CN110229530A - A kind of dual network silk fibroin hydrogel and preparation method thereof - Google Patents
A kind of dual network silk fibroin hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of dual network silk fibroin hydrogels and preparation method thereof, dual network silk fibroin hydrogel is using silk fibroin molecular as matrix, main body, object and horseradish peroxidase, built-up dual network silk fibroin hydrogel are introduced in its amino acid side chain.The present invention introduces subject and object using the good fibroin albumen macromolecule of biocompatibility as matrix, by chemical modification, then horseradish peroxidase and hydrogen peroxide are introduced in system, prepares dual network silk fibroin hydrogel.Reversible binding effect and the crosslinked action of horseradish peroxidase enzyme catalytic between subject and object unit, assign the stability of silk fibroin hydrogel structure and performance.At the same time, the presence of dual network structure increases the crosslinked action site of gel network, greatly improves the elasticity modulus of silk fibroin hydrogel, so as to improve its tensile property.
Description
Technical field
The present invention relates to technical field of biological materials, a kind of dual network silk fibroin hydrogel and its system are related in particular to
Preparation Method.
Background technique
The one kind of hydrogel as soft material is to be crosslinked to be formed in water by hydrophilic polymer chain, has
Higher water content, and oxygen and nutriment can be transported, similar to natural extracellular matrix, in organizational project, medicine
The fields such as object transmitting, regenerative medicine are with a wide range of applications.Fibroin albumen is the natural polymer fibre extracted from silk
Fibrillarin, obtaining FDA certification can be used for clinical treatment.Fibroin albumen based aquagel has excellent biocompatibility, biology can
Degradability is not only able to provide suitable microenvironment for the Proliferation, Differentiation of cell, and can realize the reparation and regeneration of tissue,
Field of biomedicine has important application value.Fibroin egg can be prepared by the methods of ultrasound, vortex, electric field and reduction pH
White based aquagel, but the gel mechanical property prepared is weaker, the elasticity and toughness of biological tissue, are not higher than 10% in strain
When plastically deformable it is poor, and with the extension of time, material is easy to happen impaired fracture, greatly limit it in biological medicine
The application in field.The silk fibroin hydrogel of existing report plastically deformable when strain is higher than 10% can be deteriorated, and material holds
Impaired fracture, which easily occurs, causes repeated stretch property to be deteriorated, and how to improve the ductile strength of silk fibroin hydrogel is that hydrogel is ground
A significant challenge in studying carefully.
Summary of the invention
It is existing to overcome the purpose of the present invention is to provide a kind of dual network silk fibroin hydrogel and preparation method thereof
The defect of the difference of tensile property existing for silk fibroin hydrogel.
For this purpose, being using silk fibroin molecular as matrix, at it the present invention provides a kind of dual network silk fibroin hydrogel
Amino acid side chain introduces main body, object and horseradish peroxidase, built-up dual network silk fibroin hydrogel.
Preferably, the main body includes cyclodextrin or Cucurbituril, and the object includes that adamantane, ferrocene, cholic acid, gallbladder are solid
Alcohol or carbazole analog derivative.
The present invention also provides the preparation methods of dual network silk fibroin hydrogel, which comprises
(1) silk fibroin powder of carboxylated is prepared；
(2) fibroin albumen-bulk solution is prepared；
(3) fibroin albumen-object solution is prepared；
(4) horseradish peroxidase solution is added in Xiang Suoshu fibroin albumen-bulk solution, is uniformly mixed, obtains the first mixing
Liquid；
(5) hydrogenperoxide steam generator is added in Xiang Suoshu fibroin albumen-object solution, is uniformly mixed, obtains the second mixed liquor；
(6) first mixed liquor and second mixed liquor are uniformly mixed, stood, obtain dual network fibroin albumen water-setting
Glue.
Preferably, the step (1) includes: that silk is obtained silk fibroin protein solution by degumming, dissolution, dialysis treatment；
Silk fibroin protein solution is passed through into borax, diazonium salt, monoxone chemical modification, obtains the fibroin egg that concentration is 0.1%-50% carboxylated
White solution；By silk fibroin protein solution dialysis, the freeze-drying of carboxylated, the silk fibroin powder of carboxylated is obtained.
Preferably, the step (2) includes: that amidized main body is dissolved in dimethyl sulphoxide solution, and being made into concentration is
The amidized bulk solution of 0.1-1000 mg/mL；EDC HCl is dissolved in dimethyl sulphoxide solution, being made into concentration is 0.1-
The EDC HCl solution of 1000 mg/mL；The silk fibroin powder of carboxylated is dissolved in dimethyl sulphoxide solution, being made into concentration is
The silk fibroin protein solution of the carboxylated of 0.05-10mg/mL；By amidized bulk solution, the silk of EDC HCl solution and carboxylated
Fibroin solution mixing, room temperature reaction, dialysis freeze-drying, obtains fibroin albumen-main body powder；By fibroin albumen-main body powder
End is dissolved in water, is prepared into fibroin albumen-bulk solution that mass fraction is 1%-50%.
Preferably, the step (3) includes: to prepare the object solution that concentration is 0.1-1000 mg/mL；EDC HCl is molten
In dimethyl sulphoxide solution, it is made into the EDC HCl solution that concentration is 0.1-1000 mg/mL；By the silk fibroin powder of carboxylated
End is dissolved in dimethyl sulphoxide solution, is made into the silk fibroin protein solution for the carboxylated that concentration is 0.05-10mg/mL；By object solution,
EDC HCl solution and the mixing of the silk fibroin protein solution of carboxylated, room temperature reaction, dialysis freeze-drying, obtain fibroin albumen-object
Powder；Fibroin albumen-object powder is dissolved in water, is prepared into fibroin albumen-object solution that mass fraction is 1%-50%.
Preferably, in the step (4), the content of horseradish peroxidase is 900-1100U/mL.
Preferably, in the step (5), hydrogenperoxide steam generator concentration is 160-170mM.
Preferably, in the step (6), the first mixed liquor and the second mixed liquor are according to the molar ratio of subject and object
The ratio of 100:1-1:100 is uniformly mixed, and the mass fraction of dual network silk fibroin hydrogel is 1%-50%.
Compared with prior art, the advantages and positive effects of the present invention are: the present invention provides a kind of dual network fibroin eggs
Plain boiled water gel and preparation method thereof, dual network silk fibroin hydrogel are using silk fibroin molecular as matrix, in its amino acid side
Chain introduces main body, object and horseradish peroxidase, built-up dual network silk fibroin hydrogel.The present invention is with biofacies
The good fibroin albumen macromolecule of capacitive is matrix, introduces subject and object by chemical modification, then horseradish is introduced in system
Peroxidase and hydrogen peroxide prepare dual network silk fibroin hydrogel.Reversible binding between subject and object unit
Effect and the crosslinked action of horseradish peroxidase enzyme catalytic, assign the stability of silk fibroin hydrogel structure and performance.With
This simultaneously, the presence of dual network structure increases the crosslinked action site of gel network, greatly improves fibroin albumen water-setting
The elasticity modulus of glue, so as to improve its tensile property.Silk fibroin hydrogel prepared by the present invention is in addition to soft, High water cut
It measures, have outside bioactivity, also there is very strong toughness and tensile resistance, be not easy impaired fracture, up to 800% can be subjected to
Elongation strain deformation is realized in 800% range of strain and is repeated as many times high-intensitive stretching, and can restore rapidly after tension failure
Its original mechanical performance.Dual network silk fibroin hydrogel of the invention is design preparation for the compound of bioengineered tissue
Material provides new thinking, has expanded silk fibroin hydrogel in fields such as biological medicine, regeneration, flexible electronic devices
Practical application.
After a specific embodiment of the invention is read in conjunction with the figure, the other features and advantages of the invention
It will become clearer.
Detailed description of the invention
Fig. 1 is the optical photograph of the stretched front and back of dual network silk fibroin hydrogel of the embodiment of the present invention 3；
Fig. 2 is the tensile stress strain curve of the dual network silk fibroin hydrogel of the embodiment of the present invention 4.
Specific embodiment
Detailed description of the preferred embodiments below, it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
It is using silk fibroin molecular as matrix, in its amino the present invention provides a kind of dual network silk fibroin hydrogel
Sour side chain introduces main body, object and horseradish peroxidase, the dual network silk fibroin hydrogel of building.
Main body can be cyclodextrin or Cucurbituril, and cyclodextrin and Cucurbituril all have the molecular structure of big ring, can and visitor
Body molecule forms clathrate complex.Object can be adamantane, ferrocene, cholic acid, cholesterol or carbazole analog derivative, Ke Yihe
Host molecule forms clathrate complex.
Main body is preferably cyclodextrin, and object is preferably adamantane.
The present invention introduces main body and visitor using the good fibroin albumen macromolecule of biocompatibility as matrix, by chemical modification
Body, then horseradish peroxidase and hydrogen peroxide are introduced in system, prepare dual network silk fibroin hydrogel.Main body and visitor
Reversible binding effect and the crosslinked action of horseradish peroxidase enzyme catalytic between body unit, assign silk fibroin hydrogel knot
The stability of structure and performance.At the same time, the presence of dual network structure increases the crosslinked action site of gel network, greatly
The elasticity modulus of silk fibroin hydrogel is improved, so as to improve its tensile property.Fibroin albumen water-setting prepared by the present invention
Glue also has very strong toughness and tensile resistance, is not easy impaired fracture other than softness, high-moisture, having bioactivity,
It can be subjected to up to 800% elongation strain deformation, realize in 800% range of strain and be repeated as many times high-intensitive stretching, and stretch disconnected
It can restore its original mechanical performance after splitting rapidly.Dual network silk fibroin hydrogel of the invention is design preparation for giving birth to
The composite material of object organizational project provides new thinking, has expanded silk fibroin hydrogel in biological medicine, regeneration, soft
The practical application in the fields such as property electronic device.
The present invention improves the drawing of Silk fibroin gel using being physical crosslinking and being chemically crosslinked the combination of two kinds of crosslinking methods
Performance is stretched, firstly, subject and object is grafted on fibroin albumen macromolecular chain by way of chemical modification, main body and visitor
Body molecule forms clathrate complex, forms physical cross-linked network, obtains the excellent Silk fibroin gel of tensile property.Secondly, mistake
Hydrogen oxide can be with the Fe(III in horseradish peroxidase) reaction, generate the intermediate (HRP I) with strong oxidizing property, silk
Phenolic hydroxyl group on fibroin tyrosine forms phenolic aldehyde free radical under the oxidation of HRP I, and then, the phenolic aldehyde on tyrosine is certainly
Two tyrosine covalent bonds are formed under the catalytic action of horseradish peroxidase by base, chemical crosslinking network is formed, further mentions
The tensile property of high silk fibroin hydrogel.Between subject and object physical crosslinking effect and horseradish peroxidase and
Chemical crosslinking effect between hydrogen peroxide improves the elasticity modulus of Silk fibroin gel, so that Silk fibroin gel is with excellent
Different tensile deformation ability.
The preparation method of dual network silk fibroin hydrogel of the invention includes:
(1) silk fibroin protein solution of carboxylated is prepared；Silk is obtained into silk fibroin protein solution by degumming, dissolution, dialysis treatment；
The silk fibroin protein solution is passed through into borax, diazonium salt, monoxone chemical modification, obtains the silk that concentration is 0.1%-50% carboxylated
Fibroin solution；By silk fibroin protein solution dialysis, the freeze-drying of the carboxylated, the silk fibroin powder of carboxylated is obtained.
The silk fibroin protein solution concentration of carboxylated is 0.1%-50%, and in this concentration range, fibroin albumen can be grafted to the greatest extent
Host cyclodextrin and object adamantane.
(2) fibroin albumen-bulk solution is prepared；Amidized main body is dissolved in dimethyl sulphoxide solution, concentration is made into
For the amidized bulk solution of 0.1-1000 mg/mL；EDC HCl is dissolved in dimethyl sulphoxide solution, being made into concentration is
The EDC HCl solution of 0.1-1000 mg/mL；The silk fibroin powder of carboxylated is dissolved in dimethyl sulphoxide solution, is made into concentration
For the silk fibroin protein solution of the carboxylated of 0.05-10mg/mL；By amidized bulk solution, EDC HCl solution and carboxylated
Silk fibroin protein solution mixing, room temperature reaction, dialysis freeze-drying, obtains fibroin albumen-main body powder；By fibroin albumen-main body
Powder is dissolved in water, is prepared into fibroin albumen-bulk solution that mass fraction is 1%-50%；In this concentration range, main ring paste
Essence can be grafted with fibroin albumen to the greatest extent.
(3) fibroin albumen-object solution is prepared；Prepare the object solution that concentration is 0.1-1000 mg/mL；By EDC HCl
It is dissolved in dimethyl sulphoxide solution, is made into the EDC HCl solution that concentration is 0.1-1000 mg/mL；By the fibroin albumen of carboxylated
Powder is dissolved in dimethyl sulphoxide solution, is made into the silk fibroin protein solution for the carboxylated that concentration is 0.05-10mg/mL；Object is molten
The silk fibroin protein solution of liquid, EDC HCl solution and carboxylated mixes, and room temperature reaction, dialysis freeze-drying obtain fibroin albumen-
Object powder；Fibroin albumen-object powder is dissolved in water, is prepared into fibroin albumen-object solution that mass fraction is 1%-50%；
In this concentration range, object adamantane can be grafted with fibroin albumen to the greatest extent.
(4) the horseradish peroxidase solution of 900-1100U/mL is added into fibroin albumen-bulk solution, mixing is equal
It is even, the first mixed liquor is obtained, the effect of horseradish peroxidase enzyme crosslinking is best in this concentration range.
(5) 160-170mM hydrogenperoxide steam generator is added into fibroin albumen-object solution, is uniformly mixed, it is mixed to obtain second
Close liquid.Hydrogenperoxide steam generator concentration is 160-170mM, and the hydrogen peroxide in this concentration range is best to the catalytic effect of enzyme.
(6) the first mixed liquor and the second mixed liquor are mixed according to cyclodextrin and adamantane molar ratio 100:1-1:100 equal
Even, standing, obtaining mass fraction is 1%-50% dual network silk fibroin hydrogel.When the first mixed liquor and the second mixed liquor according to
When the ratio mixing that the molar ratio of cyclodextrin and adamantane is 100:1-1:100, the dual network silk fibroin hydrogel of formation
Performance is best, can improve tensility energy, the adhesion property of silk fibroin hydrogel to the greatest extent.
Embodiment 1
(1) silk fibroin protein solution of carboxylated is prepared；
By silk through Na2CO3Solution degumming, the dissolution of LiBr solution, deionized water dialysis processing obtain the fibroin egg that concentration is 1%
White solution；By 5 mL silk fibroin protein solutions and 2 mL, the NaOH solution of 10 M is mixed 5 min, then by 4 mL, the chlorine of 1 M
Acetic acid is added in reaction solution, mixes 50 min at room temperature, 500 μ L are then added into above-mentioned mixed solution again, 7 mg/mL's
NaH2PO4Solution, ice bath react 30 min, obtain the silk fibroin protein solution of carboxylated processing；It is freeze-dried, obtains after dialysing
The silk fibroin powder of carboxylated processing.
(2) fibroin albumen-cyclodextrin solution is prepared；
Amidized cyclodextrin is dissolved in dimethyl sulphoxide solution, it is molten to be made into the amidized cyclodextrin that concentration is 1 mg/mL
Liquid；EDC HCl is dissolved in dimethyl sulphoxide solution, the EDC HCl solution that concentration is 1 mg/mL is made into；By 1 mg carboxylated
The silk fibroin powder of processing is dissolved in 10 mL dimethyl sulphoxide solutions, and the amidized cyclodextrin solution of 1 μ L and 1 μ L is added
EDC HCl solution, reacts at room temperature 24 h, and dialysis freeze-drying prepares fibroin albumen-cyclodextrin powder；By fibroin albumen-ring paste
Fine powder end is dissolved in water, is prepared into fibroin albumen-cyclodextrin solution that mass fraction is 1%.
(3) fibroin albumen-adamantane solution is prepared；
Amantadine hydrochloride is dissolved in dimethyl sulphoxide solution, the amantadine hydrochloride solution that concentration is 1 mg/mL is made into；It will
EDC HCl is dissolved in dimethyl sulphoxide solution, is made into the EDC HCl solution that concentration is 1 mg/mL；By the processing of 1 mg carboxylated
Fibroin albumen is dissolved in 10 mL dimethyl sulphoxide solutions, and 1 μ L amantadine hydrochloride solution and 1 μ L EDC HCl, room temperature is added
24 h are reacted, dialysis freeze-drying prepares fibroin albumen-adamantane powder；Fibroin albumen-adamantane powder is dissolved in water, is made
Standby fibroin albumen-adamantane the solution for being 1% at mass fraction.
(4) to 10mL, the horseradish peroxidase solution of 1000 U/mL is added in 1% fibroin albumen-cyclodextrin solution,
It is uniformly mixed, obtains the first mixed liquor.
(5) to 100 μ L, the hydrogen peroxide of 165 mM is added in 1% fibroin albumen-adamantane solution, is uniformly mixed, obtains
To the second mixed solution.
(6) the first mixed liquor and the second mixed liquor are mixed according to the ratio that the molar ratio of cyclodextrin and adamantane is 100:1
It closes and uniformly obtains the dual network silk fibroin hydrogel that mass fraction is 1% after standing.
Embodiment 2
(1) silk fibroin protein solution of carboxylated is prepared；
By silk through Na2CO3Solution degumming, the dissolution of LiBr solution, deionized water dialysis processing obtain the fibroin egg that concentration is 4%
White solution；By 5 mL silk fibroin protein solutions and 2 mL, the NaOH solution of 10 M is mixed 5 min, then by 4 mL, the chlorine of 1 M
Acetic acid is added in reaction solution, mixes 50 min at room temperature, 500 μ L are then added into above-mentioned mixed solution again, 7 mg/mL's
NaH2PO4Solution, ice bath react 30 min, obtain the silk fibroin protein solution of carboxylated processing；It is freeze-dried, obtains after dialysing
The silk fibroin powder of carboxylated processing.
(2) fibroin albumen-cyclodextrin solution is prepared；
Amidized cyclodextrin is dissolved in dimethyl sulphoxide solution, it is molten to be made into the amidized cyclodextrin that concentration is 10 mg/mL
Liquid；EDC HCl is dissolved in dimethyl sulphoxide solution respectively, is made into the EDC HCl solution that concentration is 10 mg/mL；By 3 mg
The silk fibroin powder of carboxylated processing is dissolved in 30 mL dimethyl sulphoxide solutions, and the 100 amidized cyclodextrin solutions of μ L are added
With 100 μ L EDC HCl solutions, 24 h are reacted at room temperature, dialysis freeze-drying prepares fibroin albumen-cyclodextrin powder；By fibroin
Albumen-cyclodextrin powder is dissolved in water, is prepared into fibroin albumen-cyclodextrin solution that mass fraction is 15%.
(3) fibroin albumen-adamantane solution is prepared；
Amantadine hydrochloride is dissolved in dimethyl sulphoxide solution, the amantadine hydrochloride solution that concentration is 10 mg/mL is made into；
EDC HCl is dissolved in dimethyl sulphoxide solution, the EDC HCl solution that concentration is 10 mg/mL is made into；At 30 mg carboxylated
The fibroin albumen of reason is dissolved in 300 mL dimethyl sulphoxide solutions, and 200 μ L amantadine hydrochloride solution and 200 μ L EDC are added
HCl, reacts at room temperature 24 h, and dialysis freeze-drying prepares fibroin albumen-adamantane powder；Fibroin albumen-adamantane powder is molten
Yu Shui is prepared into fibroin albumen-adamantane solution that mass fraction is 1%.
(4) to 10mL, the horseradish peroxidase that 1000 U/mL are added in 15% fibroin albumen-cyclodextrin solution is molten
Liquid is uniformly mixed, obtains the first mixed liquor.
(5) to 3 mL, the hydrogen peroxide of 165 mM is added in 1% fibroin albumen-adamantane solution, is uniformly mixed, obtains
Second mixed solution.
(6) the first mixed liquor and the second mixed liquor are mixed according to the ratio that the molar ratio of cyclodextrin and adamantane is 50:1
Uniformly, the dual network silk fibroin hydrogel that mass fraction is 11.8% is obtained after standing.
Embodiment 3
(1) silk fibroin protein solution of carboxylated is prepared；
By silk through Na2CO3Solution degumming, the dissolution of LiBr solution, deionized water dialysis processing obtain the fibroin egg that concentration is 7%
White solution；By 5 mL silk fibroin protein solutions and 2 mL, the NaOH solution of 10 M is mixed 5 min, then by 4 mL, the chlorine of 1 M
Acetic acid is added in reaction solution, mixes 50 min at room temperature, 1 mL is then added into above-mentioned mixed solution again, 7 mg/mL's
NaH2PO4Solution, ice bath react 30 min, obtain the silk fibroin protein solution of carboxylated processing；It is freeze-dried, obtains after dialysing
The silk fibroin powder of carboxylated processing.
(2) fibroin albumen-cyclodextrin solution is prepared；
Amidized cyclodextrin is dissolved in dimethyl sulphoxide solution, the amidized cyclodextrin that concentration is 100 mg/mL is made into
Solution；EDC HCl is dissolved in dimethyl sulphoxide solution respectively, is made into the EDC HCl solution that concentration is 100 mg/mL；By 30
The silk fibroin powder of mg carboxylated processing is dissolved in 300 mL dimethyl sulphoxide solutions, and the 1000 amidized cyclodextrin of μ L are added
Solution and 100 μ L EDC HCl solutions, react at room temperature 24 h, and dialysis freeze-drying prepares fibroin albumen-cyclodextrin powder；It will
Fibroin albumen-cyclodextrin powder is dissolved in water, is prepared into fibroin albumen-cyclodextrin solution that mass fraction is 25%.
(3) fibroin albumen-adamantane solution is prepared；
Amantadine hydrochloride is dissolved in dimethyl sulphoxide solution, the amantadine hydrochloride solution that concentration is 100 mg/mL is made into；
EDC HCl is dissolved in dimethyl sulphoxide solution, the EDC HCl solution that concentration is 100 mg/mL is made into；By 30 mg carboxylated
The fibroin albumen of processing is dissolved in 300 mL dimethyl sulphoxide solutions, and 200 μ L amantadine hydrochloride solution and 200 μ L are added
EDC HCl, reacts at room temperature 24 h, and dialysis freeze-drying prepares fibroin albumen-adamantane powder；By fibroin albumen-adamantane powder
End is dissolved in water, is prepared into fibroin albumen-adamantane solution that mass fraction is 25%.
(4) to 10mL, the horseradish peroxidase that 1000 U/mL are added in 25% fibroin albumen-cyclodextrin solution is molten
Liquid is uniformly mixed, obtains the first mixed liquor.
(5) to 10mL, the hydrogen peroxide of 165 mM is added in 25% fibroin albumen-adamantane solution, is uniformly mixed, obtains
To the second mixed solution.
(6) the first mixed liquor and the second mixed liquor are mixed according to the ratio that the molar ratio of cyclodextrin and adamantane is 1:1
Uniformly, the dual network silk fibroin hydrogel that mass fraction is 25% is obtained after standing.
Fig. 1 is the optical photograph of the stretched front and back of dual network silk fibroin hydrogel of embodiment 3, illustrates the present embodiment
Dual network silk fibroin hydrogel there is good tensility, former long 2.5 times can be pulled to.
Embodiment 4
(1) silk fibroin protein solution of carboxylated is prepared；
By silk through Na2CO3Solution degumming, the dissolution of LiBr solution, deionized water dialysis processing obtain the fibroin that concentration is 10%
Protein solution；By 5 mL silk fibroin protein solutions and 4 mL, the NaOH solution of 10 M is mixed 5 min, then by 4 mL, 2 M's
Monoxone is added in reaction solution, mixes 50 min at room temperature, 1 mL is then added into above-mentioned mixed solution again, 7 mg/mL's
NaH2PO4Solution, ice bath react 30 min, obtain the silk fibroin protein solution of carboxylated processing；It is freeze-dried, obtains after dialysing
The silk fibroin powder of carboxylated processing.
(2) fibroin albumen-cyclodextrin solution is prepared；
Amidized cyclodextrin is dissolved in dimethyl sulphoxide solution, the amidized cyclodextrin that concentration is 1000 mg/mL is made into
Solution；EDC HCl is dissolved in dimethyl sulphoxide solution respectively, is made into the EDC HCl solution that concentration is 1000 mg/mL；It will
The silk fibroin powder of 30 mg carboxylated processing is dissolved in 300 mL dimethyl sulphoxide solutions, and the amidized ring paste of 1000 μ L is added
Smart solution and 100 μ L EDC HCl solutions, react at room temperature 24 h, and dialysis freeze-drying prepares fibroin albumen-cyclodextrin powder；
Fibroin albumen-cyclodextrin powder is dissolved in water, is prepared into fibroin albumen-cyclodextrin solution that mass fraction is 4%.
(3) fibroin albumen-adamantane solution is prepared；
Amantadine hydrochloride is dissolved in dimethyl sulphoxide solution, it is molten to be made into the amantadine hydrochloride that concentration is 1000 mg/mL
Liquid；EDC HCl is dissolved in dimethyl sulphoxide solution, the EDC HCl solution that concentration is 50 mg/mL is made into；By 30 mg carboxyls
The fibroin albumen for changing processing is dissolved in 300 mL dimethyl sulphoxide solutions, and 200 μ L amantadine hydrochloride solution and 200 μ L are added
EDC HCl, reacts at room temperature 24 h, and dialysis freeze-drying prepares fibroin albumen-adamantane powder；By fibroin albumen-adamantane powder
End is dissolved in water, is prepared into fibroin albumen-adamantane solution that mass fraction is 40%.
(4) to 2 mL, the horseradish peroxidase solution of 1000 U/mL is added in 4% fibroin albumen-cyclodextrin solution,
It is uniformly mixed, obtains the first mixed liquor.
(5) to 20 mL, the hydrogen peroxide of 165 mM is added in 40% fibroin albumen-adamantane solution, is uniformly mixed, obtains
To the second mixed solution.
(6) the first mixed liquor and the second mixed liquor are mixed according to the ratio that the molar ratio of cyclodextrin and adamantane is 1:100
It closes and uniformly obtains the dual network silk fibroin hydrogel that mass fraction is 36.7% after standing.
Fig. 2 is the tensile stress strain curve of the dual network silk fibroin hydrogel for embodiment 4, illustrates the present embodiment system
Standby dual network silk fibroin hydrogel has very excellent tensile property, and tensile elongation is up to 800%.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited；Although referring to aforementioned reality
Applying example, invention is explained in detail, for those of ordinary skill in the art, still can be to aforementioned implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these are modified or replace
It changes, the spirit and scope for claimed technical solution of the invention that it does not separate the essence of the corresponding technical solution.
Claims (9)
1. a kind of dual network silk fibroin hydrogel, which is characterized in that
To introduce main body, object and horseradish peroxidase in its amino acid side chain using silk fibroin molecular as matrix, building and
At dual network silk fibroin hydrogel.
2. dual network silk fibroin hydrogel according to claim 1, which is characterized in that
The main body includes cyclodextrin or Cucurbituril,
The object includes adamantane, ferrocene, cholic acid, cholesterol or carbazole analog derivative.
3. a kind of preparation method of dual network silk fibroin hydrogel according to claim 2, which is characterized in that
The described method includes:
(1) silk fibroin powder of carboxylated is prepared；
(2) fibroin albumen-bulk solution is prepared；
(3) fibroin albumen-object solution is prepared；
(4) horseradish peroxidase solution is added in Xiang Suoshu fibroin albumen-bulk solution, is uniformly mixed, obtains the first mixing
Liquid；
(5) hydrogenperoxide steam generator is added in Xiang Suoshu fibroin albumen-object solution, is uniformly mixed, obtains the second mixed liquor；
(6) first mixed liquor and second mixed liquor are uniformly mixed, are static, obtaining dual network fibroin albumen water-setting
Glue.
4. the preparation method of dual network silk fibroin hydrogel according to claim 3, which is characterized in that
The step (1) includes: that silk is obtained silk fibroin protein solution by degumming, dissolution, dialysis treatment；Fibroin albumen is molten
Liquid passes through borax, diazonium salt, monoxone chemical modification, obtains the silk fibroin protein solution that concentration is 0.1%-50% carboxylated；By carboxylic
Silk fibroin protein solution dialysis, the freeze-drying of base, obtain the silk fibroin powder of carboxylated.
5. the preparation method of dual network silk fibroin hydrogel according to claim 3, which is characterized in that
The step (2) includes: that amidized main body is dissolved in dimethyl sulphoxide solution, and being made into concentration is 0.1-1000 mg/
The amidized bulk solution of mL；EDC HCl is dissolved in dimethyl sulphoxide solution, being made into concentration is 0.1-1000 mg/mL's
EDC HCl solution；The silk fibroin powder of carboxylated is dissolved in dimethyl sulphoxide solution, being made into concentration is 0.05-10mg/mL's
The silk fibroin protein solution of carboxylated；The silk fibroin protein solution of amidized bulk solution, EDC HCl solution and carboxylated is mixed
It closes, room temperature reaction, dialysis freeze-drying obtain fibroin albumen-main body powder；Fibroin albumen-main body powder is dissolved in water, is prepared
Fibroin albumen-the bulk solution for being 1%-50% at mass fraction.
6. the preparation method of dual network silk fibroin hydrogel according to claim 3, which is characterized in that
The step (3) includes: to prepare the object solution that concentration is 0.1-1000 mg/mL；EDC HCl is dissolved in dimethyl Asia
In sulfolane solution, it is made into the EDC HCl solution that concentration is 0.1-1000 mg/mL；The silk fibroin powder of carboxylated is dissolved in diformazan
Base sulfoxide solution is made into the silk fibroin protein solution for the carboxylated that concentration is 0.05-10mg/mL；Object solution, EDC HCl is molten
Liquid and the mixing of the silk fibroin protein solution of carboxylated, room temperature reaction, dialysis freeze-drying, obtain fibroin albumen-object powder；By silk
Fibroin-object powder is dissolved in water, is prepared into fibroin albumen-object solution that mass fraction is 1%-50%.
7. the preparation method of dual network silk fibroin hydrogel according to claim 3, which is characterized in that
In the step (4), the content of horseradish peroxidase is 900-1100U/mL.
8. the preparation method of dual network silk fibroin hydrogel according to claim 3, which is characterized in that
In the step (5), hydrogenperoxide steam generator concentration is 160-170mM.
9. the preparation method of dual network silk fibroin hydrogel according to claim 3, which is characterized in that
In the step (6), the first mixed liquor and the second mixed liquor are 100:1-1:100's according to the molar ratio of subject and object
Ratio is uniformly mixed, and the mass fraction of dual network silk fibroin hydrogel is 1%-50%.
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