance for the tissue engineering bracket material that the present invention is provided is significantly better than prior art.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.

Claims (10)

1. a kind of tissue engineering bracket, it is characterised in that the support includes degradable synthetic material and be dispersed in described to drop Solve synthetic material in natural polymer micron ball and/or natural polymer nanosphere, the degradable synthetic material with it is described The mass ratio of natural polymer micron ball and/or natural polymer nanosphere is (1:1)-(99:1).
2. tissue engineering bracket as claimed in claim 1, it is characterised in that the degradable synthetic material be PLGA, PLCL, One or more in PLLA, PLA, PCL and PVA.
3. tissue engineering bracket as claimed in claim 1, it is characterised in that the natural polymer micron ball and/or natural High molecular nanometer sphere is one kind in collagen, hyaluronic acid, chondroitin sulfate, chitosan, gelatin, fibroin and sodium alginate Or it is a variety of.
4. tissue engineering bracket as claimed in claim 1, it is characterised in that when being dispersed in the degradable synthetic material When ball is natural polymer micron ball, a diameter of 1-1000 μm of the micron ball;When being dispersed in the degradable synthetic material Ball be natural polymer nanosphere when, a diameter of 1-999nm of nanosphere.
5. a kind of method for preparing the tissue engineering bracket as described in claim 1-4 is any, it is characterised in that including following step Suddenly:
The degradable synthetic material is dissolved in solvent, stirs 24-48 hours, obtains synthetic material solution;
The natural polymer micron ball and/or natural polymer nanosphere are added in the synthetic material solution, 24- is stirred Homogenate must be mixed within 72 hours;
By freeze-drying process after the mixing homogenate machine-shaping, the tissue engineering bracket is obtained;
Wherein, the quality of the degradable synthetic material and the natural polymer micron ball and/or natural polymer nanosphere Than for (1:1)-(99:1).
6. the preparation method of tissue engineering bracket as claimed in claim 5, it is characterised in that the solvent is Isosorbide-5-Nitrae-dioxy six Alkane.
7. the preparation method of tissue engineering bracket as claimed in claim 5, it is characterised in that the processing molding method is LDM Printing shaping.
8. the preparation method of tissue engineering bracket as claimed in claim 7, it is characterised in that the process of the LDM printings is:
Pretreatment is modeled with CAD software, Aurora softwares carry out hierarchy slicing, Cark Software for Design print parameters;
When room temperature to be formed is down to -25~-35 DEG C, the solvent is smeared in shaped platform;
The mixing homogenate is poured into batch can and printed.
9. the preparation method of tissue engineering bracket as claimed in claim 8, it is characterised in that the print parameters are:Shower nozzle is straight Footpath be 1000 μm -400 μm, spinneret spacing be 300 μm -1000 μm, sweep speed be 15~30mm/s, spray head speed be 1.0~ 2.0mm/s。
10. the preparation method of tissue engineering bracket as claimed in claim 5, it is characterised in that the freezing dry process is:- Freezed 72 hours under the conditions of 50 DEG C.
CN201610977564.XA 2016-11-04 2016-11-04 Tissue engineering bracket of micron ball containing natural polymer/nanosphere and preparation method thereof Pending CN107320784A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116617468A (en) * 2023-05-10 2023-08-22 万瑞飞鸿(北京)医疗器材有限公司 Heart stent and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104623737A (en) * 2014-12-31 2015-05-20 深圳清华大学研究院 Personalized tissue repairing scaffold capable of realizing pulsed sustained release and preparation method thereof
CN105727368A (en) * 2016-01-08 2016-07-06 深圳市第二人民医院 Three-dimensional composite material support and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104623737A (en) * 2014-12-31 2015-05-20 深圳清华大学研究院 Personalized tissue repairing scaffold capable of realizing pulsed sustained release and preparation method thereof
CN105727368A (en) * 2016-01-08 2016-07-06 深圳市第二人民医院 Three-dimensional composite material support and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116617468A (en) * 2023-05-10 2023-08-22 万瑞飞鸿(北京)医疗器材有限公司 Heart stent and preparation method and application thereof
CN116617468B (en) * 2023-05-10 2024-05-28 万瑞飞鸿(北京)医疗器材有限公司 Heart stent and preparation method and application thereof

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Application publication date: 20171107