CN109912824A - A kind of electrically conducting transparent fibroin material and preparation method thereof - Google Patents
A kind of electrically conducting transparent fibroin material and preparation method thereof Download PDFInfo
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Abstract
A kind of electrically conducting transparent fibroin material of the invention and preparation method thereof, the preparation method comprises the following steps: being placed in the transparent fibroin material Jing Guo insoluble processing in the aqueous solution of the EDOT or EDOT derivative containing SDS colloid, oxidation polymerization is under the action of ferric trichloride and ammonium persulfate to be made electrically conducting transparent fibroin material.Electrically conducting transparent fibroin material obtained mainly by transparent base layer and is deposited on the transparency conducting layer on its surface and forms, the material of basal layer is fibroin albumen, the material of conductive layer is PEDOT or PEDOT derivative, the thickness of conductive layer single layer is less than 500nm, and the sheet resistivity of electrically conducting transparent fibroin material is 6 × 104~1 × 105Ω, in visible light region, highest light transmittance reaches 65~75%.Preparation process of the invention is easy to be mild, and electrically conducting transparent fibroin material obtained has excellent electric conductivity and higher transparency simultaneously.
Description
Technical field
The invention belongs to fibroin material technical field of modification, it is related to a kind of electrically conducting transparent fibroin material and its system
Preparation Method, in particular to it is a kind of to have both electric conductivity and the electrically conducting transparent fibroin material of the transparency and preparation method thereof.
Background technique
Fibroin albumen is nontoxic to the human body, nonirritant and natural with good biocompatibility and biological degradability
High molecular material has very big application potential in terms of preparing the tissue engineering material with nerve stimulation and repair function.
Electro photoluminescence can influence the growth and migration of nerve cell, electrostimulation be one kind have clinical application potentiality and
The neurotrosis treatment method gradually developed.Conductive modified is carried out to which building can apply in organism to fibroin material
The systems such as micro electronmechanical or the excellent nerve repair material of processability be the research heat in neural tissue engineering material at this stage
Point.
The method of modifying of fibroin material mainly includes using the inorganic material (metal oxides such as including zinc oxide at present
And the carbon material based on graphene, carbon nanotube), the metal material (including gold, silver, copper etc.) of micro/nano level and conductive high poly-
Object (mainly including polypyrrole, polyaniline, polythiophene etc.) three classes.With conventional conducting materials (inorganic semiconductor material, metal material
Material) it compares, the characteristics of conduction high polymer of emerging development has both high molecular material and conductive material, there is more preferably bio-compatible
Property and flexibility, with people it is intracorporal tissue and cell have more matched mechanical property, be suitble to long-term et al. Ke and be avoided that
Inflammation, therefore the concern that conductive modified has attracted a large amount of scholars is carried out to fibroin material using conduction high polymer.
Conduction high polymer includes to the modification of cocoon fiber, fabric and to regeneration to the modification work of fibroin material
The in-situ oxidizing-polymerizing of fibroin material and subsequent electropolymerization etc. mainly use polypyrrole such as 1 (Isabella of document
S.Romero.Enhancing the Interface in Silk-Polypyrrole Composites through
Chemical Modification of Silk Fibroin, ACS Applied Materials&Interfaces, 2013,5
) and (the Michael D.Irwin.Conductive Polymer-Coated Threads as of document 2 (3): 553-564.
Electrical Interconnects in e-Textiles,2011,Fibers and Polymers,12(7):904-
910.), polyaniline (such as Chinese patent CN104225685A), polythiophene such as document 3 (Youyi Xia.Fabrication and
properties of conductive conjugated polymers/silk fibroin composite fibers,
2008, Composites Science and Technology, 68 (6): 1471-1479.) and 4 (Sean of document
Y.Severt.Versatile Method for Producing 2D and 3D Conductive Biomaterial
Composites Using Sequential Chemical and Electrochemical Polymerization,2015,
ACS Applied Materials&Interfaces, 7 (45): 25281-25288.) three classes conductive functional filler.
The oxidation polymerization of conduction high polymer have it is more simple and easy to do, more for the advantage of industrial production potentiality.Although however
Materials itself transparency such as regenerated silk fibroin film or gel is good, but the oxidation by conducting polymer reported at present is poly-
The conductive fibroin material for closing modified preparation but very lacks the transparency, this is for the displaing microstructure observing ten in organizational project
It is unfavorable to divide.
Poly- (3,4- ethene dioxythiophene) and its derivative are due to having both good electric conductivity, environmental stability and oxidation shape
The transparency under state, therefore it is widely used as conduction high polymer.Application No. is report in 201610493662.6 Chinese patent
Use compared with EDOT has more preferable water-soluble polythiophene, and simultaneously [3,4-b] -1,4- dioxin i.e. EDOT-OH of -2- methanol monomer makees
For monomer, the method that regenerated silk fibroin material is modified by the in-situ oxidizing-polymerizing that ammonium persulfate causes.But due to
The thickness of conductive layer has opposite influence to material conductivity and the transparency, and obtained regenerated silk fibroin material is guaranteeing
Still very lack the transparency in the case where sufficiently conductive property.
Therefore, the modification regeneration fibroin material of electric conductivity and the transparency can be had both with particularly significant by studying one kind
Meaning.
Summary of the invention
The purpose of the invention is to overcome above-mentioned problems of the prior art, provides a kind of while having excellent
Electric conductivity and the electrically conducting transparent fibroin material of higher transparency and preparation method thereof.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of electrically conducting transparent fibroin material mainly by transparent base layer and is deposited on the transparency conducting layer on its surface
Composition；The material of basal layer is fibroin albumen, the material of conductive layer be PEDOT, that is, poly- (2,3- dihydro-thiophenes simultaneously [3,4-b] [1,
4] dioxin) or PEDOT derivative, the thickness of conductive layer single layer is less than 500nm；
The sheet resistivity of electrically conducting transparent fibroin material is 6 × 104~1 × 105Ω, in visible light region highest light transmission
Rate reaches 65~75%.
The high polymer conductive layer being deposited on transparent base layer in the prior art is generally thicker, and what conduction high polymer was formed leads
Electric layer cannot achieve electric conductivity and transparent and have both, and electrically conducting transparent fibroin material of the invention then realizes electric conductivity
It is had both with the transparency, achieves significant progress compared with the prior art.
As a preferred technical scheme:
A kind of electrically conducting transparent fibroin material as described above, the form of the transparent base layer be film, gel or
Bracket, internal with or without micropore, the pore diameter range of micropore is 500nm~1mm, and inside is micro- with or without micro scale channel structure
The equivalent diameter range of meter level channel design is 20 μm~1mm.
A kind of electrically conducting transparent fibroin material as described above, there is micropore in the inside of the transparent base layer and/or contains
When micro scale channel structure, the surface of micropore and/or micro scale channel structure is deposited with transparency conducting layer.Polythiophene of the invention
And [3,4-b]-Isosorbide-5-Nitrae-dioxin -2- methanol conductive layer is not only deposited in the outer surface of fibroin material, and is deposited on silk
Fibroin material internal micropore surface or micro scale channel surface, improve the electric conductivity of electrically conducting transparent fibroin material.
A kind of electrically conducting transparent fibroin material as described above, the transparent base layer single layer with a thickness of 10~100 μ
M, the material of the transparent base layer are regenerated silk fibroin；The PEDOT derivative is PEDOT-OH, that is, hydroxylation derivative
Poly- (thieno [3,4-b] -1,4- dioxin -2- methanol), PEDOT-Cl, that is, chloromethylation derivative it is poly- ((2- (chloromethyl) -2,
3- dihydro-thiophene simultaneously [3,4-b] [1,4] dioxin)), PEDOT-NH2I.e. amination derivative it is poly- ((2,3- dihydro-thiophene simultaneously [3,
4-b] [1,4] dioxin -2- base) methylamine) or poly- (2- ((the 2,3- dihydro-thiophene simultaneously [3,4- of PEDOT-COOH carboxylated derivative
B] [1,4] dioxin -2- base) methoxyl group) acetic acid).The thickness of base layer single layer of the invention includes but are not limited to this, can root
It is adaptively adjusted according to actual needs, transparent base layer can be also the silk of other forms or form in addition to regenerated silk fibroin material
Fibroin such as natural silk or degumed silk, but the machine-shaping property of regenerated silk fibroin is more preferable, is conducive to prepare arbitrary shape
Neural tissue engineering material.All organic chemistry names of the present invention and monomer structure can be in " Chinese Academy of Sciences Shanghai
Organic chemistry research institute chemline http://www.organchem.csdb.cn " lookup obtains.
A kind of electrically conducting transparent fibroin material as described above, electrically conducting transparent fibroin material have three-decker,
Transparent base layer and transparency conducting layer by electrostatic force and Hyarogen-bonding in conjunction with.
The present invention also provides a kind of method of electrically conducting transparent fibroin material as described above is prepared, will pass through insoluble
The transparent fibroin material of processing is placed in the EDOT (2,3- dihydro-thiophene simultaneously [3,4-b] [1,4] dioxin) containing SDS colloid
Or in the aqueous solution of EDOT derivative, electrically conducting transparent fibroin egg is made in oxidation polymerization under the action of ferric trichloride and ammonium persulfate
White material.
Electrically conducting transparent fibroin material of the invention, SDS colloid and ferric trichloride can change jointly PEDOT or
The structure and form of PEDOT derivative, the conductive coating structure even compact for forming PEDOT or PEDOT derivative, and inside is led
Electric network well-formed, at the same two kinds of oxidants of ferric trichloride and ammonium persulfate cause polymerization conducting polymer PEDOT or
PEDOT derivative can attract each other connection, and macromolecule is more prone to be dispersed in water, so that fibroin material surface deposition has
While the conductive layer of sufficiently conductive property, avoids and generate the influence that blocked up conductive layer generates material transparent, to make
Obtain the composite material of the invention that can be made and have both electric conductivity and the transparency.
As a preferred technical scheme:
Method as described above, the specific steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT or EDOT derivative that concentration is 30~50mmol/L, is contained
The molar ratio of the aqueous solution of the EDOT or EDOT derivative of SDS colloid, SDS and EDOT or EDOT derivative is 0.4~0.8:1；
(2) by the fibroin material Jing Guo insoluble processing, (the internal fibroin albumen film with or without microchannel is handed over
The Silk fibroin gel of connection, the internal silk fibroin bracket with or without microchannel) it is placed in EDOT or EDOT containing SDS colloid
It is vibrated 30 minutes at 20~30 DEG C in the aqueous solution of derivative, the mass/volume ratio of the two is 1~10mg/mL；
(3) salt acid for adjusting pH value is added to 0.9~1.0, system is adjusted to acid system, in order to prevent subsequent
SDS and ferric ion occur complexing and cause infusible precipitate；
(4) ferric trichloride and ammonium persulfate are sequentially added, ferric trichloride, ammonium persulfate and EDOT or EDOT derivative rub
You are than being 0.2~2.5:0.5~1.5:1；
(5) salt acid for adjusting pH value is added to 0.5~0.7, the oscillating reactions 15~for 24 hours at 20~30 DEG C；Work as fibroin albumen
Material internal when containing microchannel, oscillating reactions can guarantee that its microchannel penetrates through；
(6) supersonic oscillations are washed, in order to clean unadsorbed EDOT-OH, 24~36h of drying at room temperature.
Method as described above, the process of the insoluble processing are as follows: the carbon for being first 0.5% through mass fraction by silk cocoon
Acid sodium solution boils degumming, is then dissolved using 9.0M lithium-bromide solution, then in deionized water by regenerated cellulose film
It is 2~20wt% that dialysis, which is concentrated into concentration, and the fibroin material Jing Guo insoluble processing is finally obtained by the tape casting molding.
By the tape casting molding refer to will concentration drop-coated to dimethyl silicone polymer (PDMS) substrate on and drying and moulding obtain
After film, be soaked in the ethanol water that percent by volume is 80% promote product secondary structure to β-pleated sheet transformation to
Generate product not soluble in water, obtain the fibroin albumen film Jing Guo insoluble processing, or refer to will concentration drop-coated to putting down
On face and PDMS substrate with raised microchannel pattern and after drying and moulding obtains film, one layer of fibroin egg is coated in the two side
White solution simultaneously presses, and is heat-treated 18h at 70 DEG C, makes its secondary structure to β-pleated sheet transformation to not soluble in water, and with inside
Microchannel, the entrance drilling in channel, is passed through the silk fibroin bracket of (high temperature) insoluble processing, or refer to and will be concentrated
Liquid is diluted to 2~5wt%, takes 1ml silk fibroin protein solution and 20 μ L concentration are 1000~1200 units/mL horseradish peroxidase
Enzyme solutions, the hydrogenperoxide steam generator that 20 μ L concentration are 0.5~2wt% respectively mix, and obtain in 25 DEG C~30 DEG C reaction 1h by not
Dissolve the Silk fibroin gel (crosslinking condition) of processing.
Method as described above, the molar ratio of ferric trichloride, ammonium persulfate and EDOT or EDOT derivative are 0.5:1:1,
When molar ratio is the ratio, the electric conductivity and the transparency of transparent fibroin material reach best.
Method as described above, the EDOT derivative are EDOT-OH, EDOT-Cl, EDOT-NH2Or EDOT-COOH,
The structural formula of middle EDOT-OH is as follows:
Invention mechanism:
The modified fibroin material of conduction high polymer in the prior art can not have both electric conductivity and the transparency simultaneously, this
Mainly relatively thin due to working as conduction high polymer layer, when the transparency is preferable, the electric conductivity of the conductive layer of formation can be poor, and if
It conducts electricity very well, the thickness of conductive layer again can be larger, causes the transparency of material entirety lower.
Transparent fibroin material Jing Guo insoluble processing is first placed in EDOT or EDOT containing SDS colloid by the present invention
In the aqueous solution of derivative, then the obtained electrically conducting transparent fibroin albumen material of oxidation polymerization under the action of ferric trichloride and ammonium persulfate
Material, the aqueous solution of EDOT or EDOT derivative can cooperate with SDS (lauryl sodium sulfate) colloid, the anion of SDS
Form the micella in the aqueous solution of the EDOT or EDOT derivative containing SDS colloid.After causing polymerization, SDS colloform texture can have
Effect ground changes the structure and form of polymerizate PEDOT or PEDOT derivative, to reinforce its work between fibroin material
Firmly, the final conductive fibroin material obtained of the present invention can have both excellent electric conductivity and the transparency mainly due to logical
The conductive coating structure even compact of the modified material of above method formation is crossed, and its inner conductive network structure is good, it is conductive
Layer can keep good electric conductivity in the case where very thin (being less than 500nm), and concrete reason is as follows:
On the one hand, present invention introduces ferric trichloride and ammonium persulfate can cooperate and promote EDOT or EDOT derivative
The oxidation polymerization of monomer, this is because when carrying out oxidation polymerization, the anion and electronegativity group on fibroin material surface
Tendency attracts iron ion near, and causing the oxidation polymerization of EDOT or EDOT derivatives monomer on fibroin material surface is conduction
Macromolecule PEDOT or PEDOT derivative, and then it is deposited as conductive layer, and ammonium persulfate is then in oxidative polymerization edges of regions
Constantly by polymerization consumption iron ion generate ferrous ion it is reoxidized be converted to ferric ion, ensure that filling for oxidant
Foot；
On the other hand, it since there are complexings between ferric ion and SDS anion, is obtained in ferric trichloride oxidised monomer
While to conducting polymer, converting obtained divalent ferrous ion can be introduced into the conducting polymer (simultaneously with SDS
Some remaining ferric ion), and obtained by its own is converted while ammonium persulfate oxidised monomer polymerize
Sulfate ion can be also doped into conducting polymer, at this time simultaneously containing iron ion or ferrous ion and sulphur in conducting polymer
Acid ion, electrostatic force sucking action between the two is stronger, this both cause the conducting polymer PEDOT obtained in polymerization or
In PEDOT derivative and intermolecular connection of attracting each other, so that the most macromolecule near film is attracted and divides
It dissipates in the solution rather than is deposited on fibroin material surface, therefore prevent blocked up electroconductive polymer layer sedimentary, no
It will be greatly reduced translucency, ferric trichloride be only such as added, since the most macromolecule near film is mainly deposited on silk
Fibroin material surface, final product obtained are difficult to have both electric conductivity and the transparency simultaneously.
The utility model has the advantages that
(1) a kind of electrically conducting transparent fibroin material of the invention, while there is excellent electric conductivity and higher
Lightness can be used for preparing neural tissue engineering material and nerve repair material of various shapes；
(2) preparation method of a kind of electrically conducting transparent fibroin material of the invention, preparation process is easy to be mild, by adding
Add ferric trichloride, improve the structure and form of the conductive layer to be formed, conducting polymer is being led during avoiding oxidation polymerization
The bulk deposition of electrical filament fibroin material surface, is conducive to preparation structure even compact and inner conductive network structure is good
Bright conductive layer；
(3) a kind of electrically conducting transparent fibroin material and preparation method thereof of the invention, SDS colloform texture can effectively change
Become the structure and form of EDOT or EDOT derivative, while reinforcing its active force between fibroin material；
(4) a kind of electrically conducting transparent fibroin material and preparation method thereof of the invention, ammonium persulfate can guarantee to aoxidize
The abundance of oxidant ferric ion in polymerization process, at the same its oxidation polymerization generate PEDOT or PEDOT derivative and
PEDOT the or PEDOT derivative that ferric trichloride oxidation polymerization generates is attracted each other connections, and avoidable conducting polymer largely deposits
In conductive fibroin albumen material surface, to guarantee the translucency of product.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT-OH that concentration is 30mmol/L, obtains the EDOT- containing SDS colloid
The molar ratio of OH aqueous solution, SDS and EDOT-OH are 0.8:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 10wt%, finally will by the tape casting
After simultaneously drying and moulding acquisition film is concentrated in drop-coated to dimethyl silicone polymer (PDMS) substrate, being soaked in percent by volume is
Promote product secondary structure to change to generate product not soluble in water to β-pleated sheet in 80% ethanol water, is passed through
The fibroin albumen film of insoluble processing；
(3) the fibroin albumen film Jing Guo insoluble processing is placed in the EDOT-OH aqueous solution containing SDS colloid 30
It is vibrated 30 minutes at DEG C, the mass/volume ratio of the two is 10mg/mL；
(4) salt acid for adjusting pH value is added to 1.0；
(5) ferric trichloride and ammonium persulfate are sequentially added, the molar ratio of ferric trichloride, ammonium persulfate and EDOT-OH is
0.5:1:1；
(6) salt acid for adjusting pH value is added to 0.5, oscillating reactions is for 24 hours at 30 DEG C；
(7) supersonic oscillations are washed, and drying at room temperature is for 24 hours.
Final electrically conducting transparent fibroin material obtained has three-decker, mainly by transparent regenerated silk fibroin film
Layer and be deposited on its double-sided surface clear PE DOT-OH conductive layer composition, transparent regenerated silk fibroin film layer with it is transparent
PEDOT-OH conductive layer is combined by electrostatic force and Hyarogen-bonding, wherein the thickness of transparent regenerated silk fibroin film layer
Degree be 10 μm, clear PE DOT-OH conductive layer single layer with a thickness of 350nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 6 × 104Ω, in visible region
Domain highest light transmittance reaches 75%.
Comparative example 1
A kind of method of denatured conductive fibroin material, preparation step is substantially the same manner as Example 1, and difference exists
In, do not add ferric trichloride in step (5), the conductive layer single layer of formation with a thickness of 2 μm.
The sheet resistivity of denatured conductive fibroin material obtained is 4 × 106Ω, in visible light region highest light transmittance
Reach 8%, embodiment 1 and comparative example 1, which are compared, can be seen that denatured conductive fibroin material made from comparative example 1
Electric conductivity and transparency are poor, illustrate that, due to containing ferric trichloride, the present invention can be simultaneous on the basis of with good transparency
Has electric conductivity.
Comparative example 2
A kind of method of denatured conductive fibroin material, preparation step is substantially the same manner as Example 1, and difference exists
In, do not add ammonium persulfate in step (5), the conductive layer single layer of formation with a thickness of 2 μm.
The sheet resistivity of denatured conductive fibroin material obtained is 6 × 104Ω, in visible light region highest light transmittance
Reach 30%, embodiment 1 and comparative example 2, which are compared, can be seen that denatured conductive fibroin material made from comparative example 1
Transparency is poor, and when ferric trichloride is only added, the most macromolecule near film is mainly deposited on fibroin material table
Face, final product obtained are difficult to have both electric conductivity and the transparency simultaneously.
Embodiment 2
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT-OH that concentration is 30mmol/L, obtains the EDOT- containing SDS colloid
The molar ratio of OH aqueous solution, SDS and EDOT-OH are 0.6:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 20wt%, finally will by the tape casting
After simultaneously drying and moulding acquisition film is concentrated in PDMS substrate of the drop-coated to plane and with raised microchannel pattern, in the two side
It coats one layer of silk fibroin protein solution and presses, it is the fibroin albumen branch obtained Jing Guo insoluble processing that 18h is heat-treated at 70 DEG C
Frame；
(3) silk fibroin bracket Jing Guo insoluble processing is placed in the EDOT-OH aqueous solution containing SDS colloid 25
It is vibrated 30 minutes at DEG C, the mass/volume ratio of the two is 5mg/mL；
(4) salt acid for adjusting pH value is added to 0.9；
(5) ferric trichloride and ammonium persulfate are sequentially added, the molar ratio of ferric trichloride, ammonium persulfate and EDOT-OH is
2.5:1.2:1；
(6) addition salt acid for adjusting pH value is to 0.6, the oscillating reactions 20h at 20 DEG C；
(7) supersonic oscillations are washed, and drying at room temperature is for 24 hours.
Final electrically conducting transparent fibroin material obtained has three-decker, mainly by transparent regenerated silk fibroin bracket
Layer and be deposited on its double-sided surface clear PE DOT-OH conductive layer composition, transparent regenerated silk fibroin shelf layer with it is transparent
PEDOT-OH conductive layer is combined by electrostatic force and Hyarogen-bonding, wherein the thickness of transparent regenerated silk fibroin shelf layer
Degree is 90 μm, has micro scale channel structure, the equivalent diameter of micro scale channel structure inside transparent regenerated silk fibroin shelf layer
Range is 20~700 μm, and the surface of micro scale channel structure is deposited with transparency conducting layer, clear PE DOT-OH conductive layer single layer
With a thickness of 300nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 9 × 104Ω, in visible region
Domain highest light transmittance reaches 68%.
Embodiment 3
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT that concentration is 30mmol/L, it is water-soluble obtains the EDOT containing SDS colloid
The molar ratio of liquid, SDS and EDOT are 0.4:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 15wt%, is finally pressed and embodiment 1
Identical the tape casting molding obtains the fibroin albumen film Jing Guo insoluble processing；
(3) the fibroin albumen film Jing Guo insoluble processing is placed in the EDOT aqueous solution containing SDS colloid at 20 DEG C
Lower oscillation 30 minutes, the mass/volume ratio of the two are 1mg/mL；
(4) salt acid for adjusting pH value is added to 0.9；
(5) ferric trichloride and ammonium persulfate are sequentially added, the molar ratio of ferric trichloride, ammonium persulfate and EDOT is 0.2:
0.5:1；
(6) addition salt acid for adjusting pH value is to 0.5, the oscillating reactions 15h at 30 DEG C；
(7) supersonic oscillations are washed, drying at room temperature 36h.
Final electrically conducting transparent fibroin material obtained has three-decker, mainly by transparent regenerated silk fibroin film
Layer and the clear PE DOT conductive layer composition for being deposited on its double-sided surface, transparent regenerated silk fibroin film layer and clear PE DOT
Conductive layer is combined by electrostatic force and Hyarogen-bonding, wherein transparent regenerated silk fibroin film layer with a thickness of 100 μ
M, clear PE DOT conductive layer single layer with a thickness of 450nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 1 × 105Ω, in visible region
Domain highest light transmittance reaches 65%.
Embodiment 4
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT-Cl that concentration is 50mmol/L, obtains the EDOT- containing SDS colloid
The molar ratio of Cl aqueous solution, SDS and EDOT-Cl are 0.8:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 20wt%, will be concentrated by the tape casting
Liquid is diluted to 2wt%, takes 1mL silk fibroin protein solution and 20 μ L concentration are 1000 units/mL horseradish peroxidase solution, 20
μ L concentration is that the hydrogenperoxide steam generator of 0.5wt% respectively mixes, and fibroin albumen of the 1h acquisition Jing Guo insoluble processing is reacted at 25 DEG C
Gel；
(3) Silk fibroin gel Jing Guo insoluble processing is placed in the EDOT-Cl aqueous solution containing SDS colloid 30
It is vibrated 30 minutes at DEG C, the mass/volume ratio of the two is 10mg/mL；
(4) salt acid for adjusting pH value is added to 1；
(5) ferric trichloride and ammonium persulfate are sequentially added, the molar ratio of ferric trichloride, ammonium persulfate and EDOT-Cl is
0.4:1:1；
(6) salt acid for adjusting pH value is added to 0.7, oscillating reactions is for 24 hours at 25 DEG C；
(7) supersonic oscillations are washed, drying at room temperature 36h.
Final obtained electrically conducting transparent fibroin material has three-decker, mainly by transparent fibroin albumen gel layer with
And it is deposited on the clear PE DOT-Cl conductive layer composition of its double-sided surface, transparent fibroin albumen gel layer is led with clear PE DOT-Cl
Electric layer is combined by electrostatic force and Hyarogen-bonding, wherein transparent fibroin albumen gel layer with a thickness of 80 μm, inside
Have a micropore, the pore diameter range of micropore is 500nm~500 μm, clear PE DOT-Cl conductive layer single layer with a thickness of 370nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 7 × 104Ω, in visible region
Domain highest light transmittance reaches 69%.
Embodiment 5
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) in the EDOT-NH that concentration is 35mmol/L2Aqueous solution in SDS is added, obtain the EDOT- containing SDS colloid
NH2Aqueous solution, SDS and EDOT-NH2Molar ratio be 0.6:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 10wt%, by same as Example 4
The tape casting molding obtain Silk fibroin gel Jing Guo insoluble processing；
(3) Silk fibroin gel Jing Guo insoluble processing is placed in the EDOT-NH containing SDS colloid2In aqueous solution
It is vibrated 30 minutes at 25 DEG C, the mass/volume ratio of the two is 10mg/mL；
(4) salt acid for adjusting pH value is added to 0.9；
(5) ferric trichloride and ammonium persulfate, ferric trichloride, ammonium persulfate and EDOT-NH are sequentially added2Molar ratio be
0.2:1.5:1；
(6) addition salt acid for adjusting pH value is to 0.7, the oscillating reactions 20h at 22 DEG C；
(7) supersonic oscillations are washed, drying at room temperature 30h.
Final obtained electrically conducting transparent fibroin material has three-decker, mainly by transparent fibroin albumen gel layer with
And it is deposited on the clear PE DOT-NH of its double-sided surface2Conductive layer composition, transparent fibroin albumen gel layer and clear PE DOT-NH2
Conductive layer is combined by electrostatic force and Hyarogen-bonding, wherein transparent fibroin albumen gel layer with a thickness of 90 μm, in
There is micropore in portion, and the pore diameter range of micropore is 1000 μm~1mm, and the surface of micropore is deposited with clear PE DOT-NH2Conductive layer is transparent
PEDOT-NH2Conductive layer single layer with a thickness of 400nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 8 × 104Ω, in visible region
Domain highest light transmittance reaches 70%.
Embodiment 6
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT-COOH that concentration is 45mmol/L, obtains containing SDS colloid
The molar ratio of EDOT-COOH aqueous solution, SDS and EDOT-COOH are 0.7:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 15wt%, is finally pressed and embodiment 2
Identical the tape casting molding obtains the silk fibroin bracket Jing Guo insoluble processing；
(3) silk fibroin bracket Jing Guo insoluble processing is placed in the EDOT-COOH aqueous solution containing SDS colloid
It is vibrated 30 minutes at 30 DEG C, the mass/volume ratio of the two is 10mg/mL；
(4) salt acid for adjusting pH value is added to 1.0；
(5) ferric trichloride and ammonium persulfate are sequentially added, the molar ratio of ferric trichloride, ammonium persulfate and EDOT-COOH is
0.5:1.5:1；
(6) addition salt acid for adjusting pH value is to 0.5, the oscillating reactions 15h at 26 DEG C；
(7) supersonic oscillations are washed, and drying at room temperature is for 24 hours.
Final obtained electrically conducting transparent fibroin material has three-decker, mainly by transparent fibroin albumen shelf layer with
And it is deposited on the clear PE DOT-COOH conductive layer composition of its double-sided surface, transparent fibroin albumen shelf layer and clear PE DOT-
COOH conductive layer is combined by electrostatic force and Hyarogen-bonding, wherein transparent fibroin albumen shelf layer with a thickness of 80 μm,
Its internal structure containing micro scale channel, the equivalent diameter range of micro scale channel structure are 300 μm~800 μm, micro scale channel
The surface of structure is deposited with clear PE DOT-COOH conductive layer, clear PE DOT-COOH conductive layer single layer with a thickness of 420nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 7.5 × 104Ω, in visible light
Region highest light transmittance reaches 71%.
Embodiment 7
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT-OH that concentration is 50mmol/L, obtains the EDOT- containing SDS colloid
The molar ratio of OH aqueous solution, SDS and EDOT-OH are 0.8:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 9wt%, is finally pressed and embodiment 1
Identical the tape casting molding obtains the fibroin albumen film Jing Guo insoluble processing；
(3) the fibroin albumen film Jing Guo insoluble processing is placed in the EDOT-OH aqueous solution containing SDS colloid 30
It is vibrated 30 minutes at DEG C, the mass/volume ratio of the two is 5mg/mL；
(4) salt acid for adjusting pH value is added to 0.9；
(5) ferric trichloride and ammonium persulfate are sequentially added, the molar ratio of ferric trichloride, ammonium persulfate and EDOT-OH is
0.5:1.1:1；
(6) addition salt acid for adjusting pH value is to 0.6, the oscillating reactions 20h at 20 DEG C；
(7) supersonic oscillations are washed, and drying at room temperature is for 24 hours.
Final obtained electrically conducting transparent fibroin material has three-decker, mainly by transparent fibroin albumen film layer with
And it is deposited on the clear PE DOT-OH conductive layer composition of its double-sided surface, transparent fibroin albumen film layer is led with clear PE DOT-OH
Electric layer is combined by electrostatic force and Hyarogen-bonding, transparent fibroin albumen film layer with a thickness of 40 μm, clear PE DOT-
OH conductive layer single layer with a thickness of 450nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 6.4 × 104Ω, in visible light
Region highest light transmittance reaches 66%.
Embodiment 8
A kind of method of electrically conducting transparent fibroin material, steps are as follows:
(1) SDS is added in the aqueous solution for the EDOT that concentration is 50mmol/L, it is water-soluble obtains the EDOT containing SDS colloid
The molar ratio of liquid, SDS and EDOT are 0.6:1；
(2) insoluble processing is carried out to fibroin material；
Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5% first, it is then molten using 9.0M lithium bromide
Liquid dissolution, then being dialysed by regenerated cellulose film in deionized water and being concentrated into concentration is 20wt%, is finally pressed and embodiment 2
Identical the tape casting molding obtains the silk fibroin bracket Jing Guo insoluble processing；
(3) silk fibroin bracket Jing Guo insoluble processing is placed in the EDOT aqueous solution containing SDS colloid at 30 DEG C
Lower oscillation 30 minutes, the mass/volume ratio of the two are 10mg/mL；
(4) salt acid for adjusting pH value is added to 1.0；
(5) ferric trichloride and ammonium persulfate are sequentially added, the molar ratio of ferric trichloride, ammonium persulfate and EDOT is 0.5:
1.3:1；
(6) salt acid for adjusting pH value is added to 0.7, oscillating reactions is for 24 hours at 28 DEG C；
(7) supersonic oscillations are washed, drying at room temperature 30h.
Final obtained electrically conducting transparent fibroin material has three-decker, mainly by transparent fibroin albumen shelf layer with
And it is deposited on the clear PE DOT-OH conductive layer composition of its double-sided surface, transparent fibroin albumen shelf layer and clear PE DOT are conductive
Layer is combined by electrostatic force and Hyarogen-bonding, wherein transparent fibroin albumen shelf layer single layer with a thickness of 92 μm, it is internal
Structure containing micro scale channel, the equivalent diameter range of micro scale channel structure are 600~1000 μm, the table of micro scale channel structure
Face is deposited with clear PE DOT-OH conductive layer, and the material of conductive layer corresponds to PEDOT, the thickness of clear PE DOT conductive layer single layer
For 499nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 6.2 × 105Ω, in visible light
Region highest light transmittance reaches 70%.
Embodiment 9
A kind of method of electrically conducting transparent fibroin material, step is substantially the same manner as Example 7, is different only in that its step
Suddenly the fibroin albumen film side by insoluble processing that (3) use is pasted with plastic film, takes this off after step (7) processing
Plastic film.
Final obtained electrically conducting transparent fibroin material has double-layer structure, mainly by transparent fibroin albumen film layer with
And it is deposited on the clear PE DOT-OH conductive layer composition of its single side surface, transparent fibroin albumen film layer is led with clear PE DOT-OH
Electric layer is combined by electrostatic force and Hyarogen-bonding, transparent fibroin albumen film layer with a thickness of 40 μm, clear PE DOT-
OH conductive layer single layer with a thickness of 450nm.
After tested, the sheet resistivity of final electrically conducting transparent fibroin material obtained is 6 × 104Ω, in visible region
Domain highest light transmittance reaches 65%.
Claims (10)
1. a kind of electrically conducting transparent fibroin material, it is characterized in that: mainly by transparent base layer and being deposited on the saturating of its surface
Bright conductive layer composition；The material of basal layer is fibroin albumen, and the material of conductive layer is PEDOT or PEDOT derivative, conductive layer list
The thickness of layer is less than 500nm；
The sheet resistivity of electrically conducting transparent fibroin material is 6 × 104~1 × 105Ω, in visible light region, highest light transmittance reaches
To 65~75%.
2. a kind of electrically conducting transparent fibroin material according to claim 1, which is characterized in that the transparent base layer
Form is film, gel or bracket, and internal with or without micropore, the pore diameter range of micropore is 500nm~1mm, it is internal with or without
Micro scale channel structure, the equivalent diameter range of micro scale channel structure are 20 μm~1mm.
3. a kind of electrically conducting transparent fibroin material according to claim 2, which is characterized in that the transparent base layer
When there are micropore and/or structure containing micro scale channel in inside, the surface of micropore and/or micro scale channel structure is deposited with electrically conducting transparent
Layer.
4. a kind of electrically conducting transparent fibroin material according to claim 1, which is characterized in that the transparent base layer list
Layer with a thickness of 10~100 μm, the material of the transparent base layer is regenerated silk fibroin；The PEDOT derivative is
PEDOT-OH、PEDOT-Cl、PEDOT-NH2Or PEDOT-COOH.
5. a kind of electrically conducting transparent fibroin material according to claim 1, which is characterized in that electrically conducting transparent fibroin albumen
Material has a three-decker, transparent base layer and transparency conducting layer by electrostatic force and Hyarogen-bonding in conjunction with.
6. the method for preparing a kind of electrically conducting transparent fibroin material as claimed in any one of claims 1 to 5, it is characterized in that:
Transparent fibroin material Jing Guo insoluble processing is placed in the aqueous solution of the EDOT or EDOT derivative containing SDS colloid
In, electrically conducting transparent fibroin material is made in oxidation polymerization under the action of ferric trichloride and ammonium persulfate.
7. according to the method described in claim 6, it is characterized in that, specific step is as follows:
(1) SDS is added in the aqueous solution for the EDOT or EDOT derivative that concentration is 30~50mmol/L, obtains containing SDS glue
The molar ratio of the aqueous solution of the EDOT or EDOT derivative of body, SDS and EDOT or EDOT derivative is 0.4~0.8:1；
(2) fibroin material Jing Guo insoluble processing is placed in the water-soluble of the EDOT or EDOT derivative containing SDS colloid
It is vibrated 30 minutes at 20~30 DEG C in liquid, the mass/volume ratio of the two is 1~10mg/mL；
(3) salt acid for adjusting pH value is added to 0.9~1.0；
(4) ferric trichloride and ammonium persulfate, the molar ratio of ferric trichloride, ammonium persulfate and EDOT or EDOT derivative are sequentially added
For 0.2~2.5:0.5~1.5:1；
(5) salt acid for adjusting pH value is added to 0.5~0.7, the oscillating reactions 15~for 24 hours at 20~30 DEG C；
(6) supersonic oscillations are washed, 24~36h of drying at room temperature.
8. the method according to the description of claim 7 is characterized in that the process of the insoluble processing are as follows: first pass through silk cocoon
The sodium carbonate liquor that mass fraction is 0.5% boils degumming, is then dissolved using 9.0M lithium-bromide solution, then fine by regeneration
It is 2~20wt% that the plain film of dimension, which dialyses be concentrated into concentration in deionized water, is finally formed by the tape casting.
9. the method according to the description of claim 7 is characterized in that ferric trichloride, ammonium persulfate and EDOT or EDOT derivative
Molar ratio be 0.5:1:1.
10. the method according to the description of claim 7 is characterized in that the EDOT derivative be EDOT-OH, EDOT-Cl,
EDOT-NH2Or EDOT-COOH.
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