CN104233496A - Preparation method of fibroin nanofibers - Google Patents
Preparation method of fibroin nanofibers Download PDFInfo
- Publication number
- CN104233496A CN104233496A CN201410443772.2A CN201410443772A CN104233496A CN 104233496 A CN104233496 A CN 104233496A CN 201410443772 A CN201410443772 A CN 201410443772A CN 104233496 A CN104233496 A CN 104233496A
- Authority
- CN
- China
- Prior art keywords
- fibroin
- solution
- silk
- preparation
- nanofiber
- 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.)
- Pending
Links
Abstract
The invention discloses a preparation method of fibroin nanofibers. The preparation method comprises the following steps: (1) degumming silk by an alkaline process to remove sericin on the surface of the silk, washing the silk with deionized water, drying the silk, dissolving the dried silk in a CaCl2\C2H5OH\H2O ternary solution or a lithium bromide solution to obtain a fibroin and inorganic salt mixed solution, and dialyzing by a dialysis bag to obtain a fibroin solution; (2) mixing the fibroin solution with a spinning solvent in a volume ratio, and stirring for 30-60 minutes for mixing uniformly; and (3) transferring an obtained spinning solution into a cylinder with a nozzle with triangular cross section, and spraying the spinning solution out of the nozzle under the action of a high voltage electric field to form the nanofibers. The preparation method is simple and convenient to operate, the obtained fibroin nanofibers are good in spinnability, the specifications of the fibers can be adjusted by adjusting spinning parameters, and the fibers have the characteristics of small diameter, excellent performance, stable structure and glittering effect.
Description
Technical field:
The present invention relates to technical field of nano material, relate to a kind of preparation method of fibroin nanofiber particularly.
Background technology:
Silk, as the natural fabric of function admirable, is widely used in the fields such as weaving, biological medicine, militay space flight always, and along with the development of science and technology, the different silk fiber of specifications and characteristics is more and more by widespread demand.Therefore, utilize with silk as the technology of raw material reshaping is known by us.
Utilize CaCl
2c
2h
5oH H
2the ternary solution of O or lithium-bromide solution dissolve the method for fibroin, and because the preparation of its solvent is simple, technological operation is easy, environmental protection, and cost is low, affects the features such as little to fibroin structure, has become the common method of dissolving fibroin.
The method preparing nanofiber mainly contains following several: the two component composite spinning methods of extension, template, method of electrostatic spinning, molecular spinneret, fabric of island-in-sea type etc., wherein electrospinning process is the focus of research, and technology has been tending towards ripe.
The main method of the fibroin nanofiber utilizing method of electrostatic spinning to prepare at present is dissolved in spin solvent again after the silk fibroin solution film forming after dissolving being dialysed to be prepared into spinning solution, regenerated silk nanofiber is obtained again by electrostatic spinning, its technique is more complicated, and the fibre section circle obtained is in the majority.
Summary of the invention:
The object of this invention is to provide a kind of preparation method of fibroin nanofiber, this preparation method is easy and simple to handle, and the fibroin fiber diameter of preparation is nanoscale.
Object of the present invention is achieved through the following technical solutions:
A preparation method for fibroin nanofiber, comprises the following steps:
(1) adopt alkaline process to come unstuck silk, the silk gum on removing surface, after totally drying, is dissolved in CaCl by washed with de-ionized water
2c
2h
5oH H
2in the ternary solution of O or lithium-bromide solution, obtain fibroin inorganic salts mixed solution, after utilizing bag filter to dialyse, obtain silk fibroin solution;
(2) silk fibroin solution is mixed by volume with spin solvent, stir 30-60min, mix;
(3) spinning solution being transferred to cross section is in the syringe of triangular nozzle, and under the effect of high voltage electric field, spinning solution sprays from nozzle, forms nanofiber.
Preferred as technique scheme, the concentration of the silk fibroin solution of step (1) is 10%-30%.
Preferred as technique scheme, the spin solvent of step (2) is at least one in HFIP, FA and distilled water.
Preferred as technique scheme, the silk fibroin solution of step (2) with spin solvent mixed volume ratio is: 1:5-10.
Preferred as technique scheme, the cross section of the nozzle of step (3) is equilateral triangle, and the length of side is 2mm.
Preferred as technique scheme, the high voltage electric field intensity of step (3) is 10-60kV/cm.
Preferred as technique scheme, the nanofiber diameter of step (3) is 100-600nm, and cross section is triangle.
Beneficial effect of the present invention is: fibroin fiber diameter prepared by the present invention is at nanoscale, cross section is triangle, the method is easy and simple to handle, the fibroin nanofiber good spinnability obtained, by the specification regulating spinning parameter can regulate fiber, and fibre diameter is little, function admirable, Stability Analysis of Structures, has flash effect.
Detailed description of the invention:
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
Embodiment 1:
By the silk gum on the sodium carbonate liquor of the silk 0.05g/L of 10g removing surface, after totally drying by washed with de-ionized water, be dissolved in the CaCl of 100ml
2c
2h
5oH H
2in the ternary solution of O, obtain fibroin inorganic salts mixed solution, after utilizing bag filter to dialyse, obtain the 6ml silk fibroin solution that mass fraction is 10%;
Mixed with volume ratio 1:5 with HFIP by silk fibroin solution, stir 60min, be transferred in the syringe of triangular-section nozzle, under the effect of 10kV/cm high voltage electric field, spinning solution sprays from nozzle, forms fibroin nanofiber.Observed known by SEM, the average diameter of fiber is about 600nm, and cross section mostly is obtuse triangle.
Embodiment 2:
By the silk gum on the sodium carbonate liquor of the silk 0.07g/L of 10g removing surface, after totally drying by washed with de-ionized water, be dissolved in the CaCl of 80ml
2c
2h
5oH H
2in the ternary solution of O, obtain fibroin inorganic salts mixed solution, after utilizing bag filter to dialyse, obtain the 4ml silk fibroin solution that mass fraction is 30%;
Mixed with volume ratio 1:10 with HFIP by silk fibroin solution, stir 30min, be transferred in the syringe of triangular-section nozzle, under the effect of 60kV/cm high voltage electric field, spinning solution sprays from nozzle, forms fibroin nanofiber.Observed known by SEM, the average diameter of fiber is about 100nm, and cross section mostly is acute triangle.
Embodiment 3:
By the silk gum on the sodium carbonate liquor of the silk 0.05g/L of 10g removing surface, after totally drying by washed with de-ionized water, be dissolved in the CaCl of 90ml
2c
2h
5oH H
2in the ternary solution of O, obtain fibroin inorganic salts mixed solution, after utilizing bag filter to dialyse, obtain the 5ml silk fibroin solution that mass fraction is 20%;
Mixed with volume ratio 1:8 with HFIP by silk fibroin solution, stir 50min, be transferred in the syringe of triangular-section nozzle, under the effect of 45kV/cm high voltage electric field, spinning solution sprays from nozzle, forms fibroin nanofiber.Observed known by SEM, the average diameter of fiber is about 300nm, and cross section mostly is acute triangle.
Embodiment 4:
By the silk gum on the sodium carbonate liquor of the silk 0.05g/L of 10g removing surface, after totally drying by washed with de-ionized water, be dissolved in the CaCl of 80ml
2c
2h
5oH H
2in the ternary solution of O, obtain fibroin inorganic salts mixed solution, after utilizing bag filter to dialyse, obtain the 4.5ml silk fibroin solution that mass fraction is 25%;
Mixed with volume ratio 1:9 with HFIP by silk fibroin solution, stir 40min, be transferred in the syringe of triangular-section nozzle, under the effect of 40kV/cm high voltage electric field, spinning solution sprays from nozzle, forms fibroin nanofiber.Observed known by SEM, the average diameter of fiber is about 250nm, and cross section mostly is acute triangle.
Claims (7)
1. a preparation method for fibroin nanofiber, is characterized in that comprising the following steps:
(1) adopt alkaline process to come unstuck silk, the silk gum on removing surface, after totally drying, is dissolved in CaCl by washed with de-ionized water
2c
2h
5oH H
2in the ternary solution of O or lithium-bromide solution, obtain fibroin inorganic salts mixed solution, after utilizing bag filter to dialyse, obtain silk fibroin solution;
(2) silk fibroin solution is mixed by volume with spin solvent, stir 30-60min, mix;
(3) spinning solution being transferred to nozzle cross-section is in leg-of-mutton syringe, and under the effect of high voltage electric field, spinning solution sprays from nozzle, forms nanofiber.
2. the preparation method of a kind of fibroin nanofiber as claimed in claim 1, is characterized in that: the concentration of step (1) described silk fibroin solution is 10%-30%.
3. the preparation method of a kind of fibroin nanofiber as claimed in claim 1, is characterized in that: step (2) described spin solvent is at least one in HFIP, FA and distilled water.
4. the preparation method of a kind of fibroin nanofiber as claimed in claim 1, is characterized in that: step (2) described silk fibroin solution with spin solvent mixed volume ratio is: 1:5-10.
5. the preparation method of a kind of fibroin nanofiber as claimed in claim 1, is characterized in that: the cross section of the nozzle described in step (3) is equilateral triangle, and the length of side is 2mm.
6. the preparation method of a kind of fibroin nanofiber as claimed in claim 1, is characterized in that: the described high voltage electric field intensity of step (3) is 10-60kV/cm.
7. the preparation method of a kind of fibroin nanofiber as claimed in claim 1, is characterized in that: the diameter of step (3) described nanofiber is 100-600nm, and cross section is triangle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410443772.2A CN104233496A (en) | 2014-09-03 | 2014-09-03 | Preparation method of fibroin nanofibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410443772.2A CN104233496A (en) | 2014-09-03 | 2014-09-03 | Preparation method of fibroin nanofibers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104233496A true CN104233496A (en) | 2014-12-24 |
Family
ID=52222360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410443772.2A Pending CN104233496A (en) | 2014-09-03 | 2014-09-03 | Preparation method of fibroin nanofibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104233496A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017061756A (en) * | 2015-09-24 | 2017-03-30 | 日立化成株式会社 | Method for producing nanofiber and electrospinning dope |
| CN107974767A (en) * | 2017-12-29 | 2018-05-01 | 四川省丝绸工程技术研究中心 | A kind of silkworm/tussah silk fibroin composite nano-fiber membrane and preparation method thereof |
| CN109011918A (en) * | 2018-08-01 | 2018-12-18 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of mask intermediate course filtering material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587459A (en) * | 2004-09-07 | 2005-03-02 | 东华大学 | Process for producing regenerated silk protein super fine fiber |
| CN101255613A (en) * | 2008-04-14 | 2008-09-03 | 朱建清 | Production technique of special-shaped silk |
| US7682539B1 (en) * | 2006-01-11 | 2010-03-23 | The United States Of America As Represented By The Secretary Of The Air Force | Regeneration of silk and silk-like fibers from ionic liquid spin dopes |
| JP2011208286A (en) * | 2010-03-26 | 2011-10-20 | Shinshu Univ | Silk composite nanofiber and method for producing the same |
| CN102813965A (en) * | 2012-08-09 | 2012-12-12 | 东华大学 | Multilayer well-organized silk fibroin tissue engineering scaffold and preparation method thereof |
| CN102899734A (en) * | 2012-11-01 | 2013-01-30 | 苏州大学 | Silk fibroin hollow fiber and preparation method thereof |
| JP2013019093A (en) * | 2012-09-07 | 2013-01-31 | Idemitsu Technofine Co Ltd | Fiber crosslinked body and method for producing fiber crosslinked body |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
-
2014
- 2014-09-03 CN CN201410443772.2A patent/CN104233496A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587459A (en) * | 2004-09-07 | 2005-03-02 | 东华大学 | Process for producing regenerated silk protein super fine fiber |
| US7682539B1 (en) * | 2006-01-11 | 2010-03-23 | The United States Of America As Represented By The Secretary Of The Air Force | Regeneration of silk and silk-like fibers from ionic liquid spin dopes |
| CN101255613A (en) * | 2008-04-14 | 2008-09-03 | 朱建清 | Production technique of special-shaped silk |
| JP2011208286A (en) * | 2010-03-26 | 2011-10-20 | Shinshu Univ | Silk composite nanofiber and method for producing the same |
| CN102813965A (en) * | 2012-08-09 | 2012-12-12 | 东华大学 | Multilayer well-organized silk fibroin tissue engineering scaffold and preparation method thereof |
| JP2013019093A (en) * | 2012-09-07 | 2013-01-31 | Idemitsu Technofine Co Ltd | Fiber crosslinked body and method for producing fiber crosslinked body |
| CN102899734A (en) * | 2012-11-01 | 2013-01-30 | 苏州大学 | Silk fibroin hollow fiber and preparation method thereof |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017061756A (en) * | 2015-09-24 | 2017-03-30 | 日立化成株式会社 | Method for producing nanofiber and electrospinning dope |
| CN107974767A (en) * | 2017-12-29 | 2018-05-01 | 四川省丝绸工程技术研究中心 | A kind of silkworm/tussah silk fibroin composite nano-fiber membrane and preparation method thereof |
| CN109011918A (en) * | 2018-08-01 | 2018-12-18 | 苏州市天翱特种织绣有限公司 | A kind of preparation method of mask intermediate course filtering material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103866487B (en) | The preparation method of a kind of nano micro crystal cellulose/chitosan/polyvinyl alcohol composite nanometer film | |
| Yue et al. | A novel route to prepare dry-spun silk fibers from CaCl2–formic acid solution | |
| US6110590A (en) | Synthetically spun silk nanofibers and a process for making the same | |
| CN103173892A (en) | Preparation method of nano bamboo fiber composite material | |
| JP5072846B2 (en) | Use of aqueous sodium hydroxide / thiourea solution in the manufacture of cellulose products on a pilot scale | |
| CN106928729B (en) | A kind of nanometer silver antimicrobial regenerated silk fibroin material and preparation method thereof | |
| CN103320886B (en) | Bionic regenerated silk fibroin filament fiber and preparation method thereof | |
| CN103590125B (en) | One has multi-functional composite lyocell fiber and preparation method thereof | |
| CN101974800B (en) | Method for manufacturing wood-pupa protein viscose staple fibers | |
| CN109652866B (en) | Preparation method of natural silk micro-nano fibers | |
| CN106589091A (en) | Method for dissolving fiber of natural silk | |
| CN102277689A (en) | Device and method for preparing cellulose fibrous membrane with nanometer structure | |
| CN107344075B (en) | Preparation method of electrostatic spinning hollow fiber membrane | |
| CN104947244A (en) | Method for extracting and preparing lignin composite nano fibers in situ | |
| CN102817178A (en) | Method for improving heat stability and mechanical property of polyvinyl alcohol nanofiber membrane | |
| CN104233496A (en) | Preparation method of fibroin nanofibers | |
| CN103556255B (en) | A kind of bamboo charcoal cellulose fiber and preparation method thereof | |
| CN102517667A (en) | Method for preparing cellulose fibers by using reed as raw material | |
| CN101962822B (en) | Method for manufacturing wood pupa protein viscose filament yarns | |
| EP2909365A1 (en) | Method of spinning fibres or extrusion, and the products obtained | |
| CN101709512A (en) | High-whiteness bamboo-charcoal viscose fiber and manufacturing method thereof | |
| CN103352261B (en) | Sandwich-type electrostatic spinning nozzle and prepare the method for regenerated silk nano fibre yarn | |
| CN104928789B (en) | Electrostatic spinning combination anti-solvent technology prepares porous nano-fibre and preparation method | |
| CN104060358A (en) | Radiation-proof cross-blended yarn and preparation method thereof | |
| CN104593902B (en) | A kind of preparation method of carbon fiber precursor polyacrylonitrile/lignin fibre |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141224 |
|
| RJ01 | Rejection of invention patent application after publication |