CN1818163A - Blending nanometer fibre with silk protein and vinol and production thereof - Google Patents
Blending nanometer fibre with silk protein and vinol and production thereof Download PDFInfo
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- CN1818163A CN1818163A CN 200610038741 CN200610038741A CN1818163A CN 1818163 A CN1818163 A CN 1818163A CN 200610038741 CN200610038741 CN 200610038741 CN 200610038741 A CN200610038741 A CN 200610038741A CN 1818163 A CN1818163 A CN 1818163A
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- polyvinyl alcohol
- silk fibroin
- silk
- solution
- fibroin
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 41
- 239000000835 fiber Substances 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 title claims description 11
- 108090000623 proteins and genes Proteins 0.000 title description 2
- 102000004169 proteins and genes Human genes 0.000 title description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- 108010022355 Fibroins Proteins 0.000 claims abstract description 56
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000002121 nanofiber Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 238000001523 electrospinning Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- 238000009987 spinning Methods 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000011550 stock solution Substances 0.000 claims 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010041 electrostatic spinning Methods 0.000 description 7
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003519 biomedical and dental material Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- 206010002198 Anaphylactic reaction Diseases 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 230000036783 anaphylactic response Effects 0.000 description 2
- 208000003455 anaphylaxis Diseases 0.000 description 2
- 230000000680 avirulence Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000011026 diafiltration Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002062 molecular scaffold Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 2
- 241000255789 Bombyx mori Species 0.000 description 1
- 241000909829 Samia ricini Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000012292 cell migration Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
本发明涉及一种丝素蛋白与聚乙烯醇共混纳米纤维及其制备方法。它以天然蚕丝为主要原料，将丝素溶解于溶解性较好且挥发度极高的甲酸溶液中后，与聚乙烯醇溶液共混，通过加入多元醇的方法，改善丝素与聚乙烯醇组分的相容性，采用静电纺丝工艺，得到丝素蛋白含量49～95％，直径30～500纳米，断裂强度为0.3～0.5cN/dtex的纳米纤维材料。该纤维力学性能优于纯丝素纳米纤维，且由于其生物相容性好，适用于生物医用材料，特别是组织工程支架材料。
The invention relates to a silk fibroin and polyvinyl alcohol blend nanofiber and a preparation method thereof. It uses natural silk as the main raw material. After dissolving silk fibroin in a formic acid solution with good solubility and high volatility, it is blended with polyvinyl alcohol solution. By adding polyols, the silk fibroin and polyvinyl alcohol are improved. The compatibility of components adopts the electrospinning process to obtain a nanofiber material with a silk fibroin content of 49-95%, a diameter of 30-500 nanometers, and a breaking strength of 0.3-0.5 cN/dtex. The mechanical property of the fiber is better than that of pure silk fibroin nanofiber, and because of its good biocompatibility, it is suitable for biomedical materials, especially tissue engineering scaffold materials.
Description
Technical field
The present invention relates to a kind of nanofiber and preparation method, be specifically related to a kind of nanofiber and preparation method, can be widely used in fields such as biology, medical science with fibroin albumen and polyvinyl alcohol blending.
Background technology
Silk is abundant in China source, it is made up of fibroin and silk gum, fibroin is a kind of native protein, the fibroin albumen avirulence, has no stimulation, do not have anaphylaxis, has excellent biological compatibility, with low cost, particularly its biodegradability can be made into the used in tissue engineering three-dimensional stent material by the processing of road, back, is expected to replace expensive biodegradable tissue engineering materials such as import PLA, therefore, be desirable feedstock as bio-medical material.Characteristics such as that the synthetic material polyvinyl alcohol has is nontoxic, water-soluble, bio-compatible and biodegradable also are widely used in biochemistry and field of biomedical materials, and the polyvinyl alcohol as synthetic material also has good mechanical property, the good advantage of hydrophily simultaneously.
Compare with the prior other biological medical material, natural fibroin has been avoided complicated, loaded down with trivial details synthesis technique, and it is easy to purify.Fibroin fiber is existing historical for many years as surgical sewing thread; the regenerated silk film is also existing a lot of as the case of burn wound protective material; the various testing results of being carried out all illustrate from different perspectives: the fibroin albumen avirulence, have no stimulation; no anaphylaxis; and have excellent biological compatibility, can be widely used in biochemistry and biomedical material.
In addition, tissue engineering bracket material is as a kind of biomedical material, and its inner various hole is formed the living space of cell.The size and the volume in porosity height, aperture is and the direct relevant parameter of the support of a success.Nano fiber scaffold has high porosity, promptly has a kind of highly porous structure, this loose structure can provide the more structural space for cell generates, impelling the exchange of nutrient and metabolin between support and environment, this be a success tissue engineering bracket the primary condition that must possess.At present, except traditional spinning process, the exercise question that " Polymer " magazine Vol.44 in 2003 delivered on the phase is in " Preparation of non-woven nanofibers of Bombyx mori silk; SamiaCynthia ricini silk and recombinant hybrid silk with electrospinningmethod " literary composition, a kind of technology of utilizing electrospinning process to prepare the plain nano-fiber material of pure silk is disclosed, but discover, because the C-N bond distance among the peptide bond-CO-NH-on the big molecule peptide chain of fibroin protein is a little shorter than the C-N bond distance of singly-bound, and it is longer than the C=N bond distance of two keys, this just makes peptide chain have the character of the two keys of part, rigidity is bigger, influenced the compliance of fibroin protein macromolecular main chain, therefore, the physical and mechanical properties extreme difference of pure fibroin nano-fiber material, have significant fragility, be unfavorable for further processing and utilization.
Nano fiber scaffold has high porosity, promptly has a kind of highly porous structure, this loose structure can provide the more structural space for cell generates, to impel the exchange of nutrient and metabolin between support and environment, and the micropore in the supatex fabric that electrostatic spinning fiber is formed connects, and the resistance that the nano-scale fiber on cell migration causes is extremely small, and these all very help the propagation of cell.Publication number is in the patent of invention " a kind of fibre for tissue engineering scaffold and preparation method thereof " of CN137202A, disclosing a kind of is raw material with simple silk, through come unstuck, after the operation such as dissolving, make the method for fiber with the conventional wet spinning method of forming, the fiber number of the fiber of this wet spinning process gained surpasses 1 dtex, and simple fibroin fiber is generally more crisp, has limited its application on bio-medical material to a great extent; At publication number is in the patent of invention " silk-fibroin and polyvinyl alcohol blending fiber " of CN1062934, disclose that a kind of wet spinning process with routine makes what make with the blend aqueous solution is blended fiber auxilliary and polyvinyl alcohol based on silk-fibroin, fibre strength is higher, approach vinal, but because polyvinyl alcohol content is too high, and resulting also is the fiber of conventional fiber number, so also be difficult to as tissue engineering material.At present, high-load fibroin albumen and polyvinyl alcohol blending nanofiber and preparation method do not appear in the newspapers as yet.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of pliability good, and favorable tissue compatibility, biodegradability are arranged, be applicable to the nanofiber and the preparation method of tissue engineering bracket with human body.
The present invention adopts following technical scheme to realize purpose of the present invention: a kind of fibroin albumen and polyvinyl alcohol blending nanofiber are provided, and fibroin albumen content is 49～95% in the fiber, and polyvinyl alcohol content is 4～50%, and all the other are polyalcohol; The diameter of fiber is 30～500 nanometers, and fracture strength is 0.3～0.5cN/dtex.
A kind of method for preparing fibroin albumen and polyvinyl alcohol blending nanofiber is provided, and it adopts following concrete steps:
A. the fibroin after the silk raw material being come unstuck obtains the pure silk cellulosic material after dissolving, filtration, dried;
B. above-mentioned pure silk element is dissolved in the formic acid solvent, makes concentration and be 6～30% silk fibroin solution;
C. be 1750～2400 polyvinyl alcohol material dissolution with the degree of polymerization, make concentration and be 6～16% polyvinyl alcohol water solution;
D. be 49～95: 4～50 blend with prepared silk fibroin solution and polyvinyl alcohol water solution by mass ratio, add 1～6% polyalcohol again, make spinning solution;
E. adopt method of electrostatic spinning, condition is sprayed above-mentioned spinning solution and is spun routinely, obtains fibroin albumen and polyvinyl alcohol blending nano-fiber material.
Described polyalcohol is a kind of in glycerol, the hexylene glycol or their combination.
Enbrittle in order to overcome pure fibroin nano-fiber material, the defective of pliability extreme difference, the present invention has adopted the technical scheme of having introduced the preferable polyvinyl alcohol flexible chain composition of intensity and toughness in spinning solution, because fibroin and polyvinyl alcohol molecule are component hard to tolerate, in order to improve their compatibility, the present invention adds polyol component again in blend solution, this is because the polar group of polyalcohol and the polar group on fibroin and the polyvinyl alcohol macromolecular chain have formed strong coordination, interval between strand is enlarged, hindered between the fibroin strand and separately hydrogen bonded between the polyvinyl alcohol strand, and strengthened hydrogen bonded between both strands by polyalcohol, can improve the compatibility of fibroin and polyvinyl alcohol two components hard to tolerate to a certain extent; In traditional fibroin/Wet PVA spinning, adopt the solvent of deionized water as spinning solution, but under the process conditions of electrostatic spinning, owing to lacked the auxiliary of coagulating bath, and the nanometer strand is extremely short aerial hardening time, therefore, the volatility requirement that this moment, water did not promptly reach spinning solution as solvent, and very easily make strand bonding once more film forming on the collecting board of spinning, technical solution of the present invention has adopted formic acid solution better to the fibroin dissolubility and that volatility is high to come the instead of pure aqueous solvent, guaranteed the feasibility of electrostatic spinning, to reach desirable one-tenth silk effect.
Compared with prior art, the present invention has following tangible advantage:
1, the present invention is owing to be main raw material with silk, in spinning solution, introduced the preferable polyvinyl alcohol flexible chain composition of intensity and toughness, therefore, the regenerated silk fibroin blended fiber that makes had both kept natural fibroin protein to have the advantage good with the human-body biological compatibility, improve the characteristics of pure silk cellulosic material physical and mechanical properties difference again, become desirable fibre for tissue engineering scaffold material.
2, the invention solves the consistency problem that two kinds of compatible raw materials of difficulty take place after the simple physical blend, use to spray when electrostatic spinning process has been accomplished two kinds of raw materials and spin, and guaranteed the moulding of nanofiber, made fibre diameter at 30～500 nano-fiber materials, specific area can reach 30～100M
2/ g has expanded electrostatic spinning nano fiber preparation method's range of application, also makes material possess splendid absorption, filtration, ventilative and saturating multiple nano-meter characteristic such as wet simultaneously; Simultaneously, can be by the control static aggregated structure parameters such as the stretching of regenerated silk fibroin fiber, degree of crystallinity, the degree of orientation of having spun Control of Voltage, boost voltage can promote the stretching and the orientation of spinning injection stream, makes the regenerated silk fibroin fiber have certain biodegradability.
Description of drawings
Fig. 1 is that fibroin and the polyvinyl alcohol spin dope in the example of the present invention is applied to electrostatic spinning, the principle schematic of its device for spinning.
Wherein: [1] HV generator; [2] spout; [3] injection needle; [4] capillary jet pipe; [5] silk screen dash receiver.
The specific embodiment
The invention will be further elaborated below in conjunction with embodiment.
Embodiment one:
Earlier 0.1 kilogram of leftover bits and pieces raw silk (byproduct in reeling mill's silk cocoon filature) is put into 10 liters of concentration and be 0.05% aqueous sodium carbonate, boiled 0.5 hour, the silk gum of most fibroin periphery is taken off in reprocessing three times, obtains pure natural silk.
After treating that pure natural silk dries naturally, with mol ratio is water/ethanol/calcium chloride solvent of 80/20/10, and dissolving is 2 hours under 60 ℃ temperature conditions, through diafiltration, drying, water-bath dissolving under 70 ℃ of conditions in anhydrous formic acid solution again makes 12% silk fibroin solution; With deionized water dissolve polyvinyl alcohol under 80 ℃ of conditions, make 8% polyvinyl alcohol water solution, the quality proportioning by 85/10 joins in the silk fibroin solution that has made, mixes 0.5 hour under 40 ℃ of temperature conditions, and follow and add 5% glycerol additive, make spinning solution.
Referring to accompanying drawing 1, the spinning solution that makes is passed through spout 2, under the nitrogen pressure effect, through injection needle 3, to internal diameter 1.0mm Stainless Steel Capillary jet pipe 4, continuous flow rate, keep spinning solution amount 5ml in the capillary jet pipe, HV generator 1 output voltage is 9KV, spinning solution flow rate 2ml/h, and capillary jet pipe shower nozzle is 10cm to the plate distance of fiber collecting frame silk screen reception 5.
Under the room temperature, spinning solution sprays on the silk screen dash receiver, obtain the nanoscale fibroin/polyvinyl alcohol blending fibrous felt materials of fibre diameter between 30～100 nanometers, be covered in the medical surface of a wound that is fixed on the receiver sheet and cover the bed material surface of binding material, but make the medical surface of a wound cladding material of combined type, when guaranteeing working strength, nontoxic, have no stimulation, also guaranteed good contact well with the human body surface of a wound, biocompatibility or the like, it is simple to have reached preparation, respond well application target.
Embodiment two:
It is 0.05% aqueous sodium carbonate that leftover bits and pieces raw silk in 0.3 kilogram of reeling mill's silk cocoon filature is put into 30 liters of concentration, boils 0.5 hour, and the silk gum of most fibroin periphery is taken off in reprocessing three times, obtains pure natural silk.
After treating that pure natural silk dries naturally, with mol ratio is water/ethanol/calcium chloride solvent of 80/20/10, and dissolving is 4 hours under 60 ℃ temperature conditions, through diafiltration, oven dry, water-bath dissolving under 70 ℃ of conditions in anhydrous formic acid solution again made 15% silk fibroin solution after 1 hour; With deionized water dissolve polyvinyl alcohol under 80 ℃ of conditions, make 10% polyvinyl alcohol water solution, the quality proportioning by 60/38 joins in the silk fibroin solution that has made, and mixes 1.0 hours under 40 ℃ of temperature conditions, and follow and add 2% hexylene glycol, make spinning solution.
Referring to accompanying drawing 1, with internal diameter 1.5mm Stainless Steel Capillary jet pipe 4 as spinneret orifice, the spinning solution that makes is passed through spout 2, under the nitrogen pressure effect, through injection needle 3, continuous flow rate, guarantee that spinning pressure 0.2Mpa is constant in the capillary jet pipe, HV generator 1 output spinning voltage 18KV, spinning solution flow rate 5ml/h, capillary jet pipe shower nozzle is 13cm to the distance of fiber collecting frame silk screen reception 5.
Under the room temperature, spinning solution sprays on the silk screen dash receiver, makes non-woven fabrics type, the nanoscale fibroin/polyvinyl alcohol blending fibrous felt materials of fibre diameter between 100～300 nanometers.Make the fibrofelt specific area and reached 50m
2/ g, its cellular structure make material become good tissue engineering scaffold material.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100387414A CN100368610C (en) | 2006-03-06 | 2006-03-06 | A kind of silk fibroin and polyvinyl alcohol blended nanofiber and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100387414A CN100368610C (en) | 2006-03-06 | 2006-03-06 | A kind of silk fibroin and polyvinyl alcohol blended nanofiber and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1818163A true CN1818163A (en) | 2006-08-16 |
| CN100368610C CN100368610C (en) | 2008-02-13 |
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| CNB2006100387414A Expired - Fee Related CN100368610C (en) | 2006-03-06 | 2006-03-06 | A kind of silk fibroin and polyvinyl alcohol blended nanofiber and its preparation method |
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| CN100562611C (en) * | 2007-06-27 | 2009-11-25 | 哈尔滨工业大学深圳研究生院 | Fabrication device for large-area aligned polymer nanofibers |
| CN101735801A (en) * | 2009-12-03 | 2010-06-16 | 苏州大学 | Method for preparing fluorescent fiber membrane |
| CN101476172B (en) * | 2009-01-14 | 2010-08-11 | 天津工业大学 | A kind of medical fiber and its manufacturing method |
| CN101274109B (en) * | 2008-05-19 | 2011-05-11 | 福建师范大学 | Method for preparing tussah silk fibroin-high polymer stephanoporate interpenetrating grid shaped bracket material with foaming method |
| CN102936795A (en) * | 2012-11-28 | 2013-02-20 | 苏州大学 | Drug-loading nano-fiber membrane and preparation method thereof |
| CN103194818A (en) * | 2013-04-25 | 2013-07-10 | 南京信息工程大学 | Soybean protein and PVA (Polyvinyl Alcohol) blend fiber as well as preparation method and applications thereof |
| KR101447256B1 (en) | 2013-10-10 | 2014-10-08 | 경북대학교 산학협력단 | Process for preparing silk fibroin nano fiber |
| WO2017051926A1 (en) * | 2015-09-24 | 2017-03-30 | 日立化成株式会社 | Fiber, skin care sheet, wound-covering material, regenerative medical material, and non-woven fabric |
| CN107190351A (en) * | 2017-06-29 | 2017-09-22 | 顾渊 | A kind of preparation method of silk fiber fabric |
| WO2017165922A1 (en) * | 2016-03-31 | 2017-10-05 | Ear Science Institute Australia | Improved silk fibroin glycerol membranes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1030665C (en) * | 1990-12-24 | 1996-01-10 | 成都科技大学 | Silk protein and polyvinyl alcohol blended fiber |
| JP3772207B2 (en) * | 2002-06-19 | 2006-05-10 | 独立行政法人農業生物資源研究所 | Biodegradable biopolymer material, production method thereof, and functional material comprising the polymer material |
| JP4881155B2 (en) * | 2004-04-20 | 2012-02-22 | 日本新薬株式会社 | Silk fibroin film |
-
2006
- 2006-03-06 CN CNB2006100387414A patent/CN100368610C/en not_active Expired - Fee Related
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| CN100562611C (en) * | 2007-06-27 | 2009-11-25 | 哈尔滨工业大学深圳研究生院 | Fabrication device for large-area aligned polymer nanofibers |
| CN101274109B (en) * | 2008-05-19 | 2011-05-11 | 福建师范大学 | Method for preparing tussah silk fibroin-high polymer stephanoporate interpenetrating grid shaped bracket material with foaming method |
| CN101476172B (en) * | 2009-01-14 | 2010-08-11 | 天津工业大学 | A kind of medical fiber and its manufacturing method |
| CN101735801A (en) * | 2009-12-03 | 2010-06-16 | 苏州大学 | Method for preparing fluorescent fiber membrane |
| CN101735801B (en) * | 2009-12-03 | 2013-06-05 | 苏州大学 | Method for preparing fluorescent fiber membrane |
| CN102936795A (en) * | 2012-11-28 | 2013-02-20 | 苏州大学 | Drug-loading nano-fiber membrane and preparation method thereof |
| CN103194818A (en) * | 2013-04-25 | 2013-07-10 | 南京信息工程大学 | Soybean protein and PVA (Polyvinyl Alcohol) blend fiber as well as preparation method and applications thereof |
| CN103194818B (en) * | 2013-04-25 | 2014-12-17 | 南京信息工程大学 | Soybean protein and PVA (Polyvinyl Alcohol) blend fiber as well as preparation method and applications thereof |
| KR101447256B1 (en) | 2013-10-10 | 2014-10-08 | 경북대학교 산학협력단 | Process for preparing silk fibroin nano fiber |
| WO2017051926A1 (en) * | 2015-09-24 | 2017-03-30 | 日立化成株式会社 | Fiber, skin care sheet, wound-covering material, regenerative medical material, and non-woven fabric |
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