CN1486754A - Porous rack with spherical pores and its molding prepn process - Google Patents
Porous rack with spherical pores and its molding prepn process Download PDFInfo
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Abstract
The present invention belongs to the field of polymer material and biological material technology, and is especially one porous rack with spherical pores and its molding preparation process. The 3D porous rack is prepared with polymer material as base material and through molding at normal temperature. The simple process may be used in preparing both rack with simple and regular outer appearance and rack with complicated and irregular outer appearance. The prepared porous rack may be relatively thick and has regular spherical pore structure of porosity over 90%, and the pores are communicated mutually and homogeneously distributed. The rack has high mechanical strength, and is suitable as 3D porous cell rack in tissue engineering and in other application fields.
Description
Technical field
The invention belongs to macromolecular material and technical field of biological materials, be specifically related to a kind of macromolecule spherical pore porous support and room temperature mold pressing preparation method thereof.
Technical background
Porous support or porous foam can be widely used in tissue engineering bracket, cell culture vector, medicine sustained release carrier, wound dressing, diffusion barrier and many fields such as filtering material, chromatographic column filler, packing and insulant.
Combining the birth of the tissue engineering of preparation engineering tissue and organ by cell and porous support, is the tradition tissue and the major progress of organ transplantation.In organizational project, porous support all has very important effect at the cultivation of cell and amplification and final tissue or the aspects such as formation of organ.And biodegradated polymer materal is easy to process, have good comprehensive mechanical property relatively, dies away along with the formation of tissue or organ finally can not stay any external foreign body in human body, thereby is widely used as porous support materials.
For tissue engineered porous scaffold, hole dimension, porosity and specific surface area are considered to the several main parameters that plays a decisive role usually.And the connectedness in some other topological structure parameter such as hole shape, hole, shape of borehole wall etc. also are considered to play an important role for plantation and amplification, the transportation of nutrient substance and the formation of new organization and organ of cell.
Up to now, in order to prepare the tissue engineered porous scaffold that satisfies various tissues and organ needs, many method sequential use such as particle hole forming technology, non-woven fabrics technology, foaming technology, phase detachment technique and 3 D-printing technology have arrived in the preparation of high-molecule porous scaffold.And in engineered research, all shown certain application prospect at Different Organs by the porous support of method for preparing, also have many problem values to get further research in the clinical practice but will really be applied to.
Wherein, particle pore method is simple and practical, the suitability is wide, the easy independent regulation of porosity and hole dimension, be one than method in common (Mikos and Langer, Polymer, 1994,35 (5): 1068--1077), prepared porous support thin usually (＜2mm), but can obtain certain thickness three-dimensional porous rack (Mikos et al. by stacked method, Biomaterials, 1993,14 (50): 323--330).(J.Biomed.Mater.Res., 53:1--7) mixture with macromolecule, solvent, ammonium bicarbonate particle makes porous support through gas foaming, salt grain solvent extraction method for Nam and Park.
Said method has only been reported the square result who waits the porous support in simple shape hole, and can be applied to skin etc. does not need in the field of tissue engineering technology of thicker size.But the pore structure of porous support is not done too meticulous consideration, and complex forming technology, be unfavorable for mass preparation and production.
Have thicker size and the controlled porous support of rule in order to prepare, the 3 D-printing technology has obtained good application (Cima et al, J.Biomech.Eng., 1991,113:143-151 in organizational project; Park et al, J.Biomater.Sci.Polym.Ed., 1998,9 (2): 89-110).When the 3 D-printing legal system was equipped with porous support, printing head sprayed polymer powder and binding agent (being generally solvent) successively, and binding agent becomes one deck with powder-stuck, under computer control, successively prints by preset program, can form three-dimensional porous rack.3 D-printing at room temperature carries out, but the hole dimension of gained support is less than normal, and mechanical property and formed precision still await further raising (Cima et al, J.Biomater.Sci.Polym.Ed., 1996,8 (1): 63-75).The fused deposition forming technique is then without solvent, but extrudes from level to level after thermoplastic polymer is heated to fusion, form three-dimensional porous rack (Hutmacher, Biomaterials, 2000,21:2529-2543).The advantage of 3 D-printing technology is that molding time is short, relatively is suitable for automatic mass production; And can prepare three-dimensional porous rack rapidly according to the difference of individuality with personal feature; Also can prepare support that each position has Different Pore Structures to adapt to the different requirements of complex tissue.But its weak point is that the brace aperture rate is on the low side, and usually less than 80%, the profile formed precision also has much room for improvement at present.
People such as Ma (Tissue Engineering, 2001,7 (1): 23-33) once reported the porous support that has prepared high porosity with spherical paraffin particles; People such as Thomson (J.Biomater.Sci.Polymer Ed., 1995,7 (1): 23-38) also attempt preparing the ordered porous support of organizational project as porogen, for the tissue engineered porous scaffold for preparing the controllable hole structure form provides a good idea with gelatine microsphere.But because people's such as Ma pore method is very not favourable for molding, the support that is obtained is thinner, also is difficult to obtain mechanical property support preferably.
In organizational project, remove minority portion of tissue such as skin and can adopt the support that approaches with organ, more be the large scale three-dimensional porous rack that is complementary with particular organization or organ with complex appearance, thus how in conjunction with novel porogen particle prepare the internal pore structure that not only has rule, but also method and technology with three-dimensional porous rack of big thickness or complicated shape be the key issue that presses for solution in the organizational project.
The present invention then combines the hole forming technology of spheroidal particle and the forming technique of porous support, has proposed preparation and has had the method for the porous support of regular pore structure.For particle comparatively regular sphere or torispherical porogen particle, when solvent is moderate in macromolecule/porogen particle/solvent mixture, can form immobilising paste complex, can carry out compression molding at normal temperatures, and shape hold facility is preferably also arranged after the demoulding.Porous support with this method preparation has distinctive sphere of porogen or torispherical pore structure, can be used for the preparation of large-sized porous support.
Summary of the invention
High-molecule porous scaffold and the room temperature mold pressing preparation method thereof that the objective of the invention is to propose a kind of outside can be thicker, there be special spherical pore inside.
The high-molecule porous scaffold that the present invention proposes, both can be the porous support that profile is simple or profile is regular, also can be the irregular porous support of complex contour or profile, comprise and human or animal's the defective tissue or the same or analogous porous support of dissection profile of organ.Such porous support helps the final tissue of needs or the profile of organ of forming in organizational project is used.
The high-molecule porous scaffold that the present invention proposes has bigger thickness, and the thickness in its thickness reaches 3-100mm.
The high-molecule porous scaffold that the present invention proposes, the hole is sphere or torispherical, range of aperture size is 10-900 μ m, is generally 50-500 μ m.Inner porosity is 50-90% in order to be interconnected and comparatively regular macroporous structure, and porosity is more than 50% usually, generally can reach more than 85%, reaches as high as more than 95%.The high porosity support has the pore structure that is interconnected.The internal stent pore size distribution is even, and rack surface also is a loose structure, does not have fine and close surperficial cortex and forms.
The high-molecule porous scaffold that the present invention proposes adopts the room temperature die pressing to prepare.Concrete steps are as follows:
1, macromolecular material is dissolved in solvent orange 2 A, form high molecular concentrated solution, porogen particle with sphere or torispherical adds in the macromolecular solution then, stirs to mix evenly, treats to form immobilising paste macromolecule/porogen particles mixture after solvent partly volatilizees;
2, the macromolecule/porogen particles mixture with the gained paste charges in the die cavity with definite shape, and at room temperature impressed pressure is so that the mixture typing;
3, obtain having the macromolecule/porogen mix particles Tetramune of required profile after the demoulding, vacuum drying is removed residual solvent A, obtains macromolecule/porogen particle composite article;
4, the macromolecule/porogen particle composite article that will remove solvent orange 2 A is put into solvent B with stripping porogen particle, treat the complete stripping of porogen particle after, porous support is taken out from solvent B, drying removes the porous support that obtains required form behind the solvent B.
As seen, porogen particle has wherein played the negative norm plate effect of macropore, and porosity is played main contribution.Certainly, the solvent that is added also can cause the part aperture.
The used mould of the present invention can be made by the flexibility or rigidity material.Flexible material is the macromolecular elastomer material, comprises silastic material, thiorubber. material, polyether rubber material etc., is mainly silastic material.Rigid material is a metal material, comprises carbon steel, rustless steel, steel alloy, mould steel etc.Has the pressure of enough mechanical strengths when bearing molding.
The high-molecule porous scaffold that the present invention proposes, its stock adopt the synthetic or natural macromolecular material with self-adhesive, resolvability, have both comprised degradable high polymer material, also comprise nondegradable macromolecular material.Its molecular weight is 10,000～3,000,000, is generally 3～1,000,000.Also can comprise the copolymer or the blend of above-mentioned material and the mixture that contains additive.
The used natural macromolecular material of the present invention is mainly alginate, collagen, gelatin, chitosan, hyaluronic acid, acellular matrix, and any by in several copolymers of forming or the blend among them.
The used degradable macromolecular material of the present invention also comprises aliphatic polyesters such as polylactone and polyhydroxycarboxyliacid acid ester, Merlon, poe, poly-anhydride, poly-dioxane, or any by several copolymers of forming or blend among them.Above aliphatic polyester comprises poly-(D, L-lactic acid) (PDLLA), gathers (L-lactic acid) (PLLA), polyglycolic acid (PGA), polycaprolactone homopolymer and poly lactic coglycolic acid (PLGA), caprolactone copolymer or other copolymers such as (PCL).The degradation rate of above degradable macromolecule can be as required, and by changing high molecular structure or form and adjusted, the degradation time scope is 1 thoughtful 2 years, is generally 1 month to 6 months.
The used nondegradable macromolecular material of the present invention comprises polystyrene, polrvinyl chloride, polyacrylate, polymethacrylates, Merlon, nylon, polyurethane, polyformaldehyde, polyvinyl alcohol, polyvinyl acetate, polysiloxanes, and the copolymer of several compositions and blend any wherein.
The used solvent of the present invention comprises solvent orange 2 A and solvent B.Require solvent orange 2 A solubilized porous support materials, but can not change its structure and performance; The porogen particle is not dissolved, and do not change the character of porogen particle; Have suitable volatility, under vacuum condition, can remove fully.Solvent orange 2 A comprises acetone, butanone, chloroform, dichloromethane, oxolane, benzene,toluene,xylene, ethylene glycol, Ketohexamethylene, dioxane, N, any or its mixture in dinethylformamide, formic acid, benzyl alcohol, the cyclohexane extraction.Require solvent B solubilized porogen particle, but do not dissolve timbering material, also can not change their structure and performance.Solvent B has suitable volatility, can remove fully under vacuum condition.Be generally any or its mixture in pentane, hexane, heptane, octane, cyclohexane extraction, the water.
The used porogen particle of the present invention is the profile with sphere or torispherical, and the porogen particle is dissolved in solvent B but is insoluble to solvent orange 2 A.The porogen particle not with used macromolecule generation chemical reaction, also be insoluble to solvent orange 2 A.The porogen particle is scattered in the macromolecular solution equably and keeps its shape and size, and after it was by solvent B dissolving, the occupied volume of porogen particle just became hole, formed porous support.The pore structure of porous support and size are determined by porogen shape of particle, size and consumption.Used porogen particle comprises paraffin, Cera Flava, gelatin, naphthalene or the mixture of being made up of them.Particle sieves into different fractions with standard screen, and the grain size scope is 10-900 μ m, and the stock size scope is 50-500 μ m.The porosity of porous support depends on porogen particle consumption (based on macromolecule and porogen particle total weight), and the influence of solvent orange 2 A content is less.Porogen particle amount ranges is 50wt%-99wt%, and better amount ranges is 70wt%-95wt%; Corresponding macromolecule amount ranges is 50wt%-1wt%, and better amount ranges is 30wt%-5wt%.
The used macromolecular solution concentration range of the present invention is 1wt%-50wt% (percentage by weight is based on the macromolecular solution total weight), and better concentration range is 5wt-30wt%, is the macromolecule concentrated solution.The concentration of macromolecular solution is different and different according to used high molecular molecular weight, and the solution concentration of heavy polymer can be hanged down.
Among the present invention, the porogen particle is scattered in the macromolecular solution, makes the partial solvent volatilization while stirring, form finely dispersed macromolecule concentrated solution-porogen particles mixture.This mixture is paste, does not have flowability, at the goods that can have required profile by the compression molding acquisition in suitable mould under the room temperature low pressure; The goods that obtain after the demoulding have good shape hold facility.
When carrying out the room temperature compression molding among the present invention, can adopt small-sized moulding press, also can adopt any equipment with mold pressing ability of design voluntarily.
Among the present invention, macromolecular solution-porogen mix particles Tetramune that the room temperature mold pressing is obtained partly volatilizees solvent orange 2 A under room temperature environment earlier, under vacuum condition, remove residual solvent A then, treat to obtain after solvent orange 2 A removes fully the moulded products of macromolecule-porogen particles mixture.The vacuum drying temperature is no more than the fusing point or the vitrification point of timbering material, generally is not higher than 50 ℃, is generally room temperature.
Among the present invention, above-mentioned macromolecule-porogen particles mixture moulded products leaches the porogen particle in solvent B.Macromolecule-porogen particles mixture moulded products is put into container, add solvent B, solvent B consumption is excessive greatly, and its weight is generally 10-1000 times of macromolecule-porogen particles mixture weight support frame, better choice be 20-500 doubly, leach fully to the porogen particle.
Among the present invention, the above-mentioned support that leaches the porogen particle is fully taken out from container, treat to put into the vacuum drying oven vacuum drying after the most of solvent B volatilization, obtain required high-molecule porous scaffold after removing solvent B fully.The vacuum drying temperature is no more than the fusing point or the vitrification point of timbering material, generally is not higher than 50 ℃, and be 8-96 hour drying time, depends on the content of solvent B residual in drying condition and the support.
The process of above-mentioned preparation and molding can be a continuous process, also can proceed step by step.
The present invention has following characteristics:
1, the present invention is a processing object with macromolecule/porogen mixture, the molding object was the macromolecule/porogen/solvent complex of paste when support prepared, this complex solvent is few, have good plasticity and morphotropism, has good shape hold facility simultaneously, can in suitable mould, obtain required goods profile at normal temperatures, and the goods that obtain after the demoulding there is good shape hold facility by compression molding.
2,, can control the thickness of made support at an easy rate, generally at 1mm～100mm in view of the characteristics of such forming process; The thickest part＞3mm wherein.Preparation with spherical pore porous support of complicated shape has especially embodied the characteristic of the inventive method.
3, gained support mechanical property is better.
When 4, carrying out compression molding among the present invention, can under room temperature and low pressure, carry out, can adopt small-sized moulding press, also can adopt any equipment with mold pressing ability of design voluntarily.
5, the room temperature die pressing of the present invention's proposition both can prepare the porous support that profile is simple or profile is regular, also can be the irregular porous support of complex contour or profile, comprised and human or animal's the defective tissue or the porous support of the same or similar dissection profile of organ.
6, the porous support preparation method of the present invention's proposition has been avoided high temperature, helps the introducing of heat sensitive bioactive substance.
7, simple and practical, the favorable reproducibility of high-molecule porous scaffold room temperature mold pressing preparation method of the present invention's proposition helps large-scale production.
8, the high-molecule porous scaffold room temperature mold pressing preparation method adaptability of the present invention's proposition is strong, is applicable to various soluble high-moleculars and complex thereof, is a general porous support preparation method, can be used for organizational project and other multiple application.
9, the high-molecule porous scaffold of the present invention's preparation has the sphere or the torispherical pore structure of rule, is convenient to accurately design and the performances such as mechanical-physical of regulating porous support.
10, the high-molecule porous scaffold porosity of the present invention's preparation can be up to more than 90%, and hole is interconnected, and pore size distribution is even, and rack surface also is a loose structure, no dense layer surface.
When 11, the porous support of the present invention's proposition is used for the bio-medical field, adopt the good Biodegradable high-molecular preparation of biocompatibility that has obtained extensive approval, be expected to the generation of toxic and side effects such as avoiding or diminish inflammation after implanting, to meet biomedical requirement better.
12, the pore structure form of the Biodegradable high-molecular porous support of the present invention's proposition helps adhesion, propagation and the differentiation of cell, help the growth of implant site surrounding tissue cell after implanting, so, resulting support is suitable for a plurality of applications of porous foam, especially can be used for field of tissue engineering technology.
Description of drawings
Fig. 1 is spherical paraffin pore particle optics displaing micro photo figure, and particle diameter is 355-450 μ m among Fig. 1 (A); Particle diameter is 810-900 μ m among Fig. 1 (B).
Fig. 2 is that 355-450 μ m, porosity are 95% the cylindrical porous support photo of PLGA85/15 for the aperture.
Fig. 3 is that 355-450 μ m, porosity are 95% PLGA85/15 porous support electron scanning micrograph for the aperture.
Fig. 4 is that 810-900 μ m, porosity are the light micrograph of 95% PLGA85/15 column type porous support section for the aperture.
The specific embodiment
The embodiment that the invention is further illustrated by the following examples, but be not limited to these embodiment.
Embodiment 1, at first prepares spherical paraffin particles.1g gelatin, 20g paraffin are added in the deionized water of 400mL, are warming up to 80 ℃ and under the 400rpm mechanical agitation, stir, add 300mL frozen water quenching then so that microsphere can keep spherical.Filter, deionized water wash sieves not at the same level part paraffin particles (see figure 1) several times then with different standard screens after the drying, and kept dry is standby.
With the 0.5g molecular weight is that 300,000 PLGA85/15 is dissolved in the 8mL acetone, and getting the 9.5g particle diameter is that the spherical paraffin particles of 355-450 μ m adds in the solution, stirs, and solvent is partly volatilized, and makes macromolecular solution---the porogen particles mixture becomes paste; This mixture is pressed in the pre-designed silicon rubber mould (diameter 1cm, height 1cm), adds suitable pressure and kept 30 minutes; Obtain having the macromolecular solution of external ear shape after the demoulding---the compound rest of porogen particles mixture, at room temperature make the partial solvent volatilization, remove residual solvent in room temperature, vacuum under＞755mmHg the condition then, obtain macromolecule---the compound rest of porogen particles mixture; With not solvent-laden macromolecule---the compound rest of porogen particles mixture is placed in the Soxhlet extractor made solvent extraction 48 hours with pentane; Take out porous support then, at room temperature treat solvent evaporates after 8 hours, remove residual solvent in room temperature, vacuum under＞755mmHg the condition again, finally obtain columned porous support (see figure 2), the pore structure (see figure 3) that is connected, porosity 96.2%, compressive strength 110kPa.
Embodiment 2, are that 300,000 PLGA85/15 is dissolved in the 8mL acetone paraffin spheroidal particle 2.55g with the 0.45g molecular weight, particle diameter is 810-900 μ m, and other is with embodiment 1, the hole that the makes porous support (see figure 4) that is interconnected, porosity is 89.8%, compressive strength 7.1MPa.
Embodiment 3, are that 300,000 PLGA85/15 is dissolved in the 10mL acetone with the 0.6g molecular weight, and paraffin spheroidal particle 1.4g, particle diameter are 355-450 μ m, and other is with embodiment 1, and the porosity that makes porous support is 78.4%, compressive strength 15.4MPa.
Embodiment 4, are that 60,000 PDLLA is dissolved in the 10mL acetone with the 0.3g molecular weight, and paraffin spheroidal particle 2.7g, particle diameter are 280-355 μ m, and with normal hexane extracting porogen, other is with embodiment 1, and the porosity that makes porous support is 94.1%, compressive strength 2.4MPa.
Embodiment 5, are that 50,000 PCL is dissolved in the 10mL acetone with the 0.3g molecular weight, and paraffin spheroidal particle 2.7g, particle diameter are 280-450 μ m, and other is with embodiment 1, and the porosity that makes porous support is 93.7%, compressive strength 2.0MPa.
Embodiment 6, are that 60,000 PDLLA is dissolved in the 10mL acetone with the 0.3g molecular weight, and paraffin spheroidal particle 2.7g, particle diameter are 45-90 μ m, and other is with embodiment 1, and the porosity that makes porous support is 92.9%, compressive strength 2.5MPa.
Claims (10)
1, a kind of high-molecule porous scaffold is characterized in that the dissection profile of its profile and human or animal's defective tissue or organ is same or similar, and the thickness is 3-100mm; Inner for to be interconnected and comparatively regular macroporous structure, the spherical in shape or torispherical in hole, aperture size are 10-900 μ m; The porosity height is 50-99%.
2, porous support according to claim 1, the stock that it is characterized in that support is for having self-adhesive, resolvability, plastic natural or synthesized polymer material, both comprised degradable macromolecule, also comprise nondegradable macromolecule, and the copolymer of above-mentioned material, mixture or with the mixture of additive.
3, porous support according to claim 2 is characterized in that natural macromolecular material is alginate, collagen, gelatin, chitosan, hyaluronic acid, acellular matrix, and any by in several copolymers of forming or the blend among them.
4, porous support according to claim 2, it is characterized in that degradable macromolecular material is polylactic acid, polyglycolic acid, poly butyric ester, polycaprolactone, Merlon, poe, poly-anhydride, poly-dioxane, and any by in several copolymers of forming or the blend among them.
5, porous support according to claim 2, it is characterized in that the non-degradable macromolecular material is polystyrene, polrvinyl chloride, polyacrylate, polymethacrylates, Merlon, nylon, polyurethane, polyformaldehyde, polyvinyl alcohol, polyvinyl acetate, polysiloxanes, and any by in several copolymers of forming or the blend among them.
6, a kind of preparation method as one of claim 1-5 described high-molecule porous scaffold is characterized in that concrete steps are as follows:
(1) macromolecular material is dissolved in solvent orange 2 A, form macromolecular solution, porogen particle with sphere or torispherical adds in the macromolecular solution then, stirs to mix evenly, treats that partial solvent volatilization back forms immobilising paste macromolecular solution/porogen particles mixture;
(2) macromolecular solution/porogen particles mixture with the gained paste charges in the die cavity with definite shape, and at room temperature impressed pressure is so that the mixture typing;
(3) obtain having the macromolecular solution/porogen mix particles Tetramune of required profile after the demoulding, vacuum drying is removed residual solvent, obtains macromolecule/porogen particle composite article;
(4) will be remove the macromolecule/porogen particle composite article that desolvates and put into solvent B with stripping porogen particle, treat the complete stripping of porogen particle after, porous support is taken out from solvent B, drying removes the porous support that obtains required form behind the solvent B;
Wherein, solvent orange 2 A solubilized porous support materials, but do not dissolve the porogen particle; Solvent B solubilized porogen particle, but do not dissolve porous support materials.
7, the preparation method of porous support according to claim 6 is characterized in that used porogen particle is sphere or torispherical, and particle size range is 10-900 μ m, and porogen particle amount ranges is 50wt% one 99wt% of mixture.
8, the preparation method of porous support according to claim 6 is characterized in that porogen only is dissolved in solvent B but is insoluble to solvent orange 2 A, is specially any or its mixture of paraffin, Cera Flava, gelatin, naphthalene.
9, the preparation method of porous support according to claim 6, it is characterized in that solvent orange 2 A is acetone, butanone, chloroform, dichloromethane, oxolane, benzene,toluene,xylene, ethylene glycol, Ketohexamethylene, dioxane, N, any or wherein several mixture in dinethylformamide, formic acid, benzyl alcohol, the cyclohexane extraction.
10, the preparation method of porous support according to claim 6 is characterized in that solvent B is any or wherein several mixture in pentane, hexane, heptane, octane, cyclohexane extraction, the water.
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| CN102432911A (en) * | 2011-09-13 | 2012-05-02 | 复旦大学 | Particle with surface topological topography, porous bracket and preparation method thereof |
| CN102690435A (en) * | 2012-06-19 | 2012-09-26 | 上海大学 | Method for regulating pore structure of water-soluble polymer tissue engineering scaffold by use of polyester template |
| CN105153457A (en) * | 2015-07-24 | 2015-12-16 | 华侨大学 | Porous polyvinyl chloride foam ball and preparation method therefor |
| CN105749354A (en) * | 2014-12-19 | 2016-07-13 | 深圳先进技术研究院 | Normal forming method for sodium alginate containing three-dimensional scaffold |
| CN107737584A (en) * | 2017-09-20 | 2018-02-27 | 福建师范大学 | A kind of porous material with micro-nano structure and preparation method thereof |
| CN108096638A (en) * | 2015-04-07 | 2018-06-01 | 四川蓝光英诺生物科技股份有限公司 | Biological brick for biometric print and application thereof |
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| CN102432911B (en) * | 2011-09-13 | 2013-07-31 | 复旦大学 | Particle with surface topological topography, porous bracket and preparation method thereof |
| CN102432911A (en) * | 2011-09-13 | 2012-05-02 | 复旦大学 | Particle with surface topological topography, porous bracket and preparation method thereof |
| CN102690435A (en) * | 2012-06-19 | 2012-09-26 | 上海大学 | Method for regulating pore structure of water-soluble polymer tissue engineering scaffold by use of polyester template |
| CN105749354A (en) * | 2014-12-19 | 2016-07-13 | 深圳先进技术研究院 | Normal forming method for sodium alginate containing three-dimensional scaffold |
| CN108096638A (en) * | 2015-04-07 | 2018-06-01 | 四川蓝光英诺生物科技股份有限公司 | Biological brick for biometric print and application thereof |
| CN108096638B (en) * | 2015-04-07 | 2021-01-01 | 四川蓝光英诺生物科技股份有限公司 | Bio-brick for bio-printing and use thereof |
| CN105153457A (en) * | 2015-07-24 | 2015-12-16 | 华侨大学 | Porous polyvinyl chloride foam ball and preparation method therefor |
| CN105153457B (en) * | 2015-07-24 | 2018-08-24 | 华侨大学 | A kind of cellular PVC foam ball and preparation method thereof |
| CN108607118A (en) * | 2016-12-13 | 2018-10-02 | 深圳迈德科技有限公司 | The method for preparing 3D multiporous biological holders based on hot press printing technology |
| CN107737584A (en) * | 2017-09-20 | 2018-02-27 | 福建师范大学 | A kind of porous material with micro-nano structure and preparation method thereof |
| CN108912443A (en) * | 2018-05-31 | 2018-11-30 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of the effective nanocomposite of urethral catheterization |
| CN109876198A (en) * | 2019-03-18 | 2019-06-14 | 吉林大学中日联谊医院 | A kind of angiocarpy bracket |
| CN113713169A (en) * | 2021-07-23 | 2021-11-30 | 温州医科大学 | Near-infrared photosensitive ZIF8 functionalized gelatin nanofiber scaffold system and application thereof |
| CN114904058A (en) * | 2021-12-22 | 2022-08-16 | 广州锐澄医疗技术有限公司 | Regular porous scaffold, preparation method thereof and application thereof in artificial cornea |
| CN114904058B (en) * | 2021-12-22 | 2024-04-16 | 广州锐澄医疗技术有限公司 | Regular porous bracket, preparation method thereof and application thereof in artificial cornea |
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