CN1193062C - Biological material using electrostatic attraction layer-layer self-assembled modified polyester material as surface with cell compatibility - Google Patents
Biological material using electrostatic attraction layer-layer self-assembled modified polyester material as surface with cell compatibility Download PDFInfo
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- CN1193062C CN1193062C CN 02112499 CN02112499A CN1193062C CN 1193062 C CN1193062 C CN 1193062C CN 02112499 CN02112499 CN 02112499 CN 02112499 A CN02112499 A CN 02112499A CN 1193062 C CN1193062 C CN 1193062C
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Abstract
The present invention discloses a method of modifying a polymer material into a biological material with cell compatibility on the surface by electrostatic attraction layer-layer self-assembly. In the method, dualistic amine ammonolyzes the surface of a polyester polymer to obtain a polymer with free amido on the surface first; then the polymer is acidified by acid to make the surface of the polymer have positive electricity; different single layer or multiple-layer polyanions and polycations with bioactivity are alternately assembled on the surface of the polymer by an electrostatic attraction layer-layer self-assembly method; the polyelectrolyte with bioactivity can still retain the original bioactivity thereof after layer-layer self-assembly, and a planar film with cell compatibility on the surface, a three-dimensional multiporous support material and a product of the three-dimensional multiporous support material are obtained. The method of the present invention has the advantages of simple operation technology and high repetitiveness; the method of the present invention has a favorable application prospect for various biologic medical device in a complicated three-dimensional structure and the surface modification of support materials in multiporous tissue engineering.
Description
Technical field
The present invention relates to modified polyester material and have the method for cell compatible biological material for the surface.
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 developed into 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 electrostatic attraction layer-layer self-assembled modified polyester material.
Method of the present invention may further comprise the steps:
1) the dissolving polyamine prepares the polyamine solution that concentration is 0.001～1g/ml in organic solvent;
2) the polyester polymer material is immersed in the polyamine solution, under 0～100 ℃ of temperature, reacted 0.1～10 hour;
3) the polyester polymer material is taken out polyamine 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 acid solution of 0.0024～0.12mol/L, at room temperature carries out acidification reaction 1～60 minute, and reaction finishes, and takes out and water is rinsed well;
6) polyester polymer with step 5) gained surface positively charged at first immerses in the bioactive poly anionic water solution that concentration is 0.001～1000mg/ml, absorption one deck negatively charged ion, and negative charge is with on the surface; With immersing again behind the tri-distilled water flush away free negatively charged ion in the bioactive poly cationic acid solution that concentration is 0.001～1000mg/ml, wash with acid earlier behind absorption one deck positively charged ion, use tri-distilled water flush away free positively charged ion again, at this moment positive charge has been with on the surface again, repeat above-mentioned steps, biological activity zwitterion alternate group is contained on the polyester polymer material.
7) after reaction finishes, take out and rinse well with acid or water, vacuum-drying is to constant weight under the room temperature.
Among the present invention, polyamine can be small molecules polyamine and polycaprolactam polyamine, the small molecules polyamine comprises a kind of or its mixture of quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, two n-octyl amine, two positive nonyl amines, two n-Decylamines, and polycaprolactam polyamine comprises a kind of or its mixture in polyvinyl imines, the PAH.
Among the present invention, the organic solvent that is used for dissolving polyamine 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, the biological activity polyanion is optional with a kind of or its mixture in Sodium styrene sulfonate (PSS), T 500 (DS), chondroitin sulfate (CSAS), sodium alginate (NaAlg), sodium polyacrylate (PAA), polymethyl acrylic acid, heparin, the heparin sulfate; Polycation can be selected a kind of or its mixture in collagen (Collagen), chitosan (Chitosan), poly-lysine, polyvinyl inferior amine salt hydrochlorate (PEI), the PAH hydrochloride (PAH) for use.The also optional usefulness of above-mentioned polyanion or polycation has various albumen, somatomedin and the differentiation inducing factor of both sexes charge property, these albumen, somatomedin and differentiation inducing factor can obtain different charged character by regulating the pH value: positively charged under the iso-electric point, and electronegative on the iso-electric point.
In the inventive method step 6), the preferred 0.1～50mg/ml of concentration of bioactive poly anionic water solution and bioactive poly cationic acid solution.
The present invention adopts polyamine aminolysis polyester polymer surface at first to obtain the polymkeric substance of surface band free amino, make the polymer surfaces positively charged with acidifying again, then it is alternately immersed in the solution of polyanion and polycation, utilize the method for electrostatic attraction layer-layer self-assembly by the electrostatic attraction effect of polyanion and polycation, alternately assemble the different polyanions and the polycation of single or multiple lift biologically active on its surface, these biological activity polyelectrolyte still keep its original biological activity after layer assembly, 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 biological activity polyelectrolyte 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 electrostatic attraction self-assembly biological activity polyelectrolyte, the cell compatibility that more can further improve material has the biological activity of specific function with other.Technology of the present invention is simple, and the reaction conditions gentleness is easy to operate, and favorable reproducibility is applied widely, environmental friendliness.Be applicable to the finishing of 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 be on poly-(L-lactic acid) film of aminolysis after the self-assembly of PSS/ chitosan multilayer hydrodynamic(al) attitude contact angle (advancing angle) with the changing conditions of the assembling number of plies.The advancing angle of wherein unmodified poly-(L-lactic acid) is 85.3 degree.
Fig. 2 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 assembling one deck PSS poly-(L-lactic acid), d is poly-(L-lactic acid) film of assembling pair of lamina PSS/ chitosan (skin is a chitosan), e is poly-(the L-lactic acid) of assembling three double-deck PSS/ chitosans (skin is a chitosan), and f is poly-(L-lactic acid) film of assembling five double-deck PSS/ chitosans (skin is a chitosan).
After Fig. 3 is poly-(L-lactic acid) film surface-assembled individual layer PSS, 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 180 times.
After Fig. 4 is poly-(L-lactic acid) film surface-assembled three double shells glycan (outer is chitosan), the electromicroscopic photograph of people's umbilical cord endothelial cell growth after 4 days, wherein Fig. 4 a magnification is 472 times, can clearly see the situation of endotheliocyte adherent growth and intercellular contact; Fig. 4 b magnification is 180 times.
After Fig. 5 is different polyanions of PAUR film surface-assembled and collagen, the changing conditions of hydrodynamic(al) attitude contact angle.The advancing angle of blank PAUR film is 80 degree.
Fig. 6 is different polyanions of PAUR film surface-assembled and collagen (pair of lamina, outer the is collagen) adhesion rate that descendant's umbilical cord endotheliocyte was grown respectively 12 hours thereon, and a is a heparin among the figure, b is CSAS, and c is PAA, and d is DS, e is NaAlg, and f is PSS.
Fig. 7 is different polyanions of PAUR film surface-assembled and the proliferation rate of collagen (pair of lamina, outer is collagen) after descendant's umbilical cord endotheliocyte was grown respectively 4 days thereon, and a is a heparin among the figure, and b is CSAS, and c is PAA, and d is DS, and e is NaAlg, and f is PSS.
Fig. 8 is adhesion rate and the proliferation rate of growth after 4 days that the different double-deck PSS/PEI of PAUR film surface-assembled (the outer PEI of being) descendant's umbilical cord endotheliocyte was grown respectively 12 hours thereon.
Embodiment
Following example further specifies the present invention.
Example 1
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, dried under the vacuum.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).
Poly-(L-lactic acid) film of above-mentioned surface band free amino was immersed in the hydrochloric acid that concentration is 0.012mol/L acidifying 15 minutes, take out and with after the tri-distilled water rinsing, immerse in 1.0mg/ml sodium polystyrene sulfonate (PSS) solution and soaked 20 minutes, totally and with nitrogen dry up with the tri-distilled water rinsing, immerse again in the 1.0mg/ml chitosan acetic acid solution and soaked 15 minutes, with the flushing of 1% acetic acid solution, totally and with nitrogen dry up with the tri-distilled water rinsing more earlier.Repeat poly-(L-lactic acid) modified membrane that above-mentioned steps can prepare the multilayer assembling.Poly-(L-lactic acid) film is after the self-assembly of PSS/ chitosan layer upon layer electrostatic, and wetting ability obviously improves, and is alternately variation clocklike, the results are shown in Figure 1.This has also proved the generation of layer upon layer electrostatic self assembling process simultaneously.
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 (12 hours) and the proliferation rate of cultivation after 4 days.Poly-(L-lactic acid) film obviously improves the consistency of endotheliocyte after layer upon layer electrostatic is self-assembled modified, the results are shown in Figure 2,3,4.
Example 2
PAUR is dissolved in N, in the dinethylformamide, makes polymer solution concentration reach 0.13g/mL, with this solution-cast casting film-forming in becoming film die.It is 1 of 0.06g/ml that the PAUR film is immersed concentration, and in 6-hexanediamine/n-propyl alcohol solution, 37 ℃ were reacted 5 minutes down, used the tri-distilled water soaking and washing, and vacuum-drying is to constant weight.Get the aminolysis PAUR of 2 cm long and 1 centimetre wide, in concentration is to soak in triketohydrindene hydrate/ethanol solution of 1.0mol/L to take out in 1 minute, 80 ℃ of heating down, the film surface presents tangible bluish voilet, shows to have amido (NH freely on this film surface
2).The PAUR film of above-mentioned surface band free amino was immersed in the hydrochloric acid that concentration is 0.012mol/l acidifying 15 minutes, take out and with after the tri-distilled water rinsing respectively at heparin (1.0mg/mL Heparin), chondroitin sulfate (1.0mg/mL CSAS), sodium polyacrylate (1.0mg/mL, PAA), sodium alginate (1.0mg/mL, NaAlg), T 500 (1.0mg/m second DS), sodium polystyrene sulfonate (1.0mg/mL, PSS) soaked 20 minutes in, totally and with nitrogen dry up, immersed concentration more respectively and be in the PEI acetic acid solution that 0.1% collagen acetic acid solution or concentration is 1.0mg/ml 20 minutes with the tri-distilled water rinsing., totally and with nitrogen dry up with the tri-distilled water rinsing more earlier, put into vacuum drying oven and dry with 1.0% acetate rinsing.Generation with fluorescent mark and hydrodynamic(al) attitude contact angle test (the results are shown in Figure 5) provable above-mentioned electrostatic attraction self assembling process.
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 PAUR film obviously improves the consistency of endotheliocyte after layer upon layer electrostatic is self-assembled modified, the results are shown in Figure 6,7,8.
Claims (8)
1. be the method that the surface has cell compatible biological material with electrostatic attraction layer-layer self-assembled modified polyester material, this method comprises the following steps:
1) the dissolving polyamine prepares the polyamine solution that concentration is 0.001～1g/mL in organic solvent;
2) the polyester polymer material is immersed in the polyamine solution, under 0～100 ℃ of temperature, reacted 0.1～10 hour;
3) the polyester polymer material is taken out polyamine 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 hydrochloric acid soln of 0.0024～0.12mol/L, at room temperature carries out acidification reaction 1～60 minute, and reaction finishes, and takes out and water is rinsed well;
6) polyester polymer with step 5) gained surface positively charged at first immerses in the bioactive poly anionic water solution that concentration is 1.0mg/ml, absorption one deck negatively charged ion, and negative charge is with on the surface; With immersing again behind the tri-distilled water flush away free negatively charged ion in the bioactive poly cationic acid solution that concentration is 1.0mg/ml, wash with acid earlier behind absorption one deck positively charged ion, use tri-distilled water flush away free positively charged ion again, at this moment positive charge has been with on the surface again, repeat above-mentioned steps, biological activity zwitterion alternate group is contained on the polyester polymer material;
7) after reaction finishes, take out and rinse well with acid or water, vacuum-drying is to constant weight under the room temperature.
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 polyamine is small molecules polyamine or polycaprolactam polyamine, the small molecules polyamine comprises a kind of or its mixture of quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, two n-octyl amine, two positive nonyl amines, two n-Decylamines, and polycaprolactam polyamine comprises a kind of or its mixture in polyvinyl imines, the PAH.
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 polyamine 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 or 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), the multipolymer of a kind of or these polymkeric substance in PAUR, polyethylene terephthalate, polyglycolic acid, poly-(D, the L-lactic acid-be total to-oxyacetic acid).
6. modified polyester material according to claim 1 is characterized in that said polyanion is: a kind of or its mixture in sodium polystyrene sulfonate, T 500, chondroitin sulfate, sodium alginate, sodium polyacrylate, polymethyl acrylic acid, heparin, the heparin sulfate for the surface has the method for cell compatible biological material.
7. modified polyester material according to claim 1 is characterized in that said polycation has: a kind of or its mixture in collagen, chitosan, poly-lysine, polyvinyl inferior amine salt hydrochlorate, the PAH hydrochloride for the surface has the method for cell compatible biological material.
8. modified polyester material according to claim 1 is characterized in that for the surface has the method for cell compatible biological material said polyanion and polycation are albumen, somatomedin and the differentiation inducing factor with both sexes charge property.
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