CN102423272B - A kind of porous support with network channel and preparation method thereof - Google Patents
A kind of porous support with network channel and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to biomaterial and regeneration medicine technology field, be specially a kind of porous support with network channel and preparation method thereof.Namely the matrix material of porous support of the present invention can be the inorganic material such as pottery, glass, carbon element, also can be and has self-adhesive, resolvability, plastic macromolecular material, goes back composite that is inorganic and macromolecular material.Matrix material and porogen are mixed homogeneously with network-like material by preparation method, when matrix material is inorganic material, by method removing porogen and the preparation of network shape material of high temperature sintering; When matrix material is the complex of macromolecular material or macromolecular material and inorganic material, room temperature mold pressing/particle solvent extraction method is adopted to prepare the porous support with network channel.Porous support of the present invention has constructed network channel structure on three-D space structure, not only increases the connectivity between bracket holes and hole, and the passage introduced is that blood vessel is grown into the favourable space that support provides.
Description
Technical field
The invention belongs to biomaterial and regeneration medicine technology field, be specifically related to a kind of porous support with network channel and preparation method thereof.
Background technology
Tissue engineering is the ultimate principle of integrated application engineering and life sciences, basic theories, basic fundamental and basic skills.The core of organizational project is exactly set up the three dimensions complex of cell and timbering material, i.e. the vital biological tissue of tool, in order to disease damage tissue is carried out form, 26S Proteasome Structure and Function reconstruction and reach permanent substitute.Tissue induction does not then introduce alien species daughter cell, directly implants porous support, in vivo in environment, the entering of inducing cell, even to break up.Porous support plays a crucial role in organizational project and tissue induction wait regenerative medicine to study, and it is not only specific cell provides support structure ashamed use, but also plays template action, guide tissue regeneration and control organizational structure.Therefore, screen and prepare a kind of desirable timbering material for the development of regenerative medicine with apply most important.
Researcher finds that the seed cell of internal stent is after implanting, nutrient and oxygen promptly can be consumed, because cell just maintains survival by disperse in 150-200 μm around blood vessel, if inherent blood circulation can not be set up, organizational project and tissue induction can only be limited to structure thinner tissue [JeroenRouwkema, etal.
trendsinBiotechnology, 2008,26:434 – 441].So the key issue being built with the three-dimensional tissue of certain volume is exactly the vascularization problem [GriffithLG, the etal. that how to solve engineering tissue
science.2002,295:1009-1014.].At present, this viewpoint has become common recognition [WangL, the etal. of lot of domestic and foreign organizational project and tissue induction scholar
biomaterials.2010,31:9452-9461].
At present, timbering material is promoted that the research of vascularization has been reported.Wherein more is the research of material surface, Kirkpatrick [UngerRE, etal.
biomaterials.2005,26:3461-3469.] etc. people observe, at polyether sulfone surface and the online extracellular matrix of fibroin albumen, under the stimulation of somatomedin and collagen, can capillary structure be formed.Also have domestic scholars [GuoR, etal.
biomaterials.2011,32:1019-1031.] pig skin depth otch is repaired in growth factor VEGF-165 load on the timbering material of collagen-chitin, after 112 days, find that the skin histology after repairing and normal group are woven with very similar structure, and there is the tension force of normal structure 80%.And the research in scaffold three-dimensional aperture is also enlivened gradually, if any researcher [DrueckeD., etal.
journalofBiomedicalMaterialsResearchPartA.2004,68A:10-18.] construct the support of 3 kinds of different pore size sizes (250-300,75-212,20-75 μm), find that the vascularization speed of these supports is by pore size influences, wherein the stented vessel degree of maximum diameter of hole is best, after the stenting that aperture is maximum 8 days and 12 days, there is at the edge of material and center larger vessel density and erythrocyte speed, and still very active at the 20th day vascularization.Also have researcher [KubokiY, etal.
theJournalofBoneandJointSurgery2001, find 83A (Suppl.1): S105 – 15.], aperture is that the first inducing cartilage of hydroxyapatite porous support materials of 90-120 μm is formed and then ossify, and the hydroxyapatite that aperture is greater than 350 μm can directly induce osseous tissue to be formed, its critical aperture is 300-400 μm.Perhaps, this is that large aperture is more conducive to vascularization, thus brings more nutritional labeling to cause for local organization.The researcher also had is thought, interpore connection is larger on the impact of vascularization in timbering material body, and hole does not communicate and makes can not be connected to each other between new bone, and lacks seriality and conformability, and blood vessel usually can not enter into the cecum of this some holes.If any researcher [MastrogiacomoM, etal.
biomaterials.2006,27:3230 – 3237] make in two kinds of apertures, porosity and holes and be communicated with the different porous hydroxyapatite material in footpath, subcutaneous rat is implanted to after compound bone marrow stroma stem cell, postoperative histologic analysis shows: two kinds of structural material vascularization degree are all better, all blood vessel is contained in all holes, blood vessel number is also more, but what is interesting is, the blood vessels caliber had compared with being formed in the material be communicated with between macropore is larger, that is, being communicated with between hole is the bottleneck that new vessels passes in and out, and decides the tube chamber size of formed blood vessel.[BaiF, the etal. such as LuJX
tissueEngineeringPartA.2010,16:3791-3803] large quantifier elimination has been done to the connection footpath problem of bracket holes, they implant the formation of animal In vivo study blood vessel by having accurate aperture and bata-tricalcium phosphate (β-TCP) porous material being communicated with footpath, find to be communicated with footpath more important for vascularization than aperture, but then both effect is as broad as long when aperture is greater than 400 μm.In sum, supporting structure is the very important morphological properties of engineering tissue, the surface that timbering material is suitable for and three dimensional pore structures are conducive to transport and the exchange of nutrient substance, oxygen and metabolite, and provide passage for growing into of new vessels, be thus conducive to organizational project and organize the vascularization of cambium in inductive technology.
How control the structure of regenerating tissues, size and pattern by the structure of timbering material and topographic design, as the framework connecting biological cells and tissues, does transmitting tissue grow into specific modality? the present invention imagines simulated blood vessel network shape, directly select some natural network-type materials or can the material of bionic preparation blood vessel network shape material from nature, then utilize these network-type materials as the template that will be removed in timbering material excipient preparation with the porous support as blood vessel network shape passage.It not only has suitable aperture, porosity, tensile strength and degradation time; Also have biocompatibility, be suitable for cell adhesion and apposition; And, also there are some network channels in support and be applicable to cell and seek connections with and migration along channel direction, guide Growth of Cells direction and migration situation; Simultaneously because the connection of passage itself can increase again the connectedness between bracket holes, be more conducive to the discharge with cellular metabolism refuse that proceeds to of nutrient substance, make cytoskeleton can maintain it by the structure of self and survive.
Summary of the invention
The object of the present invention is to provide a kind of porous support with network channel and preparation method thereof.
The porous support with network channel that the present invention proposes, be characterized in the network channel (hole) containing simulated blood vessel network shape in this support, passage (hole) diameter is 1 μm of-5mm, and the porosity of support is 0.1-99%.Preferably porosity ranges is 40-95%.
In porous support of the present invention, can there is network channel (hole) and non-network passage (hole), wherein, the diameter dimension of non-network passage (hole) nibs is 5-2000 μm simultaneously.
In the present invention, the matrix material of described porous support is the Inorganic Non-metallic Materials such as pottery, glass, carbon element, comprises titanium oxide, aluminium oxide, calcium oxide, sodium oxide, silicon oxide, calcium phosphate series (hydroxyapatite, tricalcium phosphate, tetracalcium phosphate, calcium pyrophosphate, biphasic calcium phosphate, calcium polyphosphate), calcium sulfate, calcium carbonate, Low Temperature Isotropic Carbon and the mixture of above material or the mixture with additive.
The matrix material of porous support of the present invention also can be any one in following degradable macromolecular material: the copolymer of poly DL-lactide, PLLA, PGA, poly lactic-co-glycolic acid, poly 3-hydroxy butyrate, polyhydroxyalkanoate, poly-epsilon-caprolactone, poly-ε-alkyl replace caprolactone, poly-δ-valerolactone, Merlon, poe, polymethyl methacrylate, poly-to dioxanone, poly-dioxane, polyether ester, or is any one in any type of copolymer of above-mentioned each kind polyester or blend;
The matrix material of porous support of the present invention also can be any one in following non-degradable macromolecular material: polystyrene, polrvinyl chloride, polyacrylate, polymethacrylates, poly-carbonic acid vinegar, nylon, polyurethane, polyformaldehyde, polyvinyl alcohol, polyvinyl acetate, polysiloxanes, or is by any one in the copolymer that forms several among them or blend.
The matrix material of porous support of the present invention can also be the various forms of complex of one or more in inorganic material and macromolecular material.
The preparation method with the porous support of network channel of the present invention, that host material or its precursor are mixed mutually with the template with network structure, or host material or its precursor are mixed with network template and non-network type porogen simultaneously, then after removing network template and non-network type porogen, make precursor become host material, final acquisition has the porous support of network channel.
The porous support with network channel that the present invention proposes, when matrix material is inorganic material, preparation concrete steps are as follows:
Inorganic material, binding agent, porogen are mixed with network-like material, forms the mixture of finely dispersed inorganic material, porogen and network-like material; This mixture is poured in mould and carries out compression molding, make the mixture goods of inorganic material-porogen-network-like material, then in room temperature environment, make the dry 0-3d of mixture, be heated to high temperature 800-1500 DEG C again, sintering, except no-bonder, porogen and network-like material, just obtains required inorganic porous support.
Inorganic material is matrix material, and porogen used is divided into inorganic and organic two classes, and inorganic porogen has the decomposable salts of high temperature such as ammonium carbonate, ammonium bicarbonate, ammonium chloride, and other decomposable compound is as Si
3n
4and coal dust, carbon dust etc.Organic porogen is natural fiber, high molecular polymer and organic acid mainly, as sawdust, naphthalene, starch and polyvinyl alcohol, polrvinyl chloride, polystyrene, polyvinyl butyral resin, stearic acid, methymethacrylate, methylcellulose, carbamide etc. or by the mixture formed several among them; Porogen grain size is long is 5-2000 μm (preferably scope is 200-600 μm), porogen consumption be mixture 1-99wt%(preferably scope be 40-85wt%).
Network-like material used is vein, Retinervus Luffae Fructus, silkworm silk, sugared silk screen, or wherein several mixing; Network diameter is 1 μm of-5mm, the consumption of network-like material be mixture 0.00001-99wt%(preferably scope be 0.001-20wt%).
Because above-mentioned network-like material itself also plays a part porogen, therefore, both comprised the network-like material of simple use in the present invention and obtained porous support, also comprised the porous support simultaneously using the porogen of network-like material and other class to obtain.
Binding agent used is macromolecule, liquefied hydrocarbon material and phosphate, or by formed mixture several among them, consumption of binder is the 0.1-99wt% of mixture.(preferably scope is 1-60wt%)
The present invention propose the porous support with network channel, when matrix material be macromolecular material and the complex with inorganic material time, preparation concrete steps as follows:
(1) complex of macromolecular material or itself and inorganic material is scattered in solvent orange 2 A, forms mixed solution, porogen is scattered in mixed solution, makes partial solvent A volatilize while stirring, form finely dispersed mixed solution-porogen particles mixture; Then pour in the mould containing network-like material, compression molding in a mold, form mixed solution-porogen particle-network-like mixture of substances goods; Then, first under room temperature environment, make solvent orange 2 A part volatilize, then vacuum drying, remove residual solvent A, after solvent orange 2 A removes completely, obtain the moulded products of mixture; Described vacuum drying temperature is no more than fusing point or the vitrification point of timbering material; Solvent for use A is solubilized macromolecular material but does not dissolve the solvent of porogen and network-like material;
(2) the mixture forming goods of the complex-porogen particle-network-like material of above-mentioned macromolecular material or itself and inorganic material are placed in solvent B, leach porogen particle and network-like material; Solvent for use B is solubilized porogen and network-like material but does not dissolve the solvent of the complex of macromolecular material used or itself and inorganic material;
(3) taken out from container by the above-mentioned own support leaching porogen particle and network-like material, after most of solvent B volatilizees, put into vacuum drying oven vacuum drying, complete desolvation B, namely obtains required porous support; Described vacuum drying temperature is no more than fusing point or the vitrification point of timbering material.
Same, because above-mentioned network-like material itself also plays a part porogen, therefore, both comprised the network-like material of simple use in the present invention and obtained porous support, also comprised the porous support simultaneously using the porogen of network-like material and other class to obtain.
The complex of macromolecular material or itself and inorganic material is matrix material, and porogen used is inorganic salt particle, polysaccharide, protein, synthesis macromolecule, or by formed mixture several among them; Porogen grain size is 5-2000 μm (preferably scope is 200-600 μm), porogen consumption be mixture 1-99wt%(preferably scope be 80-95wt%).
Network-like material used is can be made into the network-like and material that can remove from macromolecular material matrix as glucose, fructose, sucrose, maltose, paraffin, polyvinyl pyrrolidone, or wherein several mixture; Network-like material diameter is 1 μm of-5mm, the consumption of network-like material be mixture 0.00001-99wt%(preferably scope be 0.001-20wt%).
Macromolecular solution concentration range used is l-99wt%.
Solvent for use A is acetone, butanone, chloroform, dichloromethane, oxolane, benzene,toluene,xylene, ethylene glycol, Ketohexamethylene, dioxane, N, any one in N dimethyl formamide, formic acid, benzyl alcohol, cyclohexane extraction, or wherein several mixture.
Solvent for use B be in the middle of water, alcohol, amine, hydrocarbon and halogenated hydrocarbons any one, or wherein several mixture.
Solvent B consumption is 10-1000 times of mixture total weight amount.
The present invention is in order to simulated blood vessel network shape, some natural network-type materials or can the material of bionic preparation blood vessel network shape are directly selected from nature, then utilize these network-type materials as the template that will be removed, in timbering material, excipient preparation is with the porous support as blood vessel network shape passage.It not only has suitable aperture, porosity, tensile strength and degradation time, also has biocompatibility, is suitable for cell adhesion and apposition; And, also there are some network channels in support and be applicable to cell and seek connections with and migration along channel direction, guide Growth of Cells direction and migration situation; Simultaneously because the connection of passage itself can increase again the connectedness between bracket holes, be more conducive to the discharge with cellular metabolism refuse that proceeds to of nutrient substance, make cytoskeleton can maintain it by the structure of self and survive.
Accompanying drawing explanation
The light micrograph figure (× 100) of Fig. 1 Retinervus Luffae Fructus.
The stereoscan photograph of the β-TCP three-dimensional porous rack with network channel that Fig. 2 utilizes Retinervus Luffae Fructus to obtain as template.
Detailed description of the invention
Below by embodiment, the present invention is illustrated further.
embodiment 11.8g β-TCP is added polyvinyl alcohol (PVA) aqueous solution of 1.1g5%, stir, grinding, then add 0.45g380-550 μm of diameter paraffin ball to stir, then pour into compression molding in the mould being placed with 0.054g Retinervus Luffae Fructus (diameter 300 μm), take out support, room temperature places 24h, put into Muffle furnace and be heated to 1050 DEG C of sintering, just obtain the porous support with network channel.Obtain about 450 μm, aperture, porosity is about the three-dimensional porous rack with passage (diameter 300 μm) of 50%.
embodiment 21.8g hydroxyapatite is added the PVA aqueous solution of 1.1g5%, stir, grinding, then add 0.45g380-550 μm of diameter paraffin ball to stir, then pour into compression molding in the mould placing 0.054g Retinervus Luffae Fructus (diameter 300 μm), take out support, room temperature places 48h, put into Muffle furnace and be heated to 1100 DEG C of sintering, obtain about 450 μm, aperture, porosity is about the three-dimensional porous rack with passage (diameter 300 μm) of 50%.
embodiment 31.8g β-TCP is added the PVA aqueous solution of 0.54g10%, stir, grinding, then add 0.45g270-380 μm of diameter paraffin ball to stir, then pour into compression molding in the mould placing 0.054g Retinervus Luffae Fructus (diameter 300 μm), take out support, room temperature places 24h, put into Muffle furnace and be heated to 1050 DEG C of sintering, obtain about 300 μm, aperture, porosity is about the three-dimensional porous rack with passage (diameter 300 μm) of 50%.
embodiment 41.8g hydroxyapatite is added the PVA aqueous solution of 0.54g10%, stir, grinding, then add 0.35g270-380 μm of diameter paraffin ball to stir, then pour into compression molding in the mould placing 0.05g Retinervus Luffae Fructus (diameter 300 μm), take out support, room temperature places 24h, put into Muffle furnace high temperature sintering to remove Retinervus Luffae Fructus and be heated to 1100 DEG C of sintering, just obtain the porous support with network channel that porosity is 50%.Obtain about 300 μm, aperture, porosity is the three-dimensional porous rack with passage (diameter 300 μm) of 45%.
embodiment 52gPLGA (85/15) is dissolved in 11g dichloromethane, sodium chloride (grain size 180 μm-280 μm) 30g is dispersed in the dichloromethane solution of PLGA, then pour into and be loaded with (the commercially available wire drawing machine wire drawing acquisition of 1g sugar fiber, diameter 10 μm) mould in, room temperature mold pressing, decompress(ion) after 24h, with 200ml deionization washing support, water is changed once every 0.5h, until with the aqueous solution of 0.1mol/L silver nitrate, be added drop-wise in leachate, there is not white precipitate, then vacuum drying is carried out, baking temperature 20 ° of C, drying time is 48h, obtain about 200 μm, aperture, porosity is the three-dimensional porous rack with passage (diameter 10 μm) of 90%.
embodiment 62gPLA is dissolved in 11g dichloromethane, then pours in the mould being loaded with 20 μ g sugar fiber (diameter 10 μm), room temperature mold pressing, decompress(ion) after 24h, with 200ml deionization washing support, changes water once every 0.5h, until with the aqueous solution of 0.1mol/L silver nitrate, be added drop-wise in leachate, do not occur white precipitate, then carry out vacuum drying, baking temperature 20 DEG C, drying time is 48h, obtains 10 μm, aperture, and porosity is the three-dimensional porous rack with passage (diameter 10 μm) of 0.1%.
embodiment 72g polylactic acid is dissolved in 11g dichloromethane, sodium chloride (grain size 50 μm-150 μm) 75g is dispersed in the dichloromethane solution of polylactic acid, then pour in the mould being loaded with 5g sugar fiber (diameter 10 μm), room temperature mold pressing, decompress(ion) after 24h, with 200ml deionization washing support, water is changed once every 0.5h, until with the aqueous solution of 0.1mol/L silver nitrate, be added drop-wise in leachate, there is not white precipitate, then vacuum drying is carried out, baking temperature 20 DEG C, drying time is 48h, obtain about 100 μm, aperture, porosity is the three-dimensional porous rack with passage (diameter 10 μm) of 99%.
embodiment 82gPLGA and 100mg β-TCP is scattered in 11g dichloromethane, sodium chloride (grain size 50 μm-150 μm) 26g is dispersed in the dichloromethane solution of PLGA and β-TCP, then pour in the mould being loaded with 4.5g sugar fiber (diameter 10 μm), room temperature mold pressing, decompress(ion) after 24h, with 200ml deionization washing support, water is changed once every 0.5h, until with the aqueous solution of 0.1mol/L silver nitrate, be added drop-wise in leachate, there is not white precipitate, then vacuum drying is carried out, baking temperature 20 DEG C, drying time is 48h, obtain about 100 μm, aperture, porosity is the three-dimensional porous rack with passage (diameter 10 μm) of 90%.
embodiment 92g polystyrene is dissolved in 11g chloroform, sodium chloride (grain size 50 μm-150 μm) 17g is dispersed in the chloroformic solution of polystyrene, then pour in the mould being loaded with 1g sugar fiber (diameter 10 μm), room temperature mold pressing, decompress(ion) after 24h, with 200ml deionization washing support, water is changed once every 0.5h, until with the aqueous solution of 0.1mol/L silver nitrate, be added drop-wise in leachate, there is not white precipitate, then vacuum drying is carried out, baking temperature 20 DEG C, drying time is 48h, obtain about 100 μm, aperture, porosity is the three-dimensional porous rack with passage (diameter 10 μm) of 90%.
Claims (6)
1. there is a porous support for network channel, it is characterized in that this network channel diameter is 1 μm of-5mm, and the porosity of support is 0.1-99% containing network channel in described porous support; There is network channel hole and non-network access opening in support, the diameter dimension of non-network passage nibs is 5-2000 μm simultaneously; The network-like material forming network channel is vein, Retinervus Luffae Fructus or both mixing.
2. porous support according to claim 1, is characterized in that its matrix material is the mixture of one or more in titanium oxide, aluminium oxide, calcium oxide, sodium oxide, silicon oxide, calcium phosphate series, calcium sulfate, calcium carbonate, Low Temperature Isotropic Carbon.
3. one kind has the preparation method of the porous support of network channel as claimed in claim 1 or 2, it is characterized in that, host material or its precursor are mixed mutually with the template with network structure, or host material or its precursor are mixed with network template and non-network type porogen simultaneously; Then remove network template and non-network type porogen, and make precursor become host material, final acquisition has the porous support of network channel.
4. preparation method according to claim 3, is characterized in that, when being inorganic material for matrix material, concrete steps are as follows:
Inorganic material, binding agent, porogen are mixed, forms finely dispersed inorganic material, binding agent, porogen mixture; This mixture is poured in the mould that network-like material is housed and carries out compression molding, make the mixture goods of inorganic material-porogen-network-like material, then in room temperature environment, make the dry 0-3d of mixture, be heated to high temperature 800-1500 DEG C again, sintering, except no-bonder, porogen and network-like material, just obtains required inorganic porous support.
5. preparation method according to claim 4, it is characterized in that porogen used is divided into and has inorganic and organic two classes, wherein, inorganic porogen is ammonium carbonate, ammonium bicarbonate or ammonium chloride, or is Si
3n
4, coal dust or carbon dust; Organic porogen is the one of sawdust, naphthalene, starch, polyvinyl alcohol, polrvinyl chloride, polystyrene, polyvinyl butyral resin, stearic acid, methymethacrylate, methylcellulose, carbamide, or by formed mixture several among them; Porogen grain size is 5-2000 μm, and porogen consumption is the 1-99wt% of mixture;
Network-like material diameter is 1 μm of-5mm, and the consumption of network-like material is the 0.00001-99wt% of mixture.
6. want the preparation method described in 5 according to right, it is characterized in that binding agent used is liquefied hydrocarbon material or phosphate, or by formed mixture several among them.
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| CN114315338B (en) * | 2021-05-24 | 2022-11-22 | 山东大学 | Si 3 N 4 /CPP composite ceramic material and preparation method and application thereof |
| CN114225111A (en) * | 2021-12-23 | 2022-03-25 | 南开大学 | Preparation method of extracellular matrix support material with controllable pore structure |
| CN114873921A (en) * | 2022-03-16 | 2022-08-09 | 苏州延生堂医疗器械科技有限公司 | Organic polymer-containing porous bioglass ceramic degradable bone wound material and preparation method thereof |
| CN114681688B (en) * | 2022-04-15 | 2022-11-08 | 东南大学 | Tissue regeneration membrane for promoting vascularization by using micro-channel and preparation method thereof |
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