CN1181892C - Porous material for scaffold of tissue engineering and its preparing process - Google Patents
Porous material for scaffold of tissue engineering and its preparing process Download PDFInfo
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- CN1181892C CN1181892C CNB021381291A CN02138129A CN1181892C CN 1181892 C CN1181892 C CN 1181892C CN B021381291 A CNB021381291 A CN B021381291A CN 02138129 A CN02138129 A CN 02138129A CN 1181892 C CN1181892 C CN 1181892C
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- sericin
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Abstract
The present invention relates to a porous material for tissue engineering scaffolds and a preparation method thereof, which belongs to the technical field of biomedical materials. The present invention uses sericin and fibroin which are respectively obtained through dissolution and purification in cultivated silk and tussah silk, the sericin and the fibroin are mixed according to a proper proportion, and are fast stirred under a certain temperature, after the mixture is frozen, a freeze drying method is adopted to processing the mixture into a blocky or filmily porous body, and cell growth factor slow release microcapsules are injected into holes of the porous body. The present invention has high biocompatibility, can guide and promote the adhesion and the growth of cells, can regulate the biodegradation rate, and is suitable for being used as cell culture substrates and tissue repairing materials for skin, dura mater, cartilage, etc.
Description
Technical field
The invention belongs to field of biomedical materials, particularly a kind of porous material that is applicable to tissue engineering bracket and preparation method thereof.
Background technology
Application and Development mainly contains polylactic acid (PLA), polyglycolic acid (PGA) and collagen protein etc. in the biodegradable porous material of organizational project at present.But synthetic material (PLA, PGA etc.) still has many problems not to be resolved at aspects such as the control of biocompatibility, physicochemical property, degradation rate and slow-releasing, and synthesis technique is complicated.Though self is just comprising many bio informations the collagen protein in the natural material, can make cell keep or produce many functions, can but the collagen protein Purification of particular types be more loaded down with trivial details, and quality control is difficulty, and avoid antigenic influence and transmission of disease to wait to observe fully.
Studies show that, contain have an appointment 75% fibroin and 25% sericin in the silkworm silk, they are native proteins that silkworm goes out in the silk glands endocrine, formed by 18 seed amino acid residues, every result of the test shows, fibroin avirulence, nonirritant have excellent biological compatibility, are the more satisfactory raw materials of making bio-medical material.Before the present invention made, it was raw material with the silk fibroin protein that Chinese patent CN1260363A " a kind of porous fibroin membrane and preparation method thereof " discloses a kind of, adopted freeze-drying to prepare the technology of porous fibroin membrane.This method is: earlier domestic silkworm silk is obtained pure silk fibroin solution after coming unstuck, dissolve, dialyse, purifying; In above-mentioned solution, add additive, wherein contain 10～60% CH
2CH (OH) CH
2OH etc., 10～60% CH
3CH
2(OH) CH (NH
2) COOH etc., all the other are that epoxide etc. is as cross-linking agent, make the preparation mixed solution, be injected in the mould, freezing 10min～24h under-4～-85 ℃ temperature carries out vacuum drying again, vacuum drying preceding 5～24h temperature is set in-4～-40 ℃ of scopes, in the process of vacuum drying, per hour heat up 1～10 ℃, can obtain this and invent described silk fibroin porous film to room temperature thereafter.On structure, because fibroin is fibrous protein, therefore, when using as tissue engineering bracket material, its biodegradable speed is slower with the perforated membrane of fibroin preparation.When tissue regeneration speed is very fast, require timbering material to be degraded and absorbed quickly, otherwise may influence the form and the function of cambium, and when tissue regeneration speed is slow, timbering material should have positive guiding, promote cell to grow into the ability of standard tissue, thereby accelerate tissue repair speed, at this moment, the speed that timbering material is degraded and absorbed also needs to accelerate simultaneously, so that adapt with tissue regeneration speed, therefore, with the porous material of fibroin preparation, its biodegradation rate just is difficult to adapt to tissue regeneration speed merely.
Summary of the invention
Purpose of the present invention is exactly the deficiency at prior art, a kind of may command biodegradation rate is provided, also can promotes porous material for scaffold of tissue engineering of cell adhesion and growth and preparation method thereof.
Porous material for scaffold of tissue engineering of the present invention is bulk or the membranoid substance that contains silk fibroin protein, and inner average hole density is 1～3000/mm
2, average pore size is 1～500 μ m, it is characterized in that: it also contains domestic silkworm silk glue protein, tussah silk fibroin; It is the cell growth factor slow-release microcapsule of wall material that the hole contains with the sericin.
The method for preparing porous material for scaffold of tissue engineering of the present invention, obtain the bombyx mori silk fibroin aqueous solution after domestic silkworm silk come unstuck, dissolves, purifies, become preparation with mixing stock solution after in spissated silk fibroin solution, adding additive, with this stock solution lyophilization, it is characterized in that also comprising the steps:
(1) preparation domestic silkworm silk glue protein, tussah silk fibroin join preparation with mixing in the stock solution, under 30～90 ℃ of temperature conditions with after stirring greater than 500 rev/mins speed, freezing under-15～-85 ℃ of temperature conditions immediately, after lyophilization, make the fibroin porous body again;
(2) preparation is the cell growth factor slow-release microcapsule of wall material with the sericin, injects in the hole of above-mentioned porous body and makes tissue engineering bracket fibroin porous material.
Above-described tussah silk fibroin preparation method is: be the thiocyanation lithium of 5～12M with concentration; bath raio is 1: 5～1: 500; dissolving tussah silk peptide fiber under 20～100 ℃ temperature conditions, makes molecular weight and be 0.35～1.50 ten thousand tussah silk fibroin aqueous solution after dialysis.
Above-described preparation is that the method for the cell growth factor slow-release microcapsule of wall material is with the sericin:
(1) be that the sericin aqueous solution of 0.01～0.20g/ml is preheated to 40～80 ℃ with concentration, dropwise splash in the vegetable oil that has been preheated to 40～80 ℃, speed while dripping with 200～2000 rev/mins stirs, and sericin gelization is treated with 100～1500 rev/mins speed stirring in the cooling back; In above-mentioned solution, add organic solvent again, after centrifugalize, crosslinked, drying, obtain the sericin microsphere;
(2) cell growth factor solution is splashed into exsiccant sericin microsphere, making with the sericin is the cell growth factor slow-release microcapsule of wall material.
Compared with prior art, used in tissue engineering porous material of the present invention has following remarkable advantage:
(1) contains bio informations such as Arg-Gly-Asp sequence in the primary structure of tussah silk fibroin, with cell special interaction is arranged, so in porous material, added the adhesion that can promote cell behind the tussah silk fibroin;
(2) injected the cell growth factor slow-release microcapsule in the porous material, so, can guide, promote cell along support propagation, growth;
(3) sericin is a chondritic, more easily by biodegradation, thereby, can be by regulating the mass ratio of sericin and fibroin albumen in the material, realize controlling the purpose that the reproduction speed of its degradation speed and cambium adapts.
(4) stock solution stirs fast, the method for quick freezing with mixing to preparing owing to having adopted, fibroin, the sericin macromole of random coil structure in the solution are fully stretched, mix homogeneously, and it is this state is fixing fast, solved fibroin and the problem that sericin is separated in the fibroin porous material, made form, structure and the performance homogenization of material.
The specific embodiment
Embodiment one:
1. tame Bombyx bombycis is through shelling cocoon, sectility, going pupa to obtain cocoon layer, behind the silkworm cocoon layer usefulness tap water thorough washing with 1 kilogram of cleaning, reuse deionized water wash 3 times, put into 20 liters of deionized waters, made the sericin dissolving in 40 minutes in 98～100 ℃ of processing, obtaining concentration after the filtration is 1.5% sericin aqueous solution, and obtains solid sericin after getting the lyophilization of part sericin aqueous solution.
2. 1 kilogram of domestic silkworm silk is put into 10 liters of concentration and be 0.025% aqueous sodium carbonate, boiled 0.5 hour, the sericin of most silkworm silk periphery is taken off in reprocessing three times, obtains the pure silk cellulose fiber; Fibroin fiber after will drying is 1: 8: 2 calcium chloride, water, an alcoholic solution with 10 liters of mol ratios, becomes the fibroin albumen mixed solution 78 ± 2 ℃ of following heating for dissolving; With cellulose membrane is the dialysis material, the fibroin albumen mixed solution water of gained is dialysed, and with removal calcium chloride, impurity such as ethanol, reuse multilamellar absorbent carbasus filters, and obtains pure silk fibroin protein solution; The pure silk cellulose solution maintains under 35 ℃, makes its evaporation and concentration while stirring.
3. implantation concentration was 3% additive in aluminum alloy mould ,-16 ℃ of following pre-freezes 2 hours.
4. sericin aqueous solution, fibroin aqueous solution are pressed 80: 20 mixed, make preparation with mixing stock solution after adding additive, to mix stock solution after stirring with 1700 rev/mins speed under 75 ± 2 ℃ the temperature conditions, inject immediately in the above-mentioned aluminum alloy mould, thickness is 10mm, and quick freezing is 2 hours under-16 ℃ of temperature.
With above-mentioned Frozen Body together with mould, place drying under reduced pressure in the freezer dryer, preceding 24 hours of dry run, temperature constant is in-16 ℃, per hour heat up 2 ℃ until room temperature, take out in the aluminum alloy mould after drying is finished and be blocky domestic silkworm silk albumen porous body thereafter.
6. preparation concentration is the sericin aqueous solution of 0.025g/ml, be preheated to 70 ℃ after, dropwise splash into 2000ml and be preheated in 70 ℃ the olive oil, the speed while dripping with 1000 rev/mins stirred 15 minutes, temperature maintenance obtains water-in-oil emulsion at 70 ℃.Emulsion is cooled to 30 ℃, stirred 60 minutes, make sericin gelization with 300 rev/mins speed.Add 700ml acetone in above-mentioned solution, the speed that continues with 300 rev/mins stirred 60 minutes, and washed with isopropyl alcohol use in centrifugalize, flooded to make it crosslinked in 1 hour in concentration is 1% glutaraldehyde solution, obtained the sericin microsphere after the lyophilization.Basic fibroblast growth factor bFGF solution is splashed into exsiccant sericin microsphere, and room temperature was placed 60 minutes, and bFGF is infiltrated in the microsphere, and making with the sericin is the bFGF slow-release microcapsule of wall material.
7. after an amount of normal saline makes the swelling of bFGF slow-release microcapsule, inject in the domestic silkworm silk albumen porous body, make the domestic silkworm silk albumen porous material that contains the bFGF slow-release microcapsule.
Use in the mixing stock solution in the preparation of present embodiment, also can add an amount of tussah silk fibroin solution (preparation method of tussah silk fibroin solution is referring to embodiment two steps 1,2).Tussah silk peptide, silkworm sericin, bombyx mori silk fibroin three can make preparation with mixing stock solution after the arbitrary proportion mixing, and adhesiveness, degradation speed and the physical property of desired pair cell decided when its ratio can be used for tissue engineering bracket according to this porous material.The ratio of tussah silk fibroin is high more, and the adhesiveness of material pair cell is good more; The ratio of sericin is high more, and biodegradation rate is fast more; The ratio of silk fibroin protein is high more, and physical properties such as the morphological stability of material are good more.Therefore, change the ratio of sericin, tussah silk peptide, bombyx mori silk fibroin in the porous material, can reach the purpose of the physical property of the adhesiveness of its biodegradation rate of control, pair cell and material, make it be adapted to the regenerated needs of different tissues.Press the fibroin porous material of present embodiment method preparation, its primary structure, performance see Table one.
Embodiment two:
1. 0.5 kilogram of antherea pernyi silk is put into 10 liters of concentration and be 0.5% aqueous sodium carbonate, boiled 0.5 hour, the sericin of most tussah silk periphery is taken off in reprocessing three times, obtains the tussah silk peptide fiber.
2. be the thiocyanation lithium of 9M with concentration, in 40 ℃ of temperature, bath raio dissolving in 1: 20 tussah silk obtains mixed solution; With above-mentioned solution to water dialysis 4 round the clock, the dialysis material is that molecular cut off is 1.10 ten thousand cellulose membrane, obtains pure tussah silk fibroin aqueous solution; Above-mentioned pure tussah silk peptide solution is maintained under 40 ℃, carry out evaporation and concentration while stirring, make the solution solid content reach 10.0%.
3.0.5 behind the cocoon layer water thorough washing of kilogram cleaning, put into 12 liters of deionized waters, handled 60 minutes down in 98～100 ℃ of temperature conditions, make the sericin dissolving, obtaining concentration after the filtration is the sericin aqueous solution.
4. implantation concentration was 1.5% additive in stainless steel mould ,-40 ℃ of following pre-freezes 6 hours.
5. with spissated tussah silk peptide solution and sericin aqueous solution mixed by 50: 50, make preparation with mixing stock solution after adding additive, the temperature maintenance that makes mixed solution is in 40 ± 2 ℃, with the quick agitating solution of 1000 rev/mins speed 60 minutes, inject subsequently in the above-mentioned stainless steel mould, thickness is 0.5mm, and quick freezing is 6 hours under-40 ℃ of temperature.
With above-mentioned Frozen Body together with stainless steel mould, place vacuum drying in the freezer dryer, preceding 18 hours of dry run, temperature constant per hour heats up thereafter 2 ℃ in-20 ℃, until room temperature, takes out and is membranaceous fibroin porous body.
7. preparation concentration is the sericin aqueous solution of 0.05g/ml, it is preheated to 60 ℃ after, dropwise splash in the olive oil that has been preheated to 60 ℃, stirred 15 minutes with 400 rev/mins speed while dripping, temperature maintenance obtains water-in-oil emulsion at 60 ℃.This aqueous emulsion is cooled to 20 ℃, stirred 60 minutes, make sericin gelization with 250 rev/mins speed.Add 500ml acetone in above-mentioned solution, the speed that continues with 250 rev/mins stirred 60 minutes, and centrifugalize with washed with isopropyl alcohol 8 times, is that dipping made it crosslinked in 1 hour in 75% the alcoholic solution in concentration, obtains the sericin microsphere after the lyophilization.Basic fibroblast growth factor bFGF solution is splashed into exsiccant sericin microsphere, and room temperature was placed 60 minutes, and bFGF is infiltrated in the microsphere, and making with the sericin is the bFGF slow-release microcapsule of wall material.
8. after an amount of normal saline makes the swelling of bFGF slow-release microcapsule, inject in the fibroin perforated membrane, make the fibroin porous material that contains the bFGF slow-release microcapsule.
Use in the mixing stock solution in the preparation of present embodiment, also can add silk fibroin protein as required in proportion as the method preparation of embodiment one.Primary structure, performance by the fibroin perforated membrane of present embodiment method preparation see Table two.
Table one: primary structure, the performance of domestic silkworm silk albumen porous material
| Outward appearance | Inner fibroin structure | The average pore size of internal void (μ m) | The hole density of internal void is (individual/mm 2) | The mean diameter of microcapsule (μ m) | Dissolve-loss ratio in the water (%) | Tensile break strength (N/cm 2) | Elongation at break (%) |
| White, spongy, do not ftracture | Impalpable structure is main | 152.0 | 16.8 | 20.5 | 13.0 | 20.2 | 17.5 |
Table two: primary structure, the performance of tussah silk albumen porous material
| Outward appearance | Inner fibroin structure | The average pore size of internal void (μ m) | The hole density of internal void is (individual/mm 2) | The mean diameter of microcapsule (μ m) | Dissolve-loss ratio in the water (%) | Tensile break strength (N/cm 2) | Elongation at break (%) |
| Pale yellow, spongy, do not ftracture | Impalpable structure is main | 52.4 | 487 | 30.8 | 15.4 | 42.6 | 53.7 |
Claims (4)
1. a porous material for scaffold of tissue engineering is bulk or the membranoid substance that contains silk fibroin protein, and inner average hole density is 1～3000/mm
2, average pore size is 1～500 μ m, it is characterized in that: it also contains domestic silkworm silk glue protein, tussah silk fibroin; It is the cell growth factor slow-release microcapsule of wall material that the hole contains with the sericin.
2. method for preparing porous material for scaffold of tissue engineering, obtain the bombyx mori silk fibroin aqueous solution after domestic silkworm silk come unstuck, dissolves, purifies, become preparation with mixing stock solution after in spissated silk fibroin solution, adding additive,, it is characterized in that also comprising the steps: this stock solution lyophilization
(1) preparation domestic silkworm silk glue protein, tussah silk fibroin join preparation with mixing in the stock solution, under 30～90 ℃ of temperature conditions with after stirring greater than 500 rev/mins speed, freezing under-15～-85 ℃ of temperature conditions immediately, after lyophilization, make the fibroin porous body again;
(2) preparation is the cell growth factor slow-release microcapsule of wall material with the sericin, injects in the hole of above-mentioned porous body, makes tissue engineering bracket fibroin porous material.
3. a kind of method for preparing porous material for scaffold of tissue engineering as claimed in claim 2, it is characterized in that: described tussah silk fibroin preparation method is: be the thiocyanation lithium of 5～12M with concentration; bath raio is 1: 5～1: 500; dissolving tussah silk peptide fiber under 20～100 ℃ temperature conditions, makes molecular weight and be 0.35～1.50 ten thousand tussah silk fibroin aqueous solution after dialysis.
4. a kind of method for preparing porous material for scaffold of tissue engineering as claimed in claim 2 is characterized in that: described preparation is that the method for the cell growth factor slow-release microcapsule of wall material is with the sericin:
(1) be that the sericin aqueous solution of 0.01～0.20g/ml is preheated to 40～80 ℃ with concentration, dropwise splash in the vegetable oil that has been preheated to 40～80 ℃, speed while dripping with 200～2000 rev/mins stirs, and sericin gelization is treated with 100～1500 rev/mins speed stirring in the cooling back; In above-mentioned solution, add organic solvent again, after centrifugalize, crosslinked, drying, obtain the sericin microsphere;
(2) cell growth factor solution is splashed into exsiccant sericin microsphere, making with the sericin is the cell growth factor slow-release microcapsule of wall material.
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| CNB021381291A CN1181892C (en) | 2002-08-14 | 2002-08-14 | Porous material for scaffold of tissue engineering and its preparing process |
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| CNB021381291A CN1181892C (en) | 2002-08-14 | 2002-08-14 | Porous material for scaffold of tissue engineering and its preparing process |
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2002
- 2002-08-14 CN CNB021381291A patent/CN1181892C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013111322A1 (en) * | 2013-05-03 | 2014-11-06 | Ars Arthro Bioteknoloji A.S. | Process for the preparation of hydrocolloid sponges |
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