CN101785877A - Method for preparing bionic composite material with lamellar multilevel structure - Google Patents
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Abstract
The invention discloses a method for preparing a bionic composite material with lamellar multilevel structure, belonging to the field of biomedical materials. Combining icy template method with composite microsphere method, the method prepares the bionic composite material with lamellar multilevel structure. The method not only includes economical advantage and environmental friendliness simultaneously, but can also be conducted under lasting low-temperature conditions, thus the denaturation of bioactive materials is hardly caused and the prepared composite material, having fine structure, high strength, light weight and good selectivity, is better advantageous for cell adhesion, furthermore, the composite material has excellent biocompatibility, regular array of laminas, good inter-lamina communication and bridging of similar mineral bridges. The microspheres in regular shape on the laminas are evenly embedded in lamellar organic matters, or partial microspheres are stringed around the laminas by taking threadlike organic matters as axis to form sugarcoated haws-like shape; concaves and convexes as well as extremely large surface area provided by the microspheres on the laminas of the material can create good adhesion and proliferation conditions for the growth of histiocyte and blood vessel.
Description
Technical field
The invention belongs to field of biomedical materials.
Background technology
The sclerous tissues of natural biological body has from microcosmic to macroscopic hierarchy, how on the mimic basis of composition, to realize the bionical manufacturing of stratification from the microstructure to the macrostructure be the design of present tissue engineering bracket material and make in the significant challenge that faced.The height biomimetic features hard tissue repair support of layered porous structure is to be made by bionic composite material with lamellar multilevel structure, this support will provide suitable space and microenvironment for the growth of cell, help making up organizational project recovery support, and layer structure can supply the favorable mechanical performance for the support material with complete three dimensional structure.Recent research result shows that laminar composite also shows at aspects such as absorption, ion exchange, synthetic material, daily-use chemical industry, catalysis, superconduction and environmental conservation has huge application potential.
Adopting the ice template legal system to be equipped with above-mentioned material, is that the ice template method is merged mutually with the template self-assembling technique, utilizes the inorganic/organic composite material manufacturing with nano bionic structure to possess bionic composite material with lamellar multilevel structure; Under low temperature environment, carry out the processing and forming of material, make bioactive substance in final support product, keep high activity.2006, people such as Deville and Halloran reported on Science that with aluminium oxide or hydroxyapatite nano particle as initiation material, the water hybrid scheme that will contain the high concentration ceramics with freezing method causes porous material.Be filled in this porous material with another kind of material then, make superpower, extra light combined material, this combined material has than the better engineering properties of traditional ceramics material.The material supply section scholar points out in relevant research comment that with engineer JohnHalloran this combined material has engineering application widely.But single ice template method has following shortcoming: material is selected more single, and structural design is meticulous inadequately.Up to the present, also be simple parallel layers structure basically, the mutual perforation degree of hole is low, the poor controllability of porosity and pore size distribution, and this will have influence on the vascularization of growing into and organizing of cell.
The complex microsphere preparation method is that a kind of different materials is uniformly dispersed is combined into the method for the spheroidal particle between 50nm～2mm, comprises emulsion-solvent evaporation method, in-situ chemical sedimentation, sol-gel method, electroless plating method, self-assembly method or the like.Complex microsphere is owing to have less controlled particle diameter, and cause it to have tangible skin effect, and the affinity of material is good, easily absorb in vivo, easily migration, be easy to preparation and functionalization and adjustable to biocompatible, help characteristics such as research and the interaction of organism composition.Complex microsphere is widely used in fields such as lightweight radar absorbing, photonic crystal, biological medicine carrying agent material, cosmetics.
Utilize the complex microsphere preparation method to combine the preparation bionic composite material with lamellar multilevel structure with the ice template method, in various documents, all do not report at present.
Summary of the invention
The objective of the invention is to address the above problem and a kind of new bionic composite material with lamellar multilevel structure and preparation method thereof is provided, specifically be equipped with bionic composite material with lamellar multilevel structure by the ice template method in conjunction with the complex microsphere legal system, the prepared composite that goes out has good performance.
The technical solution adopted in the present invention is:
A kind of preparation method of bionic composite material with lamellar multilevel structure is equipped with bionic composite material by the ice template method in conjunction with the complex microsphere legal system, may further comprise the steps:
(a) make the complex microsphere powder;
(b) the machine thing being dissolved in percent by volume is in 0.2%～2% organic solvent, the complex microsphere powder is put into organic solvent, making the organic mass ratio in complex microsphere powder and the organic solvent is 30:1～2:1, evenly stirs into the pasty state mixed slurry, removes air then;
(c) according to the needs of preparation composite shape, make freezing mould, this freezing mold bottom is equipped with metab;
(d) the pasty state mixed slurry is injected in the freezing mould, remove air once more, with heat ray filter or the tight part of freezing mould except that metab that cover of heat-barrier material, place-30 ℃～-120 ℃ freezing environment then, freezing 1h～2h freezes molding fully up to sample;
(e) take out freezing sample from freezing mould, be lower than in-30 ℃ the lyophilization environment, lyophilization 12h～36h promptly obtains bionic composite material with lamellar multilevel structure up to complete lyophilizing.
Preferably, the complex microsphere powder is that in collagen, chitosan (CS), poly-Acetic acid, hydroxy-, bimol. cyclic ester (PLA), polylactide (PGA), the copolymer Acetic acid, hydroxy-, bimol. cyclic ester-lactide (PLGA) one or more mix phosphorus Calx or bioactive substance makes in the described step (a) and (b).
Preferably, described phosphorus Calx is bata-tricalcium phosphate, hydroxyapatite or element modified hydroxyapatite.
Preferably, described bioactive substance is protein, polypeptide class biologically active drug or biological activity somatomedin.
Preferably, Organic substance is collagen, chitosan, fibroin, polylactic acid, copolymer Acetic acid, hydroxy-, bimol. cyclic ester-lactide, polycaprolactone or biodegradable polymers in the described step (b).
Preferably, organic solvent is ethanol or acetic acid in the described step (b).
Preferably, the freezing mould of described step (c), (d), (e) is polyfluortetraethylene pipe or polyvinyl chloride pipe.
Preferably, the metab material is heat-conducting metal copper, ferrum among described step (c), (d), aluminum.
Further, described step (d) freezing environment is bathed by cryogenic refrigerator, liquid nitrogen and cryosel provides.The present invention has the following advantages:
The present invention in conjunction with the complex microsphere technology, prepares bionic composite material with lamellar multilevel structure on the basis of ice template, this composite structure is meticulous, intensity is high, light weight, selection are many, is fit to cell adhesion, has excellent biological compatibility.The synusia thickness of this composite with add freezing slurry difference can be controlled, synusia thickness can reach 2 μ m～50 μ m, interlamellar spacing changes with the different of amount of porosity with solvent, and wherein interlamellar spacing can reach 2～100 μ m, and porosity can reach 50%～95%; Simultaneously synusia is regularly arranged, and the interlayer connectedness is good, and the microsphere of regular shape on the bridging synusia of class gel mineral bridge is arranged, or evenly is embedded in the thin layer Organic substance, or a little serves as that the axle string forms class sugarcoated haws on a stick shape around synusia with thread Organic substance; Concavo-convex and the great surface area that microsphere provided on its synusia can be histiocyte and angiogenic growth and creates good adhesion and proliferation conditions.On the mimic basis of composition, provide new thinking for realizing the multilevel bionic manufacturing from the microstructure to the macrostructure.
Preparation method of the present invention has economy and environment friendly concurrently, and can carry out under the consecutive low temperature condition, is difficult for causing the bioactive materials degeneration.
The bionic composite material with lamellar multilevel structure that the present invention prepares can form more near the multilamellar level bionic ceramic material of natural biological mineral by further forming processes, can have wide application prospect in biomedical materials field; Infiltration metal or polymer can further form fine and close composite in the space that forms after the vacuum lyophilization deicing.
Description of drawings
The bionic composite material with lamellar multilevel structure scale that Fig. 1 prepares for embodiment 1 is the sem photograph of 400um;
The bionic composite material with lamellar multilevel structure scale that Fig. 2 prepares for embodiment 1 is the sem photograph of 50um.
The specific embodiment
Embodiment 1
Get the 0.8g molecular weight and be 10,000 PLA and be dissolved in the 12ml acetone that concentration is 0.067g/ml, treat abundant dissolving, this is a solution A; Get the 0.2g nanometer hydroxyapatite and be distributed in the 6ml water, ultra-sonic dispersion, being emulsion form is solution B; Solution B is poured in the solution A, and being stirred to fast is uniformly dispersed is solution C; Get 0.4g polyvinyl alcohol (PVA) and be dissolved in the 200ml water, place on the agitator speed with 400rpm to stir, treat abundant dissolving, this solution is D; C solution is at the uniform velocity poured in the D solution that is stirring, got solution E; Solution E continues to stir made organic solvent volatilize in 6 hours; Then with the method flush away PVA of dialysis, collect HA/PLA microsphere powder and go in the conical flask, ultra-sonic dispersion was put into-20 ℃ of pre-freezes 12 hours; Put into freezer dryer after the pre-freeze at-50 ℃,, promptly get the HA/PLA microsphere less than lyophilization under the 20Pa condition 24 hours.
It is that collagen in 1% acetic acid mixes that the compound apatite microsphere powder 1g of screening particle diameter 50～100um and 0.15g are dissolved in the 10ml percent by volume, the mass ratio of compound apatite microsphere powder and collagen is 20:3, then stir into a paste mixed slurry, remove air at last; The making internal diameter is 10mm, highly is the cylindrical freezing mould of 40mm; The pasty state mixed slurry is carefully injected in the mould, remove air again, tightly cover the part of mould except that metab with heat ray filter or heat-barrier material then, place-80 ℃ of cryogenic refrigerators, freezing 1.5h freezes molding fully until sample; Reject the mould metab, take out freezing sample rapidly, lyophilization 36h is until complete lyophilizing, promptly to the bionic composite material with lamellar multilevel structure that will prepare.
See figures.1.and.2, the bionic composite material with lamellar multilevel structure for preparing is observed under scanning electron microscope, it is more that the PCL microsphere of mean diameter about 50～100 μ m contains HA, regular shape.After freeze-dried, the synusia structure law of sample is obvious, and synusia is made up of the microsphere that is close to one by one, the collagen gluing therein, it is all right that the hole is communicated with, the about 50 μ m of interlamellar spacing; Interlayer has formed the bridging of class gel mineral bridge.
Embodiment 2
Get molecular weight and be 60,000 10gPLA and be dissolved in the 100ml dichloromethane that concentration is 0.1g/ml, treat abundant dissolving, this is a solution A; Get 5gn-HA and be distributed in the 20ml dichloromethane, ultra-sonic dispersion, being emulsion form is solution B; Solution B is poured in the solution A, and being stirred to fast is uniformly dispersed is solution C; Get 0.5% PVA and be dissolved in the 1000ml water, place that the speed with 400rpm stirs on the agitator, treat abundant dissolving, be divided in four beakers, this solution is D; C solution slowly at the uniform velocity is added drop-wise in the D solution that is stirring, gets solution E; Solution E continues to stir made organic solvent volatilize in 8 hours; Then with method of pumping filtration flush away PVA, collect HA/PLA microsphere powder and put into conical flask, ultra-sonic dispersion was put into-80 ℃ of pre-freezes 12 hours; Put into freezer dryer after the pre-freeze at-50 ℃,, promptly get the HA/PLA microsphere less than lyophilization under the 20Pa condition 24 hours.
It is that chitosan in 1% acetic acid mixes that the compound apatite microsphere powder 1g of screening particle diameter 50～100um and 0.2g are dissolved in the 10ml percent by volume, compound apatite microsphere powder is 20:4 with the chitosan mass ratio, then stir into a paste mixed slurry, remove air at last; The self-control internal diameter is 10mm, highly is the cylindrical freezing mould of 40mm; The pasty state mixed slurry is carefully injected in the mould, remove air again, tightly cover the part of mould except that metab with heat ray filter or heat-barrier material then, place-40 ℃ cryosel to bathe, freezing 2h freezes molding fully until sample; Reject the mould metab, take out freezing sample rapidly, lyophilization 12h is until complete lyophilizing, promptly to the bionic composite material with lamellar multilevel structure that will prepare.
It is more that the PLA microsphere of the bionic composite material with lamellar multilevel structure mean diameter for preparing about 50～100 μ m contains HA, regular shape.After freeze-dried, the synusia structure law of sample is obvious, and synusia is made up of the microsphere that is close to one by one, the chitosan gluing therein, it is all right that the hole is communicated with, the about 50 μ m of interlamellar spacing; Interlayer has formed the bridging of class gel mineral bridge.
Embodiment 3
Get molecular weight and be 100,000 1.5gPCL and be dissolved in the 22.5ml dichloromethane that concentration is 6.67g/ml and treat abundant dissolving, this is a solution A; Get 1g β-TCP and be distributed in the 20ml ethanol, ultra-sonic dispersion, being emulsion form is solution B; Solution B is poured in the solution A, and being stirred to fast is uniformly dispersed is solution C; Get 0.5% PVA and be dissolved in the 400ml water, place that the speed with 400rpm stirs on the agitator, treat abundant dissolving, be divided in four beakers, this solution is D; C solution slowly at the uniform velocity is added drop-wise in the D solution that is stirring, gets solution E; Solution E continues to stir made organic solvent volatilize in 8 hours; Then with method of pumping filtration flush away PVA, collect HA/PCL microsphere powder and put into conical flask, ultra-sonic dispersion was put into-80 ℃ of pre-freezes 12 hours; Put into freezer dryer after the pre-freeze at-50 ℃,, promptly get the HA/PLA microsphere less than lyophilization under the 20Pa condition 24 hours.
It is that polylactic acid in 0.2% ethanol mixes that the compound apatite microsphere powder 1g of screening particle diameter 50～100um and 0.15g are dissolved in the 10ml percent by volume, compound apatite microsphere powder and polylactic acid mass ratio are 30:1, then stir into a paste mixed slurry, remove air at last; The self-control internal diameter is 10mm, highly is the cylindrical freezing mould of 40mm; The pasty state mixed slurry is carefully injected in the mould, remove air again, tightly cover the part of mould except that metab with heat ray filter or heat-barrier material then, place-120 ℃ of liquid nitrogen, freezing 1.5h freezes molding fully until sample; Reject the mould metab, take out freezing sample rapidly, lyophilization 24h is until complete lyophilizing, promptly to the bionic composite material with lamellar multilevel structure that will prepare.
The bionic composite material with lamellar multilevel structure for preparing, the PCL of mean diameter about 50～100 μ m the HA microsphere to contain HA more, regular shape.After freeze-dried, the synusia structure law of sample is obvious, and synusia is made up of the microsphere that is close to one by one, the collagen gluing therein, it is all right that the hole is communicated with, the about 50 μ m of interlamellar spacing; Interlayer has formed the bridging of class gel mineral bridge.
Embodiment 4
Get molecular weight and be 50,000 0.9gPLGA and be dissolved in the 12ml dichloromethane that concentration is 0.075g/ml, treat abundant dissolving, this is a solution A; Get 0.2gn-HA and be distributed in the 5ml dichloromethane, ultra-sonic dispersion, being emulsion form is solution B; Solution B is poured in the solution A, and being stirred to fast is uniformly dispersed is solution C; Get 0.5% poloxamer-188 and be dissolved in the 200ml water, place that the speed with 400rpm stirs on the agitator, treat abundant dissolving, this solution is D; C solution is at the uniform velocity poured in the D solution that is stirring, got solution E; Solution E continues to stir made organic solvent volatilize in 6 hours; Then with 4000rpm centrifugation method flush away poloxamer-188, collect HA/PLGA microsphere powder and go in the conical flask, ultra-sonic dispersion was put into-20 ℃ of pre-freezes 12 hours; Put into freezer dryer after the pre-freeze at-50 ℃,, promptly get the HA/PLGA microsphere less than lyophilization under the 20Pa condition 24 hours.
Repeatedly repeat aforesaid operations, collect the microsphere of q.s; It is that chitosan in 2% acetic acid mixes that the compound apatite microsphere powder 1g that makes and 0.2g are dissolved in the 10ml percent by volume, and compound apatite microsphere powder and chitosan mass be than being 2:1, then stir into a paste mixed slurry, remove air at last; The self-control internal diameter is 10mm, highly is the cylindrical freezing mould of 40mm; The pasty state mixed slurry is carefully injected in the mould, remove air again, tightly cover the part of mould except that metab with heat ray filter or heat-barrier material then, place-80 ℃ of cryogenic refrigerators, freezing 1h freezes molding fully until sample; Reject the mould metab, take out freezing sample rapidly, lyophilization 136h is until complete lyophilizing, promptly to the bionic composite material with lamellar multilevel structure that will prepare.
The bionic composite material with lamellar multilevel structure for preparing contains the PLGA microsphere average grain diameter of 18.2%HA about 30～150 μ m, regular shape.After the freezing knot drying, the synusia structure law of sample is obvious, and the hole is communicated with all right, the about 50 μ m of interlamellar spacing; Interlayer has formed the bridging of class gel mineral bridge.Recording porosity with hydrometer method is 91%.
Embodiment 5
Adopt self emulsifying/solvent diffusion method, get molecular weight and be 50,000 PLGA3g, curcumin 0.5g makes up the binary water-miscible solvent 500ml that organic mutual-assistance is formed in the ratio of 1:10 with acetone, and homogenizing is uniformly dispersed; Getting polyvinyl alcohol (PVA) is dissolved in the water with 2% ratio, place on the agitator speed to stir, treat abundant dissolving, the speed of organic facies with 2ml/min is slowly splashed into 400rpm, form translucent emulsion, place fume hood to continue to stir and made the organic solvent volatilization in 3 hours; The centrifugal 10000rpm of low-temperature and high-speed separates medicine carrying microballoons, tri-distilled water washing three times; Microsphere is suspended from the low amounts of water again, and-50 ℃ of vacuum lyophilizations get pale yellow powder; 4 ℃ of lucifuge sealings are preserved;
Screening particle diameter suitable PLGA carries curcumin microsphere powder 1g and 0.15g, and to be dissolved in the 10ml percent by volume be that collagen in 1% ethanol mixes, and carry out lucifuge, PLGA carries curcumin microsphere powder and the collagen mass ratio is 20:3, stir into a paste mixed slurry, remove air; The self-control internal diameter is 10mm, highly is the cylindrical freezing mould of 40mm; The pasty state mixed slurry is carefully injected in the mould, remove air again, tightly cover the part of mould except that metab with heat ray filter or heat-barrier material then, place-80 ℃ of cryogenic refrigerators, freezing 1.5h freezes molding fully until sample; Reject the mould metab, take out freezing sample rapidly, lucifuge lyophilization 36h is until complete lyophilizing, promptly to the bionic composite material with lamellar multilevel structure based on the PLGA microsphere that carries curcumin that will prepare.
The bionic composite material with lamellar multilevel structure for preparing, the about 300nm of microsphere average grain diameter, carrying drug ratio 11%, envelop rate 33.54%.Naked eyes promptly can be observed the layer structure of tangible similar page.The visible synusia of light microscopic is made up of the microsphere that is close to one by one, the collagen gluing therein, it is all right that the hole is communicated with, layer is less with interlamellar spacing.
Embodiment 6
The preparation of OGP-PLGA sustained-release micro-spheres: 1gPLGA50:50 is dissolved in the 4ml dichloromethane solution, and fully the dissolving back adds 1mg/mLOGP solution 1500uL, and the ultrasound wave homogenize forms colostrum.With the 100g/L poly-vinyl alcohol solution is the water disperse medium, and its inorganic salt concentration is 20g/L.The 4ml3g/L poly-vinyl alcohol solution is added dropwise to above-mentioned emulsion, after the homogenize, this liquid is added in the poly-vinyl alcohol solution of 8ml with concentration, the 2000r/min magnetic agitation is complete to the dichloromethane volatilization under the room temperature, promptly gets OGP-PLGA sustained-release micro-spheres solution; Conventional one 20 ℃ of lyophilizing are preserved.
It is that collagen in 1% acetic acid mixes that the suitable OGP-PLGA sustained-release micro-spheres powder 1g of screening particle diameter and 0.2g are dissolved in the 10ml percent by volume, OGP-PLGA sustained-release micro-spheres powder and collagen mass ratio are 20:4, then stir into a paste mixed slurry, remove air at last; The self-control internal diameter is 10mm, highly is the cylindrical freezing mould of 50mm; The pasty state mixed slurry is carefully injected in the mould, remove air again, tightly cover the part of mould except that metab with heat ray filter or heat-barrier material then, place-80 ℃ of cryogenic refrigerators, freezing 1.5h freezes molding fully until sample; Reject the mould metab, take out freezing sample rapidly, lyophilization 12h is until complete lyophilizing, promptly to the bionic composite material with lamellar multilevel structure based on the OGP-PLGA sustained-release micro-spheres that will prepare.
The OGP-PLGA sustained-release micro-spheres smooth surface rounding of the bionic composite material with lamellar multilevel structure for preparing, spheroid good evenness, no adhesion phenomenon.The mean diameter of microsphere is 30um～70um, and carrying drug ratio and envelop rate are 80.9 ± 2.21% and 65.9 ± 3.13%, proves that multi-emulsion method prepares the effectiveness and the feasibility of biological activity somatomedin.Naked eyes promptly can be observed the layer structure of tangible similar page.The visible synusia of light microscopic is made up of the microsphere that is close to one by one, the collagen gluing therein, it is all right that the hole is communicated with, layer is less with interlamellar spacing.
It should be noted that at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, with reference to preferred embodiment the present invention is had been described in detail as far as possible, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1. the preparation method of a bionic composite material with lamellar multilevel structure is characterized in that, is equipped with bionic composite material by the ice template method in conjunction with the complex microsphere legal system, may further comprise the steps:
(a) make the complex microsphere powder;
(b) the machine thing being dissolved in percent by volume is in 0.2%～2% organic solvent, the complex microsphere powder is put into organic solvent, making the organic mass ratio in complex microsphere powder and the organic solvent is 30:1～2:1, evenly stirs into the pasty state mixed slurry, removes air then;
(c) according to the needs of preparation composite shape, make freezing mould, this freezing mold bottom is equipped with metab;
(d) the pasty state mixed slurry is injected in the freezing mould, remove air once more, with heat ray filter or the tight part of freezing mould except that metab that cover of heat-barrier material, place-30 ℃～-120 ℃ freezing environment then, freezing 1h～2h freezes molding fully up to sample;
(e) take out freezing sample from freezing mould, be lower than in-30 ℃ the lyophilization environment, lyophilization 12h～36h promptly obtains bionic composite material with lamellar multilevel structure up to complete lyophilizing.
2. the preparation method of bionic composite material with lamellar multilevel structure according to claim 1, it is characterized in that the complex microsphere powder is that in collagen, chitosan (CS), poly-Acetic acid, hydroxy-, bimol. cyclic ester (PLA), polylactide (PGA), the copolymer Acetic acid, hydroxy-, bimol. cyclic ester-lactide (PLGA) one or more mix phosphorus Calx or bioactive substance makes in the described step (a) and (b).
3. the preparation method of bionic composite material with lamellar multilevel structure according to claim 2 is characterized in that, described phosphorus Calx is bata-tricalcium phosphate, hydroxyapatite or element modified hydroxyapatite.
4. the preparation method of bionic composite material with lamellar multilevel structure according to claim 2 is characterized in that, described bioactive substance is protein, polypeptide class biologically active drug or biological activity somatomedin.
5. the preparation method of bionic composite material with lamellar multilevel structure according to claim 1, it is characterized in that Organic substance is collagen, chitosan, fibroin, polylactic acid, copolymer Acetic acid, hydroxy-, bimol. cyclic ester-lactide, polycaprolactone or biodegradable polymers in the described step (b).
6. the preparation method of bionic composite material with lamellar multilevel structure according to claim 1 is characterized in that, organic solvent is ethanol or acetic acid in the described step (b).
7. the preparation method of bionic composite material with lamellar multilevel structure according to claim 1 is characterized in that, the freezing mould of described step (c), (d), (e) is polyfluortetraethylene pipe or polyvinyl chloride pipe.
8. the preparation method of bionic composite material with lamellar multilevel structure according to claim 1 is characterized in that, the metab material is heat-conducting metal copper, ferrum among described step (c), (d), aluminum.
9. the preparation method of bionic composite material with lamellar multilevel structure according to claim 1 is characterized in that, described step (d) freezing environment is bathed by cryogenic refrigerator, liquid nitrogen and cryosel and provided.
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| CN103191019B (en) * | 2013-04-16 | 2014-10-22 | 中国科学院理化技术研究所 | Method for preparing hydrophobic drug nanoparticles by ice template method |
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| CN108123110B (en) * | 2016-11-28 | 2020-09-04 | 中国科学院大连化学物理研究所 | Preparation method and application of nitrogen-containing large-pore-volume porous carbon material |
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| CN107261867B (en) * | 2017-08-10 | 2019-09-24 | 武汉纺织大学 | A kind of preparation method of super water-purifying filter film |
| CN107261867A (en) * | 2017-08-10 | 2017-10-20 | 武汉纺织大学 | A kind of preparation method of super water-purifying filter film |
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| CN107519847A (en) * | 2017-08-10 | 2017-12-29 | 武汉纺织大学 | A kind of preparation method of heavy metal ion adsorbed film |
| CN108404219A (en) * | 2018-02-11 | 2018-08-17 | 华中科技大学 | A kind of small-caliber artificial blood vessel and preparation method thereof based on freezing casting technology |
| CN109106984A (en) * | 2018-09-21 | 2019-01-01 | 广州润虹医药科技股份有限公司 | A kind of hydroxyapatite porous support and preparation method thereof |
| CN109106984B (en) * | 2018-09-21 | 2021-06-29 | 广州润虹医药科技股份有限公司 | Hydroxyapatite porous scaffold and preparation method thereof |
| CN109482882A (en) * | 2018-10-22 | 2019-03-19 | 中国科学院金属研究所 | Foam metal and preparation method thereof with microcosmic orientation pore structure |
| CN110464881A (en) * | 2019-07-05 | 2019-11-19 | 武汉纺织大学 | Fibroin porous support with hierarchical structure and preparation method thereof |
| CN110464881B (en) * | 2019-07-05 | 2021-09-14 | 武汉纺织大学 | Silk fibroin porous scaffold with hierarchical structure and preparation method thereof |
| CN112473577A (en) * | 2020-11-24 | 2021-03-12 | 哈尔滨工程大学 | Preparation method of universal graphene aerogel with absorption performance |
| CN112870447A (en) * | 2021-01-08 | 2021-06-01 | 东华大学 | Bone regeneration multi-bionic scaffold material and preparation method thereof |
| CN112870447B (en) * | 2021-01-08 | 2022-03-11 | 东华大学 | Bone regeneration multi-bionic scaffold material and preparation method thereof |
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