CN109912824B - Transparent conductive silk fibroin material and preparation method thereof - Google Patents
Transparent conductive silk fibroin material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a transparent conductive silk fibroin material and a preparation method thereof, wherein the preparation method comprises the following steps: and (2) placing the insolubilized transparent silk fibroin material into an aqueous solution containing EDOT or EDOT derivatives of SDS colloid, and carrying out oxidative polymerization under the action of ferric trichloride and ammonium persulfate to obtain the transparent conductive silk fibroin material. The prepared transparent conductive silk fibroin material mainly comprises a transparent substrate layer and a transparent conductive layer deposited on the surface of the transparent conductive silk fibroin material, wherein the substrate layer is made of silk fibroin, the conductive layer is made of PEDOT or PEDOT derivatives, the thickness of a single layer of the conductive layer is less than 500nm, and the surface sheet resistance of the transparent conductive silk fibroin material is 6 multiplied by 10 4 ～1×10 5 Omega, the maximum light transmittance in the visible light region reaches 65-75%. The preparation process is simple, convenient and mild, and the prepared transparent conductive silk fibroin material has excellent conductivity and higher transparency.
Description
Technical Field
The invention belongs to the technical field of silk fibroin material modification, relates to a transparent conductive silk fibroin material and a preparation method thereof, and particularly relates to a transparent conductive silk fibroin material with both conductivity and transparency and a preparation method thereof.
Background
The silk fibroin is a natural polymer material which is nontoxic and nonirritating to human bodies and has good biocompatibility and biodegradability, and has great application potential in the aspect of preparing tissue engineering materials with nerve stimulation and repair functions.
The electrical stimulation can affect the growth and migration of nerve cells, and the electrical stimulation method is a nerve injury treatment method which has clinical application potential and is gradually developed. The construction of a micro-electro-mechanical system and other systems which can be applied in a living body or the preparation of a nerve repair material with excellent performance by conducting modification on a silk fibroin material is a research hotspot in the neural tissue engineering material at the present stage.
The existing silk fibroin material modification method mainly comprises three types of inorganic materials (including metal oxides such as zinc oxide and carbon materials mainly comprising graphene and carbon nanotubes), micro-nano metal materials (including gold, silver, copper and the like) and conductive polymers (mainly comprising polypyrrole, polyaniline, polythiophene and the like). Compared with the traditional conductive materials (inorganic semiconductor materials and metal materials), the newly developed conductive polymer has the characteristics of both a high molecular material and a conductive material, has better biocompatibility and flexibility, has better mechanical properties matched with tissues and cells in a human body, is suitable for long-term in-vivo implantation, and can avoid inflammation, so that the conductive modification of the silk fibroin material by using the conductive polymer attracts the attention of a large number of scholars.
Modification of Silk Fibroin Materials by Conductive Polymers includes Modification of Silk Fibers, fabrics and in situ oxidative Polymerization and subsequent electropolymerization of regenerated Silk Fibroin Materials, among others, mainly Using polypyrroles such as document 1 (island s. Polymer. engineering the Interface in Silk-Polymer Composites through Chemical Modification of Silk fiber, 2013,5(3): 553-564) and document 2 (medium D. Conductive Polymer-Coated Threads as Electrical Interconnects in electronics, 2011, Fibers and Polymers,12(7):904-910, polyaniline (e.g. chinese patent 104225685A), polythiophene such as CN 3 (simple x. fiber. fabric, fabric and Polymer, cement, 2008, cement, 2015 ACS Applied Materials & Interfaces,7(45), 25281 & 25288).
The oxidative polymerization of the conductive high polymer has the advantages of being simpler and more convenient, and having industrial production potential. However, although the materials such as the regenerated silk fibroin film or the regenerated silk fibroin gel have good transparency, the conductive silk fibroin material prepared by oxidative polymerization modification of the conductive polymer reported at present lacks transparency, which is very unfavorable for microstructure observation in tissue engineering.
Poly (3, 4-ethylenedioxythiophene) and its derivatives have been widely used as conductive polymers because of their good electrical conductivity, environmental stability, and transparency in the oxidized state. In the chinese patent with application number 201610493662.6, a method of modifying a regenerated silk fibroin material by in-situ oxidative polymerization initiated by ammonium persulfate using a polythiophene [3,4-b ] -1, 4-dioxin-2-methanol monomer, namely EDOT-OH, having better water solubility than EDOT as a monomer is reported. However, since the layer thickness of the conductive layer has an adverse effect on the conductivity and transparency of the material, the obtained regenerated silk fibroin material still has quite poor transparency under the condition of ensuring sufficient conductivity.
Therefore, it is very important to research a modified regenerated silk fibroin material with both conductivity and transparency.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a transparent conductive silk fibroin material with excellent conductivity and higher transparency and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a transparent conductive silk fibroin material mainly comprises a transparent substrate layer and a transparent conductive layer deposited on the surface of the transparent substrate layer; the base layer is made of silk fibroin, the conducting layer is made of PEDOT (poly (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) or PEDOT derivatives, and the thickness of the conducting layer is less than 500 nm;
the surface sheet resistance of the transparent conductive silk fibroin material is 6 multiplied by 10 4 ～1×10 5 Omega, the maximum light transmittance in the visible light region reaches 65-75%.
In the prior art, the high polymer conducting layer deposited on the transparent substrate layer is generally thick, the conducting layer formed by the conducting high polymer cannot realize the combination of conductivity and transparency, and the transparent conducting silk fibroin material disclosed by the invention realizes the combination of conductivity and transparency, so that the transparent conducting silk fibroin material is remarkably improved compared with the prior art.
As a preferred technical scheme:
the transparent conductive silk fibroin material comprises a transparent substrate layer, wherein the transparent substrate layer is in the form of a film, a gel or a bracket, micropores are or are not arranged in the transparent substrate layer, the aperture range of the micropores is 500 nm-1 mm, a micron-sized channel structure is or is not arranged in the transparent substrate layer, and the equivalent diameter range of the micron-sized channel structure is 20 mu m-1 mm.
When the transparent substrate layer has micropores and/or micron-sized channel structures inside, a transparent conductive layer is deposited on the surface of the micropore and/or micron-sized channel structures. The polythiophene [3,4-b ] -1, 4-dioxin-2-methanol conducting layer disclosed by the invention is deposited on the outer surface of the silk fibroin material, and is also deposited on the surface of micropores or micron-sized channels in the silk fibroin material, so that the conducting performance of the transparent conducting silk fibroin material is improved.
According to the transparent conductive silk fibroin material, the thickness of the single layer of the transparent substrate layer is 10-100 mu m, and the transparent substrate layer is made of regenerated silk fibroin; the PEDOT derivative is PEDOT-OH (namely hydroxylated derivative poly (thieno [3, 4-b))]-1, 4-dioxine-2-methanol), PEDOT-Cl, i.e. chloromethylPoly ((2- (chloromethyl) -2, 3-dihydrothieno [3, 4-b) derivatives of alkylation][1,4]Dioxin)), PEDOT-NH 2 I.e. the aminated derivative poly ((2, 3-dihydrothieno [3, 4-b)][1,4]Dioxin-2-yl) methylamine) or PEDOT-COOH carboxylated derivative poly (2- ((2, 3-dihydrothieno [3, 4-b)][1,4]Dioxin-2-yl) methoxy) acetic acid). The thickness of the single layer of the substrate layer comprises but not limited to the thickness, the substrate layer can be adjusted adaptively according to actual needs, besides the regenerated silk fibroin material, the transparent substrate layer can also be made of other forms or forms of silk fibroin such as natural silk or degummed silk, but the regenerated silk fibroin has better processing and forming performance, and is beneficial to preparing neural tissue engineering materials in any shapes. All organic chemical names and monomer structures of the invention can be found in the chemical database http:// www.organchem.csdb.cn of Shanghai organic chemistry research institute of Chinese academy of sciences.
The transparent conductive silk fibroin material has a three-layer structure, and the transparent substrate layer and the transparent conductive layer are combined through electrostatic acting force and hydrogen bond acting force.
The invention also provides a method for preparing the transparent conductive silk fibroin material, which comprises the step of placing the transparent silk fibroin material subjected to insolubilization treatment in an aqueous solution of EDOT (2, 3-dihydrothieno [3,4-b ] [1,4] dioxin) or EDOT derivatives containing SDS colloid, and carrying out oxidative polymerization under the action of ferric trichloride and ammonium persulfate to obtain the transparent conductive silk fibroin material.
According to the transparent conductive silk fibroin material, the SDS colloid and ferric trichloride can jointly change the structure and the form of PEDOT or PEDOT derivatives, so that a conductive layer formed by the PEDOT or the PEDOT derivatives is uniform and compact, the internal conductive network structure is good, meanwhile, conductive polymers PEDOT or PEDOT derivatives initiated by two oxidants of ferric trichloride and ammonium persulfate are mutually attracted and connected, the polymers tend to be dispersed in water, the conductive layer with sufficient conductivity is deposited on the surface of the silk fibroin material, and the influence of the generated excessively thick conductive layer on the transparency of the material is avoided, so that the composite material with both conductivity and transparency can be prepared.
As a preferred technical scheme:
the method comprises the following specific steps:
(1) adding SDS into EDOT or EDOT derivative aqueous solution with the concentration of 30-50 mmol/L to obtain EDOT or EDOT derivative aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT or EDOT derivative is 0.4-0.8: 1;
(2) placing the insolubilized silk fibroin material (silk fibroin film with or without micro-channels inside, cross-linked silk fibroin gel, and silk fibroin scaffold with or without micro-channels inside) in an aqueous solution of EDOT or EDOT derivatives containing SDS colloid, and oscillating for 30 minutes at 20-30 ℃, wherein the mass/volume ratio of the silk fibroin material to the EDOT or the EDOT derivatives is 1-10 mg/mL;
(3) adding hydrochloric acid to adjust the pH value to 0.9-1.0, and adjusting the system to be an acidic system so as to prevent insoluble precipitates caused by subsequent complexation of SDS and ferric ions;
(4) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT or the EDOT derivative is 0.2-2.5: 0.5-1.5: 1;
(5) adding hydrochloric acid to adjust the pH value to 0.5-0.7, and carrying out oscillation reaction for 15-24 h at the temperature of 20-30 ℃; when the silk fibroin material contains micro-channels, the micro-channels can be ensured to be communicated through the oscillation reaction;
(6) and (3) ultrasonic oscillation water washing, wherein the purpose is to wash unadsorbed EDOT-OH, and drying for 24-36 h at room temperature.
The method as described above, the process of the insolubilization treatment is: boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 2-20 wt%, and finally forming by a tape casting method to obtain the silk fibroin material subjected to insolubilization treatment.
The method comprises the steps of forming by a tape casting method, namely, coating concentrated liquid drops on a Polydimethylsiloxane (PDMS) substrate, drying and forming to obtain a film, soaking the film in 80% ethanol water solution by volume percentage to promote the secondary structure of the product to be converted to beta folding so as to generate a water-insoluble product, and obtaining a silk fibroin film subjected to insolubilization treatment, or coating the concentrated liquid drops on a PDMS substrate with a plane and convex microchannel pattern, drying and forming to obtain the film, coating a silk fibroin solution layer on one side of the PDMS substrate and pressing the two sides of the PDMS substrate, performing heat treatment at 70 ℃ for 18 hours to convert the secondary structure to be beta folding so as to be insoluble to water, forming microchannels in the channels, drilling the inlet and the outlet of the channels, and obtaining a silk fibroin bracket subjected to (high temperature) insolubilization treatment, or diluting the concentrated liquid to 2-5 wt%, taking 1mL of the silk fibroin solution and 20 mu L of horseradish peroxidase solution with the concentration of 1000-1200 units/mL, 20 mu L of hydrogen peroxide solution with the concentration of 0.5-2 wt% are respectively mixed and react for 1h at the temperature of 25-30 ℃ to obtain the silk fibroin gel (cross-linked state) after insoluble treatment.
According to the method, the molar ratio of the ferric trichloride, the ammonium persulfate and the EDOT or the EDOT derivative is 0.5:1:1, and when the molar ratio is the ratio, the conductivity and the transparency of the transparent silk fibroin material are optimal.
The method described above, wherein the EDOT derivative is EDOT-OH, EDOT-Cl, EDOT-NH 2 Or EDOT-COOH, wherein the structural formula of EDOT-OH is as follows:
the invention mechanism is as follows:
the silk fibroin material modified by the conductive high polymer in the prior art cannot have both conductivity and transparency, which is mainly because when the conductive high polymer layer is thin and has good transparency, the conductivity of the formed conductive layer is poor, and if the conductivity is good, the thickness of the conductive layer is large, so that the overall transparency of the material is low.
The method comprises the steps of placing an insolubilization-treated transparent silk fibroin material into an aqueous solution of EDOT or EDOT derivatives containing SDS colloid, and then carrying out oxidative polymerization under the action of ferric trichloride and ammonium persulfate to obtain the transparent conductive silk fibroin material, wherein the aqueous solution of EDOT or EDOT derivatives can be matched with the SDS (sodium dodecyl sulfate) colloid, and anions of SDS form micelles in the aqueous solution of EDOT or EDOT derivatives containing SDS colloid. After polymerization is initiated, the SDS colloid structure can effectively change the structure and the form of a polymerization product PEDOT or PEDOT derivative, so that the acting force between the PEDOT or PEDOT derivative and a silk fibroin material is enhanced, and the finally prepared conductive silk fibroin material can have excellent conductivity and transparency mainly because the conductive layer of the modified material formed by the method is uniform and compact in structure and good in internal conductive network structure, and the conductive layer can keep good conductivity under the condition of being very thin (less than 500nm), and the specific reasons are as follows:
on one hand, ferric trichloride and ammonium persulfate introduced by the method can cooperate with each other to promote oxidative polymerization of EDOT or EDOT derivative monomers, because negative ions and electronegative groups on the surface of the silk fibroin material tend to attract ferric ions to the vicinity during oxidative polymerization, the EDOT or EDOT derivative monomers are initiated to be oxidized and polymerized into conductive polymer PEDOT or PEDOT derivatives on the surface of the silk fibroin material and then deposited into a conductive layer, and the ammonium persulfate continuously reoxidizes ferrous ions generated by the ferric ions consumed by polymerization at the edge of an oxidative polymerization reaction region to convert the ferrous ions into ferric ions, so that the sufficiency of an oxidant is ensured;
on the other hand, due to the complexation between ferric ions and SDS anions, while ferric trichloride oxidizes the monomer to obtain a conductive polymer, ferrous ions obtained by conversion are introduced into the conductive polymer along with SDS (while a part of residual ferric ions exist), while ammonium persulfate oxidized monomer is polymerized, sulfate ions obtained by conversion are doped into the conductive polymer, at the moment, the conductive polymer simultaneously contains ferric ions or ferrous ions and sulfate ions, the electrostatic force attraction between the ferric ions and the sulfate ions is strong, which causes the two to attract and connect with each other in the conductive polymer PEDOT or PEDOT derivatives obtained by polymerization and among molecules, so that most of the polymers near the film are attracted and dispersed in the solution instead of being deposited on the surface of the silk fibroin material, thereby preventing the deposition layer of the conductive polymer layer from being too thick, the light transmission cannot be greatly reduced, if only ferric trichloride is added, most of the polymers near the film are mainly deposited on the surface of the silk fibroin material, and finally, the prepared product is difficult to have both conductivity and transparency.
Has the advantages that:
(1) the transparent conductive silk fibroin material has excellent conductivity and higher transparency, and can be used for preparing neural tissue engineering materials and neural repair materials with various shapes;
(2) the preparation method of the transparent conductive silk fibroin material has simple and mild preparation process, improves the structure and the form of the formed conductive layer by adding ferric trichloride, avoids the accumulation of a large amount of conductive polymers on the surface of the conductive silk fibroin material in the oxidative polymerization process, and is beneficial to preparing the transparent conductive layer with uniform and compact structure and good internal conductive network structure;
(3) according to the transparent conductive silk fibroin material and the preparation method thereof, the SDS colloid structure can effectively change the structure and the form of EDOT or EDOT derivatives, and meanwhile, the acting force between the EDOT or EDOT derivatives and the silk fibroin material is enhanced;
(4) according to the transparent conductive silk fibroin material and the preparation method thereof, ammonium persulfate can ensure the sufficiency of ferric ions as an oxidant in the oxidation polymerization reaction process, and simultaneously PEDOT or PEDOT derivatives generated by oxidation polymerization of the ammonium persulfate and PEDOT or PEDOT derivatives generated by oxidation polymerization of ferric trichloride are mutually attracted and connected, so that a large amount of conductive polymers can be prevented from being deposited on the surface of the conductive silk fibroin material, and the light transmittance of the product is ensured.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) adding SDS into EDOT-OH aqueous solution with the concentration of 30mmol/L to obtain EDOT-OH aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT-OH is 0.8: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 10 wt%, finally dripping the concentrated solution on a Polydimethylsiloxane (PDMS) substrate by using a tape casting method, drying and forming to obtain a film, soaking the film in an ethanol aqueous solution with the volume percentage of 80%, and promoting the secondary structure of the product to be converted towards beta folding so as to generate a water-insoluble product, thereby obtaining a silk fibroin film subjected to insolubilization treatment;
(3) placing the silk fibroin film subjected to insolubilization treatment in EDOT-OH aqueous solution containing SDS colloid, and oscillating for 30 minutes at 30 ℃, wherein the mass/volume ratio of the two is 10 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 1.0;
(5) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT-OH is 0.5:1: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.5, and oscillating and reacting for 24 hours at the temperature of 30 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 24 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent regenerated silk fibroin film layer and transparent PEDOT-OH conductive layers deposited on the surfaces of the two sides of the transparent regenerated silk fibroin film layer, wherein the transparent regenerated silk fibroin film layer is combined with the transparent PEDOT-OH conductive layers through electrostatic acting force and hydrogen bond acting force, the thickness of the transparent regenerated silk fibroin film layer is 10 micrometers, and the thickness of a single layer of the transparent PEDOT-OH conductive layers is 350 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 6 multiplied by 10 4 Omega, the maximum light transmittance in the visible light region reaches 75%.
Comparative example 1
The preparation steps of the modified conductive silk fibroin material are basically the same as those of the embodiment 1, except that ferric trichloride is not added in the step (5), and the thickness of a single layer of a formed conductive layer is 2 mu m.
The surface sheet resistance of the prepared modified conductive silk fibroin material is 4 multiplied by 10 6 Omega, the highest light transmittance in the visible light region reaches 8%, and comparing the example 1 with the comparative example 1, it can be seen that the modified conductive silk fibroin material prepared in the comparative example 1 has poor conductivity and transparency, which indicates that the modified conductive silk fibroin material has conductivity on the basis of good transparency due to the ferric trichloride.
Comparative example 2
The preparation steps of the modified conductive silk fibroin material are basically the same as those of the embodiment 1, except that ammonium persulfate is not added in the step (5), and the thickness of a single layer of the formed conductive layer is 2 mu m.
The surface sheet resistance of the prepared modified conductive silk fibroin material is 6 multiplied by 10 4 Omega, the highest light transmittance in a visible light region reaches 30%, and comparing example 1 with comparative example 2, it can be seen that the modified conductive silk fibroin material prepared in comparative example 1 has poor transparency, and when only ferric trichloride is added, most of the macromolecules near the film are mainly deposited on the surface of the silk fibroin material, and the finally prepared product is difficult to have both conductivity and transparency.
Example 2
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) adding SDS into EDOT-OH aqueous solution with the concentration of 30mmol/L to obtain EDOT-OH aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT-OH is 0.6: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 20wt%, finally, dripping the concentrated solution on a PDMS substrate with a plane and convex microchannel pattern by using a tape casting method, drying and forming to obtain a film, coating a layer of silk fibroin solution on one side of the two, laminating, and carrying out heat treatment at 70 ℃ for 18h to obtain the silk fibroin scaffold subjected to insolubilization treatment;
(3) placing the silk fibroin bracket subjected to insolubilization treatment in EDOT-OH aqueous solution containing SDS colloid, and oscillating for 30 minutes at 25 ℃, wherein the mass/volume ratio of the two is 5 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 0.9;
(5) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT-OH is 2.5:1.2: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.6, and oscillating and reacting for 20 hours at the temperature of 20 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 24 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent regenerated silk fibroin support layer and transparent PEDOT-OH conductive layers deposited on the surfaces of the two sides of the transparent regenerated silk fibroin support layer, wherein the transparent regenerated silk fibroin support layer is combined with the transparent PEDOT-OH conductive layers through electrostatic acting force and hydrogen bond acting force, the thickness of the transparent regenerated silk fibroin support layer is 90 micrometers, a micron-sized channel structure is arranged inside the transparent regenerated silk fibroin support layer, the equivalent diameter range of the micron-sized channel structure is 20-700 micrometers, the transparent conductive layers are deposited on the surfaces of the micron-sized channel structure, and the thickness of a single layer of the transparent PEDOT-OH conductive layers is 300 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 9 multiplied by 10 4 Omega, the maximum transmittance in the visible light region is 68%.
Example 3
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) adding SDS into EDOT aqueous solution with the concentration of 30mmol/L to obtain EDOT aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT is 0.4: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 15 wt%, and finally forming by using the same tape casting method as that of the embodiment 1 to obtain an insoluble silk fibroin membrane;
(3) placing the silk fibroin film subjected to insolubilization treatment in EDOT aqueous solution containing SDS colloid, and oscillating for 30 minutes at 20 ℃, wherein the mass/volume ratio of the silk fibroin film to the EDOT aqueous solution is 1 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 0.9;
(5) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT is 0.2:0.5: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.5, and oscillating and reacting for 15h at the temperature of 30 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 36 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent regenerated silk fibroin film layer and transparent PEDOT conductive layers deposited on the surfaces of the two sides of the transparent regenerated silk fibroin film layer, wherein the transparent regenerated silk fibroin film layer is combined with the transparent PEDOT conductive layers through electrostatic acting force and hydrogen bond acting force, the thickness of the transparent regenerated silk fibroin film layer is 100 micrometers, and the thickness of a single layer of the transparent PEDOT conductive layers is 450 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 1 multiplied by 10 5 Omega, the maximum light transmittance in the visible light region reaches 65%.
Example 4
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) adding SDS into EDOT-Cl aqueous solution with the concentration of 50mmol/L to obtain EDOT-Cl aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT-Cl is 0.8: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving the silkworm cocoons by using a 9.0M lithium bromide solution, dialyzing and concentrating the silkworm cocoons in deionized water by using a regenerated cellulose membrane until the concentration is 20wt%, diluting the concentrated solution to 2 wt% by using a tape casting method, mixing 1mL of a silk fibroin solution, 20 mu L of a horseradish peroxidase solution with the concentration of 1000 units/mL and 20 mu L of a hydrogen peroxide solution with the concentration of 0.5 wt%, and reacting for 1h at 25 ℃ to obtain insoluble silk fibroin gel;
(3) placing the silk fibroin gel subjected to insolubilization treatment in EDOT-Cl aqueous solution containing SDS colloid, and oscillating for 30 minutes at 30 ℃, wherein the mass/volume ratio of the silk fibroin gel to the SDS colloid is 10 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 1;
(5) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT-Cl is 0.4:1: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.7, and oscillating and reacting for 24 hours at 25 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 36 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent silk fibroin gel layer and transparent PEDOT-Cl conductive layers deposited on the surfaces of the two sides of the transparent silk fibroin gel layer, wherein the transparent silk fibroin gel layer is combined with the transparent PEDOT-Cl conductive layers through electrostatic acting force and hydrogen bond acting force, the thickness of the transparent silk fibroin gel layer is 80 micrometers, micropores are formed in the transparent silk fibroin gel layer, the aperture range of the micropores is 500-500 micrometers, and the thickness of a single layer of the transparent PEDOT-Cl conductive layer is 370 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 7 multiplied by 10 4 Omega, the maximum transmittance in the visible light region reaches 69%.
Example 5
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) EDOT-NH at a concentration of 35mmol/L 2 Adding SDS into the aqueous solution of (1) to obtain EDOT-NH containing SDS colloid 2 Aqueous solution of SDS and EDOT-NH 2 In a molar ratio of 0.6: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 10 wt%, and forming by using the same tape casting method as that of the embodiment 4 to obtain insoluble silk fibroin gel;
(3) placing the silk fibroin gel subjected to insolubilization treatment in EDOT-NH containing SDS colloid 2 Oscillating the solution in water at 25 ℃ for 30 minutes, wherein the mass/volume ratio of the solution to the solution is 10 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 0.9;
(5) sequentially adding ferric trichloride, ammonium persulfate, ferric trichloride, ammonium persulfate and EDOT-NH 2 In a molar ratio of 0.2:1.5: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.7, and oscillating and reacting for 20 hours at 22 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 30 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent silk fibroin gel layer and transparent PEDOT-NH deposited on the surfaces of two sides of the transparent silk fibroin gel layer 2 A conductive layer consisting of a transparent silk fibroin gel layer and transparent PEDOT-NH 2 The conductive layer is combined by electrostatic acting force and hydrogen bond acting force, wherein the thickness of the transparent silk fibroin gel layer is 90 μm, micropores are arranged in the transparent silk fibroin gel layer, the aperture range of the micropores is 1000 μm-1 mm, and transparent PEDOT-NH is deposited on the surfaces of the micropores 2 Conductive layer, transparent PEDOT-NH 2 The thickness of the conductive layer monolayer was 400 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 8 multiplied by 10 4 Omega, the maximum light transmittance in the visible light region reaches 70%.
Example 6
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) adding SDS into EDOT-COOH aqueous solution with the concentration of 45mmol/L to obtain EDOT-COOH aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT-COOH is 0.7: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 15 wt%, and finally forming by using the same tape casting method as that of the embodiment 2 to obtain an insoluble silk fibroin bracket;
(3) placing the silk fibroin bracket subjected to insolubilization treatment in EDOT-COOH aqueous solution containing SDS colloid, and oscillating for 30 minutes at 30 ℃, wherein the mass/volume ratio of the silk fibroin bracket to the EDOT-COOH aqueous solution is 10 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 1.0;
(5) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT-COOH is 0.5:1.5: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.5, and oscillating and reacting for 15h at 26 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 24 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent silk fibroin support layer and transparent PEDOT-COOH conductive layers deposited on the surfaces of the two sides of the transparent silk fibroin support layer, wherein the transparent silk fibroin support layer and the transparent PEDOT-COOH conductive layers are combined through electrostatic acting force and hydrogen bond acting force, the thickness of the transparent silk fibroin support layer is 80 micrometers, a micron-sized channel structure is contained in the transparent silk fibroin support layer, the equivalent diameter range of the micron-sized channel structure is 300 micrometers-800 micrometers, the transparent PEDOT-COOH conductive layers are deposited on the surfaces of the micron-sized channel structure, and the thickness of a single layer of the transparent PEDOT-COOH conductive layers is 420 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 7.5 multiplied by 10 4 Omega, the maximum transmittance in the visible light region is 71%.
Example 7
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) adding SDS into EDOT-OH aqueous solution with the concentration of 50mmol/L to obtain EDOT-OH aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT-OH is 0.8: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 9 wt%, and finally forming by using the same tape casting method as that of the embodiment 1 to obtain an insoluble silk fibroin film;
(3) placing the silk fibroin film subjected to insolubilization treatment in EDOT-OH aqueous solution containing SDS colloid, and oscillating for 30 minutes at 30 ℃, wherein the mass/volume ratio of the two is 5 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 0.9;
(5) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT-OH is 0.5:1.1: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.6, and oscillating and reacting for 20 hours at the temperature of 20 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 24 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent silk fibroin film layer and transparent PEDOT-OH conductive layers deposited on the surfaces of the two sides of the transparent silk fibroin film layer, wherein the transparent silk fibroin film layer and the transparent PEDOT-OH conductive layers are combined through electrostatic acting force and hydrogen bond acting force, the thickness of the transparent silk fibroin film layer is 40 mu m, and the thickness of a single layer of the transparent PEDOT-OH conductive layers is 450 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 6.4 multiplied by 10 4 Omega, the maximum transmittance in the visible light region reaches 66%.
Example 8
A method for preparing transparent conductive silk fibroin material comprises the following steps:
(1) adding SDS into EDOT aqueous solution with the concentration of 50mmol/L to obtain EDOT aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT is 0.6: 1;
(2) carrying out insolubilization treatment on the silk fibroin material;
boiling and degumming silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving by using a 9.0M lithium bromide solution, dialyzing and concentrating a regenerated cellulose membrane in deionized water until the concentration is 20wt%, and finally forming by using the same tape casting method as that of the embodiment 2 to obtain an insoluble silk fibroin bracket;
(3) placing the silk fibroin bracket subjected to insolubilization treatment in EDOT aqueous solution containing SDS colloid, and oscillating for 30 minutes at 30 ℃, wherein the mass/volume ratio of the silk fibroin bracket to the EDOT aqueous solution is 10 mg/mL;
(4) adding hydrochloric acid to adjust the pH value to 1.0;
(5) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT is 0.5:1.3: 1;
(6) adding hydrochloric acid to adjust the pH value to 0.7, and oscillating and reacting for 24 hours at 28 ℃;
(7) washing with ultrasonic oscillation water, and drying at room temperature for 30 h.
The finally prepared transparent conductive silk fibroin material has a three-layer structure and mainly comprises a transparent silk fibroin support layer and transparent PEDOT-OH conductive layers deposited on the surfaces of the two sides of the transparent silk fibroin support layer, wherein the transparent silk fibroin support layer and the transparent PEDOT-OH conductive layers are combined through electrostatic acting force and hydrogen bond acting force, the thickness of a single layer of the transparent silk fibroin support layer is 92 micrometers, a micron-sized channel structure is contained in the transparent silk fibroin support layer, the equivalent diameter range of the micron-sized channel structure is 600-1000 micrometers, the transparent PEDOT-OH conductive layers are deposited on the surfaces of the micron-sized channel structure, the material of each conductive layer corresponds to PEDOT, and the thickness of the single layer of each transparent PEDOT-OH conductive layer is 499 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 6.2 multiplied by 10 5 Omega, the maximum light transmittance in the visible light region reaches 70%.
Example 9
A method for preparing transparent conductive silk fibroin material, its step is basically the same as example 7, the difference is that one side of silk fibroin film used in step (3) after insolubilization is pasted with plastic film, and the plastic film is removed after step (7) processing.
The finally prepared transparent conductive silk fibroin material has a two-layer structure and mainly comprises a transparent silk fibroin film layer and a transparent PEDOT-OH conductive layer deposited on the surface of one side of the transparent silk fibroin film layer, wherein the transparent silk fibroin film layer is combined with the transparent PEDOT-OH conductive layer through electrostatic acting force and hydrogen bond acting force, the thickness of the transparent silk fibroin film layer is 40 mu m, and the thickness of the single layer of the transparent PEDOT-OH conductive layer is 450 nm.
Tests show that the surface sheet resistance of the finally prepared transparent conductive silk fibroin material is 6 multiplied by 10 4 Omega, the maximum light transmittance in the visible light region reaches 65%.
Claims (9)
1. A preparation method of a transparent conductive silk fibroin material is characterized by comprising the following steps: placing the insolubilized transparent silk fibroin material in an aqueous solution of EDOT or EDOT derivatives containing SDS colloid, and carrying out oxidative polymerization under the action of ferric trichloride and ammonium persulfate to obtain a transparent conductive silk fibroin material; the transparent conductive silk fibroin material mainly comprises a transparent substrate layer and a transparent conductive layer deposited on the surface of the transparent substrate layer; the base layer is made of silk fibroin, the conducting layer is made of PEDOT or PEDOT derivatives, and the thickness of the conducting layer is smaller than 500 nm; the surface sheet resistance of the transparent conductive silk fibroin material is 6 multiplied by 10 4 ~1×10 5 Omega, the maximum light transmittance in the visible light region reaches 65-75%.
2. The preparation method of the transparent conductive silk fibroin material of claim 1, wherein the transparent substrate layer is in the form of a film, a gel or a scaffold, with or without micropores therein, wherein the pores have a pore size ranging from 500nm to 1mm, and optionally contain a micron-sized channel structure therein, and the equivalent diameter of the micron-sized channel structure ranges from 20 μm to 1 mm.
3. The method as claimed in claim 2, wherein when the transparent substrate layer has micropores and/or micron-sized channel structures therein, a transparent conductive layer is deposited on the surface of the micropores and/or micron-sized channel structures.
4. The method for preparing the transparent conductive silk fibroin material of claim 1, wherein the thickness of the single layer of the transparent substrate layer is 10-100 μmm, the transparent substrate layer is made of regenerated silk fibroin; the PEDOT derivatives are PEDOT-OH, PEDOT-Cl and PEDOT-NH 2 Or PEDOT-COOH.
5. The method of claim 1, wherein the transparent conductive silk fibroin material has a three-layer structure, and the transparent substrate layer is bonded to the transparent conductive layer by electrostatic force and hydrogen bonding force.
6. The preparation method of the transparent conductive silk fibroin material of claim 1, which is characterized by comprising the following steps:
(1) adding SDS into EDOT or EDOT derivative aqueous solution with the concentration of 30-50 mmol/L to obtain EDOT or EDOT derivative aqueous solution containing SDS colloid, wherein the molar ratio of the SDS to the EDOT or EDOT derivative is 0.4-0.8: 1;
(2) placing the silk fibroin material subjected to insolubilization treatment in an aqueous solution of EDOT or EDOT derivatives containing SDS colloid, and oscillating for 30 minutes at 20-30 ℃, wherein the mass/volume ratio of the silk fibroin material to the EDOT or EDOT derivatives is 1-10 mg/mL;
(3) adding hydrochloric acid to adjust the pH value to 0.9-1.0;
(4) sequentially adding ferric trichloride and ammonium persulfate, wherein the molar ratio of the ferric trichloride to the ammonium persulfate to the EDOT or the EDOT derivative is 0.2-2.5: 0.5-1.5: 1;
(5) adding hydrochloric acid to adjust the pH value to 0.5-0.7, and carrying out oscillation reaction for 15-24 h at the temperature of 20-30 ℃;
(6) and (4) washing with ultrasonic oscillation water, and drying at room temperature for 24-36 h.
7. The method for preparing the transparent conductive silk fibroin material of claim 6, wherein the insolubilization process comprises: boiling and degumming the silkworm cocoons by using a sodium carbonate solution with the mass fraction of 0.5%, dissolving the silkworm cocoons by using a 9.0M lithium bromide solution, dialyzing and concentrating the silkworm cocoons in deionized water through a regenerated cellulose membrane until the concentration of the silkworm cocoons is 2-20 wt%, and finally forming the silkworm cocoons by using a tape casting method.
8. The method for preparing the transparent conductive silk fibroin material of claim 6, wherein the molar ratio of ferric trichloride, ammonium persulfate and EDOT or EDOT derivatives is 0.5:1: 1.
9. The method for preparing the transparent conductive silk fibroin material of claim 6, wherein the EDOT derivatives are EDOT-OH, EDOT-Cl, EDOT-NH 2 Or EDOT-COOH.
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