CN105803676A - Preparation method of keratin/PEO nanofiber membrane with high keratin content - Google Patents
Preparation method of keratin/PEO nanofiber membrane with high keratin content Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/34—Extraction; Separation; Purification by filtration, ultrafiltration or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/46—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates
- C07K14/47—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans from vertebrates from mammals
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4266—Natural fibres not provided for in group D04H1/425
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4291—Olefin series
Abstract
The invention provides a preparation method of a keratin/PEO nanofiber membrane with high keratin content. The method comprises the specific steps that a keratin solution extracted from natural keratin fibers by adopting a reduction method and PEO powder are blended according the keratin/PEO mass ratio of 95-90 to 5-10, then ethylene glycol diglycidyl ether is added to the mixed solution to obtain a spinning solution having good spinnability through crosslinking, and then the nanofiber membrane is prepared by adopting an electrostatic spinning technique. The nanofiber membrane is suspended in hot air of 120-140 DEG C for thermal crosslinking, and accordingly the water-insoluble keratin/PEO nanofiber membrane with the high keratin content is obtained. The keratin/PEO nanofiber membrane has wide application prospect on the aspect of biomedical science.
Description
Technical field
The present invention provides a kind of method of keratin/PEO nano fibrous membrane preparing keratin content at high proportion, belongs to biological
Field of material technology.
Background technology
Natural keratin fiber is widely present in the derivant of humans and animals body skin and skin, but major part is taken as
Rubbish directly abandons or burns, and this not only causes keratin resource to be wasted in a large number, and serious environment pollution, to the mankind
Work the mischief.Therefore, the exploitation to natural keratin fiber have huge economic benefit and social benefit.
Keratin is a kind of fibrous protein, and basic composition is aminoacid, and aminoacid constitutes polypeptide chain, polypeptide by peptide bond
Chain forms keratic steric configuration further through lateral ties such as disulfide bond, hydrogen bond, salt type bond and Van der Waals forces, makes angle egg
White in complications the helix three-dimensional structure of crosslinking, complicated and fine and close.Due to the molecular structure that keratin is unique so that keratin
Material has the biological characteristics of excellence.The keratin of high molecular has good biological degradability and biocompatibility.
Therefore, keratin and modified product thereof have a good application prospect in technical field of biological material.
2004, in Japanese scholars mountain, clear sodium metabisulfite extracted keratin as reducing agent, then by keratin with
PVA mixes, and with water as solvent, uses wet spinning technology to prepare keratin/PVA blended fiber long filament (Preparation
And Properties of Keratin-Poly (vinyl alcohol) Blend Fiber, Journal of Applied Polymer Science,
Vol.91,2004:756-762).This report, with water as solvent, has reached the purpose of environmental protection, has proposed heat treatment energy simultaneously
Enough water solublity suitably improving blended fiber long filament.
2008, the keratin that Chinese scholar Yuan Jiang etc. extracts as reducing agent with mercaptoethanol, modified with iodoacetic acid and
PHBV is dissolved in hexafluoroisopropanol in varing proportions, prepares nanofiber by electrostatic spinning technique, and is used by nanofiber
In cultivating NIH3T3 cell (Fabrication of PHBV/Keratin Composite Nanofibrous Mats for
Biomedical Applications, Macromolecular Research, Vol.17,2009:850-855).Result of study shows
PHBV can improve keratic spinnability, and keratin/PHBV nanofiber is conducive to adhesion and the breeding of cell.
2008, scholar Alessio Varesano etc. extracted wool keratin with sulphite as reducing agent, with PEO
Keratin/PEO nanofiber is prepared for solvent by electrostatic spinning technique with water, it is thus achieved that keratin/PEO mass after Gong Huning
Than keratin/PEO nanofiber (the Structure and properties of keratin/PEO blend being 70/30
Nanofibres, European Polymer Journal, Vol.44,2008:2465-2475).But when keratin content ratio
When improving further, fiber occurs substantial amounts of beading, filamentation Quality Down.
Xing Zhi just waits the method preparing keratin/PEO nanofiber for solvent with trifluoroethanol, it is thus achieved that keratin/PEO mixes
Composition and division in a proportion example is the keratin/PEO blended nanofibre of 90: 10, (Keratin Nanofibers as a Biomaterial,
International Conference on Nanotechnology and Biosensors, IPCBEE Vol.2,2011:120-124).
But the method is prepared the organic solvent that spinning solution used and is had strong impulse, all causes human body and environment seriously
Pollute, and the price of organic solvent is the most sufficiently expensive.
Fan Jie etc. use the keratin/PEO nanofiber of the two step cross-linking method preparations content of keratin at high proportion with water as solvent
(CN 104264369 A).The human hair keratin extracted as reducing agent with sulphite is blended with PEO, with water is
Solvent preparation spinning liquid, electrostatic spinning after crosslinked for spinning liquid dose of crosslinking is successfully prepared keratin/PEO mixed proportion is
The keratin of the angle of elevation protein content of 90/10/PEO nanofiber, then by nanofiber after under the conditions of pure oxygen at crosslinking
Reason, obtains water-fast keratin/PEO nanofiber, and two step cross-linking methods improve the angle egg at high proportion with water as solvent
The spinnability of the keratin of Bai Hanliang/PEO spinning liquid.
The keratin lyophilization that sodium metabisulfite extracts is obtained keratin powder by Italy scholar Annalisa Aluigi etc.
End, then with formic acid as solvent, receives device by self assembly and successfully prepares pure keratin nanometer at upper spinning equipment
Fiber.Find that this nanofiber has good resistance to water after formaldehyde vapor crosslinking and heat cross-linking simultaneously
(Morphological and structural investigation of wool-derived keratin nanofibres crosslinked by
Thermal treatment, International Journal of Biologieal Macromolecules, Vol.57,2013:30-37).
Above patent and document report that never Tongfang is reported, on the whole, at Yi Shui in the face of regenerating ceratin fibres
During for preparing keratin nanofiber under solvent condition, owing to keratin spinnability is poor, keratin needs and other high polymers
Be blended improve spinning fluid viscosity can filamentation, therefore, the nanofiber that this kind of method prepares keratin content at high proportion is deposited
At bottleneck；When using organic solvent to prepare protein nano fiber, it is modified improving keratin by keratin and exists
Dispersibility in organic solvent, thus improve keratic content in blended nanofibre, even realize the pure keratin that spins and receive
Rice fiber, but it is higher to there is organic solvent cost, with serious pollution defect.
Therefore, the present invention is from environmental protection and the angle of low cost, by using keratin macromole destructiveness little
Keratin extracting method with to spinning liquid in keratin carry out the method that cross-linked phase is combined, improve keratin content at high proportion
The spinnability of keratin co-blended spinning liquid, the spinning keratin content keratin blended nanofibre higher than 90%, and pass through
Thermal crosslinking treatment improves the resistance to water of nano fibrous membrane, prepares keratin/PEO water-insoluble, keratin content at high proportion
Biological nano fibrous membrane.The method has the feature of environmental protection, low energy consumption, low cost.Prepared keratin at high proportion contains
Keratin/PEO biological nano the fibrous membrane of amount, in bio-medical field, tool has been widely used.
Summary of the invention
A kind of method that it is an object of the invention to provide keratin/PEO nano fibrous membrane preparing keratin content at high proportion.
In order to achieve the above object, the technical scheme is that and will be extracted through reducing process by the natural keratin fiber discarded
Keratin concentrated solution and PEO powder be blended according to keratin/PEO mass percent 95-90: 5-10, obtain keratin
/ PEO mixed solution, adds Ethylene glycol diglycidyl ether crosslinking acquisition in this mixed solution and has spinning of good spinnability
Silk liquid, then prepares keratin/PEO nano fibrous membrane by electrostatic spinning technique, by this film through heat cross-linking, prepares insoluble
Keratin content in water is the keratin/PEO biological nano fibrous membrane of 90-95%.
The concrete technical scheme that keratin solution of the present invention is extracted is:
The first step: by cutting off into the segment of fiber of 5-10mm after natural keratin fiber shredding, remove impurity, then use petroleum ether
Remove the impurity such as oils and fats, after deionized water is cleaned, naturally dry；
Second step: above-mentioned natural keratin fiber is immersed in containing reducing agent, albumen with solid-to-liquid ratio for 12-16g/250ml
In the lysate of the PH=9.0 of matter denaturant and surfactant, stirring 4-12h at a temperature of 60-80 DEG C, agitator speed is
200-400r/min；
3rd step: mixture 80-150 eye mesh screen stirring obtained filters removes undissolved natural keratin fiber,
At ambient temperature the keratin saline solution being filtrated to get is dialysed, remove the salt in solution and small-molecule substance；
4th step: the keratin obtaining dialysis is centrifuged removing the sediment fraction in dialysis solution, and centrifugal speed is 5000-
7000rpm, centrifugation time 0.2-1h, then take supernatant；
5th step: concentrate above-mentioned supernatant, obtains the keratin concentrated solution that mass percent concentration is 10-14%.
Described discarded natural keratin fiber is discarded ox hair, Pilus Caprae seu Ovis, Pilus Sus domestica, Crinis Carbonisatus, the rabbit hair or the feather of birds
Deng.
Described reducing agent is 2 mercapto ethanol (being also called beta-mercaptoethanol), dithiothreitol, DTT, TGA etc., also
The mass percent concentration of former dose is 4%-7%.
Described keratinous degeneration agent is carbamide, thiourea or lithium bromide, and the mass percent concentration of protein denaturant is 18-
25%.
Described surfactant is sodium lauryl sulphate, and the mass percent concentration of surfactant is 1-5%.
Described crosslinking be use mass percent concentration be that the Ethylene glycol diglycidyl ether of 1.86-6.21% is in spinning liquid
Keratin cross-link.The method of crosslinking is: under conditions of 50-65 DEG C, the most uniform in spinning liquid while stirring
Add Ethylene glycol diglycidyl ether keratin/PEO blend spinning liquid to cross-link.
Described electrostatic spinning can use the electrospinning process such as needle-based, bubble type, disc type, and spinning condition is:
Under room temperature condition, applied voltage 16-30KV, spinning receiving range 13-18cm, rate of flooding is 0.3-1.0ml/h.
Described heat cross-linking is to be placed in the hot-air of 120-140 DEG C and carry out heat by keratin/PEO biological nano fibrous membrane
Crosslinking.
Accompanying drawing explanation
Fig. 1 is keratin/PEO (90/10) nano fibrous membrane of first crosslinking, and the quality of spinning liquid is 13% than concentration,
The concentration of first crosslinking cross-linking agent is 3%.
Fig. 2 is uncrosslinked keratin/PEO (95/5) nano fibrous membrane, and the quality of spinning liquid is 13% than concentration.
Fig. 3 is keratin/PEO (95/5) nano fibrous membrane of first crosslinking, and the quality of spinning liquid is 13% than concentration,
The concentration of first crosslinking cross-linking agent is 6.21%.
Fig. 4 is keratin/PEO (95/5) nano fibrous membrane after heat cross-linking, and the quality of spinning liquid is 13% than concentration,
First crosslinking crosslinker concentration is 6.21%, and 120 DEG C of heat cross-linking times are 2h.
Fig. 5 is heat cross-linking keratin PEO (95/5) nano fibrous membrane after soaking in distilled water, the mass ratio of spinning liquid
Concentration is 13%, and first crosslinking crosslinker concentration is 6.21%, and 120 DEG C of heat cross-linking 2h soak 72h in water.
Detailed description of the invention
The present invention is illustrated below by embodiment.
Embodiment 1
After Crinis Carbonisatus fiber is carried out successively shredding, remove impurity, cleaning and dry, cut into the segment of fiber of 5-10mm, then
It is immersed in PH for 9 for 13g/250ml, in the solution containing reducing agent and protein denaturant, at 65 DEG C of bars with solid-to-liquid ratio
Stirring 12h under part, the rotating speed of agitator is 200r/min.Wherein reducing agent is mercaptoethanol, and quality is solution than concentration
4%；Protein denaturant is carbamide, and quality is the 24% of solution than concentration.Mixed solution after stirring 80 eye mesh screens
Unreacted fiber is gone out in filtration, and the 36h that then dialyses in the distilled water containing 0.1% mercaptoethanol removes little molecule thing
Matter, is centrifuged off deposit, and centrifugal speed is 7000rpm, and centrifugation time 0.25h then takes supernatant.To obtaining
Supernatant concentrate, obtain quality than the pure keratin solution that concentration is 10%.
Add PEO powder and appropriate distilled water to quality than in the keratin solution that concentration is 10%, make keratin/PEO
Mass ratio be 90/10, stir under the conditions of temperature is 45 DEG C and be completely dissolved to PEO powder, mix with keratin solution
Uniformly, obtain quality than the blend spinning liquid that concentration is 11%, and backward spinning liquid is added dropwise over ethylene glycol bisthioglycolate and shrinks sweet
Oil ether, the mass percent of Ethylene glycol diglycidyl ether is the 1.68% of spinning liquid, after uniform stirring 30min, adds
In needle type static spinning equipment, preparing keratin/PEO nano fibrous membrane, concrete operations condition is: under normal temperature condition,
Applied voltage 18KV, receiving range 12cm, rate of flooding 0.3ml/h, electrostatic spinning a period of time obtains keratin/PEO
Nano fibrous membrane.Above-mentioned keratin/PEO nano fibrous membrane is suspended in the hot-air that temperature is 120 DEG C crosslinking 4h.
Embodiment 2
After rabbit fur fibre is carried out successively shredding, remove impurity, cleaning and dry, cut into the segment of fiber of 5-10mm, then
It is immersed in PH for 9 for 12g/250ml, in the solution containing reducing agent and protein denaturant, at 60 DEG C of bars with solid-to-liquid ratio
Stirring 14h under part, the rotating speed of agitator is 250r/min.Wherein reducing agent is TGA, and quality is solution than concentration
5%；Protein denaturant is thiourea, and quality is the 25% of solution than concentration.Mixed solution after stirring 100 eye mesh screens
Unreacted fiber is gone out in filtration, and the 48h that then dialyses in the distilled water containing 0.1% mercaptoethanol removes little molecule thing
Matter, is centrifuged off deposit, and centrifugal speed is 6500rpm, and centrifugation time 0.3h then takes supernatant.To obtaining
Supernatant concentrate, obtain quality than the pure keratin solution that concentration is 12%.
Add PEO powder and appropriate distilled water to quality than in the keratin solution that concentration is 12%, make keratin/PEO
Mass ratio be 92/8, stir under the conditions of temperature is 50 DEG C and be completely dissolved to PEO powder, mix all with keratin solution
Even, obtain quality than the blend spinning liquid that concentration is 12%, and backward spinning liquid is added dropwise over ethylene glycol diglycidyl
Ether, the mass percent of Ethylene glycol diglycidyl ether is the 2.48% of spinning liquid, after uniform stirring 30min, joins
In needle type static spinning equipment, preparing keratin/PEO nano fibrous membrane, concrete operations condition is: under normal temperature condition, outward
Making alive 25KV, receiving range 15cm, rate of flooding 0.5ml/h, electrostatic spinning a period of time obtains keratin/PEO
Nano fibrous membrane.Above-mentioned keratin/PEO nano fibrous membrane is suspended in the hot-air that temperature is 130 DEG C crosslinking 3h.
Embodiment 3
After Pilus Sus domestica fiber is carried out successively shredding, remove impurity, cleaning and dry, cut into the segment of fiber of 5-10mm, then
It is immersed in PH for 9 for 14g/250ml, in the solution containing reducing agent and protein denaturant, at 68 DEG C of bars with solid-to-liquid ratio
Stirring 10h under part, the rotating speed of agitator is 300r/min, and wherein reducing agent is dithiothreitol, DTT, and quality is solution than concentration
4.5%；Protein denaturant is lithium bromide, and quality is the 25% of solution than concentration.Mixed solution after stirring is with 150
Eye mesh screen filters away unreacted fiber, and the 72h that then dialyses in the distilled water containing 0.1% mercaptoethanol removes little point
Sub-material, is centrifuged off deposit, and centrifugal speed is 6000rpm, and centrifugation time 0.5h then takes supernatant.Right
The supernatant obtained concentrates, and obtains quality than the pure keratin solution that concentration is 12.5%.
Add PEO powder and appropriate distilled water to quality than in the keratin solution that concentration is 12.5%, make keratin/PEO
Mass ratio be 94/6, stir under the conditions of temperature is 60 DEG C and be completely dissolved to PEO powder, mix all with keratin solution
Even, obtain quality than the blend spinning liquid that concentration is 12%.And backward spinning liquid is added dropwise over ethylene glycol diglycidyl
Ether, the mass percent of Ethylene glycol diglycidyl ether is the 3.73% of spinning liquid, after uniform stirring 30min, joins
In needle type static spinning equipment, preparing keratin/PEO nano fibrous membrane, concrete operations condition is: under normal temperature condition, outward
Making alive 20KV, receives away from spending 15cm, rate of flooding 0.5ml/h, and electrostatic spinning a period of time obtains keratin/PEO
Nano fibrous membrane.Above-mentioned keratin/PEO nano fibrous membrane is suspended in the hot-air that temperature is 140 DEG C crosslinking 2h.
Embodiment 4
After chicken feather fibers is carried out successively shredding, remove impurity, cleaning and dry, cut into the segment of fiber of 5-10mm, then
It is immersed in PH for 9 for 16g/250ml, in the solution containing reducing agent and protein denaturant, at 80 DEG C of bars with solid-to-liquid ratio
Stirring 6h under part, the rotating speed of agitator is 400r/min.Wherein reducing agent is mercaptoethanol, and quality is solution than concentration
8%；Protein denaturant is thiourea, and quality is the 20% of solution than concentration.Mixed solution after stirring 150 eye mesh screens
Unreacted fiber is gone out in filtration, and the 72h that then dialyses in the distilled water containing 0.1% mercaptoethanol removes little molecule thing
Matter, is centrifuged off deposit, and centrifugal speed is 6000rpm, and centrifugation time 0.5h then takes supernatant.To obtaining
Supernatant concentrate, obtain quality than the pure keratin solution that concentration is 13%.
Add, than in the keratin solution that concentration is 13%, the distilled water that PEO powder is appropriate to quality, make keratin/PEO
Mass ratio be 95/5, stir under the conditions of temperature is 50 DEG C and be completely dissolved to PEO powder, mix all with keratin solution
Even, obtain quality than the blend spinning liquid that concentration is 13%.And backward spinning liquid is added dropwise over ethylene glycol diglycidyl
Ether, the mass percent of Ethylene glycol diglycidyl ether is the 6.21% of spinning liquid, after uniform stirring 30min, joins
In needle type static spinning equipment, prepare keratin/PEO nano fibrous membrane.Concrete operations condition is: under normal temperature condition, outward
Making alive 30KV, receiving range 18cm, rate of flooding 0.8ml/h, and Electrospun a period of time obtains keratin/PEO
Nano fibrous membrane.Above-mentioned keratin/PEO nano fibrous membrane is suspended in the hot-air that temperature is 140 DEG C crosslinking 2h.
Embodiment 5
After ox hair fiber is carried out successively shredding, remove impurity, cleaning and dry, cut into the segment of fiber of 5-10mm, then
It is immersed in PH for 9 for 10g/250ml, in the solution containing reducing agent and protein denaturant, at 75 DEG C of bars with solid-to-liquid ratio
Stirring 6h under part, the rotating speed of agitator is 350r/min.Wherein reducing agent is dithiothreitol, DTT, and quality is solution than concentration
7%；Protein denaturant is carbamide, and quality is the 22% of solution than concentration.Mixed solution after stirring 100 mesh sieves
Net filtration goes out unreacted fiber, and the 36h that then dialyses in the distilled water containing 0.1% mercaptoethanol removes little molecule thing
Matter, is centrifuged off deposit, and centrifugal speed is 5000rpm, and centrifugation time 1h then takes supernatant.To obtain
Supernatant concentrates, and obtains quality than the pure keratin solution that concentration is 12.5%.
Add PEO powder to quality than in the keratin solution that concentration is 12.5%, add appropriate distilled water, make angle egg
The mass ratio of in vain/PEO is 95/5, stirs to PEO powder and be completely dissolved under the conditions of temperature is 50 DEG C, molten with keratin
Liquid mix homogeneously, obtains quality than the blend spinning liquid that concentration is 13%.And backward spinning liquid is added dropwise over ethylene glycol bisthioglycolate
Glycidyl ether, the mass percent of Ethylene glycol diglycidyl ether is the 4.97% of spinning liquid, uniform stirring 30min
After, joining in needle type static spinning equipment, prepare keratin PEO nano fibrous membrane, concrete operations condition is: room temperature
Under the conditions of, applied voltage 25KV, receiving range 15cm, rate of flooding 0.5ml/h, electrostatic spinning a period of time obtains angle
Albumen/PEO nano fibrous membrane.Above-mentioned keratin PEO nano fibrous membrane is suspended in the hot-air that temperature is 120 DEG C friendship
Connection 5h.
Embodiment 6
After Crinis Carbonisatus fiber is carried out successively shredding, remove impurity, cleaning and dry, cut into the segment of fiber of 5-10mm, then
It is immersed in PH for 9 for 14g/250ml, in the solution containing reducing agent and protein denaturant, at 80 DEG C of bars with solid-to-liquid ratio
Stirring 4h under part, the rotating speed of agitator is 200r/min.Wherein reducing agent is TGA, and quality is solution than concentration
5%；Protein denaturant is thiourea, and quality is the 25% of solution than concentration.Mixed solution after stirring 150 eye mesh screens
Unreacted fiber is gone out in filtration, and the 36h that then dialyses in the distilled water containing 0.1% mercaptoethanol removes little molecule thing
Matter, is centrifuged off deposit, and centrifugal speed is 5000rpm, and centrifugation time 1h then takes supernatant.To obtain
Supernatant concentrates, and obtains quality than the pure keratin solution that concentration is 13.5%.
Add PEO powder and appropriate distilled water to quality than in the keratin solution that concentration is 13.5%, make keratin/PEO
Mass ratio be 93/7, stir under the conditions of temperature is 60 DEG C and be completely dissolved to PEO powder, mix all with keratin solution
Even, obtain quality than the blend spinning liquid that concentration is 14%.And backward spinning liquid is added dropwise over ethylene glycol diglycidyl
Ether, the mass percent of Ethylene glycol diglycidyl ether is the 6.21% of spinning liquid, after uniform stirring 30min, joins
In needle type static spinning equipment, preparing keratin PEO nano fibrous membrane, concrete operations condition is: under normal temperature condition, outward
Making alive 28KV, receiving range 18cm, rate of flooding 0.5ml/h, electrostatic spinning a period of time obtains keratin/PEO
Nano fibrous membrane.Above-mentioned keratin/PEO nano fibrous membrane is suspended in the hot-air that temperature is 120 DEG C crosslinking 2h.
Claims (9)
1. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion, it is characterised in that this is prepared
Method be by the keratin concentrated solution extracted through reducing process by the natural keratin fiber discarded with PEO powder according to keratin
/ PEO mass percent 95-90: 5-10 is blended, and obtains keratin/PEO mixed solution, adds second two in this mixed solution
The crosslinking of alcohol diglycidyl ether obtains the spinning liquid with good spinnability, then prepares keratin by electrostatic spinning technique
/ PEO nano fibrous membrane, by this film after heat cross-linking, obtains keratin/PEO that water-fast keratin content is 90-95%
Biological nano fibrous membrane.
2. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, it is special
Levying and be, described discarded natural keratin fiber is discarded ox hair, Pilus Caprae seu Ovis, Crinis Carbonisatus, the rabbit hair, Pilus Sus domestica or camel hair etc..
3. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, its
Being characterised by, described reducing process agents useful for same is reducing agent, keratinous degeneration agent and the compositions of surfactant, described
Reducing agent be 2 mercapto ethanol (being also called beta-mercaptoethanol), dithiothreitol, DTT, TGA etc., the quality hundred of reducing agent
Proportion by subtraction concentration is 4%-7%；Described keratinous degeneration agent is carbamide, thiourea or lithium bromide, the quality hundred of protein denaturant
Proportion by subtraction concentration is 18-25%；Described surfactant is sodium lauryl sulphate, the mass percent concentration of surfactant
For 1-5%.
4. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, it is special
Levying and be, concrete operation step is:
1. by cutting off into the segment of fiber of 5-10mm after natural keratin fiber shredding, remove impurity, then oils and fats is removed with petroleum ether
Deng impurity, after deionized water is cleaned, naturally dry；
2. above-mentioned natural keratin fiber is immersed in containing reducing agent, protein denaturant with solid-to-liquid ratio for 12-16g/250ml
With in the lysate of the PH=9.0 of surfactant, stirring 8-12h at a temperature of 60-70 DEG C, agitator speed is
200-400r/min；
3. mixture 80-150 eye mesh screen stirring obtained filters removes undissolved natural keratin fiber, at room temperature bar
Under part, the keratin saline solution being filtrated to get is dialysed, remove the salt in solution and small-molecule substance；
4. the keratin obtained dialysis is centrifuged removing the sediment fraction in dialysis solution, and centrifugal speed is 5000-7000rpm,
Centrifugation time 0.2-1h, then takes supernatant；
5. above-mentioned supernatant is concentrated, obtain the keratin concentrated solution that mass percent concentration is 10-14%.
5. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, it is special
Levying and be, the mass percent concentration of described keratin/PEO mixed solution is 11-14%.
6. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, it is special
Levy and be, described crosslinking be use mass percent concentration be that the Ethylene glycol diglycidyl ether of 1.68-6.21% is to spinning liquid
In keratin cross-link.The method of crosslinking is: under conditions of 50-65 DEG C, the most uniform in spinning liquid while stirring
Add Ethylene glycol diglycidyl ether keratin/PEO blend spinning liquid to cross-link.
7. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, it is special
Levying and be, described electrostatic spinning can use the electrospinning process such as needle-based, bubble type, disc type, and spinning condition is:
Under room temperature condition, applied voltage 20-30KV, spinning receiving range 13-18cm, rate of flooding is 0.3-1.0ml/h.
8. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, it is special
Levying and be, described heat cross-linking is that keratin/PEO biological nano fibrous membrane is suspended in the hot-air of 120-140 DEG C and is carried out
Heat cross-linking 2-6h.
9. the preparation method of the keratin/PEO nano fibrous membrane of keratin content at high proportion as claimed in claim 1, it is special
Levying and be, the keratin content of the keratin/PEO nano fibrous membrane of the described content of keratin at high proportion is 90-95%.
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| CN110106634A (en) * | 2019-05-13 | 2019-08-09 | 天津工业大学 | A kind of keratin PEO compound bio nano fibrous membrane and preparation method thereof and bandage |
| CN111893580A (en) * | 2020-06-17 | 2020-11-06 | 中山大学 | Keratin spinning solution and prepared keratin regenerated fiber |
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Application publication date: 20160727 |