CN100356989C - Method for preparing organic and inorganic nanometer composite organization engineering stent material by using thermal phase separation - Google Patents
Method for preparing organic and inorganic nanometer composite organization engineering stent material by using thermal phase separation Download PDFInfo
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- CN100356989C CN100356989C CNB2005100309957A CN200510030995A CN100356989C CN 100356989 C CN100356989 C CN 100356989C CN B2005100309957 A CNB2005100309957 A CN B2005100309957A CN 200510030995 A CN200510030995 A CN 200510030995A CN 100356989 C CN100356989 C CN 100356989C
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Abstract
The present invention relates to a method for preparing organic and inorganic nanometer composite tissue engineering supporting frame materials by using thermal phase separation, which has the following steps: firstly, inorganic nanometer powder is ultrasonically dispersed in polymer solution to form a uniform mixture system; secondly, a temperature is dropped, the mixture system is coarsened for a certain period of time at a certain temperature to make the polymer solution generate phase separation; thirdly, solvent is removed by a freezing drying method to obtain porous tissue engineering supporting frame materials, and a supporting frame is annealed to improve the strength of the supporting frame; finally, organic and inorganic nanometer composite tissue engineering supporting frame materials are obtained. The method has a simple operation process. The obtained porous tissue engineering supporting frame materials have good connectivity. Different sizes of holes which are communicated with each other are uniformly distributed in the porous tissue engineering supporting frame materials. Hole diameters and porosities are determined by preparation process. Connectivity, hydrophilicity and strength are influenced by the mixing quantity of the inorganic powder. At the same time, the present invention has the advantages of low cost, simple process and wide application prospect.
Description
Technical field
The invention belongs to used in tissue engineering porous support materials technical field, be specifically related to a kind of thermic and be separated and prepare the method for organic/inorganic nano composite organization engineering stent material by using.
Technical background
Bone tissue engineering scaffold not only provides the support structure effect for specific cells, but also plays template action, guide tissue regeneration and control organizational structure.Therefore, in organizational project, must consider the cytoskeletal structure of porous three-dimensional, as pore morphology, size, connectedness, porosity etc., be beneficial to the sticking of cell, infiltration and the transmission of nutrient substance and the exchange of metabolite, and the structure of support depends on method for preparing 3 D porous bracket.
The preparation method of existing three-dimensional porous rack mainly contains: solvent cast/granule filter drop method, gas foaming method, supercritical CO 2 foaming and thermally induced phase separation.
Solvent cast/powder body leaching is the easiest and research one of technology the most widely in the tissue engineering bracket material method for drilling.This technology can be controlled porosity, pore-size and the form of three-dimensional rack easily, thereby be subjected to paying close attention to widely by form, granular size and the porogen of control porogen and the ratio of degradation material.But this method is not suitable for preparing the large volume three-dimensional rack, because in the mixture that porogen and high molecular polymer form, it is connective poor to be aggregated between thing parcel porogen granule, causes between the hole of support connectedness poor; When the volume of mixture of porogen and polymeric matrix formation increased, solvent can not leach porogen to come out from mixture effectively.
The gas foaming technology adopts gas as porogen, in the drilling process not with an organic solvent.The foam of polymers that this CO2 of utilization thermal instability is made has been avoided the cytotoxicity of organic solvent and the influence of high-temperature process, is a kind of comparatively ideal cell seeding carrier, is particularly advantageous in the growth factor-loaded repopulating cell that acts on.But this method is to the equipment requirements height, and microcellular structure is wayward and often form sealed porosity.
Supercritical CO
2Foaming is to utilize supercritical CO
2In multiple polymers, have good infiltrative characteristics, be that porogen carries out drilling.And supercritical CO
2Chemical property is stable, avirulence, non-corrosiveness, difficult combustion are difficult quick-fried, critical state realizes (critical temperature: 31.1 ℃ easily, critical pressure: 7.4Mpa), critical temperature is near room temperature, heat-sensitive substances such as biological active substances, enzyme and protein are not had destruction, can be used for preparing the large volume tissue engineering bracket material.But because supercritical CO
2The infiltration campaign of fluid in polymeric matrix is irregular, so the material aperture of preparation, porosity and connective being difficult to are controlled.
(Thermally Induced Phase Separation TIPS) can be applied to many because poor solubility and can not solve in the polymer of micro molding with wet, dried phase disengagement method thermally induced phase separation.From in fact, the TIPS process has been utilized a kind of potential solvent exactly, and it is a non-solvent when being solvent and low temperature when high temperature, and the immiscible property that loses the solvent ability is because lost heat energy (instant heating is as the driving force that is separated).Because potential solvent is nonvolatile, need be with being solvent for potential solvent, being that a kind of liquid of non-solvent extracts it from finished product for polymer, thus form microcellular structure.This method is the most blanket method in all phase disengagement methods, both can be used for polar polymer, also can be used for non-polar polymer; This method needs the parameter controlled less in forming process, and it is stable and continuously that process realizes easily; And according to existing material, the formed microstructure of TIPS process is varied, the easier specific (special) requirements of satisfying poromerics; Have thermally induced phase separation can produce on the thick cross section each to identical microcellular structure in addition, this characteristic makes the TIPS method have special advantages aspect the preparation large volume tissue engineering bracket material.
Nam etc.
[1]Utilize thermally induced phase separation to prepare PLGA, PLLA, PDLLA porous support, solvent is the mixture of water and dioxane, and the cryodesiccated method of employing of removing of solvent is by controlling the porous material that the cooling condition can obtain different apertures and pore morphology.Peter etc.
[2]Utilize thermally induced phase separation, adopt oxolane to prepare the PLLA porous support as solvent, the extractive method of water is adopted in the removal of oxolane, utilizes cryodesiccated method to remove at last and anhydrates.Can obtain lamellar or the strong porous support of fiber by the control phase separation temperature.Whang
[3]Mix with water to stir rapidly and be emulsion Deng the dichloromethane solution with PLGA, quenching in liquid nitrogen has obtained the PLGA porous support materials after the lyophilization then.
[list of references]
1.Nam Y.S.，Park T.G..Biodegradable polymeric microcel lular foams bymodified thermally induced phase separation method.Biomaterials，1999，20：1783-1790
2.Peter X.Ma，Ruiyun Zhang.Synthetic nano-scale fibrous extracellularmatrix.Journal of Biomedical Materials Research.，1999，46：60-72
3.Wang K.，Tomas C.H.，Healy K.E..A novel method to fabricate bioabsorbablescaffolds.Polymer，1995，36：837-842
Summary of the invention
The objective of the invention is to propose a kind ofly to prepare good hydrophilic property, intensity height, the aperture is suitable, porosity is high and the method for the connective good organic and inorganic nano combined integration engineering timbering material in hole.
The method of the organic and no nano combined integration engineering timbering material of the preparation that the present invention proposes, its concrete steps are as follows:
(1) inorganic nanometer powder is placed the solution of organic solvent and deionized water, sonic oscillation is to being uniformly dispersed in 30-70 ℃ of aqueous solution;
(2) in sonic oscillation to wherein adding degradable polymer, all dissolve until polymer, inorganic nanometer powder is dispersed in the solution, forms the mixed system of homogeneous;
(3) mixed system is reduced under the mixed system cloud point temperature 10-20 ℃, leave standstill a period of time, make it to be separated;
(4) with said mixture in-10--196 ℃ following quick-freezing molding, and insulation 0.5-24 hour is solidified thoroughly it;
(5) above-mentioned product is placed freezer dryer ,-20--60 ℃ lyophilization 24-30 hour, thoroughly to remove dilution;
(6) above-mentioned product is placed baking oven, be warming up to the above 5-20 of polymer Tg ℃, be incubated 6-24 hour, naturally cool to room temperature then, obtain described tissue engineered porous scaffold material.
The inorganic particle that step among the present invention (1) is adopted is the nano-powder of hydroxyapatite (HA), bata-tricalcium phosphate or hydroxyapatite/lithotroph potteries such as bata-tricalcium phosphate biphase calcium phosphor pottery.
The organic solvent that step among the present invention (1) is adopted is an oxolane, 1,4-dioxane or dichloromethane, and the volume ratio of organic solvent and deionized water is 95: 5 to 85: 15 in organic solvent and the deionized water solution.
The degradable polymer that step among the present invention (2) is adopted is a kind of of polyglycolic acid, lactic acid one ethanol copolymer (PLGA), polycaprolactone, polyurethane, Merlon, poly-anhydride, poly phosphazene, poly butyric ester and copolymer thereof, collagen, chitosan etc., it perhaps is above-mentioned mixture of polymers, and the copolymer between them, the product that also comprises the different spaces structure of above-mentioned polymer is as Poly-L-lactic acid (PLLA), dextrorotation polylactic acid (PDLA) and meso polylactic acid (PDLLA)
The polymer solution concentration of step among the present invention (2) is 4-15% (w/v), and the polymer that is adopted and the mass ratio of inorganic particle are 70: 30-100: 0.When the inorganic particle volume was 0, prepared porous support was the straight polymer tissue engineering bracket material.Usually, the mass ratio of polymer and inorganic particle is 70: 30-95: 5.
The present invention is fully in conjunction with the performance characteristics of lithotroph pottery and degradable polymer, inorganic nano bioceramic powder body is dispersed in the polymeric matrix, make it to make up for each other's deficiencies and learn from each other, obtained the intensity height, good hydrophilic property has the used in tissue engineering porous organic/inorganic nano compound support frame material of suitable aperture, height porosity, good hole connectedness and biocompatibility.The aperture of timbering material, porosity are determined by parameters such as the temperature in the thermal phase separation process, times, intensity, connectedness and hydrophilic are influenced by the inorganic nanometer powder volume, therefore this method can be used for preparing the controlled multi-porous tissue engineering supporting material of aperture, porosity, intensity, connectedness and hydrophilic, and simple and easy to do.
Description of drawings
Fig. 1 is a process chart of the present invention.
Fig. 2 is the stereoscan photograph of nanometer hydroxyapatite under the different resolution/Poly-L-lactic acid composite porous support material.Wherein (a) is high-resolution, (b) is low resolution.Wherein, hydroxyapatite: Poly-L-lactic acid=10: 90 (w: w), PLA concentration=10% (w/v), 1,4-dioxane: deionized water=87: 13 (v/v), 9 ℃ of alligatoring temperature, coarsening time 6 hours.
Fig. 3 be variable concentrations HA/PLGA (HA: PLGA=5: 95) 1, the stereoscan photograph of 6 hours gained supports of 5 ℃ of following alligatoring of 4-dioxane/water (87/13) solution.Wherein (a) and (b), (c) are 8% (w/v), (d), (e), (f) be 10% (w/v).
Fig. 4 be 10% (w/v) HA/PLGA (HA: PLGA=5: 95) 1, the stereoscan photograph of 4-dioxane/water (87/13) solution 6 hours gained supports of alligatoring under different alligatoring temperature.Wherein (a), (e), (c) are 9 ℃, (d), (b), (f) be 5 ℃.
Fig. 5 is 1 of 8% (w/v) PLGA, the stereoscan photograph of 4-dioxane/water (87/13) solution gained support under different coarsening times.Wherein, (a) and (b) are 2h; (c), (d) is 4h; (e), (f) is 8h.
Fig. 6 is the stereoscan photograph of 6 hours gained supports of 9 ℃ of following alligatoring of dioxane/water (87/13) solution of different HA volumes 10% (w/v) HA/PLGA.Wherein, (a) and (b) are 5wt%; (c), (d) is 10wt%; (e), (f) is 20wt%.
Fig. 7 is the curve that the HA/PLGA support water absorption rate of different HA content changes with soak time.
Fig. 8 is the influence curve of HA volume to HA/PLGA support volume comprcssive strength.
The specific embodiment
The preparation of embodiment 1. organic/inorganic nano composite organization engineering stent material by using
Take by weighing 0.1 gram nanometer hydroxyapatite and place 1 of 9ml, in 4-dioxane/deionized water (87/13) solution, sonic oscillation is to being uniformly dispersed in 50 ℃ of aqueous solutions.To wherein adding 0.9 gram Poly-L-lactic acid (PLLA), all dissolve until polymer in sonic oscillation, nano hydroxyapatite powder is dispersed in the solution, forms the mixed system of homogeneous.Mixed system is reduced to mixed system cloud point temperature following 15 ℃ (9 ℃) left standstill 6 hours, make it to be separated.Sample in subzero 50 ℃ of following quick-freezing molding, and is incubated 12 hours and makes it and solidify thoroughly.Sample is placed freezer dryer, and subzero 40 ℃ of lyophilizations 36 hours are thoroughly to remove diluent.Sample is placed baking oven, be warming up to 65 ℃, be incubated 12 hours, naturally cool to room temperature then, obtain porous support materials.Fig. 2 is the stereoscan photograph of gained timbering material.
Prepare nanometer hydroxyapatite/lactic acid one ethanol copolymer (PLGA) porous support according to the method in the application example 1, change copolymer p LGA concentration, obtain variable concentrations HA/PLGA (HA: PLGA=5: 95) 1,6 hours gained supports of 5 ℃ of following alligatoring of 4-dioxane/water (87/13) solution.Among Fig. 3 (a), (b), (c) be gained timbering material stereoscan photograph under 8% (w/v) polymer concentration, (d), (e), (f) be gained timbering material stereoscan photograph under 10% (w/v) polymer concentration.The aperture of porous support can be controlled by telomerized polymer concentration as seen from Figure 3.Can also control the porosity of timbering material by polymer concentration, see Table 1.
Prepare nanometer hydroxyapatite/lactic acid one ethanol copolymer (PLGA) porous support according to the method in the application example 1, under different alligatoring temperature, prepare porous support, obtain 10% (w/v) HA/PLGA (HA: PLGA=5: 6 hours gained supports of alligatoring under the different alligatoring temperature of dioxane/water 95) (87/13) solution.(a), (e), (c) are the stereoscan photograph of gained timbering material under 9 ℃ of alligatoring temperature among Fig. 4; (d), (b), (f) are the stereoscan photograph of gained timbering material under 5 ℃ of alligatoring temperature.The aperture of porous support can be controlled by regulating the alligatoring temperature as seen from Figure 4.
Example 4. is by the structure and the performance of coarsening time control porous support materials
Prepare pure lactic acid one ethanol copolymer (PLGA) porous support according to the method in the Application Example 1, prepare porous support through different coarsening times, obtain gained support under the different coarsening times of dioxane/water (87/13) solution of 8% (w/v) PLGA. the gained support.Fig. 5 (a) and (b) are the stereoscan photograph through gained timbering material after the 2h alligatoring, (c), (d) for being the stereoscan photograph 4h through gained timbering material after the 4h alligatoring, and (e), (f) be 8h.Be stereoscan photograph through gained timbering material after the 8h alligatoring.The aperture of porous support can be controlled by regulating coarsening time as seen from Figure 5.
Prepare nanometer hydroxyapatite/lactic acid one ethanol copolymer (PLGA) porous support according to the method in the Application Example 1, the nano hydroxyapatite powder that adds different volumes obtains 6 hours gained supports of 9 ℃ of following alligatoring of dioxane/water (87/13) solution of different HA volumes 10% (w/v) HA/PLGA.Fig. 6 (a) and (b) are (HA: PLGA=5: 95 w: the stereoscan photograph of gained timbering material in the time of w) for the nano hydroxyapatite powder volume; (c), (d) is (HA: PLGA=10: 90 w: the stereoscan photograph of gained timbering material in the time of w) for the nano hydroxyapatite powder volume; (e), (f) is (HA: PLGA=20: 80 w: the stereoscan photograph of gained timbering material in the time of w) for the nano hydroxyapatite powder volume.The aperture of porous support can be controlled by regulating the inorganic particle volume as seen from Figure 6.
Can control the porosity of porous support materials by changing the inorganic particle volume.Table 2 is 6 hours gained brace aperture of 9 ℃ of following alligatoring of dioxane/water (87/13) solution rate of different HA volumes 10% (w/v) HA/PLGA, and therefrom the porosity of visible porous support can be controlled by regulating the inorganic particle volume.
By changing the hydrophilic that the inorganic particle volume also can improve porous support materials.Fig. 7 is the curve that the HA/PLGA support water absorption rate of different HA content changes with soak time, therefrom the hydrophilic of visible porous support improve with the inorganic particle volume and be improved significantly.
By changing the intensity that the inorganic particle volume can also improve porous support materials.Fig. 8 is the influence curve of HA volume to HA/PLGA support volume comprcssive strength, and therefrom the intensity of visible porous support improves with the inorganic particle volume.
The preparation of embodiment 6. β-TCP/PLGA nanometer composite organization engineering stent material by using
Take by weighing 0.1 gram nanometer β-TCP and place 1 of 9ml, in 4-dioxane/deionized water (87/13) solution, sonic oscillation is to being uniformly dispersed in 50 ℃ of aqueous solutions.To wherein adding 0.9 gram PLGA, all dissolve until polymer in sonic oscillation, β-TCP powder body is dispersed in the solution, forms the mixed system of homogeneous.Mixed system is reduced to mixed system cloud point temperature following 15 ℃ (7 ℃) left standstill 8 hours, make it to be separated.Sample in subzero 50 ℃ of following quick-freezing molding, and is incubated 20 hours and makes it and solidify thoroughly.Sample is placed freezer dryer, and subzero 40 ℃ of lyophilizations 50 hours are thoroughly to remove diluent.Sample is placed baking oven, be warming up to 65 ℃, be incubated 12 hours, naturally cool to room temperature then, obtain porous support materials.
The preparation of embodiment 7. β-TCP/PCL nanometer composite organization engineering stent material by using
Take by weighing 0.1 gram nanometer β-TCP and place 1 of 9ml, in 4-dioxane/deionized water (87/13) solution, sonic oscillation is to being uniformly dispersed in 50 ℃ of aqueous solutions.To wherein adding 0.9 gram PCL, all dissolve until polymer in sonic oscillation, β-TCP powder body is dispersed in the solution, forms the mixed system of homogeneous.Mixed system is reduced to mixed system cloud point temperature following 15 ℃ (12 ℃) left standstill 5 hours, make it to be separated.Sample in subzero 50 ℃ of following quick-freezing molding, and is incubated 10 hours and makes it and solidify thoroughly.Sample is placed freezer dryer, and subzero 40 ℃ of lyophilizations 40 hours are thoroughly to remove diluent.Sample is placed baking oven, be warming up to 65 ℃, be incubated 12 hours, naturally cool to room temperature then, obtain porous support materials.
The preparation of embodiment 8.HA/PCL nanometer composite organization engineering stent material by using
Take by weighing 0.1 gram nanometer hydroxyapatite and place 1 of 9ml, in 4-dioxane/deionized water (87/13) solution, sonic oscillation is to being uniformly dispersed in 50 ℃ of aqueous solutions.To wherein adding 0.9 gram PCL, all dissolve until polymer in sonic oscillation, nano hydroxyapatite powder is dispersed in the solution, forms the mixed system of homogeneous.Mixed system is reduced to mixed system cloud point temperature following 15 ℃ (12 ℃) left standstill 5 hours, make it to be separated.Sample in subzero 50 ℃ of following quick-freezing molding, and is incubated 10 hours and makes it and solidify thoroughly.Sample is placed freezer dryer, and subzero 40 ℃ of lyophilizations 40 hours are thoroughly to remove diluent.Sample is placed baking oven, be warming up to 65 ℃, be incubated 12 hours, naturally cool to room temperature then, obtain porous support materials.
The preparation of embodiment 9.HA/PU nanometer composite organization engineering stent material by using
Take by weighing 0.1 gram nanometer hydroxyapatite and place 1 of 9ml, in 4-dioxane/deionized water (87/13) solution, sonic oscillation is to being uniformly dispersed in 50 ℃ of aqueous solutions.To wherein adding 0.9 gram PU, all dissolve until polymer in sonic oscillation, nano hydroxyapatite powder is dispersed in the solution, forms the mixed system of homogeneous.Mixed system is reduced to mixed system cloud point temperature following 15 ℃ (5 ℃) left standstill 10 hours, make it to be separated.Sample in subzero 50 ℃ of following quick-freezing molding, and is incubated 20 hours and makes it and solidify thoroughly.Sample is placed freezer dryer, and subzero 40 ℃ of lyophilizations 54 hours are thoroughly to remove diluent.Sample is placed baking oven, be warming up to 65 ℃, be incubated 12 hours, naturally cool to room temperature then, obtain porous support materials.
Gained HA/PLGA (HA/PLGA: 5: 95) brace aperture rate under the different PLGA concentration of table 1, the coarsening time
| PLGA concentration (% (w/v)) | Coarsening time (h) | Porosity (%) |
| 8 8 8 8 10 10 10 | 0.5 2 4 8 0.5 2 4 | 84.7 85.2 84.2 81.9 64.9 62.7 63.1 |
| 10 | 8 | 59.2 |
6 hours gained brace aperture of 9 ℃ of following alligatoring of dioxane/water (87/13) solution rate of the different HA volumes 10% of table 2 (w/v) HA/PLGA
| HA content(wt％) | Porosity(％) |
| 5 10 15 20 | 88.7 85.4 80.2 78.7 |
| 25 | 71.7 |
Claims (2)
1, a kind of thermic is separated and prepares the method for organic and inorganic nanometer composite organization engineering stent material by using, it is characterized in that concrete steps are as follows:
(1) inorganic nanometer powder is placed the solution of organic solvent and deionized water, sonic oscillation is to being uniformly dispersed in 30-70 ℃ of aqueous solution;
(2) in sonic oscillation to wherein adding degradable polymer, all dissolve until polymer, inorganic nanometer powder is dispersed in the solution, forms the mixed system of homogeneous;
(3) mixed system is reduced under the mixed system cloud point temperature 10-20 ℃, leave standstill a period of time, make it to be separated;
(4) with said mixture in-10--196 ℃ following quick-freezing molding, and insulation 0.5-24 hour is solidified thoroughly it;
(5) above-mentioned product is placed freezer dryer ,-20--60 ℃ lyophilization 24-30 hour, thoroughly to remove dilution;
(6) above-mentioned product is placed baking oven, be warming up to the above 5-20 of polymer Tg ℃, be incubated 6-24 hour, naturally cool to room temperature then, obtain described tissue engineered porous scaffold material.
Wherein, the inorganic nanometer powder that is adopted is hydroxyapatite, bata-tricalcium phosphate or hydroxyapatite and bata-tricalcium phosphate biphase calcium phosphor pottery;
The organic solvent that is adopted is an oxolane, 1,4-dioxane or dichloromethane, and the volume ratio of organic solvent and deionized water is 95: 5 to 85: 15;
The degradable polymer that is adopted is a kind of of polyglycolic acid, lactic acid one ethanol copolymer, polycaprolactone, polyurethane, Merlon, poly-anhydride, poly phosphazene, poly butyric ester and copolymer thereof, collagen, chitosan, perhaps being above-mentioned mixture of polymers and the copolymer between them, perhaps is the product of the different spaces structure of above-mentioned polymer;
The concentration of prepared degradable polymer in solution is 4-15% (w/v).
2. by the be separated method of the organic and inorganic nanometer composite organization engineering stent material by using of preparation of the described thermic of claim 1, it is characterized in that the degradable polymer that adopted and the mass ratio of inorganic nanometer powder are 70/30 to 95/5.
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| US20090197085A1 (en) * | 2006-08-07 | 2009-08-06 | Coppa Nicholas V | Organic nanoparticles and method of preparation thereof |
| US7811503B2 (en) * | 2007-04-18 | 2010-10-12 | Coopervision International Holding Company, Lp | Devices, assemblies, and methods for extracting extractable materials from polymerized biomedical devices |
| CN101766923B (en) * | 2008-12-30 | 2011-12-21 | 中国科学院生态环境研究中心 | Method for separation and redispersion of nanometer materials |
| CN101927033B (en) * | 2010-08-09 | 2013-06-12 | 华南理工大学 | PHBV (Poly (HydroxyButyrate-hydroxyValerate)) nano fiber support material as well as preparation method and application thereof |
| CN102321352B (en) * | 2011-03-18 | 2013-07-17 | 华东理工大学 | Polycaprolactone in mesoporous structure and preparation method and application thereof |
| CN102321271B (en) * | 2011-09-15 | 2012-09-05 | 西安交通大学 | Preparation method for chitosan-based porous scaffolds with biological activity |
| CN102641521A (en) * | 2012-04-24 | 2012-08-22 | 浙江大学 | Preparation method of polyester microballoon-piled porous support |
| CN103191470B (en) * | 2013-04-03 | 2014-11-26 | 中国科学院上海硅酸盐研究所 | Organic/inorganic composite three-dimensional porous scaffold with drug sustained release function, and preparation method thereof |
| CN104027840A (en) * | 2014-06-16 | 2014-09-10 | 清华大学 | Preparation method of porous scaffold for bone repair |
| CN105903082B (en) * | 2016-06-17 | 2019-01-18 | 三峡大学 | A kind of biodegradable medical nano composite porous material, preparation method and applications |
| CN106139256A (en) * | 2016-07-28 | 2016-11-23 | 复旦大学附属中山医院 | Polylactic acid/nano β tricalcium phosphate complex stephanoporate bracket and preparation method thereof |
| CN106432782B (en) * | 2016-08-01 | 2019-04-26 | 郑州大学 | Hydrophobic porous polymer integral material and preparation method thereof with nest like structure |
| CN111467565B (en) * | 2020-06-03 | 2021-11-16 | 暨南大学 | Microtubule scaffold, preparation method and application thereof |
| CN113956529B (en) * | 2021-11-29 | 2022-12-09 | 海南师范大学 | Method for preparing porous and super-hydrophobic PLA film with adjustable aperture by using solvent freezing phase separation method |
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| CN1554449A (en) * | 2003-12-24 | 2004-12-15 | 中国人民解放军第二军医大学 | Nano zirconium oxide tough-ened high porosity calcium phosphate artificial bone rack and its preparing method |
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| CN1554449A (en) * | 2003-12-24 | 2004-12-15 | 中国人民解放军第二军医大学 | Nano zirconium oxide tough-ened high porosity calcium phosphate artificial bone rack and its preparing method |
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