CN1475533A - Insoluble silk fibroin film and preparation of silk fibroin pipe - Google Patents
Insoluble silk fibroin film and preparation of silk fibroin pipe Download PDFInfo
- Publication number
- CN1475533A CN1475533A CNA031311423A CN03131142A CN1475533A CN 1475533 A CN1475533 A CN 1475533A CN A031311423 A CNA031311423 A CN A031311423A CN 03131142 A CN03131142 A CN 03131142A CN 1475533 A CN1475533 A CN 1475533A
- Authority
- CN
- China
- Prior art keywords
- silk fibroin
- solution
- water
- fibroin
- high density
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 108010022355 Fibroins Proteins 0.000 title claims description 97
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000000243 solution Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000004793 Polystyrene Substances 0.000 claims abstract description 7
- 229920002223 polystyrene Polymers 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000013019 agitation Methods 0.000 claims description 9
- 239000005357 flat glass Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000007664 blowing Methods 0.000 abstract description 5
- 238000000502 dialysis Methods 0.000 abstract description 5
- 238000005266 casting Methods 0.000 abstract description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 3
- 239000001110 calcium chloride Substances 0.000 abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000007480 spreading Effects 0.000 abstract description 2
- 238000003892 spreading Methods 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract 3
- 108090000623 proteins and genes Proteins 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000012620 biological material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 241000255789 Bombyx mori Species 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012460 protein solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 108010013296 Sericins Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A process for preparing the insoluble silk protein film (or tube) includes dissolving silk protein in the solution of calcium chloride/water/alcohol dialysis to obtain the aqueous solution of silk protein, slight stirring at 90 deg.C for concentrating it, and spreading it on polystyrene plate at 20-200 deg.C to become film or extruding out, blowing or casting to become tube. Its advantage is excellent wet-state mechanical performance.
Description
Technical field
The present invention for preparation have good biocompatibility and can be in water the novel method of the fibroin material of stable existence, relate to biomaterial.
Background technology
Silk fibroin has excellent biocompatibility and favorable mechanical and physicals as natural biological albumen, is subjected to increasing concern of biomaterial circle and research in recent years.Its excellent performance makes silk fibroin material can be widely used in biomaterials such as prosthetic ligament, artificial bone, artificial blood vessel, and can be used as the excellent drug slow-release material, the enzyme solidify material.In organizational project, promoting growth of cell that it is excellent and low inflammatory reaction also make it be with a wide range of applications.Because silk fibroin exists with the thread attitude of one dimension at nature, but in actual applications, then needs to be prepared into two-dimensional film or three-dimensional tubing form, so need dissolve regeneration meets service requirements with preparation material to fibroin.
Silk fibroin becomes water-soluble material, after the pure silk fibroin is prepared into film or other form after separating except that peptization, be fragility, its mechanical property is poor, is dissolved in the water owing to it simultaneously, in organism, may cause loss, therefore be difficult to use as the material of not degrading.In order to utilize its excellent biological compatibility, people improve its mechanical property in research always, and the method for mainly improving mechanical property now is to add other macromolecular material in silk fibroin, induces the variation of silk fibroin structure, improve its mechanical property, comprise its water miscible improvement.But because after having added some other polymer, its biocompatibility aspect then is difficult to be guaranteed.Another method of improving mechanical property is that it is remained on hygrometric state, as is immersed in the organic solvents such as methyl alcohol, and then its solvability and mechanical property can be improved, and it is the problem to the harm of human body such as methyl alcohol that such method is brought an organic solvents in particular again.Up to the present, the insoluble fibroin material with excellent mechanical performances that does not add the pure silk fibroin preparation that the methyl alcohol class organic solvent of hazardous property soaks is not more seen any report about preparation silk fibroin tubing without any report.
The present invention adopts simple method for addressing the above problem, and does not add the polymer that adds of any other type, just can obtain mechanical property excellence, water-fast fibroin material, and soak without the methyl alcohol equal solvent.Also can prepare pure silk fibroin tubular material in this way.
Silk fibroin commonly used generally exists with two kinds of crystalline states, and wherein alpha-helix is soluble in water, and beta sheet is water-fast crystal form.Silk fibroin exists with beta sheet under the state of nature, and water insoluble or solvent that other is general can be dissolved in CaCl
2In/water/ethanol (mol ratio 1: 8: 2) ternary solution or other dense saline solution, but can destroy the original beta sheet structure of silk fibroin after the fibroin dissolving, and behind drying and forming-film, mainly exist with alpha-helix, thereby in soluble in water, this has limited the use of this material in biological field greatly.Preparation and different factor for the silk fibroin regeneration membrane obtain bigger progress in recent years for the influence of material crystalline, promote that wherein silk fibroin mainly is to handle by methyl alcohol to make the silk fibroin crystal conversion from alpha-helix prepares method from water-fast film to the beta sheet crystal conversion.Though the method that this methyl alcohol is handled is more effective, simple, methyl alcohol, will use the biology of material and produce great negative impact if remaining as the bigger chemical reagent of toxicity.
Directly material such as the tubular material that obtains water-fast film and other form from the water-soluble fluid drying of fibroin is more satisfactory preparation method, the preparation condition gentleness, quality is even, easily-controlled reaction conditions, good reproducibility is fit to industrial mass production and does not have the negative impact of other chemical reagent.Can promote more than 40 ℃ that silk fibroin solution changes to beta crystal though there are some researches show temperature in drying process, never document and research report can directly obtain water-fast fibroin film from the aqueous solution.
Summary of the invention
The objective of the invention is for the shortcoming that overcomes above-mentioned silk fibroin invent a kind of preparation have good biocompatibility and can be in water the novel method of the fibroin material of stable existence.By being lower than the concentrated silk fibroin solution of 90 ℃ of following gentle agitation, obtain the transparent high density silk fibroin water solution of 100～500mg/ml, and it is dry under 20～200 ℃ of temperature, the transparent silk fibroin water solution of high density is poured on polystyrene board or the sheet glass, and 20～200 ℃ of following volatile dries become water-fast fibroin film in loft drier.
The transparent fibroin aqueous solution of high density is cast on the polyrod or Glass tubing of different diameter, under 20～200 ℃, control rate of drying in loft drier, slowly volatile dry becomes silk fibroin tubular material.
The transparent fibroin aqueous solution of high density is dried to half curdled appearance at 20～200 ℃ extrudes or be blow molded into tubulose, make the water-fast silk fibroin tubing of different diameter with very good mechanical properties through machinery.
Utilize silk fibroin to obtain water-fast fibroin film or under further spissated condition at the spontaneous crystal conversion under certain temperature and the high density, directly by extruding, blowing, the method for casting is made tubular structure.The reaction conditions gentleness, film forming is even, is easy to control, does not destroy the primary structure of silk fibroin, and this method is beneficial to the mass preparation of film and tubing, and can keep silk fibroin favorable mechanical and biological property.
Specific implementation of the present invention is: with silk at 0.5% Na
2CO
3100 ℃ are boiled 60min in the solution, repeatedly wash after drying with the sericin of removing the silk outside and the silk fibroin that will boil with distilled water, obtain pure silk fibroin.A certain amount of silk fibroin is dissolved in CaCl
2In/water/ethanol (mol ratio 1: 8: 2) ternary solution or other dense saline solution, and, remove calcium chloride and ethanol in the solution, thereby obtain purified silk fibroin water solution with dialysis band dialysis three days.This solution under the situation of magnetic force heating stirrer gentle agitation, is concentrated this solution in being lower than 90 ℃ scope, and obtaining concentration is the transparent fibroin strong solution of 100～500mg/ml, and stirring purpose is to prevent that silk fibroin solution from solidifying in concentration process.The transparent fibroin aqueous solution of this high density is poured on polystyrene or the sheet glass, is constant pressure and dry in 20～200 ℃ the loft drier in temperature, and the control rate of drying makes transparent water-fast silk fibroin film.After solution can also being spread on polystyrene or the sheet glass, by its part is covered, the evaporation rate of control solution is prepared transparent silk fibroin film.
This clear solution through casting, extrude and blowing can obtain the water-fast silk fibroin tubing of mechanical property excellence.
The present invention directly makes water-fast silk fibroin film or silk fibroin pipe by aqueous solution evaporable method first, and the preparation of silk fibroin film or tubing is simplified greatly.
The present invention is water-fast film of preparation or tubing from silk fibroin water solution directly, mild condition, and gordian technique is: solidify the concentration after 2. concentrating, 3. thickening temperature, 4. drying temperature, 5. drying rate when gentle agitation prevents to concentrate 1..
For the preparation of insoluble silk fibroin film, silk fibroin mainly is a beta sheet and water insoluble from silk, and silk fibroin was that the fibroin aqueous solution of high density is considered before silkworms spin silk, before the solution drying, concentrated earlier.For preventing that in concentration process silk fibroin tangles mutually and solidifies, and carries out slight stirring with agitator.Can obtain the transparent silk fibroin protein solution of high density like this.For choosing of thickening temperature, actual temperature when considering in silkworm body solution concentration and part document point out more than 40 ℃ in silk fibroin protein solution alpha-helix can change to beta sheet, thickening temperature be set in be lower than 90 ℃.Consider the concentration of silk fibroin protein solution before silkworms spin silk, generally silk fibroin solution is concentrated into more than the 100mg/ml, under suitable temperature, carry out drying and forming-film then or with extruding, the method for blowing or casting is prepared into tubing.In the solution drying process, can prolong time of drying, thereby further improve film forming properties by the control evaporation rate.
Fibroin film of preparing or tubing infrared spectra, infrared surperficial total reflection, X-ray diffraction, and 24 hours turnover rate of silk fibroin film is measured the structure of film and the solvability in water in water.The result shows, greater than 100mg/ml, can obtain almost completely water-fast film during 20～200 ℃ of drying temperatures in concentration, and structured testing shows that main crystal form is a beta sheet.The mechanical property of materials is measured its ultimate tensile strength of discovery be not less than 10MP, the maximum tension rate is not less than 30%, and mechanical property is good.
Advantage of the present invention has: solution concentration and drying are all at normal pressure with below 200 ℃, and reaction conditions is extremely gentle, do not destroy the primary structure of silk fibroin, and preparation condition is extremely simple, be easy to control, good reproducibility obtains uniform film of quality or tubing easily.Do not need after the moulding to handle, the deleterious solvent of biology is not existed through further chemical reagent, safe.Required equipment is simple, can produce on a large scale.Therefore, the further widespread use in technical field of biological material is significant and actual use value for silk fibroin in the present invention.
Embodiment
Embodiment 1:
With silk at 0.5% Na
2CO
3100 ℃ are boiled 60min in the solution, carefully wash after drying with the sericin of removing the silk outside and the silk fibroin that will boil with distilled water, obtain pure silk fibroin.The silk fibroin of 1 gram is dissolved in 10 milliliters of CaCl
2In/water/ethanol (mol ratio 1: 8: the 2) ternary solution, and, remove calcium chloride and ethanol in the solution, thereby obtain purified silk fibroin water solution the dialysis three days in dialysis band of this silk fibroin solution.Pour solution into beaker, be lower than under 90 ℃ of heating in water bath situations, with magnetic force heating stirrer gentle agitation, volatilization concentrates.Solution concentration to 150-300mg/ml, is clear solution.Subsequently this strong solution is sprawled on polystyrene board, 50-200 ℃ of following drying and forming-film in loft drier, its thickness can be controlled by solution quality.Become the film homogeneous transparent.
Embodiment 2:
Prepare pure silk fibroin water solution shown in embodiment 1.The pure silk fibroin aqueous solution is placed in the beaker, is being lower than under 90 ℃ of heating in water bath situations, with magnetic force heating stirrer gentle agitation, volatilization concentrates.Obtaining strength of solution is the clear solution of 200-350mg/ml, with this strong solution uniform spreading on polystyrene board, and 50 ℃ of following normal pressure volatile dry film forming in loft drier.
Embodiment 3:
Prepare pure silk fibroin water solution shown in embodiment 1.
The pure silk fibroin aqueous solution is placed in the beaker, is being lower than under 90 ℃ of heating in water bath situations, with magnetic force heating stirrer gentle agitation, volatilization concentrates.Obtaining strength of solution is the clear solution of 200-350mg/ml, and with this strong solution under static state, 50-200 ℃ of following normal pressure volatile dry becomes half curdled appearance in loft drier, and the method for extruding with machinery is prepared the silk fibroin pipe then.
Embodiment 4:
Prepare pure silk fibroin water solution shown in embodiment 1.
The pure silk fibroin aqueous solution is placed in the beaker, is being lower than under 90 ℃ of heating in water bath situations, with magnetic force heating stirrer gentle agitation, volatilization concentrates.Obtaining strength of solution is the clear solution of 200-350mg/ml, and this strong solution is dried to half curdled appearance under 50-200 ℃ in loft drier, prepares the silk fibroin pipe with the method for blowing then.
Embodiment 5:
Prepare pure silk fibroin water solution shown in embodiment 1.The pure silk fibroin aqueous solution is placed in the beaker is being lower than under 90 ℃ of heating in water bath situations, with magnetic force heating stirrer gentle agitation, volatilization concentrates.Obtaining strength of solution is the clear solution of 200～350mg/ml, and this solution-cast is in sleeve pipe, dry under 20～200 ℃, prepares the silk fibroin pipe.
Claims (4)
1. the preparation method of insoluble stable fibroin film and tubing is characterized in that: with the silk fibroin water solution gentle agitation, make it to be lower than 90 ℃ of transparent silk fibroin water solutions that are concentrated into the high density of 100-500mg/ml.
2. the transparent silk fibroin water solution of high density as claimed in claim 1, it is characterized in that: the transparent silk fibroin water solution of high density is poured on polystyrene board or the sheet glass, and 20-200 ℃ of following volatile dry becomes water-fast fibroin film in loft drier.
3. the transparent silk fibroin water solution of high density as claimed in claim 1, it is characterized in that: the transparent fibroin aqueous solution of high density is cast on the polyrod or Glass tubing of different diameter, in loft drier under 20-200 ℃, the control rate of drying, slowly volatile dry becomes silk fibroin tubular material.
4. the transparent silk fibroin water solution of high density as claimed in claim 1, it is characterized in that: the transparent fibroin aqueous solution of high density is dried to half curdled appearance at 20-200 ℃ extrudes or be blow molded into tubulose, make the water-fast silk fibroin tubing of different diameter with very good mechanical properties through machinery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03131142 CN1228345C (en) | 2003-05-13 | 2003-05-13 | Insoluble silk fibroin film and preparation of silk fibroin pipe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03131142 CN1228345C (en) | 2003-05-13 | 2003-05-13 | Insoluble silk fibroin film and preparation of silk fibroin pipe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1475533A true CN1475533A (en) | 2004-02-18 |
| CN1228345C CN1228345C (en) | 2005-11-23 |
Family
ID=34153803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03131142 Expired - Fee Related CN1228345C (en) | 2003-05-13 | 2003-05-13 | Insoluble silk fibroin film and preparation of silk fibroin pipe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1228345C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007036084A1 (en) * | 2005-09-28 | 2007-04-05 | Nantong University | Medical artificial nerve graft containing silk fibroin and its preparation method |
| CN101961509A (en) * | 2010-09-21 | 2011-02-02 | 苏州大学 | Silk fibroin/calcium phosphate bone cement composite material and preparation method thereof |
| CN102743796A (en) * | 2011-04-18 | 2012-10-24 | 北京汇亨创管理咨询有限公司 | Silk fibroin porous support made from polyvinyl alcohol, and preparation method and application thereof |
| CN104922728A (en) * | 2015-06-01 | 2015-09-23 | 北京理工大学 | Preparation method for small-diameter artificial silk fibroin blood vessel with high unblocked rate |
| CN105696099A (en) * | 2016-01-29 | 2016-06-22 | 中国科学院深圳先进技术研究院 | Material capable of being deformed by water and preparation method of material |
-
2003
- 2003-05-13 CN CN 03131142 patent/CN1228345C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007036084A1 (en) * | 2005-09-28 | 2007-04-05 | Nantong University | Medical artificial nerve graft containing silk fibroin and its preparation method |
| EA016085B1 (en) * | 2005-09-28 | 2012-02-28 | Нантонг Юниверсити | Medical artificial nerve graft containing silk fibroin and its preparation method |
| CN101961509A (en) * | 2010-09-21 | 2011-02-02 | 苏州大学 | Silk fibroin/calcium phosphate bone cement composite material and preparation method thereof |
| CN101961509B (en) * | 2010-09-21 | 2013-10-09 | 苏州大学 | Silk fibroin/calcium phosphate bone cement composite material and preparation method thereof |
| CN102743796A (en) * | 2011-04-18 | 2012-10-24 | 北京汇亨创管理咨询有限公司 | Silk fibroin porous support made from polyvinyl alcohol, and preparation method and application thereof |
| CN104922728A (en) * | 2015-06-01 | 2015-09-23 | 北京理工大学 | Preparation method for small-diameter artificial silk fibroin blood vessel with high unblocked rate |
| CN105696099A (en) * | 2016-01-29 | 2016-06-22 | 中国科学院深圳先进技术研究院 | Material capable of being deformed by water and preparation method of material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1228345C (en) | 2005-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Duan et al. | Recent advances in chitin based materials constructed via physical methods | |
| US9896561B2 (en) | Dendritic macroporous hydrogels prepared by crystal templating | |
| EP3112396A1 (en) | Preparation method and use of sericin hydrogel | |
| CN101028536A (en) | Production of polyvinyl alcohol/sericin blended gel thin film | |
| Fraser et al. | Entrapment in calcium alginate | |
| CN110743400B (en) | Preparation method of copper ion-doped alginate hydrogel antibacterial filtering membrane | |
| CN111228213A (en) | Preparation method and application of biocompatible nano composite hydrogel | |
| JP2014187901A (en) | Temperature-sensitive complex containing bacterial cellulose and production method thereof | |
| CN107149702A (en) | A kind of preparation of poly-dopamine modified lithium porous support | |
| WO2011051983A1 (en) | In vitro bioengineered animal tissue fiber and its use in the textile industry | |
| CN1228345C (en) | Insoluble silk fibroin film and preparation of silk fibroin pipe | |
| CN107519540B (en) | High-strength flexible light-transmitting implantable fibroin/bacterial cellulose/graphene composite conductive film | |
| Ul-Islam et al. | Synthesis, chemistry, and medical application of bacterial cellulose nanocomposites | |
| CN110028685B (en) | Preparation method of fibroin/chitosan/porous graphene oxide composite three-dimensional scaffold | |
| JP2507885B2 (en) | Silk fibroin hydrogel | |
| JPH02109570A (en) | Silkfibroin-containing molding | |
| Park et al. | Biopolymer-based composite materials prepared using ionic liquids | |
| CN1318583A (en) | Chitin/cellulose intermingling material and its preparation and use | |
| CN101850217B (en) | Method for preparing skin-free homogeneous structural polyvinylidene fluoride transfer film | |
| CN109575338B (en) | Polylactic acid composite membrane with surface modified with ordered chitin whisker layer, and preparation method and application thereof | |
| CN106620844A (en) | Calcium carbonate enhanced fibroin fiber scaffold and preparation method thereof | |
| CN101397695B (en) | Method for preparing stable gelatine nano fiber for bionic stent material | |
| CN1686061A (en) | Chitin contained medical nerve graft and its preparation method | |
| KR101254386B1 (en) | A method of preparing nanofibrous-structured biopolymer using phase separaton | |
| CN1255189C (en) | Prepn of anticoagulant insoluble silk protein material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20051123 |