CN1389498A - Method of modifying polyester material into biological material with cell compatible surface - Google Patents
Method of modifying polyester material into biological material with cell compatible surface Download PDFInfo
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- CN1389498A CN1389498A CN 02112170 CN02112170A CN1389498A CN 1389498 A CN1389498 A CN 1389498A CN 02112170 CN02112170 CN 02112170 CN 02112170 A CN02112170 A CN 02112170A CN 1389498 A CN1389498 A CN 1389498A
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Abstract
The invention discloses a method of denaturing the polyester materials into the biomaterials whose surface has the cell compatibility. The method uses the dualistic amine ammonolyze the surface of the polyester polymer to at first get the polymer with free-amido on the surface, and then uses the compound with double functional groups, for a example, amy dialdehyde, as the coupling agent, in order to fix the biological active molecules on its surface, it is added that these fixed biological molecules still retain their original biological activity, which get the plane film whose surface possesses the cell compatibility, the three-dimentional multiaperture brace materials and its products. The method of the invention has advantages of simple operating technique, good repetitiveness.
Description
Technical field
The present invention relates to modified polyester material for the surface has the method for cell compatible biological material, be with diamine and bioactive molecules modified poly ester base polymer specifically, prepare the surperficial method of the polyester biomaterial of cell compatibility that has.
Background technology
Polymer biomaterial is because of having good physics and chemical property, and the application in organizational project more and more widely.But because the special applied environment of this class material---need directly to contact with the body fluid of human body, organ, tissue etc., therefore preparing polymer biomaterial that a kind of surface has good biocompatibility becomes in the organizational project development very one of approach of key.
The polyester biomaterial not only has good physical and mechanical properties, nontoxicity, easy processing forming, but also has the peculiar biodegradable of tissue engineering material, therefore more and more is subjected to people's attention.With lactic acid or oxyacetic acid is the polyester polymer of skeleton unit, and licensed polymkeric substance as biological tissue's cultivation has arrived the most widely and used owing to meet clinical service requirements.But do not pass through the polyester polymer of modification because itself hydrophobicity and surface inertness cause providing the growth of a close friend's interface with effective promotion tissue and organ; The local acidity that the degraded back forms also can cause peripheral organs and tissue to produce serious inflammatory reaction.Though have the multiple surface modification method that improves its surface property at present, all there is the operating procedure complexity, the modification of surfaces poor stability does not especially fit into problems such as the timbering material of porous build complexity and goods.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operately, is the method that the surface has cell compatible biological material with diamine and bioactive molecules modified polyester material.
Method of the present invention may further comprise the steps:
1) the dissolving diamine prepares the diamine solution that concentration is 0.001～1g/ml in organic solvent;
2) the polyester polymer material is immersed in the diamine solution, under 0～100 ℃ of temperature, reacted 0.1～10 hour;
3) the polyester polymer material is taken out diamine solution, clean with deionized water or soaked in absolute ethyl alcohol, vacuum-drying is to constant weight;
4) use the indicator triketohydrindene hydrate to detect the amido of polyester polymer material surface;
5) concentration being immersed with the polyester polymer material of free amino in the surface is in the coupling agent of 0.05～5% (weight percent), carries out linked reaction under 0～90 ℃, and reaction finishes, and takes out and water is rinsed well;
6) step 5) gained polyester polymer is immersed in the aqueous solution of bioactive molecules of promotion cell growth that concentration is 0.001～1000mg/ml and react certain hour, so that bioactive molecules is fixed on the polyester polymer material.
Among the present invention, diamine can adopt aliphatic diamine, a kind of or its mixture in quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, two n-octyl amine, two positive nonyl amines, two n-Decylamines.
Among the present invention, the organic solvent that is used for dissolving diamine includes, but are not limited to a kind of or its mixture of ethanol, thanomin, n-propyl alcohol, Virahol, glycol dimethyl ether, dimethyl sulfoxide (DMSO).
Described polymer materials, normally polyester polymer film and porous support.Polyester polymer is preferred: polycaprolactone, poly-(L-lactic acid), poly-(D-lactic acid), unformed poly-(D, L-lactic acid) (PDLLA), the multipolymer of a kind of and these polymkeric substance in PAUR, polyethylene terephthalate, polyglycolic acid, poly-(D, the L-lactic acid-be total to-oxyacetic acid).
The molecular weight of employed polyester polymer can consider, is 10000～1000000 polyester polymer but preferably use molecular weight ranges.
Porous support is meant the support that the inside hole by methods such as pore-creating agent method, phase separation method, weave, the freeze-dried method of emulsion, track etching method, speed forming method or nonwoven method preparations is interconnected.
Among the present invention, coupling agent is meant the compound that contains two functional groups that can react in the molecular structure, usually, adopts the compound that contains two aldehyde radicals, isocyanic ester, lsothiocyanates or epoxide groups in the molecular structure.The amido reaction of one of them functional group and surface of polymer material, another functional group and bioactive molecules reaction, thus latter's covalence key is incorporated into surface of polymer material.Coupling agent is preferred: glutaraldehyde, hexamethylene diisocyanate, tolylene diisocyanate, 4, polyoxyethylene glycol di-epoxide, dihydroxyphenyl propane and the bisphenol-s epoxy resin of 4 '-'-diphenylmethane diisocyanate, Xylene Diisocyanate (XDI), isophorone diisocyanate, ethylene glycol and the various polymerization degree.The temperature of linked reaction is preferably in 4～50 ℃.
Among the present invention, bioactive molecules selects for use collagen, gelatin, chitosan, RGD, polypeptide, fiber adhesion albumen, poly to rely the cell growth factor that contains amido in amino acid, amino acid and other molecular structure.
Preferred 0.1～the 50mg/ml of the concentration of the bioactive molecules aqueous solution.
Among the present invention, show the existence that bluish voilet can qualitative proof free amino with the indicator triketohydrindene hydrate.But make the amido concentration of typical curve quantitative test material surface with the absorbancy of the amine of concentration known and triketohydrindene hydrate substance that show color.By adjusting reaction time, temperature of reaction and reaction solution concentration, can control material the degree of surface aminolysis reaction or the density of material surface free amino.
The inventive method operating procedure is simple, good reproducibility, at first obtain the polymkeric substance of surface band free amino with diamine aminolysis polyester polymer surface, make coupling agent with compound such as glutaraldehyde again with bifunctional, immobilizing biologically active molecule in its surface, and still keep its original biological activity after these biomolecules are fixed, obtain the surface and have the planar film of cell compatibility and three-dimensional porous timbering material and goods thereof.These free aminos not only effectively provide further and bioactive molecules reactive activity site, and the local acidity that produces in biodegradation process with polymkeric substance in the amido energy appropriateness after its degraded, be expected to alleviate the organ and tissue inflammation on every side that cause because of local acidity.Behind the immobilizing biologically active molecule, more can obviously improve the wetting ability of polymkeric substance, make the material can be affine with water base matrix phase well; Provide simultaneously one with cell paste in extracellular matrix environment like the growth phase, more can further will promote the factor of cell growth and differentiation to be incorporated into material surface, to obtain to have the biomaterial of height cell compatibility.
Reaction conditions gentleness of the present invention, required instrument and equipment is few, and can pass through adjusting reaction time, temperature of reaction or reaction solution concentration, the degree of control material surface aminolysis reaction or the density of material surface free amino, and then the content of adjusting material surface institute fixed bioactive molecules.These characteristics have determined this method applicable to the finishing to material surface, porous support materials and macroscopical goods thereof of multiple complex shape.In the finishing of multiple biomedical devices with complex shape structure and multi-porous tissue engineering supporting material, have a good application prospect.
Description of drawings
Fig. 1 is adhesion rate (■) and the proliferation rate () after people's umbilical cord endotheliocyte was grown respectively 12 hours and 4 days thereon before and after the polycaprolactone membrane surface modification, wherein a is tissue culturing polystyrene (TCPS), b is unmodified polycaprolactone film, c is that polycaprolactone film and hexanediamine reacted 3 minutes, d is that polycaprolactone film and hexanediamine reacted 10 minutes, e is that polycaprolactone film and hexanediamine reacted 30 minutes, f is that polycaprolactone film and hexanediamine reacted 2 hours, g is a fixedly gelatin of polycaprolactone surface, h is a polycaprolactone surface set casing glycan, and I is a fixedly collagen of polycaprolactone surface.
After Fig. 2 is the surperficial fixedly gelatin of polycaprolactone film, the electromicroscopic photograph of people's umbilical cord endothelial cell growth after 4 days, wherein Fig. 2 a magnification is 1800 times, can clearly see the pattern of endotheliocyte adherent growth; Fig. 2 b magnification is 160 times.
After Fig. 3 is polycaprolactone film surface set casing glycan, the electromicroscopic photograph of people's umbilical cord endothelial cell growth after 4 days, wherein Fig. 3 a magnification is 1000 times, can clearly see the pattern of endotheliocyte adherent growth; Fig. 3 b magnification is 260 times.
After Fig. 4 is the surperficial fixedly collagen of polycaprolactone film, the electromicroscopic photograph of people's umbilical cord endothelial cell growth after 4 days, wherein Fig. 4 a magnification is 1200 times, can clearly see the pattern of endotheliocyte adherent growth; Fig. 4 b magnification is 260 times.
Fig. 5 is adhesion rate, activity and the proliferation rate after people's umbilical cord endotheliocyte was grown respectively 12 hours and 4 days thereon before and after poly-(L-lactic acid) membrane surface modification, wherein a is tissue culturing polystyrene (TCPS), b is unmodified poly-(L-lactic acid) film, c is poly-(L-lactic acid) film of aminolysis, d is the surperficial fixedly gelatin of poly-(L-lactic acid) film, e is poly-(L-lactic acid) film surface set casing glycan, and f is for gathering fixedly collagen of (L-lactic acid) film surface.
After Fig. 6 is the surperficial fixedly gelatin of poly-(L-lactic acid) film, the electromicroscopic photograph of people's umbilical cord endothelial cell growth after 4 days, wherein Fig. 6 a magnification is 1000 times, can clearly see the pattern of endotheliocyte adherent growth; Fig. 2 b magnification is 120 times.
After Fig. 7 is poly-(L-lactic acid) film surface set casing glycan, the electromicroscopic photograph of people's umbilical cord endothelial cell growth after 4 days, wherein Fig. 7 a magnification is 1000 times, can clearly see the pattern of endotheliocyte adherent growth; Fig. 2 b magnification is 200 times.
After Fig. 8 is the surperficial fixedly collagen of poly-(L-lactic acid) film, the electromicroscopic photograph of people's umbilical cord endothelial cell growth after 4 days, wherein Fig. 8 a magnification is 1000 times, can clearly see the pattern of endotheliocyte adherent growth; Fig. 8 b magnification is 160 times.
Embodiment
Following example further specifies the present invention.
Example 1
Polycaprolactone is dissolved in 1, in the 4-dioxane (the polycaprolactone weight percent content is 10%), and waters and cast from casting film-forming in the film forming mould.Dissolve 1 in Virahol, it is 1 of 0.1g/ml that the 6-hexanediamine makes concentration, and 6-hexanediamine/aqueous isopropanol immerses the polycaprolactone film in the above-mentioned solution, and 37 ℃ were reacted 30 minutes down, used the deionized water soaking and washing, and vacuum-drying is to constant weight.Getting the small pieces film is in the ninhydrin solution of 1.0mol/L in concentration, shows bluish voilet detection film surface and has free amido (NH
2).
It is that room temperature reaction 3～5 hours takes out and water is rinsed well in 1% the glutaraldehyde water solution that the polycaprolactone film of above-mentioned surface band free amino is immersed in weight concentration.Above-mentioned polycaprolactone film is immersed respectively in the phosphoric acid buffer of gelatin, chitosan or collagen that concentration is 3mg/mL, after reacting 24 hours under 2～10 ℃, the cleaning that is soaked in water, vacuum-drying is to constant weight.The polycaprolactone film is after aminolysis and biomacromolecule are fixing, and wetting ability obviously improves, and the results are shown in Table 1.
The water contact angle of polycaprolactone changes before and after table 1 modification
| Sample | Water contact angle/degree |
| Unmodified polycaprolactone | ????81.2±2.4 |
| Polycaprolactone behind the aminolysis | ????68.4±1.4 |
| Chitosan is polycaprolactone fixedly | ????67.0±0.8 |
| Gelatin is polycaprolactone fixedly | ????59.5±2.0 |
| Collagen is polycaprolactone fixedly | ????65.2±1.9 |
With the type i collagen enzyme digestion of human umbilical cord's venous endothelial cell is separated, and plant in bottom tiling and have in 96 hole tissue culture polystyrene (TCPS) culture plates of polymeric film, nutrient solution is PRMI1640 and calf serum, 200 μ l are inoculated in every hole, culture plate is placed 37 ℃, 5%CO
2In the incubator, change liquid every other day, measure cell adhesion rate (12h) and the proliferation rate of cultivation after 4 days.The polycaprolactone film obviously improves the consistency of endotheliocyte after aminolysis and biomacromolecule are fixing, the results are shown in Figure 1,2,3,4.
Example 2:
To gather (L-lactic acid) and be dissolved in 1, and in the 4-dioxane (the poly(lactic acid) weight percent content is 3%), and water and cast from casting film-forming in the film forming mould.To gather (L-lactic acid) film immersion concentration is 1 of 0.06g/mL, and in 6-hexanediamine/n-propyl alcohol solution, 50 ℃ were reacted 8 minutes down, used the deionized water soaking and washing, and vacuum-drying is to constant weight.Getting the small pieces film is in the ninhydrin solution of 1.0mol/L in concentration, shows bluish voilet detection film surface and has free amido (NH
2).
It is that room temperature reaction 1～3 hour takes out and water is rinsed well in 1% the glutaraldehyde water solution that poly-(L-lactic acid) film of above-mentioned surface band free amino is immersed in weight concentration.Above-mentioned poly-(L-lactic acid) film is immersed respectively in the phosphoric acid buffer of gelatin, chitosan or collagen that concentration is 3mg/ml, after reacting 24 hours under 2～10 ℃, the cleaning that is soaked in water, vacuum-drying is to constant weight.Poly-(L-lactic acid) film is after aminolysis and biomacromolecule are fixing, and wetting ability obviously improves, and the results are shown in Table 2.
The water contact angle of poly-(L-lactic acid) changes before and after table 2 modification
| Sample | Water contact angle/degree |
| Unmodified poly-(L-lactic acid) | ????88.3±2.1 |
| Behind the aminolysis poly-(L-lactic acid) | ????81.2±0.6 |
| Chitosan fixing poly-(L-lactic acid) | ????57.7±1.2 |
| Gelatin fixing poly-(L-lactic acid) | ????66.0±0.4 |
| Collagen fixing poly-(L-lactic acid) | ????72.8±1.4 |
With the type i collagen enzyme digestion of human umbilical cord's venous endothelial cell is separated, and plant in bottom tiling and have in 96 hole tissue culture polystyrene (TCPS) culture plates of polymeric film, nutrient solution is PRMI1640 and calf serum, 200 μ l are inoculated in every hole, culture plate is placed 37 ℃, 5%CO
2In the incubator, change liquid every other day, measure cell adhesion rate (12h) and the proliferation rate of cultivation after 4 days.Poly-(L-lactic acid) film obviously improves the consistency of endotheliocyte after aminolysis and biomacromolecule are fixing, the results are shown in Figure 5,6,7,8.
Example 3:
Poly(lactic acid) is dissolved in 1, in the 4-dioxane (the poly(lactic acid) weight percent content is 3%), adopts thermally induced phase separation to prepare the polylactic acid porous scaffold that mean pore size is about 80 microns.The clip suitably polylactic acid porous scaffold immersion concentration of size is 1 of 0.02g/mL, and in 6-hexanediamine/n-propyl alcohol solution, 50 ℃ were reacted 5 minutes down, used the dehydrated alcohol termination reaction, and used the deionized water soaking and washing, and vacuum-drying is to constant weight.Is to soak in triketohydrindene hydrate/ethanol solution of 1.0mol/L to take out in 5 minutes with the polydactyl acid porous support in concentration, 80 ℃ of heating down, polylactic acid porous scaffold surface and the inside all present tangible bluish voilet, show to have free amido (NH on the polydactyl acid porous support
2).It is that room temperature reaction 5 hours takes out and water is rinsed well in 1% the glutaraldehyde water solution that poly-(L-lactic acid) porous support of above-mentioned surface band free amino is immersed in weight concentration.Above-mentioned polymkeric substance is immersed respectively in the phosphoric acid buffer of gelatin, chitosan and collagen that concentration is 2mg/ml, use the dehydrated alcohol termination reaction, and use the deionized water soaking and washing after 12 hours in reaction under 2～4 ℃, vacuum-drying is to constant weight.Poly-(L-lactic acid) porous support after aminolysis and biomacromolecule are fixing, wetting ability and fibroblastic consistency is obviously improved.
Claims (10)
1. modified polyester material has the method for cell compatible biological material for the surface, and this method comprises the following steps:
1) the dissolving diamine prepares the diamine solution that concentration is 0.001～1g/ml in organic solvent;
2) the polyester polymer material is immersed in the diamine solution, under 0～100 ℃ of temperature, reacted 0.1～10 hour;
3) the polyester polymer material is taken out diamine solution, clean with deionized water or soaked in absolute ethyl alcohol, vacuum-drying is to constant weight;
4) use the indicator triketohydrindene hydrate to detect the amido of polyester polymer material surface;
5) concentration being immersed with the polymer materials of free amino in the surface is in the coupling agent of 0.05～5% (weight percent), carries out linked reaction under 0～90 ℃, and reaction finishes, and takes out and water is rinsed well;
6) step 5) gained polyester polymer is immersed in the aqueous solution of bioactive molecules of promotion cell growth that concentration is 0.001～1000mg/ml and react certain hour, so that bioactive molecules is fixed on the polyester polymer material.
2. modified polyester material according to claim 1 has the method for cell compatible biological material for the surface, it is characterized in that said diamine is an aliphatic diamine, a kind of or its mixture in quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, two n-octyl amine, two positive nonyl amines, two n-Decylamines.
3. modified polyester material according to claim 1 is for the surface has the method for cell compatible biological material, and the organic solvent that it is characterized in that being used for dissolving diamine is a kind of or its mixture of ethanol, thanomin, n-propyl alcohol, Virahol, glycol dimethyl ether, dimethyl sulfoxide (DMSO).
4. modified polyester material according to claim 1 is characterized in that for the surface has the method for cell compatible biological material said polyester polymer material is polyester polymer film and porous support.
5. has the method for cell compatible biological material according to claim 1 or 4 described modified polyester materials for the surface, it is characterized in that said polyester polymer is polycaprolactone, poly-(L-lactic acid), poly-(D-lactic acid), unformed poly-(D, L-lactic acid) (PDLLA), the multipolymer of any and these polymkeric substance in PAUR, polyethylene terephthalate, polyglycolic acid, poly-(D, the L-lactic acid-altogether-oxyacetic acid).
6. modified polyester material according to claim 1 is characterized in that for the surface has the method for cell compatible biological material said coupling agent is meant the compound that contains two aldehyde radicals, isocyanic ester, lsothiocyanates or epoxide groups in the molecular structure.
7. modified polyester material according to claim 1 has the method for cell compatible biological material for the surface, it is characterized in that said coupling agent is glutaraldehyde, hexamethylene diisocyanate, tolylene diisocyanate, 4, polyoxyethylene glycol di-epoxide, dihydroxyphenyl propane and the bisphenol-s epoxy resin of 4 '-'-diphenylmethane diisocyanate, Xylene Diisocyanate (XDI), isophorone diisocyanate, ethylene glycol and the various polymerization degree.
8. modified polyester material according to claim 1 is characterized in that for the surface has the method for cell compatible biological material said bioactive molecules is the cell growth factor that contains amido in collagen, gelatin, chitosan, RGD, polypeptide, fiber adhesion albumen, poly bad amino acid, amino acid and other molecular structure.
9. have the method for cell compatible biological material according to claims 1 described modified polyester material for the surface, the temperature that it is characterized in that said linked reaction is 4 ℃～50 ℃.
10. modified polyester material according to claim 1 has the method for cell compatible biological material for the surface, and the concentration that it is characterized in that the said bioactive molecules aqueous solution is 0.1～50mg/ml.
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| CNB021121702A CN1331923C (en) | 2002-06-19 | 2002-06-19 | Method of modifying polyester material into biological material with cell compatible surface |
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|---|---|---|---|
| CNB021121702A CN1331923C (en) | 2002-06-19 | 2002-06-19 | Method of modifying polyester material into biological material with cell compatible surface |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101956318A (en) * | 2010-09-26 | 2011-01-26 | 中国人民解放军第四军医大学 | Method of chemically grafting and stabilizing biological coating macromolecules on polyester fibre surface |
| CN103408720A (en) * | 2013-08-14 | 2013-11-27 | 合肥市科天化工有限公司 | Method for chain re-extension of waterborne polyurethane |
| WO2015127897A1 (en) * | 2014-02-27 | 2015-09-03 | 国玺干细胞应用技术股份有限公司 | Method for preparing hollow microparticle |
| CN105254913A (en) * | 2015-11-11 | 2016-01-20 | 暨南大学 | Polyester material with antibacterial and biocompatible surface and preparing method and application thereof |
| CN106913904A (en) * | 2017-03-06 | 2017-07-04 | 苏州大学附属第医院 | A kind of micrometer-nanometer tissue engineering support with immunization therapy function and preparation method thereof |
| CN106963984A (en) * | 2017-03-02 | 2017-07-21 | 复旦大学 | A kind of preparation method of gelatin/carboxy apatite composite coating |
| CN114177363A (en) * | 2021-12-14 | 2022-03-15 | 无锡中科光远生物材料有限公司 | Anti-adhesion fiber membrane for promoting endothelialization and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5280084A (en) * | 1988-04-12 | 1994-01-18 | Pp Polymer Ab | Process for improving the hydrophilic properties on polymer surfaces |
| RU2163246C2 (en) * | 1995-06-30 | 2001-02-20 | Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн | Method of modifying at least part of polymer surface |
| US6379741B1 (en) * | 1998-11-30 | 2002-04-30 | The Regents Of The University Of California | Plasma-assisted surface modification of polymers for medical device applications |
| CN1302824A (en) * | 2001-01-08 | 2001-07-11 | 天津大学 | Process for modifying biologic hydroxylester material with amniotic fluid |
| CN1161159C (en) * | 2001-06-22 | 2004-08-11 | 清华大学 | Biological material and tissue engineering material |
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- 2002-06-19 CN CNB021121702A patent/CN1331923C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101956318A (en) * | 2010-09-26 | 2011-01-26 | 中国人民解放军第四军医大学 | Method of chemically grafting and stabilizing biological coating macromolecules on polyester fibre surface |
| CN101956318B (en) * | 2010-09-26 | 2012-07-25 | 中国人民解放军第四军医大学 | Method of chemically grafting and stabilizing biological coating macromolecules on polyester fibre surface |
| CN103408720A (en) * | 2013-08-14 | 2013-11-27 | 合肥市科天化工有限公司 | Method for chain re-extension of waterborne polyurethane |
| WO2015127897A1 (en) * | 2014-02-27 | 2015-09-03 | 国玺干细胞应用技术股份有限公司 | Method for preparing hollow microparticle |
| TWI671402B (en) * | 2014-02-27 | 2019-09-11 | 國璽幹細胞應用技術股份有限公司 | Novel hollow microparticles |
| CN105254913A (en) * | 2015-11-11 | 2016-01-20 | 暨南大学 | Polyester material with antibacterial and biocompatible surface and preparing method and application thereof |
| CN105254913B (en) * | 2015-11-11 | 2018-05-08 | 暨南大学 | A kind of surface has polyester material and the preparation and application of antibiotic property and biocompatibility concurrently |
| CN106963984A (en) * | 2017-03-02 | 2017-07-21 | 复旦大学 | A kind of preparation method of gelatin/carboxy apatite composite coating |
| CN106913904A (en) * | 2017-03-06 | 2017-07-04 | 苏州大学附属第医院 | A kind of micrometer-nanometer tissue engineering support with immunization therapy function and preparation method thereof |
| CN106913904B (en) * | 2017-03-06 | 2020-08-14 | 苏州大学附属第一医院 | Micro-nano tissue engineering scaffold with immunotherapy function and preparation method thereof |
| CN114177363A (en) * | 2021-12-14 | 2022-03-15 | 无锡中科光远生物材料有限公司 | Anti-adhesion fiber membrane for promoting endothelialization and preparation method thereof |
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