CN107261209A - A kind of method of use phyllosilicate/chitosan self-assembled modified micro/nano-fibre film layer by layer - Google Patents
A kind of method of use phyllosilicate/chitosan self-assembled modified micro/nano-fibre film layer by layer Download PDFInfo
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Abstract
The invention discloses a kind of method of use phyllosilicate/chitosan self-assembled modified micro/nano-fibre film layer by layer, belong to field of material technology.The present invention first prepares electrically charged micro/nano-fibre film as substrate, alternately the chitosan or phyllosilicate of oppositely charged are assembled on substrate according to the powered situation of substrate, and dry gained micro/nano-fibre film, obtain the composite micro/nano tunica fibrosa of double-deck number number of plies for needed for.Greatly improved by modified micro/nano-fibre film mechanical performance, hydrophily increase while possessing biocidal property, and is more suitable for Gegenbaur's cell sticking, grow and breaking up on its surface.The present invention chooses phyllosilicate separately as assembled material first, and with mild condition, technique is simple, does not have any limitation, many advantages, such as modifying process does not introduce other impurities and do not produce other accessory substances to the size and dimension of baseboard material.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of phyllosilicate/chitosan is self-assembled modified layer by layer
The method of micro/nano-fibre film.
Background technology
For decades, the development of bone tissue engineer has made millions of patients with Cranial defect and bone wound all over the world
From wrecking for the serious illness.Therefore the research of bone tissue engineering scaffold also obtain substantial amounts of concern.Preferable bone tissue engineer branch
Frame should meet two basic demands.First, support should have certain mechanical strength, can resist external force, and keep its physics
Stability Analysis of Structures, so as to ensure the cell growth and tissue development of stabilization.In addition, suitable surface nature and excellent bio-compatible
Property for its promote Gegenbaur's cell adhesion, breed and break up most important.
Micro/nano-fibre film in medicament slow release, was adsorbed as a kind of micro/nano material with special three-dimensional structure
Filter, etc. field be widely used, further, since its have the 3-D solid structure similar to extracellular matrix, being capable of analog cell
Epimatrix structure simultaneously provides cell growth and the support of adhesion, therefore it is also a kind of important tissue engineering material.Mostly micro-/
The mechanical strength of nanofiber is weak, and surface is smooth, is unfavorable for the stable growth of cell, therefore before applied to organizational project, needs
Necessary modification is carried out to it.Chitosan is as unique positively charged natural alkaline polysaccharide, with excellent bio-compatible
Property and antibacterial activity, can introduce anti-microbial property while ensure material biocompatibility not be destroyed.Phyllosilicate can
The mechanical strength of reinforcing material, the roughness on controllable micro/nano-fibre film surface, while the biocidal property of chitosan can be promoted
Can, both materials are the materials that preferably can be used for micro/nano-fibre membrane modifying.
Chinese patent " a kind of modification micro/nano-fibre film of aligned orderly and its preparation and application " (publication number
CN106283399A a kind of modification micro/nano-fibre film of aligned orderly and its preparation method and application prospect) is disclosed.Specifically
Method is：Collagen, fibroin albumen, polycaprolactone are blended in certain proportion, spinning solution is made, and carry out Static Spinning
Silk, is dried, the step such as crosslinking.Orderly micro/nano-fibre is prepared by the collector for being blended and changing Static Spinning, and reaches and changes
Property purpose.Although being modified in the patent be on micro/nano-fibre film carry out, its be by be blended and change collector come
It is modified.In field of tissue engineering technology, due to being related to adhesion, the growth of cell, the surface characteristic of material has for its performance
Important influence, the modified method of blending can not only change the surface of material, can more change the main body of material, make body of material
Structure and performance bring unknown change.And the method for modifying of LBL self-assembly is repaiied on the surface of micro/nano-fibre
Decorations, do not change original component of the micro/nano-fibre.
Layer-by-layer is as the multi-functional potential modification technology of one kind, with simple to operate, and cost is low, is applicable
Property it is strong, the advantages of size to substrate and shape no requirement (NR), can complete to controllable modified on substrate micro-/ nano yardstick, and change
The selection of property material is quite varied.During LBL self-assembly, the polyelectrolyte with opposite charges progressively, is alternately inhaled
Attached, the process operation is easy and will not produce other accessory substances.In addition, the LBL self-assembly technique phase with the progress on flat board
Than the research that LBL self-assembly modification is carried out on micro/nano-fibre film is more rare, and it includes the modification of two aspects：
(1) it is modified on the surface of every micro/nano-fibre；(2) it is modified in the macro surface of micro/nano-fibre film.In layer
After layer self assembling process, the multi-level modification of micro/nano-fibre film multi-level structure will be obtained.
Based on above-mentioned consideration, selection micro/nano-fibre is as bottom plate, and chitosan is used as positive electricity layer component and phyllosilicate
As negative electricity layer component, micro/nano-fibre film is modified using the method for LBL self-assembly, obtains and possesses stronger machinery
The micro/nano-fibre film of performance, bacteriostasis property and good biocompatibility, has in field of tissue engineering technology before boundless application
Scape.
The content of the invention
Present invention aims at provide one kind to carry out micro/nano-fibre film layer by layer certainly using chitosan and phyllosilicate
The method of assembling modification.This method can be modified to micro/nano-fibre film, improved its physics and biological property, prepared
It is more suitable for the micro/nano-fibre film of bone tissue engineer.
The purpose of the present invention is achieved through the following technical solutions：
The method of a kind of use phyllosilicate/chitosan self-assembled modified micro/nano-fibre film layer by layer, with electrically charged
Micro/nano-fibre film, as substrate, is timing when substrate institute is electrically charged, poly- in substrate over-assemble phyllosilicate and shell successively
Sugar, until double-deck number needed for reaching；When it is negative that substrate institute is electrically charged, successively in substrate over-assemble chitosan and laminar silicic acid
Salt, until double-deck number needed for reaching, the micro/nano-fibre film after assembling is dried, modified micro/nano-fibre film is obtained.
Preferably, the zeta current potentials absolute value of the substrate is not less than 10mV.
Preferably, described required double-deck number is 1-50 layers.
Preferably, described electrically charged micro/nano-fibre ilm substrate is by fibroin albumen, collagen, acetate fiber
One or more of systems in element, Chitosan-phospholipid complex, PLLA, polycaprolactone, Poly(D,L-lactide-co-glycolide
For what is obtained.
Preferably, described micro/nano-fibre ilm substrate is by method of electrostatic spinning, wet spinning process, dry spinning method, centrifugation
Any of spin processes, phase separation method or composite spinning method are prepared.
Preferably, described chitosan is assembled by the following method：Chitosan-acetic acid solution is configured, substrate is soaked in band
In the chitosan-acetic acid solution of positive charge, after certain time, take the film out, the unassembled success in membrane removal surface is cleaned with cleaning fluid
Chitosan.
Preferably, described phyllosilicate is assembled by the following method：Stratiform silicalite suspension is configured, substrate is soaked
Steep in negatively charged laminar silicic acid salt suspensioning liquid, after certain time, take the film out, membrane removal surface is cleaned with cleaning fluid not
Assemble successful phyllosilicate.
Preferably, described chitosan-acetic acid solution concentration is 0.1-10mg/mL.
Preferably, described phyllosilicate is montmorillonite or rectorite.
Preferably, described phyllosilicate assembling suspension concentration is 0.1-10mg/mL.
Preferably, described cleaning fluid is deionized water or 0.01-1mol/L sodium chloride solution.
Preferably, described immersion built-up time is 10-60 minutes.
Preferably, described drying means is natural drying, vacuum freeze drying or dried in vacuum drying chamber, described
Dry to be completely dried.
A kind of use phyllosilicate/chitosan micro/nano-fibre film self-assembled modified layer by layer, passes through above-mentioned method system
It is standby to obtain.
The present invention is using micro/nano-fibre film as assembling substrate, by electrostatic force, alternately on its multilevel hierarchy surface
Assemble chitosan and phyllosilicate.The introducing of chitosan nano fibrous membrane is provided with antagonistic property and to maintain it good
Biocompatibility.And phyllosilicate is introduced in composite nano-fiber membrane separately as negatively charged assembled material, greatly
The big mechanical performance and surface characteristic for enhancing tunica fibrosa.The present invention has many advantages, such as, including mild condition, and technique is simple,
There is no any limitation to the size and dimension of baseboard material, modifying process does not introduce other impurities and do not produce other accessory substances
Deng.
Brief description of the drawings
Fig. 1 is the shape appearance figure of silk fibroin nano-fiber film prepared by embodiment 1 and modified nano fiber film.Left side in figure
Silk fibroin nano-fiber film surface scan electron microscope, right side be phyllosilicate/chitosan that double-deck number is 15.5 layer by layer
Self-assembly modified nano fiber film surface scan electron microscope.
Fig. 2 is the fiber diameter distribution profile of silk fibroin nano-fiber film prepared by embodiment 1 and modified nano fiber film.
A is the fiber diameter distribution profile of silk fibroin nano-fiber film, b be phyllosilicate/chitosan that double-deck number is 15.5 layer by layer
The fiber diameter distribution profile of self-assembly modified nano fiber film.
Fig. 3 is the contact angle anaplasia at any time of silk fibroin nano-fiber film prepared by embodiment 1 and modified nano fiber film
Change curve.A is that the contact angle of silk fibroin nano-fiber film changes over time curve, and b is the laminar silicic acid that double-deck number is 15.5
The contact angle of salt/chitosan self-assembly modified nano fiber film layer by layer changes over time curve.
Fig. 4 is tensile strength and the fracture of silk fibroin nano-fiber film and modified nano fiber film prepared by embodiment 1
Elongation comparison diagram.In figure, a represents silk fibroin nano-fiber film, and b represents phyllosilicate/chitosan layer that double-deck number is 5
Layer self-assembly modified nano fiber film, c represents phyllosilicate/chitosan self-assembled modified Nanowire layer by layer that double-deck number is 10
Film is tieed up, d represents phyllosilicate/chitosan self-assembly modified nano fiber film surface scan Electronic Speculum layer by layer that double-deck number is 15
Figure, e represents phyllosilicate/chitosan self-assembly modified nano fiber film layer by layer that double-deck number is 15.5.
Fig. 5 is the silk fibroin nano-fiber film that Gegenbaur's cell is prepared in embodiment 1 and modified nano fiber film surface
Cultivate the scanning electron microscope (SEM) photograph of growing state after 72 h.A represents silk fibroin nano-fiber film, and b represents the layer that double-deck number is 15.5
Shape silicate/chitosan self-assembly modified nano fiber film layer by layer.
Embodiment
Technical scheme is described further below by specific embodiment, its object is to help preferably
Understand present disclosure, but these specific embodiments are not in any way limit the scope of the present invention.
1, prepare electrically charged micro/nano-fibre film
By taking fibroin albumen as an example：
Fibroin albumen is dissolved in polyglycolic acid hexafluoroisopropanol solvent, magnetic agitation 24h, obtains 7wt% fibroin albumen spinning
Liquid.Then silk fibroin nano-fiber film is prepared by electrostatic spinning technique, electrostatic spinning relevant parameter is：Voltage is 16kV,
Spinning solution fltting speed is 1mL/h, and distance is 12cm between spinning pin and receiver, and relative temperature and relative humidity are respectively 25
DEG C and 40%.Then the electrospinning silk fibroin nano-fiber film of gained is dried in vacuo at 55 DEG C so that residual solvent is abundant
Volatilization.
Those skilled in the art can also select collagen, cellulose acetate, chitosan according to actual conditions and its spread out
Biology, chitosan oligosaccharide, PLA, Poly(D,L-lactide-co-glycolide, polycaprolactone, polystyrene, polymethyl methacrylate,
One or more of conducts in polyvinyl alcohol, methacrylated polyethyleneimine, polyacrylonitrile, polyurethane, polyisobutene
The raw material of micro/nano-fibre film, and prepared according to the appropriate solvent of the raw material selection of selection and preparation method.
Available solvent includes hexafluoroisopropanol, chloroform, dichloromethane, trifluoroacetic acid, tetrahydrofuran, benzene, first
Benzene, phenetole, chlorobenzene, N, N-dimethylformamide, DMAC N,N' dimethyl acetamide, Ethyl formate, ethyl acetate, acetic acid, phosphoric acid,
One or more as solvent in methanol, formic acid, amylalcohol, water, configuration concentration is 3-30wt% spinning solution.
Available preparation method includes method of electrostatic spinning, wet spinning process, dry spinning method, centrifugal spinning, phase point
From method and composite spinning method.
It is pointed out that those skilled in the art combine general knowledge known in this field for these raw materials, solvent, preparation side
The selection of method, has no effect on the present invention to the method for modifying of micro/nano-fibre film and the product finally given, using institute of the present invention
The method stated is modified to the micro/nano-fibre film that these raw materials, solvent and preparation method are obtained, and belongs to the guarantor of the present invention
Protect scope.
In addition, when itself neutral of micro/nano-fibre film that select or institute, electrically charged less (zeta current potential absolute values are small
In 10mV), can be by sol-gel technique, liquid deposition, vapour deposition, wet chemistry method, corona treatment, grafting altogether
Poly-, in-situ polymerization strengthens its surface charge.
By taking polycaprolactone as an example：
Polycaprolactone is dissolved in hexafluoroisopropanol, magnetic agitation 24h, obtains 10wt% polycaprolactone spinning solution.
Then polycaprolactone nano fibrous membrane is prepared by electrostatic spinning technique, electrostatic spinning relevant parameter is：Voltage is 15kV,
Spinning solution fltting speed is 2mL/h, and distance is 10cm between spinning pin and receiver, and relative temperature and relative humidity are respectively
25 DEG C and 40%.Then the electrospinning pla-pcl nano fibrous membrane of gained is dried in vacuo at 55 DEG C so that residual solvent fills
Divide volatilization.Wet chemistry method then is used, polycaprolactone is soaked 2 hours in 50% ethanol solution, then be placed on 1.0
In the 0.15mol/L of mg/mL polyvinylamine sodium chloride solution, taken out after 10 minutes, flushed three times, produced with deionized water
To positively charged polycaprolactone nano fibrous membrane.
By taking cellulose acetate as an example：
By acetone and DMA with 2:1 (w/w) ratio mixing, and cellulose acetate is dissolved in the mixing
In solution, 16wt% cellulose acetate spinning solution is obtained.Then cellulose acetate is prepared by electrostatic spinning technique to receive
Rice tunica fibrosa, electrostatic spinning relevant parameter is：Voltage is 16kV, and spinning solution fltting speed is 1mL/h, spinning pin and receiver it
Between distance be 15cm, relative temperature and relative humidity are respectively 25 DEG C and 45%.Then by the electrospinning pla-pcl nanometer of gained
Tunica fibrosa is dried in vacuo at 55 DEG C so that residual solvent fully volatilizees.Then gained cellulose acetate nano fibrous membrane is soaked
Steep in 0.05mol/L sodium hydroxide solutions 7 days, rinsed after taking-up with deionized water, obtain negatively charged cellulose nanometer
Tunica fibrosa.
By taking fibroin albumen as an example：
Phosphoric acid is mixed in different proportions with formic acid, fibroin albumen is dissolved in the mixed solution, it is mixed to this
Close solution to be filtered and defoaming treatment, obtain the fibroin albumen spinning solution that concentration is 15%；Using formic acid as solidification liquid, using wet
Method spining technology prepares micro/nano-fibre film.Wet spinning relevant parameter is：Spinning solution fltting speed is 30mL/h, relatively warm
Degree and relative humidity are respectively 25 DEG C and 40%.Then by the wet spinning fibroin micro/nano-fibre film of gained in methyl alcohol
24h is soaked, it is fully cured and is crystallized, and remove residual formic acid.Then fibroin albumen micro/nano-fibre is immersed 60 DEG C again
15 minutes in distilled water, 5 times of drawing-offs are then carried out.Tension force drying is finally carried out, prevents from shrinking in drying process.
2, LBL self-assembly modification is carried out to obtained micro/nano-fibre film
Embodiment 1
(1) the fibroin albumen micro/nano-fibre film that zeta current potentials are less than -10mV is obtained；
(2) Chitosan powder is added in 0.5wt% acetum, magnetic agitation 3-5h to solution clear,
Chitosan is fully dissolved, prepare the chitosan solution for obtaining that concentration is 1mg/mL.By the immersion of fibroin albumen micro/nano-fibre film
In the chitosan solution of gained, film is fully contacted with solution, taken the film out after 20 minutes, cleaned three times using deionized water
Remove the unassembled successful chitosan in membrane removal surface；
(3) rectorite is added in deionized water, is disperseed using Ultrasound Instrument, and it is the tired of 1mg/mL to prepare concentration
Stone suspension is held in the palm, in the rectorite suspension that the silk fibroin nano-fiber film for assembling chitosan is immersed in gained, makes film
Fully contact, taken the film out after 20 minutes with solution, clean three times using deionized water and go to membrane removal surface unassembled successfully tired
Stone is held in the palm, a bilayer has so far been assembled successfully；
(4) step (2) and step (3) are repeated in several times, gained micro/nano-fibre film is dried, is respectively obtained double
The number of plies is 5,10,15,15.5 composite micro/nano tunica fibrosa.
The pattern of gained silk fibroin nano-fiber film and modified nano fiber film is shown in that on the left of Fig. 1, Fig. 1 be that fibroin albumen is received
Rice tunica fibrosa surface scan electron microscope, is rectorite/chitosan that double-deck number is 15.5 self-assembled modified nanometer layer by layer on the right side of Fig. 1
Tunica fibrosa surface scan electron microscope.As can be seen that the microscopic appearance of the nanofiber after modified there occurs obvious change, table
Face is roughening.Moreover, it is 886 ± 143nm (Fig. 2) that modified average fibre diameter, which is 594 ± 112nm increases,.Meanwhile, it is modified
Nano fibrous membrane mechanical performance be enhanced to 5.64Mpa (Fig. 4), water contact angle is reduced to 60.3 ° (Fig. 3), and water contact angle exists
To be 0, hydrophily increase in 6.4s after being contacted with film.Compared with silk fibroin nano-fiber film before modified, modified nanometer
Fibre Membrane Bio compatibility increase, Gegenbaur's cell preferably sticks, grows and migrated (Fig. 5).
Embodiment 2
(1) the polycaprolactone micro/nano-fibre film that zeta current potentials are more than+10mV is obtained；
(2) montmorillonite is added in deionized water, is disperseed using Ultrasound Instrument, prepares the illiteracy that concentration is 1mg/mL
In de- soil suspension, the montmorillonite suspension liquid that positively charged polycaprolactone nano fibrous membrane is immersed in gained, make film with it is molten
Liquid is fully contacted, and is taken the film out after 20 minutes, is cleaned three times using deionized water and is gone the unassembled successful montmorillonite in membrane removal surface；
(3) Chitosan powder is added in 0.5wt% acetum, magnetic agitation 3-5h to solution clear,
Chitosan is fully dissolved, prepare the chitosan solution for obtaining that concentration is 1mg/mL.The polycaprolactone for assembling rectorite is received
Rice tunica fibrosa be soaked in gained chitosan solution in, film is fully contacted with solution, taken the film out after 20 minutes, using go from
Sub- water cleans three times and removes the unassembled successful chitosan in membrane removal surface, has so far assembled successfully a bilayer；
(4) step (2) and step (3) are repeated in several times, gained micro/nano-fibre film is dried, you can obtains double
The composite nano-fiber membrane of number of plies number of plies for needed for.
Embodiment 3
(1) the cellulose acetate micro/nano-fibre film that zeta current potentials are less than -10mV is obtained；
(2) Chitosan powder is added in 0.5wt% acetum, magnetic agitation 3-5h to solution clear,
Chitosan is fully dissolved, prepare the chitosan solution for obtaining that concentration is 10mg/mL.Cellulose nano-fibrous membrane is soaked in institute
In the chitosan solution obtained, film is fully contacted with solution, taken the film out after 20 minutes, three removals are cleaned using deionized water
The unassembled successful chitosan in film surface；
(3) rectorite is added in deionized water, is disperseed using Ultrasound Instrument, and it is 10mg/mL's to prepare concentration
In rectorite suspension, the rectorite suspension that the cellulose nano-fibrous membrane for assembling chitosan is immersed in gained, make film
Fully contact, taken the film out after 20 minutes with solution, clean three times using deionized water and go to membrane removal surface unassembled successfully tired
Stone is held in the palm, a bilayer has so far been assembled successfully；
(4) step (2) and step (3) are repeated in several times, gained micro/nano-fibre film is dried, you can obtains double
The composite nano-fiber membrane of number of plies number of plies for needed for.
Embodiment 4
(1) the fibroin albumen micro/nano-fibre film that zeta current potentials are less than -10mV is obtained；
(2) Chitosan powder is added in 0.5wt% acetum, magnetic agitation 3-5h to solution clear,
Chitosan is fully dissolved, prepare the chitosan solution for obtaining that concentration is 1mg/mL.By the immersion of fibroin albumen micro/nano-fibre film
In the chitosan solution of gained, film is fully contacted with solution, taken the film out after 20 minutes, cleaned three times using deionized water
Remove the unassembled successful chitosan in membrane removal surface；
(3) montmorillonite is added in deionized water, is disperseed using Ultrasound Instrument, prepares the illiteracy that concentration is 1mg/mL
In de- soil suspension, the montmorillonite suspension liquid that the silk fibroin nano-fiber film for assembling chitosan is immersed in gained, make film
Fully contact, taken the film out after 20 minutes with solution, clean three times using deionized water and go the unassembled successful illiteracy in membrane removal surface
De- soil, has so far assembled successfully a bilayer；
(4) step (2) and step (3) are repeated in several times, gained micro/nano-fibre film is dried, you can obtains double
The composite nano-fiber membrane of number of plies number of plies for needed for.
Claims (10)
1. a kind of method of use phyllosilicate/chitosan self-assembled modified micro/nano-fibre film layer by layer, it is characterised in that：With
Electrically charged micro/nano-fibre film, as substrate, is timing when substrate institute is electrically charged, successively in substrate over-assemble phyllosilicate
And chitosan, until double-deck number needed for reaching；When it is negative that substrate institute is electrically charged, successively in substrate over-assemble chitosan and stratiform
Silicate, until double-deck number needed for reaching, the micro/nano-fibre film after assembling is dried, modified micro/nano-fibre is obtained
Film.
2. according to the method described in claim 1, it is characterised in that：The zeta current potentials absolute value of the substrate is not less than 10mV.
3. according to the method described in claim 1, it is characterised in that：Described required double-deck number is 1-50 layers.
4. according to the method described in claim 1, it is characterised in that：Described micro/nano-fibre ilm substrate be by fibroin albumen,
Collagen, cellulose acetate, Chitosan-phospholipid complex, PLLA, polycaprolactone, poly lactic-co-glycolic acid copolymerization
What the one or more in thing were prepared.
5. the method according to claim 1 or 4, it is characterised in that：Described micro/nano-fibre ilm substrate is by electrostatic spinning
Any of method, wet spinning process, dry spinning method, centrifugal spinning, phase separation method or composite spinning method are prepared.
6. according to the method described in claim 1, it is characterised in that：Described chitosan is assembled by the following method：Configure shell
Glycan acetum, substrate is soaked in positively charged chitosan-acetic acid solution, after certain time, is taken the film out, with clear
The unassembled successful chitosan in membrane removal surface is removed in washing lotion cleaning.
7. according to the method described in claim 1, it is characterised in that：Described phyllosilicate is assembled by the following method：Match somebody with somebody
Laminar silicic acid salt suspensioning liquid is put, substrate is soaked in negatively charged laminar silicic acid salt suspensioning liquid, after certain time, film taken
Go out, the unassembled successful phyllosilicate in membrane removal surface is cleaned with cleaning fluid.
8. according to the method described in claim 1, it is characterised in that：Described phyllosilicate is montmorillonite or rectorite.
9. the method according to claim 6 or 7, it is characterised in that：Described cleaning fluid is deionized water or 0.01-1
Mol/L sodium chloride solution.
10. a kind of use phyllosilicate/chitosan micro/nano-fibre film self-assembled modified layer by layer, it is characterised in that：Pass through power
Profit requires that the method described in any one of 1-9 is prepared.
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