CN106283399A - A kind of arrange orderly modified nano fiber film and preparation thereof and application - Google Patents
A kind of arrange orderly modified nano fiber film and preparation thereof and application Download PDFInfo
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- CN106283399A CN106283399A CN201610655944.1A CN201610655944A CN106283399A CN 106283399 A CN106283399 A CN 106283399A CN 201610655944 A CN201610655944 A CN 201610655944A CN 106283399 A CN106283399 A CN 106283399A
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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
- D04H1/74—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 orientated, e.g. in parallel (anisotropic fleeces)
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
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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
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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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/123—Polyaldehydes; Polyketones
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Wood Science & Technology (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
Abstract
The present invention relates to a kind of arrange orderly modified nano fiber film and preparation thereof and application, nano fibrous membrane is Polycaprolactone modified collagen protein/fibroin fiber film, and nanofiber membrane aperture is 10 25 μm.Preparation: collagen protein, fibroin albumen, polycaprolactone are dissolved in solvent, stirring and evenly mixing, obtain spinning liquid；Under room temperature condition, spinning liquid carries out electrostatic spinning, is dried, cross-links, washing, and vacuum drying to obtain final product.Application as cell culturing bracket.The method of the present invention is simple, simple operation, the fibrous membrane that fiber alignment is orderly is obtained by blending and modifying and change catcher, improve the porosity of fibrous membrane, and its mechanical property and biocompatibility are good, be conducive to cell to enter internal stent growth, have a good application prospect in terms of cell cultivation.
Description
Technical field
The invention belongs to nano material and preparation thereof and application, arrange orderly modified Nano fibre particularly to a kind of
Tie up film and preparation thereof and application.
Background technology
Electrostatic spinning technique is the method using most common production nanofiber in the world at present, and electrostatic spinning has to be received
Rice or the fibre dimensions of micron, aperture is little, porosity is high, and is evenly distributed, at nanofiltration material, sensing material, particularly
The aspects such as biological support modification, medical material, organizational project are widely used, and present electrostatic spinning technique has become as preparation tissue
The most important method of one of engineering rack.
Collagen protein and fibroin albumen are natural polymer, are respectively provided with preferable biocompatibility, in biomedical direction
There is boundless application prospect, can be used for preparing Electrospun nano-fibers film, but its mechanical property is poor, should in the later stage
Used time has problems.
Electrostatic spinning apparatus is typically made up of syringe pump, high voltage power supply and reception device.After spinning starts, fiber is flat
Continuous dispersed deposition on plate receptor, owing to having potential gradient between injection needle and reception plate, causes fiber preferential accumulation
In the position that distance injection point is nearest, deposit with layered form, ultimately form the close two-dimensional structure of fiber alignment, the cause of fiber
Solid matter row cause the aperture of spinning fibre less, apply in terms of tissue engineering bracket, cell can be caused to cannot be introduced into support
Growth inside.
The cell of support is cultivated performance and is had important effect by the pore size of electrospun scaffolds and order.In order
Spinning fibre can promote sticking, survive and breeding of cell, guide cell migration, increase on the basis of orderly spinning fibre
The aperture of big support, beneficially cell enter internal stent growth, and promote the transmission of nutrient substance and the row of metabolite
Go out.The method utilizing change reception device to obtain ordered nano-fibers mainly has cylinder to collect, rotating disk is collected, with isolation port
Conductive plate collection etc., collection method obtains major part is ordered fiber arranged in parallel, it is impossible to obtain bigger the having in aperture
Sequence fiber.
Therefore, for the problems referred to above, it is necessary to provide a kind of and can prepare modified collagen albumen/fibroin egg that arrangement is orderly
The method of white fiber film, to solve problems of the prior art.
Summary of the invention
The technical problem to be solved be to provide a kind of arrange orderly modified nano fiber film and preparation and
Application, the method for the present invention is simple, simple operation, obtains, by blending and modifying and change catcher, the fiber that fiber alignment is orderly
Film, improves the porosity of fibrous membrane, and its mechanical property and biocompatibility is well, and beneficially cell enters internal stent
Growth, has a good application prospect in terms of cell cultivation.
The a kind of of the present invention arranges orderly modified nano fiber film, and described nano fibrous membrane is Polycaprolactone modified glue
Former albumen/
Fibroin fiber film, nanofiber membrane aperture is 10-25 μm.
A kind of preparation method arranging orderly modified nano fiber film of the present invention, including:
(1) collagen protein, fibroin albumen, polycaprolactone are dissolved in solvent, stirring and evenly mixing, obtain spinning liquid；
(2) under room temperature condition, in step (1), spinning liquid carries out electrostatic spinning, is dried, and obtains white ordered fiber film；Its
The middle electrostatic spinning device that receives used is probe catcher；
(3) the white ordered fiber film that step (2) obtains is cross-linked, washing, vacuum drying, must arrange orderly
Modified composite fiber film.
In described step (1), collagen protein, fibroin albumen, the mass ratio of polycaprolactone are 0.5～5:0.5～5:1～10.
In described step (1), solvent is hexafluoroisopropanol；The concentration of spinning liquid is 8～10wt%.
Electrostatic spinning in described step (2) specifically comprises the processes of: electrostatic spinning voltage is 12～18kV, spinning syringe needle and reception
Distance between device is 10～15cm, and the fltting speed of syringe pump is 1～1.5mL/h.
Described step (2) middle probe catcher is to be embedded aluminium foil flat receiver by probe to form probe array made, as
Shown in Fig. 1, probe array is 4 × 4～8 × 8；Between probe catcher middle probe, spacing is 2～4cm.
Described step (2) is dried into vacuum drying oven is dried 2～3 days.
In described step (3), crosslinking is: glutaraldehyde vapor crosslinking, crosslinking time is 4-12h.
Described glutaraldehyde vapor crosslinking, particularly as follows: fibrous membrane is put in vacuum desiccator, puts into glutaraldehyde molten in exsiccator
Liquid, carries out glutaraldehyde vapor crosslinking, and wherein the concentration of glutaraldehyde solution is 25～50wt%.
Washing is in described step (3): wash 2～4 days, is vacuum dried and is: vacuum drying oven is dried 1～2 day.
A kind of application arranging orderly modified nano fiber film of the present invention, the nano fibrous membrane work that described arrangement is orderly
Application for cell injuring model support.
Beneficial effect
(1) method of the present invention is simple, easy to operate, high by natural polymer collagen protein, fibroin albumen and synthesis
Molecule polycaprolactone is blended, and strengthens the mechanical property of electrospun fibers film；
(2) present invention is by changing the shape of catcher, and the probe catcher preparation utilizing probe array to be formed is arranged with
The fiber of sequence, the needle point of probe is most advanced and sophisticated, and same probe exists point effect, and tip portion charge density is relatively big, near it
Electric field intensity is the strongest, and during electrostatic spinning, fiber drops near needle point in electric field force effect, and charged fiber is by point
The electric field of end attracts maximum, guides fiber to needle point drift so that fiber overlaps in order along the shape between needle point and direction,
Form the nano fibrous membrane that arrangement is orderly and aperture is bigger；
(3) support prepared by the present invention is when the later stage carries out cell cultivation, has certain mechanical strength can preferably support carefully
Born of the same parents grow on fibrous membrane, and the bigger fibrous membrane in aperture makes cell have three dimensional growth to be inclined to, and can promote cell adhesion and propagation, and
And promote transmission and the discharge of metabolite of nutrient substance.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of preparation method middle probe catcher；
Fig. 2 is the optical microscope photograph of ordered fiber film prepared by 6 × 6 probe catchers in embodiment 1；
Fig. 3 is the optical microscope photograph of ordered fiber film prepared by 7 × 7 probe catchers in embodiment 2；
Fig. 4 is the SEM photograph of ordered fiber film prepared by 6 × 6 probe catchers in embodiment 1；
Fig. 5 is the SEM photograph of ordered fiber film prepared by 7 × 7 probe catchers in embodiment 2；
Fig. 6 is the mechanical property figure of the ordered fiber film of preparation in embodiment 1,2,3.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Embodiment 1
(1) collagen protein, fibroin albumen, polycaprolactone are added hexafluoroisopropanol solvent with mass ratio for 3.5:3.5:3
In, the concentration of spinning liquid is 8wt%, after being sufficiently stirred for, finally gives uniform spinning liquid.
(2) spinning liquid prepared is put in syringe, and put in syringe pump, by syringe needle and high tension generator anode phase
Even, with probe receptacle for receiving device, probe array is 6 × 6, and the distance between probe is 3cm, probe receptacle and negative electrode
Being connected, voltage is 15kV, and spinning syringe needle is 12cm with the distance at probe receptacle tip, and the fltting speed of syringe pump is 1mL/h.
After electrostatic spinning, probe catcher is collected one layer of obvious uniform sequential white fiber film.The fibrous membrane obtained
Put in vacuum drying oven and be dried 2 days.
(3) fibrous membrane that electrostatic spinning obtains is put into vacuum desiccator, bottom exsiccator, put into culture dish, culture dish
In fill the glutaraldehyde solution that concentration is 25%, evacuation carries out taking out after glutaraldehyde vapor crosslinking 12h, carries out water with ultra-pure water
Wash 2 days, put in vacuum drying oven and be dried 1 day.Fig. 2 is the optical microscope photograph before the crosslinking of electrospun fibers film.Fig. 4 is quiet
The SEM photograph of electrospun fiber membrane shows that fiber is in defining bigger aperture between ordered arrangement, and fiber, fibrous membrane
Average pore size is 14.7 μm.Fig. 6 is fibrous membrane mechanical property figure, shows that the fracture strength of the fibrous membrane after crosslinking is 3.1MPa.
Embodiment 2
(1) collagen protein, fibroin albumen, polycaprolactone are added hexafluoroisopropanol solvent with mass ratio for 3.5:3.5:3
In, the concentration of spinning liquid is 8wt%, after being sufficiently stirred for, finally gives uniform spinning liquid.
(2) spinning liquid prepared is put in syringe, and put in syringe pump, by syringe needle and high tension generator anode phase
Even, with probe receptacle for receiving device, probe array is 7 × 7, and the distance between probe is 2.5cm, and probe receptacle is with cloudy
The most connected, voltage is 15kV, and spinning syringe needle is 12cm with the distance at probe receptacle tip, and the fltting speed of syringe pump is 1mL/
h.After electrostatic spinning, probe catcher is collected one layer of obvious uniform sequential white fiber film.The fiber obtained
Film is put in vacuum drying oven and is dried 2 days.
(3) fibrous membrane that electrostatic spinning obtains is put into vacuum desiccator, bottom exsiccator, put into culture dish, culture dish
In fill the glutaraldehyde solution that concentration is 25%, evacuation carries out taking out after glutaraldehyde vapor crosslinking 12h, carries out water with ultra-pure water
Wash 2 days, put in vacuum drying oven and be dried 1 day.Fig. 3 is the optical microscope photograph before the crosslinking of electrospun fibers film.Fig. 5 is quiet
The SEM photograph of electricity spinning fibre film shows that fiber is in ordered arrangement, the fibre that in comparing embodiment 1 prepared by 6 × 6 probe catchers
Dimension film is the most orderly, and the aperture formed between fiber is bigger, and the average pore size of fibrous membrane is 15.9 μm.Fig. 6 is fibrous membrane
Mechanical property figure, shows that the fracture strength of the fibrous membrane after crosslinking is 6.1MPa, 6 × 6 probe catcher system in comparing embodiment 1
Standby fibrous membrane, fibrous membrane mechanical property prepared by 7 × 7 probe catchers is more preferable.
Embodiment 3
(1) collagen protein, fibroin albumen, polycaprolactone are added hexafluoroisopropanol solvent with mass ratio for 3.5:3.5:3
In, the concentration of spinning liquid is 8wt%, after being sufficiently stirred for, finally gives uniform spinning liquid.
(2) spinning liquid prepared is put in syringe, and put in syringe pump, by syringe needle and high tension generator anode phase
Even, with probe receptacle for receiving device, probe array is 8 × 8, and the distance between probe is 2cm, probe receptacle and negative electrode
Being connected, voltage is 15kV, and spinning syringe needle is 12cm with the distance at probe receptacle tip, and the fltting speed of syringe pump is 1mL/h.
After electrostatic spinning, probe catcher is collected one layer of obvious uniform sequential white fiber film.The fibrous membrane obtained
Put in vacuum drying oven and be dried 2 days.
(3) fibrous membrane that electrostatic spinning obtains is put into vacuum desiccator, bottom exsiccator, put into culture dish, culture dish
In fill the glutaraldehyde solution that concentration is 25%, evacuation carries out taking out after glutaraldehyde vapor crosslinking 12h, carries out water with ultra-pure water
Wash 2 days, put in vacuum drying oven and be dried 1 day.The SEM photograph of electrospun fibers film shows that fiber is in ordered arrangement, and
Defining bigger aperture between fiber, the average pore size of fibrous membrane is 13.2 μm.Fig. 6 is fibrous membrane mechanical property figure, fiber
Film dynamic performance test shows that the fracture strength of the fibrous membrane after crosslinking is 4.1MPa.
Claims (10)
1. the modified nano fiber film that an arrangement is orderly, it is characterised in that: described nano fibrous membrane is Polycaprolactone modified
Collagen protein/fibroin fiber film, nanofiber membrane aperture is 10-25 μm.
2. a preparation method for the modified nano fiber film that arrangement as claimed in claim 1 is orderly, including:
(1) collagen protein, fibroin albumen, polycaprolactone are dissolved in solvent, stirring and evenly mixing, obtain spinning liquid；
(2) under room temperature condition, in step (1), spinning liquid carries out electrostatic spinning, is dried, obtains fibrous membrane；Wherein electrostatic spinning institute
It is probe catcher with reception device；
(3) fibrous membrane that step (2) obtains is cross-linked, washing, vacuum drying, orderly modified composite fiber must be arranged
Film.
A kind of preparation method arranging orderly modified nano fiber film the most according to claim 2, it is characterised in that: institute
State collagen protein in step (1), fibroin albumen, the mass ratio of polycaprolactone are 0.5～5:0.5～5:1～10.
A kind of preparation method arranging orderly modified nano fiber film the most according to claim 2, it is characterised in that: institute
Stating solvent in step (1) is hexafluoroisopropanol；The concentration of spinning liquid is 8～10wt%.
A kind of preparation method arranging orderly modified nano fiber film the most according to claim 2, it is characterised in that: institute
State electrostatic spinning in step (2) specifically comprises the processes of: electrostatic spinning voltage is 12～18kV, between spinning syringe needle and receptor away from
From for 10～15cm, the fltting speed of syringe pump is 1～1.5mL/h；Probe catcher is to be embedded aluminium foil flat board by probe to receive
It is made that device forms probe array, and probe array is 4 × 4～8 × 8；Between probe catcher middle probe, spacing is 2～4cm.
A kind of preparation method arranging orderly modified nano fiber film the most according to claim 2, it is characterised in that: institute
State and step (2) is dried into vacuum drying oven is dried 2～3 days.
A kind of preparation method arranging orderly modified nano fiber film the most according to claim 2, it is characterised in that: institute
Stating crosslinking in step (3) is: glutaraldehyde vapor crosslinking, crosslinking time is 4-12h.
A kind of preparation method arranging orderly modified nano fiber film the most according to claim 7, it is characterised in that: institute
State glutaraldehyde vapor crosslinking particularly as follows: fibrous membrane is put in vacuum desiccator, exsiccator is put into glutaraldehyde solution, carry out penta 2
Aldehyde vapor crosslinking, wherein the concentration of glutaraldehyde solution is 25～50wt%.
A kind of preparation method arranging orderly modified nano fiber film the most according to claim 2, it is characterised in that: institute
Stating washing in step (3) is: wash 2～4 days, is vacuum dried and is: vacuum drying oven is dried 1～2 day.
10. the application of the modified nano fiber film that an arrangement as claimed in claim 1 is orderly, it is characterised in that: described row
Show the nano fibrous membrane application as cell injuring model support of sequence.
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Cited By (4)
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| CN109629037A (en) * | 2018-12-10 | 2019-04-16 | 武汉大学 | Modified polycaprolactone nano fiber scaffold of a kind of triazine fibroin albumen and the preparation method and application thereof |
| CN110257930A (en) * | 2019-06-27 | 2019-09-20 | 东华大学 | A kind of three-dimensional needle plate reception device being used to prepare fluffy electrostatic spinning nano fibre web |
| CN112281316A (en) * | 2020-09-27 | 2021-01-29 | 福建华阳超纤有限公司 | High-quality imitation cow leather superfine fiber leather processing system |
| CN113604964A (en) * | 2021-09-07 | 2021-11-05 | 北京化工大学 | Ordered composite fiber membrane and preparation method and application thereof |
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| CN113604964A (en) * | 2021-09-07 | 2021-11-05 | 北京化工大学 | Ordered composite fiber membrane and preparation method and application thereof |
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Application publication date: 20170104 |