CN106046390B - A kind of conduction fibroin material and preparation method thereof - Google Patents

A kind of conduction fibroin material and preparation method thereof Download PDF

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CN106046390B
CN106046390B CN201610493662.6A CN201610493662A CN106046390B CN 106046390 B CN106046390 B CN 106046390B CN 201610493662 A CN201610493662 A CN 201610493662A CN 106046390 B CN106046390 B CN 106046390B
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fibroin material
fibroin
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methanol
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张耀鹏
庄奥
朱波
邵惠丽
胡学超
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Donghua University
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Abstract

The present invention relates to a kind of conductive fibroin material and preparation method thereof, preparation method includes mainly step：(1) the insoluble processing of fibroin material；(2) by 2 ((2,3 dihydro-thiophenes simultaneously [3,4 b] [1,4] dioxines, 2 yl) methoxyl group) acetic acid activation products graft modifications of insoluble processing fibroin material；(3) in-situ oxidizing-polymerizing on fibroin material surface of 2 methanol of thieno [3,4 b] 1,4 bioxin after graft modification.The fibroin albumen conducing composite material of surface grafting polythiophene simultaneously 2 methanol of [3,4 b] Isosorbide-5-Nitrae bioxin can be made in the present invention, and sheet resistivity is 0.9 × 105~6 × 107Ω, preparation process is easy to be mild, and what is obtained is a kind of novel biomaterial with application value, especially can be used as neural tissue engineering material and nerve repair material.

Description

A kind of conduction fibroin material and preparation method thereof
Technical field
The invention belongs to fibroin material technical field of modification, it is related to a kind of conductive fibroin material and its preparation side Method.
Background technology
Fibroin albumen is a kind of nontoxic, nonirritant, the natural height with good biocompatibility and biological degradability Molecular material (Gregory H.Altman.Silk-based biomaterials；Biomaterials,2003,24:401- 416.), there is prodigious application potential in terms of preparing the tissue engineering material with nerve stimulation and repair function.
Many document report electro photoluminescence can influence the growth and migration of nerve cell in recent years, therefore, currently in order to plus The electric conductivity of strong fibroin material, the systems such as micro electronmechanical that structure can apply in organism and the CO2 laser weld haveing excellent performance Material has many reports by the work of the conductive modified of object of fibroin albumen；Main includes using inorganic material (including oxidation The metal oxides such as zinc and the carbon material based on graphene, carbon nanotube), the metal material of micro/nano level (including gold, silver, Copper etc.) and conduction high polymer (including mainly polypyrrole, polyaniline, polythiophene etc.) three classes.
Compared to conventional conducting materials (inorganic semiconductor material, metal material), the conduction high polymer of emerging development has both The characteristics of high molecular material and conductive material, has more preferably biocompatibility and flexibility, object is held high to fibroin albumen using conduction Material carries out the concern that conductive modified has attracted many scholars.
Polypyrrole, which is used as, studies most commonly used conducting polymer, the existing modification work for being widely used in fibroin albumen, Include the modification to cocoon fiber, fabric and the in-situ oxidizing-polymerizing (Isabella to regenerated silk fibroin material S.Romero.Enhancing the Interface in Silk-Polypyrrole Composites through Chemical Modification of Silk Fibroin, ACS Applied Materials＆Interfaces, 2013,5 (3):553-564.) and electrochemical polymerization (Sean 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.) etc. different polymerizations modification.
The work being modified to silk and regenerated silk fibroin using polyaniline is same it has been reported that Publication No. The Chinese patent of CN104225685A reports a kind of method of conductive slow-release neural tissue engineering holder.In the patent, hair Polyaniline and camphorsulfonic acid doping is added by the way that fibroin albumen and lactic acid-caprol acton copolymer to be dissolved in solution in bright person As cortex solution；Load has the aqueous solution of nerve growth factor to carry out coaxial electrostatic spinning as sandwich layer solution, and carries out Suffocating treatment and vacuum drying obtain the neural tissue engineering holder of conductive energy.
Simultaneously-bioxin -2- methanol of [3,4-b]-Isosorbide-5-Nitrae, that is, PEDOT-OH is a kind of novel conducting polymer to polythiophene, is belonged to In one kind of polythiophene, since its unique epoxy construction makes it possess very strong ambient stable while having high conductivity Property, allow it to become the representative high polymer of polythiophene class；Being concentrated mainly on to the modification of fibroin material about polythiophene makes The study on the modification aspect carried out with PEDOT-OH；Also, current having been reported is essentially consisted in using physics dip coating (Michael D.Irwin.Conductive Polymer-Coated Threads as Electrical Interconnects in e-Textiles,2011,Fibers and Polymers,12(7):904-910.) and chemistry original Position oxidative polymerization method (Youyi Xia.Fabrication and properties of conductive conjugated polymers/silk fibroin composite fibers,2008,Composites Science and Technology,68(6):1471-1479.) in the modification of natural silk or degumed silk, wherein chemical modification PEDOT-OH with Matrix is combined by electrostatic force.
Relative to natural silk or degumed silk, regenerated silk fibroin (RSF) material can be molded again with incomparable Advantage can be theoretically the arbitrary shape including recovery support structure by machine-shaping, therefore for this material Conductive modified research significance it is great.And caused by regenerated silk fibroin material is in dissolving, molding and last handling process The change and recombination of silk fibroin molecular structure, conformation and condensed state structure so that its have in structure different from natural silk or Degumed silk；Meanwhile other regenerated silk fibroin materials in addition to regenerated fiber also have in macrostructure different from one-dimensional material The characteristics of material, therefore the modified system of this kind of material and difference is had been reported, need to carry out process improving to reach good Modified effect.
Compared with electrochemical polymerization, the oxidation polymerization of conduction high polymer have it is more simple and easy to do, have industrial production potentiality Advantage.The original position caused by iron chloride using pyrrole monomer is reported in the Chinese patent of Publication No. CN102168372A Method of modifying of the oxidation polymerization to collagen-fibroin protein film.And PEDOT-OH corresponds to one kind that monomer EDOT-OH belongs to thiophene, It has different states of matter (EDOT is generally solid-state, and pyrroles is liquid), clearly more compared with the latter compared with pyrrole monomer Hydrophobic, while the two is different with combination power, the effect of fibroin material in water environment, the former polymer is more Easily in the solution, polymeric modification difficulty is larger, not only needs to add other modified additives, and single in report technology for deposition Secondary bond on-link mode (OLM) can not meet the requirements such as the combination of PEDOT-OH and fibroin albumen matrix well；Thus, it closes at present In the technique side that PEDOT series of conductive high polymer carries out in-situ chemical conducting polymer modification to regenerated silk fibroin (RSF) material Method is not yet reported.
Invention content
The object of the present invention is to provide a kind of conductive fibroin material and preparation method thereof, be it is a kind of prepare with 2- ((2, 3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) acetic acid be graft modification monomer activated, it is then right Fibroin albumen matrix carries out amidation graft modification, while-bioxin -2- methanol (EDOT-OH) of thieno [3,4-b]-Isosorbide-5-Nitrae is made For polymerized monomer, and by the way that the auxiliary agents such as surfactant, dopant are added modified effect is increased causing the while of polymerizeing Strong process；Reference is provided for the conductive modified of the regenerated silk fibroin material of other structures simultaneously, and is advantageously promoted Application of the regenerated silk fibroin material in terms of neural tissue engineering.
A kind of preparation method of conductive fibroin material of the present invention, includes the following steps：
(1) graft modification of fibroin material；
A.2- the activation of ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid；
2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid is added in deionized water Monomer and Surfactant SDS (SDS) make 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2- Yl) methoxyl group) acetic acid monomer is soluble in water under the action of SDS；
It adds and the changes such as 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid monomer Learn 1- (3- the dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDC) of equivalent and same stoichiometric N- hydroxyls amber Amber acid imide (NHS) is reacted 12h or more under room temperature, is obtained 2- ((2,3- using phosphate buffered saline solution adjusting pH value to 6~7 Dihydro-thiophene simultaneously [3,4-b] [1,4] dioxine -2-yl) methoxyl group) acetic acid activation products N- hydroxysuccinimidyl acid esters (EDOT- NHS) aqueous solution；
The structural formula of the 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid is：
B.N- hydroxysuccinimidyl acid esters is grafted；
Fibroin material Jing Guo insoluble processing is placed in the N- hydroxy succinic acids aqueous solution of ester, 0.1M is used NaOH adjusts pH to 7~9, is placed in 10~12h in shaking table at normal temperatures；
Above step keeps EDOT-NHS orientations residual with the N-terminal amino in fibroin albumen and the amino in arginine, lysine Base carries out amidation process to realize graft modification.
(2) in-situ oxidizing-polymerizing of thieno [the 3,4-b] -1,4- bioxin -2- methanol on fibroin material surface；
Fibroin material after graft modification is placed in thieno [3,4-b] -1,4- bioxin -2- methanol (EDOT- OH) in aqueous solution, since dispersibility is not enough, not uniform enough with fibroin albumen surface integrated structure in water environment by EDOT-OH, because A small amount of SDS need to be added in this in the solution, and SDS will significantly be interacted with EDOT-OH, disperse itself and polymer, A small amount of small molecule dopant can also be added simultaneously and realize that the anion doped of post-consumer polymer is completed in reaction；Later at 25~35 DEG C Oscillation 15~50 minutes, is then added ammonium persulfate, and salt acid for adjusting pH value is added to 0.3~1, oscillating reactions, reaction terminates Fibroin material is taken out, is cleaned and dried, obtains conductive fibroin material；
The EDOT-OH structural formulas are as follows：
As preferred technical solution：
A kind of preparation method of conductive fibroin material as described above, is added 2- ((2,3- dihydros in deionized water Thieno [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid monomer and Surfactant SDS formed it is molten Liquid, the 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) acetic acid monomer a concentration of 20~ 30mmol/L；The amount of the Surfactant SDS is 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] bis- Evil Alkene -2-yl) methoxyl group) acetic acid monomer stoichiometric 3/10~4/10；The pH value of the phosphate buffered saline solution is 7.4, A concentration of 0.038M of middle potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate.
A kind of preparation method of conductive fibroin material as described above, the fibroin albumen by insoluble processing The mass/volume ratio of material and N- hydroxy succinic acid aqueous solution of ester is 10mg/mL.
A kind of preparation method of conductive fibroin material as described above, the fibroin albumen by insoluble processing The preparation process of material is：Silk cocoon is boiled into degumming through the sodium carbonate liquor that mass fraction is 0.5%, it is molten using 9.0M lithium bromides Liquid dissolves, and a concentration of 15~45wt% is concentrated to after dialysing in deionized water by regenerated cellulose film；Then material is pressed After forming method obtains product, then it is soaked in the ethanol water that percent by volume is 75~85% and promotes its secondary structure to β Transformation is folded to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing.
A kind of preparation method of conductive fibroin material as described above is additionally added after concentration with before molding A small amount of glycerine carries out small molecule plasticising to solution, and the mass ratio of glycerine and silk cocoon is 5~10:100；The method of forming materials For electrostatic spraying processes, spin processes, the tape casting, freeze-drying or method of molding.
A kind of preparation method of conductive fibroin material as described above, the fibroin albumen by insoluble processing The mass/volume ratio of material and thieno [3,4-b] -1,4- bioxin -2- methanol aqueous solutions containing lauryl sodium sulfate For 10~12mg/mL.
A kind of preparation method of conductive fibroin material as described above, the thiophene containing lauryl sodium sulfate And in-bioxin -2- methanol aqueous solutions of [3,4-b]-Isosorbide-5-Nitrae, the concentration of-bioxin -2- methanol monomers of thieno [3,4-b]-Isosorbide-5-Nitrae For 0.02~0.05mol/L, the stoichiometric ratio of lauryl sodium sulfate and monomer is 3~5:10；The small molecule dopant For neopelex, sodium camphorsulfonate, P-TOLUENE SULFO ACID 99's sodium or lithium perchlorate, the stoichiometric ratio with monomer is 1~3: 10；The ammonium persulfate of addition and the stoichiometric ratio of monomer are 1~1.5:1.
The preparation method of a kind of conductive fibroin material as described above, which is characterized in that the oscillating reactions refers to The oscillating reactions 12~for 24 hours at 25~35 DEG C；The cleaning, drying refers to being rinsed with deionized water and using ultrasonic washing instrument Vibration washing polymer not to be adsorbed, and be dried at room temperature for more than for 24 hours.
The conductive fibroin material obtained using preparation method as described above, the conduction fibroin material is table Face has been grafted the fibroin material of polythiophene simultaneously [3,4-b] -1,4- bioxin -2- methanol conductive layers；The conduction fibroin egg The sheet resistivity of white material is 0.9 × 105~6 × 107Ω。
Conduction fibroin material as described above, the conduction fibroin material be particle, film, nonporous fiber or Solid block material, or be porous fibre, perforated membrane, porous blocks material or the internal block materials containing microchannel；Institute When to state conductive fibroin material be porous fibre, perforated membrane, porous blocks material or internal block materials containing microchannel, Simultaneously-bioxin -2- methanol conductive layer of [3,4-b]-Isosorbide-5-Nitrae not only grafts on the outer surface of material to polythiophene, but also grafts on material Internal capillary surface or microchannel surface；The thickness of the polythiophene simultaneously [3,4-b] -1,4- bioxin -2- methanol conductive layers is 1-5μm；Perforated membrane, porous fibre or aperture of porous material ranging from 500nm-1mm；Ranging from 20 μm of microchannel equivalent diameter- 1mm。
The regenerated silk fibroin material being plasticized will be blended after insoluble processing through a small amount of glycerine in the present invention, after activation 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) acetic acid carry out amidation grafting, be placed in It, will under the action of oxidant ammonium persulfate in the aqueous solution of-bioxin -2- methanol (EDOT-OH) of thieno [3,4-b]-Isosorbide-5-Nitrae Grafting on the monomer oxidation on matrix and in solution becomes cation, while the fibroin albumen macromolecular for being carried negative electrical charge is inhaled Draw, the monomer accumulation of positive ions to be dissociated based on electrostatic force is in material surface, and then fibroin protein film passing through of material surface It learns the monomer cation that key and electrostatic force combine and causes in-situ polymerization as reactive species, the polythiophene that final oxidation polymerization is formed is simultaneously [3,4-b] -1,4- bioxin -2- methanol (PEDOT-OH) is by including the immixtures such as chemical bond, electrostatic force and hydrogen bond and silk Fibroin material connects, and obtains the regenerated silk fibroin material that surface combines PEDOT-OH conductive structures.In the process, due to EDOT classes material is very sensitive to the response of SDS, and good interaction, the hydrophobic alkyl chain part of SDS can occur for the two Monomer will be connected, and ionic portions extend in hydrone so that the dispersibility of monomer and polymer in the solution is obviously improved, While monomer solubility enhances, the product that is polymerized generate agglomeration can also be substantially eliminated so that polymer It more fully spreads on basis material so that materials conductive layer is more uniform, and electric conductivity significantly improves；Meanwhile it is a certain amount of Dopant can in solution after polymerization chlorion, doping is changed by oxidant more than needed after polymerization together with sulfate ion The conduction high polymer of state provides suitable doping counter ion, and then reinforcing material electric conductivity.
Advantageous effect：
(1) simultaneously [3,4-b] -1,4- bioxin -2- methanol (PEDOT-OH) has regenerated silk fibroin (RSF) with polythiophene There is a good biocompatibility, RSF itself can be biodegradable and promotes cytothesis, by mild oxidative polymerization, By EDOT-OH classes material in RSF material surface in-situ polymerizations so that the material after compound has good electric conductivity, can be used as Biological conductive material is applied to the culture of nerve cell and the reparation of tissue, is a kind of ideal neural tissue engineering material.
(2) regenerated silk fibroin material has reshaping advantage, it is not limited to certain macroshape, with good Under conditions of molding die, it can theoretically be shaped to arbitrary shape.
(3) pass through 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid monomers and silk The graft modification on fibroin surface so that have chemical bond connection function between functionalization monomer and basis material, it is caused with this The orientation in-situ polymerization of-bioxin -2- methanol of thieno [3,4-b]-Isosorbide-5-Nitrae afterwards, and simultaneously so that conductive and fibroin egg It is connected more securely between white basis material, can preferably bear the variability of environment.
(4) lauryl sodium sulfate that EDOT-OH class material system sensitivities can be caused to respond is used so that function monomer And its polymer can disperse to spread over fibroin material surface well, make conductive coating structure more uniform, while also with More firm connection function is formed between matrix.
Specific implementation mode
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 preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 15wt%；Then after pressing the tape casting molding acquisition product, then it is soaked in the ethanol water that percent by volume is 75% Promote its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing；
Then in the 2- of a concentration of 20mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 3/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6,12h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 7 using 0.1M NaOH, is placed in 10h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, by the fibroin material after graft modification be placed in containing SDS and neopelex thieno [3, 4-b] in-Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.03mol/L of EDOT-OH monomers, SDS and list The stoichiometric ratio of body is 3:10, neopelex is 1 with monomer chemistries equivalent proportion:10, by insoluble processing The mass/volume ratio of fibroin material and EDOT-OH aqueous solutions is 10mg/mL；Vibrate 15 minutes at 25 DEG C later, then It is 1 to be added with monomer chemistries equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.3, the oscillating reactions at 25 DEG C 12h, reaction terminate to take out fibroin material, are rinsed with deionized water and not to be adsorbed using ultrasonic washing instrument vibration washing Polymer, and be dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the sheet resistivity of conductive fibroin material obtained is 7 × 106Ω。
Embodiment 2
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 16wt%；Then after pressing method of molding molding acquisition product, then it is soaked in the ethanol water that percent by volume is 76% Promote its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin albumen block materials Jing Guo insoluble processing；
Then in the 2- of a concentration of 21mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 3/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6.5,13h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble place will be passed through The fibroin material of reason is placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS water The mass/volume ratio of solution is 10mg/mL, adjusts pH to 8 using 0.1M NaOH, is placed in 11h in shaking table at normal temperatures, completes The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) The structural formula of acetic acid is as follows：
Finally, the fibroin material after graft modification is placed in the thieno [3,4-b]-containing SDS and sodium camphorsulfonate In Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.02mol/L of EDOT-OH monomers, the change of SDS and monomer It is 4 to learn equivalent proportion:10, sodium camphorsulfonate is 1 with monomer chemistries equivalent proportion:10, by the fibroin material of insoluble processing Mass/volume ratio with EDOT-OH aqueous solutions is 11mg/mL；It vibrates 16 minutes at 26 DEG C later, is then added and singulation It is 1.1 to learn equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.4, the oscillating reactions 13h at 26 DEG C, reaction is tied Beam takes out fibroin material, the polymer for being rinsed with deionized water and using ultrasonic washing instrument vibration washing not to be adsorbed, And it is dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the block for the microchannel that inside is 1mm containing equivalent diameter Material, conductive fibroin albumen outer surface and microchannel surface are grafted the polythiophene that thickness is 5 μm simultaneously [3,4-b]-Isosorbide-5-Nitrae-two Evil English -2- methanol conductive layers, sheet resistivity are 6 × 107Ω。
Embodiment 3
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 18wt%；It is 6 to be added with the mass ratio of silk cocoon:100 glycerine carries out small molecule plasticising；Then it is obtained by method of molding molding After obtaining product, then it is soaked in the ethanol water that percent by volume is 82% and its secondary structure is promoted to change to β-pleated sheet to not It is dissolved in water, that is, obtains the fibroin albumen block materials Jing Guo insoluble processing；
Then in the 2- of a concentration of 26mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 4/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 7,12h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 9 using 0.1M NaOH, is placed in 12h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, by the fibroin material after graft modification be placed in containing SDS and neopelex thieno [3, 4-b] in-Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.02mol/L of EDOT-OH monomers, SDS and list The stoichiometric ratio of body is 5:10, neopelex is 3 with monomer chemistries equivalent proportion:10, by insoluble processing The mass/volume ratio of fibroin material and EDOT-OH aqueous solutions is 12mg/mL；Vibrate 30 minutes at 31 DEG C later, then It is 1.4 to be added with monomer chemistries equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.8, it is vibrated at 35 DEG C anti- Should for 24 hours, reaction terminates to take out fibroin material, is rinsed with deionized water and is not inhaled using ultrasonic washing instrument vibration washing Attached polymer, and it is dried at room temperature for 28h, obtain conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the block for the microchannel that inside is 0.5mm containing equivalent diameter Body material, conductive fibroin albumen outer surface and microchannel surface are grafted the polythiophene that thickness is 5 μm simultaneously [3,4-b]-Isosorbide-5-Nitrae- Bioxin -2- methanol conductive layers, sheet resistivity are 5 × 107Ω。
Embodiment 4
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 18wt%；Then after pressing method of molding molding acquisition product, then it is soaked in the ethanol water that percent by volume is 80% Promote its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing；
Then in the 2- of a concentration of 25mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 3/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 7,12h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 8 using 0.1M NaOH, is placed in 11h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, by the fibroin material after graft modification be placed in containing SDS and neopelex thieno [3, 4-b] in-Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.04mol/L of EDOT-OH monomers, SDS and list The stoichiometric ratio of body is 2:10, neopelex is 1 with monomer chemistries equivalent proportion:10, by insoluble processing The mass/volume ratio of fibroin material and EDOT-OH aqueous solutions is 10mg/mL；Vibrate 26 minutes at 30 DEG C later, then It is 1 to be added with monomer chemistries equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.3, the oscillating reactions at 25 DEG C 12h, reaction terminate to take out fibroin material, are rinsed with deionized water and not to be adsorbed using ultrasonic washing instrument vibration washing Polymer, and be dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the block for the microchannel that inside is 20 μm containing equivalent diameter Material, conductive fibroin albumen outer surface and microchannel surface are grafted the polythiophene that thickness is 5 μm simultaneously [3,4-b]-Isosorbide-5-Nitrae-two Evil English -2- methanol conductive layers, sheet resistivity are 3 × 107Ω。
Embodiment 5
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 16wt%；Then after pressing freeze-drying molding acquisition product, then it is soaked in the ethanol water that percent by volume is 78% Solution promotes its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing；
Then in the 2- of a concentration of 23mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 4/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 7,12h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 9 using 0.1M NaOH, is placed in 11h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, by the fibroin material after graft modification be placed in containing SDS and neopelex thieno [3, 4-b] in-Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.03mol/L of EDOT-OH monomers, SDS and list The stoichiometric ratio of body is 2:10, neopelex is 1 with monomer chemistries equivalent proportion:10, by insoluble processing The mass/volume ratio of fibroin material and EDOT-OH aqueous solutions is 10mg/mL；Vibrate 25 minutes at 28 DEG C later, then It is 1 to be added with monomer chemistries equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.3, the oscillating reactions at 25 DEG C 12h, reaction terminate to take out fibroin material, are rinsed with deionized water and not to be adsorbed using ultrasonic washing instrument vibration washing Polymer, and be dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the porous blocks material that aperture is 500nm, conductive fibroin egg The polythiophene that white outer surface and internal capillary surface grafting thickness are 4 μm simultaneously lead by [3,4-b] -1,4- bioxin -2- methanol Electric layer, sheet resistivity are 2 × 107Ω。
Embodiment 6
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 15wt%；Then after pressing freeze-drying molding acquisition product, then it is soaked in the ethanol water that percent by volume is 82% Solution promotes its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing；
Then in the 2- of a concentration of 25mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 4/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6.5,13h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble place will be passed through The fibroin material of reason is placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS water The mass/volume ratio of solution is 10mg/mL, adjusts pH to 8 using 0.1M NaOH, is placed in 11h in shaking table at normal temperatures, completes The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) The structural formula of acetic acid is as follows：
Finally, the fibroin material after graft modification is placed in the thieno [3,4-b]-containing SDS and sodium camphorsulfonate In Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.04mol/L of EDOT-OH monomers, the change of SDS and monomer It is 4 to learn equivalent proportion:10, sodium camphorsulfonate is 1 with monomer chemistries equivalent proportion:10, by the fibroin material of insoluble processing Mass/volume ratio with EDOT-OH aqueous solutions is 11mg/mL；It vibrates 20 minutes at 26 DEG C later, is then added and singulation It is 1.3 to learn equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.4, the oscillating reactions 13h at 26 DEG C, reaction is tied Beam takes out fibroin material, the polymer for being rinsed with deionized water and using ultrasonic washing instrument vibration washing not to be adsorbed, And it is dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the porous blocks material that aperture is 1mm, conductive fibroin albumen Simultaneously [3,4-b] -1,4- bioxin -2- methanol is conductive for the polythiophene that outer surface and internal capillary surface grafting thickness are 4 μm Layer, sheet resistivity are 9 × 106Ω。
Embodiment 7
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 30wt%；Then after pressing method of electrostatic spinning molding acquisition product, then it is soaked in the ethanol water that percent by volume is 75% Solution promotes its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains by the silk fibroin porous of insoluble processing Membrane material；
Then in the 2- of a concentration of 26mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 4/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 7,12h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 9 using 0.1M NaOH, is placed in 11h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, by the fibroin material after graft modification be placed in containing SDS and neopelex thieno [3, 4-b] in-Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.03mol/L of EDOT-OH monomers, SDS and list The stoichiometric ratio of body is 2:10, neopelex is 1 with monomer chemistries equivalent proportion:10, by insoluble processing The mass/volume ratio of fibroin material and EDOT-OH aqueous solutions is 10mg/mL；Vibrate 25 minutes at 28 DEG C later, then It is 1 to be added with monomer chemistries equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.3, the oscillating reactions at 25 DEG C 12h, reaction terminate to take out fibroin material, are rinsed with deionized water and not to be adsorbed using ultrasonic washing instrument vibration washing Polymer, and be dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the perforated membrane that aperture is 500nm, conductive fibroin material The polythiophene that outer surface and internal capillary surface grafting thickness are 3 μm simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae, table Face sheet resistance is 7 × 106Ω。
Embodiment 8
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 31wt%；Then after pressing method of electrostatic spinning molding acquisition product, then it is soaked in the ethanol water that percent by volume is 75% Solution promotes its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing；
Then in the 2- of a concentration of 25mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 3/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6,12h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 7 using 0.1M NaOH, is placed in 10h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, by the fibroin material after graft modification be placed in containing SDS and neopelex thieno [3, 4-b] in-Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.03mol/L of EDOT-OH monomers, SDS and list The stoichiometric ratio of body is 3:10, neopelex is 1 with monomer chemistries equivalent proportion:10, by insoluble processing The mass/volume ratio of fibroin material and EDOT-OH aqueous solutions is 10mg/mL；Vibrate 15 minutes at 25 DEG C later, then It is 1 to be added with monomer chemistries equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.3, the oscillating reactions at 25 DEG C 12h, reaction terminate to take out fibroin material, are rinsed with deionized water and not to be adsorbed using ultrasonic washing instrument vibration washing Polymer, and be dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the perforated membrane that aperture is 1mm, outside conductive fibroin material The polythiophene that surface and internal capillary surface grafting thickness are 3 μm simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae, surface Sheet resistance is 5 × 106Ω。
Embodiment 9
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 28wt%；Then after pressing core-skin method of electrostatic spinning molding acquisition product, then it is soaked in the second that percent by volume is 78% Alcohol solution promotes its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin albumen Jing Guo insoluble processing Hollow fiber material；
Then in the 2- of a concentration of 22mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 3/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 7,14h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 9 using 0.1M NaOH, is placed in 12h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, the fibroin material after graft modification is placed in the thieno [3,4-b]-containing SDS and P-TOLUENE SULFO ACID 99's sodium In Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.03mol/L of EDOT-OH monomers, the change of SDS and monomer It is 5 to learn equivalent proportion:10, P-TOLUENE SULFO ACID 99's sodium is 3 with monomer chemistries equivalent proportion:10, by the fibroin material of insoluble processing Mass/volume ratio with EDOT-OH aqueous solutions is 12mg/mL；It vibrates 18 minutes at 27 DEG C later, is then added and singulation It is 1.2 to learn equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.5, the oscillating reactions 15h at 28 DEG C, reaction is tied Beam takes out fibroin material, the polymer for being rinsed with deionized water and using ultrasonic washing instrument vibration washing not to be adsorbed, And it is dried at room temperature for 25h, obtain conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin albumen doughnut internal diameter of preparation is 500nm, conductive fibroin albumen outer surface The polythiophene simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae for being 1 μm with internal capillary surface grafting thickness, sheet resistivity It is 4 × 106Ω。
Embodiment 10
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 30wt%；Then after pressing wet spinning process molding acquisition product, then it is soaked in the ethanol water that percent by volume is 76% Solution promotes its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains by the silk fibroin porous of insoluble processing Fibrous material；
Then in the 2- of a concentration of 20mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 3/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6,12h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 7 using 0.1M NaOH, is placed in 10h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, by the fibroin material after graft modification be placed in containing SDS and neopelex thieno [3, 4-b] in-Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.03mol/L of EDOT-OH monomers, SDS and list The stoichiometric ratio of body is 3:10, neopelex is 1 with monomer chemistries equivalent proportion:10, by insoluble processing The mass/volume ratio of fibroin material and EDOT-OH aqueous solutions is 10mg/mL；Vibrate 15 minutes at 25 DEG C later, then It is 1 to be added with monomer chemistries equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.3, the oscillating reactions at 25 DEG C 12h, reaction terminate to take out fibroin material, are rinsed with deionized water and not to be adsorbed using ultrasonic washing instrument vibration washing Polymer, and be dried at room temperature for for 24 hours, obtaining conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is the porous fibre that aperture is 1mm, conductive fibroin material The polythiophene that outer surface and internal capillary surface grafting thickness are 1 μm simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae, table Face sheet resistance is 2 × 106Ω。
Embodiment 11
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 16wt%；It is 8 to be added with the mass ratio of silk cocoon:100 glycerine carries out small molecule plasticising；Then press electrostatic spraying processes at Type obtain product after, then be soaked in percent by volume be 83% ethanol water promote its secondary structure to β-pleated sheet transformation from And it is not soluble in water, that is, obtain the fibroin albumen granular materials Jing Guo insoluble processing；
Then in the 2- of a concentration of 28mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 4/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6,13h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 7 using 0.1M NaOH, is placed in 10h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, the fibroin material after graft modification is placed in the thieno [3,4-b]-containing SDS and P-TOLUENE SULFO ACID 99's sodium In Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.04mol/L of EDOT-OH monomers, the change of SDS and monomer It is 5 to learn equivalent proportion:10, P-TOLUENE SULFO ACID 99's sodium is 2 with monomer chemistries equivalent proportion:10, by the fibroin material of insoluble processing Mass/volume ratio with EDOT-OH aqueous solutions is 10mg/mL；It vibrates 34 minutes at 32 DEG C later, is then added and singulation It is 1.5 to learn equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.9, the oscillating reactions 18h at 32 DEG C, reaction is tied Beam takes out fibroin material, the polymer for being rinsed with deionized water and using ultrasonic washing instrument vibration washing not to be adsorbed, And it is dried at room temperature for 29h, obtain conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is particle, and conductive fibroin albumen material surface grafting thickness is 1 μm polythiophene simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae, sheet resistivity is 9 × 105Ω。
Embodiment 12
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 18wt%；Then after pressing the tape casting molding acquisition product, then it is soaked in the ethanol water that percent by volume is 80% Promote its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing；
Then in the 2- of a concentration of 24mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 3/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6,15h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble processing will be passed through Fibroin material be placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS are water-soluble The mass/volume ratio of liquid is 10mg/mL, adjusts pH to 7 using 0.1M NaOH, is placed in 10h in shaking table at normal temperatures, completes silk The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second The structural formula of acid is as follows：
Finally, the fibroin material after graft modification is placed in the thieno [3,4-b] -1 containing SDS and lithium perchlorate, In 4- bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.04mol/L of EDOT-OH monomers, the chemistry of SDS and monomer Equivalent proportion is 3:10, lithium perchlorate is 1 with monomer chemistries equivalent proportion:10, fibroin material by insoluble processing with The mass/volume ratio of EDOT-OH aqueous solutions is 10mg/mL；It vibrates 20 minutes at 28 DEG C later, is then added and monomer chemistries Equivalent proportion is 1.3:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.6, at 30 DEG C oscillating reactions 18h, reaction terminate Fibroin material is taken out, the polymer for being rinsed with deionized water and using ultrasonic washing instrument vibration washing not to be adsorbed, and It is dried at room temperature for 26h, obtains conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is film, and conductive fibroin albumen material surface grafting thickness is 2 μm polythiophene simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae, sheet resistivity is 4 × 105Ω。
Embodiment 13
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 45wt%；It is 10 to be added with the mass ratio of silk cocoon:100 glycerine carries out small molecule plasticising；Then dry spinning method is pressed After molding obtains product, then it is soaked in the ethanol water that percent by volume is 85% and its secondary structure is promoted to change to β-pleated sheet To not soluble in water, that is, obtain the fibroin albumen nonporous fiber material Jing Guo insoluble processing；
Then in the 2- of a concentration of 30mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 4/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6.5,14h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble place will be passed through The fibroin material of reason is placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS water The mass/volume ratio of solution is 10mg/mL, adjusts pH to 8 using 0.1M NaOH, is placed in 12h in shaking table at normal temperatures, completes The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) The structural formula of acetic acid is as follows：
Finally, the fibroin material after graft modification is placed in the thieno [3,4-b] -1 containing SDS and lithium perchlorate, In 4- bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.05mol/L of EDOT-OH monomers, the chemistry of SDS and monomer Equivalent proportion is 5:10, lithium perchlorate is 3 with monomer chemistries equivalent proportion:10, fibroin material by insoluble processing with The mass/volume ratio of EDOT-OH aqueous solutions is 12mg/mL；It vibrates 50 minutes at 35 DEG C later, is then added and monomer chemistries Equivalent proportion is 1.5:1 ammonium persulfate, and salt acid for adjusting pH value is added to 1, the oscillating reactions 22h at 35 DEG C, reaction terminates to take Go out fibroin material, the polymer for being rinsed with deionized water and using ultrasonic washing instrument vibration washing not to be adsorbed, and 30h is dried at room temperature, obtains conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is nonporous fiber, and conductive fibroin albumen material surface grafting is thick Simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae, sheet resistivity are 2 × 10 to the polythiophene that degree is 3 μm5。
Embodiment 14
A kind of preparation method of conduction fibroin material, it is first that silk cocoon is molten for 0.5% sodium carbonate through mass fraction Liquid boils degumming, is dissolved using 9.0M lithium-bromide solutions, and is concentrated to after being dialysed in deionized water by regenerated cellulose film A concentration of 19wt%；It is 5 to be added with the mass ratio of silk cocoon:100 glycerine carries out small molecule plasticising；Then it is obtained by method of molding molding After obtaining product, then it is soaked in the ethanol water that percent by volume is 80% and its secondary structure is promoted to change to β-pleated sheet to not It is dissolved in water, that is, obtains the fibroin material Jing Guo insoluble processing；
Then in the 2- of a concentration of 25mmol/L ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxies Base) acetic acid aqueous solution in be added its chemical equivalent 4/10 lauryl sodium sulfate (SDS), etc. stoichiometric 1- (3- bis- Methylaminopropyl) -3- ethyl-carbodiimide hydrochlorides (EDC) and same stoichiometric n-hydroxysuccinimide (NHS), make With phosphate buffer solution (pH value 7.4, a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate) PH value is adjusted to 6.5,16h is reacted under room temperature, obtains N- hydroxysuccinimidyls acid esters (EDOT-NHS) aqueous solution；Insoluble place will be passed through The fibroin material of reason is placed in EDOT-NHS aqueous solutions, the fibroin material by insoluble processing and EDOT-NHS water The mass/volume ratio of solution is 10mg/mL, adjusts pH to 8 using 0.1M NaOH, is placed in 11h in shaking table at normal temperatures, completes The graft modification of fibroin material；Wherein, 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) The structural formula of acetic acid is as follows：
Finally, the fibroin material after graft modification is placed in the thieno [3,4-b]-containing SDS and sodium camphorsulfonate In Isosorbide-5-Nitrae-bioxin -2- methanol (EDOT-OH) aqueous solution, a concentration of 0.05mol/L of EDOT-OH monomers, the change of SDS and monomer It is 4 to learn equivalent proportion:10, sodium camphorsulfonate is 2 with monomer chemistries equivalent proportion:10, by the fibroin material of insoluble processing Mass/volume ratio with EDOT-OH aqueous solutions is 11mg/mL；It vibrates 25 minutes at 30 DEG C later, is then added and singulation It is 1.3 to learn equivalent proportion:1 ammonium persulfate, and salt acid for adjusting pH value is added to 0.7, the oscillating reactions 20h at 32 DEG C, reaction is tied Beam takes out fibroin material, the polymer for being rinsed with deionized water and using ultrasonic washing instrument vibration washing not to be adsorbed, And it is dried at room temperature for 27h, obtain conductive fibroin material；Wherein, EDOT-OH structural formulas are as follows：
Test shows that the conductive fibroin material of preparation is solid block material, and conductive fibroin albumen material surface connects Simultaneously-bioxin -2- methanol conductive layers of [3,4-b]-Isosorbide-5-Nitrae, sheet resistivity are 0.9 × 10 to the polythiophene that branch thickness is 5 μm5Ω。

Claims (10)

1. a kind of preparation method of conduction fibroin material, it is characterized in that including the following steps：
(1) graft modification of fibroin material；
A.2- the activation of ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid；
2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid monomer is added in deionized water And Surfactant SDS, make 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxies Base) acetic acid monomer is soluble in water under the action of Surfactant SDS；
It adds and works as with chemistry such as 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid monomers 1- (3- the dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides of amount and same stoichiometric n-hydroxysuccinimide, Adjust pH value to 6~7 using phosphate buffer solution, 12h or more reacted under room temperature, obtain 2- ((2,3- dihydro-thiophenes simultaneously [3, 4-b] and [1,4] dioxines -2-yl) methoxyl group) acetic acid activation products N- hydroxy succinic acid aqueous solution of ester；
The structural formula of the 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid is：
B.N- hydroxysuccinimidyl acid esters is grafted；
Fibroin material Jing Guo insoluble processing is placed in the N- hydroxy succinic acids aqueous solution of ester, 0.1M is used NaOH adjusts pH to 7~9, is placed in 10~12h in shaking table at normal temperatures；
(2) in-situ oxidizing-polymerizing of thieno [the 3,4-b] -1,4- bioxin -2- methanol on fibroin material surface；
Fibroin material after graft modification is placed in thieno [the 3,4-b] -1,4- Er Evil containing lauryl sodium sulfate In English -2- methanol aqueous solutions, and small molecule dopant is added；It vibrates 15~50 minutes at 25~35 DEG C, is then added later Ammonium persulfate, and salt acid for adjusting pH value is added to 0.3~1, oscillating reactions, reaction terminates to take out fibroin material, and cleaning is dry It is dry, obtain conductive fibroin material；
Thieno [the 3,4-b] -1,4- bioxin -2- methanol structural formulas are as follows：
2. a kind of preparation method of conductive fibroin material according to claim 1, which is characterized in that in deionized water Middle addition 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid monomer and surfactant ten Sodium dialkyl sulfate forms solution, the 2- ((2,3- dihydro-thiophenes simultaneously [3,4-b] [Isosorbide-5-Nitrae] dioxines -2-yl) methoxyl group) second A concentration of 20~30mmol/L of acid monomers；The amount of the Surfactant SDS is 2- ((2,3- dihydro-thiophenes And [3,4-b] [1,4] dioxines -2-yl) methoxyl group) acetic acid monomer stoichiometric 3/10~4/10；The phosphate-buffered salt The pH value of solution is 7.4, the wherein a concentration of 0.038M of potassium dihydrogen phosphate, a concentration of 0.04M of disodium hydrogen phosphate.
3. a kind of preparation method of conductive fibroin material according to claim 1, which is characterized in that described by not The mass/volume ratio of the fibroin material and N- hydroxy succinic acid aqueous solution of ester that dissolve processing is 10mg/mL.
4. a kind of preparation method of conductive fibroin material according to claim 1, which is characterized in that described by not The preparation process for dissolving the fibroin material of processing is：By silk cocoon through mass fraction be 0.5% sodium carbonate liquor boil it is de- Glue is dissolved using 9.0M lithium-bromide solutions, and a concentration of 15 are concentrated to after dialysing in deionized water by regenerated cellulose film ~45wt%；Then press method of forming materials obtain product after, then be soaked in percent by volume be 75~85% ethyl alcohol it is water-soluble Liquid promotes its secondary structure to β-pleated sheet transformation to not soluble in water, that is, obtains the fibroin material Jing Guo insoluble processing.
5. a kind of preparation method of conductive fibroin material according to claim 4, which is characterized in that after concentration Before molding, it is additionally added a small amount of glycerine and small molecule plasticising is carried out to solution, the mass ratio of glycerine and silk cocoon is 5~10: 100；The method of forming materials is electrostatic spraying processes, spin processes, the tape casting, freeze-drying or method of molding.
6. a kind of preparation method of conductive fibroin material according to claim 1, which is characterized in that described by not The fibroin material and thieno [3,4-b] -1,4- bioxin -2- methanol-waters containing lauryl sodium sulfate for dissolving processing The mass/volume ratio of solution is 10~12mg/mL.
7. a kind of preparation method of conductive fibroin material according to claim 1, which is characterized in that described to contain ten In the-bioxin -2- methanol aqueous solutions of thieno [3,4-b]-Isosorbide-5-Nitrae of sodium dialkyl sulfate, thieno [3,4-b]-Isosorbide-5-Nitrae-Er Evil The stoichiometric ratio of a concentration of 0.02~0.05mol/L of English -2- methanol monomers, lauryl sodium sulfate and monomer is 3~5: 10；The small molecule dopant is neopelex, sodium camphorsulfonate, P-TOLUENE SULFO ACID 99's sodium or lithium perchlorate, with monomer Stoichiometric ratio be 1~3:10；The ammonium persulfate of addition and the stoichiometric ratio of monomer are 1~1.5:1.
8. a kind of preparation method of conductive fibroin material according to claim 1, which is characterized in that the oscillation is anti- It should refer to the oscillating reactions 12~for 24 hours at 25~35 DEG C；The cleaning-drying refers to being rinsed with deionized water and using ultrasonic wave Cleaning device vibration washing polymer not to be adsorbed, and be dried at room temperature for more than for 24 hours.
9. the conductive fibroin material obtained using any preparation method of claim 1~8, it is characterized in that：The conductive filament Fibroin material is the fibroin material of surface grafting polythiophene simultaneously [3,4-b] -1,4- bioxin -2- methanol conductive layers； The sheet resistivity of the conduction fibroin material is 0.9 × 105~6 × 107Ω。
10. it is according to claim 9 conduction fibroin material, which is characterized in that it is described conduction fibroin material be Particle, film, nonporous fiber or solid block material, or contain for porous fibre, perforated membrane, porous blocks material or inside The block materials of microchannel；The conduction fibroin material is that porous fibre, perforated membrane, porous blocks material or inside are contained When the block materials of microchannel, simultaneously-bioxin -2- methanol conductive layer of [3,4-b]-Isosorbide-5-Nitrae not only grafts on the outer of material to polythiophene Surface, and graft on material internal micropore surface or microchannel surface；The polythiophene simultaneously [3,4-b] -1,4- bioxin -2- The thickness of methanol conductive layer is 1-5 μm；Perforated membrane, porous fibre or aperture of porous material ranging from 500nm-1mm；Work as microchannel Amount diameter range is 20 μm of -1mm.
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