CN100368610C - 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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- CN100368610C CN100368610C CNB2006100387414A CN200610038741A CN100368610C CN 100368610 C CN100368610 C CN 100368610C CN B2006100387414 A CNB2006100387414 A CN B2006100387414A CN 200610038741 A CN200610038741 A CN 200610038741A CN 100368610 C CN100368610 C CN 100368610C
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Abstract
The present invention relates to a blending nanometer fiber of fibroin protein and polyvinyl alcohol and a production method thereof. The present invention uses natural silk as main raw materials, and fibroin after dissolving in a formic acid solution with good solubility and high volatility is blended with a polyvinyl alcohol solution; the compatibility of the fibroin and polyvinyl alcohol components is improved by adding polyol; nanometer fiber material with silk fibroin content of 49 percent to 95 percent, diameter of 30 nanometers to 500 nanometers and breaking strength of 0.3cN/tax to 0.5cN/tax is obtained by an electrostatic spinning technology. The mechanical property of the fiber is superior to a pure fibroin nanometer fiber, and the fiber is used as biologic medical material because of good biocompatibility, particularly tissue engineering support material.
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. with the degree of polymerization be 1750 ~ 2400 polyvinyl alcohol material dissolution in deionized water, 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 fiber collecting frame silk screen reception 5 apart from height.
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 (2)
1. method for preparing fibroin albumen and polyvinyl alcohol blending nanofiber, it is characterized in that: 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 solution concentration and be 6～30% silk fibroin solution;
C. with the degree of polymerization be 1750 ~ 2400 polyvinyl alcohol material dissolution in deionized water, make concentration and be 6～16% polyvinyl alcohol water solution;
D. with prepared silk fibroin solution and polyvinyl alcohol water solution by mass ratio 49～95: 4～50 proportioning is carried out blend, adds 1～6% polyalcohol again, makes 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.
2. the method for preparing fibroin albumen and polyvinyl alcohol blending nanofiber according to claim 1 is characterized in that: described polyalcohol is a kind of in glycerol, the hexylene glycol or their combination.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100387414A CN100368610C (en) | 2006-03-06 | 2006-03-06 | Blending nanometer fibre with silk protein and vinol and production thereof |
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| CNB2006100387414A CN100368610C (en) | 2006-03-06 | 2006-03-06 | Blending nanometer fibre with silk protein and vinol and production thereof |
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| CN1818163A CN1818163A (en) | 2006-08-16 |
| CN100368610C true CN100368610C (en) | 2008-02-13 |
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Families Citing this family (15)
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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 | The polymer nanofiber preparation facilities that large tracts of land aligns |
| 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 | Medical fiber and manufacturing method thereof |
| 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 |
| 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 |
| JP2019512352A (en) * | 2016-03-31 | 2019-05-16 | イアー サイエンス インスティテュート オーストラリア | Improved silk fibroin glycerol membrane |
| CN107190351A (en) * | 2017-06-29 | 2017-09-22 | 顾渊 | A kind of preparation method of silk fiber fabric |
| CN107287884B (en) * | 2017-08-01 | 2019-05-31 | 浙江理工大学 | A kind of preparation method attaching ventilative artificial skin receptor |
| WO2019151440A1 (en) * | 2018-01-31 | 2019-08-08 | Ｓｐｉｂｅｒ株式会社 | Production method for protein molded article, production method for protein solution, and production method for protein |
| CN110409007A (en) * | 2019-09-03 | 2019-11-05 | 重庆大学 | A kind of electrostatic spinning equipment making micro-nano fiber bracket and method |
| CN113509587B (en) * | 2021-04-25 | 2022-06-21 | 浙江理工大学 | Preparation method of bionic composite fiber film with anti-inflammatory activity |
| TWI800080B (en) * | 2021-11-05 | 2023-04-21 | 亞格生技股份有限公司 | Method for making nanofiber film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062934A (en) * | 1990-12-24 | 1992-07-22 | 成都科技大学 | Silk-fibroin and polyvinyl alcohol blending fiber |
| CN1467248A (en) * | 2002-06-19 | 2004-01-14 | 独立行政法人农业生物资源研究所 | Biodegradable biopolymers, method for their preparation and functional materials constituted by these biopolymers |
| WO2005103158A1 (en) * | 2004-04-20 | 2005-11-03 | Nippon Shinyaku Co., Ltd. | Silk fibroin film |
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- 2006-03-06 CN CNB2006100387414A patent/CN100368610C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062934A (en) * | 1990-12-24 | 1992-07-22 | 成都科技大学 | Silk-fibroin and polyvinyl alcohol blending fiber |
| CN1467248A (en) * | 2002-06-19 | 2004-01-14 | 独立行政法人农业生物资源研究所 | Biodegradable biopolymers, method for their preparation and functional materials constituted by these biopolymers |
| WO2005103158A1 (en) * | 2004-04-20 | 2005-11-03 | Nippon Shinyaku Co., Ltd. | Silk fibroin film |
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Assignee: Jiangsu Wenfeng Chemical Fiber Group Co., Ltd. Assignor: Soochow University Contract record no.: 2011320000279 Denomination of invention: Blending nanometer fibre with silk protein and vinol and production thereof Granted publication date: 20080213 License type: Exclusive License Open date: 20060816 Record date: 20110315 |
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